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By F. E. Bash

About three years ago, the writer presented a paper1 on the rate of heating and cooling of a 24-in. round ingot. The present paper deals with work done on larger ingots at the plant of the Allis Chalmers Mfg. Co., Milwaukee, Wis., in August, 1919. Sufficient data on ingots of all sizes were desired to enable one to calculate in advance the rate at which any ingot could be raised to a forging temperature without injury to the steel, determining also the temperature gradient between different sections of the ingot and the length of time necessary to heat to the center. This has now been experimentally determined for 24-in. and 45-in. ignots by the writer and for a 18-in. cube by E. F. Law.2 J. F. Harper has also made tests on heat-treating temperatures on 30-in, ingots; which data are included in this paper. No attempt is made here to work out a formula for the heat penetration of steel, for too many factors are involved concerning which we have not sufficient information, as for instance, the specific heat of steel up to 2300' F. It is hoped that eventually a set of formulas will be developed so that one may calculate maximum allowable temperature differences within an ingot for any particular kind of steel and the rate of absorption of heat and temperature gradient within the ingot for a definite temperature head. EXPEEIMENTAL INGOT The ingot tested was 45 in. in diameter, having been forged into the shape shown in Fig. 1 from 54 in. diameter. Seven -in. holes were

Jan 1, 1923

By Leendert de Witte, Fred J. Radd

In many areas caring failures can be directly related to electrical currents observed in the casings. It is the thesis of this paper that the observed casing currents are mainly due to electrochemical potentials of the type in evidence on spontaneous potential curves of electrical logs. The general nature of these potentials are discussed and an equivalent circuit is given for current and potential distributions around open holes. The casing forms a short circuit to these potentials and tends to average the effects of local cells. The case of casing corrosion opposite the Dakota water sands in the salt-mud area of Kansas is discussed anil used us a qualitative, illustration of the relation between SP's and casing currents. A method of quantitative derivation of casing current distribution frorn electric log SP curves, using linear transform theory, is described and results are compared with a measured current profile. The effects of hydrogen over-potentials at the cathodic portions of the pipe are considered and some laboratory data are given in support of conclusions regarding the over-1.01tuge.s. INTRODUCTION To date an appreciable amount of work has been done on the measurement of oil well casing currents and on the correlation of the anodic portions of the current profiles with corrosive casing failures. Speculations on the origin of the casing currents have, however, remained rather vague; and although almost every plausible cause has been mentioned, there is to the writers' knowledge no clear-cut expose' on the details of the causes of the corrosive currents in the literature. A study of current surveys and casing failures in the N.W. Burnett field, Ellis County. Kan.. indicated the probability that concentration cell emf's between the Wellington salt section and the relatively fresh waters in the Dakota sands were a major cause of the corrosion currents. A more general concept evolved upon analysis of the severe corrosive conditions in the Pleistocene sands in the Ventura Avenue and San Miguelito fields in California. In this area no major variations in the salt content of the formation waters occur and yet large casing currents are observed. An explanation is found in the fact that the local spontaneous potentials which are set up due to concentration contrast between the drilling fluid and the connate water are short circuited when casing is set. The very conductive path through the casing increases the magnitude of the currents and has the tendency to average local sources over fairly large intervals. Current will flow between the sections that are predominently shaly and the sections that are mostly sandy. At the places where the current leaves the pipe, corrosive attack will occur. This same phenomenon will be present wherever unprotected pipe is set through sections that show large SP kicks on the electric logs over reasonably thick interval~. GENERAL- NATURE OF THE SPONTANEOUS POTENTIALS When a sequence of sedimentary rocks is penetrated by a drill hole filled with a mud which has a different salt concentration from that in the formation waters, various types of electrochemical potentials are established between the formations and different parts of the mud column. Opposite clean sand sections. a simple liquid-liquid junction potential will be observed; while opposite argillaccous formations, a membrane potential, often referred to as shale potential, will be established. The first quantitative analysis of these emf's in terms of liquid junction and membrane potentials is due to Wyllie.1

