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By P. B. Venuto, E. T. Strom, S. A. Dixon, W. F. Johnson, T. C. Vogt

Prior to assessing potential for in-situ leaching, it is advantageous to identify the nature of the probable reactants in the ore horizon, including both the uranium species and those in the gangue material. We report mineralogical data on an areally-broad suite of samples from the Westwater Canyon Member of the Jurassic Morrison Formation in the Crownpoint area of the Grants Mineral Belt. Optical microscope, electron micro-probe, X-ray diffraction, spectroscopic and wet chemical analyses were conducted. In these samples, the uranium occurs predominantly as either coffinite or uraninite. The host rock is arkosic sandstone, comprised mainly of detrital quartz and feldspar. The minerals kaolinite and chlorite are present in claystone clasts and calcite occurs as a cement. Major trace elements include molybdenum, vanadium, iron, selenium and sulfur. Carbonaceous organic material is present in the ore and is intimately associated with the uranium mineral when it is coffinite. Geochemical, pyrolytic and 13C NMR analyses indicate organic material is probably a very mature, coaly-type kerogen derived from plant components.

Jan 1, 1982

By Theodore Marvin

NOW that real progress is being made in building airplanes that can stand up under adverse conditions in isolated parts of the world, utilization of aviation by mining and petroleum companies is proceeding rapidly. This isolation, offering such handicaps to ordinary methods of transportation, also was the thorn in the flesh of aviation until the recent advances in plane and englue design. The accompanying illustration shows one of the six new planes just delivered to the U. S. Government for map making. The planes will be used in Department of Commerce, Coast and Geodetic Survey, Navy Hydrographic, and Insular work. There is a trap door in the bottom of the hull for a Fairchild camera which takes five pictures-vertical, N60°, E60°, S60°, and W60°-at regular intervals. It is manufactured by the Grumman Aircraft Engineering Corp., Farmingdale, N. Y.

