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By T. H. Dunn, P. L. Menaul

This paper discusses the results of an investigation made to develop a method of combatting corrosion of subsurface oil-well equipment caused by brines containing hydrogen sulphide. Carbon monoxide, aldehydes, and certain cyanide compounds were found by laboratory tests to effectively inhibit corrosion of steel by sulphide brines. Experiments were made for one year in eight wells in West Texas fields using formaldehyde as an inhibitor. It was found that the inhibitor treatment successfully prevented the severe corrosion previously experienced in these wells, and effected important net savings in operating costs. Introduction Corrosion of oil-field equipment has long been a problem in areas producing sour crudes. These areas include the major fields of Arkansas, Western Kansas, West Texas and New Mexico. Corrosion in these fields is caused primarily by the chemical action of hydrogen sulphide in the presence of water and by electric currents entering the wells through flow lines. Hydrogen sulphide is noncorrosive to iron or steel in the absence of water but under the usual conditions prevailing in oil wells where more or less water is present, hydrogen sulphide is very corrosive. This type of corrosion occurs over the pH range below 9, which includes all natural oil-field brines. If air is present in addition to hydrogen sulphide and water, corrosion proceeds at an extremely rapid rate. It was reported several years ago that a string of oil-well tubing was literally dissolved within 50 days where an air lift was used on a well producing considerable water and hydrogen sulphide. Air is generally absent in wells producing sour crude. After hydrogen sulphide corrosion starts, it proceeds with increasing severity and its correction becomes progressively more difficult. This characteristic of sulphide corrosion has been attributed to the formation of galvanic couples between the iron and steel equipment on one hand and the products of corrosion on the other.' Severe corrosion of subsurface oil-well equipment leads to a multitude of troubles. In addition to destruction of costly equipment, producing sands often are damaged by flooding with water leaking through corroded casing; bad mechanical conditions may develop in a well due to obstructions caused by corroded equipment lost in the hole, or partly collapsed casing; pumping operations are interfered with, and severe emulsification problems may result from the homogenizing action of corroded balls and seats.% A typical case of severe corrosion caused by hydrogen sulphide was reported in Howard County, Texas, where it was necessary to pull tubing once a week to repair leaks after the tubing had been in use for only one year. On one well in this area a string of tubing was pulled 11 times in 8 months; 11 joints of tubing being replaced because of leaks. In Ector

Jan 1, 1946

By T. H. Dunn, P. L. Menaul

This paper discusses the results of an investigation made to develop a method of combatting corrosion of subsurface oil-well equipment caused by brines containing hydrogen sulphide. Carbon monoxide, aldehydes, and certain cyanide compounds were found by laboratory tests to effectively inhibit corrosion of steel by sulphide brines. Experiments were made for one year in eight wells in West Texas fields using formaldehyde as an inhibitor. It was found that the inhibitor treatment successfully prevented the severe corrosion previously experienced in these wells, and effected important net savings in operating costs. Introduction Corrosion of oil-field equipment has long been a problem in areas producing sour crudes. These areas include the major fields of Arkansas, Western Kansas, West Texas and New Mexico. Corrosion in these fields is caused primarily by the chemical action of hydrogen sulphide in the presence of water and by electric currents entering the wells through flow lines. Hydrogen sulphide is noncorrosive to iron or steel in the absence of water but under the usual conditions prevailing in oil wells where more or less water is present, hydrogen sulphide is very corrosive. This type of corrosion occurs over the pH range below 9, which includes all natural oil-field brines. If air is present in addition to hydrogen sulphide and water, corrosion proceeds at an extremely rapid rate. It was reported several years ago that a string of oil-well tubing was literally dissolved within 50 days where an air lift was used on a well producing considerable water and hydrogen sulphide. Air is generally absent in wells producing sour crude. After hydrogen sulphide corrosion starts, it proceeds with increasing severity and its correction becomes progressively more difficult. This characteristic of sulphide corrosion has been attributed to the formation of galvanic couples between the iron and steel equipment on one hand and the products of corrosion on the other.' Severe corrosion of subsurface oil-well equipment leads to a multitude of troubles. In addition to destruction of costly equipment, producing sands often are damaged by flooding with water leaking through corroded casing; bad mechanical conditions may develop in a well due to obstructions caused by corroded equipment lost in the hole, or partly collapsed casing; pumping operations are interfered with, and severe emulsification problems may result from the homogenizing action of corroded balls and seats.% A typical case of severe corrosion caused by hydrogen sulphide was reported in Howard County, Texas, where it was necessary to pull tubing once a week to repair leaks after the tubing had been in use for only one year. On one well in this area a string of tubing was pulled 11 times in 8 months; 11 joints of tubing being replaced because of leaks. In Ector

