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By MARSHALL D. DRAPER

CHINA is one of the large producers of the world's tin. About 95 per cent of the total Chinese production comes from the Kotchiu district in the southern part of the province of Yunnan. Yunnan occupies the southwestern part of China, bordering on Burma,. Siam and. French Indo-China. From the British port of Hong Kong,' small steamers sail southwest at about four-day intervals, reaching Haiphong in French Indo-China in two or three days. This, one of the principal ports in Indo-China, is a modern French city of some 50,000 population which, with its tropical surroundings, has much natural beauty. It is a few miles from the sea on the Red River, which has its source in China. Both at Haiphong and Hanoi, the capital of Indo-China, sixty-three miles north of Haiphong and also on' the Red River, there are foundries, shipyards, machine shops, cement and brick plants and various similar industries.

Jan 1, 1931

By C. G. Dunn

WITH respect to theories of recrystallization in metals plastically deformed, it has been said that the present status of this subject is far from satisfactory.1 It may also be said that before any mechanism of recrystallization for metals and alloys can be set forth in a satisfactory manner, there must be made available considerable data on orientation changes that occur during the deformation and recrystallization processes. Although extensive data have been published on recrystallization in single crystals and in polycrystalline specimens, more results of a type that can be classified according to simple orientation changes would be desirable in this complex field. It might even be said that before classifications are made according to types of orientation changes, it may be possible to classify a considerable amount of data into certain kinds of orientation states if groups of common or nearly common orientation occur. Methods for computing the probability of occurrence for various types of groups have been published2 and it has been pointed out in particular that it should be possible to analyze orientation data for high-order twin relationships between old and new grains even when agreement is not at all exact. In this connection, work on recrystallization in silicon ferrite reported in a paper concerned with complex groups of annealing twins' indicated that some data were consistent with primary nucleation occurring according to a second-order or a third-order twin transformation. However, further work in this latter direction was definitely needed. It is, therefore, the purpose of the present paper to report data and analyses for primary nucleation in silicon ferrite following small deformations that have been carried out at the Pittsfield Works' Laboratory of the General Electric Co. Analyses have been made with the aid of standard groups of twins that are reported elsewhere .4 PREPARATION OF SPECIMENS AND EXPERIMENTAL PROCEDURE The material used in the present investigation was taken' from the same heat of steel as that used in a prior report.3 The finished strip in both cases was made by the Allegheny-Ludlum Steel Corporation according to methods that produce a high degree of preferred crystal orientation. Samples with large grains had the following composition: 3.45 per cent Si, 0.003 C, 0.008 P, 0.020 S, 0.075 Mn, 0.031 Al and 0.072 Cu. Thickness of specimens was 0.012 inches. Plastic deformation was produced by cold-rolling the samples on a mill with

Jan 1, 1945

By H. F. Bishop, F. A. Brandt, W. S. Pellini

M. S. Fisher and D. R. F. West (Imperial College of Science and Technology, London, England)—It may be of value to compare certain features of the results recorded in this very interesting paper with those of an investigation11 involving determinations of temperature gradients and rates of solidification of steel blocks of 3 in. sq section, cast horizontally in sand molds, some of which contained chills. Castings in plain carbon steels containing up to 0.8 pct C were made and, throughout this range of compositions, both inverse-rate and direct cooling curves, obtained from thermocouples placed within the mold cavity, showed a major arrest, the temperature of which was taken as the "effective liquidus" for the particular steel in question, solidifying under the conditions of the investigation. At the completion of the arrest, the curves showed a comparatively rapid de- crease in temperature. Some of the steels investigated lay within the peritectic region, and a second arrest at 1485°C was detected. In Fig. 15, which shows the effective liquidus temperatures, the limit of the 8 + liquid field has been placed at approximately 0.5 pct C. In inverse-rate curves corresponding to the thermal center of each casting, there was always a discontinuity, viz: an abrupt change of slope, at a temperature about 10 to 20°C below the "liquidus arrest," after which there seemed to be no significant irregularity in the rate of cooling. Curves corresponding to other positions in the casting generally showed some irregularities below the main arrest, probably as a result of heat flow from the solidifying interior. Even the reproducible discontinuity in the curves for the central positions appeared to have no theoretical or practical significance, though it probably corresponded to a stage in the solidification process at which only a relatively small amount of interdendritic liquid remained. Its temperature, rela-