Jan 1, 1935

By Peter R. Drummond

THE final casting of refined copper has been re-J- stricted for generations by the following sequence of operations: Filling the reverberatory furnace, melting, skimming, blowing or flapping, and poling. The hoped-for 24 hr cycle, producing 300 tons or more, has been taken up largely with the necessary bat time-consuming tasks of cleaning the bath, sulphur elimination, and in turn removal of excess oxygen to produce tough-pitch copper. Incidental to comparatively slow melting under combustion gases, copper oxides react with the furnace lining, and the slag so-formed must be completely recycled. The three-phase arc furnace has eliminated some of the cycle stages, and telescoped the remainder into a continuous operation. Electrical energy, supplied to graphite electrodes enclosed in high grade refractories, rapidly melts copper cathodes and sustains a stream of metal, containing approximately 0.01 pct oxygen, without contamination from fuel. The arc was struck on the first large electric furnace for melting copper in the United States on April 13, 1949. The earliest use of this type of furnace was at Copper Cliff, Ont., in 1936, and an admirable description of their installation has been published? Copper, melted in the Baltimore furnace, is used to cast billets, and the installation differs somewhat from the Canadian, as will be described. The arc furnace is a heavy-duty, three-phase furnace, holding 50 tons, the general outline of which appears on Fig. 1. The steel shell is 15 ft ID with a bottom radius of 14 ft 2 in. The roof, separate and distinct from the body, consists of a 15-ft water-cooled, cast-steel ring of the same outside diameter as the furnace. The center line of the furnace lies 9 ft 6 in. from that of the trunnions, permitting a 5" backward tilt for skimming, and a 40" maximum nose tilt forward for complete draining. Normally, the furnace overflows by displacement, and the use of the forward tilt arrangement is restricted to covering charging delays. The charging slot, 3 ft 8 in. x 5 in., lies on the north center line, the tap hole on the south, and the 30x30 in. skim door 45" to the west of the slot. The original 20-in. graphite electrodes were replaced with 14 in. in December 1949. Three conventional direct current winch drives, governed by electrical controls, position each electrode which has individual mast supports and counterweights. An independent circulation supplies cooling water for the electrode glands, the roof ring, charge slot, and the skim door frame. Arc Furnace Refractories Hearth: Fused-in monolithic bottoms had been used in copper arc furnaces, installed prior to April 1949. These consisted of thin layers of periclase, successively fused in place over preliminary brick courses. Heat was obtained from the arc, using a T-like arrangement of broken electrodes resting directly on the periclase to be fused. The operation, taking weeks to perform, was very expensive. The chemically-bonded magnesite-brick bottom, installed at Baltimore, was the first of its kind and a radical departure from previous practice. It consists of a 1 to 6-in. layer of castable refractory laid on the steel shell, modifying it to a 12 ft 2 in. bottom radius. Two courses of 9x2 % -in. fireclay straights and keys follow. The third course is made of 9-in. magnesite blocks of special shape to form circles of an inverted arch. It was started by a four piece keystone with skew-backs forming the outer course. The fourth course also started on a central keystone, or button, of four 90" segments, 12 in. diam x 13 Vz in. deep, and continued with 13%-in. blocks. Skewbacks at the shell completed the course to produce a horizontal surface for the side walls with a single course of No. 2 arch fireclay against the steel. Dry chrome-magnesite cement was brushed over each course after laying, and a 1-in. expansion space between the brick and the shell was filled with the same mixture. The total bottom thickness, excluding the castable material, was 5 in. of clay plus 22% in. of chemically-bonded magnesite. Tap Hole: A 5-in. OD and 3-in. ID silicon-carbide tube constitutes the tap hole and is set tangential to the upper course of the furnace bottom. Molten metal fills the tube when the furnace is level and filled to capacity. Side Walls: The lining, against the shell, consists of a 9x4Y2x3 in. soldier course of fireclay, using straights and No. 1 arches to turn the circles. A second soldier course of 9x4'/2x2'/2-in. fireclay was laid in a somewhat similar fashion. Three courses of 13Y2x6x3 in. and 9x6~3 in. of final magnesite, laid flat, completed the lining, using Nos. 1 and 2 keys to turn the circles. Cardboard spacers were placed between every two bricks in horizontal courses, and a thin coat of chrome-magnesite cement filled the joints between the firebrick and magnesite. A sprung-arch spanned the skim door with jambs of suitable magnesite shapes. Charge Slot: The slot is 3 ft 8 in. wide x 5 in. high. A silicon-carbide sill of special shapes has a 30" slope to allow cathodes to slide easily into the bath. The original arch was flat, and composed of Nos. 1 and 2 wedge magnesite with a 6-ft radius. It projected 5 in. over the sill, and, being a flat arch, gave an 18 15/16-in. opening between the inner edge and the metal line. The whole assembly was later raised 9 in., and the flat arch replaced with an arch, the lower edge of which maintained the 5-in, width from the outer to inner edges as shown in Fig. 2. A water-cooled, cast-copper jacket protects the steel shell behind the slot.

Jan 1, 1952

F. AT. FARMER*, New York (written discussion?)- The paper presents many phases of the welding art concerning which there are very divergent views. In many cases, the wide differences of opinion are based on the results of mechanical tests, but an examination of the mechanical test data discloses a wide variation in character of the tests made and in the details of procedure, so that it is frequently not only difficult to analyze and check the basis of the conclusions but impossible to correlate various groups of test results. It would seem, therefore, that the technique of testing welds is one of the phases of the welding art that should be studied and standardized in order that the results of mechanical tests made by different people may be strictly comparable and have the same significance to all. The vital difference between testing a specimen of steel that includes a welded joint and testing an ordinary specimen is the non-homogeneity of the weld specimen. The weld specimen has at its center a section composed of material that usually has physical, chemical, and metallurgical characteristics distinctly different from the adjoining metal. Furthermore, the section of added metal is more or less irregular and the ratio of added metal to original metal in the section is quite variable. Consequently the details of procedure and of recording data should be more minutely prescribed than in the testing of ordinary specimens. A conspicuous example f a mechanical test that requires standardization is the cold bending test, a standard test for mild steel. With the usual method, the specimen is bent around. a pin of prescribed diameter and, as all specifications usually require bending to 180° without fracture, the manner of applying the load is immaterial because the specimen is ultimately completely wrapped around the pin. But a specimen containing a welded joint at the center will usually not withstand bending to 180° because of the much lower ductility of the deposited metal in the weld. It is therefore obvious that the farther apart the points of support are the greater will be the angle attained before cracking occurs, simply because most of the bending will take place in the original metal. It is therefore highly desirable that there be prescribed a standard test that fixes exactly the distance between the supports, the curvature of the surface of supports, and the relation between this curvature, that of the loading surface, and the thickness of the specimen.

