Search Documents

By John M. Bostwick

Bitumen is a general term for a group of materials composed of mixtures of hydrocarbons that are fusible and soluble in carbon disulfide. Included in the group are petroleum, asphalts, asphaltites, and mineral waxes. Asphalt is a dark-colored, cementitious solid or semisolid, which generally softens on heating and resumes a more viscous or solid state when cooled (personal communication). It is found in native form in fissures and pore spaces in rocks and as lakes. It is also obtained from the residues produced in petroleum refining. Asphaltites are black, naturally occurring solid bitumens. They are generally shiny and break with a conchoidal fracture. Common asphaltites are gilsonite (uintahite), grahamite, and glance pitch. Mineral waxes are solid or semisolid, relatively nonvolatile bitumens of various colors, having an unctuous feel and waxy luster. Of the native waxes, ozokerite is the best known. Montan wax is also classed as a natural wax, although it never occurs in the pure state and must be extracted from lignite or cannel coal (Ladoo, 1920). Mineral waxes may also be obtained by pyroprocessing of petroleum, lignite, and peat. Pyrobitumens are dark-colored, solid hydro- carbons that are infusible and relatively insoluble in carbon disulfide. They are so-called because they will yield liquid and gaseous hydrocarbons only when heated. Asphaltic pyrobitumens are defined as "substantially free of oxygenated bodies" and include wurtzilite (elaterite), albertite, and impsonite (Thrush, 1968). Nonasphaltic pyrobitumens contain oxygenated bodies; examples are coal and peat. The nonasphaltic type will not be discussed further. Petroleum Asphalts Asphalts refined from crude petroleum have almost completely replaced the native types. Refineries can produce asphalts in every desirable grade more economically and in greater quantity than the native types and with a variety of properties that meet the requirements of the various manufacturers using them. For all practical purposes, it is estimated that more than 95% of the asphalts consumed in the United States are refined from crude petroleum (private communication).

Jan 1, 1975

By K. Matsuda, H. Tanaka, M. Mamiya, H. Majima

Copper cementation was studied from both thermodynamic and kinetic aspects. The temperature effect of copper cementation, which has been recognized as an anomalous result, and the rate enhancement phenomenon observed after the initial linear step are, in particular, focused in this work. The main results obtained are as follows; 1) Free energy changes of copper cementation reactions, calculated by the use of the "Correspondence Principle" of Criss and Cobble are rather insensitive to temperature. 2) A Flow-cell assembly consisting of a special cupric ion electrode, a calomel electrode and a potentiometer is particularly useful for the continuous measurements of copper cementation rate. 3) Two first-order reaction rate constants for the CU2+- Fe system were successfully determined by the use of the flow-cell assembly. 4) Activation energies determined for the initial rate and the 9 maximum rate of CU2+ - Fe system are both 4.6 kcal/mole. This fact suggests that the mechanisms of the initial reaction and the final reaction are essentially the same and both reactions are rate controlled by the diffusion in a boundary layer. The difference in the rate constants of them may fie explained by the effect of the nature of surface deposits. 5) Qualitative explanation of the rate enhancement phenomenon from the initial rate was successfully made by applying Bockris "Penetration Model."

Jan 1, 1976

By Albert Sauveur

The instrument about to be described meets so perfectly the special needs of the metal microscopist that there eeeme to be little doubt but its merits must be readily appreciated by those who have had any experience in the microscopical examination of metals. The Microscope-Stand.—The microscope-stand proper, Fig. 1, consists of a microscope-tube, provided with both coarse and fine adjustments of the best construction, and with a draw-tube, rigidly mounted on a bar supported at both ends on substantial and firm cast-iron legs. The height between the table and the under side of the supporting bar is 5 in. and the distance between the supporting legs 12 inches. This arrangement affords free space below the objective for the examination of large epecimens of metals, such as full rail-sections, without detracting in the least from the value of the

Jan 1, 1912

By Harry M. Mikami

Chromite is the only ore mineral of metallic chromium and chromium compounds and chemicals. Because of this fact, chromite and chrome ore are used synonymously in trade literature. In commercial market quotations, chrome ore is the term commonly used. Chromite per se, because of properties imparted by its chromium content, is used in refractories and in special purpose molding sands for metal casting. There are many other minerals containing some, generally minor, amounts of chromium, but none are commercial sources of the element (Thayer, 1956). Chromium and chromite have many diverse uses that, directly and indirectly, critically affect vast segments of our modern industrial system. Most important are probably the metallurgical applications wherein chromium is a component of heat-, abrasion-, corrosion-and oxidation-resistant and high-strength alloys of many types. Stainless steels are the largest volume category of chrome-bearing alloys. Chromium chemicals are used in leather tanning, in pigments, dyes and mordants, printing, chemical process industries, photography, pharmaceuticals, metal plating, pure chromium metal production, and for many other purposes. Chromite is a necessary constituent in basic refractories indispensable for the production of steel, copper, cement, and glass. Under present conditions, the US and North America, with the possible exception of Cuba, have no commercial ore reserves. There are chromite deposits, as will be described, but they would be used only under highly abnormal conditions if all outside sources were cut off for an extended period. All chromite used in the US is imported from the eastern hemisphere in which are contained the principal world reserves. The main suppliers in 1980 were the Republic of South Africa (43%), the USSR (21% ), the Philippines (12%), Albania (11 %), Turkey (8%), and others (5%). The strategic nature of chromite is obvious. End Uses-Grades and Specifications As noted before, the three principal uses for chromite are metallurgical, refractories, and chemical with a fourth minor use as foundry molding sand. For metallurgical applications chrome ore is first reduced in electric carbon arc furnaces to various types of ferrochromium alloys. There are high, medium, and low carbon ferrochromiums with carbon ranging from 0.01 up to 10%. Chromium itself ranges from 50 to 73 %. Ferrosilicon chromium and ferrochromium-silicon grades have chromium from 33 to 67% and silicon from 3 to about 48%. Since iron is reduced with chromium, the Cr:Fe ratio of the ore will determine the ultimate grade of the ferrochromium whereas carbon and silicon can be controlled during processing. MgO, A12O3, CaO, and excess SiO2, are removed in slag. A small amount of pure chromium metal is prepared by alumino-thermic and electrolytic processes from essentially iron-free chrome components that have been made via the chemical route. The higher grades of ferrochromium with chromium in the 66 to 73% range can only be made from ores with not only high chromium content, but low iron, i.e., high Cr:Fe ratio. These ores, conventionally termed metallurgical grade, have Cr2O3 contents of 45 to 56% with Cr: Fe ratios of 2.5 to 4.3. A standard composition is generally 48% Cr2O3 and 3:1 Cr:Fe ratio. Very high grade ores are often blended with lower grades even with the high iron chemical grade. For some ferrochromiums, additions of high alumina refractory grade are used as slag conditioners to facilitate smelting while still contributing chromium values. A lower grade ferrochromium, the high carbon charge chrome, has become the predominant grade in use today for making chromium-bearing steel alloys. This

