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By K. Takahashi, I. Iwasaki

The methyl stretching vibrations for a series of normal xanthates, isoxanthates and normal amines were determined with the aid of an infrared spectro-photometer, and the results were compared with published information on the corresponding alcohols. The frequency shifts of methyl stretching vibrations may be attributed to the inductive effect of polar groups. The hydrogens in the shorter chain alkyl groups are somewhat polar and can be expected to interact with water molecules by hydrogen bonding. Contact angle, surface tension lowering, solubility, and critical micelle concentration appear to be related to the induced polarity of the alkyl groups. Traube's rule states that in homologous series of compounds solubility decreases and surface activity increases regularly with the size of the hydrocarbon group. Analyzing the work of transfer of a solute from solution to surface, Langmuir' interpreted this rule to mean that each CH2 group added to a molecule produced its effect independently of the others. It is also well known2 that the maximum equilibrium contact angle with sulfhydryl collectors is independent of the polar groups and of the sulfide minerals, and that it increases to a certain limit with the number of carbon atoms in the alkyl group. This observation is thought to demonstrate the orientation of the collector molecules at the sulfide surfaces. The dependence on the hydrocarbon chain length is usually explained as due to the screening of the force field of polar mineral surfaces.3-5 Here again, Langmuir's principle of independent surface action appears to be implied. Heteropolar compounds consist of nonpolar and polar groups, the former being the hydrocarbon group and the latter containing such electronegative atoms as O, N, S, P, or halogens. According to Palit6 the hydrogens in the alkyl groups are more electroposi- tive than in the paraffins owing to the negative inductive effect of the polar groups and a possibility that a hydrogen bond with water molecules ensues. Goto and Takenaka7 provided direct evidence of the inductive effect by measuring the shift of the C-H stretching vibrations of alcohols, acids, and alkyl bromides with an infrared spectrophotometer. Their approach appeared to be directly applicable to the studies of surface activity both at air-water and water-mineral interfaces encountered in flotation systems. The present article attempts to relate the C-H stretching vibrations of alkyl xanthates, alcohols, and amines with such flotation chemistry parameters as contact angle, surface tension lowering, solubility, and critical micelle concentration. MATERIALS AND METHODS Normal xanthates from methyl to octyl inclusive and the isopropyl, isobutyl, and isoamyl xanthates used in this investigation were prepared in the usual manner.8 Normal amine hydrochlorides with carbon chain lengths of 1, 2, 4, and 6 were from Distillation Products Industries, of 8 from Archer-Daniels-Midland Co., and of 10, 12, 14 and 16 from Armour and Co. Normal propylamines, pentylamines and heptylamines from Distillation Products Industries were used both as received and as hydrochloride formed by converting the amines according to the procedure described by Li9 Perkin-Elmer Model 521 and 621 infrared spectro-photometers were used to investigate the spectra in the frequency region of 3050 to 2800 cm-' with frequency scale expansion. The accuracy of the frequency readings was within + 1 cm-1. The KBr micropellet technique was used to prepare the xan-thate samples for measurements, and the halocarbon mull technique was used for amines and amine hydrochlorides. EXPERIMENTAL RESULTS Fig. 1 shows the CH3 asymmetric stretching vibrations as a function of the number of carbons in the alkyl group for normal xanthates, isoxanthates and amines. Also included in the figure are data for normal alcohols and isoalcohols taken from the article

Jan 1, 1970

By Raymond O. Dannenberg

Potential processes for the recovery of precious metals and copper from diverse types of complex electronic scrap were investigated. Leaching-type processes were not successful, and attempts to physically separate the various gangue metals and plastics from more valuable components were also unsuccessful. The most promising approach was a smelting process, followed by electrolytic treatment to separate precious metal from copper. Recovery of precious metals from the anode sludge may follow conventional procedures. An alternative to the above process is incorporation of the scrap with the concentrate fed to an industrial copper reverberatory or converter furnace, possibly preceded by direct melting to form an assayable bullion and dross.

