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By J. E. Neal, C. T. Naber, O&apos

Silicon thin films were deposited by electron beam evaporation in an ultrahigh vacuum onto (0001) and (1102) sapphire substrates. Attempts were made to correlate the structural properties of the deposited silicon films with the following: 1) substrate orientation, 2) substrate surface condition, 3) substrate temperature, and 4) deposition rate. The substrate temperatures were varied between 500° and 1000°C and the deposition rates were varied between approximately 50 and 700A per min. The following sapphire surface treatments were investigated: 1) annealing in the ultrahigh vacuum at 1200° C; 2) heating in a hydrogen atmosphere at about 1350°C; and 3) etching with silicon by evaporating silicon onto sapphire substrates heated to 1200° or 1300°C. Twinned silicon films were occasionally formed at substrate temperatures between the 800° and 1000°C on unprocessed mechanically polished substrates; however, the reproducibility and crystallinity of these films were generally poor. Single-crystal and twinned silicon films were formed at substrate temperatures between 700° and 1000°C on substrates which were silicon-etched at 1300°C prior to deposition. Fiber texture films were formed at substrate temperatures between 500° and 700°C. The (111) lattice plane of the silicon single-crystal films was parallel to the (0001) sapphire plane and the (100) silicon plane was parallel to the (1102) sapphire plane. TECHNIQUES are well-established for growing single-crystal silicon thin films on sapphire by chemical methods.'-* Vacuum epitaxial techniques have a number of advantages over chemical epitaxial techniques in the fabrication of thin film microcircuits.5 One of the most significant is that vacuum techniques are compatible with well-established procedures for forming vacuum-deposited thin-film resistors, capacitors, and interconnections. Salatna, Tucker, and young6 recently reported the formation of relatively poor crystalline-quality silicon films on sapphire by electron beam evaporation in a vacuum of about 7 x 10-7 Torr. The purpose of the investigation described here is to determine the relationships between the structural properties of silicon thin films deposited on sapphire substrates by electron beam evaporation in an ultra-high vacuum and the following: 1) substrate orientation; 2) substrate surface condition; 3) substrate temperature; and 4) deposition rate. The substrate temperatures were varied between 500° and 1000° C and the deposition rates were varied between approximately 50 and 700A per min. Two orientations of sapphire were used: (0001) and (1102). The thick-nesses of the films were between 8000 and 16,000A. The morphology and crystallinity of the deposited films and substrate surfaces were investigated by optical microscopy, electron microscopy, and electron diffraction. APPARATUS AND PROCEDURE A cross section of the ultrahigh-vacuum thin-film evaporator is shown in Fig. 1. The bell jar is stainless steel and copper gaskets are utilized at all seals. High vacuum is attained by a 6001iter per sec ion pump and a titanium sublimation pump. Sorption pumps are used to rough the system to a pressure of about 10 µ prior to starting the ion pump. Vacuums in the 10- 10 Torr range were attained after baking the system at about 250°C for 8 hr. Vacuums in the 10-8 to 10-9 Torr range were maintained during silicon evaporation. The silicon charges, which were cut from p-type single-crystal boules which had resistivities between 2000 and 4500 ohm-cm, were placed in the water-cooled copper crucible of a 180 deg bent-beam 5-kw electron beam evaporator. During evaporation, a molten zone was formed in the top center of the silicon charge, and the portion of the silicon charge in contact with the water-cooled crucible remained solid. The substrate heater, which has been described

Jan 1, 1969

By W. E. Johnston

At last year's Annual Meeting a paper by Haultain and Johnston was presented entitled Is the Gold in Tellttrides Soluble in Cyanide? Since then the writer has continued the study of various phases of this problem. Samples and specimens of ore from some of the Kirkland Lake mines have been studied and non gold-bearing tellurides have been found in these that are not soluble in ordinary mill solutions. Samples of tailings, both old and recent, from this district have been examined with apparatus and methods that have proved very successful in detecting the presence of extremely minute quantities of tellurides. Tellurides, both base-metal and gold-bearing, have been discovered in these tailings, but only in such minute quantities that their presence would not affect the ordinary assay results. More free gold particles have been found in the tailings than gold-bearing tellurides. Much experimental work has been done on tellurides, concentrated from high-grade material and from ordinary run-of-mine ore. The gold-bearing tellurides behave very much as does gold itself. Finely divided particles are dissolved fairly rapidly, coarser particles more slowly. All the tellurides are soft and brittle and also have a high specific gravity, with the result that they are extremely finely divided in ordinary mill practice. The ordinary high-lime solution of Kirkland Lake practice is suitable for the dissolving of the gold tellurides. Oxygen is necessary, but apparently not more so than in dissolving gold. Some particles have been found that appear under the microscope to be ordinary metallic gold particles, but on heating they show a small telluride content. These appear to dissolve more slowly than gold. There is considerable variation in the ratio of tellurides to gold from different points in the mines. So far the writer has failed to find any connection between this ratio and the richness of the ore. Generally speaking, the base-metal tellurides predominate. Some of these contain gold but this may be due to a mixture of tellurides in the one particle.

Jan 1, 1933

By Nina Panteleeva, Elena Afonina, Stanislav Titkov, Jury Buksha

"Flotation processing of water-soluble minerals (potassium ores, sedimentary salts of salt lakes) is currently the main method for production of potassium fertilizers and concentrated carnallite which is the initial product for production of metallic magnesium. Flotation of sylvite (KCl) and halite (NaCl) is carried out in the electrolyte solutions: KCl-NaCl-H2O and KCl-NaCl-MgCl2-H2O. The report presents the results of studies of the effect of concentration and the electrolyte type on the size of air bubbles in a flotation cell in comparison with the floatability of mineral constituents of potash ores. The floatability in electrolytes of various compositions has been studied: - of sylvite (KCl) by alkylamines, - of halite (NaCl) by alkylmorpholines, - of silicate-carbonate slimes contained in the ore by ethoxylated surfactants. The reagent modes (regimes) activating the flotation desliming of potash ores have been developed."

Jan 1, 2014

By P. D. Merica

The remarkable phenomena exhibited by the aluminum alloy known as duralumin were discovered during the years 1903-1911 by A. Wilm1,2 and have been described by him and by others. 3 4 5 6 The unusual feature of this alloy is the fact, as was shown by Wilm, that it can be hardened quite appreciably by quenching from temperatures below its melting point followed by aging at ordinary temperatures, which consists merely f allowing the material to stand at these temperatures. The hardness is not produced by the quenching alone but increases during the period of aging, which may be from one to three days. Cohn3, 5 gives data showing the increase of hardness of duralumin during aging, after quenching in water from about 450° C. Upon annealing, the alloy so hardened by aging is softened exactly as is hardened steel. The composition of this alloy usually varies within the following limits: Copper, 3 to 4.5 per cent.; magnesium, 0.4 to 1.0 per cent.; manganese, 0 to 0.7 per cent.; aluminum, balance; iron (as impurities), 0.4 to 1 per cent.; silicon, 0.3 to 0.6 per cent. Its density is about 2.85. It is used only in the forged or rolled condition. This alloy has been produced for some years commercially and is in demand for the fabrication of parts for which both lightness and strength are required, such as for aircraft. Its tensile strength will average 50,000 to 60,000 lb. per. sq. in. (3515 to 4218, kg. per sq. cm.) after appropriate heat treatment, such as that described by Wilm.