Jan 1, 1983

By Persifor Frazer

It has been the aim of the writer, by measuring his base line on the territory of theoretical chemistry, to attempt to fix by triangula tion certain points within the domain of mineralogy. As the barest first experiment in this direction, a few of the hydrated oxides of iron have been selected, their theoretical construe tion reduced to percentage of the constituents into which the ordinary analytical methods would resolve them, and the results compared with actual analyses compiled from the most reliable sources; the accidental errors being as much as possible eliminated. This method seems to be a simple one and one easily pursued, but, as will shortly appear, it is beset with grave difficulties, all of which the writer does not pretend to have satisfactorily surmounted. In the first place arises the important question, what are we to understand by the hydrated oxides of iron ? In all books of chemistry and lexicons of minerals, the proposition, long ago taught by the earlier chemists, that water might exist in two forms of combination, viz., as water of crystallization or as water of constitution, is tacitly assumed. There is nothing in the principles of the new chemistry which is opposed to this; for (to carry the mind's eye into the process of con struction of the least units into which a definite chemical compound is capable of being divided without losing its characteristic proper ties), however unlikely it may seem, it is, nevertheless, possible that a given molecule of iron may, under certain conditions of heat, pressure, etc., attract to itself as many molecules of the water in which it is natant as: from the relative size, shape, attractive force, etc. of either, it is capable of taking up, and this complex system of associated molecules might oscillate as a physical unit so long as the conditions on which its existence was dependent remained unchanged. Moreover, it is highly probable that the first effect upon such a mole cule produced by physical or chemical forces would be to separate it into two or more simple ones of different kinds, while a further ap plication of these forces might rend asunder the bonds of the simpler compounds themselves.

Jan 1, 1879

By Persifor Frazer

(Read at the Amenia Meeting, October, 1877.) IT has been the aim of the writer, by measuring his base line on the territory of theoretical chemistry, to attempt to fix by triangulation certain points within the domain of mineralogy. As the barest first experiment in this direction, a few of the hydrated oxides of iron have been selected, their theoretical construction reduced to percentage of the constituents into which the ordinary analytical methods would resolve them, and the results compared with actual analyses compiled from the most reliable sources; the accidental errors being as much as possible eliminated. This method seems to be a simple one and one easily pursued, but, as will shortly appear, it is beset with grave difficulties, all of which the writer does not pretend to have satisfactorily surmounted. In the first place arises the important question, what are we to understand by the hydrated oxides of iron ? In all books of chemistry and lexicons of minerals, the proposition, long ago taught by the earlier chemists, that water might exist in two forms of combination, viz., as water of crystallization or as water of constitution, is tacitly assumed. There is nothing in the principles of the new chemistry which is opposed to this ; for (to carry the mind's eye into .the process of construction of the least units into which a definite chemical compound is capable of being divided without losing its characteristic properties), however unlikely it may seem, it is, nevertheless, possible that a given molecule of iron may, under certain conditions of heat, pressure, etc., attract to itself as many molecules of the water in which it is natant as from the relative size, shape, attractive force, etc. of either, it is capable of taking up, and this complex system of associated molecules might oscillate as a physical unit so long as the conditions on which its existence was dependent remained unchanged. Moreover, it is highly probable that the first effect upon such a molecule produced by physical or chemical forces would be to separate it into two or more simple ones of different kinds, while a further application of these forces might rend asunder the bonds of the simpler compounds themselves.