Jan 5, 1919

By Emil-Paul Lorenz

Considered as a whole, the mineral resources of the Turkish Republic (Anatolia) are in their untapped virgin state, and the little development shown is not the result of modern systematic geologic exploration but the continuation of the ancient open-pit mining methods of the Orient. When I came to Turkey in 1924, I found myself confronted by a formidable task because of the lack of preliminary geologic mapping. Today this condition has not essentially changed; less than one per cent of the country is covered by topographic mapping adequate for modern requirements. However, I was able to bring a semblance of order in a presentation of the mineral deposits of this country, by tracing the story of the mineral deposits that showed surface evidence of their existence. At present only the easily discovered mineral deposits of coal, copper, and lead-silver ores are being exploited. In the case of coal, of 3,000,000,000 metric tons available, only 100,000,000 have been mined. The same is also true for copper, lead-silver, and other ores, as shown in Table 1.

Jan 1, 1948

By Benjamin Smith Lyman

There seems to be dire need of repeated preachment against the too-frequent sad neglect of instrumental surveying and mapping in geological surveys. The value of the map as an illustration of the statements and opinions of a report is too apt to be overlooked; and its essential necessity in working out during its construction the proper conclusions from the observed facts is generally altogether misunderstood. Practical geology seeks, of course, to ascertain and indicate the character of workable or unworkable beds or veins, their depth, position, dip, and horizontal course, or strike, even below the surface; also their outcrops, and therefore, if workable, their extent; and so, taking account of their thickness and specific gravity, their weight in tons. It might, therefore, be called quantitative geology. For the study of more abstruse geological questions, too, it is in many cases necessary to gain some knowledge, or reasonable opinion, in regard to such hidden facts. In some cases, careful instrumental surveys are made; in others, from necessity or choice, there are few or no instrumental observations. It was said, 15 or 20 years ago, that there was an engineer in the anthracite-regions who was capable of telling, on first glancing at a new place, exactly what coal-bed was to be found there at a certain depth, and how thick—a splendid second-sight! "' 0, there be,' " you may be tempted to exclaim, " geologists ' that I have seen' geologize ' and heard others praise, and that highly, not to speak it profanely, "'—but let them pass without being fully characterized, lest the temptation towards profanity be altogether too strong. Yet such second-sight does not exceed the expectations of many men of imperfect geological knowledge, men who have heard of marvel-ously successful geological predictions, but are unaware of

Jan 1, 1910

By AIME AIME

THE 129th meeting of the American Institute of Mining and Metallurgical Engineers convened at New York City, in the Engineering Societies Building, Feb. 18-20, 1924. On February 21 an excursion was made to the Bethlehem Steel Co., at Bethlehem, where about 200 members and guests were splendidly entertained. An illustrated description of the Bethlehem Plant will be published next month. The meeting and excursion were largely attended; the registration at New York totalled 1276 versus 1201 in 1923. William Kelly, long identified with the iron-mining industry of the Lake Superior district, was elected President of the A. I. M. E. for the coming year, at ,the annual business meeting, Feb. 19, succeeding E. P. Mathewson. The following Directors were also elected (the date signifies year of termination of office; the final figure indicates the "District" the Director represents).

Jan 1, 1924

By JOHN R. SUMAN

IT appears now that the conflict with the totalitarian states will be a long-drawn-out struggle. The course of this war up to now indicates that this may well be the first major conflict where man power has not been the vital and determining factor. Mechanized warfare has made it possible for relatively small, well-equipped groups to outmaneuver and defeat large armies which lack the necessary modern equipment. Under these circumstances, ultimate victory becomes a matter of resources and productive ability. The important question is not how many soldiers can he put into the field, but the volume and speed in producing the armaments essential to ensure a victory. The resources available to the opposing nations and the efficiency of their systems of enterprise and production will be primary factors in determining the ultimate outcome. Germany had a head start of eight years in the armament race, and it is not easy to overcome such an advantage overnight.