Jan 6, 1919

By S. H. Ash

California leads the Nation in the number of operating metal mines and the small number of persons employed at individual mines, which reached a minimum irk 1932 with an average of seven men. The mines are scattered over the entire State, which is the second largest in area (155,562 square miles) in the United States. The mines are situated at various altitudes, with portals ranging from approximately 300 feet below sea level to almost 12,000 feet above. Many of the mines can be reached only during the summer, while at others the heat of the regions adds so the difficulties during the summer months Supplied of explosives the use (or, probably more correctly, the misuse) of which constitutes one of California's gravest mining problems; are handled and stored under condition that contribute many hazards. The problem of providing medical care is serious and complicated, especially at small mines and more particularly in the almost inaccessible mountainous regions; instances in which a knowledge of first aid would have been beneficial but was lacking, or when first aid was instrumental in saving life or limb because it was available are too numerous to be mentioned.

Jan 1, 1936

By C. S. Thompson, P. A. Ciullo

Pyrophyllite is a naturally occurring hydrous aluminum silicate with the molecular formula SiO,,AI,,(OH), or, as more commonly expressed, the oxide formula A120,~4Si02~H20. Pyrophyllite is rarely found in deposits as the pure mineral and is often intimately associated with quartz, sericite, kaolinite, and diaspore. These associated minerals, to a large degree, help determine the most appropriate commercial application for a given pyrophyllite ore. Structural similarities plus the generally soft platy nature of pyrophyllite has in the past caused it to be included with talc in applications and production data. The Minerals Yearbook, published annually by the US Bureau of Mines (USBM), still reports on talc and pyrophyllite together, although admitting that they do not share the same uses. Pyrophyllite has also at times been considered a clay mineral because of its structure and chemistry. The refractory properties of pyrophyllite have been known for nearly 200 years, but it has only been in the past 60 to 70 years that a variety of applications have been developed to exploit the unique characteristics of this mineral. Worldwide, pyrophyllite is a component of refractories, whiteware, foundry mold dressings, pesticides, paint, plastics, rubber, cement, fiberglass, and soap. Historical Overview The most salient refractory features of pyrophyllite are its low coefficient of thermal expansion, high thermal conductivity, low moisture expansion, and good resistance to corrosion by molten metals and basic slags. One of the first recorded uses of this mineral was as firebrick in Japan in the early 1800s. This followed its discovery in 1797 on Mount Omotoyama at the site of the present Mitsuishi mine. In addition to firebrick, sawn blocks of ore were used for carvings and in the manufacture of slate pencils and signature seals. The Mitsuishi mine is still one of Japan's largest. By the mid-1800s, refractories were being made in Japan from roseki (a pyrophyllite-bearing ore) for the construction of metal melting furnaces. The mineral did not get its name until 1829 when R. Herman, testing a sample of supposed talc from the gold-quartz veins at the Berezovo deposit in the Urals, showed that it was actually an aluminum silicate and designated it pyrophyllite. This name was derived from the Greek pur for fue and phullon for leaf, in allusion to the effect of heat in causing separation of the laminae in foliated varieties (Mellor, 1927). The exact date of the discovery of pyrophyllite in the United States is uncertain, but it is believed that the talc and soapstone deposits noted in an 1827 report on the geology of the slate belt of North Carolina were actually pyrophyllite occurrences (Olmstead, 1827). Pyrophyllite was first used in North Carolina on a local basis in the early 1800s. Blocks were sawn and cut for use as stove linings, mantels, chimneys, fireplaces, and gravestones. This was the material of choice because it did not shrink when heated, but cut easily and hardened as it weathered. Pyrophyllite crayons were sold commercially by local gold miners for steel marking and as tailor's chalk from about 1800 until 1922. It was during this period that pyrophyllite was discovered near the town of Hemp (later renamed Robbins), NC. The large quantity of scrap resulting from the sawing of crayons at this deposit prompted the construction in 1921 of a grinding plant. The ore scrap was ground to fine granules and sold to asphalt producers to prevent shingles from sticking together. By the mid-1930s, milled pyrophyllite from North Carolina was also being successfully utilized by the ceramics industry in whiteware for its low cost and ability to shorten firing time. Also during the 1930s, pyrophyllite was first used in kilncar furniture in the United States. Canada was another early entrant in the pyrophyllite business. Mining at the Foxtrap deposit on the Avalon Peninsula of Newfoundland began in 1904, with ore shipped to the United States. Production from this deposit was mostly sporadic in the ensuing years until 1956 when mining began for shipment and captive use in US tile manufacture. This production has remained continuous and still essentially captive to the present. The Foxtrap deposit is currently the sole commercial source of pyrophyllite in Canada.

Jan 1, 1994

By Robert L. Dean, Michael Hoch, Samuel M. Wolosin, Chung K. Hwu

The general shape of the 1450°C isotherm of the Ti-TiO-ZrO2-Zr region was evaluated from the surrounding binary phase diagrams and from thermo-dynamic data on the metal-oxygen binaries. The phase boundaries were accurately determined using X-ray and metallographic techniques. At 1450°C the system shows a large bcc ß field, which extends from the two metal-oxygen binary systems as a Gaussian error function, and is stable up to 30 at. pct 0 when Ti and Zr are present in equal amounts. At higher O Concentrations, the ß field is in equilibrium with t-ZrO . The following four regions, with three solid phases, are present: two a ß t-ZrO,, a TW t-ZrO,, and TiO t-ZrO2 c-ZrO2. On cooling the ß phase transforms into the a phase, going through the w transition phase. The isotherm at 1500°C for the region TiO-TiO,-ZrO, was obtained by using X-ray diffraction. At 1500°C a large c-ZrOz region is present as well as a large two-phase field, Ti0 c-ZrO,. The following regions, with three solid phases in equilibrium, were found These regions are relatively small. The solidus and liquidus relationships were determined by observing samples suspended in a tungsten crucible by means of a fine tungsten wire and heated in vacuum. Eleven univariant points were found. C-ZrO, decomposes through a peritectic reaction into liquid t-ZrO2. The activities of Ti and TiO in the TiO t-ZrOz and in the two a ß t-ZrO regions were measured using the Knudsen effusion method. In the a TiO t-ZrO, region the activities of Ti and Ti are the same, as in the a — Ti TiO binary. In the two a t-ZrO, regions, the Ti activity is high and the Ti0 activity very low, although all phases present contain at least 30 at. pct 0. This indicates a short-range order in the solid phases, Zr atoms being preferentially surrounded by 0. 1 HE system Ti-Zr-0 is of interest because of the wide ranges of solid solubility exhibited by the boundary systems; as titanium and zirconium both belong to the same group of the periodic table, large single-phase regions should occur within the system, with a great variation of properties (as the composition changes within the single-phase region). Furthermore, the possibility of modifying ZrO, to make it a more usable refractory by the addition of other metals makes this system also of interest. Because of the high affinity of titanium and zirconium for oxygen, the oxygen partial pressure is very low at all compositions; thus, there exists a ternary metal-metal-oxygen system in which the oxygen pressure is not an important variable, so long as it is low enough. When a sample is heated in vacuum to a temperature high enough for vaporization to occur, the vapor phase will consist of metal and metal-oxide gas, the oxygen concentration being very low. The phase relationships in the surrounding binary systems have already been reported in the literature; therefore, the study of the ternary diagram