Jan 1, 1878

By Charles Mabery

So FAR as the elementary composition of petroleum is -known, it may be briefly stated. Petroleum consists principally of a few series of hydrocarbons, with admixtures of sulfur, nitrogen, and oxygen derivatives in comparatively minute proportions, which may be regarded as impurities to be removed in the preparation Of commercial products. But as each series is represented by many homologs, in the aggregate, crude petroleum is an extremely complex mixture of hydrocarbons and their derivatives. In part, these hydrocarbons individually conform in structure to the system of synthetic hydrocarbons whose structure is well defined and -represented by the typical series CnH2n+2, CnH2n, the series CnH2n-2, CnH2n-4, the members of which have not been sufficiently studied to establish their structure, and the series CnH2n-6 composed of the aromatic group, benzene and its homologs. Hydrocarbons of greater density contained in the portions of petroleum that cannot be distilled without decomposition doubtless have less hydrogen than is represented by these formulas. Since to every hydrocarbon there is a definite temperature, even in vacuum, at which its constituent carbon and hydrogen atoms fall apart, and since for the heavier bodies this temperature is not much above 360° C. in vacuum, it is evident that some other method than distillation must be devised for their separation if anything further is to be learned concerning their individual constitution. CLASSIFICATION OF PETROLEUMS There is such a wide variation in the composition of petroleum from different fields, it would seem possible to make a classification on this basis were it not that no single variety is entirely free from hydrocarbons contained in others. Such a classification has been suggested of the exceptionally pure Pennsylvania petroleum, the sulfur oil from Trenton

Jan 2, 1920

By E. J. Haug, M. M. Fine

FOR several years work has been carried on by the U.S. Bureau of Mines at Rolla, Mo., to develop improved methods of concentrating the oxidized ores of lead and zinc. Various samples have been investigated, and results on some have been published 1,2 lished.l, 2 Details of the progress to date are given in a mineral dressing study now being conducted for an extensive oxidized lead-bearing tract in southeast Missouri, property of St. Joseph Lead Co. These oxidized ores present problems typical of many encountered in modern mineral dressing research in that recovery of very fine particles is of

Jan 1, 1956

By R. P. Laforce, ZJ. R. Low, A. M. Turkalo, D. F. Stein

The interaction of the crlloying eletnenls, nickel and chromium, with the impurity elements, antimony, pIzosphorus, tin, and arsenic, to producse reversible temper brittleness in a series of high-purity steels containing 0.40 wt pct C has been investigated. The alloyed steels contained approximately 3.5 pcl Ni, 1.7 pct Cr, and 0.05 to 0.08 pct of the particular irnpurity to be investigated. Susceptibility to teirlper embrittlement was measured by comparing the notched-bar transition temperature of each steel after quenching from the final temper and after very slow cooling (step cooling;) following the final temper. A plain carbon steel without alloying elements, bu/ ud/h 0.08 pel Sh, does not embrittle when step-cooled through the emzbrittling range of temperatures. The same embrittling treatment, applied to a steel with about the same antinzony content but with nickel and chvonziunz added, causes a 700°C increase in transition temperature. If chromium or nickel is the only alloying element, the increase in transition temperature is only 50%, again with antimony present. A carbon-free iron containing nickel, chromium, and antimony shou~s a 200°C shift in transition temperature for the same thermal treatment. Specific alloy-impurily interactions are also observed for the other impurity elements, phosphorus, tin, and arsenic. Additional investigations involving electron microscopy, trzicrohard-ness tests of vain boundaries, minor additions of zirconiutn and the rare earth and noble metals, nzainly with negative results, are also described. HE particular type of embrittlement investigated is that which is encountered in alloy steels tempered in the temperature range from about 350" to 525'C or slowly cooled through this range of temperatures when tempered above this range. This type of embrittlement is sometimes called reversible temper brittleness to distinguish it from the embrittlement indicated by a minimum in the room-temperature V -notch Charpy energy vs tempering-temperature curve encountered in the range 28 0" to 350°C. Temper brittle-ness seriously restricts the use of many alloy steels since it precludes tempering or use in the embrittling range of temperatures and may significantly raise the ductile-brittle transition temperature of heavy-section forgings and castings tempered above the embrittling range, since such sections cannot be sufficiently rapidly cooled after tempering to avoid embrittlement. The very voluminous literature of temper brittle-ness up to about 1960 has been reviewed by woodfine' and LOW.' Of particular significance to the present investigation was the demonstration by Balajiva, Cook, and worn3 that high-purity Ni-Cr steel does not exhibit temper brittleness and the subsequent detailed and systematic study by Steven and Balajiva~ of the effect of impurity additions on the susceptibility to embrittlement of Ni-Cr steels. Steven and Balajiva showed that, of the impurities which may be found in commercial steels, Sb, As, P, Sn, Mn, and Si could all produce temper brittleness in a high-purity Ni-Cr steel. The principal purpose of the present investigation was to study the effects of particular alloy-impurity combinations on susceptibility to temper embrittlement. The steels used were high-purity 0.30 to 0.40 wt pct C steels containing 3.5 wt pct Ni and 1.7 wt pct Cr, separately or in combination. The susceptibility of these steels was then determined when approximately 500 ppm by weight of antimony, arsenic, phosphorus, or tin were added as an impurity. The melting, casting, and forging practices used in the preparation of the materials investigated are described in Appendix A. Table A-I in this appendix shows the analysis of all steels to be discussed. The steels were produced as 20- or 2-lb heats. The smaller heats were used after it had been demonstrated (see Appendix B) that a small, round, notched test specimen could be used to measure the shift in the ductile-brittle transition temperature caused by temper brittleness with about the same result as that obtained by Charpy testing. HEAT TREATMENT Unless otherwise noted, all steels were tested for embrittlement in the tempered martensitic condition. A typical heat treatment for a 0.40 C, 3.5 Ni, 1.7 Cr steel was: 1 hr at 870"C, in argon, quench into oil at 100"C, quench into liquid nitrogen, temper 1 hr at 625"C, and water-quench. The warm oil quench was used where quench-cracking was encountered; otherwise the initial quench was into room-temperature oil or water. For other compositions austenitizing temperatures were 50°C above Acs with the remainder of the thermal cycle the same. Steels in this condition, with no further heat treatment, are designated as non-embrittled. The above quenching and tempering cycle for the 0.40 pct C steels resulted in as-quenched hardnesses of 48 to 53 RC and as-tempered hardnesses of 24 to 31 Rc except in the case of the plain nickel or plain carbon steels. In these, the as-tempered hardness was as low as 80 to 90 Rg. No attempt was made to adjust the tempering temperature to obtain the same hardness in ali steels since it was felt that a uniform thermal cycle was more important than exactly equivalent hardness values. Pro- the standard quench and temper described above, the standard embrittling treatment was "step-cooling". For this the thermal cycle was: 593"C, 1 hr; furnace-cool to 538"C, hold 15 hr; cool to 524"C, hold 24 hr; cool to 496"C, hold 48 hr; cool to 468'C, hold 72