Jan 1, 1956

By William Plank

IN PAST YEARS, engineering educators and others have been able to study the problems relating to en-gineering education in the United States with only inadequate and, frequently, inaccurate data at their command. For the first time there is now available fairly full and accurate information on this subject, gathered and compiled by the Board of Investigation and Coordination of the Society for the Promotion of Engineering Education. This board, of which W. E. Wickenden is the director, has for the past four years been carrying out fact-finding investigations into "the objects of engineering education and the fitness of the present day curriculum," under a grant of funds from the Carnegie Corporation of New York. Twelve bulle-tins have already been published by the board and others are in the process of preparation. The studies made, thus far, have been of the various phases of engineering education in general as well as of the major branches of engineering. Within the past year. the board has completed a study of mining engi-neering education by means of a questionnaire sent to members of the Institute. A special committee, con-sisting of Charles E. Locke, Allen H. Rogers and the writer, cooperated with the board in drafting certain parts of the questionnaire and in selecting the mailing list. Similar studies have been made through the mem-bers of the four other national societies. The results of these studies have been published only in mimeo-graphed form, therefore, in order to place the data before the members of the Institute an incomplete sum-mary of the replies to the A. I. M. E. questionnaire is here given. The full report will be available for distri-bution at the annual meeting in February. The questionnaire was sent to 306 members of the Institute, a proportion about equal to the proportion of the membership of the other national societies can-vassed; 152 members replied to the questionnaire, 55 per cent of whom had received college degrees in some branch of engineering connected with the mineral in-dustry. Forty-seven educational institutions were rep-resented in the replies. Seventeen different positions were held by the members who replied, with 24 con-sulting engineers at the head of the list, 20 managers, 16 superintendents, 11 presidents, 10 professors, 6 deans, and others.

Jan 1, 1928

By G. R. Mansfield

THE third year of Government exploration f or potash by the U. S. Geological Survey and-the U. S. Bureau of Mines under the authorization of the act approved June 25, 1926 (Public 424-69th Cong.) is drawing to a close. The results thus far obtained are thought to be sufficiently interesting and satisfactory to justify the presentation of a brief preliminary account of the work. REVIEW OF EARLIER EXPLORATION The general geologic similarity of the Permian basin of Texas and New Mexico to the potash field of Germany had long ago suggested the possibility of the presence of potash salts somewhere in that basin, but petroleum exploration was then making little headway there and the necessary data could not be obtained. The discovery by Udden in 1912 of potash in brine from the Spur well in Dickens County, Texas, was the first direct evidence of its presence. In 1915-17 the U. S. Geological Survey drilled a test well with standard tools at Cliff side near Amarillo, but failed to find potash. Nevertheless, an observer has been kept in the field, at first in cooperation with the Texas Bureau of Economic Geology but since 1922 by the Survey alone, to `secure data and samples from oil and gas tests. Since the discovery of oil in Reagan County in 1923 exploration by drilling has been rapidly extended to many parts of western Texas and southeastern New Mexico. The identification of the potash-bearing mineral polyhalite was first announced by the Geological Survey in June, 1921, the material having come from cuttings from the Bryant well in Midland County and the Burns well in Dawson County, Texas. Successive discoveries and announcements of similar purport aroused widespread interest in potash exploration, which culminated in the action by Congress already noted.

Jan 1, 1929

By William E. Ford, Edward Salisbury Dana

Normal phosphoric acid is H3P04, and consequently normal phosphates have the formulas R3PO4, R3(P04)2 and RPO4, and similarly for the arsenates, etc. Only a comparatively small number of species conform to this simple formula. Most species contain more than one metallic element, and in the prominent Apatite Group the radical (CaF), (CaCI) or (PbCI) enters; in in the Wagnerite Group we have similarly (RF) or (ROH).

Jan 1, 1922

By M. E. Wadsworth, L. H. Raby, A. S. Peck

Infrared spec troscopy was used to study the adsorption of oleate collector on three varieties of hematite. Each of the minerals was found to react with either oleic acid or a solution of sodium oleate to form a mineral cation-collector anion chemisorbed layer at the solid-liquid interface. The chemisorption reaction displaced surface hydroxyls and was found to be pH dependent. The infrared band characteristic of the antisymmetrical C = 0 structural group of chemisorbed oleate appears between 1520 and 1540 cm-'. Evidence is presented which shows that molecular filming of the mineral surfaces with un-dissociated oleic acid precedes chemisorption. Infrared absorbance is correlated with the flotation behavior of the mineral. Adsorption processes are usually classified into two types which are distinguished and character- ized by the nature of the bond formed between the adsorbate and adsorbent. The process in which molecules chemically bond to solid surfaces is termed activated adsorption or chemisorption. If only weak van der Waals forces bind the molecules to the surface then the process is termed physical adsorption. Chemisorption is of primary interest in flotation systems since selectivity may be obtained if a single mineral is rendered air-avid by a specific collector mineral adsorption reaction. In previous studies infrared spectroscopy was used to define the mechanisms involved in the adsorption of oleic acid and sodium oleate on fluorite, barite, and calcite. Infrared techniques were particularly useful since adsorbed monolayers were identified in situ. Further, the infrared method permitted identification of reaction products in the solid, liquid, and vapor phases of the systems. The chemisorption reactions displaced F- from fluorite, SO4 from barite, and CO3 from calcite. This investigation was pursued in an effort to characterize and interpret the adsorption processes for synthetic hematite, compact red hematite, and specular hematite (crystalline hematite). Adsorption tests were performed using either oleic acid or