Jan 1, 1962

By P. N. Richards, M. K. Ormay

The present Paper extends the previous work on cold reduced, low carbon steels to preferred orientations developed after various heat treatments. In recrystal-lized rimmed steel, cube-on-comer orientations increased with cold reductions up to 80 pct. Above that {111}<112> and a partial fiber texture with (1,6,11) in the rolling direction dominated. During grain growth, cube-on-corner orientations have been observed to grow at the expense of {210}<00l>. In re-crystallized Si-Fe (111) (112) and cube-on-edge type orientations are dominant near the surface and the (1,6,11) texture near the midplane for reductions up to 60 pct. With larger reductions {111)}<112> and the (1,6,11) texture are dominant. In cross rolled capped steel a relationship of 30 deg rotation was observed between the (100)[011] of the rolling texture and the main orientations after re crystallization. Most orientations present in recrystallized specimens can be related to components of the rolling texture by one of the following rotations: a) 25 to 35 deg about a (110) b) 55 deg about a (110) C) 30 deg about a (Ill) THE orientation texture of recrystallized steel is of interest where the product is to be deep drawn, because preferred orientation is related to anisotropy of mechanical properties such as the plastic strain ratio (r value);1,2 and in electrical steel applications where a high concentration of [loo] directions in the plane of the sheet improves the magnetic properties of the material. It is interesting to note that both these aims are to a large extent achieved commercially, even though the orientation texture of cold rolled steel does not show large variation3 and the recrystallized orientations are generally given as being related to the as rolled orientations mostly by 25 to 35 deg rotations about common (110) directions.4-6 There is, as yet, no single completely accepted theory on recrystallization. The three mechanisms that have been investigated and discussed are: a) Oriented growth b) Oriented nucleation c) Oriented nucleation, selective growth Largely from the observations of the recrystalliza-tion process by means of the electron microscope,7-11 there is now considerable evidence that the "nucleus" of the recrystallized grain is produced by the coalescence of a few subgrains to form a larger composite subgrain, which finally grows by high angle boundary migration into the deformed matrix. From the intensive work on the recrystallization of rolled single crystals of iron, Fe-A1 and Fe-Si al-loys4-" he following observations have been made: 1) The change in orientation during primary recrys-tallization can usually be described as a rotation of 25 to 36 deg about one of the (110) directions. 2) The (110) axes of rotation often coincide with poles of active (110) slip planes. 3) If several orientations are present in the cold rolled structure, the (110) axis of rotation will preferably be a (110) direction that is common to two or more of the orientations. 4) With larger amounts of cold reduction (70 pct or more) departure from these observations became more frequent. 5) After larger cold reductions, rotations on re-crystallization about (111) and (100) directions have been observed. K. Detert12 infers that a rotation relationship of 55 deg about (110) directions is also possible, by stating that the recrystallized orientation {111}<112> can form from the orientation {100}<011> of cold reduced partial fiber texture A.3 The observation by Michalak and schoone13 that (lll)[l10] formed during recrys-tallization in fully killed steel containing (111)[112],— as well as (001)[ 110] which is related to the {111}<011> by a 55 deg rotation about <110>-implies a possible 30 deg rotation relationship about the common [Ill]. Heyer, McCabe, and Elias14 have recrystallized rimmed steel after various amounts of cold reduction, by a rapid and by a slow heating cycle and found that the preferred orientations strengthened with increased cold reduction. The most pronounced orientation up to about 70 pct cold reduction was found to be {1 11}< 110>, after 80 pct cold reduction both {111}<110> and {111}<112>, after 85 and 90 pct cold reduction, {111}<112>, and after 97.5 pct cold reduction it was {111}<112> and (100)(012). In the present work, the orientation textures of the recrystallized specimens are examined under various conditions of steel composition, amount and method of cold reduction, and method of recrystallization. The relationships between the preferred orientations of the as rolled and recrystallized specimens, and the conditions for the formation of the various orientations during recrystallization are investigated.

Jan 1, 1970

By R. P. Abendroth

This study is concerned with the kinetics of selective oxidation of chromium in a commercial Fe-Cr-Ni alloy. Selective oxidation of chromium in this alloy, by use of a low oxygen-potential atmosphere, leads to the formation of a compact, protective layer of Cr2O3. This layer serves to protect this alloy from gross scaling when it is subsequently exposed to severe oxidizing conditions at high temperature. The interaction of low oxygen-potential atmospheres close to equilibrium with Fe-Cr and Ni-Cr alloys has been studied by others."&apos; These studies werk concerned with the surface-structure variations under slightly oxidizing conditions. NO detailed study was made of the oxide scale formation kinetics, however. The alloy samples were cut from 0.012-in.-thick sheet, with an apparent surface area of 7.1 sq cm. These sheet samples were abraded through 4/0 metallographic paper, and washed in alcohol and acetone. The analysis of the sheet alloy is (in weight percent): 42 pct Ni, 5.5 pct Cr, 0.09 pct C, 0.18 pct Al, 0.36 pct Si, 0.26 pct Mn, balance Fe. The weight gain vs time data were obtained with a 2-g capacity fused-silica spring—cathetometer system. The spring deflection was optically magnified ten times before being read by the cathetometer. A sensitivity of about 0.01 mg was attainable. The spring was enclosed in a water jacket maintained at 60°C to minimize the effect of temperature changes. The sample was suspended from the spring with a fused-silica hangdown and was positioned in the thermal center of a mullite furnace tube. Sample temperature was read with the aid of a thermocouple placed outside the mullite tube and an inside vs outside temperature calibration. Temperature change during the course of a run was ±0.25°C, with a temperature gradient of less than l.O°C over the length of the sample. Total temperature uncertainty was no more than ±3.0°C. Alignment difficulties between the hangdown and radiation shields in the furnace tube required that the sample be positioned in the furnace when cold, and heated with the furnace until the temperature stabilized at the desired point. This required 5 to 6 hr, and was carried out in Matheson ultrahigh-purity hydrogen. Oxidation was started, after evacuation, by introducing a hydrogen-water vapor mixture, obtained by saturating hydrogen with water vapor at 31.00o ± 0.02oC. Oxidation was continued for 90 min. Gas flow was 300 ml per min during heat up and oxidation. Since only several milligrams of oxide are formed on each sample, chemical analysis of the oxide is difficult. A representative analysis is: 80 pct Cr2O3, 5 pct Fe2O3, 3 pct Al2O3, 4 pct MnO, 7 pct SiO2, 1 pct or less NiO. X-ray diffraction analysis of the oxide as formed on the alloy gives rhombohedra1 Cr2O3, and barely distinguishable amounts of a cubic spinel phase, and possibly AlZOs and SO2. The identification of these latter two compounds is by no means certain. The spinel phase could be based on iron or manganese as these elements are present in significant amounts in the oxide. The results of the kinetic studies using 31°C dew-point hydrogen-water vapor mixtures were found to conform to a parabolic rate law. In many cases the parabolic plot consisted of two intersecting straight lines, defining an early and a late rate for a particular run, and in the other cases the parabolic plot consisted of one straight line for the entire run. The slopes of the various straight lines were determined by the method of least squares. Reproducibility of the data was good enough for multiple runs at the same temperature such that the value given for the rate constant is the average for two or more closely similar values, rather than widely varying values of the rate, where more than one determination is indicated in Table I. The exhibition of only one or of two rate constants during a run can happen at the same temperature. Thus, Table I shows that at 11&apos;74°C a single rate constant was obtained from one sample, while other samples oxidized at the same temperature gave an early and a late rate constant. It should be noted that the single rate constant corresponds very closely with the early rate constant. This is also true at 1153°C. The time at which the late rate started to appear was variable, usually occurring 20 to 40 min after oxidation had started.