Jan 1, 1946

By A. B. Kinzel

A PREVIOUS study1 of the relations of impact strength to inclusions showed that the dynamic strength of steel is lowered by the presence of visible counted inclusions, but that other factors comprised in the term "body" have a marked influence. The previous work was carried out on selected steels from a single source, so that the body factor was purposely minimized, but even under these conditions it was found that inclusion counting or the use of the commercial inclusion rating is not satisfactory. The tensile-impact test, however, was indicated as a satisfactory measure of dynamic strength. It was further suggested that the tensile-impact test should be so standardized as to be suitable for use in specifications, and that the hardness factor should be worked out over a sufficient range to admit ready commercial use of the tensile-impact test. In accordance with these suggestions, and in view of the fact that the steels reported in the previous paper were selected and treated so as to have a minimum variation in body, hardness and structure, further work has been performed on a variety of steels which are not limited by these conditions. The word "body" is used here for want of a better term. It is simply a convenient expression which comprises the effect of the various unknown factors that modify the dynamic strength of the steel. Thus at our present state of knowledge, the writers have chosen to consider hardness, structure and counted inclusion content as factors not comprised in the term "body," and such factors as raw materials, process of melting, fabricating, etc. as comprised in the term "body." Numerous grades of steels made in several ways have been taken from different sources and have been heat-treated to varying hardness by normalizing and by quenching and drawing. The results, therefore, may be considered to be generally applicable to current engineering steels. A certain limitation with respect to the hardness at which steel should be

Jan 1, 1931

By Samuel H. Dolbear

THE value of a mine is basically dependent on its capacity to yield profits. Since the ore must be mined, treated, and sold, some of it in various future years. there is a risk involved as to future costs, selling price, and working conditions. It cannot be expected that the economic condition existing at the time of valuation will continue unchanged for long periods in the future. During the past 20 years, mineral production in the United States has been conducted under a changing economy in many respects more exacting than that applied to other businesses. There have been increased production incentives, technical aid, exploration of privately owned mineral deposits by government at federal expense, and liberal loans for development and equipment, with risk partially assumed by government.. Some of these benefits have been counterbalanced by price ceilings, consumption controls, and stimulation of competition from foreign producers who have been offered the same advantages extended to American operators. For the present, mines will operate under a government policy directed toward reducing federal aid and control. The tenure of this change will depend upon future elections and the status of foreign relations. War and threat of war are now of the most vital significance to the mineral industries. Other factors which influence cost of production, markets, and price of mine output might be classified as Acts of God or Acts of Government. In some countries expropriation and the difficulty of exporting earnings or investment returns are risks that must be considered by foreign capital. Recognizing that this retards American investment in foreign countries, the Mutual Security Agency offers insurance against such expropriation and guarantees the convertibility of capital and profits. Since it is impossible to predict with certainty either cost of production or selling prices of metals for long periods, some assumptions must be made as to profits in the future. The basic assumption must be that the price of the company's product will vary in proportion to changes in operating cost. There is often a lag in this reaction, however, for prices of minerals are generally more sensitive to declines and less sensitive to increases than are costs. This reflects in part the resistance of labor to downward wage revision and a corresponding alertness in realizing its share of price advances. Some labor contracts include automatic adjustments to metal prices. Notwithstanding the complexity of the, problems involved and the difficulty of weighing their effect on value, such risks may be appraised with reasonable accuracy and a rate of earnings adopted that is compatible with the risk. It is, of course, possible to revert to a yardstick of value such as the commodity dollar, which has been advocated from time to time, but while revaluation in 1933 disturbed public confidence, the theoretical gold dollar continues to be the standard of greatest stability. Its gain or loss in purchasing power is reflected ultimately in cost of production and selling price of the mine product. At present 35 dollars are allocated to one ounce of gold. Measurement of Risk In the application of the Hoskold and most other formulae, a yearly dividend rate commensurate with the risk involved is set aside out of annual earnings. If the risk is great, this rate may be 15 to 25 pct of the amount invested. The remainder is placed in a sinking fund invested in safe securities such as high grade bonds or conservative equities, and the interest or dividends from these securities are added to the sinking fund. The sum of these sinking fund payments and the compounded interest at the end of the mine life is taken as the value of the mine. Admittedly the decision as to the size of the risk rate is the most difficult element in valuation and one requiring the most exacting consideration. It is necessary to look years ahead in an effort to determine future costs, market prices, demand, competition which may develop, including that of substitutes, and other influences common to the mine and to the region in which it is situated. Another phase of risk is the enactment of unfavorable legislation, taxes, and what appears to be an alarming spread of nationalization and expropriation. Capital is sometimes borrowed from the government to finance strategic production. Such loans may be collectable only out of production and involve no liability otherwise. Valuation in these cases must recognize the effect of such a reduction in liability. Offsetting some of these risks are the possibilities of mechanization and other cost-reducing discoveries, improvements in mining and treatment methods, new uses for minerals and metals, and normal growth of markets. In this paper, the terms risk rate, dividend rate, and speculative rate are synonymous. Safe rate and redemption rate are also used interchangeably. These alternatives are used here because they are commonly found in the literature on mine valuation. In Michigan, the State Tax Commission has long employed a risk rate of 6 pct in its valuation of iron mines. There the outline of reserves is well established and operating costs and conditions are based on adequate experience. The following comment on rates appears in the report of the Minnesota Interior commission on Iron Ore Taxation submitted to the Minnesota Legislature of 1941.1 Most engineers agree that 7 percent for the specu-lative rate is "an absolute minimum". C. K. Leith in

