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By Y. C. Liu, G. A. Alers

Using X-ray pole-figure information and the single-crystal elastic constants, the angular variation of an elastic modulus in a polycrystal can be calculated and compared to measured clalues. This procedure has been used in the past to provide supporting ecidence for a particular choice of ideal orientations in the description o the X-ray pole figure. Since it is well-known that the absolute value oj an elastic modlus oj a poly crystal cannot be acczrralely calculated from the single-crystal elastic constants, there exists a serious question about the reliability oj this modulus method in the study of textures. This paper deriz-es sez3eral simple fornzulae for the ntzgular lariatiion of Young's modulus in the plane o a rolled sheet sing the same ssuinptions which lead to the lack oj detinztion of the absolute c'alre OJ the elastic ,nodulus. The vesults show that, although the absolute isallre oj Young's modulus depends strongly on the assumptions made, the shape of the modulus vs angle curve is not very sensitive to the assumptions and thus can be used reliably in texture studies. Exatzples oj' using this criteriotz are illustrated in the text. NeARLY all poly crystalline materials have some preferred orientation in the arrangement of their grains and hence exhibit anisotropy in their properties. This preferred orientation is usually measured and studied by X-rays which yield detailed information on the statistical distribution of grain orientations in the form of pole figures. The usefulness of these pole figures in theories of texture formation and in predictions of properties has come to depend almost entirely on the characterization of the pole figure by one or more ideal orientations. Unfortunately, this characterization is not unique and different authors often present different ideal orientations to characterize a given pole figure. In order to distinguish between these different choices of ideal orientations, it is necessary to go beyond X-rays and consider other physical properties which reflect the texture' simply because any choice of ideal orientations must predict correctly the observed anisotropy in all physical properties. The most common example of this procedure has made use of the angular variation of Young's modulus with respect to the rolling direction in the plane of a rolled sheet.3 4 Here the anisotropy can be measured easily and it can also be calculated from the single-crystal elastic constants and the chosen ideal orientation. Unfortunately the methods used to calculate this anisotropy were chosen for their simplicity rather than for their mathematical rigor so that there exists a serious question as to the validity of conclusions reached by this modulus method. It is well-known5 that the absolute value of the Young's modulus of a polycrystalline aggregate cannot be calculated very accurately because different mathematical averages over the grains yield different results. It is one purpose of this paper to examine the effect of different averaging procedures on the calculated anisotropy of Young's modulus in the rolling plane of rolled sheets in order to see if this property can be used reliably in texture studies. This particular modulus and type of material were chosen because the modulus is easily measured and rolled sheet is technologically important. The results show that, although different averages yield different absolute values for Young's modulus, the shape of the modulus vs angle curve is not very sensitive to the averaging procedure and thus can be used as a criterion to check the various ideal orientations used to characterize the X-ray pole figure. Examples of this checking procedure are given in the final section. Another purpose of this paper is to examine the possibility of using the anisotropy of Young's modulus as an indicator of texture without reference to pole figures or ideal orientations. Such a use would require that different textures yield quite different shapes for the modulus vs angle curve so that the distinction between textures would be quite clear. The experimental results presented in the final section indicate that there is easily enough variation in shapes to allow modulus measurements to be useful texture indicators, par-