Jan 1, 1969

By N. A. Gokcen, John Chipman

SILICON is the most commonly used deoxidizer and an important alloying element in steelmak-ing; hence a detailed study of this element in liquid iron containing oxygen is of considerable interest. The equilibrium between silicon and oxygen in liquid iron has been studied by a number of investigators but generally with inconclusive or incomplete results. The variation of the activity coefficients of silicon and oxygen with composition is entirely unknown. Published investigations deal with the reaction of dissolved oxygen with silicon in liquid iron and the results are expressed in terms of a deoxidation product. For consistency and convenience in comparison of the published information, the deoxidation product as referred to the following reaction is expressed in terms of the percentage by weight of silicon and oxygen in the melt in equilibrium with solid silica: SiO (s) = Si + 2 O; K'l = [% Si] [% 012 [I] Theoretical attempts to calculate the deoxidation constant for silicon in liquid iron from the free energies of various reactions yielded results which were invariably lower than the experimental values. Thus, the deoxidation "constants" calculated by McCance,1,2 Feild,3 Schenck, and Chipman were of the order of 10, which is below the experimental values by a factor of more than 10. Experiments of Herty and coworkers" in the laboratory and steel plant resulted in an average deoxidation constant of 0.82x10 ' at about 1600°C. The technique employed in their investigation was crude and the reported temperature was quite uncertain. The concentration of silicon was obtained by subtracting silicon in the inclusions from the total. Since at least some of the inclusions resulting from chilling must represent a fraction of the silicon in solution at high temperatures, such a subtraction is not justifiable. Results of Schenck4 for K'1 from acid open-hearth plant data yielded a value of 2.8x10-5, which was later revised as 1.24x10 at 1600°C. Similarly Schenck and Bruggemann7 obtained 1.76x10-5 at 1600OC. The discrepancies and errors involved in the acid open-hearth plant data as compared with the results of more reliable laboratory techniques were attributed by these authors to the lack of equilibrium and the impurities in liquid metal and slag, and are sufficiently discussed elsewhere." Korber and Oelsen" investigated the relation between dissolved oxygen and silicon in liquid iron covered with silica-saturated slags containing varying concentrations of MnO and FeO. The deoxidation products obtained by their method scatter considerably, and their chosen average values of 1.34x10, 3.6x10-5, and 10.6x10-5 1550°, 1600°, and 1650°C, respectively, represent the best experimental results which were available until quite recently. Darken's10 plant data from a steel bath agree approximately with their data at 1575° to 1625°C. Zapffe and Sims" investigated the reaction of H2O and H2 with liquid iron containing less than 1 pct Si and obtained deoxidation products varying by a factor of more than 20. Inadequate gas-metal contact and lack of stirring in the metal bath should require a longer period of time than the 1 to 5.5 hr which they allowed for the attainment of equilibrium. Furthermore, their oxygen analyses were incomplete and irregular and confined to a few unsatisfactory preliminary samples. Their results did indeed indicate that the activity coefficient of oxygen is decreased by the presence of silicon, although they made no such simple statement. They chose to attempt to account for their anomalous data by the unlikely hypothesis that SiO is dissolved in the melt. Hilty and Crafts" investigated the reaction of liquid iron with acid slags under an atmosphere of argon, making careful determinations of silicon and oxygen contents at several temperatures. Despite erroneous interpretation of the data at very low silicon concentrations, their data represent the most dependable information on this equilibrium that has been published. In the range 0.1 to 1.0 pct Si, their data yield the following values for the deoxidation product: 1.6x10-5, 3.0x10- ', and 5.3x10 at 1550°, 1600°, and 1650°C, respectively. The purpose of the work described herein was to study the equilibrium represented by eq 1 as well as the following reactions, all in the presence of solid silica: SiO2 (s) + 2H2 (g) = Si + 2H2O (g);

Jan 1, 1953

By N. P. Goss

ASTERISM appearing in X-ray Laue dia-grams is an extremely sensitive index of changes in the internal structures of indi-vidual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.1-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not con-clusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made be-tween mosaic and distorted grain struc-tures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example,7 has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-14 to 10-15 c.c., or 10 5 cm. in size.

