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By E. P. Polushkin, Henry L. Shuldener

THIS paper describes the results of microscopic examination of a series of brass pipes removed from apartment and office buildings in New York City, adjacent localities on Long Island, and Philadelphia. They were selected as typical of approximately four hundred pipe specimens obtained over a period of five years during an investigation of corrosion in hot-water installations. A part of the investigation is reported in this paper and includes a brief history of the pipes, a description of their inside surface and microstructure, and a study of the effects of corrosion, with particular reference to the structural aspects of local and selective dezincification. Although the bibliography on the corrosion of brass pipes is quite extensive, it refers almost entirely to corrosion in sea water. The authors believe that their examination of this series of pipes, which had been subjected to the corrosive action of fresh water for various lengths of time, may throw some additional light on the problem of corrosion. PIPES EXAMINED The pipes were made by different manufacturers and their sizes range from ¾ in. to 4 in. nominal inside diameter, the majority being within I to 2 in. They can be divided into two groups according to chemical composition: (I) with a copper content of 60 to 62 per cent and (2) with a copper content of 65 to 68 per cent. The first group (pipes made of Muntz metal) comprises 22 pipes and the second (pipes made of high brass) comprises 18 pipes. The pipes had been in service in various locations in the hot-water systems of the buildings involved. Some were taken from horizontal lines in the basement, some from overhead distributors and some from vertical risers. The distance, in terms of feet of pipe, of the specimens from the hot-water generator was no less than 75 ft. and often 100 to 300 ft. In the majority of cases the water-heating equipment was provided with a regulator to limit the temperature of the hot water supply. The normal range of temperature in pipe systems of this kind is 100° to 160°F. WATER SUPPLIES The average chemical composition of the water supplies carried by the pipes is shown in Table I. In evaluating the corrosiveness of a natural water, four factors are considered of prime importance: namely, hardness, alkalinity, pH and silica content. The waters listed in Table I are characterized by relatively low hardness, low alkalinity, low pH and low silica content. The waters of lower pH and higher CO2 content are more corrosive. A characteristic of all of these waters is that they do not deposit a protective mineral coating as do waters with high bicarbonate of lime content, which would be reflected

Jan 1, 1944

By G. W. Healy, L. F. Sander

was investigated by reacting thin discs of calcium oxide with gas mixtures of CO2, CO, and Son. Its value was 19,300 * 300 cal independent of temperature in this range. No solid solubility of sulfur in calcium oxide was detected within the limits of the experimental method and it is estimated to be below 0.025 pct by weight. The importance of lime in desulfurization is well-established but complete information on the pure phase equilibrium: CaO + 1/2 s2 = CaS + +02 [11 is not yet available. The goal of this work was to evaluate solid solubility of CaS in CaO and to determine the free-energy change associated with Reaction [I] at temperatures of 1400" to 1650°C. The equilibrium constant for Reaction [1] can be written: It is convenient to rewrite Eq. [2] in the form: where A = {Ps /PqJ1'2 has been referred to' as the "sulfurizing power' of a gas mixture. In this work, thin discs of CaO were suspended in a vertical tube furnace and exposed to CO + CO2 + SOz gas mixtures having known values of A. The samples were then analyzed for sulfur. As expected, X-ray diffraction confirmed that CaS was the only sulfur-bearing phase formed at the relatively low oxygen pressures used. EXPERIMENTAL PROCEDURE Reagent-grade CaCO3 was pressed in a 3/8-in.-diam pill die and prefired in air to produce CaO discs weighing between 0.004 and 0.01 g. Several discs were used to provide a suitable weight for chemical analysis while maintaining a large surface area to react with gas mixtures. These were placed in a platinum mesh basket and suspended in the gas stream in the hot zone of a vertical tube furnace. Desired gas mixtures were prepared from cp grade CO and CO2 and anhydrous grade SO2. The method of soap bubble displacement was used to calibrate capillary flow meters. While this gave excellent results with CO and Con, some problems with bubble insta- bility and soap film "drag" arose with the use of SO2 at low flow rates. Hence, frequent sampling and analysis of gas mixtures was carried out to insure proper control of the ingoing SOZ. The furnace used for gas:solid equilibration was a vertical mullite tube externally wound with 60 pct Pt-40 pct Rh wire having a diameter of 0.028 in. An inner tube of $ in. ID served as the reaction chamber having Pyrex ground joints sealed to the mullite to provide gas-tight connections at top and bottom. A Pt-Pt 10 pct Rh thermocouple was inserted into a protection tube adjacent to the sample basket to measure sample temperature during a run. Constant-temperature control to 2C was observed at any desired set point within the range of this investigation. This was accomplished by a control thermocouple imbedded in the furnace windings which served to actuate an electronic controller wired for high-low operation. The sulfur analyses of the solid samples were carried out using a stoichiometric combustion technique based on the method of Fincham and Richardson. Some analyses were done using a modified evolution method3 but these were used primarily to check the results of the combustion method. The results were in good agreement but the combustion technique of-ferred an advantage in economy of time and material. CALCULATION OF GAS EQUILIBRIA Heating a given mixture of CO + CO + SO2 to high temperatures gives rise to a large number of product species. The details of calculating the partial pressures of these products of interaction and dissociation can be found in several references4,5 and need not be repeated here. The thermodynamic data selected for the major species in the gas mixtures are shown in Table I. Equilibrium constants from these reactions were combined with oxygen, carbon, and sulfur balances and a computer program written to facilitate the calculations. Some early difficulties in reproducing experimental results were finally traced to the effect of atmospheric pressure changes. No reference to consideration of this question had been found in the