Jan 1, 1954

By Laurence Delisle, Aaron Finger

THE alloys formed by the addition of nickel to iron by convelltional metallurgical procedures show physical properties that differ widely from those of the individual metals. The effect of alloying on the mechanical properties is most pronounced in alloys containing between 15 and 25 per cent nickel. The tensile strength of an alloy containing, for example, 20 per cent nickel and 80 per cent iron (with 0.06 per cent carbon), in an annealed condition, is above 150,000 lb. per sq. in.? owing to a martensitic type of transformation, as compared with about 50,000 lb. per sq. in. for pure iron in the same condition. The object of this work was to determine whether the same beneficial alloying effect could be obtained in alloys of iron and nickel prepared by powder metallurgy technique. PROCEDURE Bars and pellets for tension and compression tests, respectively, were made. Two groups of specimens were prepared: (I) by cold-pressing the powders and sintering; (2) by cold-pressing the powders, sintering, repressing and resintering. Raw Materials Nickel powder supplied by Metals Disintegrating co., marked MD-151, was used. A typical analysis of this powder was as follows: sulphur, 0.040 per cent; copper, 0.18; iron, 0.23; manganese, 0.002; magnesium, 0.001 5 ; lead, 0.035; tin, 0.025 ; silicon, 0.08; chromium, 0.008. Electrolytic iron powder supplied by Plastic Metals Inc. was used. A representative chemical analysis for impurities other than gases, supplied by the vendor, gave the following results: carbon, 0.005 per cent; manganese, 0.002; silicon, 0.003; phosphorus, 0.001; sulphur, 0.004; nickel, 0.008. The fractions from these powders passing a 3 2 5-mesh sieve were reduced in hydrogen at 600°C. for one hour, to clean the surfaces of the particles. The reduced powders, slightly caked, were ground in a mortar and screened again through a 325- mesh sieve. Mixing The proper proportions of the powders were mixed overnight on rolls, in glass jars fitted with iron-wire baffles to break aggregates of particles that might form. Pressing All specimens were compacted on hydraulic presses. The pellets were compacted in a cylindrical die, ½ in. diameter. The ratio of thickness to the diameter of the pellets was maintained as nearly as possible at 0.9, as specifed for standard short compression pieces. The tensile bars were made by compacting 30 grams of powder. Their shape is shown in Fig. I. The compacting pressures for the pellets and the tensile bars were:

Jan 1, 1946

By J. W. Downey, M. V. Nevitt

The phase boundaries for the 950" isothermal sections in the ternary systems Zr-Co-0 and `Zr-Ni-0 have been determined for the composition range from 50 to 100 at. pct Zr. The two systems show very similar phase relations, having no extensive solid solution phase fields. Each contains a ternary phase. These phases are apparently isostructural, but their structure has not been determined. Some aspects of the phase relations are discussed in terms of the alloying behavior of transition metals. THE work described in this paper is the outgrowth of a recent study of the occurrence of phases having the Ti2Ni-type structure (structure-type E9,) in certain ternary systems involving Ti, Zr, or Hf with another transition metal and O.", In the Zr-CO-0 and Zr-Ni-0 systems no Ti2Ni-type phases were found to occur. However, there are several interesting aspects of the phase relations in the two systems which have significance from the point of view of the alloying behavior of transition metals. The results of this investigation may also have some importance in studies of the oxidation of Zr-Co and Zr-Ni alloys. In both the Zr-Co-0 and Zr-Ni-0 systems only the 950" isothermal sections were investigated and, as a further restriction, the study was limited to the composition range from 50 to 100 at. pct Zr. A tentative Zr-Co binary diagram has been published by Larsen, Williams, and Pehin. In the composition range pertinent to the present work they report a eutectic at 980°C and 75.9 at. pct Zr, the products of which are the terminal solid solution based on /3 Zr and the compound Zr2Co, and a eutectic at 1080" and 64.8 at. pct Zr whose products are Zr,Co and ZrCo. The solid solution based on /3 Zr is shown to decompose eutectoidally at 826°C into a Zr and Zr2Co. The limits of solubility of Co in a and /3 Zr have not been established. The structure of Zr2Co is not identified in the publication just cited. Dwight has reported that ZrCo has the CsC1-type strcture. The Zr-rich portion of the Zr-Ni diagram has been determined by Hayes, Roberson, and Paasche." The phase relations are very similar to those of the ZrCo system. A eutectic reaction whose products are /3 Zr containing 2.9 at. pct Ni and Zr,Ni occurs at 961°c, and a eutectic between Zr,Ni and ZrNi is found at 985". The solid solution based on /3 Zr decomposes eutectoidally at 808°C. The solubility of Ni in a Zr is not known accurately but is believed to be very small. Smith, Kirkpatrick, Bailey, and Williams7 have found that Zr2Ni has a tetragonal structure of the A1,Cu-type and that ZrNi is orthorhombic. Domagala and McPherson8 have published a constitution diagram for the system Zr-ZrO,. At 950" their diagram indicates that the solid solution of 0 in 0 Zr is stable from 0 to 0.5 at. pct while the phase field of 0 in a Zr extends from 6 to 29 at. pct. These solubility limits were adopted in the present study and no binary Zr-0 alloys were made. No previous data on the phase diagrams of the ternary systems are known to exist. EXPERIMENTAL PROCEDURE The experimental details involved in the preparation of alloys in this laboratory by arc melting have been described in several previous papers"3 and they will not be repeated here. Information concerning the purity of the metals used is given in Table I. Oxygen was added in the form of reagent grade ZrO,. All of the cast specimens in both alloy systems were annealed in air-atmosphere tube furnaces at 950 3' for 72 hr and water quenched. The specimens were protected from oxidation by wrapping them in Mo foil and sealing them in quartz tubes that had been evacuated at room temperature to a pressure of 1 x 10B mm of Hg. The phase boundaries were determined by metallography, and identification of the phases was accomplished primarily by X-ray diffraction methods which employed a powder camera having a diameter of 114.6 mm. The diffraction techniques which are in use in this laboratory have been previously described.' An etchant that proved satisfactory for most of the alloys consisted of 5 pct by vol of AgNO