Jan 1, 1967

By G. H. Kessler

ALTHOUGH considerable attention has been devoted to reaction mechanisms and equilibria of a number of endothermic reactions through which metals or their refractory compounds can be formed upon heated surfaces, only a comparatively small amount of work has been done to develop rate information for these systems. The interestin and very worthwhile work of Holden and Kopelman, Runnalls and Pidgeon,Dijring and Moliere, and Herrick and ICrieble4 is to be noted; however, their work was done under very specific conditions and the rate information which they have developed is not applicable to many systems which have been studied experimentally. That a more generalized approach is needed is shown by the diversity of these systems and of the experimental conditions which they require. These include the preparation of titanium, zirconium, tungsten, molybdenum, chromium, co-lumbium, aluminum, and silicon by decomposition or disproportionation of their halides, in some instances through hydrogen reduction; the preparation of nickel and iron by decomposition of their car-bonyls; and the preparation of copper by decomposition of the acetylacetonate. They may be carried out at temperatures ranging from 100" to over 2000°C and at pressures of from less than one mm Hg to superatmospheric. The physical mechanism of the overall process can be broken down into several steps, any one of which may be rate-determining; and the rate associated with each of these basic physical processes can be predicted. Consequently, by proper application of the present technology of rate processes, it is possible to arrive at a rate of metal deposition in the system of interest and to reach an understanding of the influence of' each major variable upon the deposition rate. It is the purpose of this paper to illustrate how this can be done and to present experimental results for a specific system for comparison with theory. The overall process of deposition of metal upon a heated surface which is immersed in vapors of a compound of the metal can be broken down into the following steps: 1) Transport of the reactant vapors to the surface. 2) Decomposition of the reactant in the immediate vicinity of the surface to a) establish chemical equilibrium if reaction rates are high; or to b) establish a dynamic equilibrium in accordance with the several reaction rates. 3) Diffusion of reaction products away from the vicinity of the surface, with or without simultaneous recombinations to form still other products. The overall process is said to be diffusion controlled if Step 1, or the equivalent Step 3, is slow; it is reaction-rate controlled if Step 2b is slow. When experimental evidence shows the reaction rate to be controlling, the well-known theories of Eyring' and others can be used as a basis for correlating and extrapolating the experimental data. Although these theories give only approximate estimates of reaction rates, they are of considerably greater value in correlating experimental data. Most deposition systems operate at surface temperatures sufficiently high that reaction rates near the surface are very high. Mass-transport rates then become controlling; and it is this regime of diffusion controlled rates which is most often of concern and Which will be considered here. When the system pressure is very low, i.e., in the micron range, then the transport processes are those of molecular movement, and the results of kinetic theory can be applied to specify a rate of arrival of reactant molecules at the heated surface. If the condensation coefficient can be estimated, then the deposition rate will be given by the product (rate of arrival) x (condensation coefficient), Conversely, experimental data can be used to determine a condensation coefficient, as was done by Holden and Kopelman' for the decomposition of zirconium tetraiodide upon a heated molybdenum surface, who found the coefficient for zirconium on molybdenum to be 1.0 at temperatures of 1382°C and above. In this pressure range, the geometry of the system. and in particular the distance between the source of reactant molecules and the heated surface, can exert a considerable effect upon the deposition rate;

Jan 1, 1961

By Ralph H. Sweetser

C. H. Herty, Jr.,* Pittsburgh, Pa.—The procedure of the Open-hearth Committee in studying pig iron and its effects in the open hearth has been influenced by the discussions at a number of meetings of the Committee. Those discussions have brought out very clearly that, as far as the pig iron affects the quality, interference with quality should be studied for three definite types of pig iron: (1) low-silicon pig iron; (2) very high-silicon pig iron, and (3) pig iron in which the silicon varies over a wide range in short periods, such as 1 to 3 casts. If a blast furnace is running steadily at 1 per cent. silicon iron, practically no trouble, apparently, can be traced to the pig iron, but if the furnace is running from 0.60 up to 1.50 and then down to 0.60 per cent., trouble in the finished steel is liable to occur, which apparently cannot be corrected by open-hearth practice. The open-hearth discussions have shown fairly definitely that with low-silicon iron, one type of trouble arises on the finished product and with the high-silicon iron, another. Our experience with the high-silicon is that any non-metallic matter that may form, does so when the pig iron is put into the furnace; that is, silicates immediately form which are more liable to be high in silica than would happen with low-silicon iron. I think Mr. Sweetser will agree with mc that if a blast furnace is very irregular, different points in the furnace may be working irregularly, in other words, the temperature gradient all over the furnace is not uniform. We have made many determinations on that point which indicate that a varying blast furnace causes hot spots and cold spots around the periphery. If some of those spots are hot and others are cold, although the analysis of the iron may be constant, then unreduced oxide, going through on one side, and good iron, going through on the other, may mix and the average temperature of the iron is not high enough to get completely rid of the oxides. So our method of attack is directly on that point; it is our first objective. Our procedure is to make a number of consecutive tests at a blast furnace, making a detailed study of the blast-furnace operation. We follow the iron through the open-hearth heat, being sure that we know just how much of each kind of iron gets into the open hearth, and take out specified samples at certain times during the process, working on steel where no finishing additions are made in the furnace. We are following one type of iron through the billet mills and into the finished product and are obtaining complete data on open-hearth operation. Besides the ordinary chemical analyses on the samples of slag and metal, we are running samples of the plg iron, the steel in the open hearth and the finished steel, for oxygen and silicates. We are going to find out whether or not oxygen, as silicates or oxides, has some connection with this trouble. If not, we may be able to locate some other factor. I am inclined to think that the silicates are responsible, judging from the indications in some other work that the Bureau of Mines is doing in Pittsburgh. We have laid out a very definite method of testing to which we will adhere at the different plants where we are now working and at others in the future. Our aim is to

Jan 1, 1927

By R. D. Nelson, F. E. Bowman

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.' The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970

