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By E. von Maltitz

In his highly interesting paper, Piping and Segregation in Steel Ingots,' Prof. Howe emphasizes the effect of successive phases of internal pressure in the ingot in the evolution of gas, and the consequent formation of blow-holes. From his statements in other places, it may be inferred that he does not here intend to ignore the other variable factor, temperature, but rather to discuss this one more particularly. At all events, it is my purpose not to engage in controversy with Prof. Howe, but, rather to contribute, towards the complete elucidation of this important subject which we all desire, my own views and experience. If, in doing so, I specially emphasize other factors than pressure, I need not be understood as denying what I do not think it necessary to discuss fully. Nor, in presenting my own original conclusions, need I be understood as claiming to be the first who ever reached or announced them. Many things are asserted or suggested upon inconclusive evidence; and to confirm such tentative propositions may be as valuable a service as to overthrow them. In the following passage, Prof. Howe adduces analogies, based upon the behavior of charcoal and of water, respectively, which seem to me questionable : "In general, the solvent power falls as the pressure falls ; and in general it rises as the temperature falls. Thus, to heat a solid, for instance charcoal, may expel part of its dissolved gas ; and a tumbler of water drawn cold from the faucet gradually evolves gas, as it stands and warms up on the sideboard." (p. 72.) Charcoal is a solid body, which has the property not only of absorbing gases in large quantities, but also of expelling the thus absorbed gases upon heating. A comparison between charcoal and iron as to the absorption of gases is scientifically not possible; the gas-content of charcoal is partly due to the

Jan 1, 1908

By W. G. SWART

THE best estimate on reserves of iron ore in the Lake Superior district is that made, in 1920, by Mr. R. C. Allen, amounting to 2,947,225,000 tons of assured and probable ore. This includes direct- shipping or so-called merchantable ores, and those capable of beneficiation by demonstrated processes. De- ducting from this the 287,000,000 tons shipped since 1920, leaves a present reserve of approximately 2,500,- 000,000 tons, or; about 50 years' supply. The assured ore in this estimate is given as 1,560,500,000 tons, which checks Mr. Lake's estimate of 1,528,948,000 tons, or about 30 years' supply. This is not a long time in the life of the steel industry, and it can be readily appreciated that the matter is important enough to war- rant the attention it is beginning to receive. The first question that engages our attention is, What is merchantable ore? In 1902 the average of all Mesabi shipments was 56.07 per cent iron and 4.35 per cent silica. Twenty-five years later it had dropped to 51.99 per cent iron, with silica up to 7.92 per cent. It has remained around these figures for' ten or twelve years and, except for a probable rise in silica, can stay there for an indefinite period. Most of these figures I am giving cover the Mesabi Range. Including the other ranges does not change the figures greatly, and the Mesabi Range commands the situation, since it produces about 65 per cent of the total annual tonnage and, according to Mr. Allen, contains 81 per cent of the assured reserves, 50 per cent of the probable reserves, and 66 per cent of both the assured and the probable reserves.

Jan 1, 1926

By A. S. Yue

It was deemed desirable to obtain an understanding of the vacuum desulfurization process. McKechnie1 has reported that the sulfur content of nickel- and cobalt-base alloys is reduced in vacuo. Keverian and Taylor2 have observed that vacuum melting causes desulfurization of iron-carbon-silicon alloys. Garnyk and samarin3 have desulfurized transformer steel by vacuum treatment. Experiments were conducted in order to investigate the desulfurization of liquid iron under reduced pressures, and to establish the effect of some alloying elements, and various crucible materials. A vacuum-induction furnace of 50-lb capacity was used. The charge was Armco iron. Silicon was added as 90 pct ferrosilicon, carbon as electrode graphite, and aluminum as high-purity aluminum metal. Magnesia and silica crucibles were used, their inside diameters were 5 1/2 and 5 3/8 in., respectively. The temperature was measured with an optical pyrometer and it was held at 1600 1 15°C. Samples were withdrawn with quartz tubes of 6 mm ID, without disturbing the furnace atmosphere. Pressures were measured with an alphatron gage. The experimental results are shown in Fig. 1. They indicate that: 1) Sulfur can be removed from liquid iron alloys by vacuum treatment; 2) The desulfurization is enhanced by the presence of silicon, carbon, and aluminum, all these elements increase the activity of sulfur dissolved in liquid iron;4 3) The pronounced effect of silicon indicates that probably a volatile silicon sulfide is formed, Alcock and Richardson5 have observed a similar phenomenon; 4) The same rate of desulfurization was obtained when the metal was contained in either magnesia or silica crucibles. Dr. J. Keverian has contributed many discussions and recommendations. M. S. Sutliff has helped in conducting the heats. The permission of General Electric Co. for this publication is gratefully acknowledged.