Jan 1, 1969

By Robert K. Waits

The resistivity, temperature coefficient of resistance, stability at 200°C, and structure of annealed Si-Cr films have been studied as a function of film cowposition. Colorimetric analyses of the films indicated 20 to 60 wt pct Cr over the resistivity range of 1 to 10-4 ohm-cm. Resistors were delinealed by photolithographic etching, contacted with aluminum, and mounted in TO-5 packages. The average temperature coefjicient of resistance, a, between 50" and 150°C is related empirically to the film resistivity, p, by a (ppm per °C) = -2900 - 1140 log p (ohm-cm). Near a resistivity of 3.5 x 10-3 ohm-ctn (30 at. pct Cr) , the temperature coefficient changes from positive to negative. The temperature at which the resistance maximum occurs increases with decreasing resistivity. The conduction mechanism between —196" and +360 C appears to have two components—an activated conduction dominating a1 lord chromium content and higher temperatures and a linearly temperature-dependent conduction dominating at high chromium content and low temperatures. Electron diffraction patterns showed the films to consist of Cr3Si and amorphous silicon. Resistors thicker than 150A typically drifted less than 0.6 pct after 5000 hr stor-age at 200°C. Resistors as thin as approxinzately 80°A that had a silicon overlayer showed similar stability. Such films had sheet resistivities of 10 kilohm per square and temperature coefficients near —600 ppm per "c. THIN-FILM resistors having sheet resistivities greater than 1 kilohm per square are required in many integrated circuit applications. A process for producing such resistors should be compatible with present circuit fabrication and packaging, including exposure to maximum temperatures of 300° to 570°C during contact alloying, die-attach, and ceramic package sealing. In addition, the resistors should have a low temperature coefficient of resistance and change less than 1 pct during storage at temperatures up to 200°C for 1000 hr or longer. Reports of work beginning in 1949 at Battelle Memorial Institute indicated that, among other materials, the silicides of chromium, Cr-Co, molybdenum, tantalum, and tungsten were worthy of further study as high-stability resistive films. Later work on Si-Cr films vacuum-deposited by flash evaporation from a tungsten boat1 led to the conclusion that Si-Cr had "excellent properties for development into high- stability ... resistive elements". More recently, Si-Cr films have been vacuum-deposited from a tantalum boat,2 from a BeO-coated tantalum boat,3 by flash evaporation from an electron-beam-heated tungsten Source,4 and by triode sputtering.5 This paper describes a study of Si-Cr films vacuum-deposited by electron-beam heating of Si-Cr alloys. Resistivity, temperature coefficient of resistance, stability at 200°C, and structure were studied as a function of film composition. EXPERIMENTAL PROCEDURE Film Deposition. Si-Cr sources were prepared by vacuum-melting pressed pellets of mixtures of powdered chromium (99.9 pct, -100 mesh, Lunex Co., Pleasant Valley, Iowa) and silicon (99.99 pct, -325 mesh, United Mineral and Chemical Co., New York). A permanent-magnet focused electron-beam gun having a water-cooled copper crucible was used to heat the pellet until complete melting occurred. The mixture was then kept molten for an additional 5 min. The alloy thus formed was used as the source material for Si-Cr film depositions using the same electron-beam gun. Pieces of semiconductor-grade silicon ingots were used as sources for silicon depositions. The films were deposited within a standard vacuum evaporator having an 18-in.-diam Pyrex bell jar, a liquid-nitrogen-cooled trap, and a Consolidated Vacuum Corp. 6-in. diffusion pump containing Dow Corning DC-705 pump fluid. The substrates were thermally oxidized* silicon wafers 2 to 2.5 cm in diam. The

Jan 1, 1969

By P. Pietrokowsky

lntermediate phases in the binary metal alloy systems Ti-Zn, Ti-Hg, Zr-Zn, Zr-Cd, and Zr-Hg have been investigated by X-ray powder diffraction methods. Gamma-TiBHg and Zr3Hg have a beta tungsten structure; TiHg and ZrHg are analogous to ordered AuCu (L l0 type); delta-TixHg and ZrHg, are isomorphous with ordered AuCu,, (L l2 type); ZrZnz is face-centered cubic (C 15 type); TiZna crystallizes in a C 14 type structure; and Zrll-, occurs in cubic and tetragonal modifications in which a random distribution of atoms exists. Additional information for the intermediate phase TiZn, is presented. THE physical metallurgy of titanium and zir-conium when alloyed with elements in subgroup 11-B of the periodic table has received comparatively little attention in the literature. Laves and Wallbaum' reported the existence of several intermediate phases in the system Ti-Zn. They identified TiZn as a CsCl (B 2) structure and described TiZn, as an ordered Cu,Au (L 1, type) crystal structure. Gebhardt' investigated very limited zinc-rich regions in the systems Ti-Zn and Zr-Zn. Phase relationships in these partial constitution diagrams were deduced from the results of thermal analysis and metallography, X-ray results being inconclusive. The first zinc-rich intermediate phase in either system was not identified. More recently, Anderson, Boyle, and Ramsey" have had occasion to refer to a partial Ti-Zn phase diagram (unpublished data) covering the region 0 to 10 atomic pct Ti, wherein two intermediate phases corresponding approximately to TiZn,, and TiZn,, were indicated. The metals used in this investigation and typical analyses as determined by the suppliers are given in Table I. The iodide-process zirconium which was used was not hafnium free. Experimental Methods Alloy Preparation: The relative ease with which titanium and zirconium combine with other elements places extensive restrictions on the methods by which alloying can be achieved. The direct current electric arc melting procedure was found to be unsatisfactory for preparing these binary alloys and for this reason solid state diffusion methods were utilized. The iodide process titanium and zirconium rods were filed by hand. Fines were subjected to a magnetic separation and classified as to size as either finer than 200 mesh or coarser than 200 but finer than 80 mesh. Powder mixtures of various binary combinations of titanium and zirconium with zinc and cadmium were compacted in a 12 mm diameter die and then placed in Vycor or quartz vials which were evacuated and sealed. The mercury alloys were prepared in a similar manner; the proper weight of liquid mercury being placed in a vial with minus 200 mesh titanium or zirconium. These ampoules were then heat treated at various temperatures and times depending on the characteristics of the particular alloy system. Upon completion of the heat treatment the ampoules were cooled rapidly and the specimens weighed. The loss in weight varied from 1 to 3 pct (except as noted in the text) and for this reason the calculated compositions were accepted as a fair measure of the actual alloy compositions. X-Ray Dif raction Techniques: Powder diffraction experiments were conducted at room temperature with a 143.2 mm Debye-Scherrer X-ray camera in which the film was placed in the Straumanis arrangement. When copper radiation was used, a nickel filter was employed, and for the cobalt target a filter of iron oxide was used. In both cases, the /i? filter was placed between the X-ray target and the powder specimen which was mounted on a glass fiber. The lack of information based on optical metallography placed reliance on the results obtained from the X-ray experiments for determination of

