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By John P. Norton

Microcrystalline silica has been mined in Illinois from the Clear Creek Formation since the turn of the century, especially in the area around Tamms in Alexander County, in the southernmost part of the state. This silica is consumed mainly by the abrasives and coatings industries, but is also sought after for many filler/extender uses. Production has grown with the economy with several new applications overshadowing traditional markets in recent years. Many of these applications are directly or indirectly related to energy saving factors. As a result of the "energy crisis" and "resin crunch," fillers have received a great deal of renewed attention as a desirable way of stretching the available resin supplies. With feedstocks in short supply and shortages existing in the entire petrochemical industry, the use of bulk materials to improve and extend existing resin is becoming an every increasingly important facet of plastics and coatings technology. Silica is the choise of fillers in applications where inertness, hardness, and low absorption are necessary characteristics. Microcrystalline silica has the additional advantage of being relatively easy to grind because the crude ore is a friable rock composed of tiny crystallites, many less than 0.1 u in diameter. Grinding represents a significant energy input in the production of silica flours. With energy costs increasing rapidly, comparable grades of silica flour made from microcrystalline silica have advanced less in price and it is expected this trend will continue in favor of the microcrystalline silica.

Jan 1, 1978

By A. G. Raine

For the technological age in which we live, with the constant goal of further improvement in the efficiency of mechanized systems, the need for a replacement of the antiquated drill and blast method of shaft construction has been recognized. For over a decade now; the trend in shaft construction has been toward large diameter bored shafts using either raise boring methods or more flexible, rodless "down the hole" boring machine. The limits of conventional shaft sinking have been reached, the mining regulations are more stringent, and the environmental agencies more aggressive, all contributing to the growing need for development of the rodless shaft boring machine. In the last three years in the United States, world shaft construction records have been achieved using a V-Mole machine, designed by Mirth GmbH of West Germany, using American electrics and hydraulics. Shafts of 7.0 meters (23 feet) diameter, totaling 2,255 meters (7,400 feet) in depth have been constructed at high advance rates, yet with unusually low accident rates. Bearing in mind the high cost of today's mining labor and the inherent danger associated with conventional shaft sinking, this alternative method of shaft construction achieves a fast, competitive, low manpower requirement, whilst enhancing a safer environment for the labor force. Recent results have proven that program time savings of 50 percent over conventional shaft sinking can be achieved which can be directly translated into improved client cash flow projections and more accurate project budgeting.

Jan 1, 1984

By T. M. Dr. Drown

(Read at the Philadelphia Meeting, February, 1878.) ZINC is, as is well known, very brittle at a temperature of about 210° C. (410° F.), and may then be readily pulverized in a mortar. By sifting it may be obtained of uniform grain. I have been accustomed to prepare products passing through 40, 60, and 80-mesh sieves, and also by bolting through a fine handkerchief. The principal analytical uses to which I have hitherto applied this material are to the reduction of iron directly from the ore by heating it with the pulverized zinc, and the reduction of ferric to ferrous compounds in solution. In the first case the pulverized ore, 0.5 gram or less, is intimately mixed with about ten times its weight of the pulverized zinc (the finer the zinc the better), in a porcelain crucible, and this mixture is covered with about the same amount of zinc. The crucible is then heated at the top of the flame of a Bunsen burner, at a dull red heat, for about ten minutes. The crucible should not be covered. When cool, the crucible, with its contents, is placed in a flask treated with hot dilute sulphuric acid, and brought quickly to a boil. The zinc and reduced iron are dissolved in a few minutes and the flask is then tightly corked and allowed to cool. When cool, the iron is directly titrated by potassium permanganate.

Jan 1, 1878

By J. R. Low

The brittle fracture of a Tic-lnconel cermet at room temperature is shown to occur primarily as a result of the cracking of the larger carbide particles (at a tensile strain of approximately 0.3 pct), followed by cracking of adjacent, smaller carbides and, finally, by the rupture of the lnconel matrix between cracked carbides (at a strain of-1.2 pct). No evidence was found for separation at the interface between carbide and matrix at any point in the fracture process. MATERIAL used in this study was a Tic-Inconel cermet prepared by infiltration (50 pct Tic, 50 pct Inconel: designated as TC66-I). A thin section of this material was brazed to a piece of low carbon steel and then mounted in lucite for metal-lographic preparation." After grinding, polishing, Deformation and fracture of the specimen was accomplished by bending the specimen as a simply supported, centrally loaded beam, in a bending fixture which could be placed in the stage of a microscope, with the tension side of the bend specimen under the microscope objective.? This method of deformation and observation has the advantage that the surface under examination is the most severely deformed portion of the specimen. The procedure followed was to deform the specimen a small amount, scan the surface at Xl OOO for any evidence of deformation or cracking, deform another small increment, scan the surface again, and so on until a