Jan 1, 1964

By Irving B. Cadoff, Ernest Levine

The crack formation and propagation in the single -phase Cu-4 pct Ag alloys were studied. The alloys were loaded in mercury to various stress levels, the mercury was removed, and the specimen examined for cracks. Cracks were found to develop below the fracture stress; the frequency of such cracks increased with increasing stress level. Some cracks were nmpropagative. Fracture in mercury was found to occur by the link-up of cracks formed at various stress levels rather than by the growth and propagation of a single crack. If the mercury environment is removed prior to a critical amount of crack formation, then continued loading results in ductile fracture. The appearance of the cracks at selected grain boundaries is related to the relative orientation of the boundaries, as are the propaga-tive characteristics of the crack. The mercury interaction appears to be one of lowering the strength of the metal-metal bonds in the high-stress area of the grain boundary. GRIFFITH&apos;S microcrack theory1 proposed a critical crack size above which a crack in an elastic material grows with decreasing energy at a stress of From his theory it was proposed that the presence of a liquid tends to lower the surface energy of the microcrack faces2 leading to a decrease in the critical crack size necessary for spontaneous fracture propagation. stroh3 proposed that the stress concentration at a grain boundary due to pile-up may initiate a microcrack at the grain boundary. petch4 and Stroh5 evaluated the stress distribution at the head of a pile-up in a polycrystal-line material and deduced that the critical crack size and hence of is dependent on the grain size. Experimental verification of this dependence was found by petch6 for hydrogen embrittlement of steel. Studies in stress-corrosion cracking7 have provided a picture of fracture which shows that initial separations occur in a scattered, independent fashion in regions of high tensile stress. A minimum or threshold stress is necessary to produce a sufficient stress concentration to initiate frac- ture. These separations join up to form a crack. The extension of fracture is largely discontinuous and consists of a joining up of cracks. In recent worka evidence of this scattered crack network was found in a Cu-Ag alloy embrittled by mercury. For the Cu alloy-Hg couple, the crack path has also been found to be dependent on the orientation of adjacent grains, and with the addition of zinc to mercury a reduction in embrittlement along with a change in fracture morphology was found.9 In this present study, a mercury-dewetting method was used to observe crack initiation and fracture morphology when a Cu-4 pct Ag alloy is deformed in mercury and Hg-Zn solutions. PROCEDURE Specimens of Cu-4 pct Ag were prepared as in previous crack-path studies.&apos; The specimens were heated at 770°C for 24 hr and water-quenched Tension tests using a table-model Instron were carried out in mercury and in various concentrations of Hg-Zn. Loading was in steps up to the fracture stress, with the load being removed and the specimen examined for surface cracks at each step. The specimens were dewetted after each load to permit examination of the surface structure and rewetted prior to continued loading. The specimens were wetted by electro polish ing in phosphoric acid, rinsing in alcohol, and then immersing in a pool of mercury. Dewetting was accomplished by flame heating the specimen for 30 sec in a vacuum. Some surface contamination was found, but not enough to obscure crack configurations and grain boundaries. RESULTS Fracture Characteristics in Mercury. Fig. 1 is a stress-strain curve showing the progressive step-wise loading of the specimen. As may be seen from the graph, the first position stopped at a is at a stress 5000 psi below the expected fracture stress of 25,000 psi. Examination of the specimen after removal of mercury showed only one crack. The appearance of this crack at a stress far below the fracture stress of this alloy in mercury did not affect the stress-strain curve in any manner. The specimen was then recoated with mercury and deformation was continued (curve b, Fig. 1) raising the stress by 4000 psi, and the same procedure re~eated. The initial crack was located and appeared as in Fig. 2 (crack lb). In this figure the crack is

Jan 1, 1964

By M. J. Sinnott, H. B. Probst

AN extensive survey of the factors which affect austenite grain growth has already been made.&apos; These factors are temperature, time at temperature, rate of heating, initial grain size, hot-working, alloy content, ofheating,initialand rate of cooling from the liquidus-solidus temperature. In the present work, a vacuum-melted temperature.electrolytic iron was used and the variables studies were temperature, time at temperature, and prior ferrite grain size. Other factors were maintained constant. The iron used in this study was vacuum-melted electrolytic iron of nominal composition of impurities of 0.07 wt pct. It was supplied as a ½ in. round cold-drawn bar. This iron was tested in three conditions: as-received, annealed 6 hr at 1200°F, and annealed 6 hr at 1600°F. Samples were ? in. disks cut from the bar. The prior anneals were carried out in vacuum and the isothermal treatments were carried out in vacuum-sealed Vycor tubing. The thermal etch technique was employed to determine the austenite grain size. Prior to sealing the test specimens, one surface of the sample was polished metallographically. This surface, after heating, was examined to determine the austenite grain size, since the austenite boundaries are revealed by thermal etching. This is essentially the only technique available for measuring the austenite grain size of low carbon steels or pure irons without altering the composition. It has been shown to yield results that are in agreement with other methods used for determining austenite grain sizes.&apos; The specimen size was quite large compared to the grain size measured, so inhibition of growth due to size effects is probably negligible. After vacuum sealing, each sample was placed into a furnace at temperature and at the completion of the run was quenched into a mercury bath. The growth temperatures used were 1700°, 1800°, 1900°, and 2000°F controlled to -~10"F. Growth times were varied from 10 to 240 hr. The long times were used in order to eliminate the nucleation and growth effects occurring during the initial transformation. Time was measured from the introduction of the capsule into the hot furnace to the time of quench. Grain-size measurements were made with the use of a grain-size eyepiece of a microscope. By determining the number of grains per square millimeter at X100 and taking the square root of the reciprocal of this number, the average linear dimension of the grains was determined. Figs. 1 and 2 are plots of these data as a function of time and temperature for the various conditions investigated. The variation of D, the linear dimension of the grains, was assumed to follow the equation3 D = A tn. The curves of Fig. 1 were obtained from the data by the use of the least-squares method of analysis. Fig. 1 is for the growth of the as-received stock and Fig. 2 is for growth after prior treatments. Differentiating the foregoing equation gives an expression for the rate of growth dD/dt = G = nAtn-1 = nD/t. Both D and G as functions of t are given in Table I. It should be noted that G is a function of time; the growth rate is rapid at early stages and decreases with increasing time. Since increasing temperature increases the growth rate, it has been common practice to use the empirical relationship G = Go e-Q/RT to relate temperature to growth rate. The growth rate customarily has been taken at constant values of D on the basis that the rate of growth is related to the boundary surface tension and this is measured by the curvature of the boundary. At constant D values, the growth rate is a function of time and temperature. The growth rate can be related however to temperature at constant time, and this has the advantage that under these conditions the growth rate is a function only of temperature. Obviously the Q values, activation energies, obtained for each assumption will not be the same and the question of which is the more correct is a moot one, since the assumed exponential relationship in either case has no particular theoretical significance. By plotting G, at constant grain size, vs 1/T, the activation energy over the temperature range of 1800" to 2000°F is found to vary from 30,000 cal per mol at the smaller grain sizes to 50,000 cal per mol at the larger grain sizes. The 1700°F data do not correlate with the data at higher temperatures. The activation energies for the 1200" and 1600°F prior annealed materials were calculated as 50,000 and 62,000 cal per mol, respectively, using the reciprocal time to a given grain size as a measure of the growth rate. Plotting G, at constant times, vs 1/T yields an activation energy of 12,300 cal per mol for the tem-