Jan 1, 1960

By Ellis H. Gates

BENEFICIATION of the manganese oxide ores at Three Kids Mine near Henderson, Nev., has evolved over a period of years. Commercial application of the process is on a secure basis, and an effective working hypothesis has been formulated to help solve the problems encountered in flotation. An outstanding difference between the Manganese Inc. operation and other flotation processes is the necessity for high recovery of slime mineral values. Part of the manganese minerals in the Three Kids ore deposit occurs as primary slime or as minerals that are easily slimed by grinding. High recovery of this slime portion is essential to an economic overall manganese recovery. The aim of much of the research at Manganese Inc. was to recover these slimed and finely ground minerals by flotation. Early Agglomeration Processes: Tunbridge' in 1880, followed by Everson2 in 1886 and Cattermole" in 1904, discovered that under certain pulp conditions precious metals and sulfide minerals could be agglomerated if enough soap or oil were mixed into the pulp slurry. These agglomerated particles, Which under ideal conditions ranged from 1/16 to 1/4 in. diam, were recovered by screening, tabling, and hydraulic classification. Even flotation by air occluded in the agglomkrate particles by vigorous stirring was suggested. Cattermole nearly succeeded in getting his process into commercial operation, but it was finally abandoned, presumably because he could nat compete with the low reagent requirements of the new agitation froth process. Since Cattermole's time Christensen in 1921, Borcherdt4 in 1926, and Chapman and Littleford- in 1934 have attempted to apply the principles of agglomeration. In the light of current research at Manganese Inc. on conditioning of pulp at high energy input levels, it is interesting to note the variety of equipment such as tumbling mills, mixing drums, and shakers described by Borcherdt in his patent to produce the agglomerated particles. Ore Characteristics: Manganese in the Three Kids ore occurs as a 'complex mixture of manganese oxides commonly Known as wad. The manganese minerals have Been identified as psilorflelane, hollandite, coronadite, and pyrolusite with minor amdunts of rhodonite and rhodochrbsite. The ppincipal gangue miherals are quaktz, opal, kaolinite, montmoril-lonite, calcite, gypsum, fcelesitite, and barite. Most of the mangandse ore minerals are either porous and sponge-like in structure or soft clay-like masses composed of fine grained mineral particles approaching the size range of colloids. Consequently the ore minerals from the Three Kids mine have relatively large surface areas and high void content per unit weight. The specific area of various manganese ore samples measured at the California Research Corp. laboratories ranged from 32 to 58 sq m per g. The great surface area and high void content explains in part the unusually high reagent consumption required in the treatment of this ore. Current Milling Practice: At Henderson6 he ore is crushed to —1 in. and ground with rod mills in a closed circuit with spiral rake classifiers and cyclones. Sulfur dioxide solution is added to the pulp as it leaves the grinding circuit, immediately followed by addition of a reagent mixture of soap, oil, and wetting agent in the form of an emulsion. The reagents are initially well mixed into the pulp during their passage through centrifugal pumps to the conditioning equipment. All reagents are added prior to conditioning. The intense conditioning or mechanical stirring of the pulp, in which large amounts of power are consumed, is the principal difference between the flowsheet used at Manganese Inc. and a standard flotation circuit. As much as 38 kw-hr of energy per dry short ton of ore in a pulp containing 18 to 23 pct solids is used for conditioning. After conditioning, the pulp passes to a flotation circuit that consists of one roughing stage, a scav-