By W. A. Jr. Slippy, E. P. Dahlberg, R. B. Reed-Hill

A large room-temperature mechanical-hysteresis effect under cyclic tensile loading was observed in zivconium specimens prestrained at 77°K so as to form large numbers of (1121) twins. The observed hysteresis loss was a maximum when the prestrain was just under 1 pct It also depended strongly on the maximum applied cyclic stress, but only moderately on loading rate and temperature (-72°to 100°C). The phenotnena have also been studied in terms of the elastic aftereffect where the data has been found to cotlforln closely to the functional relationship between strain and time, c = -RT/a In tank ft. t to)/Zr, for strains cts large as about 10-4 This eyication can be derived directly from the strain-rate equation There may be important commercial implications to the present discovery since it appears that within rather wide limits it may be possible to obtain any desired magnitude of damping capacity in zirconium melal. The damping propevties may also be given directional characteristics. It is shown that the observed anelaslic phenomena can he explained on the assumiplion that they are the resuilt of stress-induced twin-boundary movements in which the average twin increases its thickness by only a few percent. In polycrystalline zirconium, a grain is least favorably oriented for slip when its basal plane, containing the (1130) slip directions, lies nearly perpendicular to the principle normal stress. Mechanical twinning is favored by this orientation and under simple tensile deformation at room temperature the primary twinning mode is {1012).' The (1012) twinning shear is small (0.17) so that, during deformation, twin growth does not greatly enhance ductility. At 77°K, on the other hand, the predominant twinning mode shifts to {1121), and many thin (1121) twins can form at small strains.' Twins thus nucleated can grow readily during subsequent room-temperature deformation and permit easy deformation in unfavorably oriented grains. In addition, the (1131) twinning shear is large: 0.63. These facts have lead to a process' for greatly improving the room-temperature ductility of zirconium when it contains a sizable fraction of grains with basal planes nearly normal to the stress axis. Optimum results are obtained by slightly less than 1 pct prestrain. The effect is large so that a 50 pct elongation increase is readily attained. A large room-temperature mechanical-hysteresis effect has also been observed in zirconium specimens prestrained at 77°K. The present paper is concerned with some aspects of this effect which the experimental observations strongly indicate is primarily the result of strain-induced {1121) twin-boundary movements. This clearly suggests that mechanical twins formed by plastic deformation can cause anelastic effects similar to those previously observed2 for annealing twins and twins associated with phase transformations. EXPERIMENTAL PROCEDURES All specimens were prepared from arc-melted sponge zirconium plate stock as previously described,3 which has a preferred orientation with basal planes aligned parallel to and uniformly distributed around the rolling direction. Both lonti-tudinal and transverse tensile specimens, with axes parallel and transverse, respectively, to the plate rolling direction, were cut from this plate. In a longitudinal specimen most grains are favorably oriented for slip, while in a transverse specimen a large fraction are unfavorably oriented. Prestraining at 77°K was performed in two ways. In one, annealed zirconium plate stock was cooled in liquid nitrogen and then rolled in the transverse plate direction to strains varying from 0.5 to 12 pct. Cylindrical 1/8-in.-diameter by 1-1/4-in.-gage-length tensile specimens were machined from this material. In the other, previously machined tensile specimens were prestrained in tension at 77°K between 0.2 and 3.8 pct. Type FA 25-12 SR4 strain gages were cemented to all specimen gage sections. All tests were performed on an Instron testing machine of 10,000-lb capacity. EXPERIMENTAL RESULTS Fig. 1 shows a typical two-cycle room-temperature stress-strain diagram for a specimen prestrained 0.65 pct by rolling at 77°K. The maximum stress in both cycles was 14,500 psi. Note that in the first cycle the loading and unloading curves are unsymmetrical so that a residual strain, er, remains after unloading. In the second cycle the stress-strain curves form a nearly symmetrical hystere-