Jan 1, 1953

By B. C. Wonsiewicz, G. Y. Chin

THE presence of deformation bands in cold-worked metals is known to influence the development of deformation textures1 but has not been considered in any theoretical treatments. At the present time the most rigorous theory of deformation textures appears to be based on Taylor's concept of homogeneous deformation of a crystal within a polycrystalline aggregate.' For each crystal the Taylor theory allows the operation of several equivalent combinations of five or more slip systems. Hence deformation bands can arise from the operation of a separate combination of slips in each of several portions within a crystal. On the other hand, a second type of band may occur as a consequence of slip on systems other than those selected on the basis on homogeneous deformation. This type appears to be associated with crystals of symmetrical orientations, such as the [loo] and [lll.] axial orientations in drawn wires of fcc single crystals studied by Ahlborn.3 In this note we propose a simple mechanism of deformation banding of the second type, and compare the theoretical results for wire drawing of [loo] and [Ill] with Ahlborn's observations. In outlini the model requires that the work to accomplish a given overall shape change by banding be less than or equal to the work to accomplish the same change by homogeneous deformation. While the work by homogeneous deformation, WH = ?T ;dri, can be calculated exactly by the equivalent methods of Taylor2 or of Bishop and Hill,4 the work by banding, WB, is less certain. The latter consists of 1) Wi, work by slip within a band, 2) Wb, work associated with formation of a boundary between bands, and 3) Wc, work to correct the difference in shape change arising from banding and homogeneous deformation. The Wi term can be evaluated explicitly for a band with an assumed set of slip systems, but a satisfactory analysis of Wb and Wc has not been obtained. Since WB = Wi + Wb + Wc WH, for banding to occur, however, a necessary condition is Wi = WH . Hence it seems reasonable to choose a band with the lowest value of Wi among competing bands consistent with Wi = WH, and then minimize Wb and Wc by arranging the physical configuration of the selected band. Wc is minimized by combining neighboring bands such that their net strain matches the macroscopic strain as closely as possible, and Wb is minimized by enforcing strain compatibility across the boundary between two neighboring bands, similar to the case of a grain boundary.5 It is realized that this procedure is not completely satisfactory, but it does seem to explain Ahlborn's observations reasonably well. The procedure is now outlined for the two corner orientations. a) [l00]. Fig. 1 shows a (100) stereographic projection. The results of the Taylor analysis for axi-symmetric flow by homogeneous deformation6 show that, while [loo] itself is unstable, the rotation of the tensile axis will nevertheless be confined to within about 15 deg from [loo]. Alternatively, less work may be expended by banding with slip on a pair of systems with primary-conjugate relationship, e.g., (ll1)[10l.I + (li1.)[110]. The latter represents minimum Wi for all possible bands.* Since there are four symmetrically

Jan 1, 1970

By Theodore W. Robinson

WHEREVER the amount of work renders it practicable the plan of using permanent standard solutions, in connection with the colorimetric carbon test, affords such manifold advantages that it is to be strongly recommended. That it has not attained a wider and more general application, is mainly due to the fact that, as the method is generally employed, the difficulty attending the production of the colors, and their doubtful stability when produced, have been only too evident to those who have undertaken their composition. The old method of using standard solutions made from sugar, coffee, etc., has always been hampered by the tendency of the colors to change upon exposure to the light, and the consequent liability to serious error, unless they are closely watched. Appreciating these difficulties, while recognizing the desirability of permanent colors, Mr. Magnus Troilius, at the suggestion of Prof. F. L. Erkmann, investigated the properties of cobalt, copper and ferric chlorides, with the view of determining their efficacy in the production of standard solutions. His results, as obtained, seem to have been satisfactory, but his treatment failed to eliminate many of the objections that have rendered the use of organic colors undesirable. The

Jan 1, 1888

By AIME AIME

MICA is perhaps our No. 1. strategic mineral problem because of its large requirements in a variety of equipment for use in the military services, and because the principal source of this material has heretofore been British India, a source now threatened partly because of distance and lack of ships. [Block mica and bauxite were added to the "most critical" list published by the W.P.B. on Nov. 6.] No satisfactory substitute has yet been found for most of the uses of mica, which largely involve electrical insulation. Brazil is now our nearest and best major source of this material. No splitting plants have yet been established there but in 1941 we imported about a million pounds of block mica from that country and in 1942 that quantity will be considerably exceeded. In Brazil, mica is found almost exclusively in the pegmatite dikes along the mountain range bordering the eastern part of Minas Gerais. A belt, roughly 180 miles long by 100 miles wide, extends from Theophilo Ottoni to Carangolo. The principal mica-mining districts in this belt are the Governador Valladares area to the north and the Espera Feliz district to the south. The dikes are usually 10 to 50 meters wide and a mile or two long and intrude the old metamorphic schist formation. They are weathered and easily mined.

