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US 4,192,852-Precipitation of iron values as a jarosite from a sulfate solution obtained as a byproduct in the hydrometallurgical processing of zinc sulfide ore The solution is cooled, partially neutralized, and clarified. The clarified solution is heated to a temperature of 80 to 100°C in the presence of sodium, potassium, or ammonium ions to precipitate substantially all of the ferric iron as jarosite The precipitate is thickened, filtered, and washed The residual solution may be processed for zinc or other nonferrous metal values R V. Pammenter and C J Haigh, assigned to Electrolytic Zinc Co of Australasia Ltd. Mar. 11, 1980. 16 pp. (423-42) Filed: 5-8-78 (903,524). Priority- Australia, 5-9-77 (PD0030) (Drawings below.)

Jan 1, 1982

By R. J. Keene

The South Works high-tonnage billet caster was started in late March 1971, with the first heat being successfully cast to completion. Currently, over 31,500 tons per month are being produced. U. S. Steel designed and built this caster with the objective of producing quality-steel billets for critical bar, rod, and wire applications. The essential design parameters were based on studies conducted on the Research Laboratory's pilot caster, also located at South works. 1,2,3)* The caster is a four-strand, straight-mold machine that produces 7.5-inch- square billets at rates exceeding 300 tons per hour. An in-line-reduction mill reduces each strand to either 6-inch-, 5-inch-, or 4-inch-square billets.

Jan 1, 1972

By William Buell

As used in connection with open-hearth or other high-temperature operations, "insulation" refers to a multitude of substances, natural or manufactured, that have the one principal property of preventing the flow of heat by conduction to a greater degree than refractories can prevent it, the principal properties of the latter being resistance to tem-perature and/or chemical action. The term "control" as commonly applied to the mechanization of management functions is inappropriate without qualification, for without some degree of control of every operation we could produce no steel worthy of the name. Although grouped together in this paper, insulation and control in open-hearth furnaces have little, if any, interrelationship, therefore the paper is made up of two distinct parts.

Jan 1, 1935

By G. J. Armstrong, K. S. Lynch, C. G. Thomas, L. A. Baker, R. J. Cornelius

The presence of geothite in a hematite ore has been shown to strongly affect the time of heating to the firing temperature. The investigation of spalling of single pellets and of packed beds has enabled free water and goethite spalling to be identified as separate phenomena. In addition, it has been shown that even for an 18-in. deep bed of green balls, the free water and goethite drying periods can be considered separately. Based on this observation, a method of predicting production rate and hood temperature profile is presented. The method required knowledge of the ore goethite content, ore grind, and the green pellet bulk density. Laboratory results were found to be in good agreement with actual plant practice and have led to improved process performance.

Jan 1, 1974

Occasionally it is interesting, and sometimes useful, to review the past for early references to our industry, and to learn of the trials and travail passed through before it arrived where it now is- and the results of such a review follow. Some time ago one of our modern playwrights and poets, Arthur Guiterman, turned to coal, with the following result: Afar in the Carboniferous time I grew in Paleozoical slime, A lepidodendron with boughs on my stem And lepidostrobuses grew out of them. My roots in the mud of the ages I spread And up to the heavens I vaunted my head, I throve in the heat of tropical sun, And now I am coal at two dollars a ton