Jan 1, 1955

By John Garcia

IN some districts of the bituminous coal field the problem of construct-ing bulkheads to seal off water under pressure is becoming increasingly important. Recently this matter has been brought very much to the front by the loss of a large Illinois mine due to failure of a bulkhead that separated it from several old, flooded mines. As this great misfortune has provoked much inquiry about proper bulkhead design, it-is felt that a description, of the successful and extensive water-sealing practice at three mines that have different natural conditions will be of considerable interest to those connected with properties having a present or future water problem and to engineers that may have to design safe bulkheads of economical construction. These three mines are the Saxton and Dresser, near Terre Haute, Ind., and the Hegeler, near Danville, Ill. All three have water conditions that make it necessary to regularly seal off all worked-out sections of the mine, and there are considerably over a hundred bulkheads in each. As far as the writers know, these three mines are the only ones in the bitu-minous coal fields of the United States with anything like so large number of water seals and experience, although a number of other mines are known to have a few bulkheads. More detail will be included herein on the Saxton mine than on the others, as the writers are more familiar with it.

Jan 1, 1937

Jan 1, 1885

By B. L. Landrum, P. B. Crawford

The rise of a new laboratory model for studying tran-sient fluid flow problems, is described. The theory of he model is based on the analogy between the equa-ions which describe the flow of compressible fluids in porous media and the conduction of heal m solids. The "thermal model" is used to study the Iransient Pressure distributions during fluid displacement in five Standard well patterns. The studies indicate quantita-ively how die pressures change with lane at any poit in the reservoir. It was found that, in general, the equipressure contours are more radial about the wells early in the program than after steady-state conditions are established. In addition two studies of fractured five-spot patterns are presented to illustrate the opplicability of the model for a wide range of reservoir conditions. INTRODUCTION In reviewing the oil recovery techniques involving fluid displacement it was found that a very considerable quantity, if not all of the fluid within the pattern, mav be displaced (during a time-dependent or transient period rather than the usually applied steady-state conditions. Since the oil is displaced during a transient period, it was believed desirable to study the nature of the transients for several of the commonly used fluid displacement patterns. A literature review indicated fairly complete studies of the streamlines and isopotentials for steady-state: yet few data were available on the transient displacement process. Several simulated steady-state multiwell displacement programs were carefully mapped by Foster and Lodge on an electrical conducting sheet as early as 1875, hut the more recent work of Muskat provides the best source for steady-state phenomena having direct petroleum production applications. In order to study the transient phenomena a new lab-oratory model was developed which is based on the similarity of the equations that describe the flow of fluids and the conduction of heal. The equations describing heat flow were developed early in the nineteenth century. Regorous solutions tor most transient problems are in gcneral complex and usually limited to fairly restricted houndary conditions.2 the thermal model may be used to obtain approximate solutions for many transient problems without some of the restrictions required for analytical solution. The application of the analogy between heat conduc-. tion in solids. electrical flow and fluid flow, in a porous media has long been recognised. Techniques originally developed for the solution of heat conduction prol?lems have in many instances proved useful in ohtaining solutions to fluid flow prohlcms. Ir is not surpri5ing then that a heat conduction or thermal model might bf usefull in sludying transient fluid flow. As an example ol the problems suitable for the study with the thermal model, transient pressure distributions during fluid displacement programs are studied for the five-spot, line-drive, staggered line-diibe. seven-spot 211 two fractured patterns. A model was constructed of an iron plate of geometry similar to the reservoir patterns under study. The principle of mirror images as suggested by Bryan was employed in shaping the model. A temperature differential was obtained by soldering two sections of copper tubing to the plate at points analogous to the well location in the field. Hot and cold water was passed through the tubing. The temperature distribution, analogous to the pressure distribution in the field. was obtained a a function of time from thermocouplcs distributed over the plate.