Jan 1, 1942

By H. B. Heller, T. J. LaChapelle

Phosphorus nitride has been used as a diffusant for introducing phosphorus into silicon under various conditions. It has a temperature -dependent rate of decomposition beginning in the 500°C range, increasing very rapidly above 1000 C, producing gas -eous phosphorus and nitrogen. Best control was obtained with a two-temperature arrangement, with silicon at the proper higher diffusion temperature. It is an easier compound to use than the usual P2O5 because it is nonhygroscopic and yields temperature-controlled surface concentrations together with excellent final surfaces. Surface doping nearly as high as that produced by phosphorus pentoxide has been observed for sources at 850" to 900°C. Reproducible high sheet resistances were obtained by using slow flow rates (1 linear in. per min) and staggered-baffle gas mixing with the nitride at 550°C. Both inert gas (argon, nitrogen) and oxidizing ambients have been examined. Oxygen reacts to produce anhydrous P2O5, consuming the source at a rapid rate. Nitrogen, except for short diffusion times, suppressed the dissociation reaction and sometimes produced inferior surfaces. Argon appears to be a more useful ambient. PHOSPHORUS is a common impurity atom which may be introduced into a semiconductor lattice to create a p-n junction or an nn contact region. Various investigators1-4 have described techniques which can be used with either elemental phosphorus or certain of its compounds. This paper discusses a newly available compound of phosphorus, phos- some processes silicon wafers are precoated with a phosphate glass which acts as the doping source. Although a nonoxidizing form like elemental phosphorus or a phosphine can be used, most diffusion methods usually involve the use of phosphorus pentoxide. Because of the rapid volatility of this compound, a two-step process is often used, combining a gaseous deposition to introduce a predetermined quantity of phosphorus into the silicon with a later redistribution to obtain the desired distribution and surface concentration. Such a process usually involves predepositing phosphorus at surface concentrations greater than 1020 cm-'. At such doping levels the phosphorus-diffusion coefficient appears to be strongly concentration-dependent.596 Distribution profiles5'9 for these high concentrations of phosphorus do not follow Fick's laws, having extended subsurface regions which appear electrically to be nearly uniformly doped with ionized impurity atoms. Radioactive-tracer experiments also show near-surface anomalies in the distribution profile. Additionally, it has been shown1' that the introduction of very high surface concentrations of impurity atoms into silicon (a step necessitated by the subsequent lowering of concentration during the redistribution) creates dislocations, even in material having no dislocations originally. For device fabrication the use of oxide masking introduces certain difficulties and limitations.7'8 The standard practice of using phosphorus pentoxide as an impurity source adds other problems to these because of the speed and ease with which this compound reacts with moisture present in any gas in contact with it. In fact, P2O5 is one of the fastest and most effective drying agents for gases. Because it is such an excellent desiccant, completely anhydrous phosphorus pentoxide is difficult to obtain and is even more difficult to keep dry. Adequately dry gloved boxes must be used for storage and transfer of the chemical. The presence of even traces of moisture will cause formation of phosphoric acids which, during the high-temperature diffusion, results in polyphosphoric acids of variable composition. Such reaction by-products end up as gradually accumulating viscous fluids in the cooler parts of the diffusion furnace. The calculation of the final solute distribution for

Jan 1, 1964

The Delegation of American Engineers constituted by the American Institute of Mining and Metallurgical Engineers, the American Society of Civil Engineers, the American Society of Mechanical Engineers, and the American Institute of Electrical Engineers, that visited France in December, 1918, in acceptance of the invitation extended by the Congrés General du Genie Civil consisted of the following: Representing the American Society of Civil Engineers, Major James F. Case, past president, Geo. F. Swain, vice-president, Nelson P. Lewis, treasurer, Geo. W. Tillson, past director, Geo. W. Fuller, director, A. M. Hunt. Representing the American Society of Mechanical Engineers, president, Chas. T. Main. Representing the American Institute of Electrical Engineers, past president, L. B. Stillwell. Representing the American Institute of Mining and Metallurgical Engineers past-president, E. C. Spilsbury. The delegation organized on the way over by the choice of Major James F. Case as chairman, and Geo F. Swain as secretary. On arriving at Bordeaux, the Delegation was met by Mr. S. D. Brown, associate member of the American Society of Civil Engineers; and on its arrival in Paris it was joined permanently by the following attaches: Captain P. Charton, of the French Engineers, Delegate of the Commissariat-General to accompany the Delegation and serve as liaison officer; Captain Carpenter of the American Army; and Mr. Geo. Herdt, representing the Society of Civil Engineers of France. The object of the visit was to discuss with the French engineers the large engineering, problems now facing France. Engineering problems in their restricted technical sense came up for discussion practically not at all, for the French do not need advice nor assistance along strictly scientific lines. It was in the -larger and economic aspects of engineering, to aid in building up the industries and commerce of France, that our French associates desired to learn from the experience of the American Delegation.

Jan 9, 1919

RAYMOND M. Howe (author's reply to discussion*).-Dr. Unger states that magnesite will hardly supersede dolomite in fettling after a heat; that it is hard to believe a slag composed of oxide of iron containing about 6 per cent. of phosphorus is the active corroding, agent in a boil in a furnace; and that boiling cannot be said to be the result of the chemical action of a high-phosphorus slag on a basic bottom. These are well-established facts that no one would venture to question. The authors were misinterpreted in the statement that "in the summary, it is claimed that magnesite low in lime, or of greatest purity, ranks first in resistance to slaking," etc. On the contrary, the position has been taken throughout that while a low lime content is advantageous, the presence of several per cent. of iron oxide (an impurity), is necessary in order to confer the proper bonding and sintering properties in dead-burned grain magnesite to be used for furnace hearths. We cannot subscribe to the view that pure magnesia is no better fitted for a refractory than pure lime,' nor that the pure natural varieties of magnesite; such as Grecian or Washington, must necessarily be burned with silica and oxide of iron to produce a satisfactory material. On a small scale, pure magnesia has been satisfactorily used as a refractory in the form of crucibles. In the production of dead-burned grain magnesite from the Grecian or Washington mineral, iron oxide is added but the addition of silica is neither customary nor desirable. It is possible to manufacture brick of good quality from both the Grecian and the Washington material without adding either silica or iron oxide, providing they are burned at a sufficiently high temperature. This is regularly done on a commercial scale both in America and abroad when brick of. exceptionally high refractoriness or special purity are desired. The following analysis is of an English brick of Grecian magnesite which is extremely low in all impurities.1