Jan 1, 1967

By George H. Found

During recent years considerable interest has been focused on the energy-absorption characteristics of metal when it is cyclically stressed in vibration. The most familiar manifestation of this phenomenon, which is called the "damping capacity" or "internal friction" 06 a material, is involved in the dissipation of mechanical energy of vibration, which otherwise would build up to stress levels where the problems of noise and fatigue are involved. In addition to its engineering importance in structures, the damping behavior of metals, particularly at low stress amplitudes, has also been used as a unique metallurgical research tool with which to provide sensitive means for indicating certain structural changes within metals. Important contributions toward understanding the energy-dissipating -mecha-nisms that are responsible for internal friction in metals have been made in the last few years. The information is not yet sufficiently extensive, however, to provide a useful metallurgical concept describing exactly how the structure affects the internal friction, or to encourage more general use of this technique among metallurgists. Three fundamental mechanisms have been proposed, as a result of recent experi- mental investigations, to account for the internal friction in nonferrous metals in low-stress amplitude tests. These include damping due to internal thermal currents that are created and flow in metal because of differential vibratory stress effects,' damping due to localized inelastic stress relaxation at inhomogeneities within the meta1,2,3 and damping related to plastic flow of a localized type for which an explanation has been sought in terms of the dislocation theory.' How each of these mechanisms functions as a result of structural changes in the metal is, in general, not well understood because of insufficient experimental data for which the controlling variables ham been segregated and because of uncertainties in regard to the nature of the structural changes themselves. In several investigations the effects of cold-working on the internal friction of polycrystalline brass and aluminum have been described. As reported by Köster and Rosenthal,5 and by Förster and Breitfield,6 there is an initial large increase in the damping when the metal is worked. The initial high value is not stable, but declines rapidly, at first, in a hyperbolic manner. About Ioo hr. after straining, a stable value is reached of magnitude proportional to the amount of strain.' In Fig. I is shown the relationship found by Zener and his collaborators between the internal friction due to cold-working of alpha brass and the amount of cold-working.8 Several investigators have made internal-friction measurements on worked poly-

Jan 1, 1945

By Harry E. Cross

Kiln Products commissioned a Waelz kiln 4 metres in diameter by 75 metres long, in South West Africa in March, 1969, to recover nine in a form suitable for the production of electrolytic zinc. The raw material consists of a mixture of zinc silicate concentrates and zinc rich tailings purchased from an adjacent zinc mine - the mixture containing 20% to 25% zinc. The chemical composition of the ore is tabulated and the initial test results are described. Due to the comparatively low temperature at which the ore starts softening the kiln has certain unusual features to enable the temperature to be controlled within the necessary limits. A detailed description of the kiln, the starting-up problems and present operating conditions and results are presented.

Jan 1, 1970

By Arthur Phillips, R. M. Brick, A. J. Smith

A previous publication1§ has described the effect of quenching stresses on the lattice parameter values of high-purity aluminum-copper alloys particularly with reference to the solution and precipitation of CuAl². A similar study has been made of the aluminum-rich aluminum-magnesium alloys. Attention has been directed in the present investigation to the magnitude of the quenching stresses as affected by the specimen size and shape, the number of solute atoms and the quenching rate. The effect of cooling stresses in causing plastic defomation or cracking has been considered in relation to the physical properties of the alloy On reheating alloys in the two-phase field, the time required for precipitation to occur has been observed in connection with the degrec of supersaturation, the rate of diffusion of the solute atoms as a function of the comparative atomic radii, degree of strain, temperature of reheating and grain size. A few qualitative comparisons on the relative effect of these factors have been drawn between the aluminum-copper alloys and the aluminum-magnesium alloys. Strain in Solid-solution Alloys A 10 per cent magnesium alloy ill the form of chill-cast bars was furnished by the Aluminum Company of America through the courtesy of L. W. Kempf. Additional alloys were prepared using alllminum (99.95 per cent Al) and high-grade magnesium. The alloys listed in Table 1 were melted in an Acheson graphite crucible under a flux of fused MgCl², CaC12, NaCI. Chill-cast rods were sealed under vacuum in Pyrex glass, homogenized several days at 450' C., air-cooled and machined to rods of from 1/8 to ¾-in. dia. Metal powders taken from these rods with a fine-toothed saw were again sealed under vacuum in