Jan 1, 1940

By N. F. Schulz, H. A. Lex, J. D. Zetterstrom

A green ball of iron ore faces many perils from the time it is formed until it finally emerges from the pelletizing furnace as a hardened pellet. For instance, if the rate of heat transfer into a ball is sufficient to produce vapor from either the free or combined water more rapidly than it can escape at a tolerable pressure, the ball may split, spall, or even explode, a failure commonly known as decrepitation. To avoid such failures, one must either limit the rate of heat transfer during the drying and preheating stages, at the expense of production rates, or improve the decrepitation resistance of the green balls. The latter remedy may often be accomplished through changes in ore preparation, balling procedures, or the judicious use of binders or other additives. INTRODUCTION Pelletization has become established as an especially desirable method for the agglomeration of fine taconite concentrates and it promises to be equally satisfactory for improving the physical structures of certain natural ores. A high-quality pelletized iron ore consists of uniformly sized spheres, usually about 1/2-in. diam, which are strong enough to resist abrasion and breakage during handling and which reduce well without disintegration in the blast furnace. The unfired agglomerates, "green balls", are subject to several destructive effects that must be avoided or minimized if a high-quality product is to be obtained by pelletization. Among these are abrasion and impact deformation or breakage during handling of the wet green balls, deformation and breakage by compressive forces in the bed of ore in the pel-letizing furnace, decrepitation during drying and preheating, wind erosion, and radial cracking at firing temperatures. Moisture condensation from the warm saturated gases downstream from the drying zone on wet, cool balls may cause bed collapse if it becomes excessive. Decrepitation is defined as the sudden disintegration of green balls, usually with an audible pop, that occurs when they are heated too rapidly during the drying or preheating stages of the pelletization process. The extent of ball disintegration may vary from merely splitting off a small fragment to almost total disintegration into the original ore particles making up the ball. Such ball destruction results in a decreased yield of pellets, and the fragments, which also tend to interfere by obstructing the gas flow through the bed, must eventually be screened from the fired product and recycled. The closely related type of ball failure that sometimes occurs during the high temperature firing stage, resulting in radial cracks without fragmentation, was not considered to be decrepitation for the purpose of this investigation. Failure by decrepitation is not usually a serious problem in the pelletization of taconite concentrates. The problem is significant, however, in the pelletization of some natural ores, especially those containing hydrous iron oxides. In some instances, economicd production rates cannot be maintained if the drying and preheating rates are slowed down enough to avoid decrepitation. OBJECTIVES This investigation was undertaken to: (1) Develop a practical laboratory means for quantitatively measuring the tendency for green balls to decrepitate in iron ore pelletizing furnaces, and (2) Investigate the causes and cures of ball decrepitation. MATERIALS Two iron ores were used in the work reported here: a taconite concentrate at 90% minus 325 mesh, containing 65.0% Fe, 8.4% SiO2, and no loss-on-ignition; and a crude oxidized ore at 54% minus 325 mesh, containing 59.1% Fe, 3.6% SiO2, 1.1% A12O3, and 9.5% loss-on-ignition. For a special test of effect of particle size distribution on decrepitation, two other

Jan 1, 1967

By John T. Eash

During the course of the war the supply of tin in this country has steadily decreased and a continued effort has been made since the beginning of the emergency to use alloys that are either tin free or contain appreciably lower quantities of it. Even with the use of emergency materials, the tin supply has become particularly acute, and it is estimated that after recovery of the far eastern mines probably one to two years will be required before our normal annual supply is attained. One of the major tin-consuming fields is the bronze industry. Recommendations were made several years ago by the War Production Board toward the use of bronzes of lower tin content and manganese bronze and yellow brass for the customarily used tin-bronze alloys. The substitution of 88-5-5-2 copper-nickel-tin-zinc for composition G received considerable attention before the war, and consequently this alloy and modifications of it have been adopted for some current structural and pressure castings requiring high mechanical properties. Another of the commonly used bronzes is the 10 per cent tin 10 per cent lead copper alloy for heavy-duty bearings. It has been known for some time that about 2.5 per cent nickel could be substituted for an equal amount of tin with retention of equivalent casting and tensile properties; however, it was desirable that a still greater conservation of tin be made. Consequently the present paper deals with the development of an alloy of low tin content that could be used for bearings. Selection or Composition While the final criterion of the suitability of an alloy for a bearing must of course be determined by practical applications where all the ramifications of service conditions are encountered, certain short cuts in the initial selection of compositions are necessary to avoid an extensive and time-consuming investigation. The present program has been to match certain metallurgical properties of the 80-10-10 bronze that have been shown by previous investigations to be related to good bearing qualities. Such properties as microstruc-ture, hardness, compressive yield strength, ductility, and castability have been considered, and certain simple wear tests have been made. Of the readily assessed characteristics desired in a good bearing alloy, one can be certain that a uniform distribution of lead is required in a leaded bronze. It has generally been found that segregation of lead is one of the chief difficulties with this type of material. Tin has a powerful effect on lead distribution, and with 10 per cent present produces a random distribution of chunky particles, such as are shown in Fig' 1. I' In the tin bronze contains the hard alpha + delta