Jan 1, 1939

By E. L. Anderson, J. R. Long, R. S. Dean, F. S. Wartman

Titanium has been estimated to comprise about 0.65 per cent of the earth's crust and ranks fourth in abundance among the metallic elements suitable for engineering uses. In spite of this, applications of titanium for structural purposes have not as yet been developed. Its commercial exploitation has been largely confined to the chemical industries and the production of paints and pigments; no doubt because of the difficulties that lie in the way of preparing the pure ductile metal. Published reports, however, indicate that ductile titanium can be prepared and possesses some unique properties. This, together with the occurrence in this country of several important titaniferous deposits, has led the Bureau of Mines to investigate processes for the production of metallic titanium, methods required for its fabrication, and the properties that may be produced in this interesting metal. Methods of Preparing Metallic Titanium Many early investigators claimed to have isolated metallic titanium; but in the light of present knowledge, it seems that they really had produced various mixtures of carbides and nitrides that have a metallic appearance but are brittle, hard, and unworkable. The first metallic titanium pure enough to be malleable when cold was produced by Hunter1 in the early part of the twentieth century. Kroll,~ van Arkel,~ and Fast,4 subsequently confirmed the facts that pure titanium is a. ductile metal and that small amounts of impurities were responsible for previous reports of brittleness. When heated, titanium reacts chemically with various gases, such as hydrogen, oxygen and nitrogen; if the volume of gas thus absorbed is too great, the metal becomes brittle and unworkable. The principal difficulty in making ductile titanium is prevention of such contamination, and the success of a given process may be judged by the completeness with which it solves this difficulty in a practical manner. Of the gases mentioned, hydrogen is the least objectionable, since its absorption by the metal is completely reversible and, although dimensional changes occur and absorption of hydrogen embrittles the metal, the gas may be removed readily by heating in a high vacuum for a short time. On the other hand, the absorption of oxygen or nitrogen results in the formation of permanent solid solutions of the oxide and nitride, which cannot be decomposed by the strongest reducing agentsz with sufticient completeness to restore the inherent ductility of the metal. Because of

Jan 1, 1946

By Thomas Egleston

All industrial establishments whose operations depend upon chemical reactions use gases. In the simplest case the oxygen of the atmosphere, heated or not, as the case may be, is used, and in other cases, gases which are produced by a special apparatus of more or less complex composition. The manufacturer depends, for the success of his operations, entirely upon having these gases arrive at the right time, in the proper proportions, at the required temperature. It often requires but a slight variation in their composition to make a given process a success or a failure. In most cases the gas used is formed from fuel, and according as variations in its composition are produced by alterations in the manner of charging the grate, not only different, but often directly opposite, results are obtained. The great industrial question of the present time, and one upon which the prosperity of the world depends, is how to get the greatest amount of useful effect from fuel, whether the caloric is used directly or is transformed into horse-power. In almost all industrial pursuits this translates itself into the question of how to construct a fireplace and its adjuncts in such a way that the heat of the flame and of the products of combustion shall be made to produce a maximum effect. Unfortunately, until very recently, except by comparison, there was no means of ascertaining whether the loss of useful effect was 80, 40, or 20 per cent. of the total amount of fuel employed. It seems now strange that there should have been furnaces so constructed as to produce 20 per cent. of carbonic acid in the fireplace, but this has been proved by analysis to have been true. It does seem incredible that, notwithstanding the immense number and variety of furnaces used for different processes, and the great difference in kind, quality, and quantity of fuels consumed, there should formerly have been used for them all, the same stereotyped fireplace, varied only in its dimensions of height, length, and breadth. It is true that, with a good fireman, excellent effects may be, and have been, produced, but the manufacture is here, as in many other cases, dependent on the intelligence of the workman, a very uncertain reliance for capital to rest upon. The workman, unless he receives a prime for fuel saved, or is fined for excessive use of it, may be said

By T. Prof. Egleston

ALL industrial establishments whose operations depend upon chemical reactions use gases. In the simplest case the oxygen of the atmosphere, heated or not, as the case may be, is used, and in other cases, gases which are produced by a special apparatus of more or less complex composition. The manufacturer depends, for the success of his operations, entirely upon having these gases arrive at the right time, in the proper proportions, at the required temperature. It often requires but a slight variation in their composition to make a given process a success or a failure. In most cases the gas used is formed from fuel, and according as variations in its composition are produced by alterations in the manner of charging the grate, not only different, but often directly opposite, results are obtained. The great industrial question of the present time, and one upon which the prosperity of the world depends, is how to get the greatest amount of useful effect from fuel, whether the caloric is used directly or is transformed into horse-power. In almost all industrial pursuits this translates itself into the question of how to construct a fireplace and its adjuncts in such a way that the heat of the flame and of the products of combustion shall be made to produce a maximum effect. Unfortunately, until very recently, except by comparison, there was no means of ascertaining whether the loss of useful effect was 80, 40, or 20 per cent. of the total amount of fuel employed. It seems now strange that there should have been furnaces so constructed as to produce 20 per cent. of carbonic acid in the fireplace, but this has been proved by analysis to have been true. It does seem incredible that, notwithstanding the immense number and variety of furnaces used for different processes, and the great difference in kind, quality, and quantity of fuels consumed, there should formerly have been used for them all, the same stereotyped fireplace, varied only in its dimensions of height, length, and breadth. It is true that, with a good fireman, excellent effects may be, and have been, produced, but the manufacture is here, as in many other cases, dependent on the intelligence of the workman, a very uncertain reliance for capital to rest upon. The workman, unless he receives a prime for fuel saved, or is fined for excessive use of it, may be said

