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By D. J. Jr. McAdam

RESULTS of investigation of corrosion-fatigue of metals at the U. S. Naval Engineering Experiment Station have been presented by the author in four papers. 1,2,3,4 In those papers references were given to the work of Haigh in 1917.5 The investigation at Annapolis included a variety of ferrous and non-ferrous alloys. The experiments showed that even slight corrosion simultaneous with fatigue may cause failure at stresses far below the ordinary endurance limit. The experiments also showed that, for most metals, severe stressless corrosion prior to fatigue is much less damaging than even slight corrosion simultaneous with fatigue. The term "corrosion-fatigue" was restricted to mean the simultaneous action of corrosion and fatigue. The combined effect of corrosion followed by fatigue was called "prior-corrosion fatigue." A stress-cycle graph representing corrosion-fatigue is a curve approaching a horizontal asymptote, the ordinate of which may be called a "corrosion-fatigue limit." To avoid confusion in later discussion, the term "endurance limit" will be restricted to mean the fatigue limit obtained by tests in air with specimens as free as possible from stress concentration and from corrosion. The endurance limit as thus obtained presumably represents an inherent property of the metal.

Jan 1, 1929

By Robert Henderson

SEVERAL very interesting articles have been written on the caving system of mining, but most of these papers have dealt separately with the slusher system or the chute and grizzly system. In this paper, a comparison will be made of the two methods, both of which are being used at the Climax mine. The mine is on the Continental Divide, in central Colorado, at an altitude of approximately 11,500 ft. above sea level. The long, cold winters, characteristic of the high Rockies, create a number of operating problems not usually found in other mining areas. THE ORE BODY The Climax ore body is just east of the Mosquito fault. This structural deformation has brought the granite on the east against the sedimentary rocks on the west. The ore occurs in an intensely altered granite and schist around a silicified granite core. The ore is in a highly fractured zone of moderate silicification. The principal mineral, molybdenite, is found in these fractures. Barren dikes of granite porphyry cut through the ore body and core with no apparent regularity. The grade of the ore is fairly uniform and gradually decreases toward the footwall core and also into the hanging-wall granite. The footwall and hanging wall are determined entirely by assays. The ore body is roughly dome-shaped, with the apex truncated at the surface. It is covered to varying depths with talus. A horizontal section of the ore body on the Phillipson level appears as an annular ellipse surrounding the footwall core. The ring of ore varies in width from 300 ft. to as much as 800 ft. The north-south axis of the core is about 1200 ft. and the east-west axis is about 1800 ft. In the ore zone, the rock is sufficiently strong to maintain reasonably large openings, and openings larger than haulage drifts usually have to be supported. The ore is cut by a great many fractures and shears and breaks into rather large blocks when caved, necessitating considerable secondary blasting. The waste that overlies the ore body breaks relatively fine in comparison with the size of the blocks of the caved ore and tends to run through the broken ore in the cave, causing dilution unless the draw is carefully controlled. MINING SYSTEMS For several years the ore was mined by the chute and grizzly system, a system that differs from that used in other caving mines only in the size of openings and equipment. In the chute and grizzly system, main haulage laterals were driven along the footwall core and also along the

Jan 1, 1944

By Otto H. Henry, J. J. Cordiano

THOUGH powder metallurgy is one of the oldest of metallurgical processes, it is in its infancy as a branch of the modern field of metallurgy. As early as 3000 B.C., the ancients produced implements and weapons of iron by reducing iron ore in a charcoal fire and forging the resultant sponge while still hot into the desired shape. Melting and casting soon superseded the powder metallurgy practice, and it was not until the turn of the twentieth century that powder metallurgy was applied to the commercial manufacture of tungsten lamp filaments. From this beginning, the use of the powder metallurgy process spread to the manufacture of porous oil-impregnated bearings, cemented carbide tools, contact points, diamond grinding wheels, clutch facings, starter brushes, resin-bonded radio cores, magnets, metallic filters, and other parts. More recently, and particularly during the present war, there has been a definite trend toward the manufacture of machine parts by this process in competition with the more conventional fabricating methods. Notwithstanding these many developments, scientific progress has been slow. While many articles on powder metallurgy have appeared in the press and various publications, there have been too few contributions to our technical societies, with the result that there is a dearth of the type of information necessary for the full development of this science. It is of primary importance that the results of research and development be freely disseminated if powder metallurgy is to realize its fullest potentialities. PURPOSE OF INVESTIGATION Excluding the refractory metal field, all commercial powder metallurgical products made by a cold compressing and sintering operation contain voids. These voids can be substantially eliminated by subsequent severe working and heat-treatment, but such practice has not proved economical in most applications. By applying heat during the compressing operation, plastic deformation of the powder particles is substantially increased, and the resultant compact or briquette is practically free of voids. However, hot-pressing has many attendant problems, which at present preclude its use in the manufacture of precision parts. The more important of these are to devise: I. A die steel capable of withstanding high pressures at elevated temperatures. 2. A high-temperature lubricant capable of preventing excessive die wear and welding of the compact to the die walls. 3. A method of retaining a neutral or reducing atmosphere in the compacting zone of the die assembly. 4. A means of ejecting the hot-pressed specimen into a neutral atmosphere until reasonably cold.