Jan 1, 1970

By T. Toda, R. Maddin

A study has been made of the microstructure and mechanical properties of splat-cooled aluminum-base gold alloys with gold concentration from 0.25 to 5.0 wt pct. These alloys have been quenched from the liquid state by a torsion-catapult technique, which has made it possible to pepare specimens suitable for mechanical property measwements. From the electron micrographs it has been shown that the solid solubility of gold in aluminum can be extended to 2.5 wt pct (0.35 at. pct) by splat-cooling, while the maximum equilibrium solubility is known to be less than 0.3 wt pct (0.04 at. pct). The very fine grain size (several tenths of a micron), the extended solid solubility, and the fine dispersion of a second phase (AuAl2) contribute concurrently to a substantial strengthening effect. In Al-5 wt pct Au splat-cooled specimens of less than 50 thickness, the yield strength is 17 kg per sq mm or 6 times as large as the strength of bulk specimens. For the Al-1.0 to 2.5 wt pct Au solid solution obtained by splat-cooling, the yield strength reaches 7.5 kg per sq mm after an aging treatment (for 10 hr at 200°C), while it is 3.7 kg per sq mm for the corresponding bulk specimens. A great deal of research has been done in recent years on the structure and the properties of metals and alloys rapidly quenched from the liquid state.' The term "splat-cool" has been used with the meaning of a rapid quenching from the liquid state., The splat-cooling techniques have produced large numbers of new structures, which are expressed in terms of metastable phases,3 concentrated solid solutions,4 amorphous phases,5'6 new phases,7 and so forth. Nearly all previous studies have concentrated on the physical properties; i.e., crystallography, structure, electrical resistivity, magnetism, and so forth, of the splat-cooled metals and alloys. The mechanical strength of splat-cooled metals and alloys has hardly been investigated except for some recent work by MOSS' on A1-V alloys. The principle common to all experimental techniques developed to obtain very rapid quenching rates is based on the heat transfer by conduction. Liquid must be in good thermal contact with a substrate of high heat conductivity. Both of the published devices known as the "gun" and the "piston and anvil" techniques suffer from certain shortcomings. For example, the specimen obtained by the gun technique is very small and flaky, and hence inadequate for mechanical properties measurements. On the other hand if the material is forced to yield a continuous speci- men by the piston and anvil technique, it is probable that some plastic deformation occurs during the quench. A novel method for rapid quenching of a liquid metal or alloy, the "torsion-catapult", has been devised by Roberge and Herman9 at the University of Pennsylvania. In the apparatus the melt is thrown out of a curved furnace by a catapult and impinges on a copper substrate. The apparatus has the advantage of producing a continuous foil which is relatively large in size and of a quality suitable for the measurements of mechanical properties. The quenching rate is estimated to be of the order of l05 to l06 ºC per sec, (comparable to rates achieved by the piston and anvil technique). In selecting an alloy to be studied we were made aware of the fact that gold was believed to be "insoluble" in in and consequently age hardening in the A1-Au system appeared to be interesting. Quite recently Heirnendahl13-15 revealed that the solid solubility, as determined by transmission electron microscopy, was 0.3 wt pct Au at 640°C and 0.25 wt pct Au at 600°C, decreasing with decreasing temperature. In an A1-0.2 pct Au alloy after quenching from a solution treating temperature of 600°C the yield stress was 2 kg per sq mm, and it increased up to 6 kg per sq mm after aging for 1 to 10 hr at 200°C. The precipitation occurred in the form of platelike particles mainly on (100) matrix planes. The intermediate phase n', the equilibrium phase n (AuAl2), and lattice relationships between both precipitates and the matrix were also investigated by electron microscopy. One of the purposes of the present research is to determine whether or not the solid solubility in this system, in which gold has a very small solubility in

Jan 1, 1970

By A. L. Mular

This paper provides a worthwhile contribution to the knowledge needed for calculating and using mathematical models of grinding circuits. The computer search algorithm proposed should remove much of the guesswork as well as reduce computer processing costs and improve the accuracy of estimated parameter values for grinding mill models.

Jan 1, 1970

By C. L. Horn

All the tunneling machines discussed in this chapter are Calweld machines. I have divided the machines designed for soft-to-medium formations into three groups, correlated with typical formations and estimated compressive strengths: 1) Running sand and silt requiring blade cutters. 2) Chalk and clay, requiring drag-type cutters, for compressive strengths ranging from 0 to 2000 psi. 3) Sandstones, hard clays, and limestones, requiring disk cutters, for compressive strengths ranging from 2000 to 20,000 psi. All of the soft-to-medium-formation machines are powered by electric hydraulic or diesel hydraulic pumps. The pumps in turn drive hydraulic motors for the torque reaction. The soft-to-medium-formation machines are enclosed in a 360º shield with a cutting shoe, a center portion of the shield housing the mechanical equipment, and a tail shield. Tunnel supports are usually required, and the supports are normally erected in the tail shield. Our first machine was built in 1963, and all but five of the machines illustrated in the figures with this chapter were built in 1966 and 1967. Some of the machines manufactured will be discussed in the following sections; specific features as development has progressed will be pointed out. HARD-ROCK MACHINE The Calweld hard-rock machine has been designed along basic and accepted principles for a hard-rock mechanical borer. The features of this machine are as follows: 1) Direct electric motor drive through a planetary gear reduction ring and pinion gear, and then to the cutting head through a hollow drive shaft.