Jan 1, 1962

By T. R. Cass, M. R. Achter

A technique for measuring the creep and rupture strength of nickel specimens bonded by sintered oxide layers has been developed for the investigation of the role of grain-boundary oxide in the oxidation strengthening of nickel during creep at 817 °C. Prom the inverse dependence of the rate of bonding on the thickness of the starting oxide, it is suggested that the rate of diffusion of Ni++ through NiO is the controlling process at the start of sintering. Cornparisons of the creep and rupture strength and of the microstructure of sintered couples with conventionul creep specimens suggest rupture in nickel is prevented by load-bearikzg, ikltergranular layers of oxide. A number of recent investigations have shown that at high temperature and low stress the creep-rupture strength of nickel and nickel-base alloys may be much greater in air than in an inert gas or vacuum.'-7 For example, at 817°C and 2500 psi, nickep failed in vacuum in 48 hr but not in air after 4000 hr, and a Ni-Cr-A1 alloy5 at 1038°C and 3000 psi failed in vacuum in 4 hr but not in air after 731 hr. Fig. 1 is a typical creep curve in air for materials experiencing this pronounced environmental strengthening. A common feature of these curves is the entry into a third stage of accelerating creep, concurrent with the for-

Jan 1, 1962

By Benjamin F. Tillson

The hammer drill rightly receives the credit for having made the one-man drill possible, and so many economies seem possible through the proper application of different types of hammer drills to various mining, quarrying, and excavating operations, that an indication of the 'economies effected by the New Jersey Zinc Co. at its Franklin mines may be of pertinent interest. When this company commenced its trials of hammer drills in 1907, these tools had not been developed to one-fourth the capacity and refinement which they have at present. At that time it was frequently stated that such a small tool, drilling holes of less diameter than the reciprocating rock drill, could not drill enough holes in a shift to permit the placing of sufficient explosive to break a tonnage of ore comparable with that produced by the "rock drills;" that the placing of small holes inclined upward, at angles steeper than 40' above the horizontal, could not be expected to produce results equal to the large flat, wet or dry, holes in the breasted back of an overhand stope, and would only shatter the ground so as to make the back unsafe. In spite of these adverse opinions, the hammer drills first showed their superiority over both heavy and light reciprocating drills in raising and in stoping, and then in drifting and quarry work. As a result, all of the reciprocating drills at the Franklin mines were scrapped three years ago, all of the mining work being accomplished with increased efficiency, as shown in detail in this article. With the advent of the hammer drill in this property, it was considered advisable to make comparative tests of all the tools accessible, and it has since been the policy to investigate the merits of any advance of the drilling art in order to get the maximum amount of work from the tools. The necessity of devising some means of standardizing drill tests, and of measuring the consumption of compressed air as well as the drilling speed, was early realized. The common test was to fill a measured air receiver with compressed air at a certain gauge pressure, run the drill until the pressure had dropped to too low a figure, then compute from the time, drop in pressure, and

Jan 1, 1915

By Adrien Berton

FOR nearly a century, the Corocoro deposit has been renowned among geologists from the fact that it shares with the Lake Superior deposits of the United States the distinction of being the only important copper districts where native copper is worked commercially. The Corocoro district, named after the city of Corocoro, the capital of the Province of Pacajes (Department of La Paz, Bolivia) is situated towards the western edge of the Bolivian high plateau, at an altitude of a little over 13,000 ft. The most interesting part of the district is that immediately surrounding the city of Corocoro, at a distance, by railway, of 65 miles from La Paz and 210 miles to the Chilean port of Arica on the Pacific Coast. The climate of the region is that of the semi-desert, dry and relatively cold, with big differences of temperature between day and night. The rainy season begins in December and ends in March. The cupriferous lodes of Corocoro have not attracted as much interest as the silver mines of Potosi but they have been known for a long time. In the precolonial period the Indians were using the charquis, or natural native copper sheets, to make small brass objects, and the beautiful pale green brochantite of the outcrops as a source of green pigments. During the colonial period, the oxidized ores of the outcrops were worked for copper, which was used by the mint at Potosi for making currency. The native copper ores were neglected because the Spanish miners were at a loss how to concentrate and smelt them. About 1830, work by rudimentary processes, which were improved little by little, was begun on the native copper ores. The total production of native copper in the following hundred years amounted to 100,000 tons. This native copper, which was remarkably pure, was much appreciated on the European markets before the introduction of electrolytic copper. It was useful for making special ornamental brass or bronze and the granular concentrates of native copper, called barrilla, containing 80 to 85 per cent copper were suitable for making copper sulfate by direct oxidation and subsequent leaching with sulfuric acid.