Jan 1, 1957

F. E. Thompson, Pottstown, Pa.: If Mr. Webster's endeavor to open up the subject of cast-iron should prove as prolific of results as did the discussion on " The Physics of Steel," he must certainly feel richly repaid. His remarks concerning the secretiveness and conservatism of the average foundry-man recall to my mind an instance of a blast-furnace which, for the last year, has been producing much foundry-iron. The manager, believing that much more of his product could be used in the foundry than the foundry-men were will-

Jan 1, 1896

Masjid-i-Su1aiman.—There have been no new developments in the Masjid-i-Sulaiman oil fields during the year 1938. In spite of the age of this field, the fall in dome pressure shows no appreciable variation from the low rate of about 0.3 lb. per sq. in. per million tons net production. Drilling has been limited to deepening old wells and to new wells required for maintenance of production and general reservoir control. The rate of offtake has been reduced over the past few years, partly because of depletion of the oil column, and it is expected that future offtake from the Masjid-i-Sulaiman field will be stabilized for some years at around the present figure of 3,000,000 tons per annum. Haft Ke1.—An exploratory well to test deeper formations in the Haft Kel field has proved the existence of productive conditions in the Eocene, which underlies the Asmari limestone (the main producing horizon). Drilling to the northwest in the white-oil springs area has revealed the presence of a separate structure with productive potentialities. One well with a satisfactory production rate has been completed. Offtake from the Haft Kel field has steadily increased since it first came on to production in 1929. Naft-i-Shah.—Production from this field has continued to supply market requirements in northwest Iran. The policy of returning surplus products to the reservoir, which was adopted at the beginning of 1936, has been continued.

Jan 1, 1939

Masjid-i-Su1aiman.—There have been no new developments in the Masjid-i-Sulaiman oil fields during the year 1938. In spite of the age of this field, the fall in dome pressure shows no appreciable variation from the low rate of about 0.3 lb. per sq. in. per million tons net production. Drilling has been limited to deepening old wells and to new wells required for maintenance of production and general reservoir control. The rate of offtake has been reduced over the past few years, partly because of depletion of the oil column, and it is expected that future offtake from the Masjid-i-Sulaiman field will be stabilized for some years at around the present figure of 3,000,000 tons per annum. Haft Ke1.—An exploratory well to test deeper formations in the Haft Kel field has proved the existence of productive conditions in the Eocene, which underlies the Asmari limestone (the main producing horizon). Drilling to the northwest in the white-oil springs area has revealed the presence of a separate structure with productive potentialities. One well with a satisfactory production rate has been completed. Offtake from the Haft Kel field has steadily increased since it first came on to production in 1929. Naft-i-Shah.—Production from this field has continued to supply market requirements in northwest Iran. The policy of returning surplus products to the reservoir, which was adopted at the beginning of 1936, has been continued.

Jan 1, 1939

Roof Bolts An expansion shell and plug Westinghouse roof bolting assembly made for use with threaded steel rods and large flat washers or steel channel employs a plug larger in diameter than those for trolley wire service. The notched plug helps prevent shell and plug from turning. The unit is shipped complete. Circle No. 1 Fan The Jeffrey Mfg. Co. Aerodyne Midget fan is a self contained blower or exhauster for auxiliary ventilation through tubing. Operating rating with 5 hp motor is 6.5 in. maximum static pressure, and 6200 cfm free delivery volume. Weight is 340 to 475 lb and it may be furnished in open or permissible form. Circle No. 2 Heavy-Density Initial installation in the Mesabi Range country of the Wilmot-Daniels heavy-density concentrating system was a 175 ton per hour plant at the [ ] Skubic Bros. Virginia, Minn., operation. This Wilmot Engineering Co. unit has a separatory vessel providing unidirectional medium flow and as the only moving part uses a standard drag-line conveyor for lifting sink out of the bath. Circle No. 3 Portable pH Meter A low priced battery-operated portable pH meter of utmost simplicity announced by the Photovolt Corp. uses only 3 ordinary radio batteries which give over 2000 hours of service. Accuracy of 0.03 pH is claimed by the manufacturer for the model 125, and AC power line supply is available. Circle No. 4