Jan 1, 1935

By R. M. Brick, Arthur Phillips, A. J. Smith

A previous publication1§ has described the effect of quenching stresses on the lattice parameter values of high-purity aluminum-copper alloys particularly with reference to the solution and precipitation of CuAl². A similar study has been made of the aluminum-rich aluminum-magnesium alloys. Attention has been directed in the present investigation to the magnitude of the quenching stresses as affected by the specimen size and shape, the number of solute atoms and the quenching rate. The effect of cooling stresses in causing plastic defomation or cracking has been considered in relation to the physical properties of the alloy On reheating alloys in the two-phase field, the time required for precipitation to occur has been observed in connection with the degrec of supersaturation, the rate of diffusion of the solute atoms as a function of the comparative atomic radii, degree of strain, temperature of reheating and grain size. A few qualitative comparisons on the relative effect of these factors have been drawn between the aluminum-copper alloys and the aluminum-magnesium alloys. Strain in Solid-solution Alloys A 10 per cent magnesium alloy ill the form of chill-cast bars was furnished by the Aluminum Company of America through the courtesy of L. W. Kempf. Additional alloys were prepared using alllminum (99.95 per cent Al) and high-grade magnesium. The alloys listed in Table 1 were melted in an Acheson graphite crucible under a flux of fused MgCl², CaC12, NaCI. Chill-cast rods were sealed under vacuum in Pyrex glass, homogenized several days at 450' C., air-cooled and machined to rods of from 1/8 to ¾-in. dia. Metal powders taken from these rods with a fine-toothed saw were again sealed under vacuum in

Jan 1, 1935

Through the generosity of Sir Robert Hadfield, Honorary Member, the Directors of the American Institute of Mining Engineers are enabled to announce the Hadfield Research Prize of $1,000 for the best contribution to the publications of the Institute upon the general subject of The Different Forms and Combinations of Carbon with Iron, including those in Iron Alloys. The prize will be awarded at the Annual Meeting of the Institute in February, 1916, to the best paper upon this subject which is presented to the Institute before Nov. 1, 1915, provided such paper is deemed worthy by the Institute's Iron and Steel Committee. The following suggestions are also added for the guidance of those who may take part in this research. While it is not desired to define closely the exact lines or scope of the proposed research, as it is advisable to make these as broad as possible, the object in mind may be said to be generally as follows: To elaborate and find out the best methods of determining the forms of carbon in steel or iron, including those in iron alloys. A portion of the work would probably be a continuation of the researches which have in the past been carried out by Jullien, Abel, Muller, Ledebur, T. Sterry Hunt, Akerman, Arnold, Stead, E. D. Campbell, Hogg, Parry, Upton, and others.Through the generosity of Sir Robert Hadfield, Honorary Member, the Directors of the American Institute of Mining Engineers are enabled to announce the Hadfield Research Prize of $1,000 for the best contribu¬tion to the publications of the Institute upon the general subject of The Different Forms and Combinations of Carbon with Iron, including those in Iron Alloys. The prize will be awarded at the Annual Meeting of the Institute in February, 1916, to the best paper upon this subject which is presented to the Institute before Nov. 1, 1915, provided such paper is deemed worthy by the Institute's Iron and Steel Committee. The following suggestions are also added for the guidance of those who may take part in this research. While it is not desired to define closely the exact lines or scope of the proposed research, as it is advisable to make these as broad as possible, the object in mind may be said to be generally as follows: To elaborate and find out the best methods of determining the forms of carbon in steel or iron, including those in iron alloys. A portion of the work would probably be a continuation of the researches which have in the past been carried out by Jullien, Abel, Muller, Ledebur, T. Sterry Hunt, Akerman, Arnold, Stead, E. D. Campbell, Hogg, Parry, Upton, and others.