Jan 1, 1970

By Roger J. Araujo

A photochromic material is one which undergoes a change of color when exposed to light and reverts to its original color when the light is removed. Review articles carrying extensive bibliographies have been written by Brown and Shaw (1) and by Schwab and Bertelson (2). Organics. Schwab and Bertelson divide the reactions in different organic photochromic materials into some half-dozen categories; Windsor (3) reduces these to the following three main classes of general interest, based on how they work. 1. Stereoisomers. Absorption of light breaks one of the chemical bonds in a. ring molecule, thus allowing the molecule to unwind and form a different geometrical arrangement. The reverse process is a reforming of the bond. Examples of this class are the spiropyrans and the anils. 2. Dyes. A triphenyl methane dye, for example, is oxidized by energetic light; the absorption characteristics of the positive ion so formed are different from those of the original electrically neutral benzene rings. 3. Triplet States. In the class of polynuclear aromatic hydrocarbons, ground-state molecules are excited first to a singlet state by irradiation, and then go, via the lowest triplet state, to an excited triplet state. Visible light is absorbed in the triplet-triplet transition.

Jan 1, 1970

The production of harmful pollutants from coal mines and/or from coal and associated strata has been a recognizable fact in the United States for over two hundred and seventy years. In 1698, Gabriel Thomas observed(l) that the colored water flowing from streams in this country was similar to that which flowed from the coal mines in Wales. Hence, water pollutants such as acid were being produced before any known coal mines were operating in this country. The coal mining industry has contributed to the increase of pollution by exposing large amounts of sulfide materials that enable the reaction of water, oxygen and sulfur containing materials to form acid. A map of the United States coal fields can be seen on Figure 1. The anthracite regions of Pennsylvania, although small when compared to the total reserves, have produced some of the country's major water problems. The map indicates the extent of bituminous reserves of the Appalachian and midwest regions. Also evident are the bituminous, subbituminous and lignite coal reserves in the west which have recently come into greater demand. Acid mine pollution is encountered in numerous states, but the major problem is found in the Ohio, Susquehanna, and Potomac River basins.(2) Most coal beds contain some sulfur which may be in the inorganic, sulfate, or sulfide form, and thus have the potential to produce sulfuric acid. However, much of the strata that overlays the coal beds also contains acid neutralizing materials. Therefore, the amount of acid produced depends upon the amount of both acid and alkali materials that dissolve in the water in any given mine. The common sources of sulfurous material in the seam or surrounding rock are generally called sulfur balls or "nigger heads" by the miners. Sulfur balls that have been observed(3) seem to be equally divided between those containing sulphuritic iron capable of producing sulfuric acid upon oxidation and those that are primarily calcium carbonate. It has been observed in many instances that two types of water, acid and alkaline, are being produced in the same mine. A study of the geological strata and a survey of subsidence, faults and sulfur balls will usually give some indication of why this happens. The reaction of pyrite (FeS2) with oxygen and water to form ferrous sulfate (FeSO4) and sulfuric acid (H2SO4) by a series of complex chemical interactions is well documented but not well understood.(4,5) However, it is well known that the reactions to form the acid cannot occur unless all three constituents are present. Since pyrite is inherent in most coal seams and air is needed to sustain the miner, the most logical answer is to eliminate water infiltration into the mine, or to remove it from the mine before acids can form.