Jan 1, 1874

By J. R. Long, E. L. Anderson, R. S. Dean, F. S. Wartman

Titanium has been estimated to comprise about 0.65 per cent of the earth's crust and ranks fourth in abundance among the metallic elements suitable for engineering uses. In spite of this, applications of titanium for structural purposes have not as yet been developed. Its commercial exploitation has been largely confined to the chemical industries and the production of paints and pigments; no doubt because of the difficulties that lie in the way of preparing the pure ductile metal. Published reports, however, indicate that ductile titanium can be prepared and possesses some unique properties. This, together with the occurrence in this country of several important titaniferous deposits, has led the Bureau of Mines to investigate processes for the production of metallic titanium, methods required for its fabrication, and the properties that may be produced in this interesting metal. Methods of Preparing Metallic Titanium Many early investigators claimed to have isolated metallic titanium; but in the light of present knowledge, it seems that they really had produced various mixtures of carbides and nitrides that have a metallic appearance but are brittle, hard, and unworkable. The first metallic titanium pure enough to be malleable when cold was produced by Hunter1 in the early part of the twentieth century. Kroll,~ van Arkel,~ and Fast,4 subsequently confirmed the facts that pure titanium is a. ductile metal and that small amounts of impurities were responsible for previous reports of brittleness. When heated, titanium reacts chemically with various gases, such as hydrogen, oxygen and nitrogen; if the volume of gas thus absorbed is too great, the metal becomes brittle and unworkable. The principal difficulty in making ductile titanium is prevention of such contamination, and the success of a given process may be judged by the completeness with which it solves this difficulty in a practical manner. Of the gases mentioned, hydrogen is the least objectionable, since its absorption by the metal is completely reversible and, although dimensional changes occur and absorption of hydrogen embrittles the metal, the gas may be removed readily by heating in a high vacuum for a short time. On the other hand, the absorption of oxygen or nitrogen results in the formation of permanent solid solutions of the oxide and nitride, which cannot be decomposed by the strongest reducing agentsz with sufticient completeness to restore the inherent ductility of the metal. Because of