Jan 1, 1965

By H. Habenicht, J. J. Scott

An experimental method is described to compare strain data for rock and rock bolts when exposed to shock waves released by blastings. Static and dynamic strains were measured. Bolt gage response indicated a static decay of the bolt anchorage coupled with a reaction due to blasting vibrations. A distinct loss of bolt tension was indicated during vibrations and this was accompanied by a smaller but steady loss of tension due to static loading. The strain losses were found to relate to the shock source distance and the vibrational amplitude in the rock and bolts. Millions of roof bolts are used each year to stabilize mine openings and prevent their failure. Frequently, bolts become loose and lose their effectiveness as reinforcement to the mine structure. Many attempts have been made to determine the cause of loosening, including observation of the bolt tension or bolt torque through the use of torque wrenches, compression pads, and load cells. Pull tests have been used extensively to determine anchorage characteristics.102 These investigations have shown that even when bolts are loaded below the nominal anchorage capacity of the rock under 'static' conditions they exhibit a decay of load through adjustments and slippage at the bolt anchor. Since bolts are quite often found with the plate hanging loose from the rock surface, this condition suggests that some additional mechanism may have played a part in loosening the anchorage. Vibration from blasting or shock loading have been suggested as one cause in this type of anchorage deterioration. This paper gives the results of an investigation carried on at the University of Missouri at Rolla to determine the influence of shock waves on rock-bolt anchorage stability. ROCK BOLT ANCHORAGE UNDER DYNAMIC LOADING CONDITIONS In this report dynamic loading conditions are defined as conditions under which rock and bolts are exposed to vibrations occurring as a consequence of blasting, machine vibrations, earthquakes, rock bursts, etc. Whatever the location of the shock source, the waves created suffer extensive alterations along their travel paths, depending upon the vibrational properties and geometric parameters of the transmitting media. Together with reflection, refraction and diffraction at material boundaries, waves suffer changes in their nature to form tensile, compressive and shear waves. They become polarized, retracted, accelerated, dispersed, so that the waves incident at a point in the material can be the result of either one or a combination of this wide range of processes. A certain fraction of the wave energy will be lost due to friction, deformation, and material failure at the anchor-rock contact. Thus, the physical nature of wave propagation is such that it inhibits an exact analytical solution. For this reason this investigation should be considered qualitative rather than quantitative even though numerical data have been used as a base. CONCEPT OF THE INVESTIGATION Experiments were designed to find, from a series of rock bolts installed in natural mine rock, whether or not, and to what extent, bolt tensions would be influenced when bolts were exposed repeatedly to shock waves such as those produced by blasting. Electronic instrumentation available in the rock mechanics laboratory of the University of Missouri at Rolla was used to observe wave development in the rock and vibrational reactions in the bolts. EXPERIMENTAL PROCEDURE Fig. 1 illustrates schematically the experimental equipment. Electric resistance wire strain gages were used as sensors for the strain response of the rock and the bolts. Bolts were 5 ft long and 5/8 in. in diam, equipped with two-leaf type expansion shells for 1 3/8 in. boreholes. The bolt gages were mounted by use of Du Pont Household Cement, covered with an epoxy insulation and then enclosed in a copper foil for electronic shielding. For details of placement and the wiring diagram see Fig. 2 and 3. The output of both the rock gages and the bolt gages was fed into cathode ray oscilloscopes from which the vibrational traces could be photographed. A static strain indicator was also used to read the output of all gages.

Jan 1, 1968

By B. S. Butler

AN understanding of mineralizing solutions and how they carry and deposit metals is of prime importance to students of ore deposits. Lindgren states: "The whole problem surely is very complicated. One difficulty is that we know so little about the stability field of ore minerals."1 Lindgren further states: It is believed that they [the solutions] were in small part oxidized to sulphates, for instance, but in large part they were composed of hydrogen sulphide, alkaline sulphides and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker's view of the double sulphides as important constituents of the solutions probably holds good. In the fourth edition of Mineral Deposits2 Lindgren had changed his views somewhat: From the work of Day, Allen, Shepard, and others, it would seem probable that many of the volcanic gases are acid when given off but are in unstable equilibrium, and could not have preserved this acid character after having been long in contact with the surrounding rocks. It is believed that they were in small part oxidized to sulphates, for instance, but in larger part they were composed of hydrogen sulphides, alkaline sulphide, and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker's view of double alkaline sulphides as important constituents of the solution probably holds good. The writer wonders if progress would not result from an attack on the problem in steps, the steps to contribute to the attack on the whole. The initial step would deal with the simpler bodies of supposed magmatic (hydrothermal) origin, that is, those composed essentially of silicates, oxides, sulfates, and sulfides. The following discussion attempts to develop one step of a method that was proposed on a more comprehensive scale in 1929 by the writer and W. S. Burbank.3 The accompanying partial table (Table I) of the electromotive series is from a table distributed by Merck & Co. Inc., manufacturing chemists, prepared in turn from Fundamental Chemistry.& The electromotive arrangement brings together elements that in hypogene ore deposits occur: 1) in oxygen combination only; 2) in combination with sulfur as well as with oxygen; and 3) as sulfides, arsenides etc., and as native metals, see Table 11. The writer clearly recognizes that he is not qualified to discuss the formation of ore deposits as a chemical problem, but he feel that some of the relations that are met by the geologist can well be stated with the hope that the chemical explanation will be forthcoming. By consideration of a group including mainly the elements oxygen, hydrogen, sulfur and iron, complications are avoided, especially with elements of the lower electromotive group. The results can only contribute to the solution of the problem, not to the completion of it. The pH and Eh of the solutions and also temperature probably determine what minerals form. The mineral groups that contain elements high in the electromotive series are alumino-silicates, titanites, simple silicates, spinels, oxides, carbonates and sulfates, in all of which the elements are combined with oxygen. These groups are also recognized as the general order of temperature at which the minerals start to form, see Table 11. At low temperature are sulfides, arsenides, antimonides, sulfo-salts, and native metals, in all of which the elements are characteristically not combined with oxygen. The intermediate temperature group contains elements that form both oxygen compounds and sulfur compounds.