Jan 1, 1958

By G. V. Jere, C. C. Patel

Chlorination of the various constituents of ilmenite by different chlorinating agents in presence of various reducing agents, have been considered on the basis of the standard free energy and standard enthalpy changes as a function of temperature. The standard free energy change considerations show that it is beneficial to chlorinate ilmenite by chlorine in the presence of carbon and also that iron constituent of ilmenite can be preferentially chlorinated by clzlorine, titanium tetrachloride or their mixture. These findilzgs have been corroborated from the published work. METALLURGICAL processes involving the use of titanium tetrachloride have gained in importance because of the use of the latter in the manufacture of titanium metal. Since ilmenite is more abundant in nature than any other titanium mineral, the future of the metallurgical processes depends on the utilization of ilmenite for the production of titanium tetrachloride. In these laboratories, investigations have been carried out on the chlorination of ilmenite under a variety of conditions.1'2 During these studies, it was noticed that 1) preferential chlorination of iron was effected at low temperatures (400° to 600°C) and at low carbon content (6 to 7 pct), 2) carbonyl chloride retarded the chlorination of iron oxides and titania perceptibly, while 3) carbon-tetrachloride, compounds of sulphur and some other catalysts favored the chlorination. Moles3 has found that oxides of iron are chlorinated in preference to titania at high temperatures, while wilcox4 has claimed the preferential chlorination of titania between 1200" and 1500°C. It has been shown in this paper that preferential chlorination of titania claimed by Wilcox is not likely to occur. Daubenspeck and coworkers5,6 have claimed the preferential chlorination of iron by chlorine or by a mixture of titanium tetrachloride and chlorine between 700° and 1050°C in the absence of carbon. Even when plain titanium tetrachloride is employed as the chlorinating agent, pascaud7 noticed the preferential chlorination of iron and other oxides. The purpose of this paper is to explain from thermodynamical considerations, the various chlorination reactions studied so far. ILMENITE CONSTITUENTS AND THEIR CHLORINATION PRODUCTS Although the general composition of the ilmenite mineral is represented as FeTiO,, most of the ilmenites found in nature have variable quantities of TiO2 (44.6 to 64 pct), FeO (4.7 to 36 pct) and Fe2O3 (6.9 to 28 pct).8 The higher content of ferric iron in ilmenites was attributed by Millerg to the presence of arizonite (Fe2O3.3TiO2). But the X-ray studies by Overholt, Vaw, and odd" have shown that arizonite is a mixture of haematite, ilmenite, anatase, and rutile. Except for the anatase, similar views have been advanced by Lynd, Sigurdson, North, and Anderson8 from magnetic, X-ray, and optical and electron microscope studies. The ilmenite ores can, therefore, be assumed to consist of mineral aggregates of ilmenite, rutile and haematite. From the free energy of formation of ilmenite (FeTiO3), it has been shown by Kelley, Todd, and King11 that ilmenite is stable even up to its melting point (1367°C) and would not undergo decomposition into its constituent oxides. Schomate, Naylor, and Boericke12 have found that in the presence of a reducing agent the iron constituent of ilmenite is selectively reduced. The reaction of chlorine with ilmenite in presence of a reducing agent can, therefore, be synonymous with that of the reaction of chlorine with the constituents of ilmenite, viz., TiO2, FeO, and Fe2O3. Most of the reaction products of chlorination of ilmenite in the presence of reducing agents will be in equilibrium with their dissociation products, depending on the temperature. The titanium tetrachloride is, however, quite stable up to 1500°C due to its covalent nature. The equilibrium for the ferric chloride system has been investigated by Kangro and Bernstorff, 13, schafer14 and Kangro and petersen,15 and the results are summarized in Fig. 1, curves a, b, and c respectively. From these results, it is clear that the ferric chloride disociates as follows: 324° to 700°C FeaCl6(g) ?2FeCl2(c) + Cl2(g) [1] 324°to 900°C Fe2Cl6(g) =2 Fe Cl2 Reaction [I] (curve a) occurs in the forward direction to about 6 pct at 400°C but falls off very rapidly with increase in temperature and beyond 600°C, it is practically negligible, perhaps due to the formation of the stable monomer, FeC13(g). As the temperature is further increased, the amount of FeCl,(g) in-

Jan 1, 1961

By W. S. Ayres

THE boiler from which these stay-bolts have just been obtained was that of the locomotive Catasauqua, Lehigh Valley Railroad, built at the company's shops, South Easton, Pa., in 1864. The iron is Lowmoor, and has been in use nearly ten years. The stay-bolts have become highly crystallized from some cause, and are very brittle, only requiring three blows of an ordinary machinist's hammer to break them. On the other hand, when annealed they are remarkably tough, as shown by the doubled sample. The majority of the broken bolts were found to be along the curve of the shell from a to c, Fig. 6. All of them were broken just inside the shell, and in no case next the fire-box. The fractures seen to have been of slow procedure, beginning at the top of the bolt, gradually working deeper and deeper until the pressure of steam overcame the tenacity of the remaining parts. Unequal contraction and expansion of the parts of the boiler seems in this case to be the only existing cause for a fracture. We cannot, from the data obtained, prove to an absolute certainty the manner in which the combined forces generated by the unequal contraction and expansion of the parts have arrived at their resultant work ; but we can, from these data and from existing circumstances, arrive at what seems to be a fair supposition, and thus at least anticipate the truth. The contraction and expansion in locomotive boilers has a large range between its extremes, and is very variable, both with reference to time and to their component parts. The shell and fire-box do not, perhaps, at any time, contract and expand at the same rate, nor proportionally ; but, on the contrary, owing to the great changes in temperature that take place both in the atmosphere around the shell, and in the fire in the fire-box, their condition is often changed suddenly, and widely from that which they just previously had. This racking tendency produces strains in the different parts, and it is fair to suppose that the continual motion of the two

Jan 1, 1874

By W. S. Ayres

The boiler from which these stay-bolts have just been obtained was that of the locomotive Catasauqtia, Lehigh Valley Railroad, built at the company's shops, South Easton, Pa., in 1864. The iron is Lowmoor, and has been in use nearly ten years. The stay-bolts have become highly crystallized from some cause, and are very brittle, only requiring three blows of an ordinary machinist's hammer to break them. On the other hand, when annealed they are remarkably tough, as shown by the doubled sample. The majority of the broken bolts were found to be along the curve of the shell from a to c, Fig. 6. All of them were broken just inside the shell, and in no case next the fire-box. The fractures seem to have been of slow procedure, beginning at the top of the bolt, gradually working deeper and deeper until the pressure of steam overcame the tenacity of the remaining parts. Unequal contraction and expansion of the parts of the boiler seems in this case to be the only existing cause for a fracture. We cannot, from the data obtained, prove to an absolute certainty the manner in which the combined forces generated by the unequal contraction and expansion of the parts have arrived at their resultant work ; but we can, from these data and from existing circumstances, arrive at what seems to be a fair supposition, and thus at least anticipate the truth. The contraction and expansion in locomotive boilers has a large range between its extremes, and is very variable, both with reference to time and to their component parts. The shell and fire-box do not, perhaps, at any time, contract and expand at the same rate, nor proportionally; but, on the contrary, owing to the great changes in temperature that take place both in the atmosphere around the shell, and in the fire in the fire-box, their condition is often changed suddenly, and widely from that which they just previously had. This racking tendency produces strains in the different parts, and it is fair to suppose that the continual motion of the two