Jan 1, 1946

By Philip R. Strand, O. F. Stewart

Vermiculite is the name generally applied to the group of hydrated ferromagnesian aluminum silicates that are characterized by the ability to expand when heated. This process, called exfoliation, results in a lightweight product of commercial value. Most uses of vermiculite are for the expanded material. The chief markets are in construction, agriculture, and horticulture, with lesser uses in general industry. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit, a perfect basal cleavage which causes splitting into thin laminae that are soft, pliable, and inelastic. The structure of vermiculite is basically that of a talc. The prominent monoclinic crystal faces are often marked by lines at 60° and 120°. Hardness varies from 1.5 to 2 or more; specific gravities are between 2.1 and 2.8; color varies from almost clear to amber, bronze, brown, green, or black. Vermiculite feels like talc, especially when wet. Although much research has been performed on the chemical and structural composition, there is not yet complete agreement on the exact formula. This is to be expected when different workers have examined the many different varieties. Vermiculite is not considered to be a single mineral species but a family of related minerals. The structural formula for a trioctahedral vermiculite may be written: (H20)-(Mg,Ca,K)-(A12,Fe,Mg)-(Si,A1,Fe)4O10 (OH) 2 Hydrobiotite also occurs with vermiculite and is usually considered a vermiculite for commercial uses. When heated quickly to elevated temperatures, vermiculite expands by exfoliating at right angles to the cleavage into wormlike particles. The name vermiculite is derived from the Latin vermiculare, to breed worms. This characteristic of expansion is the result of the mechanical separation of the layers by the rapid conversion of contained water to steam. The decrease in bulk density of commercial grades is usually approximately 10 times, from 50 to 5 lb/ft3, but varies depending on the quality, size, and furnace efficiency. Individual flakes may expand up to 30 times. Vermiculite may also be expanded by soaking in chemicals such as hydrogen peroxide, weak acids, and other electrolytes. Color change during expansion is dependent upon the type of vermiculite and furnace conditions. Heating in an oxidizing atmosphere produces a dull gray or tan color, whereas a reducing atmosphere can produce a bronze or gold color. The expansion of the vermiculite crystal results in large pores being formed between the platelets. Thus, exfoliation makes available a large increase in void volume which is important in the application of vermiculite as a chemical carrier. Mathieson and Walker (1954) state vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation exchange capacity, organic complexing ability, and variable interlamellar distance are very similar to those of montmorillonite. The cation exchange capacity of vermiculite is one of the highest of all the clay minerals. The interplatelet space is accessible to penetration by some electrostatically neutral molecules. Water and glycerine are two common substances whose molecules may be so imbibed. In the natural state and under normal atmospheric conditions, water occupies the spaces between the silicate layers. The crystal d-spacing is near 14.2A. By differential thermal analysis, it has been determined that the water

Jan 1, 1983

By C. Chiou, D. P. Seraphim

The effect of clustering on the superconducting properties of Al-Zn alloys has been studied by the ballistic induction techniques. The superconducting critical temperature, T,, changes when zinc-rich clusters are formed. The change in T, depends on the concentration and may be positive or negative, but always correlates with an effective decrease in the solute concentration of the alloy. Reversion after clustering effectively returns a 5 at. pct Zn alloy to the quenched state. These methods might be use&lly extended to the Al-Mg system, where X-ray data are difficult to obtain. In very dilute Al-Zn alloys, as in other tin,' indium, aluminum,2 or tantalums base solid solutions, there is a decrease in the superconducting critical temperature, Tc, roughly proportional to the temperature independent resistivity, i.e., -0.2°K per pS2cm. With increasing solute concentration, the T, generally reaches a minimum and then increases4 to a value well above that for the pure solvent. The change of T, with solute concentration follows an empirical formulation involving two constants which correlate with the scattering cross section of the impurities. As will be shown below, the Al-Zn alloys more concentrated than 1or2at. pct do not follow the empiricism, probably because they are unstable even when rapidly quenched.5 However, it seems possible to study at least the later stages of solute clustering by precise measurements of the 1', following various thermal treatments. A few experiments on quenched alloys, aged alloys, and tests on reversion are reported here. The heat treatments selected for obtaining the quenched and aged states were mainly deduced from the work of Dash and Fine.6 For the quenched state, specimens were homogenized at 480°C, quenched to -160°C, and immediately transferred and mounted in liquid nitrogen. Measurements on the superconducting properties and residual resistivities were then made at helium temperatures, after which the specimens were aged at room temperature for 3 to 5 hr, i.e., much longer than the time required for clustering to be essentially completed. The superconducting properties and residual resistivities were once again examined. To reach the reverted state of the A1-5at. pct Zn alloy, the aged specimen was heated for 5 min at 200°C and then tested as above.