Jan 1, 1957

By B. B. Rath, Hsun Hu

Rates of migration of large-angle boundaries have been studied in zone-refined aluminum crystals, defonned 80 pct by rolling in the (110)[112] orientation at -78°C followed by a recovery anneal at 80°C. Artificially nucleated grains show a marked variation. by an order of magnitude, in their growth rates in different directions. The average activation energy for the migration of all boundaries was found to be about 16,000 cal per mole. The anisotropy of the boundary migration is rationalized on the basis of the boundary structure. It has been observed by Beck and HU,1 Kohara el al,2,3 and Czjzek and Haessner4 that recrystallized grains formed upon annealing Of deformed sing1e crystals of aluminum show anisotropic growth characteristics. Kohara et al. found that single crystals rolled in the (110)[112] orientation, when random nuclei were provided on one side of the crystal by rubbing with emery paper and annealing, developed a sharp recrys-tallization texture on the other side of the crystal upon further annealing. This sharp recrystallization texture consisted of four components, which were related to the deformation texture of the crystal, i.e. (110)[112], by rotations of ±40 deg around each of the two common [ 111] axes' They also noted that recrystallized grains were elongated in directions perpendicular to either of these two common [1111 axes. They attributed this anisotropic growth to the difference in the rate of self-diffusion or diffusion of impurity atoms along the tilt and the twist boundaries. A somewhat similar investigation was conducted by Czjzek and Haessner4 On strained single-crystal sheets Of alum- inum. These authors claimed that the matrix structure of the deformed crystal had a greater effect on the growth anisotropy of the recrystallized grains than did the boundary orientation itself. In the present investigation quantitative measurements of the rate of grain boundary migration in anisotropic growth have been made in zone-refined aluminum (99.9999+pct pure) crystals deformed 80 pct by rolling in the (110) 112] orientation. Crystals of this particular orientation were chosen because of the following desirable features: 1) the crystal does not change its orientation during rolling; 2) the rolling plane contains all the significant crystallographic directions; and 3) when annealed, following deformation, the crystal does not re-crystallize spontaneously but polygonizes to a stable and homogeneous structure. Hence, the initial orientation of the crystal and a constant strain energy in the matrix can be maintained during subsequent grain boundary migration studies. It is essential to keep the driving force constant for the study of boundary mobility.5 EXPERIMENTAL PROCEDURE A cylindrical single crystal of 1 in. diam was grown by the Bridgman method in a high-purity graphite mold. The resistance ratio, R(4.2°K) /R(298°K) , of the grown crystal was approximately 2.0 x 10-4. A number of slices, 1/4 in. thick, were cut from the crystal along the (110) plane and were mechanically and electrolyti-cally polished to remove the strained surface layer. The crystals were then rolled along the [112] direction to 80 pct reduction in thickness at -78°C. To minimize surface friction, the crystals were rolled between two layers of 0.005-in. teflon sheet. Rolling was interrupted, prior to completion, to remove the surface layers and the edges by electropolishing. These and similar precautions in handling the rolled crystals

Jan 1, 1967

By Leon Merker

FLAME fusion growth of strontium titanate crystals was undertaken to obtain large transparent crystals on which physical data could be gathered. The fact that strontium titanate is a cubic crystal and probably has a high index of refraction indicated that it might be useful in optics. No large boules* of strontium titanate had been synthesized previously, and none have been found as natural occurrences. The flame fusion process, invented by Verneuil in 1904,1 was first applied to grow large crystals of ruby and has since been used extensively to grow crystals of corundum and spinel on a commercial scale. Only during the past nine years has this technique been applied to the growth of large single crystals of other high melting compounds such as rutile,2 mullite,3 and ferrites4 One of several significant advantages of the flame fusion technique over more conventional methods of growing crystals from a melt is that the crystals are grown without the use of melt containers. This fact alone excludes other methods of growing crystals from a melt whenever there are compounds with a melting point near 2000°C or above. Growth of the crystal, similar to that of a stalagmite, takes place inside a circular refractory furnace that does not contact the crystal, Fig. 1. This eliminates a serious source of impurities as well as the likelihood of multi-crystalline solidification along the container walls. The flame fusion technique is particularly advantageous for research because it produces large crystals quickly and at lower cost. A corundum crystal 25 mm long and 12 mm in diam can be grown in 2 to 3 hr. Operating conditions permit observation of the growing crystal during any stage of the process. The various flame patterns and a wide range of oxidation-reduction conditions can be investigated in a relatively short time. It should be pointed out that formation of the foot of the boule is the most critical step in growing an unfractured boule. When the tip of the sintered cone is fused to initiate crystal growth, the original area of fusion should be kept as small as possible so that one crystallite can assume dominance over all the others and propagate as a single crystal. If the boule start happens to consist of several crystals, usually the entire boule also contains several crystals. In many cases these tightly cohering crystals exhibit different crystallographic orientations. Although the basic technique of the original Verneuil process has been retained, refinements in method and burner design have been developed in recent years. For example, boule growth may be initiated on a seed crystal rather than by fusion of a sintered cone. The danger of multicrystalline or twinned boule starts is thus eliminated, and this procedure may also be used to grow boules of predetermined crystallographic orientation. Prior Art: Of the many attempts to produce artificial gem crystals, most early efforts% ere directed toward synthesis of .rubies and sapphires and diamonds. None of these efforts resulted in a process that was commercially practical. Without exception only tiny crystals of corundum were obtained, and those at excessive cost. Verneuil announced his process in 1904; Ravier6 in 1934 presented a detailed description of a commercial boule production plant. Descriptions of the German synthetic stone industry, the process details, and the equipment used have been published by Barnes7 and by Merker.'