Jan 1, 1952

A. 0. ASHMAN, Palmerton, Pa. (written discussion *).-From a theo¬retical point of view the best method to maintain the cold junction at a constant temperature is by means of a pipe driven in the ground, to which the so-called cold-junction compensating leads are run, ;and of course there are many times and places where it can be successfully used. There are, however, several objections to this method. In the vicinity of any furnace there are apt to be underground flues for preheated air or gases, recuperators, water mains, etc., which will eliminate the probability of a constant temperature. These, of course, can be avoided by carrying the leads to distant locations known to be free, but this is not good practice because the so-called compensating leads have a rather high re¬sistance, which materially affects the accuracy of even the high resistance instruments, unless they are specially calibrated for it. Moreover, the cost of these long leads is almost prohibitive. A better way is to run short lengths of compensating leads to electrically heated constant¬ temperature boxes conveniently located near the furnace in a place that is of fairly uniform temperature. These boxes are on the market and can be procured at a cost that is approximately equal to the cost of 100 ft. of compensating leads. They can be connected to any power or lighting circuit and once set require very little care. One box will ac¬commodate a number of couples.

Jan 12, 1919

W. Morton Webb, Germiston, Transvaal, South Africa (communication to the Secretary*):—The experience of Mr. Boeh-mer in the Leadville district and his reputation as an engineer assure the interest of anything he may write on the ore-bodies of that district; and all engineers who have operated in Leadville will agree that the theory of the origin of the Leadville deposits, as given by Mr. Emmons in his famous monograph, does not adequately explain the genesis of all the deposits. The solutiou of the problem does not, however, appear to be quite so simple as Mr. Boehmer would make it; and the advance pamphlet issued by the U. S. Geological Survey, pending the completion of the main report, shows that there is still much ground for controversy. No doubt the later eruptive0 had a greater influence on the deposition of the ore-bodies than was thought at the time of the first investigation by the Survey; but it has always appeared to me that the influence exerted by these dikes mas more in the nature of a physical than a chemical one. The weight of evidence in recent years is mostly in the direction of ascension rather than lateral secretion; and one of the strongest evidences is the fact that most of the ore-bodies lie under one of the comparatively impervious layers which help to make up the structure of these hills.

Jan 1, 1911

WALTER N. CRAFTS,* Toronto, Canada (written discussion?).-During the forging of 9.2-in. shells -for the United States Army, it was noticed that better results were obtained in certain instances when test bars had been held sometime before pulling. An investigation, therefore, was made by our metallographer, Mr. F. M. Arnold, to determine the effect of seasoning. The forging consists of a single operation, piercing a solid cast blank. The test sections were cut from the walls by an oxyacetylene flame, one piece from the nose end and one from the base on the opposite side. The test pieces were not heat treated in any way and the tests and seasonings were carried on at normal atmospheric temperatures. The specifica-tions were as follows: Standard 2-in. test bar, 0.505 in. in diameter; elastic limit, over 19 long tons, or 42,500 lb.; ultimate stress, 39.6 to 49.1 long tons, or 87,500 to 110,000 lb. per sq. in.; elongation, over 13 per cent. As a preliminary test two heats were selected; BP555, which was tested and reported failed on elongation on Aug. 20; and B01771, which was tested and reported failed on Aug. 24. On Aug. 29, retests were cut and machined from the same shells and held till Sept. 3 (5 days) when they were pulled. Both sets of results are given below.