Jan 1, 1963

By E. F. Ketterer, D. B. Collyer, A. B. Wilder

AISI constructional alloy steels are a series of steels in which a numbering system signifies the chemical composition limits. SAE (Society of Automotive Engineers) and AISI (American Iron and Steel Institute) use basically the same numbering system. The steels contain, in part, alloy additions of chromium, molybdenum, nickel, and vanadium. They are used widely in the automotive industry but have not been adopted for high temperature service. The purpose of this investigation was to study changes in microstructure observed in typical AISI constructional alloy steels in the welded and un-welded conditions after exposure for 34,000 hr at 900" and 1050" and, in several instances, 1200°F. The tensile and creep rupture properties after exposure for 10,000 hr were also evaluated. The investigation is a continuation of the work previously discussed. Little was known concerning the existence of graphite in medium or low carbon steels before 1943. It is important to note that continued exposure at elevated temperature is required in order to develop graphite in steels. Interest in the presence of graphite in steel, and also in changes in the properties of steels after long service at elevated temperatures, developed after 1943 when a failure of a welded joint of high temperature piping was associated with the graphitization of a relatively low carbon content steel with 0.50 pct Mo,8,0 Numerous investigations have beeen made in recent years studying the relationship of this type of failure to changes in properties. Attempts have been made to evaluate the performance of a number of steels, particularly in the heat-affected zone of welds. It was the unfortunate failure of a weld-heated zone in high temperature piping in the steam-power industry which focused attention upon possible failures, and upon the need for improved steels for high temperature piping service. Investigation by the National Tube Div., U. S. Steel Corp., Lorain Works, has included a wide variety of steels in an attempt to learn the effects of numerous factors and elements upon the long time performance of steels, although many of the compositions studied will never be used at elevated temperatures.1,4-7 Included were the well established AISI steel series, which offered opportunity to test moderately high carbon content steels as well as observe the effect of nickel, chromium, molybdenum, etc., upon the properties of these well known steels. The properties of the AISI steels were also studied for comparison with the previously reported properties of the Cr-Mo steels, now used by the steam-power industry.5,7 Materials and Testing Procedure The AISI alloy steels in Table I were exposed for 10,000 and 34,000 hr at 900°, 1050°, and 1200°F.

Jan 1, 1958

By H. W. Seamon

The data here given were obtained by 1500 tests made by the United Verde Copper Co. to determine the most economical air pressure for the operation of hammer drills under the varying conditions of use, and to investigate the variation in drilling speed at different air pressures. Twelve models of drills were used at gage pressures ranging from 40 to 130 Ib. No effort was made to harmonize theory and practice; but rather to formulate empiric rules that would cover the average variation of the results obtained. These rules on the performance of hammer drills, based on the air pressure as the main variable, however, are not necessarily of universal application, but they apparently satisfy the results obtained in this series of tests. The drilling conditions at this property vary widely; an average of twenty-one machine shifts to a 3-ft. (0.9-m.) round has been found necessary in some of the development work, while an advance of 56 ft. has been made in seven shifts in the "oxide" ground. This range precludes the adoption of one type of drill as a standard; consequently almost every kind of hammer drill sold in this country has been tested. At present, sixteen models are in use, of which two types of the heavy (150 to 160 lb.) mounted drills, one of the light mounted drill, one stoper, and two hand plugging drills are considered as standard. Method of Conducting Tests All machines were of the wet type, and were selected as being representative of the several types in use at this property; all had been in use from two to four months except the Waugh 66 and the Sullivan DX61, which were new. All machines were thoroughly overhauled before they were sent to the testing ground. Tests were made on the following machines: Ingersoll-Rand, No. 248 Leyner-Ingersoll, No. 18 Leyner-Ingersoll, No. 26 Baby Leyner, BCRW430 Jackhamer, and CCW11

Jan 1, 1922

By H. C., Simpson

MANY metals by virtue of their place of occurrence as ore, and their uses are travelers! Iron and steel, for instance, is one of the greatest of travelers in the form of ships and the romance of iron in this respect is only just beginning to be superseded by the stories which can be told of the travels of aluminum and its alloys, used in the building of airplanes. Tin is a traveler from the Straits Settlements to this country and Europe, for use in the canning industry; afterward traveling all over the civilized world as a part of the container for preserved foods. Silver is somewhat of an aristocrat, when its uses are measured against those of the baser metals. From earliest times it has been used for adornment (first perhaps o4 the person and later for the embellishment of weapons and' buildings), for the making of fine ar¬ticles used in the household, and as money. While its uses have been widened by the discoveries in chemistry, electricity and other sciences, its early uses are still much in evidence in our modern life.