Jan 1, 1942

By J. C. Smock

THE magnetic iron ores of New Jersey are found in the northern part of the State, in the Highland Mountain range, which runs from the New York line on the northeast, to the Delaware River, near Easton, at the southwest. The same range continues across Orange County to the Hudson River, and towards the southwest it is known in Pennsylvania as the South Mountain. It is more properly an elevated table-land, quite deeply furrowed by several narrow, longitudinal valleys, and shorter cross-valleys or gaps. The ridges or lines of elevation, as well as the lower valleys, conform in their general direction very closely to the general trend of the whole belt or table-land, that is, from northeast to southwest. This also agrees with the prevailing strike of the rocks. This great uniformity in the altitudes of the hills and ridges, and the direction of the lines of depression corresponding to the strike of the strata, point to an original table-land, which, through the long action of denuding agents, has been quite deeply eroded, giving rise to the present surface configuration, so that some of the former and uniform features have been partially obliterated. The very few cross-valleys or depressions are much more irregular in their course, and serve as outlets through which the drainage is carried either into the Kittatinny Valley on the northwest, or to the broad, red shale and sandstone plane bounding the highlands on the southeast. The area of this highland

Jan 1, 1874

By Mark E. Emerson

INTRODUCTION A long time has passed since geologists encountered encouraging mineralization in their regional exploration program for base metals deposits. Detailed drilling during the following two field seasons served to delineate the configuration of the deposit. Various statistical techniques were employed to provide confidence levels regarding the extent of the reserves and to categorize them according to whether proved, indicated or inferred. At this juncture, it appears that the company has an orebody. Time elapsed? - three years; money spent? - $2.5 million. Much remains to be done before the orebody becomes a mine. The company urgently needs to develop new orebodies to replace its existing mines which are being depleted. It therefore has expended sizable amounts in exploration, the life blood of the company. A staff of specialists is maintained to evaluate new projects and to conduct feasibility studies. The scale of new mining projects today is beyond the resources of most mining companies. Bank financing, therefore, is often vital if the company is to survive. The following scenario describes how a company goes about evaluating mine projects and what is needed to meet lender's criteria in securing the needed financing. MINE PLANNING Now that the company engineers have taken over the project, their concern is no longer with finding ore but in developing it. An exploration shaft has been put down and a tunnel driven into the orebody to verify, on a large scale, what has been seen so far only in pencil- like drill cores. A large tonnage bulk sample is mined and shipped off to an independent metallurgical process laboratory for beneficiation testing. The budget is expended to cover engineering studies. Preliminary capical and operating costs are developed in- house and profitability studies are made based or1 assumptions concerning the markets for the main product and the indicated gold, silver, and other by-products. Time elapsed? - four years; cost to date? - $3.5-$4.5 million. The staff prepares its own pre-feasibility study. After review, the Executive Committee authorizes management to proceed with full-scale studies. The task is to make preliminary designs and to develop definitive capital and operating cost estimates. Specialized consultants will be engaged to study slope stability for the open pit and rock strength if underground recovery proves more feasible. If it is near the sea, an oceanographic report might be commissioned to see if the tailings can be disposed of off shore. Environmental impact studies are commissioned from a firm familiar with government requirements and regulations in this important area. The company subscribes for an expensive multi-client study of the supply- demand-price outlook for the product to support its own long-range price forecast. Now all the numbers are available to make a definitive appraisal of the value of the project. Cash flow analyses and sensitivity studies follow. Reams of computer printouts are generated. Time elapsed: five years. Amount spent? - up to $9 million, depending on the size, complexity and attractiveness of the project. Marginal projects always take longer. Finally, an engineering and construction (E&C) company is given the task of integrating and compiling all the data into a feasibility study. The results of dozens of reports, memoranda, computer printouts, and charts are boiled down to one final summary report of a few hundred pages together with conclusions and recommendations. After thoughtful review at a board meeting, the directors authorize management to proceed with detailed engineering work - provided that