Jan 1, 1945

By Kenneth A. Gutschick, Robert S. Boynton

Lime has become a general and loosely used term to denote almost any kind of calcareous material or finely divided form of limestone or dolomite, as well as burned forms of lime. However, according to Webster, lime is only calcined limestone (known as quicklime, unslaked lime, or calcium oxide). It also embraces the secondary product of quicklime, i.e., hydrated lime or slaked lime (calcium hydroxide). There are two basic types of limestone used for lime manufacture-high calcium and high magnesium (dolomitic). The dolomitic quicklimes and hydrated limes correspond to their "high calcium" counterparts. The only difference is that the dolomitic types are a combination of the elements calcium and magnesium, in varying percents, whereas high calicum limes contain less than 5% MgO down to 1/2%. In either case a pure form of limestone of at least 97% combined carbonate content is needed to make salable lime, barring a few exceptions. The calcination of both types is diagrammed chemically as follows: [ ] In the foregoing reversible reactions the limestone is burned (calcined) in lime kilns, with the carbon dioxide content of the stone expelled as a gas. The weight loss during calcination of pure high calcium limestone is 44%; with equimolecular dolomitic limestone, the weight loss is 48%. Since lime has a strong affinity for CO_, particularly if moisture is present, it will readily revert to its original carbonate form. This occurs when quicklime "air-slakes" and adsorbs CO.. from the air. Thus, quicklime is perishable and should be stored in dry, water-tight areas. Depending upon the type of kiln used and the physical structure of the stone, the size of the quicklime may range from sandlike granules to 8 in. lumps. However, pebble sizes ranging from 1/4 in. to 2 in. are the most common. Screened quicklime fines are also com¬pressed (pelletized) into 1 in. pellets. For some purposes ground or pulverized forms of quicklime are used, ranging from No. 10 mesh to dust. Generally a pebble of quicklime is about the same size as the pebble of limestone before calcination (perhaps shrinking slightly). A more stable form of lime is hydrated lime. This is obtained by adding water to quicklime, slaking it into a dry, fine, subsieve size white powder. Because its affinity for moisture has been satisfied, it is not vulnerable to further moisture like quicklime. However, it has the same strong affinity for CO_. The following reversible chemical reactions illustrate how hydrated lime when heated (or dehydrated) can revert to the original oxide form:

Jan 1, 1975

By F. V. Shallcross

Physical properties of thin films of CdS and CdSe formed by vacuum deposition onto glass sibstrates have been studied as a function of deposition and processing conditions. The crystallinity and surface features of CdS films were examined using electron microscopy and electron and X-ray diffraction techniques. The films were poly crystalline; the preferred orientation and crystallite size increased with film thickness, substrate temperature, and deposition time. The CdS films consisted primarily of hexagonal-phase material, in contrast to similarly prepared CdSe films which have previously been observed to contain mixtures of cubic and hexagonal phases. As-deposited CdS films showed no major dependence of Hall mobility on crystallite size or degree of preferred orientation. Hall mobility and carrier concentration in CdS and CdSe .films were measured at various temperatures; both parameters increased with temperature and yielded activation energies which depended on fabrication conditions. Surface-desorption phenomena and overcoating of the semiconductor with SiO affected the observed electrical properties significantly. THIN films of cadmium sulfide1,2 and cadmium sele-nide3,4 have been employed by various workers as semiconductors in the insulated-gate thin-film field-effect transistor, known as the TFT. These devices are most commonly made by vacuum deposition of all materials onto an amorphous substrate such as glass. A knowledge of the microstructure and electrical properties of semiconductor layers used in the thin-film transistor is essential in order to form a realistic model for the device and to improve its performance, reproducibility, and reliability. This paper will describe studies of the physical properties of vacuum-deposited CdS and CdSe films prepared under various conditions. Structural characteristics examined in- cluded phases present, crystallite size, nature of preferred orientation of crystallites, surface roughness, and structural homogeneity throughout the film thickness. Electrical properties measured were Hall mobility and conductivity and their dependence on temperature and ambient. Thin-film properties are affected by many fabrication parameters including purity and physical form of evaporant, deposition rate, film thickness, design and temperature of the evaporation crucible, geometry of the deposition chamber, nature of the residual atmosphere, composition and temperature of the substrate, and details of postdeposition processing. PREPARATION OF FILMS In this work the semiconductor films were deposited in a conventional oil-diffusion-pumped system with pressures in the 10-8 torr range. The CdS evaporant was obtained from the Eagle-Picher Co. as a high-purity coarse-grained crystalline powder; the CdSe was a high-purity sintered powder supplied by the Harshaw Chemical Co. The evaporation crucible was a resistance-heated molybdenum-wire basket coated with aluminum oxide and filled with a quartz wool plug at the top. The source to substrate distance was usually 10 cm. This region was enclosed by a Pyrex inner cylinder. The substrate was heated with an overlying Pyrex plate coated with tin oxide. The substrate temperature was controlled using a thermocouple attached to the lower side of the heater. This thermocouple was calibrated against another thermocouple attached to a dummy substrate and by observation of melting points of various metal films deposited in the system. The substrates were polished borosilicate glass plates and conventional glass microscope slides. Substrate preparation included cleaning with an ultrasonically agitated detergent bath followed by isopropanol-vapor de-greasing. Film thickness was measured interferomet-rically during and after deposition. STRUCTURE OF CdS FILMS Structural studies were performed on CdS films using electron diffraction, electron microscopy, and

Jan 1, 1967

By Steven Mitchell

BACKGROUND Homestake Mining Company began milling operations at the Bulldog Mountain Mine near Creede, Colorado in 1969. The Bulldog Mill, rated at 350 tpd, produces a bulk flotation condentrate assaying about 180 oz/T Ag and 20% Pb, from heads of about 16 oz/T Ag and 2% Pb. The circuit is straightforward with two-stage grinding to 1-5% plus 65 mesh, followed by rougher and cleaner flotation. Reagents used are Z-6, Z-11, Aerofloat 242 and Aero Promoter 404, with an Aerofroth 65-MIBC mixture for a frother. Additional information on the geology, mine and mill are available in references (1) and (2). A flow sheet for the mill and CIP plant together is attached as Figure 1. Final flotation tailings normally vary from 1.5 - 2.0 oz/T Ag. These tailings are cycloned to produce sand for underground backfill. After cycloning, the sands are repulped and given a final scavenger float. This sand scavenger recovers a small additional amount of silver which recycles back to the main flotation circuit. The tailings are recycloned and pumped to the mine or, if the mine cannot accept sand, to tailings. The majority of the silver in the flotation tailings exists in the fine fractions; cycloning upgrades the slimes and lowers the assay of the sand. The sand, after scavenging, typically assays 0.5 oz/T Ag, and the slimes assay about 3.0-3.5 oz/T Ag. From 1969 to 1976 all of the slime tailings and the sand tailings not used underground were impounded in a tailings pond located about

Jan 1, 1983

By W. A. Doble

Opinions differ as to whether the water-wheel almost universally known as the Pelton type belongs to the impulse, the tangential, the reactive, the jet or the percussion class, or to a cross between two or more of these classes. The fact is, that for an almost infinitesimal part of a second the axis of the jet of water strikes the bucket of this wheel at a true tangent to its base-line. The percussion of the water, striking the bucket, imparts an impulse to the wheel, causing rotation; and generally the bucket is so shaped that the direction of the jet is

Jan 1, 1900

By S. H. Ash

More than 100 minerals are mined and processed in the U. S. Management and labor have negotiated wage-scale agreements that have balanced wages and affected cost of labor in such a manner that comparisons can be made of transportation costs. Transportation of materials underground has become of vital importance. This report describes underground haulage methods and equipment, presents cost analyses, and discusses future plans for underground transportation in metal mines. It does not cover hoisting in shafts or slopes by cage, skip, or cars. Advancements have been made by the metal mining industry in lowering transportation costs in several mines, making it possible to mine orebodies or portions of orebodies not considered economically recoverable a few years ago. Numerous reports have been written on transportation at metal mines; this report covers recent haulage at some representative mines throughout the U.S. The term metal mine is used to include all noncoal mines from which up-to-date information was obtainable.