Jan 1, 1936

By J. E. Johnson

OF the many items of information necessary to the successful management of the blast-furnace, few are more important than knowledge of the location and movement of the stock: line:—whether the furnace is full and has been kept so; whether the stock is settling regularly or slipping; and, if slipping, how often it has slipped, at what times, and how far at each time. To obtain these data, a man is sometimes stationed at the top of a pair of mechanically-filled furnaces, sim-ply to watch and gauge them by hand in the old-fashioned way. A more recent practice is the suspension of test-rods from ropes leading over pulleys to the ground-level, where the ropes are mound on small drums with graduated peripheries and provided with crank-handles, whereby the skip-man or some other person can quickly and conveniently gauge the position of the stock-line in the furnace. I believe the credit for this great improvement belongs to Messrs. McClure $ Phillips of Sharon, Pa., who were, as far as I know, the first to apply it, and who have a patent for it. The valuable indications gained by application of the Uehling pyrometer to the down-comer are not to be ignorcd; but the information thus furnished is somewhat indirect, and there is no scale for the translation of " top-temperatures " into " feet down." Moreover, this apparatus, as a whole, is delicate, and the cost of installation and maintenance is high. If the record furnished by the Uehling pyrometer is not in the most desirable form, the test-rods, on the other hand, give no record at all, except through the memory or notes of a man who, to say the least, is not gauging continuously, and who may omit to report an improperly low stock-line, if it be due to a fault of his own.

Jan 1, 1906

By D. A. Dukelow

By using the U. S. Steel oxygen sensor to measure the oxygen content of the steel, deoxidation practices have been developed for silicon-killed fine-grain steel produced by the basic oxygen process. Measurements of oxygen content taken at final turndown are related to the amount of the aluminum addition to the ladle necessary to obtain the desired aluminum analysis for proper grain refinement. In comparison with heats deoxidized by the standard approach, which is based on carbon content, the heats deoxidized according to the oxygen-sensor-based schedule showed a 25 percent decrease in variability from the desired aluminum content. As more heats of a particular grade are made, it is expected that improved quality will result in decreased rejections and better analysis control. Sensor-based deoxidation schedules are also being developed for semikilled, rimmed, and capped steels.

Jan 1, 1972

By Ernest F. Burchard

The Pao deposits of iron ore are in the State of Bolivar, Venezuela, near Upata, about 30 miles south of the Orinoco River and 90 miles east of Ciudad Bolivar. They were discovered 4 or 5 years ago and have not yet been developed to the stage of mining. In March-April, 1929, the writer devoted a week to the examination of these deposits. The maps, drill records and chemical analyses presented herewith were derived from original sources, and the field photographs were made by the writer. The petrographic and metallographic data are from notes by C. S. Ross and M. N. Short, of the U. S. Geological Survey, who have kindly collaborated in these special phases of the study. The Iron Obebodies Topography and Accessibility The deposits are in a region of low mountains representing northern outliers of the Guayanan Highlands. These mountains reach altitudes of 1800 to more than 2000 ft. above sea level, as determined by aneroid barometer. The iron ore is found on mountain crests that reach altitudes of 1915 to 1930 ft., and may be followed down precipitous slopes for 200 • to 300 ft. or more. The greatest vertical range in outcrop is nearly 400 ft., and drilling has indicated that the ore extends to this depth below the surface in one place, at least. The superior hardness of the iron ore accounts for the preservation of the local mountain crests with the intermediate valleys eroded in softer granitic rock. The deposits of iron ore are reached by a private road for automobiles branching northeast from the Ciudad Bolivar-Upata road, a distance of about 12 miles. This road was used in 1928-29 by trucks for transportation of food and camp supplies, gasoline, drilling equipment, etc., but was not suitable for the transportation of iron ore. Between Ciudad Bolivar and the iron-ore area the western two-thirds of the automobile road passes through nearly level, open country known as the savanna, largely used for grazing cattle. About 96 km. (60 miles) east of Ciudad Bolivar at

Jan 1, 1931

By W. L. Chu

It was observed that chromized coatings on low carbon steel could be embrittled by cooling slowly through the 475°C range. A higher chromium coating was more susceptible to embrittlement than a lower chromium coating. Coating structure and composition could be correlated with the chromizing process and prior carbon content of the steel. IT was recently observed that during the fabrication of rectangular tubings made with chromized thin gage 1010 steel, a high percentage of these parts were fractured readily in a brittle manner under the light impact-forming load employed. Ensuing investigation indicated the cause for such brittle failures to be the so-called 475°C embrittlement of the chromized coatings. The experimental work and results are briefly reported. Rectangular tube sections of normalized AISI C1010 steel, which had a cross-section of 0.5x1.5 in. and a wall thickness of 0.030 in., were chromized to yield coatings having several ranges of thickness, varying from 0.0005 to 0.002 in. Essentially, the chromizing process is similar to that described by Samuel and Lockington,' which consists of heating the parts in a sealed container at about 955°C for 4 hr in intimate contact with a chromizing mixture* samples in a hydraulic press, and the other employed a simple beam bending test of the flat sides of the tubing walls. Neither, however, was able to differentiate the relative brittleness of samples known to include both the brittle and tough types, since the impact-brittle samples were found to deform readily in a manner similar to the tough ones. Both the tough and brittle samples were studied by reflection microscopy. Observation showed that the microstructures of the steel cores were similar in content and distribution of inclusions as well as in the ferritic grain size. Results of Filar micrometer measurements showed that coating thicknesses+ of the brittle samples averaged 0.0007 in., whereas those of the tough samples averaged 0.0016 in. The micrographs of Fig. 2 illustrate the structural differences between coatings of both types of samples. By dissolving the steel cores in nitric acid, coatings of both the brittle and tough samples were isolated. Simple bending tests showed that coatings of the brittle samples cracked readily at about 90" bend, whereas those of the tough samples could be bent nearly 180° without cracking. The coatings as well as the steel cores were analyzed for carbon and