Jan 1, 1956

By J. R. Hornaday, A. E. Morris, N. A. Parlee, D. C. Carmichael

Rates of absorption and effusion of hydrogen in solid iron were measurede by a Sieverts type of apparatus. With clean a iron these rates are diffusion controlled down to 420°C and are represented by the equation D = 6.70 x e-'100' crn2 sec-I Certain surface impurities can affect these rates at all temper-atuves. Thin oxide films lower, the apparent diffusivity of annealed iron markedly. Cold-worked iron (75 pct) annealed at 430°C has practically the same solubility and diffusivity as anealed iron. THE mechanism of absorption and evolution of hydrogen in solid iron alloys is not fully understood despite the large number of investigations on the subject. While there appear to be many instances of simple solid-state diffusion control of rate, there are many cases where investigators have either concluded that surface reactions are rate controlling or that some "nondiffusible" hydrogen resides in discontinuities. The purposes of this research were 1) to develop a sound method for studying this absorption and evolution behavior, 2) to examine it in pure annealed iron, and 3) to determine the effects of important variables, such as cold work, surface condition, and composition. This paper relates the progress toward these objectives. Much of the present knowledge of the movement of hydrogen through iron alloys comes from permeability studies which involve the measurement of the rate of passage (under steady state conditions) through membranes of the order of 1 mm in thickness. This method is open to question on various grounds. If surface reactions are involved, two different surfaces operating under two different conditions must be considered. The presence of defects in the membrane even of microscopic dimensions may lead to erroneous results. A few people have studied evolution of hydrogen into vacuum, under carefully controlled (unsteady state) conditions, and some of the best diffusivity data come from these sources. Most of these methods measure rates of evolution only and thus do not make a rigorous test for reversibility of behavior. It appeared that an "unsteady state" method that would permit the measurement of both rates of evolution and absorption under controlled temperature, pressure, and other conditions would offer several advantages. Accordingly the modified Sieverts apparatus described below was designed and built. APPARATUS This apparatus is shown in Fig. 1. The sample bulb is detailed in Fig. 2. Hydrogen of 99.5 pct purity and argon of 99.99 pct purity were used. The hydrogen was deoxidized and dried by means of a Deoxo unit followed by a "Dri-erite" tower. The argon was only dried. The gas burette was graduated in tenths of a cubic centimeter, and, with the aid of a travelling magnifier, readings could be estimated to the nearest 0.01 cc. The level of mercury in the burette was adjusted by means of a leveling bulb operated by a fine screw adjustment. An electrical system, consisting of two slightly separated platinum electrodes inserted in one leg of the manometer and a small light bulb was used to obtain rapid accurate adjustment of the pressure. The capillary tubing of the Vycor sample bulb was 3 mm bore as was all tubing back to the gas burette. The samples were discs made from vacuum-melted Ferrovac-E iron of greater than