Jan 1, 1956

By H. E. Stauss, J. Hino

INTEREST in silicon has arisen again in the past decade as a result of improvements in crystal rectifiers.&apos; Although the preparation of silicon was first reported by Berzelius in 1880, the early product was of relatively low purity, and only the need for rectifiers in World War II led to the production of a 99.9+ pct pure powder. This material in crystalline form was consolidated into massive silicon for use, and the method developed was to melt it with selected added constituents as "doping" agents. Melting techniques, therefore, are of great importance. There are two basic problems in producing silicon ingots free of doping additions; one is the prevention of spitting and the other is prevention of cracking of the ingot during freezing. The most satisfactory arrangement yet developed for producing massive silicon is to melt and freeze in a cylindrical quartz crucible surrounded by a concentric heating element and concentric radiation shields or insulation. For example, use can be made of a tubular heater with a high frequency generator as the source of power and reflecting shields of alundum cylinders. The spitting of silicon is related to gas evolution, and the gas comes from two primary causes—adsorbed gas and the reaction products of silicon and the crucible. Gas is also released from bubbles contained in the quartz crucible walls. Improved removal of adsorbed gas can be achieved by means of controlled melting and freezing. The seriousness of the problem in vacuo is reduced with an electrically operated mechanical movement of the high frequency power coil. The upper portion of the powder charge is melted first and the high frequency coil lowered until the powder is completely molten. During cooling the high frequency coil is raised slowly. These means also reduce the final nonviolent extrusion of large beads of metal through the ingot top during freezing. Better control of spitting and bead extrusion is obtained when melting is done under helium at. atmospheric pressure instead of in vacuo. The problem of reaction between silicon charge and crucible in practice is confined to the reaction between silicon and quartz. This2 apparently is: Si + SiO2 + 2SiO The part that this reaction plays in spitting has not been isolated for separate study. SiO is a volatile vapor at the melting point; of silicon and is released freely during melting in vacuo, but hardly at all in helium at atmospheric pressure. The cracking of ingots is a major difficulty in melting silicon, and its prevention requires special melting techniques or the addition of "toughening" agents such as aluminum or beryllium.&apos; The cracking of the ingots has been explained as being the result of the expansion that occurs upon freezing; although direct observation of freezing ingots reveals visible cracks on the surface only after a red heat has been reached, suggesting that cracking is the result of differential contraction of silicon and quartz. Silicon wets quartz, and the ingot adheres tightly to the crucible. Therefore as ingot and crucible cool, the two either have to pull apart, or at least one must crack. Surprisingly, in spite of the relative thinness of the quartz and the thickness of the ingot, the ingot and the crucible both crack. Microscopic and X-ray4 studies fail to show any plastic flow other than twinning in the ingots. Slow cooling fails to prevent cracking. Another possible solution to cracking is to weaken the crucible. Use of thin-walled crucibles finally led to success with fused quartz crucibles with a wall thickness of 0.25 to 0.50 mm. With such thin-walled fused quartz crucibles consistently uniform success is secured in producing sound ingots 30 mm in diam from the purest available grade of silicon (99.9+) without the use of any type of addition. Melts are made in the size range of 50 to 100 g. Omission of a deliberately added doping agent is not sufficient to insure pure ingots. The reaction of silicon with crucibles and the resultant solution of impurities in the silicon is well-established." In this laboratory, the presence of Al, Be, and Zr has been found spectroscopically in ingots melted in contact with alumina, beryllia, and zircon. The best crucible materials reported in the literature are MgO and SiO2. Use of MgO in this laboratory has resulted in a heavy deposit of magnesium on the furnace walls, showing that a reduction of the magnesia occurred and the resulting magnesium removed from the melt by volatilization. In the case of quartz, the silica is reduced and SiO liberated to deposit on the equipment walls. There probably is real danger that oxygen is dissolved in the ingot when either magnesia or silica is used as the crucible material. Preliminary analyses by Dean Walter in his vacuum unit in this laboratory6 indicate the presence of oxygen in undoped silicon melted in quartz.

Jan 1, 1953

By R. C. Himes, K. Zanio, J. B. Wagner, J. W. Moody, J. F. Miller, W. Johnson

The recent research with which this paper deals has been concerned with the preparation of pure PbTe crystals suitable for control of radiative processes and othe.v electronic applications. The research has been directed toward the developrnent of methods for the preparation of puve, homogeneous, loul-ca,wier-density PbTe crystals suitable for use in the fabrication of optically pumped and electrically pumped diode lasers. Steps in the preparation of the crystals include 1) purification of the starting materials, 2) synthesis and purification of the PbTe, 3) growoth of PbTe crystals, and 4) adjustt~zertt of composition of the crystals This Paper describes the general preparation procedure employed and discusses some investigntiotzs of purification processes. THE as-received lead and tellurium are nominally 99.999 to 99.9999 pct pure. Assays furnished by the suppliers, obtained by emission spectrographic analysis, show only the presence of about 2 ppm Mg in the tellurium. Such analyses are not very informative, however, since they give no information on the concentrations of normally gaseous impurity elements such as oxygen. Both the lead and the tellurium in the as-received state usually contain appreciable concentrations of oxygen—primarily in the form of oxides on the surfaces of the material. To reduce the oxygen content, the lead is held in the molten state in hydrogen at -700°C for several hours. For this treatment, the lead is contained in a graphite boat which is rf-heated, and the hydrogen is passed through a liquid-nitrogen trap prior to use. Tellurium is subjected to multiple distillation in hydrogen to remove oxygen and other foreign impurities. If, in conducting the distillation, approximately the last 10 pct of the charge at each "stage" is left as the discard cut, purification of the tellurium proceeds as indicated in Fig. 1.l Tellurium used in this work has been distilled two or three times to reduce carrier concentration to about 10" per cu cm. The PbTe is prepared from the purified elements by reacting them in the molten state in sealed, evacuated, or hydrogen-filled silica ampoules. The charge is usually held above the melting point of PbTe (923°C) at 1000 C for 24 hr to ensure that it has been homogenized. Two methods have been employed for the growth of the required single crystals of PbTe: growth from the melt, which will be discussed first, and growth from the vapor phase. Large single crystals of p-type PbTe can be grown readily from the melt by the Bridgman method. For this method of crystal growth, the PbTe is synthesized in situ from proper proportions of the purified elements. Growth (dropping) rates in the range 1.3 to 6.5 mm per hr are employed. Material near the maximum melting composition (about 50.012 at. pct Te) is utilized to avoid composition change on freezing, and thus to obtain crystals of nearly uniform composition. Crystals prepared by use of procedures described up to this point were sufficiently pure and perfect that they could be used for the preparation of laser crystals in studies at Lincoln Laboratory.2-5 ADJUSTMENT OF COMPOSITION Good n-type crystals of PbTe cannot readily be grown from the melt. Further, growth from the melt of crystals of any compositions (n or p type) other than those near the maximum melting composition is difficult because of the large composition changes that must occur on freezing.&apos;" However, melt-grown crystals can rapidly be brought to other desired compositions by isothermal equilibration through the vapor phase with a two-phase Pb-Te stock material, essentially as described by Brebrick and Allgaier.1 The work to be discussed has been concerned with the preparation of n-type crystals; thus, the two-phase stock which was employed contained excess lead, and all ensuing discussion is of the preparation and properties of n-type crystals. The equilibration was designed to the shift composition to the lead-rich limit of stability at the selected temperature. Initial treatment of the crystals at high temperature was employed to minimize the total time required for the equilibration. Final adjustments of the composition and state of the crystals were made by use of low-temperature heat treatment at temperatures in the range 200" to