Jan 1, 1956

By Laurence Delisle, Arron Finger

The alloys formed by the addition of nickel to iron by conventional metallurgical procedures show physical properties that differ widely from those of the individual metals. The effect of alloying on the mechanical properties is most pronounced in alloys containing between 15 and 25 per cent nickel. The tensile strength of an alloy containing, for example, 20 per cent nickel and 80 per cent iron (with 0.06 per cent carbon), in an annealed condition, is above 150,000 lb. per sq. in.$ owing to a martensitic type of transformation, as compared with about 50,000 lb. per sq. in. for pure iron in the same condition. The object of this work was to determine whether the same beneficial alloying effect coulcl be obtained in alloys of iron and nickel prepared by powder metallurgy technique. Procedure Bars and pellets for tension and compression tests, respectively, were made. Two groups of specimens were prepared: (I) by cold-pressing the powders and sintering; (2) by cold-pressing the powders, sintering, repressing and resintering. Raw Materials Nickel powder supplied by Metals Disintegrating Co., marked MD-151, was used. A typical analysis of this powder was as follows: sulphur, 0.040 per cent; copper, 0.18; iron, 0.23; manganese, 0.002; magnesium, o.oo15; lead, 0.035; tin> 0.025; silicon, 0.08; chromium, 0.008. Electrolytic iron powder supplied by Plastic Metals Inc. was used. A repre-sentative chemical analysis for impurities other than gases, supplied by the vendor, gave the following results: carbon, 0.005 per cent; manganese, 0.002; silicon, 0.003; phosphorus, 0.001; sulphur, 0.004; nickel, 0.008. The fractions from these powders passing a 325-mesh sieve were reduced in hydrogen at 600°C. for one hour, to clean the sur-faces of the particles. The reduced pow-ders, slightly caked, were ground in a mortar and screened again through a 325-mesh sieve. Mixing The proper proportions of the powders were mixed overnight on rolls, in glass jars fitted with iron-wire baffles to break aggregates of particles that might form. Pressing All specimens were compacted on hy-draulic presses. The pellets were com-pacted in a cylindrical die, 34-in. diameter. The ratio of thickness to the diameter of the pellets was maintained as nearly as possible at 0.9, as specified for standard short compression pieces. The tensile bars were made by compacting 30 grams of powder. Their shape is shown in Fig. I. The compacting pressures for the pellets and the tensile bars were:

Jan 1, 1946

By Arron Finger, Laurence Delisle

The alloys formed by the addition of nickel to iron by conventional metallurgical procedures show physical properties that differ widely from those of the individual metals. The effect of alloying on the mechanical properties is most pronounced in alloys containing between 15 and 25 per cent nickel. The tensile strength of an alloy containing, for example, 20 per cent nickel and 80 per cent iron (with 0.06 per cent carbon), in an annealed condition, is above 150,000 lb. per sq. in.$ owing to a martensitic type of transformation, as compared with about 50,000 lb. per sq. in. for pure iron in the same condition. The object of this work was to determine whether the same beneficial alloying effect coulcl be obtained in alloys of iron and nickel prepared by powder metallurgy technique. Procedure Bars and pellets for tension and compression tests, respectively, were made. Two groups of specimens were prepared: (I) by cold-pressing the powders and sintering; (2) by cold-pressing the powders, sintering, repressing and resintering. Raw Materials Nickel powder supplied by Metals Disintegrating Co., marked MD-151, was used. A typical analysis of this powder was as follows: sulphur, 0.040 per cent; copper, 0.18; iron, 0.23; manganese, 0.002; magnesium, o.oo15; lead, 0.035; tin> 0.025; silicon, 0.08; chromium, 0.008. Electrolytic iron powder supplied by Plastic Metals Inc. was used. A repre-sentative chemical analysis for impurities other than gases, supplied by the vendor, gave the following results: carbon, 0.005 per cent; manganese, 0.002; silicon, 0.003; phosphorus, 0.001; sulphur, 0.004; nickel, 0.008. The fractions from these powders passing a 325-mesh sieve were reduced in hydrogen at 600°C. for one hour, to clean the sur-faces of the particles. The reduced pow-ders, slightly caked, were ground in a mortar and screened again through a 325-mesh sieve. Mixing The proper proportions of the powders were mixed overnight on rolls, in glass jars fitted with iron-wire baffles to break aggregates of particles that might form. Pressing All specimens were compacted on hy-draulic presses. The pellets were com-pacted in a cylindrical die, 34-in. diameter. The ratio of thickness to the diameter of the pellets was maintained as nearly as possible at 0.9, as specified for standard short compression pieces. The tensile bars were made by compacting 30 grams of powder. Their shape is shown in Fig. I. The compacting pressures for the pellets and the tensile bars were:

Jan 1, 1946

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

THE complicated nature of the property changes that accompany age-hardening has made it necessary to reconsider and to elaborate the simple dispersion theory.1 It has been apparent for some time that more direct information is needed concerning the atomic mechanism of precipitation from solid solution if the theory of age-hardening is to be developed past a purely qualitative stage.‡ Fortunately, in recent years information has been developed which allows us to trace in detail the lattice changes accompanying the process of precipitation from solid solution. This information relates chiefly to the sequence of the several stages of lattice alteration by which the matrix lattice is transformed to the equilibrium precipitate lattice, and permits reasonable inferences to be drawn concerning the states of internal strain that accompany these stages. This information is most complete for the solid solution of copper in aluminum. The equilibrium precipitate is the ?' phase," CuA12." This forms in plates, parallel to the {100} matrix planes. The atom pattern and atom spacing on the plane in ?' lying parallel to this plane are roughly similar to those opposite it in the matrix.' The formation of ?', however, is preceded by the formation of a transition lattice ?', which again lies parallel to the matrix {100} plane, but in this case the matching of atom pattern and spacing across the matrix-precipitate interface is nearly perfect; thus there is lattice coherency across the interface and the interface is a plane of separation in only a very limited sense.4-8 Particles of ?' may be recognized microscopically and form a well-defined Widmanstätten figure.* The ?' lattice is recognized by the occurrence of diffraction lines on powder photograms or of spots on Laue photograms which may be analyzed in the usual ways to determine the lattice type and the lattice spacings. Very recent research 6.7,1 has shown, however, that streaks occur on the Laue photogram at an earlier point in time during the aging process. These streaks have been attributed to a preferential clustering of copper atoms into small platelike elements of only a few atoms in thickness and a few hundred atoms in diameter, probably of the composition of "CuA12," which may be designated as Guinier-Preston zones or aggregates.1 It is difficult if not impossible to determine the lattice type and lattice spacing in these aggregates. It is possible1 that these aggregates are in fact merely ?' in a high state of dispersion; the inclination to argue this is strong, as we shall see later. Never-

Jan 1, 1941

By J. R. Long, C. E. Armantrout, A. H. Roberson, T. R. Graham

The preparation and fabrication of copper-manganese-zinc alloys and the evaluation of their engineering properties have for some time been an integral part of a research program of the Federal Bureau of Mines. In this project, the use of electrolytic manganese, along with high purity copper and zinc, has permitted the preparation of alloys which contain a minimum of impurities which are capable of producing detectable effects in the properties studied. The initial work on the physical properties of wrought alpha solid solution alloys and a general outline of the alpha solid solution area for alloys containing up to 40 pct manganese have been presented in previous reports. 1,2,3,4,5 The evidence accumulated in these investigations clearly showed that additions of manganese to the copper-zinc alloys improve the strength properties of the brasses without seriously reducing their characteristic ductility and that considerable quantities of manganese could be added to the copper-zinc alloys without exceeding the mutual solubilities of manganese and zinc in copper. In continuation of these studies, additional data have been obtained in a more extensive investigation of the phase relationships of the copper-manganese-zinc ternary system. The present report delineates the solid phase boundaries of the ternary system from the copper-zinc binary to the manganese-zinc binary for alloys containing up to 50 pct zinc. Summary The alloys used in this investigation were conditioned by working schedules designed to homogenize the structures prior to heat treatments required for the equilibrium phase sludy. The treated alloys were examined by metallographic methods including hardness and X ray data for confirmation. The composite data of the investigation are summarily presented in a series of isothermal sections of the ternary system at 1100, 1200, 1300, 1200, and 1500°F. The salient features of the system as outlined by these data are: (1) the continuous alpha solid solution which extends across the diagram to the gamma-manganese phase of the manganese-zinc system at temperatures of 1200°F and higher, (2) the beta phase of the copper-zinc system similarly forms a continuous solid solution with its counterpart the beta field of the manganese-zinc binary, (3) at 1100°F (593°C) these alpha and beta fields are greatly restricted by complications arising from the allotropic transitions of manganese and the decreasing solubility of manganese in the alpha solid solution. The alpha + beta fields intersect the alpha + alpha manganese field to produce the beta + alpha manganese field and two adjacent three phase fields consisting of alpha + beta + alpha manganese and gamma + beta + alpha manganese. Typical microstructures representative of the various phase areas at each temperature are also presented. Review of Previous Work The copper-manganese-zinc alloys have periodically been the subject of numerous investigatioris of both prac-