Jan 6, 1919

By S. R. Maloof, W. R. Mitchell, J. A. Mullendore

Preliminary experimental evidence is presented to show that the metallic impurities aluminum, iron, and silicon, and beryllium oxide as found in commercially pure hot-pressed beryllium powder can be reduced to lower Concentrations by Zone -Purification techniques. The reduction in the concentration of aluminum to extremely low levels (10 PPm) is noteworthy, since earlier work demonstrated that aluminum is a major factor contributing to the hot-tearing of beryllium during fusion welding. On the basis of present findings, a method is suggested for producing beryllium metal of improved weldability. EXPERIMENTAL research now being conducted on the purification of beryllium indicates that several of the metallic impurities and beryllium oxide can be reduced to lower concentrations by employing standard horizontal zone-refining techniques. For the preliminary work, commercially-pure hot-pressed beryllium having a purity of 97.84 pct was used. The chemical composition is given in Table I. The hot-pressed beryllium was machined into bars 5/8 by 5/8 by 4 to 6 in. in length. Beryllium-oxide boats which had been conditioned by prior heating in a vacuum of 10"5 mm of Hg at 1100°C for 3 hr were used to hold the beryllium while it was zone melted. The boat with its charge, along with a smaller beryllium-oxide boat containing scrap beryllium to be used for gettering purposes, was loaded into a quartz tube and evacuated to 10-6 mm of Hg. Alter alternately evacuating and flushing three times with purified argon, the furnace tube was backfilled to a pressure of 1/6 atm of A and sealed off by means of a vacuum-tight stopcock. It was then removed from the pumping equipment and mounted on the traveling carriage of the zone-refining apparatus. Heating was accomplished with a 10 kw 450 kc induc- tion heating unit using an induction coil consisting of two turns of 3/16-in. diam copper tubing. Before starting to zone melt, the atmosphere in the furnace tube was gettered by heating the scrap beryllium in the smaller boat to above its melting point and holding at temperature for several minutes. The carriage was then shifted so as to locate one end of the beryllium ingot in the large boat within the induction coil. A molten zone approximately 3/4 to 1 in. was established by loading directly into the ingot. The molten zone was moved very slowly along the length of the ingot. Before each pass was made the procedure for evacuating, flushing, and backfilling, and so forth was repeatedI' Speeds of 1 1/2 and 3 in- per hr were used with up to twelve zone passes. The appearance of a typical zone-refined ingot is shown in Fig. 1. After zone refining, the grains in the ingot appear to be elongated in the direction of zone travel, whilst before, they are essentially equi-axed. A microexamination revealed the presence of a network in the beryllium grains as seen in Fig. 2. Laue spots in back reflection pictures taken of the sample were not sharp, indicating the presence of subgrains in the structure. As can be seen, however, many of the network boundaries cross beryllium grain boundaries. It has been shown by Martin and Moore1 that beryllium solidifies as a bcc structure which then transforms to the hexagonal structure at about 1250oC.It is believed that the observed network is merely the outline of the bcc structure which formed from the melt and are not subgrain boundaries. In order to eliminate surface contaminants, approximately 1/16 of an inch of material was removed from the outer skin of each ingot after zone refining.

Jan 1, 1962

By J. J. Pye, J. B. Drew

Mzasurements of the surface diffusion coefficients of metals have been made. Diffusion profiles for the Ag-Ag system were obtained by means of a radioactive point source and a precision auto-radiographic technique. The activation energy for silver self diffusion (=8.1 kcal per mole) is lower than that previously reported (-10 kcal per mole) on poly crystalline wire by Nickerson and Parker. The bresent data indicate an effect due to parasitic volume diffusion at temperatures above 500°C. RELATIVELY few measurements have been made of the surface self-diffusion coefficients of metals. Nickerson and arker' measured the diffusion of silver over the surface of poly crystalline wires and estimated that the activation energy was 10.3 kcal per mole. Winegard and chalmers2 carried out measurements on both polycrystalline and single crystal surfaces but did not report a value of the activation energy. They found, however, that at temperatures between 250" and 400°C the diffusion coefficients were on the order of lo-' sq cm per sec and that there was an acceleration of the migration of silver on the polycrystalline sample when a change of surface shape occurred. Winegard and Chalmers used an autoradiographic technique, hereafter designated ARG, and Nickerson and Parker used a surface scanning geiger counter in order to determine the diffusion profiles. More recently, Hackerman and simpson3 measured the surface self-diffusion coefficient of copper at a single temperature (750°C), and the value of the diffusivity (- 10-5 sq cm per sec) is in agreement with that given by jostein from his thermal grooving measurements. This paper reports the results of an investigation of the surface self-diffusion coefficients of silver over a large temperature range and describes the adaptation of autoradiographic (ARG) techniques for the determination of diffusion profiles obtained from a radioactive point source. EXPERIMENTAL PROCEDURE The experimental procedure is a modification of the method employed by Hackerman and simpson3 in their measurements on copper. A brief description of their technique is as follows: A radioactive needle which sinters to the surface during the diffusion an- neal serves as the source of diffusing atoms. After the diffusion run the needle is removed and the surface is scanned with a shielded counting arrangement. The diffusion profiles reported in this paper were obtained by a modification of the above procedure which employs a precision ARG technique. Previous investigations in this laboratory and elsewhere51B have shown that under carefully controlled developing conditions and by the use of calibration sources a linear relation exists between the concentration of the isotope and the photographic density for values below unity. The use of ARG under these conditions has advantages over the counter scanning method in that cumbersome shielding and requirements for great mechanical precision of the scanner are eliminated. Also the ARG gives a complete picture of the surface which is advantageous in studies of anisotropic diffusion. A recording microdensitometer having a 0.1 p wide slit was employed. At low temperatures the disturbing effects of subsurface radiations are negligible. The diffusion anneals are carried out in the cell shown in Fig. 1. The needle is formed by grinding down a 1.0 mm rod of high-purity silver until a tip of 0.2 mm radius or smaller is formed. This tip is plated withA"' which becomes the source of the diffusing atoms that are detected by ARG. The needle carrier and the crystal holder, Fig. 1 are constructed of quartz and ports are provided in the holder pedestal which allow free vapor circulation ((2.0 oz) and the carrier apron fits snugly over the crystal holder cap, insuring that the needle does not move and scratch the surface. Temperatures are provided by a stabilized tubular furnace which can be quickly positioned around the cell, thus bringing the crystal up to temperature in a time that is short compared to the diffusing times. The diffusion anneals range from 2 hr for the high-temperature samples to about 25 hr for those at the lowest temperature. The possibility of vapor transport of the radioactive metal as a contributing factor in the diffusion profile was investigated in two ways. One method was to suspend the needle directly over a dummy sample, raise the temperature, for periods of time equal to the diffusion times, and then take an auto-radiograph of the surface. Negligible radioactivity appeared. In the second method a thin slot in the crystal face on one side of the source provided a "cong path" for surface diffusion. If evaporation was the primary source of surface atoms the region of radioactivity around the source would be symmetrical. This was not the case. The profile dipped abruptly at the edge of the slot but on the other side of the source the usual diffusion profile appeared.