Jan 1, 1985

By Theodore A. Blake

At the Chicago meeting of the Institute, May, 1884,I had the pleasure of announcing the introduction of a new machine for fine crushing, or The Blake multiple-jaw crusher, which, in combina tion with the ordinary Blake breaker, could be used in the reduc tion of ores or any hard and brittle substance to almost any degree of fineness. I am now able to give some practical results derived from its use on an extensive scale, on the gold ores of South Caro lina and the iron ores of Lake Champlain, together with some accurate and detailed statistics of the cost of crushing over one hundred thousand long tons of magnetic iron ores of the Chateaugay Ore and Iron Company at Lyon Mountain, Clinton County, N. Y., about thirty miles west of Plattsburgh. The construction of the multiple jaw-crusher, since the date of my first paper, is the same, except in the substitution of main swinging, instead of main sliding, or toggle jaw,—thus doing away with the upward thrust on the tension rods and the wear incident thereunto. (See Fig. 1.) It has also been found, in case of the fine crusher, that is, in machines of not over 4 inch width of opening, that the use of several small machines with a series of jaw openings, say 15 inches by 4 inch, is better than one large machine with a series of openings 24 by 4 inch, or 36 inches by 4 inch, as at first constructed. Many details of the method of holding in jaw-plates, etc., have been perfected. Without giving any details with respect to the different mills built upon the Blake 'system, let me state that, although it has proved possible to carry any hard and brittle material with crushers alone to a fineness such that all particles will pass a 30-mesh wire screen, still the economical limit of such crushing will be found somewhere between 14 and 20. If it is necessary to carry all the material to a fineness greater than this, the system must be supple

Jan 1, 1888

By M. G., Corson

1. In addition to the alloys of copper with iron previously found by Hanson and Ford to show an increase in the concentration of the alpha range with increase in temperature the following binary and ternary systems have been found by the author to exhibit: the same feature: (a) Copper-chromium. (b) Copper-cobalt. (c) Copper-silicon. (d) Copper-nickel-silicon and its pseudo-binary section Cu-Ni2Si (formula of compound definitely established). (e) Copper-cobalt-silicon and its pseudo-binary section Cu-Co2Si (formula of compound established with some probability but not as definitely as for Ni2Si). (f) Copper-chromium-silicon; formation of a compound definitely established (compare Figs. 1 and 2). The formula of this compound may be either Cr2Si or Cr3Si. (g) Copper-iron-silicon; presence of a phase containing both iron and silicon established in an indirect way only. No definite microconstituents observed. 2. RANGES OF SOLID SOLUBILITY (percentage at various tempera¬tures). (a) For copper-chromium: 0.8 at 1000° C.; 0.5 at 900° C.; 0.25 at 800° C.; 0.05 to 0.1 at 500° C. (b) For copper-cobalt: 3.4 at 1000'C.; 2.4 at 900'C.; 1.7 at 800'C.; 0.9 at 600°C.; 0.35 at room temperature. (c) For copper-silicon (Fig. 3) : 6.8 ± 0.1. per cent. at 800° C.; 3 per cent. at 400° C. and probably below 2 per cent. at room temperature if sufficiently long annealed. (d) For copper-cobalt silicide: 3.3 at 1000° C.; 2.4 at 900° C.; 1.6 at 800° C.; 0.7 at 600° C.; 0.3 at 300° C. (e) For copper-nickel silicide (Fig. 4): 8.2 at 1000° C.; 5.5 at 900° C.; 3.6 at 800° C.; 1.6 at 600° C.; 0.7 at 300° C.

Jan 1, 1927

By R. W., Ludt

THE use of froth flotation for the separation of minerals has become one of the most important of ore dressing processes. Its particular adaptability to the enrichment of low grade ores has made the process an important factor in the national economy. The methods have been extended to the recovery of a great number of minerals. Among the few minerals which have resisted efforts toward industrial flotation is chrysocolla, a hydrated partly colloidal copper silicate. Chrysocolla, being a product of natural oxidation, has been found to occur in small quantities with many ores which are recovered by flotation methods. In present practice, these small quantities of copper silicate pass off with the tailings and are lost. The advantages to be gained by a satisfactory process for the recovery of chrysocolla is apparent. Any application of principles which points a way toward the satisfactory industrial flotation process for copper silicate would be of advantage. This paper presents an attack on this problem.