By Walter Showak

The published phase diagrams for the copper-zirconium system1,2 indicate that the solid solubility of zirconium in copper is not accurately known. Studies made on relatively impure alloys by Pogodin, Shumova, and Kugucheva3 yielded a maximum solubility value of 1 wt pct Zr at the eutectic temperature. Allibone and sykes5 reported that an as-cast 0.2 wt pct Zr alloy is single phase at room temperature. Limited results obtained by Raub and Enge14 indicated that zirconium solubility in copper is less than 0.13 wt pct Zr at 940°C. Tn 1960, on the basis of a microstructural examination of several copper-rich Cu-Zr alloys, saarivirta6 placed the maximum solubility of zirconium in copper at 0.15 wt pct at the eutectic temperature, 980°C. The present note describes results obtained during a re-investigation of the Cu-Zr system for the purpose of accurately establishing the solidus and solvus curves and the eutectic temperature in copper-rich alloys. High-purity copper (99.99 pet) and zirconium (99.64 pet) consolidated reactor grade sponge were used to prepare several alloys, containing up to 2 wt pct Zr, by induction melting in graphite crucibles in vacuum and chill casting into a split steel mold. The melting procedure consisted of first melting the copper charge and then adding the bulk zirconium wrapped in pure copper foil. Chemical analyses were made of both the cold-rolled alloy ingots after homogenization at 925°C for 450 hr in evacuated quartz capsules and of small specimens which had been used in the phase diagram studies. 'The carbon content of each alloy was also determined and was found to be less than 0.001 wt pct in every case. Metallographic and electrical resistivity measurements were used as the primary methods for this investigation, although some thermal analysis studies were also performed. Heat treatments of all the alloys were carried out with the specimens wrapped in molybdenum or alloy foil (of the same composition as the specimen) and sealed in quartz tubes either in vacuum or under a purified helium atmosphere. Following high-temperature anneals for long periods of time, slight depletion of zirconium from the specimen surface was observed. Therefore, careful preparation of samples for microscopic examination and chemical analysis of the samples themselves was necessary to check the composition of samples used in determining phase boundaries. Points on the solvus curve were determined on quenched specimens by both isothermal reaction after solution heat treatment at 950°C for 8 hr and by isothermal annealing of alloy specimens at successively higher temperatures for times ranging from 24 to 500 hr. Liquation studies for positioning of the solidus and eutectic temperatures were performed by holding a pre-

Jan 1, 1962

By A. J. Mortlock

Cobalt and nickel have been diffused at tracer concentrations in gold at several temperatures in the range from approximately 700° to 950°C. The diffusion penetration profiles were determined by a serial sectioning technique in which the gold is first anodized and then the anodic layer is dissolved in acid. In this ulay sections as thin as 250A could be removed reproduci-bly. In all cases, the region close to the specimen surface was characterized by irregular behavior in the sense that the logarithm of concentration was not linear in the square of the penetration distance. In sotne cases, there zuas an indication of the operation of very slow dijfusion in this region, while in others the apparent diffusion coejj'icient was negative. Possible reasons for this anomalous behavior are briefly discussed. In recent years it has been found that the region close to the surface of a metal can sometimes exhibit anomalously slow diffusion characteristics relative to the interior of the metal. One of the best examples of this fact is the work of Styris and omizuka,' who showed that the apparent diffusion coefficient for zinc in the region withi: about 1 p of the free surface of copper was about ,,,, that at deeper penetrations. This result is particularly interesting, because it is free from the possibly complicating effects of low solubility of the diffusing tracer in the solvent metal. In the case of diffusion under conditions of low solubilitjr, interpretaticn of the results in terms of lattice diffusion is difficult because of the enhanced short-circuiting produced by segregation to dislocations.2'3 Measurements by Duhl et 1. suggest that cobalt diffusing in gold may also show a near-surface effect of this type. Once again the solubility is high, so that this result could be of great interest. However, the technique used for analyzing the diffusion penetration zones by Duhl, viz. the counting of residual gamma activity in the specimen following sectioning, appears to have indicated a near-surface effect in a parallel experiment on the self-diffusion of gold reported at the same time. The latter result is known to be spurious, since Kidson5 has demonstrated that self-diffusion in gold does not show this effect. Duhl et 01. also reported some measurements on the diffusion of nickel in gold, but failed to give any data for the near-surface region. As the solubility of nickel in gold is high, such data would also be of special interest. We, therefore, decided to conduct another set of experiments on the diffusion of nickel and cobalt in gold, using a sectioning technique that allows the individual sections to be assayed for solute content and thus gives direct determinations of penetration profiles. Also, by sectioning with an anodizing/stripping tech- nique, very thin layers can be removed and the region close to the surface studied in detail. MATERIALS The gold specimens were supplied as single crystal disks $ in. in diam by a in. high by Monocrystals Co. of Cleveland, Ohio. The gold itself was of spectro-scopic purity, i.e., better than 99.99 pct pure. METHOD Specimen Preparation. One flat end face of each gold crystal was spark planed with a Servomet spark erosion machine set for minimum spark energy. Following this treatment the crystals were preannealed for 2 to 4 days at temperatures of either 400" or 700°C. The three crystals preannealed at 700°C showed signs of recrystallization. The spark-planed end face of each crystal was then coated with the appropriate amount of 63i or 60 radioactive tracer. This deposit was laid down in a simple plating bath containing the as-supplied solution of the radioactive isotope as well as sufficient ammonium oxalate to saturate the solution. Some ammonium oxalate remained undissolved on the floor of the bath for this purpose. During plating further additions of ammonium oxalate were sometimes required to allow the plating to continue satisfactorily, perhaps due to passivation of the undissolved oxalate already present. The thickness of the deposited layer was determined by comparison of the apparent surface activity of the plated specimen with that of a similar specimen having a weighable deposit of the isotope on its end face. Correction for self-absorption of the radiation was made in this calculation. Annealing. The deposited crystals were annealed in a hydrogen atmosphere in sealed silica tubes. During this heat treatment they were supported, active face down, on optically flat silica plates. The temperature was measured with calibrated Pt vs Pt-10 pct Rh thermocouples, and the tabulated values can be taken to be correct to Z°C. All the crystals showed evidence of recrystallization following these heat treatments, suggesting that initially they may not have been good single crystals or had suffered strain during delivery. Concentration Profile Analysis. After annealing, the crystals were sectioned by the anodizing-stripping technique.6 The anodizing involved suspension of the specimen with its cylindrical axis horiz6ntal by a gold wire in a 200-ml beaker containing 1 M Hg304. A cathode in the form of a strip of gold sheet, 2 in. wide and positioned to be in contact with the curved side of the beaker, completely encircled the specimen. An anodizing current of 30 ma, corresponding to a current density of 5 ma per sq cm on the surface of the specimen, was passed for times ranging from 5 to 150 min depending on the thickness of gold to be removed; the solution was stirred continuously during this process. Following this treatment, the specimen