Jan 1, 1970

By A. D. Kennedy

No major breakthroughs in concentration technology were made during the year, but solid advances were made in engineering. Perhaps the most significant was the growing acceptance of the unified or "systems approach" to mineral extraction, processing, refining, transportation and marketing. Under the systems approach, transportation is no longer some- one else's business, but a high cost item within the planning engineer's purview. The Savage River pipeline 1,2 and the Marconaflo process3,4 for land and ocean transport of iron ore slurry, are examples showing that evaluation of transportation as part of a unitized system can lead to innovation, and the determination of the physical location of some of the operations. There is even speculation that the cost reductions possible by ocean transport of iron ore slurry may bring in more plants using direct-reduction steelmaking processes.4 Some perennial problems can be solved by application of the systems approach; for example, under this concept the replacement of three small shovels in the pit with two larger shovels is not permissible on the basis of lower operating costs; the resulting change in ore blending upon metallurgical performance must first be evaluated to prove whether or not the change is economically beneficial to the entire operation (perhaps new storage-blending facilities will be indicated).

Jan 1, 1970

By J. E. Murphy

Purification of samarium metal by sublimation and by vaporization from a low-melting metal flux, at the same temperature, were compared. Vaporization proved more effective for removing impurities such as magnesium, calcium, and manganese. Recovery of samarium, however, is more rapid by sublimation because of its constant rate of distillation.

Jan 1, 1970

By H. Stuart, L. Zwell, N. Ridley

specimen that was subjected to 700°C for 250 hr is shown in Fig. 2(c). The precipitates in this foil appear round and exhibit only very faint strain contrast. From this evidence, along with that described above for the symmetry of the strain field, it may be concluded that this coherent precipitate is spherical, which is generally the favored shape for coherent precipitates when the lattice parameter mismatch is small.12 These observations are consistent with the assumption that this precipitate is the y' (Ni3Al, Ti) phase. y' is known to be spherical in the early stages of precipitation. It is fcc and is similar in composition to the matrix and thus would have contrast similar to that of the matrix as do these precipitates. Direct identification of the spherical precipitate did not prove possible because of its low volume fraction and small size. The results of this investigation suggest that the increases in yield strength and the decreases in elongation observed in 45-Fe 30-Ni 20-Cr alloys containing about 0.4 pct A1 and 0.4 pct Ti on prolonged aging at 550" to 700°C are very likely due to the presence of a coherent, spherical precipitate, thought to be y'. Mi-crohardness measurements indicated that the precipitation of semicoherent M23C6 resulted in some matrix hardening. However, this precipitation process occurs much more rapidly than the changes in mechanical properties at these temperatures. 1C. L. Clark, J. J. B. Rutherford, A. B. Wilder, and M. A. Cordovi: J. Eng. Power, 1962, vol. 84, p. 258. 2 F. A. Comprelli and U. E. Wolff: USAEC Report GEAP-4745, General Electric Company November, 1964. 3C. N. Spalaris: A Monograph, USAEC Report GEAP-4633, General Electric Company, July, 1964. THERE have been many X-ray investigations of the room temperature lattice parameters of austenite which has been retained in quenched steels of various carbon contents. The results of these investigations have been collected by Wrazej,1 Wever et al.,2 and by Roberts3 and are included in Fig. 1 due to Pearson.4 The dashed line in Fig. 1 was considered by Roberts3 to most reliably describe the variation with carbon content of the lattice parameter of retained austenite. This line is given by the equation: a (Å) = 3.555 + 0.044 wt % C and recent unpublished measurements by one of the authors (LZ) support this relationship. The object of this communication is to draw attention to a relationship which describes the variation of the room temperature lattice parameter of 'equilibrium' austenite with carbon content, and which is different from that for retained austenite. The relationship a(Å) = 3.573 + 0.033 wt % C has been obtained from lattice parameter measurements made on equilibrium Fe-C austenites at elevated temperatures, which have been extrapolated to room temperature. The room temperature lattice parameter of 3.555Å which the Roberts' relationship gives for pure y-Fe is no: in agreement with the value of 3.573Å obtained when the high temperature lattice parameter data of Basinski et aL.5 and of Goldschmidt6 is extrapolated to room temperature. A linear extrapolation was

Jan 1, 1970

By Robert H. Merrill, Raymond M. Stateham

Recently, the Denver Mining Research Center of the U.S. Bureau of Mines began tests to detect hazardous or potentially hazardous conditions in or around mines with infrared measurement devices. Among the many potential uses of infrared detection techniques are the location of misfires, underground mine fires, combustion in waste dumps, underground water courses and loose rock. However, the primary emphasis has been placed upon the detection of loose rock in roofs, pillars and faces in underground mines. The rock along the edge of an underground opening is subject to two temperature environments: the temperature of the air in the opening, and the temperature of the rock surrounding the opening. Assuming that the rock on the edge of the opening is solid, the rock will reach an equilibrium temperature that depends upon the temperature and flow of the air, the thermal conductivity of the rock and its ambient temperature. Presume that a loose rock exists among this solid rock; because there is a temperature barrier, to some extent, between the loose and the solid, the loose rock will be affected more than the solid rock by the temperature of the air. Therefore, depending upon the temperature differences between the rock and the air, the loose will be warmer or cooler than the solid.