Jan 1, 1963

By J. H. Bowden

The water-hoisting tanks herewith illustrated have been designed for removing large quantities of water from recently-flooded mines, through their hoisting-slopes, with rapidity proportional to the capabilities of the hoisting machinery available, the tanks being adaptable to slopes of small sectional areas and varying pitches. The following features may be of interest to those operating mines liable to be flooded. 1. The arrangement of doors on each tank by which it may be automatically filled by immersion at any point on the varying pitch of a slope, the water being retained while hoisting on the flat as well as on the steep pitches, and quickly and autoniatically discharged at the top. 2. The arrangement, in connection with the above-mentioned doors, of side-wheels over the rear wheeh of each tank and of sidedumping tracks at the top of the hoist, for the automatic emptying and quick return of the tank. 3. The arrangement of two or more tanks, one in front of the other, so as to give as large a capacity in a single hoist as the enginepower will permit, yet without making any tank too large for the sectional area of the slope, or of unwieldlp length, or of such a shape that it cannot easily pass over vertical curves; and without concentrating too much weight on any one pair of wheels or on any point of the track. The details of construction and method of operating are shown by the accompanying sketches (Figs. 1 and 2), and the following more detailed description. At the end of each tank is a large iron door of almost the full size of the end of the tank, opening inwards, so that when immersed the tanks fill almost instantly. To provide for holding the water while it is hoisted up flat pitches, a wooden door is attached to the front of each tank, opening outward. Each front door is attached to the