Jan 1, 1917

By Walter Miller

AFter a year's continued impact of war, the task of the petroleum-refining industry stands out clearly and looms up in larger aspect. This time it is not, as it was so largely in the first World War, simply a matter of increased quantity—more and more of the same petroleum products that had substantially been standard for years. In this era the emphasis is largely on newer and improved materials which had been produced, if at all, in comparatively insignificant quantities, and for which manufacturing equipment was not available on a large scale. At the beginning of 1942 four great product needs (besides a number of lesser ones) confronted the industry: 100-octane aviation gasoline, toluene for T.N.T. production, high-quality lubricating oils for aviation and Army equipment service, and petroleum chemicals for synthetic rubber manufacture. The difficulty in presenting a review of engineering progress in petroleum refining during 1942 is that there is so little one is free to say about so much which has been and is being accomplished. At the opening of 1942 the program was to increase the then existing capacity of 50,000 bbl. a day of aviation gasoline to over 150,000 bbl. daily by building new plants at an estimated installation cost of $150,000,000. Later in the year. after the announcement by President Roosevelt of a large increase in the program for war-plane building, additional contracts were made between the Reconstruction Finance Corporation and rehers to raise the capacity to 250,000 bbl. per day. The greatly increased scope of the war activities in all parts of the world, the obligation of the United States as the arsenal of the United Nations, and the greater importance and use of bomber, transport, and cargo planes will undoubtedly bring about plans and installations for a further increase in production of aviation gasoline over the present announced plan. In this connection, Jesse Jones, Reconstruction Finance Corporation Chairman, announced that as of Oct. 31 the R.F.C. had through its subsidiary Defense Plant Corporation entered into contracts for the construction, expansion, or equipping of 28 plants to increase 100-octane aviation gasoline production, but gave no data on 'capacity involved or completion dates. His list did not, of course, include a number of existing plants, and some installations being made by companies who are themselves financing the construction. Production from existing operating installations was materially increased in a number of instances as a result of pooling knowledge of improvements in operation and also by the exchange of Components going into 100-octane blend to enable greater quantities of aviation gasoline to be produced from the over-

Jan 1, 1943

By Walter Miller

AFter a year's continued impact of war, the task of the petroleum-refining industry stands out clearly and looms up in larger aspect. This time it is not, as it was so largely in the first World War, simply a matter of increased quantity—more and more of the same petroleum products that had substantially been standard for years. In this era the emphasis is largely on newer and improved materials which had been produced, if at all, in comparatively insignificant quantities, and for which manufacturing equipment was not available on a large scale. At the beginning of 1942 four great product needs (besides a number of lesser ones) confronted the industry: 100-octane aviation gasoline, toluene for T.N.T. production, high-quality lubricating oils for aviation and Army equipment service, and petroleum chemicals for synthetic rubber manufacture. The difficulty in presenting a review of engineering progress in petroleum refining during 1942 is that there is so little one is free to say about so much which has been and is being accomplished. At the opening of 1942 the program was to increase the then existing capacity of 50,000 bbl. a day of aviation gasoline to over 150,000 bbl. daily by building new plants at an estimated installation cost of $150,000,000. Later in the year. after the announcement by President Roosevelt of a large increase in the program for war-plane building, additional contracts were made between the Reconstruction Finance Corporation and rehers to raise the capacity to 250,000 bbl. per day. The greatly increased scope of the war activities in all parts of the world, the obligation of the United States as the arsenal of the United Nations, and the greater importance and use of bomber, transport, and cargo planes will undoubtedly bring about plans and installations for a further increase in production of aviation gasoline over the present announced plan. In this connection, Jesse Jones, Reconstruction Finance Corporation Chairman, announced that as of Oct. 31 the R.F.C. had through its subsidiary Defense Plant Corporation entered into contracts for the construction, expansion, or equipping of 28 plants to increase 100-octane aviation gasoline production, but gave no data on 'capacity involved or completion dates. His list did not, of course, include a number of existing plants, and some installations being made by companies who are themselves financing the construction. Production from existing operating installations was materially increased in a number of instances as a result of pooling knowledge of improvements in operation and also by the exchange of Components going into 100-octane blend to enable greater quantities of aviation gasoline to be produced from the over-