Jan 1, 1949

By Carl E. Swartz

The Joint Session on Continuous Casting, of the Institute of Metals Division and the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers, convened in the Jade Room of the Hotel Waldorf-Astoria, New York City, on Feb. 23, 1944, at 9:15 o'clock, Carl E. Swartz presiding. C. E. SWartz.—It is gratifying to see so many out at what may seem an early hour for the beginning of A.I.M.E. sessions, but I think this number-—some fifty or sixty of you —is an adequate expression of the interest in these processes all over the United States, and possibly in foreign countries. I would like to ask those who feel that this type of program is of value to you to write or speak to some one of the Institute of Metals Division officers and suggest other topics for symposiums. We have a feeling that some of these current practices are of interest and we believe that under proper sponsorship many of the companies mill be willing to give publicity to processes such as those that will be discussed today. Also, we would like suggestions and criticisms, so that the next ones can be better. The subject of continuous casting is not new, of course. The two papers on the program this morning will adequately cover the history and some of the earlier processes, some of the theory and some of the practice, some of the reasons why these various methods did not work. I was rather interested in discovering, when thumbing through one of the A.I.M.E. publications tile other night, an article on continuous casting. I was not aware that the A.I.M.E. had published any papers on continuous casting, but there may be a number. The one that I happened to find was published in the 1915 volume, on the Mellen rod-casting process, and so we might say this is not the first session in which these subjects have been under discussion. However, there have been many improvements since then in all fields of metallurgical and mechanical engineering; consequently, I think that the papers today will be a little more involved and a little more complete in their technique. The first paper today will be given by one of our gentlemen of the press, who has done one of the outstanding jobs in this country in calling to our attention some of the newer processes that are being considered and being used in the metallurgical indus-

Jan 1, 1945

By W. S. Ayres

The construction of a new breaker at the Cranberry Colliery, Hazleton, Pa., was forced upon the operators, A. Pnrdee & Co., by a fire which destroyed the entire plant early in January, 1896. The loss included, in addition to the breaker, three boilerhouses and three engine-houses. The boilers were not injured, but the steam-pipes and connections were all broken and warped by the fire. The boilers were probably saved from injury by the presence of mind of the fireman., who started all his feed-pumps and filled the boilers with water. The hoisting-engines were more or less warped and cracked, but by patching and replacing the injured and broken parts, they were made to do satisfactory service in the new plant. It may be worthy of mention that the wrought-iron shaft of one of the hoisting-drums, 12 inches in diameter by 17 feet long, was so heated in the fire that the weight of the drum caused it

Jan 1, 1899

By C. R. Dale

IT IS the purpose of this paper to point out a number of the most common causes of crooked holes; to outline methods of drilling and straightening which to my personal knowledge have proved successful in numerous cases; to describe some of the characteristics of holes which, though not crooked in an exaggerated sense, may still cause serious mechanical trouble if not recognized and properly remedied; and to define clearly the part of oil-well surveying in the concerted effort operators generally are making to keep their wells straight from spudding to completion

Jan 1, 1931

By AIME AIME

A. A. Holland, Consulting Engineer, Toronto, Ont.-I noticed in this discussion of locations in which radium is found, no mention is made of the recent deposits discovered in Ontario. While radium is not a subject with which I am very familiar, I took an interest in this deposit on account of its novel occurrence. It is found in Haliburton County, near Wilberforce, Ontario, associated with a quartz free pegmatite, in a "break" that I understand can be traced for two miles. This "break" marks the contact between the limestone and syenite and contains numerous cavities or vugs. The gangue, on account of its deep purple, appears to :be amethyst.