Jan 1, 1970

By G. L. Gates

Five possible sources of water for waterflooding of petroleum reservoirs in the arid San Joaquin Valley of California were considered. Three of them (water produced with petroleum, water from a shallow saline aquifer, and waste irrigation water) were analyzed chemically; laboratory information for one (sea water) had been developed during a previous study. A series of laboratory tests made on the fifth source (fresh water) determined the solubility of calcium sulfate dihydrate in water. Laboratory analyses included the following: Chemical analyses of water produced with petroleum and waste irrigation water; solubility of calcium sulfate dihydrate in water and brines; the effect of excess sulfate on the solubility of calcium sulfate in brines; the presence of sulfate-reducing bacteria; and the permeability of cores from a petroleum reservoir to air, to water from other petroleum reservoirs, and to waste irrigation water. The results showed that most of the waters and mixtures of waters are compatible with petroleum reservoir waters and are generally suitable for injection. The calcium content of some of the formation waters is quite high, and care must be taken to prevent precipitation of calcium sulfate dihydrate. The permeability of the few cores tested was about the same to water and brines as to air, indicating that formation damage due to clay swelling will not be serious. The waters most likely to be available for injection are water produced with petroleum, water from shallow saline aquifers, and waste irrigation water.

Jan 1, 1970

By Martin F. Littmann

Inclusions of MnS and Fe3C have been introduced into single crystals of 3 pct Si-Fe to study their effects on recrystallization behavior and textures after cold rolling and annealing. The presence of MnS in (110) [001] and (111)[112] crystals inhibited primary grain growth and promoted secondary recrystallization but did not alter the texture significantly after annealing at 1200°C. The presence of Fe3C in (llO)[OOl] and (100)[001] crystals caused a refinement of the primary re crystallized grain size but did not promote secondary recrystallization. THE texture behavior of single crystals of 3 pct Si-Fe during deformation and recrystallization has been studied by numerous investigators. The early work of Dunn&apos; followed by Decker and Harker2 involved relatively small cold reductions. More detailed studies of Dunn3&apos;4 and of Dunn and Koh5&apos;6 involved a reduction of 70 pct and recrystallization at 980°C for several crystals. Walter and Hibbard7 studied a greater variety of initial orientations and sought to relate the textures to those of polycrystalline material. Attention was focused on the nucleation process during early stages of annealing and on surface energy effects in studies by Walter and Dunn8 and by HU.9&apos;10 One of the most extensive investigations has been reported by T. Taoka, E. Furubayashi, and S. Takeuchi.11 Most of this work has been conducted using relatively pure crystals with minimal amounts of precipi-tate-forming elements such as carbon, oxygen, sulfur, and nitrogen. Recently, however, S. Taguchi and A. Sakakura have observed that AIN precipitates can alter the recrystallization textures of rolled (100)[001] crystals.12 The present studies were initiated to determine effects of MnS and Fe3C precipitates on recrystalli-zation and grain growth behavior of rolled single-crystals of 3 pct Si-Fe. Both of these types of inclusions play significant roles in the recrystallization behavior leading to the formation of the (110)[001] or cube-on-edge texture in commercial grain-oriented silicon iron. It is well known that (110)[001] primary grains are formed by recrystallization of (110)[001] or (11 l)[ 112] crystals after cold reduction of about 60 pct or more. Crystals of these orientations, therefore, were selected for study of the effect of MnS in-clusions on grain growth. On the other hand, a major component of the texture of cold-rolled, polycrystal-line 3 pct Si-Fe is the (100)[011] orientation. The function of Fe3,C inclusions is of interest for this orientation. EXPERIMENTAL PROCEDURE The single crystals used are listed in Table I and were obtained from commercial Si-Fe alloy processed to produce (110)[001] and (100)[001] texture by secondary growth. The cube-on-edge material was 0.59 mm thick. Suitably large (110)[001] crystals 25 mm wide were selected and their orientations were determined using an optical goniometer. Etch pits for texture determination were formed by a ferric sulfate solution. The other crystals used in the study with (100)[001], (100)[011], and (111)[112] orientations were obtained from sheet which contained large grains developed from secondary recrystallization by a surface-energy driving force.13 Most crystals had a (100) plane very nearly parallel to the sheet surface and the rolling direction could be selected readily. The same sheet also contained a few crystals with (111) planes parallel to the sheet surface, these also being a result of growth by surface energy. The crystals selected from the sheet were about 25 mm wide and 0.25 to 0.28 mm thick. As shown in Table 11, the crystals already contained about 0.070 to 0.10 pct Mn. Inclusions of MnS were incorporated into crystal 36 in the following manner. The crystals were first sulfurized by holding them Table I. Initial Orientations of Crystals Crystal No. Initial Orientation Thickness, mm Special Treatment 34 (I10) [00l]* 0.59 None 36s (110) [001] 0.59 Sulfide precipitates added 30,40 (111)[Ti21 0.28 None 43s (III) [Ti21 0.28 Sulfide precipitates added 37 (100) [Oll] 0.30 None 37C (100) [01I] 0.27 Carbon added 41 (100) (01I] 0.25 None 41C (100) [OI11 025 Carbide precipitates added 42 (100) [OOl] 0.25 None 42C (100) [001] 0.25 Carbide precipitates added *Tilted 4 deg to r~ght about R.D. Table II. Compositions of Crystals Special Treatments Base Analysis ~ ______________________£________________Crys- Crystals Pct Si Pct C Pct Mn Pct S Pct N Pct Al tal Pct C Pct S 34.36 2.93 • 0.099 <0.005 - 0.0014 36S 0.011 30.37 to 42 2.78 0.0057 0.070 0.001 0.0008 0.0011 43S 0.022 37C 0.029 -41C 0.028 -42C 0.026 *Estimate 0.004 pct. Oxygen estimated <0.003 pct on all samples