Jan 1, 1950

By J. Szekely, V. Stanek

Heat and gas flow interactions in nonisothermal packed beds were examined in the paper. A study was made of the response of the system to a step or pulse change in the inlet gas temperature, with a fixed value of the overall pressure drop across the bed. Under these conditions the heat flow and fluid flow transients are coupled because the convective heat transfer rate is alfected by the mass flow rate of the gas which, in turn, for a fixed pressure drop will depend on the temperature profile in the system. The Problem was stated in terms of differential equations, which were integrated numerically. The parameters used in the computation were so chosen to reflect the operation of the stack region of blast furnaces and sinterbeds. The computed results showed that the pressure drop-flou1 relationships and the rate of progress of the temperature fronts (waves) were strongly interrelated and were also markedly affected by variations in particle size and in void fraction. MANY metallurgical processes involve the contact of solid particles with a gas stream in a packed bed arrangement under nonisothermal conditions. Examples are shaft furnaces, regenerators, pebble heaters, and the sinter process. Although the heat and mass transfer aspects of packed bed processing have been extensively studied, the associated flow phenomena and in particular the effects of nonisothermality on the flow, have received little attention to date. :In fact, most of the previous workers considered the flow rate of the carrier gas time invariant and independent of the heat or mass transfer processSzekely and carr2 have shown that the pressure drop-flow relationships in nonisothermal packed beds may be strongly affected by the temperature profile within the system. These authors have devised a method for relating the pressure drop to flow for a given temperature profile. thus providing an extension of the Ergun equation to steady nonisothermal systems. Finally, in a recent paper willmot3 examined the response of regenerators to externally imposed changes in the gas flow rate. Both these investigations were somewhat specialized since, in general, neither the temperature distribution nor the gas flow rate may be regarded as truly independent variables, thus the heat transfer and the fluid flow problems have to be solved simultaneously. The work reported here is divided into two parts: in Part 1 the general formulation is given and a detailed discussion is presented of fixed bed systems. Part is devoted to systems in which a gas and particulate solids are contacted in a counter flow arrangement. FORMULATION Consider a nonisothermal fixed packed bed, extending from through which a gas is flowing. The problem is to develop a relationship between pressure drop and gas flow (with the gas flow being the dependent variable) and to evaluate the rate at which a change in the gas temperature, imposed at the inlet, travels through the system. Let us consider an infinitesimal section of the bed and establish differential heat, mass, and mechanical energy balances over this region. In addition, relationships are needed describing the temperature dependence of gas density (equation of state) and the temperature dependence of viscosity. These may be written as: where c, and are constants. It is noted that in this formulation we neglected any temperature gradients within the solid particles, thus assuming these to be either sufficiently small or of sufficiently high thermal conductivity to meet this condition. The justification and consequences of this assumption will be mentioned in the discussion.

Jan 1, 1970

By L. S. Darken, H. A. Wriedt

THE constitution diagram of the iron-copper system derived by Daniloff' exhibits, at the iron-rich end, phase fields similar to those of the iron-carbon diagram. At 1484° 1094°, and 850°C there are, respectively, a 6-y-L peritectic, a y-E-Lperitectic, and a a-y-E eutectoid. The phase designated E is copper-rich, containing 4 pct Fe or less according to the temperature. The composition of copper-saturated ferrite (a-solid solution) has been determined previously only twice as a function of temperature. By electrical conductivity measurements, Buchholtz and Köster2 found 3.4 pct Cu in ferrite at a eutectoid temperature of 810°C. They represented the composition of saturated ferrite by the equation, log (%Cu) = 4.32-4125 (1/T) Gregg and Daniloff3 reported that Köster later modified his opinion, raising the indicated eutectoid temperature to 833 °C and the copper content of eutectoid ferrite to 3.7 pct. The literature contains several indications4-7 that the work of Köster and his co-workers is not reliable. Norton,8 using an X-ray method, found that 1.4 pct Cu dissolved in ferrite at the approximate eutectoid temperature of 850°C and that the solubility decreased to about 0.3 pct at 700°C. Below 700°C his experimental data show almost no change in solubility. These findings, although inconsistent with the work of Ruer and Goerens4 and of Smith and Palmer,7 have been used generally since their publication. In investigations involving the observation of arrests in temperature during continuous heating or cooling the precise location of the eutectoid temperature has been obscured by a large hysteresis. The more reliable work 579 where the results are not effected by this hysteresis indicates a eutectoid temperature between 840° and 850°C. The foregoing discrepancies, along with a few observations in this Laboratory relating to the precipitation of copper from ferrite, prompted us to rein-vestigate the lower temperature portion of the Fe-Cu system. In this investigation the solubility of copper in ferrite was obtained by the chemical analysis of high-purity iron equilibrated with copper-silver alloys. This method eliminated the necessity for retaining by a quench the physical state of the specimen existing at the equilibration temperature. EXPERIMENTAL The reaction of the iron with the copper alloy was

Jan 1, 1961

By Merrill Horine

IT has been stated and accepted for many years that the automotive industry was the instigator, the principal sponsor for and the largest user of alloy steel and nonferrous alloys. The only universally recognized standard specifications and heat-treatments for these materials are those adopted by the Society of Automotive Engineers. It is this same auto-motive industry that has been the chief inspiration for and consumer of modern production machine tools. The production curve of steel ingots is more sensitive to fluctuations in automotive production than any other influence or group of influences. In every other important steel-con-suming industry, automotive materials and automotive processes are the outstanding features of modern progress. In this connection I need only mention the prefabrication of buildings, following the automotive system of straight-line, interchangeable mass production; the motorization of ships and railroads, employing automotive types of prime movers; the production of pressed-steel stoves, plumbing and furniture by methods originated in the automobile-body industry and the extensive use of rubber for the cushioning of all manner of machinery as pioneered by the automotive and tire industries. Dr. Jeffries has brought out this point in his address (p. 21), assuring us that the transportation industry is the largest user of these materials. In the transportation industry, or as we might more accurately express it, the transportation group of industries, the. automotive industry pre-dominates as a user of light alloys. One out of every four tons of aluminum produced is consumed by the automotive industry. Similarly, the automotive industry ranks first in the consumption of the following metallurgical materials: steel, 24.04 per cent; malleable iron, .57; alloy steels, 72.2; nickel, 30; lead, 39 per cent.

Jan 1, 1936