Jan 1, 1968

By Horace Pops

Martensitic transformation has been studied during cooling and heating in ß-phase Cu-Zn alloys to which small additions have been made of Ni, Ag, Au, Cd, Ga, In, Si, Ge, Sn, and Sb. The start and finish of the martensitic reaction and the variation of transformation temperature with third-element content were determined by electrical-resistivity measurements from alloys which had either constant zinc contents or constant values of electron concentration. All of the third elements, except nickel, lowered the transformation temperature if the results were plotted along the lines of constant zinc contents in each ternary system. A significant difference in the rate of lowering of the transformation temperature per atomic percent of the third element was observed for elements which had the same nominal valence. No systematic variation of transformation temperature with the valence of the third element was observed. It is suggested that the observed increase in transformation temperature for nickel-bearing alloys is due to the transfer of electrons from the conduction band of the alloy to virtual bound states. However, electron concentration is not the most important factor controlling the instability of the 0 phase. The transformation temperatures of the ternary alloys can be predicted from the following approxilnate expression: Ms (°K) = +3280 - 80 Zn + 8 Ni - 30 Ag - 12 Au - 140 Cd -90 Ga- 145 In - 80 Ge -175 Sn - 120 Si - 150 Sb MOST binary ß -phase alloys based upon the noble metals copper, silver, and gold are unstable at low temperatures and transform spontaneously by a martensitic reaction. This transformation has been studied recently in the ordered bcc ß&apos;-phase Cu-Zn binary al1oys1,2 where the transformation temperature is below the room temperature and decreases with an increase in zinc content. It has been reported that the transformation temperatures can be raised above room temperature by small additions of a third element such as silicon3,5 or gallium,4,5 but no quantitative study has been made. The transformation temperature of different binary alloys can be altered by third-element additions. For example, it was shown that nickel and copper may have a large effect on the Ms temperature of CU-Al6 and Au-cd7 alloys. The present investigation was made to determine systematically the influence of various third elements on the martensite-transformation temperature of Cu-Zn ß-phase alloys. Since these alloys have an electronic origin,&apos; alloy compositions were chosen so that the transformation temperatures could be determined at constant zinc contents or at constant values of electron concentration. I) EXPERIMENTAL PROCEDURE Ten ternary alloy systems were obtained by adding nickel, the noble metals silver and gold, and some B-subgroup elements to a Cu-Zn matrix. These are arranged according to their rows and columns in the Period Table as follows: Each ternary alloy was prepared by melting and casting weighed quantities of high-purity metals (99.99+ pct) in sealed quartz tubes under a partial pressure of helium to make a 4-g ingot. The molten alloys were shaken vigorously and then quenched in water. Since the weight loss was negligible, the compositions of the ingots after casting and annealing were assumed to be the same as the nominal compositions. The ingots were homogenized after casting in helium-filled Vycor tubes for 24 hr at temperatures between 750" and 810 C and quenched into brine. Metallographic examination revealed that all alloys were homogeneous, poly crystalline ß-phase alloys, and that the grain size was in the range 1 to 5 mm. Electrical-resistivity measurements were made to determine transformation temperatures of the ternary alloys during continuous cooling or heating. Transformation temperatures of the ternary alloys can be determined by electrical-resistivity measurements since the resistance of the martensitic phase is much higher than that of the 0&apos; phase. The technique has been described previously in connection with a study of Au-Zn alloys.9 The reproducibility of transformation temperature was approximately ±6°C. II)RESULTS A hysteresis was always observed in electrical-resistivity curves and was usually less than about 12°C.

Jan 1, 1967

By R. R. Vandervoort, W. L. Barmore

Tensile creep experiments were conducted on high-purity, poly cvystalline rhenium from 1500" to 2300°C at stresses from 1500 to I0,OOO psi in a vacuum of 10-a torr. The apparent activation energy for creep was 60 kcal per mole, and the steady-state creep rate varied directly with stress to the 3.4 power. Dislocation substructure that developed during creep was studied by transmission electron microscopy. Possible rate-controlling deformation mechanisms are discussed. The creep behavior of most metals at elevated temperature can be represented by the following equation:&apos;&apos;&apos; t = Cf(s)(^)(s/E)nD [1] where i = steady-state creep rate, C = constant, f(s) = a function involving microstructure, s = applied stress, E = the average elastic modulus at test temperature, n = constant, D = diffusion coefficient According to this well-established relationship, metals with higher elastic moduli and lower diffusion coefficients should have greater creep resistance at the same stress and temperature and equivalent mi-crostructures. While no diffusion data are available, the diffusivity of rhenium should be less than that for most other refractory metals because of its high melting point and hcp crystal structure. The Sherby-Simnad relation for calculating atomic mobility in metallic systems3 predicts that the diffusion coefficient for rhenium is less than that experimentally determined for tungsten4 in the temperature region 1500. to 2200°C. At these temperatures the elastic modulus for tungsten5 is only slightly larger than the extrapolated modulus for rhenium.6 Thus, rhenium is a good possibility for a a high-temperature structural material, but few data on the creep of rhenium have been reported. This investigation was undertaken to study the high-tempera-ture deformation behavior of rhenium in detail. EXPERIMENTAL TECHNIQUES The material used in this study was consolidated from high-purity powder. After cold pressing the powder to a plate a in. thick, the billet was sintered in hydrogen at 2250°C for 24 hr. The plate was reduced to 0.100 in. by cold cross rolling with intermediate anneals at 1650°C for 20 min between passes. The plate was further reduced to 0.060 in. by unidirectional cold rolling with similar heat treatments between passes, and then finally stress-relieved in hydrogen at 1650°C for 30 min. Specimens tested at 1900°C and below were pretest-annealed at 1900°C for 2 50 hr. Specimens tested above 1900°C were pretest-annealed at 2400°C for 5 hr. The impurity content in the "as-received" plate was quite low, table I. Essentially no change in impurity levels was detected in specimens after creep testing. All creep tests and annealing treatments were conducted in a vacuum of 10-8 torr in a test furnace heated by a tungsten mesh element. The load was applied to the specimens through a bellows, and stresses were maintained to ±1 pct of the selected value by periodic corrections for changes in specimen cross-sectional area during creep and for changes in the bellows spring force due to load column extension. One-inch-diameter tungsten force rods were used in the hot zone of the furnace. Deformation at temperature was measured by optically tracking gage marks on the specimen. Temperature was measured by a calibrated optical pyrometer and was determined to ±5"C. Grain sizes were determined by the linear intercept method and specimens were examined in the "as-polished" condition, using polarized light. Specimens annealed at 1900°C had a grain size of 52 ± 5µ , and those annealed at 2400°C had a grain size of 148 * 11 µ. Pieces were cut from the gage section of creep-tested specimens and planed to a thickness of about 0.010 in. by spark discharge machining. Thin foils for viewing by transmission electron microscopy were obtained by electropolishing in a solution of 6:3:1 ethyl alcohol, perchloric acid, and butoxy ethanol, respectively, using the window technique. Bath temperature was —4OoC, and the cell potential was 35 v. The foils were examined in Siemens Elmiskop I, operating at 100 kv. RESULTS AND DISCUSSION In order to analyze the results from creep experiments, Eq. [I] is rewritten in the following form: <=Kf(s)ne-/RT [2] where K = constant, ?// = apparent activation energy for creep,