Jan 1, 1970

By Pedro Bolsaitis, Paul M. Sullivan

The activities of zinc in liquid Zn-A1 alloys in the temperature range of 1000&apos; to 1160°K were determined by means of the isopiestic technique. The results are in reasonable agreement with the previous values determined by the radioactive tracer dew point method. Slightly negative excess entropies of mixing were found. The measured activities suggest that the a function for these alloys is not a constant, as has frequently been assumed, but is better represented by two straight line segments of different slopes. THE thermodynamic data of Al-Z alloys have been the subject of investigation by many authors. However, in the recent compilation of such data by Hult-gren et al.,5 the conclusion is reached that none of the previous measurements are reliable or consistent with each other. Since then two new sets of measurements have been reported,2, 8 both laying claim to good accuracies, yet showing very significant disagreement in the measured activity coefficients of zinc in Zn-A1 alloys and in the magnitude and sign of the excess entropies of mixing. Information on the thermodynamics of the system is of particular interest for interpreting results of the Bureau of Mines research on refining of zinc by distillation of die cast scrap. The present study was undertaken as an independent check on the recent values obtained from dew point measurements 8 and electromotive force measurements.&apos; The isopiestic method, first introduced by Herasy-menko,&apos; was chosen because it is one of the few thermodynamic techniques which, in principle at least, is carried out under perfect equilibrium conditions. The disadvantage of the method is that data are obtained at various random compositions and temperatures, which makes the interpretation somewhat cumbersome. The random errors arising from temperature gradients and fluctuations appear to be comparable to those of other techniques, as evidenced by the magnitude of the estimated uncertainties in the calculated integral thermodynamic quantities. An advantage of the method is that each run provides a relatively large amount of data; thus, it is less time consuming than those methods where samples of each composition must be measured individually. EXPERIMENTAL PROCEDURE The activities of zinc in liquid Zn-A1 alloys were measured by the isopiestic method which uses the principle of the tendency toward equilibrium of a series of samples at various temperatures under an imposed vapor pressure of the more volatile component (i.e., zinc, in this case). The basic apparatus is shown in Fig. 1. The small graphite crucibles that contained the metal samples were 15 mm ID and 13 mm deep with approximately 3 mm wall thickness. Each crucible was notched at the top and bottom to allow easy passage of vapor from one to another. At the beginning of an experiment each crucible was weighed on an analytical balance. Zinc and aluminum of spectrographic purity (99.999 pct) were then weighed into the crucibles. The amounts of each metal added were such that initial compositions varied above and below equilibrium values. One crucible contained only pure zinc. After weighing, the crucibles were stacked with the pure zinc on the bottom (corresponding to the lowest temperature in the furnace) and richest aluminum alloys at the top. The entire stack of crucibles was then placed in the silica glass container "E" which was then sealed under vacuum. Sixteen to twenty calibrated Chromel-Alumel thermocouples were attached by wire along the length of the silica tube, one or more adjacent to each sample.