Sep 1, 1956

By A. A. Bauer, M. S. Farkas, F. A. Rough

An investigation of the d-phase relationships between the uranium-zirconium and uranium-molybdenum systems was conducted. A ternary cut joining U-31.5 at. pct Mo to U-74 at. pct Zr is presented on the basis of differential thermal analysis, metallographic and X-ray diffraction data. HyDothetical isothermal ternary sections, inferred from the determined d-phase relationships, are presented for the uraniztm-zirconium-molybdenum system. A ternary eutectoid, at 454ºC, was found in zirconium-rich alloys. Its composition, based on metallography and electron-beam micro-analysis, is estimated as U-61.7 at. pct Zr-7.1 at. pct Mo. URANIUM binary systems have been studied extensively in the past to supply basic information needed in reactor-fuel development. Alloys of uranium with zirconium, molybdenum, and titanium are of particular interest because, in these binaries, extensive or complete solid solubility between the body-centered-cubic forms of these elements and y uranium exists. In addition, an intermediate phase of limited solid solubility forms in each of these systems by transformation of the high-temperature ?-uranium phase. Previous investigation of the phase relationships existing between the intermediate 6 phases in the uranium-zirconium-titanium and the uranium-molyb- denum-titanium ternaries have already been reported.1,2 The results of an investigation of the phase relationships existing between the 6 phases in the uranium-zirconium-molybdenum system is reported here. The phase equilibria that occur in the solid-state portions of the pertinent binary systems are shown in Fig. 1. Phase nomenclature appearing throughout the report is as shown in these diagrams. The crystal structure of the phases in this system are given in Table I. EXPERIMENTAL PROCEDURES Alloys were cast and fabricated to 1/4-in.-diam rod. Specimens were heat treated and examined by metallographic and X-ray techniques. Thermal-analysis data were obtained.

Jan 1, 1960

By Norman B. Pilling, George P. Halliwell

The effects of lead and tin up to maximum contents of about 0.1 per cent. each, in the presence of oxygen between 0.04 and 0.30 per cent., have been studied. Tin is retained efficiently in the oxidized condition, whereas lead is not. An approximate relation between the lead-oxygen and tin-oxygen contents is deduced which, if observed, permits the presence of these elements without detrimental effect. Excess of lead beyond this limit affects ductility and rolling properties adversely and an excess of tin correspondingly diminishes the conductivity. It is shown that copper carrying a combined lead and tin content of several hundredths per cent., yet fully equal in quality to electrolytic wirebar, may be produced under commercial conditions. Tin is not normally found in more than bare traces in current grades of American electrolytic copper, and lead is rarely found to more than a few thousandths per cent. In the electrolytic refining of copper these metals do not present great difficulty in separation and their presence in any considerable amount in copper that has been refined by this method need not be tolerated. On the other hand, the effect of these elements is not entirely academic, as a considerable tonnage of scrap copper liberally contaminated with them has been reclaimed by the fire-refining process into metal with a residual lead and tin content of several hundredths per cent., yet having excellent working properties and fully equal in quality to current grades of electrolytic wirebar. Such copper has been found entirely suitable for use in the manufacture of electrical apparatus. In the absence of oxygen, tin is known to depress the conductivity rapidly, and lead to impair ductility and the rolling properties, yet the effects of these metals on commercial grades of copper—i. e., copper containing from 0.03 to 0.10 per cent. of oxygen—apparently has not received systematic attention. Occasional reference is made to the fact that in the presence of oxygen lead may be tolerated, yet Addicks says,1 in regard to overpoling: "The unstable condition can be controlled by adding certain substances, notably lead, in small quantities, but as mere