Jan 1, 1961

By N. E. Brown, F. L. Versnyder

THE apparent dependency of the electrical characteristics of hexagonal crystalline selenium on microstructure has aroused much interest in microscopical studies of selenium. Microscopic observations on the crystallization of selenium have been made by Escoffery and Halperin,' P. H. Keck,' and other investigators. It is the purpose of this paper to discuss the microstructural changes observed on polished cross-sections of single layers of selenium after various heat treatments. Observations were also made on crystallization of the free-surface layer of these deposits. In general, all of the transformations studied were either transformations of the vitreous selenium to hexagonal selenium or micro-structural transformation of the hexagonal selenium itself. Procedure The selenium used in this work was obtained from the American Smelting and Refining Co. and was approximately 99.96 pct pure. An intentional impurity of 1 part per 2,000 of bromine was added to the material prior to evaporation. A thickness of approximately 0.002 in. of this selenium was vapor deposited on an aluminum base plate. The maximum plate temperature during the vacuum vapor deposition was 140°C. Mounting of the cross-sectional specimens for metallographic study could not be done in plastic mounting media, as is customary, since temperatures in excess of 50°C would cause unwanted transformations. Consequently, a simple clamp-type device was used to mount the specimens for preparation. All grinding operations were then done carefully by hand in order that the specimen not become heated during this operation. Wet polishing was done on the conventional metallographic polishing laps, using successively finer grinding powders. An extremely careful polish is necessary, since observation and micrography of the specimens are done in the unetched condition under polarized light. The two observations of crystallization made on the free surface of vitreous selenium deposits (Figs. 4 and 5) were made on surfaces which were perpendicular to the cross-sections studied. These free-surface layers were examined directly, i.e., no pre- vious metallographic preparation, as obtained from the vacuum vapor deposition. Microscopic Observations A study was made of polished cross-sections of the vitreous selenium as-deposited. It was noted that in all cases there was columnar crystallization adjacent to the base plate, which appeared to occur during the vacuum deposition process. This observation has also been made by Keck? It also was observed that vagrant spherulitic crystallization occurred in the vitreous selenium. The term "vagrant" is used, since these spherulitic grains appear to crystallize at random throughout the vitreous selenium during the vacuum deposition process. Columnar crystallization at the A1-Se interface and a typical spherulite observed in a polished cross-section of "as-deposited" vitreous selenium may be seen in Fig. 1. Cross-sectional samples of vitreous selenium studied after heat treating individual samples for 20 min in 10" steps from 80" to 220°C revealed that crystallization—in this case, columnar crystal growth —proceeds from the aluminum base plate to the surface of the specimen (Fig. 2). Crystallization was microscopically observed to be complete after the 130°C heat treatment. Visual examination of the free surface of the specimen after the 130 °C heat treatment revealed the readily recognizable grey appearance of the completely crystallized selenium, in corroboration of the microstructural observations. No microstructural transformations then appeared to take place between 130" and 190°C. At 190°C the beginning of recrystallization appeared and proceeded until the columnar grain structure had been completely transformed to equiaxed grains between 210" and 220°C (Fig. 3). Naturally, the grain size of the recrystallized grains at the lower temperatures (190" to 210°C) was smaller than is illustrated in Fig. 3. In addition, polished cross-sections of deposits heat treated at 140°C for 10 min to cause complete crystallization and, subsequently, heat treated in 10" steps from 80" to 220°C for 20 min were studied. As expected, no microstructural transformations took place until the beginning of recrystallization was observed at 190°C. A comparison with the previously studied specimens revealed that recrystallization proceeded almost identically in the two experiments although in the first case the deposits were vitreous prior to the series of heat treatments and in the second case they had been crystallized by a previous heat treatment. By heat treating for longer times (180 min) at lower temperatures, the

Jan 1, 1956

By R. E. Pollard

The National Bureau of Standards received, in August 1940, a number of samples of bridge wire taken from the cables of the General U. S. Grant suspension bridge over the Ohio River at Ports- mouth, Ohio. These cables were 7% in. in diameter under the wrapping and each was made up of 1458 ungalvanized wires of No. 8 gage in 3 parallel-wire strands. The choice of ungalvanized wire was based on the previous satisfactory performance of similar wires in other bridges over periods of 20 to 50 yr. of service(1).2 After about 12 yr. of service a number of breaks were discovered in the Portsmouth bridge cables, most of them at the anchor- age shoes, and they were replaced by cables made up of galvanized wire(2).

Jan 1, 1945

By Leon Nelson

SEVERAL factors which affect the segregation and solidification of killed hot-topped steel ingots are: (1) pouring temperature, (2) volume in the hot top, (3) taper in the ingot, (4) pouring rate by varying the nozzle size, (5) segregation of several elements, (6) moving ingots before completely solidified. In most of this discussion, segregation will be measured in terms of carbon variation only. All the data given are results on S.A.E. 1040 analysis of fully killed steel direct-poured in hot-topped molds giving 20-in. square ingots. Thus the variables of analysis and ingot size and contour are eliminated. Segregation results are all on the rolled-bloom size, not on the ingot itself. They are results from plant-control work and not results of special research on ingot segregation.

Jan 1, 1937

By F. R. Hensel

THE alloy under discussion is a nickel-silicon bronze and is one of many age-hardening or precipitation-hardening FIG. I.-EFFECT OF QUENCHING AND AGING TEMPERATURES ON HARDNESS OF TWO TYPICAL NICKEL-SILICON BRONZES, NO. 2351 AND No. 2362. copper-base alloys. The hardening con-stituent is a nickel-silicon compound.1 The quenching temperature necessary to pro-duce hardening by a subsequent aging treatment is a function of the composition and extends from about 700'C. to ()50'C.; the aging temperature range extends from 400° to 600°C. The work carried out by the authors of this paper was confined to cast alloys having compositions within the ranges of 1.5 to 3.00 per cent Ni; 0.4 to 0.75 per cent Si; balance, copper.