By J. L. Jorstad

The hypereutectic Al-Si alloys 390 and A390 have wear characteristics superior to any of the more common aluminum casting alloys. This excellent wear resistance, coupled with good mechanical properties, high hardness, and low coefficient of thermal expansion, has made these alloys candidates for the all-aluminum internal combustion engine, the application for which they were primarily developed. A390 alloy is intended for sand and permanent mold casting, and requires a lower iron ccxltent (0.5 pct maximum) than its die casting companion 390 alloy (0.6 to 1.1 pct Fe). The 17 pct nominal silicon in these alloys provides sufficient quantities of the hard primary silicon phase to assure a high degree of wear resistance, yet little enough of this phase, to minimize the casting and m achining problems associated in the past with the hypereutectic alloys. The mechanical and physical properties of 390 and A390 alloys are competitive with the best of the common aluminum casting alloys with the exception of low ductility. This low ductility is not considered a detriment, since in many applications these alloys replace cast iron. Corrosion resistance is similar to the standard alloys 380 and 333. Numerous parts, of varying degrees of complexity, have been cast of alloys 390 and A390, including engine blocks and heads. The deviations from normal good handling and casting practices that are required for the alloys are those associated with the presence of the primary silicon. To obtain optimum strength and machinability, the molten alloys should be treated with phosphorus to refine the primary silicon phase. Care must be exercised to properly control the pouring temperature and rate in order to minimize primary silicon growth and segregation. AUTOMOTIVE engineers have for years recognized the advantages of lighter weight and better heat transfer that aluminum could offer as material of construction for engine blocks. These advantages alone, however, are insufficient justification for acceptance of aluminum engines by the automotive industry. To be acceptable, an aluminum engine first must pass all tests to which cast-iron engines are subjected, and, in addition, must represent no cost penalty in manufacturing. None of the conventional aluminum casting alloys have sufficient wear resistance to withstand the tests to which cast iron is subjected as a cylinder bore material, and recent attempts to manufacture aluminum engines with cast-in-place iron sleeves could not compete costwise with the equivalent cast-iron engine. The prerequisite to an acceptable aluminum engine seemed to be a casting alloy with a high degree of wear resistance that would eliminate the necessity of cast-in iron sleeves or liners. The hypereutectic A1-Si alloys 390 and A390 have met this challenge.' Combined with modified pistons and a patented cylinder bore surface finish,2 the performance of these alloys in more than 1300 cold start and cold scuff tests, over 3500 hr of dynamometer wear and endurance tests, and more than 350,000 miles of road tests leaves no doubt as to the feasibility of running on bare aluminum cylinder bores. ALLOY DEVELOPMENT The desirable characteristics of the hypereutectic A1-Si alloys have been recognized for some time. Their excellent wear resistance and low coefficient of thermal expansions have been used to advantage in the production of diesel-type pistons in Europe and to a limited extent in this country. The major contributor to the good wear resistance of these alloys is the extremely hard primary silicon phase in the microstructure. Although the percent silicon used experimentally has been much higher, most commercial alloys have ranged from about 14 to 25 pct. Generally, as the silicon content is increased, wear resistance increases, and the coefficient of thermal expansion decreases. With increases in silicon, however, machinability and cast-ability tend to suffer. The development of a satisfactory aluminum engine block material at Reynolds involved the testing and evaluation of many alloys, covering a wide range of silicon contents and numerous variations of iron, copper, magnesium, manganese, and other alloying additions. Castability, mechanical and physical prop-

Jan 1, 1969

By A. H. Geisler, F. Keller

Although the subject of precipitation from solid solution appears to be one of the more profitable fields in metallurgy for study with the electron Microscope, few comprehensive studies have yet been made. Occasionally electron micrographs have been published that illustrated alleged precipitation in various alloys, but frequently the apparent size, shape and distribution of the particles do not fully agree with those expected from theory or from observations of the Precipitate when the particles have grown to a size resolvable with the light microscope. The presence of a Widmanstatten pattern for submicroscopic precipitate particles has been demonstrated for only a few aged a1loys.l The initial problem has been the development of suitable techniques for applying the transmission-type instrument to a field that has been inherently associated with reflection-type microscopes. The various techniques have been the subjects of numerous publications, and instead of describing them individually here it will sufficc to say that the oxide film method has proved to be the most satisfactory method yet found for studying the microstructure of aluminum alloys with the electron microscope. This method has the definite characteristic advantage that the actual surface layer of the specimen is examined and not a plastic or silica replica. Doubtless suitable methods for forming and removing the oxide film could be developed for alloys of other metals. The purpose of this report is to point out the characteristics of the oxide film method that have been observed during the studies of numerous aged aluminum alloys and to present the results of these studies. Preparation OF Specimens The oxide film method for preparing specimens of aluminum alloys for examination in the electron microscope has been described in detail previously,¹,² Briefly, the procedure consists of preparing the metallographic specimen, forming the film by anodic oxidation and removing the film from the prepared surface of the oxidized specimen, The specimen is polished accordillg to the usual procedure for microscopic examination.³ he specimen may then be etched to remove flowed metal but etching to attack the alloy constituents or to leave them in relief as in the replica processes is not necessary. Electrolytic polishing is not generally recommended, Deep-etched specimens are used frequently, however, since they provide information that is not revealed by polished specimens and frequently present the same information more clearly than do the polished specimens, The surface preparation of specimens to be deep-etched is not important, since specimens that have been subjected to the first wet PoliShing operation are generally used, but frequently the as-rolled surface is Suitable. These specimens are then etched using a suitable macroetching reagent.