Jan 1, 1969

By Frank Rieber

THE study of earthquakes long ago developed the fact that by studying the travel times of the various groups of waves from the same earthquake, as received on seismographs at varying distances, major discontinuities in the earth's crust could be reasonably well defined. Using this original discovery, and adapting the mathematical methods originally devised in seismology for determining the depth below the surface at which such discontinuities occur, other investigators were able to develop a new branch of seismology which promises to be extremely useful in extending the boundaries of our information on local conditions below the earth's surface. As an outstanding example of the applications of this work, we have the so-called "seismograph" exploration of the Gulf Coastal region, which has resulted in the discovery of a large number of salt domes, from many of which oil fields may be developed. The original seismological investigations, from which different major discontinuities in the earth's crust were deduced, as well as these later successful experiments in locating salt-dome structures, involve relatively simple problems. In each case we are dealing with surface materials in which elastic waves will be propagated with a fairly definite velocity. Under this material we have something quite different, in which the elastic waves will be propagated with a much higher velocity. The transition from one medium to the other is likewise relatively abrupt. For example, in the Gulf Coastal region the sedimentary formations have a velocity of 6000 or 7000 ft. per sec., while the velocity of elastic waves in the cap rock of a salt dome may exceed 15,000 ft. per sec. Under such conditions, delineation of the formation is a relatively simple matter, and, furthermore, there is very little opportunity for ambiguous results.

Jan 1, 1928

Held at San Francisco, Cal., Thursday to Sunday, Sept. 16 to 19, 1915 COMMITTEES Arrangements CHARLES W. MERRILL, Chairman EDWARD H. BENJAMIIN H. C. HOOVER FRED `V. BRADLEY W. C. RALSTON ABBOT A. HANKS G. H. CLEVENGER Excursion and Accommodations ABBOT A. HANKS, Chairman E. T. BLAKE R. H. BEDFORD C. G. DENNIS FREDERICK BRADSHAW C. E. GRUNSKY, JR. EDMUND JUESSEN ARTHUR B. FOOTE F. A. KEITH GEORGE 0. BRADLEY CHARLES JANIN E. N. ENGELHARDT R. S. HASELTINE N. CLEAVELAND