Jan 1, 1930

By J. W. Richards

There are two essentially different 'types of case-hardening processes; that using a dry mixture in which the object to be case-hardened is packed and kept for the necessary time at the necessary temperature, and the "liquid" proccss, employing a bath of fused salts into which the object is immersed and which by immediate contact case-hardens the surface of the article. The Shimer process belongs to the second class, and was a war emergency invention. Of the liquid melts used as baths, the most effective and most frequently used are melted potassium cyanide and melted sodium cyanide. These may be used either pure or mixed with salts that reduce the melting point and the percentage of .cyanide present. The use of these baths since 1914 has met many commercial difficulties because of the high price and frequent commercial scarcity of the cyanide salts; at present sodium cyanide has practically entirely displaced potassium cyanide. Another trouble is the danger to the workmen handling the cyanide salts, which are extremely poisonous, and the annoying and poisonous vapors or gases given off in the workshop, unless an effective system of hoods and ventilation is provided, so as to prevent the gases from the baths mixing with the air of the room. Porter W. Shimer, of Easton, Pa., has invented a substitute1 for the bath of melted cyanides which case-hardens with equal or greater facility and effectiveness, gives off no poisonous vapors, and costs for chemicals materially less than the cyanide costs in the previously used baths. The process has been in use over a year in a large American works and the following statement embodies the results of practical experience in the use and operation of the process. The Shimer liquid or melted bath consists of a mixture of easily fusible salts that do not possess case-hardening properties, into which is immersed fresh calcium eyanamid, which imparts to the bath case-hardening properties. The composition of the non-case-hardening salts appears rather immaterial. Good results have been obtained by using a mixture of sodium chloride, calcium chloride, and barium chloride in equal proportions by weight; also a mixture of one part sodium chloride

Jan 1, 1920

By Louis A. Rosales, Kanji Ono

The anomalous behavior of hydrogen in iron is examined and a new model is proposed It is postulated that hydrogen single and di-interstitials are in equilibrium with each other. When the binding enthalpy of the di-interstitial, B, is assumed to be about 10 kcal per mole, the predicted temperature dependence of the solubility agrees reasonably well with the reported data. Effective diffusiuity is calculated assuming the di-interstitials to be immobile. Since the number of mobile single interstitials is greatly reduced at lower temperatures, the effective diffusivity is decreased. A good agreement in the temperature dependence of diffusivity between theory and experiment is provided with B - 10 kcal per mole. The predicted diffusivity is also a function of total concentration of hydrogen and this appears to be Partly responsible for the large scatter in the reported data. HYDROGEN is known to form an interstitial solid solution with iron.''' At elevated temperatures, it has been well-established that hydrogen enters iron in the dissociated form and occupies the interstices, and that diffusion of hydrogen in iron is via the interstitial mechanism. The concentration, c, permeability, P, and diffusivity, D, of hydrogen in iron have been separately determined and are consistent with each other under the steady-state condition for temperatures above approximately 400°C; that is, the relationship P = c-D holds. At lower temperatures, however, anomalous behavior of hydrogen in iron has been observed by many investigators. The results of experimental studies4-'' of the diffusion of hydrogen in iron are summarized in Fig. 1, in which the values of D are plotted against the reciprocal temperature. Although there is an increasing divergence in observed values of D with decreasing temperature, the values of D at temperatures below approximately 200°C are definitely small as compared with the extrapolation from high-temperature data. The lines shown bracket the region containing the most probable data. The observed values of c6," are plotted against the reciprocal temperature in Fig. 2, where the dashed lines represent Geller and sun's'' most probable isobars at 1 and 100 atm. At high external hydrogen pressure and low temperatures, the values of c observed are higher than those expected from high temperature data. It is generally accepted that certain trapping mechanism is responsible for the anomalies, but the nature of the trapping mechanism has not been clarified. Various types of hydrogen traps were suggested in the literature, such as "rifts" in the lattice dislocations, voids, microcracks, and so forth. However, no quantitative account of the observed behavior has been given in terms of these trapping mechanisms. Formation of methane in hydrogen-charged steel was found by ~odgurski." This appears to explain the existence of the so-called "residual" hydrogen,4 but not the observed anomalies of hydrogen in iron. McNabb and Foster' proposed a mathematical analysis in terms of a trapping mechanism. However, the physical significance of the traps was not clarified. The necessity of evaluating five parameters in their theory made comparison with experiment difficult. In the present paper, a model is proposed in which the anomalous behavior of hydrogen is attributed to the formation of hydrogen di-interstitials at lower temperatures. In this model, it is postulated that single and di-interstitials are in equilibrium with each other. (The hydrogen di-interstitial is to be distinguished from a hydrogen molecule which may exist in voids.) It can then be shown that most of the anomalies can be explained by assuming that the di-interstitials are virtually immobile and that the binding enthalpy of the di-interstitial, B, is approximately 10 kcal per mole. Predictions of the theory agree with the available experimental data reasonably well. THEORY The basic postulate of the present analysis is that single and di-interstitials are in equilibrium with each