Jan 1, 1947

By F. Keller, A. H. Geisler

Although the subject of precipitation from solid solution appears to be one of the more profitable fields in metallurgy for study with the electron Microscope, few comprehensive studies have yet been made. Occasionally electron micrographs have been published that illustrated alleged precipitation in various alloys, but frequently the apparent size, shape and distribution of the particles do not fully agree with those expected from theory or from observations of the Precipitate when the particles have grown to a size resolvable with the light microscope. The presence of a Widmanstatten pattern for submicroscopic precipitate particles has been demonstrated for only a few aged a1loys.l The initial problem has been the development of suitable techniques for applying the transmission-type instrument to a field that has been inherently associated with reflection-type microscopes. The various techniques have been the subjects of numerous publications, and instead of describing them individually here it will sufficc to say that the oxide film method has proved to be the most satisfactory method yet found for studying the microstructure of aluminum alloys with the electron microscope. This method has the definite characteristic advantage that the actual surface layer of the specimen is examined and not a plastic or silica replica. Doubtless suitable methods for forming and removing the oxide film could be developed for alloys of other metals. The purpose of this report is to point out the characteristics of the oxide film method that have been observed during the studies of numerous aged aluminum alloys and to present the results of these studies. Preparation OF Specimens The oxide film method for preparing specimens of aluminum alloys for examination in the electron microscope has been described in detail previously,¹,² Briefly, the procedure consists of preparing the metallographic specimen, forming the film by anodic oxidation and removing the film from the prepared surface of the oxidized specimen, The specimen is polished accordillg to the usual procedure for microscopic examination.³ he specimen may then be etched to remove flowed metal but etching to attack the alloy constituents or to leave them in relief as in the replica processes is not necessary. Electrolytic polishing is not generally recommended, Deep-etched specimens are used frequently, however, since they provide information that is not revealed by polished specimens and frequently present the same information more clearly than do the polished specimens, The surface preparation of specimens to be deep-etched is not important, since specimens that have been subjected to the first wet PoliShing operation are generally used, but frequently the as-rolled surface is Suitable. These specimens are then etched using a suitable macroetching reagent.

Jan 1, 1947

By W. Hodge, A. F. Haskins, R. M. Evans

Refractory boron compounds are shown to resist corrosion by molten zinc. Coatings were made from ferroboron and manganese boron by several methods: welding, hard facing, and pack diffusion; and techniques of coatings are very important. Mechanical failure of the diffusion coatings can be partially eliminated by applying them to type 416 chromium steels rather than carbon steels. Welded coatings made with a tungsten arc are better than those made by other welding methods. Sintered compacts of mixtures of iron and chromium borides developed strengths of about 30,000 psi. They resisted corrosion of zinc at 600°C and oxidation at higher temperatures. MOLTEN zinc rapidly attacks common metals of construction. The rate of attack is greatly amplified at temperatures over 500°C. However, there are many applications where it is necessary, or at least advantageous, to use metal construction, such as for galvanizing pots and zinc smelter equipment. Condensers and agitator linings used in continuous zinc smelting processes are eroded and corroded by violently agitated molten zinc. Pumps, tubing, and other parts to permit transfer of molten zinc would be desirable in many zinc handling operations. The development of metallic materials which are resistant to molten zinc also might permit its use as a heat-transfer medium in modern high efficiency power plants. In reviewing previous work on zinc-resistant metals, it was evident that most of the available data refer to corrosion at temperatures just above the melting point. Tungsten and high Mo-Fe alloys containing more than 80 pct Mo resist corrosion by molten zinc.', ' Imhoff states that because chromium is not attacked by zinc, chromium plating improves galvanizing pot life." Nitrided cast iron has been used in die-casting machines' where the molten alloy is 96 pct Zn and 4 pct Al. Other metals that have been suggested as of possible value for zinc resistance are columbium, tantalum, and titanium.V he corrosion of steel by zinc has been discussed by many authors,z, "2 None of these materials resisted corrosion by molten zinc at the temperatures used in this investigation, i.e., 600" to 700°C. I. Exploratory and Resistant-Coating Tests To make a study of zinc-resistant metals, exploratory tests were conducted to sort out roughly those materials which seemed most worthy of further development. This preliminary study included both solid metals and surface coatings. Exploratory Corrosion Tests in Molten Zinc—In initiating a study of this problem, numerous samples of metals and alloys were evaluated by dynamic corrosion tests made at 440 °C. Each metal was tested in its most readily available form, which, because of shape and size, was often unsuited for standard corrosion testing. The equipment used for dynamic corrosion testing of all materials, except in a few initial experiments, is shown in Fig. 1. Samples were tied to tungsten rods with tungsten wire, immersed in the zinc, and revolved at 12 rpm about the circumference of a 4 in. diam circle. Speed of travel was about 12.5 fpm. The molten zinc was protected from oxidation by an atmosphere of carbon monoxide, or, at a later period in the program, by a 9:1 mixture of nitrogen and hydrogen. When the effect of both molten metal and atmosphere was desired, the zinc level was lowered. Special high grade zinc was used in all of the corrosion tests. Corrosion losses for materials tested are shown in Tables I and 11. Whenever the materials were available in suitable form, the losses are reported in mils per year. It was recognized that weight losses on irregularly shaped specimens did not show the corrosion rate but the important consideration—poor resistance to corrosion—could be determined readily.