Jan 12, 1915

By R. H. Hiltz, R. W. Douglass

Large-grain specimens of iodide titanium prepared metal-lographically were stain etched using the technique of New York University as modified by Watertown Arsenal Laboratories. Orientations of grains showing an abnormal response to stain etching were determined by back-reflection X-ray techniques. X-ray results showed that a-titanium grains, oriented such that their basal planes were parallel to the polished surface, have a slower reactivity to stain etching than any other orientation. Grains oriented such that their basal planes made small angles with the polished surface exhibited reaction rates between that of the true basal orientation and the normal rate. As the angle with the surface increases the reactivity increases up to a maximum angle of 14 deg. Basal planes making an angle with the surface of greater than 14 deg show normal reactivity to stain etching. These data, plus work on polycrystalline specimens, indicate that the oxidation rate of titanium might be reduced by correct alignment of crystal planes. ThE earliest observed phenomenon in the micrography of titanium was the occurrence of a grains which exhibited no birefringency. Even though a titanium possesses a hexagonal-close-packed structure and should be optically anisotropic, it can appear optically isotropic, when the crystal is so oriented that its intersection with the polished surface is perpendicular to the axis of symmetry. During the develoment of color staining techniques for titanium: it was noted that the a phase did not stain uniformly. Staining of specimens of commercially pure titanium resulted in a micro-structure of blue-colored grains, among which were randomly oriented a few grains exhibiting colors between the initial yellow and the final blue color. Under polarized light, these off-colored grains appeared to be optically isotropic. More intense study with polarized light, however, showed only the yellow grains to be isotropic. The intermediate colored grains exhibited weak birefringency, which at first glance is not detectable due to the strong birefringency of the surrounding structure. Aminoff2 and Straumanis3 have previously shown that in zinc the basal orientation is less reactive than other orientations. Leidheiser4 showed the same thing to be true for the hexagonal-close -packed configuration of cobalt. Thus, it would appear that the basal-plane orientation is responsible for the abnormality in stained titanium. Later work by Leidheiser5 on cobalt has shown that other planes besides the basal plane exhibited reaction rates slower than the normal rate. Reported planes were the (100), the (1011) and several planes making small angles with the basal plane. The last observance appears not to be due to the reactivity of the reported plane but due to the reactivity of the basal plane which is very close to being parallel to the surface. There are, then, two possible explanations for the range of colors observed in stain-etched a titanium. Since extensive research on the effect of orientation on surface reaction has failed to provide any definite trend, these two explanations are not adequate in themselves. Planes showing the retarded reactivity differ not only for different crystal structures but for metals of the same crystal structure and even for different reactions of the same metal. Tragert,6 Leidheiser,7 Tammann,6 and wagner9 have shown copper to exhibit retarded reactivity on the (111) plane. However, Leidheiser10 has shown that under other conditions the retarded reactivity of copper is associated with the (100)

Jan 1, 1960

By S. R. Zimmerley, John Gross

The method of measurement of surface on quartz particles was given in a previous paper.' With such a method the relation of surface produced in crushing quartz can be compared to the work in crushing without recourse to sieve sizing or microscopic measurement. In crushing, the work input must be known with a fair degree of accuracy. With crushers, rolls, ball mills, and similar apparatus the measurement of the work in crushing is subject to possible errors, due to friction in the transmission as well as in the machine itself. Moreover, relatively large quantities of material must be crushed to get an average figure. In the selection of a method of crushing, simplicity in design and operation was desired and this was most readily obtained by the use of a free-falling body. A description of the apparatus embodying this principle is given herewith. The Crushing Device The apparatus used is shown in Fig. 1 and in cross-section in Fig. 2. The material to be crushed is placed in the crushing chamber C in the steel mortar M. The mortar is 3 in. dia. by 3 in. high. Two mortars are used, one having a crushing chamber 1 in. dia. by 36 in. deep, with a capacity of 4 g. of quartz, the other having a crushing chamber 1 1/2-in. dia. by % in. deep, with a capacity of 12 g. of quartz. The position of the mortar is adjusted by means of three centering screws A. The steel plunger P, which fits neatly into the chamber, is placed on top of the material to be crushed. Plungers of different lengths were tried and as they were found to give practically identical results the length adopted was equal to the depth of -the chamber. The mortar rests on a solid steel base B but is separated therefrom