Jan 1, 1928

President Howe : It is not so clear to me that the facts which Dr. Waldo brings forward really argue that the nature of the combination between copper and aluminum differs from that of the combination between copper and zinc or copper and tin. As regards electric conductivity, I suppose that the fact, which he thinks points to a special intimate kind of union between aluminum and copper, is that the line in his Fig. 1 is neither straight nor uniformly curved, but that its curvature varies rapidly, not to say abruptly. But we find just such variation in like curves for the copper-zinc and copper-tin alloys. Thus, a slight addition of zinc or tin to copper causes a change in color wholly out of proportion to the quantity added; and, as we add zinc or tin to copper, the tenacity rises very greatly, only to fall off abruptly with further additions of either of these metals. Dr. Waldo : My curve related only to electrical conductivity. The President : If irregularity in one physical property argues

Jan 1, 1895

By W. R. Ingalls

WHAT proportion of the national wealth is represented by' the producing mines of the country?' Or by the- mining and metallurgical industry-as a whole, for it is impossible to make-an economic distinction between the mines that produce the ore and the plant that is used to get the metals from it. The total national wealth in fixed property is about $270,000,000,000. How much for the mines? I do not know that any one 'else has ever tried to furnish answers to these questions. In making such an attempt I am conscious that the result can be nothing more than a rough approximation. Yet even that will give an idea of relative values. No separate valuation for the mines of the country has appeared in any inventory of the national wealth previous to that which I compiled and published for 1916. -In earlier census estimates mines were supposed to be included under the head of real estate. However, an examination of the laws and practices of the several states with respect to mine taxation will make it evident that no good idea of the value of the mines of the coun¬try is obtainable from the assessment rolls. In my previous estimate for 1916, I computed the value of the mines at $8,000,000,000, which was approxi¬mately 10 times their net income as reported to the Bureau of Internal Revenue. In making that estimate I fell grossly into error, for several reasons that it is unnecessary to explain, but chiefly because the net income of the mines of the country in that year was exceptionally large. The whole subject of valuing the mines of the country en bloc is extraordinarily difficult At the best, no one can hope to arrive at, anything more than a rough idea about it. However, elements of reason may be introduced and may be made to serve as chief bases.

Jan 1, 1921

By Roman Šejnoha, Karel Mazanec

A pronounced tendency for delayed fracture zoas observed in the martensite structure of low-alloy steels in the as-quenched condition. Cracks of predominantly intercrystalline nature nucleated and propagated at stresses substantially lower than the short-titne tensile strength of- the steels, and were observed even in hydrogen-free speciunens. The occurrence of delayed fractures in the as-quenched condition is interpreted as a supevposition of the effect of free dislocations generated during the martensite transforlnation, and of a weakening of the prior austenite grain boundaries caused by dynamic shocks exerted on the boundaries by growing martensite plates. AN important metallurgical problem, connected with the production and use of high-strength steels, is delayed fracture in martensitic structures. Such fractures occur in quenched steels as a result of prolonged loading with external stresses far lower than the short-time tensile strength of the steel. The same effect can be produced by sufficiently high internal stresses: it is well-known that quenched structures will in some cases crack intergranularly at room temperature if not tempered quickly enough even in the absence of any externally applied stress. In Troiano's papers1,2 on delayed fractures in high-strength steels, the fundamental role of hydrogen migrating under the influence of multiaxial stress towards the nuclei of cracks was found. Fig. 1 shows the typical relationship between stress and the time to fracture found by Troiano in hydrogen-charged high-strength steels. On the other hand, Shurakov 3,4 explains the realization of delayed fractures in martensite as due to a "quasi-viscous" behavior of the austenite grain boundaries immediately after the martensitic transformation. 1) MATERIALS AND EXPERIMENTAL METHODS Two low-alloy steels of commercial purity were used for the experiments reported in this paper. Their chemical composition is shown in Table I. The heats were melted in a laboratory furnace, cast to ingots, forged to bars of 3/4 in. diameter, and annealed. Machined test pieces were heat-treated as follows: Ni-Cr-Mo steel held at 900°C for 30 min and quenched in oil; Mn-Si-Cr steel held at 900°C for 30 min and quenched in water. For the delayed-fracture tests, notched cylindrical test pieces, Fig. 2, stressed in torsion, and unnotched cylindrical tensile-test pieces, 1/4 in. diameter, were used. The specimens were normally loaded with a constant static load 45 min after quenching for the torsional tests and 10 min