Jan 1, 1943

By O. Schaaber

THE existence of isothermal martensite without the presence of the athermal form thus far has been established only in a 6 pct Mn, 0.6 pct C steel' and a 23 pct Ni, 3.5 pct Mn-Fe alloy.' " Theoretical calculations, moreover, predict this phenomenon to be observable only within narrow composition limits.' In all other steels, it is generally considered that martensite inevitably forms upon cooling below the M, temperature. Even the possibility of isothermal martensite transformation has been questioned for the common steels, although Averbach and Cohen" showed that martensite formation does not stop when the cooling is arrested and that as much as 5 pct retained austenite may transform isothermally to martensite at room temperature. This note presents some observations made on a number of low alloy steels by dilatometric and inductive measurement of isothermal austenite transformation at various temperatures close to the Ms. In the dilatometer studies reported previously, austenitized specimens were immersed in a salt bath maintained at proper temperature and immediately inserted into the dilatometera8' already at thermal equilibrium with the bath. The dilation was read on a dial gage divided into 0.001 mm intervals. Induction measurements were made with a separate excitation source and a test coil, sealed together in a salt-tight case. The increase in the induced voltage caused by the transformation products was recorded at a paper speed of 4 mm per sec. The steels studied are listed in Table I. Specimens prepared from steels 1 and 2 were in the form of hollow cylinders 60 mm long, 10 mm ID, 14 to 16 mm OD, while specimens of steels 3 and 4 were in the form of notched-bar impact test specimens, DVM type. Specimens of steel 5 were in the form of strip, 7x0.3 mm. In the bainitic range, curves representing the amount of transformation vs log time have a single step appearance, as is shown by the curve of isothermal transformation at 320°C in Fig. 1.Y ransformation proceeds in accordance with the Austin-Rickett equationo P -----------= k t" 100-P where P is the percentage of transformed austenite, t is time, and k and n are constants. Near the M, temperature, however, complex curves having two steps are observed. As shown in a previous papera for steel 3 isothermally transformed at 245"C, such complex curves can be separated into two separate transformations or reactions each following the Austin-Rickett equation. The values of n in the equation for a number of such two-step transformations are listed in Table 11 for steel 1. At transformation temperatures of 250" and 235"C, evidence of a second transformation is very

Jan 1, 1956

By H. D. Outmans

The author applies the theory of hydrodynamic stability to fluid flow in porous media and concludes that the displacement of miscible liquids is stable if the stability coefficient, as defined by Eq. 19.2 or Eq. 27.0, is positive. The conclusion is invalid, however, since it is based on a faulty argument. To demonstrate this, the reader is referred to Eqs. 4.1 through 4.5 of the paper which describe, in differential form, the first-order disturbances c, u, v, w and p. In these same equations, cx, cz, gl, g3 and are functions of the stable concentration c. This concentration c is known and depends on x, z and t (the author assumes cy = 0). It follows that cx, cz, gl, g3 and µ are also functions of x, z and t. With this in mind, we turn to Eqs. 8.1 through 8.5 which were derived from Eqs. 4.1 through 4.5 by substituting Eq. 6.0. The significance of this substitution is that the author thereby limits the solutions of Eqs. 4.1 through 4.5 to equations of the form of Eq. 6.0. Eqs. 8.1 through 8.5 represent an infinite linear system with five unknowns: c, u, v, w and p. The coefficients cx, cz, gl, g3 and µ in this system are known at each point and at each instant; the coefficients containing derivatives of f are unknown. If this infinite linear system in c, u, v, w and p is to have a nontrivial solution, then it is indeed necessary (as the author states) that the determinant of the coefficient matrix of Eqs. 8.1 through 8.5, i.e., ( A 1, be equal to zero. This condition, however, is not sufficient. A non-trivial solution exists if, and only if, the rank of the coefficient matrix of the entire infinite system is smaller than five. In other words. all minors of order five must vanish and only if all the coefficients in Eqs. 8.1 through 8.5 are constant is this equivalent to the condition |A| =0. Constant coefficients means that gl, g3 and µ, for instance, are constant; and, since they depend on c it follows that c must be constant. We conclude that the condition I A I = 0, on which the author bases his calculations, is necessary and sufficient for a nontrivial solution only if the concentration c is constant. In other words, the author does not investigate the stability of a miscible displacement but, rather, only the stability of the flow of a homogeneous liquid. Using the initial condition and the fact that the coefficients are constant, we find