Jan 1, 1969

By P. G. Shewmon, H. E. Collins

A study has been made to determine the sites at which sulfur adsorption occurs on copper surfaces. measurements were made of the relative torques, Ys, at the intersection of twin boundaries with surfaces near the three low-index orientations, i.e., (100), @lo), and 011), over a range of H2S/H2 ratios. HZS concerztvations j'ro~n 3 to 1500pp)n between 830" and 1050°C were used. It is concluded that sulfur adsorption occurved preferentially though not exclusively at edge sites near the (100) and (110) surfaces in the HzS range — 700 Ppm giving rise to negative torques near these orientations. Beyond this HzS range, adsorption occurred at all sites. Near the (111) surface, 7/y little with HzS concentration up to approxiwzately 75pptn. Above this range, the results indicate adsorption is occurring OH both terrace and edge sites. SCIENTIFIC interest in surfaces and their interactions with a gaseous environment dates back to the beginning of the 19th century. The scientific luminaries of that period—Faraday, Maxwell, Rayleigh, Dewar, and Gibbs—were already concerned about such processes. However, it has only been within the past several decades that adsorption on metal surfaces has been actively studied. This increased interest in adsorption has been brought about by the advent of new and improved experimental techniques and apparatus, e.g., ultrahigh vacuum, and field-emission and ion microscopes. However, most of the work done using these techniques has been carried out at low temperatures. When adsorption studies have been made at either low or high temperatures, they usually gave no indication of the particular surface orientations or type of sites on which adsorption was occurring. In the last few years, there have been a series of studies in which the surface tension, y,, and/or its derivative with respect to orientation, 7, have been studied as a function of orientation and atmosphere.'-7 Nearly all of the work on the relative torque,* ~/y, silver annealed in hydrogen and air.6 Recently Winterbottom and Gjostein" have used a modified and more accurate Mykurian method to determine the y plot of gold in hydrogen The only work in which T/~, has been measured over a range of chemical potentials for a given solute, p2, is that of Robertson and shewmon7 on the Cu-0 system. They measured T/Y, vs Po, (10"" to 10- l3 atm) at 1000°C in various mixtures of Hz0 and HZ. From this work they estimated the value of p2 at which one half of the surface sites are occupied with oxygen, pg, as being in the range 10- l6 to 10- l5 atm of oxygen. They also found that increasing Pa increased the magnitude of ~/y, near the (111) and (100) orientations. This indicates that oxygen is not adsorbed preferentially at step edges, but uniformly over all surface sites. In addition, they did one experiment on sulfur adsorption on copper surfaces, which indicated that sulfur adsorption decreases ~/y, near the (100) orientation, while not affecting ~/y, near the (111). This could be interpreted as indicating that sulfur adsorbs preferentially at step edges near the (100). In this paper the primary objective of the work has been to carry out a study of sulfur adsorption on copper surfaces over a range of temperatures and p,. In conjunction with this work, thermal grooving at grain boundaries has been examined as a method of determining the effect of sulfur adsorption on y,. METHODS Ideally, one would like to have information on the quantity of solute adsorbed on a surface and the types of sites at which it is absorbed as a function of p2. The total quantity adsorbed or the surface excess is given by the thermodynamic equation Thus data on the variation of y, with pz indicates the value of p2 at which adsorption becomes appreciable and the quantity adsorbed. The type of adsorption site is more difficult to deduce but information on this can be obtained from the variation of rz with 8, the angular deviation of the surface orientation. This is obtained from the thermodynamic equationlg Data on t and ys as functions of p2 have been obtained by the following methods. 1) Twin Boundary Grooving—By determining the effect of adsorption on the torque, 7, where T is the variation of surface energy, y,, with orientation, it is possible to obtain some indication as to the preferred sites of adsorption. Experimentally, the torque value measured is the relative torque, 7/ys The twin boundary grooving technique suggested by Mykura'' was used in this study to determine near the three low-index orientations— (loo), (110), and (111). Mykura's equation relates 7 /yS to measurements of the di-

Jan 1, 1967