Jan 1, 1965

By Raymond B. Ladoo

The Paley report made little attempt to project future production and consumption for any industrial mineral except fluorspar and only about a dozen minerals were mentioned by name. Except for fluorspar the treatment consisted mainly of statistics of production, consumption, imports, and sometimes reserves up to 1950. FLUORSPAR In 1954 the author had occasion to evaluate the Paley fluorspar estimates. At that time a fairly detailed study of the world picture was made and bases for the Paley estimates were studied. Data for later years confirm, in the main, the conclusions reached in this earlier report and it will be drawn upon here.

Jan 11, 1959

By E. C. W. Perryman

The wide grooves formed at the grain boundaries when high purity aluminum is attacked by hydrochloric acid or sodium hydroxide have been attributed by earlier workers to the high energy of the grain boundary material. The effect has been investigated for high-purity AI-Fe alloys with up to 0.055 pct Fe as a function of iron content and heat treatment. It is shown that the explanation given above is untenable, but that the results can be explained on the assumption that iron segregates to the grain boundary in solid solution. IN 1934, Rohrmann¹ showed that aluminum of 99.95 pct purity suffered intercrystalline corrosion when immersed in 10 to 20 pct hydrochloric acid, and that the susceptibility to intercrystalline corrosion depended upon the heat treatment given. The greatest susceptibility was found for specimens quenched from a high temperature (600°C) and the lowest susceptibility for specimens cooled slowly from that temperature. Lacombe and Yannaquis2 have shown that super-pure aluminum (99.9986 pct) annealed at 600°C suffers intercrystalline attack in 10 pct hydrochloric acid and that this attack is intensified by anodic dissolution in the same solution at a current density of 10 milliamperes per sq dm. No difference in extent of intercrystalline attack was found between the 99.993 and 99.986 pct Al, which led the authors to suggest that impurities played only a secondary role in the mechanism of intercrystalline corrosion. It was found, however, that the attack at the grain boundaries depended upon the relative orientation of the grains, large differences in orientation favoring rapid attack. Boundaries where the two neighboring grains were similarly orientated showed high resistance to attack as did boundaries between grains which were in twin relationship. These observations led Lacombe and Yannaquis to suggest that the intercrystalline attack was due to lattice discontinuities present at grain boundaries. Assuming that the grain boundary is a layer three to five atoms thick and has a crystal structure which is a compromise between the two neighboring grains it is clear that the discontinuities will increase with increasing difference in orientation between the neighboring grains and hence the increasing tendency to intercrystalline attack. Roald and Streicher³ investigated the effect of heat treatment of aluminum alloys ranging in purity from 99.2 to 99.998 pct on the corrosion resistance in 20 pct hydrochloric acid and 0.30N sodium hydroxide. They found that in hydrochloric acid the intercrystalline attack appeared to be determined by the type and quantity of impurities present and by the relative orientation of the grains. No difference in the susceptibility to intercrystalline attack was observed between specimens quenched and those furnace cooled, from 575°C. In 0.30N sodium hydroxide some materials exhibited intercrystalline attack, this taking the form of V-notches. Rohrmann¹ offered no explanation for the greater susceptibility to corrosion of material quenched from 600°C. It seems possible that this difference is connected in some way with a different distribution of impurity elements in the quenched and slowly cooled specimens. The fact that Roald and Streicher8 observed no difference between quenched and slowly cooled specimens may possibly be due to differences in either rate of cooling or silicon content or possibly both. Both these would be expected to have an effect on the distribution of impurity elements. Although the rate of cooling used by Rohrmann was slightly more rapid than that used by Roald and Streicher the position cannot be clarified because Rohrmann does not give the silicon content and Roald and Streicher give the silicon contents of only a few of their alloys. That Lacombe and Yannaquis2 found no difference in corrosion behavior attributable to impurities between the two materials they used may be because both were of high purity compared with the aluminum used by Rohrmann.¹ Although they found no difference in the corrosion behavior of their two materials it is possible that the results obtained by Lacombe and Yannaquis may, nevertheless, have been influenced by impurity distribution, since, on the transition lattice theory of grain boundary structure, it would be expected that sparingly soluble impurities would tend to segregate to boundaries where the orientation difference is such that there is a greater density of atomic sites of suitable size to contain them. It was considered worth while, therefore, to examine the corrosion properties of a series of materials of differing impurity content with the objects of confirming the experimental observations made