Jan 1, 1892

By F. A. Crossley

The titanium-rich end of the Ti-A1 system has been investigated up to 35 at. pct A1 (23 wt pet). One conzpound Ti3Al was found to occur between primary a and TiAl. It is ordered hcp with DO19 structure, it has virtually no solid-solubility range, and it has a closed maximum at about 875°C. OIL either side of the compound are a +Ti3Al two-phase fields. The limiting a1uminum solubility in primary a at the titanium-rich end is indicated to be 7.5 at. pct A1 (4.4 wt pet) at 550°C and about 6.8 at. pct Al fl wt pct) at 500°C. Quenching alloys from above the a + Ti3Al two-phase field produces the following structures with respect to alloy composition: Up to 13 at. pct A1 (7.8 wt pet), a solid solution; from 15 to 18 at. pct A1 (9 to 11 wt pct), shear transformation product or martensite; from 19 to approximately 30 at. pct (11 to 19 wt pet), submicro-scopic coherent Ti3Al in an a malvix. The twin hcp phase fields reported in the literature are the result of nonequilibrium corzdztions. Ti-A1 alloys, once partitioned by dwelling- in the a + ß phase field during either hot working or heat treatment, are extremely difjicult to homogenize at temperatures below 1000°C. Such partitioned alloys exhibit the characteristics or symptoms of two-phase materials, and may be said to suffer the "twin-phase syndrome". THE earliest investigations of the Ti-A1 system by Ogden et al.1 and Bumps et al.2 reported wide solubility of the primary solid solutions. Aluminum was reported soluble in the low-temperature allomorph to the extent of 37 at. pct (25 wt pct), and the first intermediate phase was reportedly TiA1. Somewhat later Kornilov et al.3 reported a similar diagram with phase boundaries displaced towards lower aluminum contents and higher temperatures. Beginning about this time (1956) reports in the literature made it very clear that one or more intermediate phases occurred at lower aluminum contents than TiAl.4-17 These reports included five major investigations of the titanium-rich end of the Ti-A1 diagram.4,12,14,16,17 Three of these diagrams show two two-phase fields below 37 at. pct Al, while two of them show a single two-phase field. The existence of the phase Ti3A1 is firmly established and is included in each of the diagrams, except one—that of Sato and Huang.12 The new phases are reportedly hcp and differ from primary a only slightly when disordered, and when ordered the "a" parameter is approximately one,4,12,15 two, 6-10,13,14 or four14 times that for primary a. Beyond this, however, the diagrams are remarkable for their lack of agreement. Two tacit assumptions are usually made in phase-diagram determinations of metal systems. These are: 1) equilibrium anneals bring the alloy to equilibrium or to indistinguishable closeness to it, and 2) equilibrium conditions established at elevated temperatures are either "frozen" by rapid quenching for evaluation at room temperature, or quench-transformation products are recognized as such. In the current investigation evidence was obtained that over substantial composition ranges neither of these two conditions was met in any of the more recent major investigations. I) MATERIALS, METHODS, AND TECHNIQUES The alloys of this investigation were prepared by nonc on sum able electrode arc melting. Materials used in the preparation of the alloys are summarized in Table I. The investigative tools employed were: optical and electron microscopy, differential thermal analysis (DTA), disatometry, X-ray diffraction, electron diffraction, and resistometry. Alloys for microscopic and X-ray investigations were prepared as 15-g melts. Alloys containing from 7 through 11 at. pct A1 were hot-rolled out of a furnace at 900°C, from 12 through 15 at. pct out of a furnace at 1000°C, and from 16 through 18 at. pct out of a furnace at 1125°C. Alloys containing more than 18 at. pct A1 could not be hot-rolled. The ingots were covered with Markal coating prior to hot rolling to minimize atmospheric contamination. After hot rolling, alloys containing up to 15 at. pct A1 were ground and pickled to remove 7 mils from each surface; alloys containing 16 and 18 at. pct A1 were skinned to a

Jan 1, 1967

By Robert D. Pehlke, Weldon L. Daines

The reduction of manganese oxide from a basic slag by silicon dissolved in liquid iron at steelmaking temperatures was studied to determine the rate-controlling step for the process. The experiments were carried out under an argon atmosphere in a resistance-heated vertical-tube furnace. The two liquid phases, slag and metal, were held in zirconia crucibles. Sampling and chemical analysis of the slag phase led to time-concentration curves for the system. Results obtained by varying parameters such as temperature, stirring rate, concentration, and melt geometry defined the limiting reaction mechanism. The reduction of manganese oxide by silicon is a fast reaction and reached equilibrium within 90 min. The rate of stirring has a marked effect on the reaction rate, while, on the other hand, the effect of temperature is very small. This identifies the rate-controlling step as diffusion rather than interfaciul chemical reaction. The variation of other parameters revealed that a) diffusion of manganese in the iron phase is the slow step, b) the value of D/6 for manganese in iron at 1550°C is 7x 10-4 cm per sec, c) the energy of activation for the apparent rate constant is 7 kcal per mole, and d) increasing the amount of silicon in the iron decreases the diffusion coefficient of manganese. THE equilibrium relations pertinent to the reduction of manganese oxide from a steelmaking slag by silicon dissolved in liquid iron have been studied, but little is known about the mechanisms that control the rate of the process. The purpose of the present investigation was to study the rate of reduction by silicon and to determine the rate-limiting step. The effects of stirring rate, temperature, composition, and melt geometry were investigated as a means of identifying the controlling step. On the laboratory scale, relatively little work has been done in the area of slag-metal kinetics, primarily because of the problems confronted in attempting to contain liquid slags and metals in laboratory crucibles at steelmaking temperatures. Since graphite is an ideal material for a crucible, several investigations have been carried out on the reduction of various oxides from a slag by carbon in graphite-saturated iron and on the transfer of sulfur between a slag and graphite-saturated iron. Most of this work has been performed in induction furnaces. Studies where the container was not graphite are extremely limited. A single kinetic study of manganese transfer between molten iron and basic slags was carried out by Sano, Shiomi, and Matsushita.' These investigators prepared calcium oxide and titanium oxide crucibles to contain the two-phase system. Only a few experiments were carried out and the results had to be treated qualitatively. Despite the paucity of kinetic data, a large quantity of information is available in the literature concerning the thermodynamics2-12 and physical properties'3-21 of the slags containing manganese oxide and the dilute liquid iron alloys containing manganese and silicon which were involved in this research program. EXPERIMENTAL METHOD A vertical-tube resistance-heated furnace was used in this investigation to study the slag-metal reaction Although most previous slag-metal studies were carried out in induction furnaces, a resistance furnace has several advantages including better control of temperature and stirring rate. Hence, a resistance furnace was selected for this study, and its design is shown schematically in Fig. 1. Slip-cast, fine-grained, low-porosity, lime-stabilized cubic zirconia crucibles were used for the kinetic experiments. The crucibles were 4 1/2 in. high and 2 1/8 in. OD with a 1/16-in. wall. The crucibles were only slightly