By Walter Miller

Hundred-octane aviation gasoiine, toluene for T.N.T. production, high-quality lubricating oils for the needs of aviation and the armed forces, and synthetic chemicals for rubber manufacture again commanded the top priorities of the petroleum refining industry in 1944, the third year of America's active participation in the war. The objective continued to be to produce more and more of these materials—to keep up with increasingly greater requirements. By the end of the year all of the new installations projected before 1944, with the exception of possibly two or three that will tail over into January or February of 1945, had been completed and put into operation. And with the completion and putting into operation of these various units and the consequent lessening of construction responsibilities and problems, the industry was put into position to concentrate on the new operations and devote much more of its time and effort looking toward maximum output, both as to quantity and quality from the new facilities. Aviation Gasoline Making high-octane aviation gasoline continued to be the prime requisite of refining activities during 1944 as it was in the two previous war years, with the sights at the end of the year set to still higher figures than those which had been previously projected. About July I the daily output had been raised to 400,000 bbl., with some few large plant installations still to be completed and put into operation. Indications were that by December production would be up to all requirements, with good inventories. However, although by the end of the year the industry was turning out something over 500,000 bbl. a day, the estimated requirements of the armed services had been raised by a considerable figure, owing to the greatly increased aerial activities both in the European and Far Eastern combat areas. By the end of the year, therefore, the picture had changed, with the prospect for a much longer continuation of the European war, so that even with the completion and putting into operation in the United States by January 1945 of the last two or three 100-octane units authorized prior to 1944, it was evident it would be necessary to make still greater efforts to increase output of existing facilities to keep safely ahead of the game. Efforts of the industry and the Petroleum Administration for War as well as the Technical Advisory Committee and other research and development groups are concentrated therefore on methods and means of further augmenting the produc. tion of all existing refinery facilities engaged in making 100-octane aviation gasoline and components entering into it. The goal will be reached.

Jan 1, 1945

By W. C. Ellis, M. E. Fine

In the iron-cobalt system there are several property-composition relationships of theoretical importance. The alloys are ferromagnetic exhibiting a maximum saturation at approximately 33 at. pct cobalt;' the interatomic distances at room temperature show large positive deviations from Vegard's rule;2 and in the region of 50 at. pct cobalt there is an order-disorder transition2 which has a large effect on other properties. The thermal expansion data for the system have been reported only from room temperature to 100 C and for this temperature range a minimum in coefticient in the rcgion of 50 at. pct cobalt is well established.3,4,6 This paper reports the expansion properties in the iron-cobalt system for temperatures from 30 to 850°C, shows the correlation with other physical properties, and proposes an explanation for the tcrrelation. Experimental Procedure The thermal expansivities of iron-cobalt alloys in 10 pct steps in composition were determined from 30 to about 850°C. The major series of alloys was prepared by induction melting from Armco iron and cobalt rondelles with the addition of about 0.6 wt pct manganese. This series was supplemented by three compositions: high purity electrolytic iron, high purity electrolytic cobalt, and an alloy of 52.1 wt pct cobalt prepared from the high purity electrolytic iron and electrolytic cobalt by vacuum-melting. The compositions of both series of alloys are given in Table I. The specimens for measurement were prepared from the cast ingots by first hot-swaging followed in most instances by cold-swaging to 0.180-in. diam rod. Some alloys in the region of 5c pct cobalt, because of inherent cold-brittleness, were swaged hot to the final diameter. The expansion specimens were approximately 2 1/2 in. long with flat-ground and polished ends. Before measurement they were annealed in hydrogen for I hr at 900°C. In the apparatus used for the thermal expansivity measurements (Fig I), a modification of that designed by Hidnert and Sweeney,? the differential expausion between the specimen and vitreous silica was measured by a dial micrometer reading to 0.001 mm. An invar fixture supported the dial gauge, and this fixture, in turn, was connected to a split invar collar which supported the outer silica tube. A pyrex "T" was placed over the outcr silica tube and was sealed to the invar collar by Apiezon Q sealing compound. A movable hollow vitreous silica rod which rested on top of the test specimen slid through a flexible rubber diaphragm cemented to the top of the pyrex "T." The specimen rested On a vitreous silica pedestal fused into the outer tube and was kept centered by a silica sleeve. A nonoxidizing atmosphere was obtained by admitting hydrogen into the