Jan 1, 1954

By R. F. Rolsten

The preparation of pure metals by the thermal decomposition of volatile halides was developed byde boer' and van Arkel.2 This has proved to be a useful technique for the refining of columbium,the mechanical and physical properties of which are seriously altered by such interstitial contaminants as oxygen, nitrogen, hydrogen, and carbon. The conventional deposition surface of a resis-tively heated metal filament was replaced, Fig. I, with an indirectly heated clear quartz surface. The impure columbium (feed) was contained in the annular space between the Vycor deposition bulb and the perforated molybdenum retaining cylinder. The head assembly was attached to the deposition bulb by fusing the Vycor at "A". This unit was then connected to a vacuum system composed of a three-turn glass coil to eliminate fracture due to vibration or expansion, a McLeod gage, a cold trap, a two-stage mercury diffusion pump, and a mechanical pump. The entire system was cold outgassed, and the 10 to 20 g of iodine in the auxiliary bulb (reservoir) was held in dry ice to prevent excessive loss of iodine. The columbium was hot outgassed at 800" to 825oC with the pressure maintained at l0-5 to 10-6 mm Hg for 48 hr and cooled under vacuum to 200° to 240oC. Iodine was sublimed from the reservoir and collected in the deposition bulb. The feed material temperature was adjusted to give the desired iodide vapor pressure and the finger temperature of 1000" C was independently attained and measured with a platinum-platinum 10 pct Rh thermocouple located in the center of the nichrome wire helical heating element, "F." The system was attended until temperature equilibrium was established, whence it operated without attention. This is a definite ad- vantage over the conventional "hot-wire" technique which required either constant attention or automatic control. In operation, the iodine vapor originally introduced into the vessel reacted with the crude metal to form a columbium iodide. This iodide vapor diffused to the hot deposition surface where it thermally decomposed, depositing columbium and releasing iodine. This liberated iodine then diffused back to the crude columbium where iodide was formed again. Thus, by repetition of this process, the iodine carried pure columbium from the crude material to the filament, where it deposited. The success of the "iodide" process in producing ductile metals depends on preventing the transfer of oxygen, nitrogen, hydrogen, and carbon from the feed material to the deposit. In many cases relatively minor quantities of these interstitial contaminants impair the ductility of metals. The material produced by the iodide process has such exceptional ductility that it is frequently and mistakenly assumed that iodide metal is always of very high purity. This assumption is not necessarily true since a number of metallic impurities can also be transferred. In the present investigation, the temperature of the feed material was adjusted to iodinate selectively and the deposition temperature adjusted to decompose the iodides selectively. By this technique, some metals present in the feed material were prevented from codepositing with the columbium. It is quite important to have the feed material symmetrically located around the deposition surface in order to obtain a uniform deposit at the maximum rate. For example, Runnalls and pidgeon3 observed that, when the base of a titanium filament was about 1 cm from the feed material, deposition was rapid on that section close to the feed, but that the rate decreased with distance from the feed so that a

Jan 1, 1960