Jan 1, 1970

Jan 1, 1970

By Peter Soo

Pvestrained Ferrovac E iron has been neutron-irradiated at approximately 90°C to an integrated flux of 1020 nut (E > 0.82 mev]. The irradiation was found to produce an incveased temperature dependence of the flow stress in addition to a greatly increased athemal stress. Measurements of the flow stress and stress relaxation, from which the activation volume and activation energy for slip were deduced, show that neutron irradiation changes the rate -controlling slip process to one based on dislocation interactions with tetragonal distortions which are Produced around submicroscopic interstitial loops in the lattice. The study indicates that without prestraining prior to irradiation the chances of detecting a change in the rate -controlling slip process are greatly reduced because in the initial stages of slip a substantial fraction of the radiation defects are swept out of the slip plane by gliding dislocations. Thus, activation parameters which are subsequently measured are representative of a greatly reduced defect density and would not differ appreciably from those for unirradi-ated material. The large increase in the athermal component of the flow stress is probably connected with the presence of depleted zones in the lattice which are introduced by irradiation. ALTHOUGH fast neutron-irradiation has not been observed to markedly alter the activation parameters for slip in bcc metals,&apos; small but significant changes do occur. Most experimenters agree that irradiation predominantly increases the athermal component of the yield stress.&apos;-= In addition to this, Laidler and smidt7 have shown that in iron irradiated to 5 X 10" nvt and molybdenum irradiated to 10" nvt, changes occur in the activation volumes for slip. A similar conclusion has been reached by Milasin and Malkin8 for irradiated iron. Work by Ohr et a1.5 shows that for Ferrovac E iron, irradiated to 1.2 X 1016 nvt, small increases in the activation energy for slip also occur. So far these changes in the activation parameters have not been explained on a firm theoretical basis. One important factor which would minimize the chances of detecting a change in the slip mechanism upon irradiation is the presence of "channeling" which has been observed in molybdenum,9 niobium,10 and iron.11These channels are formed by gliding dislocations which sweep irradiation defects out of the active slip planes and thereby create zones in which continued dislocation motion is encouraged. The activation parameters for the dislocations gliding in the defect-free channels would, therefore, be similar to those for unirradiated iron and a change in the rate-controlling slip process would be difficult to detect. In the present work, an attempt has been made to reduce the effect of uneven deformation on the measured activation parameters for slip in neutron-irradiated Ferrovac E iron polycrystals, so that a more realistic assessment of the effects of neutron-irradiation could be made. Primarily, the experiments involve the irradiation of specimens which had been prestrained to 9 pct elongation at room temperature prior to insertion into the reactor. It was hoped that the introduction of a large number of evenly distributed dislocations would substantially decrease any channeling effect which might otherwise occur. MATERIAL AND EXPERIMENTAL PROCEDURE The starting material was vacuum-melted Ferrovac E iron, an analysis of which is given in Table I. The standard tensile specimen had a gage length of 1.125 in., a cross-sectional diameter of 0.120 in., and a re-crystallized grain size of 1.2 x 10-3 in. All tensile tests were conducted on a floor model "Instron" tensile machine at a strain rate of 3 x 10-4 per sec. The irradiation of the prestrained specimens was performed in the Brookhaven High Flux Beam Reactor to an integrated flux of 1020 nvt (E > 0.82 mev) at a temperature of about 90°C. All specimens were excap-sulated in high-purity aluminum sheaths which were lightly swaged around the samples to ensure good thermal contact. Subsequent measurements on the irradiated specimens showed that within experimental accuracy the swaging had not deformed them. EXPERIMENTAL RESULTS Fig. 1 shows the flow stresses for a series of unirradiated control samples. In order to produce a comparable dislocation substructure throughout the test sm range, all specimens were prestrained