Jan 1, 1930

By K. G. Kreider, J. H. Brophy, J. Wulff

The technology of nickel-activated sintering of tungsten powder has been successfully applied to the densification of plasma-sprayed tungsten. Nickel was added by infiltration in a zinc solution followed by evaporation of the solvent. After sintering one hour at 1300°C density 95 pct of theoretical and transverse rupture strength of 74,000 psi were obtained. Shrinkage was found to be anisotropic and the mechanism of densification was comparable to that found in the nickel-activated sintering of tungsten powder. 1 HE use of a plasma spray gun for the fabrication of massive tungsten parts has become increasingly interesting. Applications now exist where a deposit in the as-sprayed condition is satisfactory. However, these deposits are generally characterized by a lamellar anisotropic microstructure containing 15 pct porosity of which, typically, two-thirds is open to the surface. Mechanically, the as-sprayed deposits fail at relatively low stress levels with a biscuit-like fracture. As a result of these problems the possibility of improving structure and strength by sintering treatments subsequent to spraying is particularly attractive. Preferably this sintering treatment should be adaptable to large bodies of sprayed metal. The similarity between the as-sprayed tungsten structure and that of a powder compact suggests that the relatively low-temperature activated sintering technique1 might be profitably employed in the densification of plasma-sprayed tungsten. It was the purpose of the present investigation to develop a technique for introducing the nickel-activating agent into the sprayed structure, to evaluate the amount and mechanism of densification obtained as a function of time and temperature, and to obtain an indication of the relative strength before and after sintering. EXPERIMENTAL PROCEDURE Powder used for spraying was purchased from the Wah Chang Corp. in several size fractions ranging from an average size of 4 to 150 . These powders were sized further for an explicit study of the influence of average feed size on densification. All powders were dried at 200°C before use. Spraying was accomplished with a Plasma Flame unit manufactured by Thermal Dynamics Corp. Several modifications of the unit were helpful in conducting the investigation. A variable speed auger feed mechanism coupled with the carrier gas mecha nism facilitated the use of fine particle sizes. A coil of ten turns of copper tubing in series with the arc power and concentrically would around the nozzle improved nozzle life and extended the range of operating currents available. The function of the auxiliary coil was to cause the arc to spin and to prevent impingement at only one point in the nozzle. Normally air sprayed deposits were made with an arc maintained at 400 amp at 50 to 70 v. The arc was blown by a gas mixture containing from 5 pct H, 95 pct N for the finest powder feed sizes ranging to 20 pct H, 80 pct N for the coarsest size. The flow rate was maintained at 100 cu ft per hr NTP through a nozzle of 0.25 in. ID. When apraying in air, the powder stream was directed toward an aluminum substrate for ease of mechanical removal of the deposit. The substrate was cooled by diverting the plasma flame with an air jet, and a second jet was directed on the deposit surface. In this configuration a gun-to-work distance of 2 to 3 in. was found to be satisfactory. Fig. 1 represents a typical as-sprayed deposit micro-structure. Laboratory studies of protective atmosphere spraying were carried out in cylindrical chamber 8 in. in diam by 18 in. in length. In operating the nozzle attached to such a chamber, particular care was required to avoid nozzle burn out due to reduced gas flow. The structure and density of the chamber sprayed deposits varied over wide ranges depending on substrate temperature. For the purposes of this investigation, flat deposits were made approximately 2 in. sq by 3/8 in. thick. From these deposits individual samples were cut an ground to a rectangular shape typically 1 1/2 in. by 1/8 in. sq such that the long dimension was perpendicular to the spraying direction. For the study of shrinkage anisotropy deposits up to one inch thick were produced. From these, rectangular samples were cut having a longer dimension parallel to the spraying axis. Prior to the addition of activating agent, the samples were deoxidized in hydrogen at 800°C for 20 min. No detectable dimensional or microstructural change was observed after this treatment. The addition of nickel was accomplished by infil-

Jan 1, 1963

By H. Sherman

The general curtailment of activities, so marked in 1931, was continued and intensified in 1932 and although production was maintained at approximately the level of the previous year, 1932 was chiefly characterized by the virtual cessation of drilling in many of the proven fields, a further decline in wildcatting activities, particularly in the Maracaibo Basin, and the relinquishment of large blocks of unfavorably located acreage. A total of only 60 wells was completed during the year of which six were wildcats, while at the same time concessions aggregating approximately. 3,222,000 acres were renounced and reverted to the National Government. The maintenance of production at the previously established level was made possible through the large potential built up by drilling in previous years and by a gradual increase in pumping and gas-lift installations. Towards the end of the year there was a slight but perceptible tendency towards increased drilling in certain of the proven fields. Total production for the year came to 118,076,000 as compared to 118,418,000 bbl. for 1931, while exports amounted to 114,758,000 as against 116,683,000 bbl. in 1931. Table 1 shows production and exports and the average rate per day for the first half of 1932 as compared to the second half. Table 1.—Petroleum Production and Exports in 1932, Venezuela (Barrels of 42 Gallons) Production Rate per Day Export Rate per Day I January-June............ 61,943,000 1 390, 347 July-December.......... 56,133,000 305,071 50,788,000 276,022 Total.........,....... 118,076,000 322,612 114,758,000 313,546 During 1932 the number of active vessels comprising the Lake Maracaibo fleet of shallow-draft tankers was still further reduced, some being temporarily laid up and some transferred to service in other coun-

Jan 1, 1933

By R. Rocca, M. B. Bever

THE adiabatic elastic deformation of a body is accompanied by a change in temperature. This phenomenon is known as the thermoelastic effect. Under adiabatic conditions the temperature of a metal bar is decreased by an elastic elongation and is increased by an elastic compression. All materials which elongate on heating behave in this manner. The sign of the thermoelastic temperature change is reversed for the few materials which have a negative coefficient of thermal expansion. The following equation for the thermoelastic effect can be derived from fundamental thermody-namic theorems, as shown in the Appendix: dT8 =-a1/cs T dss [1] Cs In this equation, T is the absolute temperature, S is the entropy, a, is the coefficient of linear thermal expansion, cs' is the heat capacity per unit volume at constant stress and s is the stress (positive in tension). Eq 1 can be applied to small, but finite changes in stress in the following form: ?Ts =- a1/cs T?ss [2] The sign of the temperature change AT is opposite to that of the change in stress s for materials which have a positive coefficient of thermal expansion. Eq 2 has been verified for many different materials and stresses at room temperature. No previous publication appears to have been devoted to an in- vestigation of the thermoelastic effect over a range of temperatures. Review of Literature Lord Kelvin (W. Thomson) presented a general theory of the thermoelastic effect in 1851' and later applied it to a solid, subject to an arbitrary system of stresses'. His analysis was based on a cycle of isothermal and constant-strain transformations and led to Eq 2 above. Even today, one of the clearest expositions of the thermoelastic effect is found in Lord Kelvin's article on elasticity in the Ninth Edition of the Encyclopedia Britannica (1878). R. ROCCA, Junior Member, and M. B. BEVER, Member AIME, are Research Assistant in Metallurgy and Associate Professor of Metallurgy, respectiuely, Massachusetts Institute of Technology, Cambridge, Mass. AIME New York Meeting, Feb. 1950. TP 2760 E. Discussion (2 copies) may be sent to Transactions AIME before APT. 1, 1950, and is scheduled for publication Nov. 1950. Manuscript received Oct. 15, 1949.