Jan 1, 1956

By P. E. Baker

An experimental study of heat flow in steam flooding was carried out with steam displacing water in a plane-radial fluid-flow model. Temperature distributions in the model reservoir, overburden, and substratum were measured at frequent intervals during flooding by means of a fixed array of thermocouples. Heat losses to overburden and substratum and the division of heat between the steam and hot-water zones in the reservoir were calculated from the temperature data by performing numerical integrations over the appropriate volumes. Temperature profiles and heat distribution results are presented. Some results were (1) the fraction of injected heat that is lost to overburden and substratum, when expressed as a function of time, did not depend on injection rate; (2) a significant portion of the injected heat was contained in the hot-water zone ahead of and underlying the steam front in the reservoir. The division of heat between the steam and hot-water zones did depend on injection rate; and (3) considerable gravity override was observed. The experimental results are compared with those of several published theoretical studies of heat transfer in hot-fluid injection; approximate agreement on heat losses is found with some of the most idealized theories. A valid comparison cannot be made in regard to steam us hot-water zone; basic interpretation of the hot-water zone, in terms of a vertical steam front, is clouded by gravity override in the experiments. INTRODUCTION The experimental study reported here primarily concerns two problems of heat transfer in steam flooding that have economic and engineering importance. These are (1) the fraction of injected heat lost to the overburden and substratum, and (2) the division of the remaining heat between a zone containing steam and a zone of hot water at lower-than-boiling temperature. The volume of the steamed region, which has a direct effect on oil recovery, can be calculated readily from these results. Several valuable theoretical studies have been published on this problem, but no experimental tests of the theories have previously appeared. Tests were needed because the effects of the necessary simplifications in the theories could not be determined otherwise. The basic, untested theoretical problem is the effect of "decoupling" heat and mass transfer, and the resulting inability to include the effects of heat transfer and condensation on fluid flow. The theoretical problem solved so far has been a heat transfer problem in which fluid is present as a heat carrier and flows in a stipulated manner, either linear or plane-radial. The simplifications that have sometimes been made in regard to thermal conductivity by, for example, Marx and Langenheim,l Lauwerier2 and Thomas3 apparently do not have an important effect on heat loss calculations, although the results of the different methods disagree to a certain extent, as shown by Spillette4 and by Ramey.5 A recent paper by the author6 compared the results of experiments in hot-water flooding with several theoretical results and showed a rather poor agreement. It will be seen that the experimental heat loss results for steam flooding, however, show acceptable agreement. These comparisons are discussed in a later section. EXPERIMENTAL APPARATUS AND PROCEDURE The system studied was one in which a sand pack, initially water saturated and at a uniform temperature, was flooded with steam at a constant rate and temperature. The temperature distribution in the "reservoir" and adjacent "strata" was measured with an array of thermocouples, and heat losses were determined from these measurements. The sand pack contained no oil because the only concern of the experiments was heat flow, and it was important to have the flow pattern as simple

Jan 1, 1970

By Paul M. Tyler

MILITARY power stems from industrial power and industrial power in turn depends predominantly upon an ample and assured supply of mineral raw materials. It thus becomes the duty of mineral economists to collate the vast array of data and logical deductions in order to reach an unemotional judgment as to the ability of the Soviet economy to withstand the strain of prolonged military action on the modern scale. Russian publications, reports: and official speeches have been laboriously screened and analyzed. Since these are the sources of information for the lower echelons of the Soviet industrial organization itself, they carry factual data that can be pieced together to show the present-day pattern. Apparent contradictions and obvious distortions or omissions can often be rationalized on the basis of observations made by foreign engineers and consultants during the 1930'5 and by checking against the technical literature published before even so-called technical articles were riddled by bombastic and presumptuous claims.

Jan 6, 1951

By Clarence P. Linville

(Pittsburg Meeting, March, 1910.) IT is recognized that, in all metallurgical operations, the greatest possible uniformity in all conditions is essential to the best results. It is the constant aim of metallurgists to secure this uniformity, and their success in this respect has been in many cases the cause of great advances in the metallurgical processes themselves. Of all such processes, the production of pig-iron in the modern blast-furnace is perhaps the most complex and the most difficult of control. Notwithstanding the great progress of recent years, there is still great difficulty in obtaining anything like uniform conditions and results in the manufacture of pig-iron. The reason is not far to seek. The ores vary in composition and physical properties, often carrying a varying amount of gangue material, unevenly distributed The coke may vary in composition, cell-structure, moisture, hardness, and other properties. The blast, the weight of which far exceeds that of any other constituent, varies in its moisture-content and consequently in its chemical composition ; and its temperature, by reason of the method of heating, is not uniform, but, besides varying from time to time with atmospheric and other outside conditions, has a maximum and minimum for every changing of stoves. Now, with regard to these variations, the modern demand for uniformity has been greatly aided. Chemical analysis has made it possible to select ores so that the composition of the charge can be kept fairly constant; coal may be obtained from a given field, and coked in the same kind of ovens under conditions which . make the fuel practically uniform ; the Gayley