Jan 1, 1926

By Welton J. Crook

Unless present, in considerable praportion, metals of the precious-metal group—other than gold and silver—are not readily detected by the methods of fire assaying usually applied to ores and metallurgical products. Platinum, when present in small quantity, will ordinarily be reported as silver unless special methods of parting are used. Other elements occurring in the gold itself are all fluxed and slagged in the assay operation and if analyses are made on bullions the melting and slagging operations to which the bullion has been subjected may eliminate most of the associated elements. On the other hand, the analysis of precipitate from the cyanide treatment of gold ores may reveal the presence of many unexpected elements, such as tungsten and molybdenum. It is uncertain, however, whether many of the elements present in the precipitate are derived from the ore gangue or from the gold itself. No very general survey of the distribution of metallic elements in gold seems to have been made. Rose and Newman,l in connection with the composition of native gold, say in part as follows: Gold is occasionally found alloyed with copper and sometimes also with iron, bismuth, lead, mercury, tin, antimony, palladium or rhodium. Rhodium gold from Mexico was found to be of the specific gravity 15.5 to 16.8 and contained 34 to 43 per cent of rhodium. The native alloy of palladium, gold, and silver from Porpez contains 85.98 per cent of gold, 9.85 per cent palladium and 4.17 per cent silver. Mal-donitk, from Victoria, contains gold 64.5 per cent, bismuth 35.5 per cent (Louis). Dana2 says that native gold is usually alloyed with silver in varying amounts, and that sometimes it also contains traces of copper and iron. Rare varieties contain palladium, rhodium and bismuth. Other authors, for instance Zeigler3 and Clark,4 give similar information. Most references on the subject agree that ordinary native golds contain, in common, the elements silver, copper and iron. After completion of the work of which this paper is a record, the conclusion is reached that all ordinary native gold probably does contain these elements and, although in certain cases other elements may be found to be present, that it is difficult to

Jan 1, 1943

By Welton J. Crook

Unless present, in considerable praportion, metals of the precious-metal group—other than gold and silver—are not readily detected by the methods of fire assaying usually applied to ores and metallurgical products. Platinum, when present in small quantity, will ordinarily be reported as silver unless special methods of parting are used. Other elements occurring in the gold itself are all fluxed and slagged in the assay operation and if analyses are made on bullions the melting and slagging operations to which the bullion has been subjected may eliminate most of the associated elements. On the other hand, the analysis of precipitate from the cyanide treatment of gold ores may reveal the presence of many unexpected elements, such as tungsten and molybdenum. It is uncertain, however, whether many of the elements present in the precipitate are derived from the ore gangue or from the gold itself. No very general survey of the distribution of metallic elements in gold seems to have been made. Rose and Newman,l in connection with the composition of native gold, say in part as follows: Gold is occasionally found alloyed with copper and sometimes also with iron, bismuth, lead, mercury, tin, antimony, palladium or rhodium. Rhodium gold from Mexico was found to be of the specific gravity 15.5 to 16.8 and contained 34 to 43 per cent of rhodium. The native alloy of palladium, gold, and silver from Porpez contains 85.98 per cent of gold, 9.85 per cent palladium and 4.17 per cent silver. Mal-donitk, from Victoria, contains gold 64.5 per cent, bismuth 35.5 per cent (Louis). Dana2 says that native gold is usually alloyed with silver in varying amounts, and that sometimes it also contains traces of copper and iron. Rare varieties contain palladium, rhodium and bismuth. Other authors, for instance Zeigler3 and Clark,4 give similar information. Most references on the subject agree that ordinary native golds contain, in common, the elements silver, copper and iron. After completion of the work of which this paper is a record, the conclusion is reached that all ordinary native gold probably does contain these elements and, although in certain cases other elements may be found to be present, that it is difficult to

Jan 1, 1943

By R. F. Mehl, B. Lustman

The formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.' It is necessary here only to cnumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type—i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained—the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [i] where X is the thickness of the alloy layer, k thc reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.$ In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varics with temperature according to the Arrhenius equation: k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. Ali phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942

By M. C. Udy, C. H. Lorig

THROUGH the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the general effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. LITERATURE Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H20, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H20, FeO¬Fe-CO-C02 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnas1 published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at one temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1942

By R. F. Mehl, B. Lustman

The formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.' It is necessary here only to cnumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type—i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained—the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [i] where X is the thickness of the alloy layer, k thc reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.$ In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varics with temperature according to the Arrhenius equation: k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. Ali phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942