Jan 12, 1919

By Michael Tenenbaum

THE importance of semikilled steel as a high tonnage grade has long been recognized. The increasing severity of the applications for which semikilled steel is used makes it desirable to obtain further information regarding the features of open hearth practice and ingot structure that can affect steel performance in subsequent rolling and fabricating operations. Accordingly, an investigation is being carried out studying the structure of various types of semikilled steel ingots. This paper reviews some of the observations made and information gathered in this investigation. By definition, semikilled steel may be considered to include all nonrimming steels in which the natural shrinkage occurring during ingot solidification is offset to an appreciable degree by gas formation. Accordingly, this type of steel includes the entire range intermediate between rimmed and fully killed steel. The resultant ingot structures range from those of steels that have been capped to suppress a weak rimming action to those steels that have been killed in the furnace or ladle to the extent that no mold deoxidizer is required. A survey reported to the 1946 AIME Open Hearth Conference' reviewed the practices being used at 28 major plants for the deoxidation of semikilled steel. It was found that most plants divide the deoxidizing additions between the ladle and the mold many of the plants adding only minor amounts of deoxidizer to the bath or none at all. Silicon, aluminum and titanium were the only elements used for ladle and mold deoxidation. Mold deoxidizers were added as capping additions or as uniformly fed additions. Several practices were reported in which the steel was deoxidized in the ladle to the extent that little or no mold deoxidation was needed. No reference was made to grades capped by using special mold designs or special closures over the top of molds. Accordingly, specific examples of this type of practice will not be considered in this paper. It appeared from this survey of deoxidation practice that semikilled steel can be divided into three types, namely, capped semikilled, in which aluminum is added near the end of pour or after shut-off, intermediate semikilled steels, in which aluminum is fed uniformly throughout the pour, and semikilled steels requiring no mold deoxidation. In an attempt to cover the ingot structures obtained by the range of practices reported in the preceding survey, three series of experimental heats were made using increasing amounts of aluminum, silicon and titanium for ladle deoxidizers. The ladle deoxidizers were added as stick aluminum, 50 pct ferrosilicon and 20 pct ferrotitanium (4 pct carbon), respectively. Two methods of studying ingot structures were used. Ingots were removed from production, burned longitudinally and machined to allow observation of the central pipe and coarse blowholes. During the machining operation much of the finely porous subsurface structure was obliterated. Accordingly, observations were also made

Jan 1, 1947

By J. B. Seabrook

The accompanying Fig 1 is a graphical scheme of intermediate accuracy for expediting interconversions of mol, weight, and volume percents. This chart consists of a family of curves of mol or atomic or volume percent plotted against weight percent, each curve in the family providing for a certain ratio of molecular or atomic weights or densities. Thus, the whole range of variations is presented in a very familiar format, and the conversion is effected simply by choosing the proper curve and reading off the required values. An entire series of conversions for a given binary system can be found by following the appropriate curve. It is interesting to examine the analytical geometry of the plots. The curves, which must fit into a square and all join at the 0 and 100 pet points, may be shown to be hyperbolas with their centers on the extension of the diagonal of the square which they intersect. Multiplying out the expression x A atomic fraction of A = y = ------ where x is the weight fraction of A, and A and B are atomic weights, we get xy+A/By- A/Bxy=x Upon rotating and translating axes and avoiding imaginaries, it is found that the angle of rotation is —45°, the origin moves upv2/2 units andv2/2(A/B+1/A/B-1) units to the right, and the standard form is Thus the curves are equilateral hyperbolas, their centers are units away from their intersection with

Jan 1, 1950

The following is an incomplete list of members and guests who called at Institute headquarters `during the period Aug. 10, 1918 to Sept. 10, 1918. Amil A. Anderson, Hill City, S. D. A. A. Holland. H. G. S: Anderson, Hurley, N. Al. Paul S. King, Wilmington, Del. Louis A. Barton, Capt., Engineers, U. S. A. Herbert G. Officer, Washington, D. C. K. Baumgarten, lst Lieut., U. S. R. A. B. Parsons. Charles W. Boise, Belgian Congo. Robert R. Pollock, San Francisco, Cal. Henry C. Carlisle, The Pas, Manitoba. Frank A. Smith, Edgewood, Md. J. Ross Corbin, Boyertown, Pa. Edward C. Thompson, Kennett, Cal. S. Le Fevre, Forest Glen, N. V. Malcolm M. Thompson, Morsemere, N. J. Harold P. Ford, Cleveland, 0. Lester C. Uren, Berkeley, Cal. William L. Hogg, Waynesboro, Va. Harold W. Aldrich has been appointed assistant general superintendent of the Inspiration Consolidated Copper Co. at Inspiration, Ariz. Capt. Percy E. Barbour, formerly with the New York State Troopers, has been granted a leave of absence from the Department for the period of the war, by the Governor, and has been appointed Captain in the Engineer Corps, U. S. A. He served on the Mexican border in the New York State National Guard. A. C. Barke, formerly with the United States Smelting, Refining and Mining Exploration Co., has accepted a position with the United States Fuel Co. at' Salt Lake City, Utah.