Jan 1, 1969

By J. W. Freeman, R. F. Decker

A microstructural investigation was pursued to establish the mechanism of the pronounced benefits of traces of boron and zirconium on creep properties of a 55 Ni-20 Cr-15 (20-4 MO-3 Ti-3 A1 alloy at 1600°F. The mechanism of improvement of creep properties was found to be a pronounced stabilizing effect of traces of boron and zirconium on the grain boundaries of the alloy. The alloy with low boron and zirconium was subject to rapzd agglomeration of M23 C6 and in the grain boundaries, followed by depletion of y ' and intergranular microcracking at the grain boundaries transverse to applied stress. Brittle fracture then occurred by linking of microcracks. However, additions of zirconium, boron, and boron plus zirconium decreased this tendency in that order, allowing longer creep exposure and higher creep defor.mations before fracture occurred. VERY little information has been published describing the mechanism by which trace amounts of boron or zirconium improve the creep properties of complex nickel-base heat-resistant alloys, although the effect is now well recognized.1-4 Because the phenomenon is so important to properties and the effects are so striking, a study was made of the mechanism in a 55 Ni-20 Cr-15 Co-4 Mo-3 Ti-3 A1 alloy. It was believed that such a mechanistic approach would increase knowledge in theory of alloying and give a more basic understanding of alloy design to resist creep. The basic premise of the study was that boron or zirconium would alter the microstructural characteristics controlling creep and fracture to the extent that the effects could be identified by light and electron microscopy and by electron diffraction techniques. Characteristic of the microstructure of the Ti + Al-bearing nickel-base alloys is the dispersed precipitation of the intermetallic compound Ni,(Al, Ti), the ? ' phase, which is generally con- sidered to be the major source of high creep resistance.5-7 In addition, carbide phases have been identified8-10 and these can alter creep properties markedly.11 Since both the ?' and carbide transformations have been found to control properties, careful attention was paid to the effect of boron and zirconium on these transformations.

Jan 1, 1961

By Carl F. Floe, Michael B. Bever

ACCELERATED by the demands of war, research and development work in nonferrous physical metallurgy has continued at a rapid pace during the past year. In particular, advances have been made in processing and fabrication, especially of the light alloys, and in the surface treatment of metals. Theoretical physical metallurgy, although less active, has not been neglected and the year has brought forth some -notable contributions to our understanding of the fundamental structure of metals and their behavior in service. Of course, much work that has been done cannot be publicly discussed because of wartime restrictions.

Jan 1, 1945

By R. Taggart, D. H. Polonis, W. C. Gallaugher

In the Ti-Cu system, the a' phase can be produced over a wide range of alloy composition witJwut the retention of measurable amounts of the ß or ? phases. This paper reports on the decomposition of this hexagonal martensite phase front the standpoint of solute corzcentratiorz, tempering temperature, and coherency strain condition. The mechanism of precipitation during tempering comprises localized precipitation which is followed by discontinuous precipitation if sufficient coherency strains are present. The localized precipitation process in hypoeutectoid alloys is described by the generalized Johnson-hiehl equation and an activation energy of 46,000 cal per mole. In hypereutectoid alloys the corresponcEing activation energy is 51,000 cal per mole. The rate-controlling process has been proposed as the difision of copper along a' platelet interfnces. SEVERAL investigations have been reported concerning the kinetics of decomposition of the mar-tensitic a' phase in titanium binary alloys.' In the Ti-Mo system,' two modes of a' decomposition have been observed in the presence of /3 phase; one of these involves the precipitation of fine a from a', and the other involves diffusion across the a'-ß interface. In studies of the Ti-Cr system, Rostoker2 did not detect the formation of TiCr2 during tempering. In Ti-Ni alloys,3 the intermediate phase Ti2Ni has been found to precipitate directly from a' along the interfaces between plates. With the exception of the study of Ti-Ni alloys the previous investigations of tempering phenomena in substitutional martensites are mainly qualitative and do not present a detailed description of the precipitation processes. The following limitations restrict the correlation of the microstruc-tural processes and reaction kinetics during tempering in most binary-alloy systems. 1) A mixture of at least two phases characterizes the constitution of quenched alloys. 2) Difficulties have been encountered in obtaining uniform structures throughout quenched samples. 3) The reaction products, and in particular their morphology. have not been clearly resolved. 4) The martensitic a' phase forms over only a limited composition range for most titanium-base binary alloys. Gomez and polonis4 showed that the Ti-Cu system provides an excellent basis for investigating the tempering of a' over a range of composition without the complication of retained P or the transition w phase. In the present work the effects of solute concentration, tempering temperature, and coherency strain conditions are considered with reference to the over-all precipitation process in quenched alloys of the Ti-Cu system. Both microstructural observations and kinetic data are correlated to define the rate-controlling processes which govern the observed localized and discontinuous precipitation reactions. An earlier paper5 was devoted to a discussion of the modes of heterogeneous nucleation of Ti2Cu from the martensitic a' structure. The present paper will therefore emphasize the progress of the tempering reaction beyond the initial stages. EXPERIMENTAL METHODS The Ti-Cu alloys for this study were prepared by conventional arc-melting procedures. Chemical analysis revealed that the alloy buttons contained approximately 0.02 wt pct 0, 0.04 wt pct N, and within 0.1 wt pct of the intended copper concentration. The progress of the tempering reaction was followed by means of electrical-resistance measurements utilizing a Kelvin double bridge, microhard-ness readings with a 400-g load, and X-ray dif-fractometry patterns to reveal line-broadening effects. Metallographic specimens examined at magnifications greater than X1000 were shadowed with germanium to reveal fine structural details. Direct carbon replicas were prepared for the electron-microscopy studies. EXPERIMENTAL RESULTS Property Changes. The changes of microhardness that accompany the precipitation of Ti2Cu from a' are shown in Figs. 1 and 2. As the solute concentration increases the peak hardness, for a given tempering temperature, increases. In alloys of given composition the time to reach the peak hardness agreed with the time to attain maximum X-ray diffraction peak breadth, as shown in Fig. 3. The maximum hardness and the maximum line breadth increased with lower tempering temperatures, and the time to reach the maximum also increased. The a' peaks broadened during the initial stages of tem-