Jan 1, 1949

By S. Brunauer

The hydration of portland cement is treated as a chemical reaction and the changes in matter, in energy and the rate of change of the process are discussed, Portland cement is a mixture of four major and at least as many important minor constituents. In the hydration process, the four major compounds (trical-cium silicate, dicalcium silicate, tricalcium alumi-nate and tetracalcium aluminoferrite), plus gypsum and water form five or six new compounds. In spite o the great complexity of the reaction, considerable progress has been made in its understanding, primarily with the help of such research tools as X-ray diffraction and electron microscopy. The rate of the reaction can be followed by direct and indirect methods of measurements. The effects o composition, particle size (or specific surface), temperature and water-cement ratio on the rates of hydration are discussed. The hydration of portland cement is a chemical reaction accompanied by such highly important physical phenomena as heat evolution, setting and hardening. It is a vast and complex subject, on which hundreds of papers have been published. At the time of the writing of this paper, in October 1962, a two-volume book, which alone contains dozens of papers pertaining to cement hydration appeared in print.' The present paper deals with a few aspects of this vast subject, and the selection was not easy. The work reported here deals with some of the most recent investigations in the field. In any chemical reaction, the physical chemist is primarily interested in three things: changes in matter, changes in energy and the rate of change of the process or the speed of the reaction. This is true also of the chemical reaction between portland cement and water, and all three aspects of the reaction will be discussed. These three aspects are of vital interest to the engineer as well. Portland cement is not a cementing material — the hydration products, the new materials which form in the reaction, have the cementing action. The energy changes manifest themselves in a considerable evolution of heat, which may be useful or harmful. It is useful, for example, in winter concreting, but in very large concrete structures like dams, a large evolution of heat, which cannot be easily dissipated, may produce distress in the structure. Primarily for such a purpose was the Type IV or low heat portland cement developed. The speed of the chemical reaction is important because it determines the time of setting and hardening. The initial reaction must be slow enough to permit placing of the concrete before setting occurs. On the other hand, after the placing of concrete it is often highly desirable to obtain as rapid chemical reaction as possible. For this purpose the Type 111 or high early strength portland cement was developed. CHANGES IN MATTER Portland Cement: In a basic investigation, before one begins to study a reaction, one either knows the quantities and compositions of the starting materials, the reactants, or one determines them. This is obvious; the chemist expresses the changes in matter that occur in a reaction by a chemical equation, which has the quantities and compositions of the reactants on the left side of the equation and the quantities and compositions of the reaction products on the right side. The first question is then what to put on the left side of the equation in the reaction between portland cement and water? It is not very easy to answer this question. Portland cement is not a single chemical compound but a mixture of many compounds. Four of these are considered the major compounds, and at least four of the minor compounds also play important roles in the hydration reaction. In order to avoid complicating matters, the present discussion will be restricted primarily to the four major compounds, which constitute usually more than 90% of a portland cement. The relative amounts of these compounds vary from cement to cement. Actually not only the amounts but the compositions of these constituents also vary to some extent, but the variation in composition of the individual components will be neglected for simplicity.

Jan 1, 1963

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale formation) in alloys of silver with 2, 7 5, and 30 per cent of copper The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver' Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail 5,6 The present research confirms this anticipation The oxidation of a series of 20 dilute alloys of silver has been studied metallographically, some types of subscale not encountered among the copper alloys have been found Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation, i e , they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found The probable reasons for this difference in behavior will be discussed presently EXPERIMENTAL PROCEDURE Silver -The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99 993 per cent Ag)* and the purest avail-

Jan 1, 1942

By R. F. Mehl, C. S. Barrett, A. H. Geisler

THE studies of the mechanism of precipitation and of the resulting property changes in aluminum-silver alloys1-3 have presented some new concepts of the aging reaction-concepts that may be fundamental in establishing a complete quantitative theory of age-hardening. With both aluminum-copper and aluminum-silver alloys, thin platelike aggregates form parallel to the Widmanstätten planes of precipitation.1,4 These platelets grow in lateral dimensions and in thickness with aging time until they are thick enough to produce an X-ray diffraction line pattern. Their structure is that of a transition lattice which is coherent with the matrix, since the atomic spacings in the matrix and the precipitate are the same on each side of their common interface.2,4 The equilibrium precipitate forms later from and at the expense of the transition lattice. Since age-hardening occurs during the formation and growth of the transition lattice, the major contributor to the hardening no doubt is the stress condition in the matrix resulting from the matrix holding the precipitate in the coherent condition. The development of these stresses also appears to be responsible for an increase in the electrical resistance superimposed on the normal decrease resulting from a change in the concentration of the matrix during aging.3 The two consecutive reactions constituting the aging process are accompanied by characteristic microstructural alterations. The initial precipitation process results in the formation of a Widmanstätten figure, while the later transformation of the transition lattice to the equilibrium lattice is accompanied by a coalescence, in the case of aluminum-copper alloys,5 and by the appearance of light areas at the grain boundaries with aluminum-silver alloys showing a structural rearrangement of matrix and precipitate.3 This latter reaction is similar microscopically to the so-called "discontinuous precipitation." Possibly discontinuous precipitation is a process that often if not always follows true precipitation of a coherent lattice and during which the transformation of the coherent transition lattice to the equilibrium lattice takes place accompanied by matrix recrystallization.3 EXPERIMENTAL PROCEDURE The alloys were made using 99.97 per cent Al or distilled magnesium, with

Jan 1, 1943