Jan 10, 1918

By J. Burns Read, S. Tour

It is the purpose of this paper to summarize, as far as possible, the metallurgical information and experience gained by the Ordnancc Department, during the war, in the manufacture of artillery cartridge cases, to describe the tests to which artillery cartridge cases were put, and to summarize the knowledge and experience gained in this testing. The authors wish to acknowledge the aid given by manufacturers, army officers, and civilian employees of the Department in obtaining data. Artillery cartridge cases are cold drawn from circular disks punched from strips of rolled brass. The rnanufacture involves from 25 to 30 main operations, which are done almost entirely on a punch press. Descriptions of the operations have appeared in various periodical:: and, therefore, will not he given here. After each cupping, or drawing, operation, except the last, the cases are annealed at from 540" to 650" C. (1000" to 1200°F.), to remove all the hardening stresses set up in the metal and to allow complete recrystallization. After each annealing, the cases are pickled in niter cake or sulfuric-acid solution and then washed in water to remove all traces of acid. In some instances, the cases arc then immersed in a cyanide-salt solution, and afterwards rinsed in water, to remove the thin layer of copper that forms on the surface of the cases during the acid pickle. The last cold-drawing operation is followcd by the heading operation which, by flattening the head of the case on the outside, causes the metal to flow on the inside to approximately the proper finished dimensions. The mouth, or open end, is then annealed at 430" to 450" ('. 1800" to 900" F.) by immersion in a salt bath or by gas flames. After being washed, the eases are tapered, when they arc ready for machining, inspection, and testing. Cartridge-case Disks Good disks of proper composition and physical properties are essential to the production of good cartridge cases. The Ordnance Department

Jan 1, 1923

By J. Burns Read, S. Tour

It is the purpose of this paper to summarize, as far as possible, the metallurgical information and experience gained by the Ordnancc Department, during the war, in the manufacture of artillery cartridge cases, to describe the tests to which artillery cartridge cases were put, and to summarize the knowledge and experience gained in this testing. The authors wish to acknowledge the aid given by manufacturers, army officers, and civilian employees of the Department in obtaining data. Artillery cartridge cases are cold drawn from circular disks punched from strips of rolled brass. The rnanufacture involves from 25 to 30 main operations, which are done almost entirely on a punch press. Descriptions of the operations have appeared in various periodical:: and, therefore, will not he given here. After each cupping, or drawing, operation, except the last, the cases are annealed at from 540" to 650" C. (1000" to 1200°F.), to remove all the hardening stresses set up in the metal and to allow complete recrystallization. After each annealing, the cases are pickled in niter cake or sulfuric-acid solution and then washed in water to remove all traces of acid. In some instances, the cases arc then immersed in a cyanide-salt solution, and afterwards rinsed in water, to remove the thin layer of copper that forms on the surface of the cases during the acid pickle. The last cold-drawing operation is followcd by the heading operation which, by flattening the head of the case on the outside, causes the metal to flow on the inside to approximately the proper finished dimensions. The mouth, or open end, is then annealed at 430" to 450" ('. 1800" to 900" F.) by immersion in a salt bath or by gas flames. After being washed, the eases are tapered, when they arc ready for machining, inspection, and testing. Cartridge-case Disks Good disks of proper composition and physical properties are essential to the production of good cartridge cases. The Ordnance Department

Jan 1, 1923

By Fred D. Fox

INTRODUCTION Approximately two years have elapsed since the first summary of the Grizzly Gulch Tailings Disposal Project was presented (1). Since that time, various physical modifications and additions to the existing treatment system have transpired. Further, Homestake and the entire mining industry have been impacted severely by additional modifications and additions concerning regulatory reform aimed at total disciplinary permitting and hazardous waste management. The following paper summarizes the past accomplishments relating to the Grizzly Gulch Tailings Disposal Project, correlating these accomplishments with future plans that are being developed to comply with regulations and to continue Homestake's commitment to environmental protection. The famous Homestake Gold Mine, located in Lead, South Dakota, has been operating in the Black Hills region for over a century, approximately 12 years before the south half of Dakota Territory was admitted to the Union as the State of South Dakota (2). During the 104 years of operational development, Homestake's Gold Mine, as well as the entire mining industry, have been influenced by numerous governmental regulations dating back to the Refuse Act of 1899 which regulated the deposit of debris from mines and stamp works. The enactment of the National Environmental Policy Act of 1969 may be thought of as the beginning of a long line of unplanned steps to deal with the many concerns of matters pertaining to the environment. Environmental awareness continued into the 1970’s, in which the Clean Air Act, Federal Water Pollution Control Act, Safe Drinking Water Act, Toxic Substances Control Act, and the Resource Conservation and Recovery Act (RCRA), to name a few, surfaced.