Jan 1, 1970

By B. J. Bayles, J. A. Ford, M. J. Salkind

Unidirecltonally sulidijied AL-A13Ni was found to exliibit excellent microstructural stability to 508°C. Above this temperature the transverse micvostructure coarsened in a manner analogous to "Ostwald Ripening", but the A13Ni whiskers did not spheroidize or foreshorlen. The coarsened whiskers reinforced the matrix as effectirely as the finer whiskevs and no reduction in room-temperature tensile strength mas noled after exposure for 90 hr at 96 pel 0-1 the absollite melling temperature of the eulectic. The slability was auribucted to the presence of low-index (and presurrlably lor-energy) cvystallographic interjaces between phases. The driving force for microstructural coursening was presumed to be the reduction of interfacial energy between the phases. Finer micvoslructures were found to coarsen more rapidly than those which weve imitally coarser. FIBER-reinforced metals have been shown to exhibit good short-time tensile properties at elevated temperatures.1-4 However, many elevated-temperature applications require long-time property retention which dictates the necessity for microstructural stability. Two types of instability are common to fiber composities. The first, chemical instability, is due to chemical reaction between the matrix and the relnforcing phase. Petrasek and weeton5 have shown that chemical reaction between tungsten wire and several copper alloy matrices resulted in degradation of the reinforcing phase and reduction in strength of the composite materials. Kreider and Leverant4 have noted similar behavior for boron-reinforced aluminum above 400°C. The second type of instability arises in systems in which the phases are essentially chemically stable with respect to each other and is characterized by spheroidization and/or agglomeration of the reinforcing phase. parratt6 has reported this type of degradation to occur relatively rapidly at moderate temperatures for nickel and cobalt alloys containing whiskers of silicon nitride, aluminum oxide, and silicon carbide and has identified it as "physicochemical" instability. Although both types of instability are the result of the differences in the chemical potential between the fibrous phase and the matrix, they may be differentiated by the fact that the second type, "physicochemi-call&apos; instability, results in little or no net change in the composition or amount of each phase present. It does, however, result in a morphological change which profoundly affects the strengthening mechanism. Chemical interaction. on the other hand, results in a change in the composition and amount of one or more of the phases present, or the appearance of a new phase. In the latter case, the appearance of the mi-crostructure, that of a fibrous phase aligned in a matrix, may remain essentially unchanged, but the chemical degradation of the fiber results in markedly reduced composite strength. This investigation was initiated in an attempt to evaluate the microstructural and related mechanical property changes of a whisker-reinforced eutectic composite after elevated-temperature exposure. The composite system chosen for this study was the uni-directionally solidified A1-A13Ni eutectic which Lemkey. Hertzberg, and Ford7,8 demonstrated to behave as a whisker-reinforced composite. The microstructure of the unidirectionally solidified material consists of aligned needles of A13Ni in a matrix of aluminum. EXPERIMENTAL PROCEDURE Eutectic ingots having a nominal composition of 6.2 wt pct Ni were produced by melting 99.99+ pct A1 and 99.99 pct Ni in recrystallized alumina crucibles in an argon atmosphere. The analyses of the starting materials are listed in Table I. These master heats were cut up? melted by induction heating, and unidirectionally solidified vertically in 1/2 -in.-ID. 6-in.-long graphite crucibles, in a dynamic argon atmosphere. Therma1 gradients in the liquid were determined by measuring the temperature in the melt as a function of apparatus travel distance, as discussed by Kraft and Albright.9 The rate of solidification was assumed to be equal to the uniform rate at which the crucible assembly was withdrawn from the furnace. Ingots representative of nominal growth rates of 2, 5, and 11 cm per hr were produced and the solidification parameters are summarized in Table 11. Ingots used for met allographic analysis were pre-

Jan 1, 1968

By F. Weinberg

Measurements have been made of solute segregation during dendrilic growth by using radioactive solute elements and ,measuring the activity of den(12-ites cut from decanted specimens. This has been done for both lead awl tin based binary alloys contaitzing the following solute additions: Ag, T1204, was dependet on ko, the equilibrium distribution coefficient in the following way Fay k &apos;c 0.1, C/C 0.6; for k0 >0.1. 0.6 <c,/c,< I. Qualitative obse?-vations were madc of dendritic segregation, by using autoradiographic techniques, for the Sn + Ag110 and Sn + Tlo4 systems. The observation were found to he in general agreement with the measurements ofCA/Co. Autoradiographic were also obtained of scctiolccl delzr11-iie stalks. These indicated that the stalks had a substructure, dclileated by solute corzetlt?atio?zs nlolg the substructure walls. A new dendrite growth direction <JI2> is reported for tila. SOLUTE segregation in dilute binary alloys has been investigated by Pfann,&apos; Smith, Tiller, and Rut-ter,&apos; and others. They considered the case of a slowly advancing plane solid interface, and derived expressions for the distribution of solute in both solid and liquid during solidification. To determine these expressions, they assumed no diffusion in the solid and either complete mixing in the liquid:&apos; or diffusion controlled solute movements in the liquid without any convective mixing.&apos; The present investigation considers solute segregation during dendritic growth, in which case the solid-liquid interface is not plane, and the growth rates are rapid. Segregation under these growth conditions has not been treated mathematically, because of the relative complexity of the system. It has been suggested by Chalmer, on the basis of preliminary results, that an alternative to the diffusion and heat flow controlled conditions during growth is &apos;diffusionless" dendritic growth in which solid is formed with the same composition as the liquid. He suggests this type of growth may depend upon a solvent-solute relationship that permits some solid solubility without excessive increase in internal energy, as is the case for solutions of tin in lead. On the other hand, Montariol,4 and others, have shown experimentally that some segregation does occur during dendritic growth in metals using etching and radioactive tracer techniques to indicate the concentrations of the solute. The present investigation was undertaken to determine, both qualitatively and quantitatively, the extent of solute segregation associated with dendritic growth in a series of binary alloys, as a function of solute concentration. PROCEDURE The solvent materials used were Vulcan Electrolytic tin (99.997 pct purity) and Tadanac lead (99.998 pct purity). The solute materials were Zn, Sn, and Sb (better than 99.998 pct purity), Ag and Co (99.5 pct purity), and T1 (Fisher "purified" metal sticks). Activation of the solute metals was carried out in the reactor at Chalk River, Canada. Master alloys were prepared by induction heating from the radioactive solute metal and the pure solvent, under argon, in graphite crucibles. Pieces of these alloys were then added to the solvent to give the required solute concentration. Dendrites were grown in essentially the same manner as that described by Weinberg and Chalmer, , in which controlled orientation single crystals were grown dendritically in horizontal graphite boats, and the liquid decanted. The crystals were grown and decanted in an atmosphere of tank argon. Before decanting, a sample of the liquid was drawn up in a glass tube and allowed to solidify rapidly. The orientations of the single crystals were such that <loo> was parallel to the growth direction, and (100) in the horizontal plane for lead, and [1101 and (110) respectively for tin. With these orientations long dendrite stalks formed along the bottom of the boat in the dendrite direction (<100> for lead and [I101 for tin) from which secondary branches grew. Only these secondary branches, which grew freely in the liquid from the dendrite stalk to the liquid surface, were used in the measurements. Accordingly, effects due to substrates and oxides on the surface of the liquid need not be considered. In order to measure the solute concentration C, of the dendrites, individual dendrite stalks were cut from the decanted specimens, remelted, and formed

Jan 1, 1962

By Walter W. Fisher

Cement copper was flash roasted in a vertical tube furnace to convert the copper to acid-soluble oxides as part of a postulated process for refining cement copper by oxidation roasting, acid leaching, and electrowinning. The results of the study showed that the oxidation was a linear function of oxygen concentration between 0 and 20 percent, but above 20 percent oxygen there was no further increase in oxidation. Therefore, air was the optimum oxidizing atmosphere in this flash roasting system. The oxidation followed a parabolic rate law as the roasting temperature was increased from 400° to 800° C. Extrapolation of the data, based on the parabolic law, indicated that at 400°, 500°,600°,700°, and 800° C, the roasting times required for complete conversion to soluble oxides were 75, 37, 21, 7.7, and 4.6 seconds, respectively. Cyclic-roasting test results did not substantiate the predictions obtained through data extrapolation.