Jan 1, 1946

By John T. Eash

During the course of the war the supply of tin in this country has steadily decreased and a continued effort has been made since the beginning of the emergency to use alloys that are either tin free or contain appreciably lower quantities of it. Even with the use of emergency materials, the tin supply has become particularly acute, and it is estimated that after recovery of the far eastern mines probably one to two years will be required before our normal annual supply is attained. One of the major tin-consuming fields is the bronze industry. Recommendations were made several years ago by the War Production Board toward the use of bronzes of lower tin content and manganese bronze and yellow brass for the customarily used tin-bronze alloys. The substitution of 88-5-5-2 copper-nickel-tin-zinc for composition G received considerable attention before the war, and consequently this alloy and modifications of it have been adopted for some current structural and pressure castings requiring high mechanical properties. Another of the commonly used bronzes is the 10 per cent tin 10 per cent lead copper alloy for heavy-duty bearings. It has been known for some time that about 2.5 per cent nickel could be substituted for an equal amount of tin with retention of equivalent casting and tensile properties; however, it was desirable that a still greater conservation of tin be made. Consequently the present paper deals with the development of an alloy of low tin content that could be used for bearings. Selection or Composition While the final criterion of the suitability of an alloy for a bearing must of course be determined by practical applications where all the ramifications of service conditions are encountered, certain short cuts in the initial selection of compositions are necessary to avoid an extensive and time-consuming investigation. The present program has been to match certain metallurgical properties of the 80-10-10 bronze that have been shown by previous investigations to be related to good bearing qualities. Such properties as microstruc-ture, hardness, compressive yield strength, ductility, and castability have been considered, and certain simple wear tests have been made. Of the readily assessed characteristics desired in a good bearing alloy, one can be certain that a uniform distribution of lead is required in a leaded bronze. It has generally been found that segregation of lead is one of the chief difficulties with this type of material. Tin has a powerful effect on lead distribution, and with 10 per cent present produces a random distribution of chunky particles, such as are shown in Fig' 1. I' In the tin bronze contains the hard alpha + delta

Jan 1, 1946

By E. W. Johnson, M. L. Hill

Cold working of iron-carbon alloys was found to increase greatly the hydrogen solubility and to decrease the diffusivity at temperatures up to 400° C. These effects are increasing functions of both the carbon content and the degree of deformation. The hydrogen behavior is consistent with the idea that cotd working creates "traps", which are concluded to be microcracks in which the hydrogen is chemisorbed. Hydrogen embrittlement is explained by the Petch theory of metal crack surface energy loss due to hydrogen adsorption. HYDROGEN embrittlement of steel has been studied for many years and has been the subject of an extensive literature, but the mechanism of the effect has not been completely understood. The embrittlement is unusual in that the ductility loss is not accompanied by an increase of the yield strength, being primarily a decrease of the fracture strength alone. The loss of fracture strength is usually most severe in the temperature range between 0°and 100°C. Here the solubility of hydrogen in the iron lattice at ordinary H2 pressures is extremely low while the diffusivity is still quite high. From the relationships between the ductility and the hydrogen content, test temperature and strain rate, it is apparent that the hydrogen atoms causing the ductility loss difbse to and concentrate in small regions of the metal which are especially susceptible to the initiation and propagation of fracture. This hydrogen segregation apparently occurs after plastic straining has begun. Below 0°C the ductility loss persists only at low strain rates in confirmation of the view that the embrittlement is diffusion .controlled. The tendency of the embrittlement to disappear above 100°C can be explained by the increasing lattice solubility of hydrogen with rising temperature. A common view of hydrogen embrittlement of steel is that the hydrogen initially dissolved in the metal lattice diffuses to structural discontinuities and there precipitates as H2 gas at very high pressures which assist the external stress in causing premature failure.1,2 The idea of a high H2 pressure in equilibrium with ordinary amounts of hydrogen in steel at room temperature is due to observations of hydrogen behavior in fully annealed material, for which the Sieverts' law constant relating solute concentration to H2 pressure is extremely small. Hydrogen-embrittled steel, however, is always plastically deformed to some extent, and therefore it is important that hydrogen embrittlement be explained primarily in terms of hydrogen behavior in plastically deformed material. Such an explanation is attempted in this paper. Previous studies of hydrogen in cold-worked steel have shown that both the solubility and the diffusion rate are significantly chaned when the steel is cold worked. Darken and Smith discovered that the amount of hydrogen absorbed from acid by cold-rolled steel at 35°C is many times greater than that absorbed by hot-rolled steel. They found also that the hydrogen permeability of the steel is unaffected by cold working. Keeler and Davis4 confirmed the high apparent solubility of hydrogen in cold-worked iron-carbon alloys at temperatures up to and even beyond the recrystallization temperature. They also found that this solubility increase accompanying cold work is a sensitive function of the carbon content, being absent when no carbon is present. The present experimental study was undertaken primarily to obtain an improved understanding of the behavior of hydrogen in cold-worked steel. Data were obtained on the effects of temperature, H, pressure, carbon content, and degree of cold work on the hydrogen solubility and diffusivity in iron-carbon alloys. These data have been helpful in elucidating the nature of the cold-worked steel structure as well as in providing information on the mechanism of hydrogen embrittlement of steel. EXPERIMENTAL Cylindrical specimens for hydrogen absorption and diffusion rate measurements were prepared from three iron-carbon binary alloys and a commercial SAE 1010 steel. The iron-carbon alloys were prepared by vacuum melting electrolytic iron with graphite in a magnesia crucible. The alloys were cast in vacuum as 2 1/2-in. sq ingots weighing about 20 lb each. The ingots were hot rolled (above 1900°F) to 5/8-in.-diam round bars and then cooled in air to room temperature. The resulting metallographic structure consisted of islands of fine pearlite surrounded by free ferrite. Chemical analyses of the materials are given in Table I. The 5/8-in. diam bars were turned to diameters such that cold reduction to the desired final specimen diameters would result in either 30 or 60 pct reduction in area (RA). The machined bars were then cold worked by swaging at room temperature