Jan 1, 1983

By T. K. Redden

Protective coatings based on the formation of a surface coating of nickel aluminide (NiAl) were applied to the nickel-base superalloys IN 100, SEL 15, and U-700. Coated specimens were exposed to an oxidizing environment at temperatures between 1600 and 2200 F for times up to 1000 hr. The oxidation resistance and stability of the coating were evaluated by weight gain measurements, metallographic examination, and X-ray diffraction study of surface oxides and coating. The composition of the coating and diffusion zone was determined by electron microprobe traverse of samples before and after high-temperature exposure. Intermediate phases formed in the coating and diffusion zone were identified by X-ray diffraction in situ and after electrolytic extraction. The outer coating was found to consist of the inter-metallic compound, NiAl, while the diffusion zone contained MC, M23C6 or M6C carbides, and a phase in a matrix of NiAl + Nidl. Oxidation resulted in formation of an A1203 n'ch scale containing some Tz02. Depletion of aluminum during oxidation resulted in degradation of the outer coating to Ni3Al and the nickel alloy matrix. Diffusion of aluminum into the base metal was found to be slight and did not influence coating life significantly. The o formed in the diffusion zone during coating decomposed during elevated-temperature exposure to form stable carbide phases characteristic of the base metal. Diffusion zone phase changes were found to have no effect on the life of the aluminide coating in the oxidizing envzron?nent. THE oxidation resistance of many high-strength nickel-base superalloys is inadequate for extended exposure at temperatures above about 1600°F. In addition, some applications for these materials require that they be exposed to environments containing sulfur compounds and sodium salts which can cause surface attalk known as sulfidation or hot corrosion. In order to provide the necessary corrosion resistance to the high-strength alloys, protective coatings based on an aluminizing process have been developed. These processes, usually based on a pack cementation technique, result in the formation of a NiAl-rich outer coating layer either during the coating process or by a subsequent diffusion treatment. The performance of the aluminide coatings is affected by interactions between the coating layer and the base metal both during the coating process and during subsequent exposure at elevated temperatures. Knowledge of these interactions is required to guide the development of coatings capable of longer life and improved reliability. Goward et al.' recently reported the metallurgical factors which influence coating per- formance on MAR-M200. The present work is concerned with correlating the interactions and performance of coating compositions on several representative materials. EXPERIMENTAL PROCEDURES Materials. Three cast nickel-base superalloys which are used for turbine buckets in air-breathing engines were studied: IN 100, U-700, and SEL 15. Their chemical compositions are given in Table I. The alloys were vacuum-induction-melted and cast to slabs approximately 0.3 in. thick from which rectangular specimens 0.25 by 0.5 by 1 in. were machined. Coating Procedures. The machined specimens were coated by CODEP processes which were developed at the author's laboratory. These are based on pack cementation in various media to deposit either aluminum or aluminum in combination with titanium. The coating process which deposits only aluminum is designated CODEP-C, while the CODEP-D process deposits titanium in combination with aluminum. The CODEP-D process was applied only to IN 100. Both CODEP processes are applied at 1950" or 2000°F for 4 hr without need for a subsequent diffusion treatment. An outer coating about 1 mil in thickness is produced by these processes. Test Procedures. Coated specimens were exposed to static oxidation for periods ranging from 24 to 1000 hr at temperatures of 1600" to 2200°F. Terminal weight gain measurements and visual examination were used to evaluate oxidation resistance. including oxide spalling and coating failure. Both as-coated and exposed specimens of each alloy were studied by metallographic examination, electron microprobe analysis (EMA), and X-ray diffraction analysis either of the exposed surfaces or of phases extracted from the coating and diffusion zone. RESULTS As-Coated Condition. The microstructures of as-coated conditions were generally similar, irrespective of base materials or the particular coating process. They are typified by IN 100 coated by CODEP-D as shown in Fig. 1. The predominately single-phase outer layer, area A, Fig. 1, was identified by X-ray diffraction as the intermetallic compound NiA1. The NiAl zone extended inward to the original base metal interface. The diffusion zone, area B, Fig. 1, included carbide phases, a lamellar phase oriented perpendicular to the base metal surface, and a matrix phase consisting of a mixture of NiAl and Ni3Al. The phases in the diffusion zone were electrolytically extracted using a 10 pct HCl in methanol solution at approximately 1.3 amp per sq cm. The extracted phases were found to be M6C, MC, or M=C6 carbides and o as shown in Table I1 for each of the alloys. The d spacings from a typical diffraction pattern are

Jan 1, 1969

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick's law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert's law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick's Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970

By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.' The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.' The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-' M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"'" due to a

Jan 1, 1971