Jan 1, 1940

By Wasyl Kunda

High grade jig and low grade flotation concentrates used in the following experiments, are produced from silver ore at the mine. The study was carried out to recover the silver and other metals from these concentrates by hydrometallurgical methods. The concentrates were subjected to two stage oxida¬tion leaches in a HNO3-H2SO4 medium. The dissolved metals were recovered by selective precipitation of: (a) silver chloride, (b) iron-arsenic-bismuth residue, (c) copper sulphide, (d) cobalt-nickel sulphide. The effluent solution contained only ammonium sulphate and ammonium nitrate. The silver chloride was further processed to the high purity silver powder by the AgCl ? Ag2S ? Ag2SO4 ? Ag° route. The recovery of silver from the concentrates was over 98% and other metals from 95 to 99%.

Jan 1, 1984

By T. C. Desollar

THE group of iron-ore mines known as the Red Ore Mines, owned and operated by the Woodward Iron Co., is on Red Mountain approximately ten miles southwest of Birmingham, Ala. At the, present time No. 1 and No. 3 mines are active, No. 2 mines having been abandoned in 1928. Ore from this group of mines was first mined in 1882, and originally came from open cuts along the outcrop, but, when the "soft ore" (weathered hematite) was mined out and the harder ore was encountered, it became necessary to develop the orebody by means of slopes driven in the ore formation. The three mines to date have produced more than 22,000,000 tons, and the two operating mines now have a capacity of over 1,000,000 tons per year.

Jan 1, 1933

By R. S. Shoemaker, F. W. McQuiston

CAMPBELL RED LAKE MINES Balmertown, Ontario 1974 Operating Data MINE LOCATION: Balmertown, in Red Lake mining area of Ontario TYPE OF MINE: Underground mine developed by vertical shaft to 4300 feet. Mining active above 3000 ft depth. ORE DESCRIPTION: Gold and minor silver.. Sulfur content about 1.3%. Ar senopyrite , pyrite, pyrrhotite, and stibnite. CAPACITY IN TONS124 HRS: 825 ASSAY: 0.66 oz Au per ton heads MILL PROCESS: Amalgamation, flotation, roasting of concentrate and separate treatment of calcines and flotation tails by cyanide. PLANT BUILDING: Mine mill and service facilities all housed in insulated and heated buildings POWER: Total consumption, mine and mill - 100 Kwh/T WASTE DISPOSAL: Impoundment of tailings. Arsenic to sealed underground storage EMPLOYEES: Total of 300 men on payroll. Housing in Balmertown and nearby communities.

Jan 1, 1975

By T. D. Yensen

EFFECT OF ELEMENTS ON MAGNETIC PROPERTIES OF IRON THE elements aluminum,1 arsenic,2 silicon,3 tin2 and vanadium,4,8 when used in relatively small amounts as alloying elements, seem to have a beneficial effect on the magnetic properties of iron-i. e., they increase the maximum permeability and decrease the coercive force-whereas there are definite indications that boron,5 carbon,6 nitrogen,7 oxygen,8' phosphorus,6 sulfur6 and titanium,4 as well as the metals of and adjacent to the ferro-magnetic group, nickel,9 cobalt,10 copper,11 and manganese,6 have a detrimental effect on these properties. The effects of calcium4 and magnesium4 are small, if any, while the effect of chromium 12 in small amounts is unknown and in large amounts is generally detrimental.

Jan 1, 1931

By H. Jehn

The high-temperature oxidation of Pt metals results' in the formation of volatile oxides. The evaporation of which considerably increases the metal losses in oxygen-containing atmospheres when compared with high-vacuum or inert-atomosphere conditions. The paper describes gravimetric investigations carried out to determine the metal losses of polycrystalline samples of Ru, together with earlier studies on Ir and Pt at oxygen pressures of 10-3 to 1000 mbar and temperatures > 1000 °C. A strong pressure and temperature dependence is noted. Preliminary results of the oxidation of Pd are reported, too (665 mbar 02, 1100-1300 °C). The oxidation mechanism is discussed and the oxidation rates of Ru, Pd, Ir and Pt are compared with those of the other Pt metals Rh and 0s and of refractory metals.

Jan 1, 1984

By PAUL AUDIBERT

THE downward trend of metal prices seems to act something like a reagent that precipitates selfishness in most business men's hearts; in the same way the upward trend precipitates altruism. Operators do not say: "I continue working my mine without curtailment because I can afford the present prices while my neighbor cannot and thus will give me way." They say: "I continue working my mine because 1 consider it a service for consumers. They will get better prices on a free market. Any curtail¬ment would be an attempt to raise prices artificially, that is to say, bad economics." Copper producers have learned how fallacious is such an opinion. It perhaps was not fallacious in olden times when all mines were worked on a small scale even if operating on a big deposit. At that time the supply and demand law played fair. When prices were too low and profits were vanishing for many mines, they would. shut at once, then little by little the metal scarcity would induce prices to climb up again; finally these prices would reach the point when it became profitable to again work the closed mines. Re-opening and shutting down mines was then a normal custom. Workers and operators weakly deplored this unstability, but there was nothing effective they could, do about it.

Jan 1, 1931