Jan 1, 1965

By H. R. Deeth, C. J. Koenig

ABOUT ten years ago nepheline syenite was introduced to the ceramic industry and the material has now found application in the various branches of the industry, namely, as a vitrifying agent in white-wares and as a source of alumina and alkalies in glasses, glazes, and porcelain enamels. Spence1 described the early mining and processing developments regarding this material. Since the time of his article many research papers have appeared relating to the usage of nepheline syenite but little has been published relative to subsequent mining and processing methods. A complete indexed review of the literature was issued recently by Ohio State University.2 Since "Lakefield" nepheline syenite from Blue Mountain, Ontario (Fig I); is the only commercial ceramic-grade nepheline syenite now being marketed on this continent, discussion is limited to this operation carried on by American Nepheline Limited, Lakefield, Ont., and its subsidiary in the United States, American Nepheline Corp. at Rochester, N. Y. THE DEPOSIT Blue Mountain is a long ridge rising to an elevation of about 350 ft at its highest point above the surrounding country and extending for about six miles in a northeasterly direction across Methuen township, Peterborough County. The rock of the Blue Mountain central alkaline intrusive is fine grained, light colored and of even granitic texture. The solidified mass consists predominately of the minerals albite, nepheline and microcline in order of abundance. The average mineralogical composition for the deposit obtained by a study of 112 samples taken regularly over the whole formation is as follows:3 [VOLUMETRIC MINERAL PER CENT Albite54 Microcline20 Nepheline22 Muscovite2 Mafics2 (Biotite, hastingsite, magnetite) Total100] The mineral nepheline (or nephelite) belongs to the feldspathoid group but is lower in silica content than are the feldspars. It is a silicate of soda, potash, and alumina (NaKAl2O32SiO2). Its presence with albite (Na2O A1203 6SiO2) and microcline (K20 A12O3 6SiO2) gives the Blue Mountain deposit an alkali content of 15 pct and an alumina content of approximately 24 pct. While this huge alkaline mass is somewhat variable mineralogically, it has a uniform chemical composition. When the iron, mostly in the form of magnetite, is removed during processing, a remarkably uniform finished product is obtained. Geological surveying has disclosed many million tons of nepheline syenite in the Blue Mountain deposit. Diamond drilling in the area where mining is now being carried out indicates a block of about one million tons.

Jan 1, 1947

By Eugene McAuliffe

THE heavy shrinkage in the production of bituminous coal has reflected adversely in the matter of tonnage produced by stripping arid mechanical loading machinery. The purchase of stripping and underground loading equipment has likewise been circumscribed. How- .ever a growing percentage of bituminous coal is being loaded by stripping and mechanical loading machinery. This situation is due to the fact that numerous strip pits were able to operate in Illinois and Indiana when under- cover mines were subjected to labor interference, a further advantage gained by their ability to produce and market coal at a price below that of the undercover mines. The mines equipped with mechanical loading. apparatus have enjoyed more continued operation for the double reason that the companies using coal-loading machinery are, generally speaking, more substantial and in better financial condition than many of the smaller properties who maintain hand-loading methods, and the market advantage due to lower production costs also reflects to the advantage of the undercover mines using mechanical loading equipment. Where a number of mines are con- trolled by one company, those not equipped with loading machinery and suffering from higher producing costs have often been closed, with the available tonnage concentrated in the more modernly equipped mines.

Jan 1, 1933

By David T. Day

In the summer of 1898, a demand suddenly arose for commercial quantities of the element osmium. At least half a ton was wanted for the manufacture of a new incandescent light. This led the writer to examine localities where platinum had been reported, in order to determine whether osmiridium mas contained in the crude platinum. With the co-operation of the concern most interested, the Welsbach Light Company, and in company with its President, Col. William E. Barrows, I visited most of the leading American localities where platinum has been obtained. I also wrote to every available placer-mine in the West for samples of the heaviest sands, in order to test them for platinum. The results of this inquiry are given in the present paper. Distribution. The notices of the occurrence of platinum in this country given in scientific journals include two interesting observa tions in the East. One concerns a nugget described by Peter Collier of Washington, D. C.,* and said to have been found on land adjacent to the village of Plattsburgh, N. Y., which weighed 104.4 grammes, and contained sufficient chromite to reduce the specific gravity from 17.35 for the heaviest portion to

Jan 1, 1901