By Donald W. Scott

This paper describes the application of ore-dressing methods to the reclamation of milled frit from over-spray, or waste, porcelain enamel. Frit is the name given by enamelers to a granulated glass produced by the smelting and subsequent water quenching of various ingredients capable of forming a glass, usually including a compound to produce opacity. It is the major component of porcelain enamel, and normally commands a price ranging from 7 to 12 cents a pound. In the *preparation of a white enamel slip, usually 6 or 7 parts of clay, 2 parts of opacifier, small amounts of electrolytes, in some cases inorganic color stabilizeis and organic dyes, and 35 parts of water are added to 100 parts of frit; the mixture then is milled to a fineness of the order of 92 to 95 pct through a 200-mesh sieve. The frit forms the base of the enamel; the opacifier imparts opacity or reflectance; the clay suspends the frit while in slip form and serves as a binder in bisque form (dry and unfired); and the electrolytes control the workability. Spraying is used commercially, in many cases, to apply the finish coat of enamel to the ware, prior to drying and firing. In the spraying operation, only about 50 pct, by dry weight, of the enamel slip adheres to the surface of the ware, the remainder forms the over-spray. From 1/2 to 2/3 of the overspray goes up the flue where it is lost or recovered, depending on whether the plant is equipped with a dust-collecting installation; the coarser portion of the over-spray is collected in the spray booth. The former product is termed flue reclaim enamel, and the latter booth reclaim enamel. Although the spraying operation is done in specially constructed booths, which are partially or completely enclosed, it is extremely difficult to keep out contaminating dirt, which joins the reclaim. Some present-day large enameling plants use 20 tons of frit a day, of which 10 tons go into reclaim with a potential value of $1400 to $2400. When two-coat finish enamels were common, the reclaim was used satisfactorily for the undercoat, but the relatively recent advent of one-coat finish enamels prevented use of the reclaim because, even when blended with first-run enamels, it gave dirty finishes with poor gloss. It was thought that the pitting and specking encountered with reclaimed enamels were caused by the contaminating dirt, and that the poor gloss was caused, primarily, by the high clay content; more clay usually was added to give proper suspension properties to the slip when the reclaim was used. A clay content in excess of about 10 pct usually imparted refractoriness to porcelain enamels. Present-day one-coat porcelain enamels must combine high gloss and opacity with freedom from surface defects. Methods of beneficiating the over-spray,

Jan 1, 1948

By Donald W. Scott

This paper describes the application of ore-dressing methods to the reclamation of milled frit from over-spray, or waste, porcelain enamel. Frit is the name given by enamelers to a granulated glass produced by the smelting and subsequent water quenching of various ingredients capable of forming a glass, usually including a compound to produce opacity. It is the major component of porcelain enamel, and normally commands a price ranging from 7 to 12 cents a pound. In the *preparation of a white enamel slip, usually 6 or 7 parts of clay, 2 parts of opacifier, small amounts of electrolytes, in some cases inorganic color stabilizeis and organic dyes, and 35 parts of water are added to 100 parts of frit; the mixture then is milled to a fineness of the order of 92 to 95 pct through a 200-mesh sieve. The frit forms the base of the enamel; the opacifier imparts opacity or reflectance; the clay suspends the frit while in slip form and serves as a binder in bisque form (dry and unfired); and the electrolytes control the workability. Spraying is used commercially, in many cases, to apply the finish coat of enamel to the ware, prior to drying and firing. In the spraying operation, only about 50 pct, by dry weight, of the enamel slip adheres to the surface of the ware, the remainder forms the over-spray. From 1/2 to 2/3 of the overspray goes up the flue where it is lost or recovered, depending on whether the plant is equipped with a dust-collecting installation; the coarser portion of the over-spray is collected in the spray booth. The former product is termed flue reclaim enamel, and the latter booth reclaim enamel. Although the spraying operation is done in specially constructed booths, which are partially or completely enclosed, it is extremely difficult to keep out contaminating dirt, which joins the reclaim. Some present-day large enameling plants use 20 tons of frit a day, of which 10 tons go into reclaim with a potential value of $1400 to $2400. When two-coat finish enamels were common, the reclaim was used satisfactorily for the undercoat, but the relatively recent advent of one-coat finish enamels prevented use of the reclaim because, even when blended with first-run enamels, it gave dirty finishes with poor gloss. It was thought that the pitting and specking encountered with reclaimed enamels were caused by the contaminating dirt, and that the poor gloss was caused, primarily, by the high clay content; more clay usually was added to give proper suspension properties to the slip when the reclaim was used. A clay content in excess of about 10 pct usually imparted refractoriness to porcelain enamels. Present-day one-coat porcelain enamels must combine high gloss and opacity with freedom from surface defects. Methods of beneficiating the over-spray,