Jan 1, 1951

By F. Keller, A. H. Geisler

Some of the important changes that take place in the structure of aluminum alloys are largely submicroscopic in character. This is especially true of the changes that accompany age-hardening and recrystallization. Although improved metallographic practices have been helpful in indicating some of these changes indirectly, results are limited by the resolving power of optical microscope lenses. The electron microscope, however, provides a new and important means for investigating the fine structure of metals in a range not possible heretofore. It is anticipated that this microscope will yield new and useful information to metallurgists when suitable techniques are developed to utilize its very high resolving power. Several unique methods have been devised to permit the examination of the structure of opaque samples by the electron microscope. These are all based on the principle of producing a very thin film that represents the prepared surface of the opaque metal sample, which can be examined in the transmission microscope; however, the available methods fall into three categories, depending on the manner in which the film is obtained. With the oxide-film method developed by Mahl3-17 a very thin surface layer of the metallographic sample is converted into oxide by a thermal, chemical or anodic treatment. After removal from the metal sample by one of the special techniques described by Evans,19 this oxide film is examined in the electron microscope, and is found to portray the structure of the original metal surface. Films formed on aluminum,8,17 nickel,7 iron 3,8,9 and a nickel-beryllium alloy" by heating; films formed on iron 8.9 by chemical action; and films formed on aluminum3-16 by anodic oxidation, have been examined. The other two are more recent methods developed principally in this country; they consist in making the thin film in the form of a mold or replica of the surface contour of an etched sample. With the negative replica method the thin film is made directly on the sample; with the positive replica method it is made on a negative reproduction of the sample. With both methods, variations in the contour of the metal sample, caused mainly by etching, produce variations in the thickness of the surface replica. Because of the direct dependence of the amount of scattering of the illuminating electrons upon the thickness of the film penetrated, only the variations in thickness of the replica are responsible for tones in the electron image. Negative replicas are made by forming a thin film of some suitable material directly on the polished and etched metal sample, and derive their name from the fact that after removal from the sample they have the high and low points in the sample reversed, as shown in Fig. I. Nega-

Jan 1, 1944

By Francis C. Blake

Although the use of gaseous fuel in blast-furnaces has been often proposed, I hope the description of a very simple, yet practical and valuable, application of natural gas to the smelting of lead-ores and residues, at the works of the Pennsylvania Lead Company, will prove interesting. In May, 1886, directly after replacing the use of bituminous coal at the above works by that of natural gas, half-inch pipes from a branch gas-main were inserted directly into the tuyeres of a lead blast-furnace, and through these pipes gas was delivered into the furnace, with the air-blast at a pressure a little more than double that in the tuyere-pipes. At the same time the blast-pressure at the tuyeres was increased by an amount estimated to give a sufficient air-delivery when mixed with the gas-supply. The amount of gas delivered to the furnace is easily regulated by stop-cocks at each tuyere, and is under the immediate control of the furnace manager. Upon the introduction of gas into the tuyeres of the furnace the coke charged at the mouth was reduced 30 per cent., this being the amount of coke which I thought could be advantageously replaced by gas. This first estimate has proved to be very close to the working results, though probably the average gas-consumption corresponds to a little less than 30 per cent. of the former coke used. The proportion that we use varies, with the nature of the furnaceburden, between 20 and 40 per cent. of the total fuel. We have used 60 per cent. of gas; but there is difficulty in keeping a cool furnace-mouth when the proportion is so high. With some residues, notably metallic drosses containing some zinc, we have found it best not to use over 20 per cent. gaseous fuel. The percentage used with ore-charges has generally been higher than that used in smelting the higher-lead charges of residues from our refining works. It results from this use of natural gas that the temperature of the hearth is under almost immediate control, and, for this reason chiefly, a cleaner and more uniform slag can be run, and the furnaceworking can be made more nearly independent of the effects of atmospheric conditions or the variable moisture in the furnace-burden.

Jan 1, 1887

By C. D. Thurmond

Jan 1, 1968

By C. McDermid

At the request of Mr. C. McDermid, Secretary of the Institution of Mining and Metallurgy, Salisbury House, London, E. C., England, the following reports of standardization committees are here republished. Mr. McDermid invites members of-the American Institute of Mining Engineers to write him and express their opinion of the various proposals made by the committees. COPY OF THE REPORT OF THE WEIGHTS AND MEASURES STANDARDIZATION COMMITTEE OF THE INSTITUTION OF MINING AND METALLURGY, as adopted by the Central Standardization Committee; Dec. 20, 1906, and submitted to the Council, Jan. 16, 1907.

Mar 1, 1907