Mar 1, 1910

By R. I. Jaffee, E. S. Bartlett, D. N. Williams

The oxidation resistance and fabricability of molybdenum powder-metallurgy alloys containing up to 20 wt pct nickel in the form of a fine dispersion were studied. The effects of dispersion distribution and of amount and type (pure nickel or nickel compounds) of additive were considered. A definite improvement in oxidation resistance was observed, but the amount of improvement fell far short of requirements for an oxidation-resistant alloy. Fabricability by hot-rolling was limited. INVESTIGATIONS at Ohio State university1 and Battelle Memorial institute2 have indicated that the attainment of a truly oxidation-resistant molybdenum-base alloy for high-temperature service, with the coincident retention of high-temperature strength and toughness, will be a difficult, if not impossible, feat. Among the most promising alloy systems studied was the molybdenum-nickel system shown in Fig. 1. Alloys in this system show good oxidation resistance at temperatures well above the normal melting point of molybdenum trioxide because of the regenerative formation of protective nickel-molyb-date (NiMoO4) on the surface of the alloy during exposure at high temperatures. Unfortunately, the required alloy content to obtain oxidation resistant molybdenum-nickel alloys far exceeds the limits of the narrow terminal solid-solution boundary, and closely approaches the peri-tectic composition involving the brittle intermetal-lic compound, MoNi. Because of the peritectic reaction, fusion alloys are characteristically brittle, since the MoNi phase, being the last to form, tends to occur as a continuous grain-boundary network around each molybdenum grain. An added problem with this system is that the protective nickel-molybdate layer formed at high temperatures is unstable, undergoing one or more allotropic modifications upon cooling. The volume changes associated with this modification during cooling are such as to cause violent expulsion of the protective molybdate coating from the surface of the piece. This is, of course, quite detrimental in material exposed to cyclic temperature during service. The research reported here resulted from an attempt to overcome the aforementioned problems associated with the molybdenum-nickel alloys primarily by controlling the amount, size, and location of the MoNi phase. By using powder-metallurgy techniques of alloy preparation and sintering the blended molybdenum-nickel powder mixtures at a temperature below the peritectic reaction temperature, molybdenum-nickel alloys with a randomly dispersed MoNi phase were produced. MATERIALS The molybdenum powder used in the preparation of alloys for this study was commercial hydrogen reduced, minus 325-mesh (Tyler) material. Master alloys, by which nickel was added, consisted of elemental carbonyl nickel powder (12 average particle size), an alloy of 50 wt pct Ni-50 wt pct Cr, and compounds of MoNi, Ni,Si, and Ni2B. The nickel-chromium powder was prepared by filing a vacuum-arc-melted ingot, separating impurities magnetically, and screening to minus 200-mesh. The MoNi powder was prepared by pulverizing a hydrogen-sintered powder-metallurgy compact to minus 325-mesh material. Further sizing of this powder for study of effects of dispersion distribution was accomplished by air classification of the minus 325-mesh powder. The Ni2Si and Ni2B powders were prepared by crushing vacuum-sintered powder-metallurgy compacts to minus 200-mesh material. EXPERIMENTAL PROCEDURE Specimen Preparation—The general procedure followed in the preparation of alloys for testing is described as follows: 1) Blending. Either hand-blending of the powders in a ceramic mortar and pestle for X 1/2 or mechanical blending was used. Hand-blending seemed preferable for optimum homogeneity. 2) Compacting. Most of the blended powders were pressed to green compacts at pressures of 15 tons per sq in. in a single-action die, although some were pressed at 80 tons per sq in. A 1 X 11/4 X 1/4-in. green compact was the standard size for oxidation test material, and 7 X 1/2 X 1/4-in. compacts were used for fabricability test specimens. 3) Sintering. All green compacts were sinteredat

Jan 1, 1959

By D. V. BURR

THE ORIGINAL HUDSON RIVER TUNNEL. NOT quite forty years ago a man of uncommon character entered New York. He had several hundred thousand dollars earned by railroad building in the Nest. He was not an engineer, but he had ideas of engineering work which he was destined to prove correct.. He introduced new ways of tunneling, but his plans had only one distinguishing feature-they were simply interesting as showing how such work could be done; they added nothing to the science, have never been used since his clay, and never will be used again. Engineers of repute ridiculed his proposition ; he was an Ishmael in the profession. But if engineers looked askance at him, he certainly returned their contempt in the heartiest fashion, and had no hesitancy about expressing his views of them individually and collectively. This worked to. his disadvantage when he afterward tried to raise the means to go on with the work. He found that the opinion of engineers was respected by financiers, and that money would not flow contrary to their advice. While his conception of large constructions was distinguishingly original, much more marked was his method of demonstrating the feasibility of, his schemes. In the present clays of great undertakings it is the custom to make the other man pay for the experiments. But the man from the West had other notions of how the thing ought to be done. Having wonderful confidence in his own ability and in his perception of the task before him, he used up all his own money before seeking outside assistance. By building several hundred,, feet of tunnel he proved the correctness of his theory, and the tunnel then dug forms a part of the present tube. The result-he failed to finish the tunnel. He was blind in

Mar 1, 1908

New Jersey Zinc Co. - The Mines Franklin-Sterling Friedensville Development Austinville Ivanhoe Development Eagle Mine Hanover

Jan 12, 1953

By W. H. Emmons

MOST mineral deposits change as they are followed downward on their dips. Some of these changes are due to primary arrangement; different ores were precipitated at different depths when the deposits were formed. Other changes are due to weathering or secondary enrichment. The chief changes resulting from weathering, in the main, are understood and standard changes are recognized. The processes are relatively simple. They take place at ordinary temperatures and pressures and can be duplicated in the laboratories. Moreover, there are thousands of deposits available for study, because the processes take place near the surface where the development of mines is begun. The changes due to primary arrangement of the deposits of the metals are not so well understood. Deposition has taken place at higher temperatures and our knowledge of the chemistry of the processes leaves much to be desired. Very few experimental data are available. The deposits, moreover, offer fewer examples because many mines are not, developed to depths where the changes can be studied and a change to unprofitable material usually results in stopping work. Most, students of ore deposits now accept, as confirmed, the hypothesis that nearly all lodes and related deposits were formed by solutions originating in intrusive igneous masses. Outward from these masses, the deposits at many places are grouped in zones and the arrangement noted from the intrusions outward are commonly the reverse of the changes noted from the surface downward in a single lode. A study of the changes in groups of deposits, from the parent intrusion outward, will throw light on the changes to be expected in a single lode downward. Because the changes in series of deposits from the intrusive outward may all be observed near the surface, where more data are available, it is possible to increase the number of examples many fold and to apply the statistical method of study with greater confidence of avoiding error.