Jan 1, 1973

By G. Baralis, P. Gondi, I. Tangerini, G. Scandola

The precipitation behavior of Zn-0.5 pct A1 alloy single crystals was studied by means of electrical resistivity measurements and by optical and electron microscopy. The single crystals for the resistivity measurements were prepared by an original method in - 100-p -thick sheets. The order of the precipitation kinetics ranged between 1 and 1.5. The dislocations play a relevant role in the first-order kinetics. Precipitation always occurs both on dispersed particles and on dislocations. Statistical examinations have shown that the first-order kinetics can have two different activation energies; i.e., the precipitation can have dz;fferent mechanisnrs which could not be identified, however, in the course of the research. During the tnetallographic exanzination of the precipitation structures a specific process of dislocation decoration was obsereed. The main purpose of this work was to study the contribution of dislocations to the precipitation. A number of authors have observed precipitation on dislocations and reference might be made to several monographs on the ubject.&apos;&apos; The possibility that dislocations also accelerate precipitation has been considered by Turn-bull3 and Fischer et al.4 The studies described in the present paper were carried out on zinc, chosen as a base metal owing to the ease with which dislocations can be introduced into it and because of the absence of excess vacancies after quenching in conditions where phenomena of accelerated precipitation still occur. Aluminum was preferred as alloying element because of the accelerated precipitation phenomena that resulted in a preliminary reearch. EXPERIMENTAL METHODS The observations refer to a Zn-0.5 pct A1 alloy. The zinc was 99.995 pct pure; a typical spectroscopical analysis is given in Table I. As a rule the alloy was subjected to homogenization, quenching, or slow cooling and annealing. Homogenization was carried out by heating at 390" to 410°C for 24 hr. From the homogenization temperature, some specimens were quenched and some slowly cooled at a rate of 2°C per sec. At this rate no precipitate was detectable under the optical microscope just after cooling. Quenching was carried out simply by dropping the specimens into water, aqueous ethylene glycol solution at -30" c, or liquid-nitrogen baths placed close to the homogenization oven. Vaseline oil baths were used with a thermal stabilization of 10-20 for both the aging treatments and the measurements; aging was generally carried out at 90" or 130°C. To avoid oxidation phenomena during heating, the vaseline oil baths had to be frequently renewed. The precipitation kinetics were studied by means of electrical resistivity measurements, using ans potentiometric method (reproducibility ± 5 x 10 5 v, that is 0.5 pct of the total voltage decreases on the specimens during precipitation). First, various types of specimens were tested, i.e., polycrystals, single crystals grown in capillary quartz tubes, and thin single-crystal sheets prepared by means of an original method requiring no container except for the natural oxide. Even if fully annealed, the polycrystals and the capillary grown single crystals showed resistivity in -creases, most probably due to dislocations introduced in the course of the measurements. Similar resistivity increases in pure zinc were noticed by another author. Only the single-crystal sheets showed no resistivity change; thus they were chosen for the subsequent tests. As already mentioned, these single crystals were obtained by using, as a container, the natural oxide on the zinc surface; the oxide strength is sufficient to maintain the original shape during melting with sheets up to 500 p thick. An initial zone melting and subsequent zone leveling, which led also to formation of the single crystals, were thus carried out on rolled sheets of the required thicknesses (- 100 p) and shape, lying on a flat silica surface. The resistivities were first evaluated by measurements at the liquid-nitrogen temperature. This method gave poor reproducibility, however, and this was attributed to the thermal cycles which had to be operated. To avoid cycles and handling, it was therefore decided to make measurements directly in the annealing oil baths; this required thermal stabilization at ilo-&apos; "C. In this way only the resistance changes were measured. Specimens of pure zinc and of completely annealed alloy were always examined as controls together with those under consideration; only those measurement runs were taken into account where the reference samples showed no resistance increases. Again, the main inconvenience was due to oxidation and this was avoided by renewing the oil baths; even so data reproducibility was poor and the observations were therefore carried out on a large number (many hundreds) of specimens so as to provide indications of statistical value. For the transmission observations under the elec-

Jan 1, 1969

By A. R. Orban, R. B. Engdahl, J. D. Hummell

The initial phase of a research program on smoke abatement from Bessemer converters is described. In work sponsored by the American Iron and Steel Institute, a 300-lb experimental Bessemer converter was assembled to simulate blowing conditions in a commercial vessel. Measurements of smoke and dust were also made in the field on a 30-ton commercial vessel. During normal blows the dust loading from the laboratory converter averaged 0.51 lb per 1000 lb of exhaust gas. This was similar to the exhaust-gas loading of a commercial vessel. The addition of hydrogen to the blast gas of the laboratory converter caused a decided decrease in smoke density. Smoke was also reduced markedly when methane or ammonia was added instead of hydrogen. The research is continuing on a bench-scale investigation of the mechanism of smoke formation in the converter process. DURING the past 2 years, on behalf of the American Iron and Steel Institute, Battelle has been conducting a research program on the control of emissions from pneumatic steelmaking processes. The objective of the research program is to discover a practical method for reducing to an unobjectionable level the emission of smoke and dust from Bessemer converters. PRELIMINARY INVESTIGATION Although conceivably some new collecting technique may be devised which would be economically practicable for cleaning Bessemer gases, no such system based on presently known principles seems feasible because of the extremely large volume of high-temperature gases involved. Hence, the research is being directed toward prevention of smoke formation at the source. A thorough review was first made of former work to determine the present status of the cleaning of converter gases. No published work was found on work done in the United States on collecting smoke or on preventing its formation in the bottom-blown, acid-Bessemer converter. In Europe, however, a number of investigations have been made on the basic-Bessemer converter. Kosmider, Neuhaus, and Kratzenstein1 conducted tests on a 20-ton converter to obtain characteristic data for dust removal and the utilization of waste heat. They concluded that because of the submicron size of the dust, special equipment would be necessary to clean the exhaust gases. Dehne2 conducted a large number of smoke-abatement experiments at Duisburg-Huckingen in a 36-ton Thomas converter discharging into a stack. A number of wet-scrubbing and dry collectors were tried unsuccessfully. A waste-heat boiler and electrostatic collector with necessary gas precleaners was felt to be the best solution for this particular plant. Meldau and Laufhutte3 determined that the particle size was all below 1 µ in the waste gas of a bottom-blown converter. Sel&apos;kin and zadalya4 describe the use of oxygen-water mixtures injected into a molten bath in refining open-hearth steel. They claim that with use of oxygen-water mixtures the amount of dust formed was reduced between 33.3 and 20 pct of its previous level, and emission of brown smoke almost ceased. Pepperhoff and passov5 attempted unsuccessfully to find some correlation between the optical absorption of the smoke, the flame emission, and the composition of the metal in a Thomas converter in order to determine automatically the metallurgical state in the melt. In a recent U. S. Patent (NO. 2,831,762)&apos; issued to two Austrian inventors, Kemmetmuller and Rinesch, the inventors claim a process for treating the exhaust gases from a converter. By their method the inventors claim that the exhaust gases from the converter are cooled immediately after leaving the converter to a degree that oxidation of the metal vapors and metal particles to form Fe2O3 is inhibited in the presence of surplus oxygen. Gledhill, Carnall, and sargent7 report on cleaning the gases from oxygen lancing of pig iron in the ladle. They claim the Pease-Anthony Venturi scrubber removed 99.5 + pct of the smoke, thereby reducing the concentration to 0.1 to 0.2 grain per cu ft, which resulted in a colorless stack gas after the evaporation of water. Fischer and wahlster8 developed a small basic converter and compared the metallurgical behavior of the blow with that of a large converter. Later work by Kosmider, Neuhaus, and Hardt9 on the use of steam for reduction of smoke from an oxygen-enriched converter confirmed that the cooling effect of steam is detrimental to production. From review of all of the published information on the subject, it was concluded that a practical solution to the smoke-elimination problem had not been found. Accordingly, it was deemed desirable to investigate the feasibility of preventing the initial formation of smoke in the converter.

Jan 1, 1961