Jan 1, 1960

By L. F. Mondolfo

R301 is a clad aluminum alloy, composed of a core of a duralumin-type alloy clad with a magnesium silicide alloy. It differs from other well-known clad alloys in that the cladding and the core respond to the same heat-treatments, and therefore the cladding contributes appreciably to the mechanical properties of the material. In Table 1 are reported the compositions of the core and cladding alloy for the material used for the experiments. [ ] In clad aluminum alloys where the core contains copper and the cladding does not, at elevated temperatures the copper tends to diffuse from the core through the cladding. This fact is well known and many investigations have been conducted to determine the features of this diffusion.1-7 Most of those investigations cover materials clad with pure aluminum; the present investigation covers a material clad with an alloy. Since the cladding thickness on R301 varies with the gauge, as shown in Table 2, several gauges were investigated. [ ] MATERIAL AND PROCEDURE The material used was sheet of the following gauges: 0.025, 0.040, 0.064, 0.102, 0.170. Cut in pieces approximately 3 by 5 in., it was in the cold-rolled state and was soaked for increasing times at the following temperatures: 910°F., 940°F., 970°F. A Lindberg cyclone furnace was used for the experiments. The procedure was as follows: The furnace was started empty with controlling pyrometer set at the determined temperature. After the furnace had reached that temperature, it was run for some 20 to 30 min. empty, in order to allow the temperature inside to become stabilized. Then the first samples were introduced. A load thermocouple, with recording pyrometer, was connected with the sample of the heaviest gauge. About 10 min. was required for the material to reach temperature and the soaking time was counted from that point. After 200 min. soaking, the second group of samples was introduced without stopping the furnace. After 200 min. more, the third group of samples was introduced, and so on, until the last sample had been introduced. Every time the furnace was opened and new samples were added, a drop of temperature was registered by the thermocouple connected with the material

Jan 1, 1945

By W. A. Backofen, D. Lee

Tlze condition of superplasticity or neck-resistanl flow that results front high strain-rate sensitivity has been observed in isothermal tension tests on several titanium alloys and one of zirconium hi general, il was associated with reasonably fine-grain micro-structures being stvained in the transformation range at rates below i - 10 -3 sec-&apos;. The metallographic mean-free path, L, was measured at room temperature after rapid cooling from the temperature of test-ing. The flow stress of Ti-GAL-4V at 950°C was proportional to La at different constanl <; the value of a decreased with increasing. E but at E< 1.5 x 10-4 sec-1 it varied only from 0.9 to 1.25. The findings were interpreted to mean that viscous boundary shear is the rate-controlling process of deformation at high levels of strain rate sensitivity in these materials. Elongation of over 1000 pet could be obtained, but a1 temperatures so high and rates so low that any practical application of the full effect would probably be difficult. As the transformation range was narrowed, by turning from Ti-6AL-4V to Ti-5Al-2.5sn to nomznally pure titanium, the allowable temperature varialion was correspondingly reduced. Superplasticily was not found in Armco iron, presumably because the transformation range was too narrow to allow the developtnenl of a reasonably stable microstructure for isolhermal lesting. THE work represented by this paper grew out of a recent study of texture hardening in a(hcp) titanium and zirconium-alloy sheet,&apos; of which part has now been published.2 It was found that, with heating, the tensile plastic-anisotropy index, R,* was decreased from well above 1 towards 1 as the temperature range for the a(hcp) -ß(bcc) phase change was entered. The clearest example of that trend is illustrated with previously unpublished data in Fig. 1. It might have been thought that such a development resulted simply from introduction of the cubic and therefore plastically less anisotropic phase. However, the accompanying change in the index of tensile strain-rate sensitivity, m = a log a/a log E, was rapidly upwards, to a high of 0.85 in some cases (also illustrated in Fig. 1). At the same time, the total tensile elongation rose to a maximum and the flow strength dropped away as R (and m) approached 1. Taken together, the observations cannot be understood as resulting from the presence of cubic phase, per se. It has been concluded instead that they reflect the largely noncrystallographic deformation which characterizes superplasticity. As demonstrated in other recent work? a necessary condition for super-plasticity is strain-rate sensitivity of flow stress sufficiently high that m is above a lower limit of -0.3. The origin of large m has been traced, in turn, to grain size so small that a substantial amount of viscous deformation is introduced by such processes as Nabarro-Herring diffusional flow4 and/or grain boundary shear.5,6 Because of problems in the processing of titanium and zirconium alloys—problems of high strength, limited ductility, and excessive springback, originating largely in slip resistance-it was natural to wonder if something useful might be done with superplasticity in those materials. Therefore experiments were made for more closely identifying and generally bounding the phenomenon with temperature and strain-rate limits, before attempting to decide about its exploitation. The results are being reported here. EXPERIMENTAL Materials. The two of primary interest were the titanium alloys of nominal composition (in wt pct) 5A1-2.5Sn and 6A1-4V. Others were a 4A1-1/4O2 titanium alloy, titanium of commercial purity (RC-70), Zircaloy-4. and Armco iron. All were received as annealed 3/16 in. thick sheet, except RC-70 which was & in. thick, and tested in that condition. Details of transformation temperature and grain size are given in Table I. The results of dilatometry for the measurement of transformation temperatures were unsatisfactory. Data were finally obtained by metallographic examination of each specimen after test, to determine from the amount of transformed 4 where the specimen had been heated in relation to the critical temperatures. Results were in reasonable agreement with information from the supplier. Strip tensile specimens were of full sheet thickness and taken along the rolling direction, except for those