Jan 1, 1970

By W. E. Horst

In Part I of this paper we describe two techniques that were employed in the development of mathematical descriptions of the size reduction process which takes place in a ball mill. In Part II we show how the comminution model was imbedded in a process model to effect steady-state and dynamic simulation of a closed-circuit grinding operation. Increasing emphasis is being placed on development of approaches whereby the essential characteristics of a process can be succinctly represented in terms of a mathematical description of the relationships that exist among important process variables. This activity, commonly known as mathematical modeling, predates modern electronic computers: however, these computers with their tremendous computational capability have given new impetus to the whole field. Although the computer is quite helpful in the development of mathematical models, the real value to the engineer lies in the fact that computers represent such a powerful tool for simulating systems described by mathematical models. As a consequence, engineers may simulate and thereby study the behavior of complex. interacting, systems over a broad range of process variables and configurations once appropriate process models have been developed for the sequence of steps comprising the process.

Jan 1, 1970

By W. G. Davenport, M. Paneni

Experiments in sheets of mercury and water have confirmed that the dynamics of bubble rise are simi-lur in Liquid metal and aqueous systems. RECOGNITION that bubble/metal interactions are important in pyrometallurgical refining processes (e.g., steelmaking, vacuum degassing, deoxidation of copper) has led to a number of investigations into the dynamic behavior of bubbles rising in liquid metals. Terminal velocities of bubbles rising in mercury (20°C)&apos; and silver (1000" to 1050"c)1,2 have been measured. Good agreement between aqueous and liquid metal systems has been obtained. Shapes of air bubbles rising in mercury have been determined experimentally by Davenport, Bradshaw, and Richardsonl who used a system of electric probes to measure maximum horizontal and vertical dimensions, Fig. 5. In the present work the motion and shape of nitrogen bubbles rising in a thin sheet of mercury (i.e., a "two-dimensional" environment) have been studied with the view of confirming dynamic similarity between aqueous and metallic systems. The use of thin sheets of liquid permitted direct visual and photographic comparisons of bubble behavior in clear liquids and in mercury. EXPERIMENTAL METHOD The thin sheets of mercury or water were held in a clear acrylic plastic container, Fig. 1. The sheets of liquid were 80 cm high by 30 cm wide and 0.47 cm thick. Single bubbles were formed by injecting the desired volume of nitrogen into an inverted semicircular cup (stainless steel). The cup was then rotated into the upright position using an external handle thus releasing a single bubble of measured volume. Nitrogen was injected into the cup from a nitrogen cylinder through the external handle and a hollow rotating axle. The volume of a bubble (volume range 0.01 to 10 cu cm) at any instant was obtained by connecting a soap film meter to a small gas space above the liquid. By this technique any change in the volume of a gas bubble in the liquid (i.e., during cup filling or during rise) produces an equivalent displacement from gas space A into the buret B. This displacement is determined by measuring the movement of a horizontal soap film in the buret. Bubble shapes were determined using single-frame photography. Rising velocities were determined by cinephotography with a 1/100-sec stopwatch in the field of view. In both cases dimensions were referenced to a rule attached to the container surface, also in the field of view. Linear dimensions were measured on projections of the single-frame negatives. Rising velocities were calculated from measured heights of rise (10 to 20 cm) and times of rise. The effects of disturbances caused by cup rotation and by bubble release were minimized by photographing bubbles at a point not less than 25 cm above the cup. MATERIALS Mercury: Technical-grade purified: minimum 99 pct Hg; Johnson Matthey and Mallory Limited, Toronto. Nitrogen: Technical-grade purified nitrogen: 99.99 pct Nz, 0.01 pct 02, trace argon; Air Liquide Canada Limitee, Montreal.

Jan 1, 1970

Jan 1, 1970

By Garrett R. Hyde

Sintered yttria and sintered dysprosia can be used to make single-component thermistors having typical thermistor geometries and operable in the temperature range 500° to 1,200° C. However, at these temperatures, instability of platinum electrodes can contribute a slight aging effect if the thermistor is kept near 1,200° C for long periods. Typical characteristics at 500° C for an yttria disk thermistor 12 mm in diameter and 2 mm thick are a resistance of 12.4 megohms and a temperature coefficient of resistance of -3.8 percent per degree C. Typical characteristics at 500° C for a dysprosia thermistor of the same dimensions are a resistance of 1.84 kohms and a temperature coefficient of resistance of -1.6 percent per degree C.

Jan 1, 1970