Jan 1, 1948

By G. W. Healy, W. D. Forgeng, N. R. Griffing

The liquidus surface of the C-Cr-Fe system to 1900°C has been mapped from carbon solubility and freezing point measurements, metallographic observations, and published data. In the graphite field, the surface drops precipitously to meet a slope descending from the Cr3C2-C join through the mixed carbide fields to a meandering eutectic valley; this flows from the Cr-C to the Fe-C edge. On the low-cavbon side of the valley, the surface rises to the chromium corner. 1 HE purpose of this inquiry was to gain a more complete knowledge of the C-Cr-Fe liquidus surface. This required an extensive study of carbon and chromium-rich alloys which, in the past, have received the least attention. Sanbongi el al.1 measured the solubility of carbon in liquid alloys containing up to 25 wt pct Cr at temperatures of 1460" and 1545°C and found that it increased with chromium content and temperature. Lucas and wentrup2 also made solubility experiments in graphite crucibles, but at higher chromium contents in the range of 38 to 80 pct and at temperatures of 1550" to 1700°C; however, their experiments were relatively few, and the effect of temperature was not consistent. The present investigation included compsitions ranging from 0 to 94 pct Cr and 1.4 to 11.7 pct C at temperatures up to 1800°C. Saturation experiments in graphite crucibles, thermal analyses during freezing, and metallographic and X-ray diffraction studies were employed to obtain desired information which, together with published data from other investigations about the binary edges and the ternary system at lower carbon levels, made possible the construction of a comprehensive C-Cr-Fe liquidus surface. C-CR-FE LIQUIDUS SURFACE The derived ternary liquidus surface is shown in Fig. 1 where the solid curves are liquidus isotherms. The dashed curves and the binary edges are the liquidus field boundaries of the primary crystals, the arrows along these boundaries indicating their direction with decreasing temperature. Each intersection of three internal boundaries is the composition of liquid involved in four-phase isothermal equilibrium with the three primary crystals whose liquidus fields touch there. It may be observed that a total of six four-phase equilibria occur at melt temperatures. The general topography of the liquidus surface consists of a eutectic valley sloping down from the Cr-C edge at 3.2 pct C to the Fe-C edge at 4.25 pct C. The liquidus surface rises in two directions from the valley, one hillside terminating at the Cr-Fe edge while the opposing hillside rises toward the carbon corner out beyond the top edge of Fig. 1. Both hillsides are interrupted by intersections of surfaces or joints representing the liquid colmpositions of various three-phase equilibria. Seven primary crystals occur, namely a(bcc), ?(fcc), graphite, (Fe, Cr)3C capable of dissolving as much as 15 pct Cr, and three different chromium carbides in which iron is partially soluble by substitution for chromium. The composition ranges of the primary l~hases at melt temperatures are shown

Jan 1, 1962

By S. E. Maddigan

MANY experimental and theoretical investigations have been made on the processes involved in annealing and recrystallization of metals. Most of these, however, have treated the time element as constant and heat-treatments used have been for relatively short times. Aside from the early work by Carpenter and Elam,1 the few that have investigated the effect of time on the processes have usually done so for fairly short time periods. During recent years the growing interest in long-time creep properties of metals and alloys under stress has made increasingly important a better knowledge of the recrystallization during prolonged heating. The recrystallization temperature of 70-30 brass given by Clark and White2 in 1932 was somewhat above 400°F. (204°C.) but under 500° (260°C.), whereas in our laboratory recrystallization has been observed in creep specimens at 204°C, the lowest temperature of Clark and White's range. Since the creep properties are quite different above and below the recrystallization temperature, erroneous conclusions can readily be drawn by the application of short-time recrystallization data to creep problems. It was thus considered of both practical and theoretical value to make long-time annealing studies near the minimum recrystallization temperature. In this way useful additions could be made to data on recrystallization temperatures and, since the reactions in this range are relatively slow, additional insight could be obtained into the factors involved in annealing. Several comprehensive reviews of recrystallization processes have been written,3-5 therefore only a brief review of the generally accepted facts will be given here.