Jan 1, 1968

By V. R. Garfias, R. V. Whetzel, J. W. Ristori

Since the entry of the United States into global war, virtually all data and information necessary for compiling figures on world petroleum consumption have become unavailable. This situation undoubtedly will continue until the world petroleum industry can return to a peacetime basis. During the past 10 years, the authors, by publishing annual estimates of .world consumption, have attempted to emphasize the importance of a yearly world-wide survey of petroleum supply and demand. It is beconling more and more evident that statistics for the United States alone can no longer give a comprehensive idea of the state of the petroleum industry, even within the United States itself. Therefore, when conditions in the industry again become normal, it is the hope of the authors that those bureaus equipped to do so will carry forward the study of petroleum supply and demand on a world-wide basis. Enough data and information are available, however, to attempt a rough estimate of world output of crude petroleum and petroleum substitutes for 1942, which to some extent may reflect the trend of world consumption. This estimate by countries, as compared with the output in 1941, is shown in Table I. The world production of crude petroleum and petroleum substitutes for 1942 is estimated at 2,208,000,000 bbl., or a decrease of 171,000,000 bbl. under 1941. Crude production is believed to have decreased by about 200,000,000 bbl., (about 9 per cent); while petroleum substitutes increased by 28,500,000 bbl., (nearly 20 per cent). The decline of crude output in the United States is estimated at 19,000,000 bb1.—less than 2 per cent; while that in foreign countries is estimated at 180,000,000 bbl., or more than 20 per cent. The marked decline abroad is due largely to losses in Venezuela and Colombia, where the lack of ocean transportation became the controlling factor, and in the East Indies and Burma, where military invasion brought about the destruction of the fields. The production of petroleum substitutes in 1942 apparently reached a new high figure of 7.5 per cent of the total world petroleum output. The important features of petroleum production outside of the United States are the changes that have taken place during the year in the supply of the Axis countries. In Japan the output for 1941 was estimated at 8,800,000 bbl., 5,500,000 of which were petroleum substitutes. It is believed that the output of synthetic oils during 1942 substantially increased, raising the total interior production of Japan to nearly 10,-ooo,ooo bbl. Also, during 1942 Japanese armed forces gained possession of oil fields having a normal peacetime output of about 78,000,000 bbl. per year. The production of these areas for 1942 is estimated at some 23,000,000 bbl., which indicates that Japan is now getting at least 33,000,000 bbl. a year, which exceeds by 8,000,000 bbl. Its

Jan 1, 1943

By J. W. Ristori, V. R. Garfias, R. V. Whetzel

Since the entry of the United States into global war, virtually all data and information necessary for compiling figures on world petroleum consumption have become unavailable. This situation undoubtedly will continue until the world petroleum industry can return to a peacetime basis. During the past 10 years, the authors, by publishing annual estimates of .world consumption, have attempted to emphasize the importance of a yearly world-wide survey of petroleum supply and demand. It is beconling more and more evident that statistics for the United States alone can no longer give a comprehensive idea of the state of the petroleum industry, even within the United States itself. Therefore, when conditions in the industry again become normal, it is the hope of the authors that those bureaus equipped to do so will carry forward the study of petroleum supply and demand on a world-wide basis. Enough data and information are available, however, to attempt a rough estimate of world output of crude petroleum and petroleum substitutes for 1942, which to some extent may reflect the trend of world consumption. This estimate by countries, as compared with the output in 1941, is shown in Table I. The world production of crude petroleum and petroleum substitutes for 1942 is estimated at 2,208,000,000 bbl., or a decrease of 171,000,000 bbl. under 1941. Crude production is believed to have decreased by about 200,000,000 bbl., (about 9 per cent); while petroleum substitutes increased by 28,500,000 bbl., (nearly 20 per cent). The decline of crude output in the United States is estimated at 19,000,000 bb1.—less than 2 per cent; while that in foreign countries is estimated at 180,000,000 bbl., or more than 20 per cent. The marked decline abroad is due largely to losses in Venezuela and Colombia, where the lack of ocean transportation became the controlling factor, and in the East Indies and Burma, where military invasion brought about the destruction of the fields. The production of petroleum substitutes in 1942 apparently reached a new high figure of 7.5 per cent of the total world petroleum output. The important features of petroleum production outside of the United States are the changes that have taken place during the year in the supply of the Axis countries. In Japan the output for 1941 was estimated at 8,800,000 bbl., 5,500,000 of which were petroleum substitutes. It is believed that the output of synthetic oils during 1942 substantially increased, raising the total interior production of Japan to nearly 10,-ooo,ooo bbl. Also, during 1942 Japanese armed forces gained possession of oil fields having a normal peacetime output of about 78,000,000 bbl. per year. The production of these areas for 1942 is estimated at some 23,000,000 bbl., which indicates that Japan is now getting at least 33,000,000 bbl. a year, which exceeds by 8,000,000 bbl. Its

Jan 1, 1943

By S. Fugleberg

As a result of research work done during the planning of the Kokkola zinc plant it was found that a very efficient cementation of impurities from the suspension obtained after leaching copper and cadmium cakes was achieved by adding zinc dust to the batch without filtration after the leaching. All elements nobler than cadmium are precipitated with the exception of lead, which must be removed in a separate step. Using pure zinc dust, free from noble metals, the cadmium sponge produced will only contain elements that can be re- moved from cadmium by meltrefining. The process is thus : 1. Leaching and purification 2. Removal of lead (with BaCO3) 3. Precipitation of cadmium sponge with pure zinc dust 4. Meltrefining of briquetted sponge with NaOH for removal of Zn (and others) The paper deals with the removal of the most critical elements, i.e. Co, Ni, As, Sb, Cu, Pb, T1 in the liquid phase and Zn and T1 in the melt. A survey is also given of the behaviour of most of the other elements normally found in Cd raw material, such as Ge, Te, Se, Sn, In, Ga. It is shown that in most cases the benefit of an electrolysis in Cd production is very limited. In Kokkola 99.998% Cd is achieved by this method, but in favourable cases it may be possible to come quite close to five nines.

Jan 1, 1973