Jan 3, 1924

McCulloch, Leon.-Experiments with Sherardizing. Discussed by Fred. L. Wolf, Willis M. Peirce, Jesse L. Jones, O. W. Storey, David R. Kellogg, William H. Finkeldey, L. H. Marshall 2 Bassett, W. H. and Davis, C. H.-Spectrum Analysis in an Industrial Laboratory. Discussed by C. S. Brainin, C. H. Davis, W. H. Bassett, George K. Burgess, George K. Elliott, Leonard Waldo, Keivin Burns 8 Roast, Harold J. and Pascoe, Charles F.-Arsenical Bearing Metals. Discussed by Jesse L. Jones, William A. Cowan,. William K. Frank, William M. Corse, Harold J. Roast 10 Bain, Edgar C.-Crystal Structure of Solid Solutions. Discussed by Ancel St. John, Edgar C. Bain, Paul D. Merica 14 Peirce, Willis M.-Studies on the Constitution of Binary Zinc-base Alloys. Discussed by George K. Burgess, Willis M. Peirce, D. H. Ingall, J. L. Haughton, K. E. Bingham 16 Webster, William R.-Application in Rolling of Effects of Carbon, Phosphorus and Manganese on Mechanical Properties of Steel. Discussed by George B. Waterhouse, J. O. Liebig, Ralph H. Sweetser, H. T. Morris, F. D. Carney, W. P. Barba, John H. Nelson, George K. Burgess 19 Barba, W. P. and Howe, Henry M.-Acid Open-hearth Process for Manufacture of Gun Steels and Fine Steels. Discussed by W. J. Priestley, Haakon Styri, C. T. Patterson, Harry Brearley, W. P. Barba, George F. Comstock, Alexander L. Feild 24 Kellogg, David R.-Electrolytic Deposition of Iron for Building up Worn or Undersized Parts. Discussed by Jesse L. Jones, William Blum, C. R. Hayward, George K. Burgess, C. P. Perin, David R. Kellogg 33 McQuaid, H. W. and Elm, E. W.-Effect of Quality of Steel on Case-carburizing Results. Discussed by H. J. French and L. Jordan, W. J. Priestley, M. H. Schmid, A. E. White, H. J. Stagg and S. C. Spalding, Henry S. Rawdon, J. S. Vanick 35 Phillips, Arthur and Davenport, E. S.-Malleableizing of White Cast Iron. Discussed by Samuel Epstein, H. A. Schwartz, A. E. White, R. S. Archer.... 58 Priestley, William J.-Effect of Sulfur and Oxides in Ordnance Steel. Discussed by Harry T. Morris, William J. Priestley, C. P. Perin, James H. Gray, W. P. Barba, Haakon Styri, Frank D. Carney, W. L. Harbrecht, George F. Comstock, E. J. Janitzky 67

Jan 5, 1922

By P. Duwez, C. B. Jordan

The phenomenon of the change of volume of pressed powder compacts upon sintering is well known in the field of powder metallurgy. Depending upon the metal or metals involved and the pressure used in forming, a compact may, in the course of time of sintering at a given temperature, expand mono-tonically, contract monotonically, or first show a volume change of one sign followed by a change of the opposite sign. It is clearly desirable to have accurate knowledge of the magnitude and sign of the change in dimensions to be expected in any given case, both from the point of view of direct usefulness in the fabrication of parts by powder metallurgy, and from the longer range viewpoint of elucidating the fundamental mechanism of metallic sintering. The present study was therefore undertaken as a first step in acquiring systematic and reasonably quantitative knowledge of the change in density of metal powder compacts during sintering. For practical reasons, copper was selected as the material to be studied first, and its densification followed as a function of temperature and time of sintering in hydrogen and in vacuum. Experimental Procedure The copper powder used was that designated by the manufacturer (Metals Disintegrating Co., Elizabeth, N. J.) as MD-151. This powder was sifted through Tyler standard screens to separate the fraction having particle size range between 200 mesh and 325 mesh, and this fraction was used in all the subsequent work. Compacts weighing about 10 g were then pressed in a 1 in. diam round die, using a pressure of 20,000 psi throughout. Sintering was carried out in commercially built electric furnaces in which the resistance windings are so disposed as to produce a nearly uniform temperature along the axis of the furnace for a length of about 18 in. centrally located. In order to be able to sinter in a controlled atmosphere, a 2 in. stainless steel tubing was inserted in the furnace. Each end of the tube was cooled by a water jacket about 7 in. long, and closed with a rubber stopper. The hydrogen used for one series of specimens was purified as described in Ref. 1. For the other set, a pressure of about 0.5 mm Hg was maintained during sintering by a Welch Duo-Seal Pump. The specimens were heated on square trays made of stainless steel. In placing specimens in the trays, a thin even layer of powdered aluminum oxide was first sprinkled on the bottom of the tray. A copper guard disk about half the thickness of the specimen was then placed in the tray and covered with a second layer of alumina. The actual specimen was then set on the guard disk, and a final coat of alumina sprinkled over the specimen. This technique was evolved for sintering the specimens in such a way as to reduce the influence of unknown extraneous factors to a minimum. If the specimen is placed directly on the tray and sintered, it is found that the resulting shape is that of a frustum of a cone, rather than a section of a right circular cylinder, since friction with the tray prevents the bottom of the specimen from contracting at the same rate as the top. In the arrangement used in these experiments, the guard disk provided a support which shrank at the same rate as the specimen, and the alumina powder reduced to a minimum friction between guard disk and tray, and between specimen and guard disk. The procedure followed in sintering consisted of bringing the furnace to the required temperature, and then inserting the specimen into the central heated portion of the furnace tube in one of the two atmospheres used. At the end of the heating period, the specimen was cooled by bringing it into a portion of the furnace surrounded by a water jacket. These manipulations were carried out without opening the furnace, by means of rods which were attached to the trays and operated through a sliding seal in the rubber stopper. The progress of densification of the copper compacts was studied at 1300, 1400, 1500, 1600, 1700, and 1800°F. At each of these temperatures, a specimen was allowed to sinter for each of the following time intervals: M, 1, 2, 4, 8, 16, 32, and 64 hr. The thickness and diameter of each specimen were measured with micrometers before and after sintering, and each was weighed on an analytical balance after sintering. Results The techniques described in the preceding section were found to give satisfactory results. The specimens were not detectibly warped after sintering, and were usually of uniform diameter (that is, truly round) to within 0.001 in., a very few showing a variation in diameter of ±0.002 in. All specimens were found to have the same diameter

Jan 1, 1950