Jan 1, 1940

By E. B. Hunt

Paraffin deposition has been studied in the laboratory under conditions simulating deposition in well tubing. A theoretical analysis has been made of the cooling of the oil and the precipitation of paraffin from the oil as it flows up the well tubing and through surface flowlines. It is proposed that paraffin deposits are initiated by the precipitation of paraffin directly on or adjacent to the pipe wall and grow by diffusion of paraffin from solution to the deposit. This mechanism is consistent with laboratory and field observations, and has proved useful in the design and interpretation of laboratory paraffin-deposition tests. Tests have been made of the effect of plastic pipe coatings and chemical additives on paraffin deposition. INTRODUCTION Paraffin deposits which form in well tubing and surface flowlines interfere with production and must be removed. Over the years much progress has been made in developing and improving methods of removing these deposits after they form. Much less progress has been made in developing methods of preventing or inhibiting the formation of paraffin deposits. This is due, it is believed, to the lack of knowledge of the mechanism of paraffin deposition, the absence of satisfactory laboratory testing methods and the difficulties in evaluating the results of field tests of preventive treatments. The present investigation was undertaken to elucidate the mechanism of paraffin deposition and to develop suitable laboratory tests for studying the inhibition of paraffin deposition in well tubing and surface flowlines. Current theories on the mechanism of paraffin deposition have been evolved from field observations, from laboratory studies of various factors which might be involved in paraffin deposition, and from laboratory paraffin-deposition tests.1-9 Paraffin deposits have been formed in the laboratory by immersing a cold finger into a hot wax-oil solution and by flowing hot wax-oil solutions through cooled pipe or over cooled plates. These laboratory conditions differ in important features from field conditions, and the observed deposition behavior is not entirely field-like." Thus, there is reason to question the field applicability of the results of these tests. The present investigation was undertaken to determine how to perform and interpret laboratory paraffin-deposition tests to obtain information on the inhibition of deposition in the field. The paraffin problem in the broadest sense encompasses the formation of any predominantly organic deposit in well tubing, surface flowlines and other equipment in contact with crude oil or gas. The present investigation was limited to paraffin deposition involving the precipitation of paraffin wax from solution by cooling and its concentration in a deposit on a cooled surface. This probably excludes its applicability to those problems arising from asphaltic-base crudes, but not those arising from paraffin-or mixed-base crudes. This also excludes its applicability to emulsion and congealing oil problems which are often included as part of the paraffin problem. The phenomenon of cooling appears to be the controlling factor in paraffin deposition involving the precipitation of paraffin wax and its concentration in the deposit. Deposits of this type are usually found in the field only where cooling occurs. Early in this laboratory investigation, it was not found possible to form deposits under constant temperature conditions from a wax-oil slurry, either by steady flow through pipe or by gas-lift up a pipe. Thus, the investigation was limited to situations involving cooling. THEORY The relationships involved in establishing the temperature profiles in an oil stream as it flows up well tubing with a linear (geothermal) pipe-wall temperature distribution or through surface flowlines with essentially constant pipe-wall temperature are presented in the Appendix. The relationship between radial distance in the pipe and the rate of cooling of the oil is then combined with a relationship between cloud point and rate of cooling to develop the pattern of formation of a wax cloud in the oil. The following discussion of paraffin deposition under various laboratory and field conditions is based upon this development which is presented in the Appendix. PARAFFIN DEPOSITION IN SURFACE FLOWLINES The average temperature of the oil coming out of a well is somewhat higher than the ground temperature. Thus, the oil continues to cool on its trip through the surface flowline, and wax deposition can occur. The temperature distributions calculated from Eq. A-4 are given in Fig. 1. As can be seen, almost all the cooling occurs in the first 500 ft from the wellhead. In addition, the radial temperature gradient near the wall decreases rapidly with distance and becomes very small after a few hundred feet. Thus, growth of a paraffin deposit would be expected to decrease rapidly with distance from the wellhead and become negligible after a few hundred feet, since growth is dependent on concentration gradient. Wax precipitation and diffusion of wax to the already