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By R. P. Agarwala, M. S. Anand, S. P. Murarka

Using the residual radioactivity technique, grain boundary diffusion of chromium in the a phase and lattice diffusion in the a and the ß phases of zirconiuttz have heen studied. The diffusivities (in units of square centiwzeters per second) have heen expressed as THE rate of diffusion of atoms along surfaces and grain boundaries is much greater than that through the bulk of metals. These processes dominate over volume diffusion at lower temperatures and can be isolated from it by virtue of the fact they yield high diffusion coefficients and low activation energies. In zirconium, however, it has been difficult to identify the volume-diffusion parameters separately. The values of diffusivities in a and ß phases yield activation energies which are much lower than those for volume diffusion calculated from semiempirical or empirical relations.1-3 Diffusion frequencies (Do) are also low, especially in the a phase, and they yield negative entropies of activation.4 Similar results have been obtained for the diffusion studies in titanium.5 It is yet to be investigated whether in these cases diffusion is controlled by some extraneous factor like high reactivity of these metals, or some different mechanism is operative as suggested by Pound et a1.6 However, Federer and Lundy,7 in a recent study of the diffusion of zir-conium-95 and columbium-95 in zirconium, and Gibbs et al.,8 in the study of impurity diffusion in titanium, found a temperature dependence of D, Do, and Q. Their study yielded low values of Do and Q at low temperatures, as has been found by other workers, and fairly high values at high tempera-

Jan 1, 1965

By A. B. Young

THERE were produced in this country in 1923 probably in the neighborhood of 12,000 or 13,000 tons of refined and crude arsenic, by far the greater portion coming as a by product of smelting operations. Early this year copper smelters were producing arsenic at the rate of about 425 tons per month and lead smelters at the rate of 7;0 tons per month. During the entire eighteen years prior to 1919, there were produced in the United States only 47,000 tons of arsenic, which amounts to only 25 per cent. of the present output. The great increased demand has come about through the augmented use of arsenates as insecticides and arsenates as weed killers. In an extract from "Mineral Resources of the United States" on "Arsenic in 1922," Messrs. Heikes and Loughlin say, "The minimum possible demand for arsenic in 1923 was estimated at the end of 1922 to be about 13,000 tons, including 2000 tons for plate glass manufacturers, 3000 tons for lead arsenate, 3500 tons for calcium arsenate, 1500 tons for weed killers, 1200 tons for Paris green, 1000 tons for sheep dips and 750 tons for proprietary mixtures. More recent information, however, indicates twice as great a demand for calcium arsenate." The latter has found great use in the last three or four years as a weapon to combat the boll weevil pest of the southern cotton belt. ~t the present writing refined white arsenic is being quoted on the New York market at from 13)d c. to 1455 c. per Ib., while the average price during the eighteen-year period just mentioned was 4.8 c.

Jan 1, 1924

By A. McLean, D. W. Gomersall, R. G. Ward

An experimental study has been made of the solubility of nitrogen in liquid iron and liquid Fe-C alloys using levitation melting and a rapid quenching device. Iron alloy droplets were equilibrated with nitrogen gas at 1 atm pressure, quenched, and analyzed. Previous techniques for studying the Fe-C-N system have produced data which me in marked disagreement. This disagreement is due largely to errors caused by reaction between the molten alloy and the crucible material. With the levitation procedure, errors from this source have been eliminated and precise solubility data obtained for temperatures between 1450° and 1750°C. C-N interactions in molten iron have been expressed in terms of first- and second-order free energy, enthalpy, and entropy parameters. ALTHOUGH the solubility of nitrogen in iron base alloys is in general small, the effects of nitrogen on the properties of steel may be quite profound. For most purposes nitrogen in finished steels is undesirable, particularly in the low-carbon grades, since on cooling to room temperature the solubility limit of nitrogen in the steel may be exceeded and this can lead to embrittlement and loss of ductility on aging. On the other hand, nitrogen can improve the work-hardening properties and machinability of steels while in certain stainless grades nitrogen is important in order to stabilize the austenite phase. It is, therefore, desirable that one should be able to predict the solubility of nitrogen in liquid iron alloys. To do this, information is required concerning the interactions between nitrogen and the various alloying elements which may be present in liquid iron. There have been several investigations of these effects in recent years1"7 and the interactions between nitrogen and many elements dissolved in liquid iron are now known to a high degree of precision at steel-making temperatures. Unfortunately, a number of iron alloy systems which are of interest in steelmaking have been difficult to deal with by the experimental techniques generally used for this type of investigation. Among the most important of these are the Fe-C alloys. In the past, two methods have been widely used for determining nitrogen solubilities: the Sieverts' technique, in which the amount of nitrogen required to saturate a given mass of liquid metal at a particular temperature and pressure is measured volumetrically, and the sampled-bath technique in which liquid metal held in a crucible is equilibrated with a gas phase containing a known partial pressure of nitrogen, and samples drawn from the melt are quenched and analyzed. These two methods have been discussed in detail elsewhere.5,8 With the Sieverts' technique, errors may be introduced from the following sources: i) Gas adsorption on metal films which have condensed on the cooler parts of the reaction chamber. ii) Uncertainty in the determination of "hot volume" calibrations. iii) Crucible-melt interaction, particularly if a gaseous reaction product is formed or if the melt becomes contaminated with material from the crucible walls. The sampled-bath method may also suffer from errors due to reaction between the melt and the crucible material. In addition, there is the possibility that gas may be lost from the sample during solidification and cooling. In the present investigation, the solubility of nitrogen in liquid iron alloys has been studied by means of a new technique based on the use of levitation melting equipment and a rapid quenching device. In addition to the fact that problems of the type outlined above are avoided, this particular approach has the following advantages: i) The high-frequency current induces vigorous stirring within the levitated droplet so that gas-metal equilibration is rapidly attained. ii) The gas phase surrounding the melt can be changed very quickly and is easily controlled. For example, a droplet may be levitated in helium, deoxidized in hydrogen, equilibrated with nitrogen, and quenched, within a period of 15 min. ii) Melts can be readily under cooled or superheated, thus extending the effective temperature range of an investigation and allowing temperature-dependent data to be determined with a high degree of precision. Excellent reviews of levitation melting techniques and their application to physical-chemistry studies at high temperature have been published recently by Jenkins et al.,9 Peifer,10 and Rostron.11 In the present investigation a levitation melting technique has been used to obtain data for the solubility of nitrogen in pure liquid iron and liquid Fe-C alloys at temperatures between 1450° and 1750°C. The solution of nitrogen in liquid iron can be described by the reaction:

Jan 1, 1969

H. M. HOWE, Bedford Hills, N. Y.-One wonders, whether it might not be well to check, by a rather simple and direct way, the inferences that would be drawn from this investigation. Suppose we quench, in these various liquids cylinders of steel, selecting material that is not likely to split in hardening, and then examine their cross-sections micro-scopically. If the cylinder is of any size, you will find a series of concentric bands, a very hard band, a softer band, and a hard band-but it seems that here would be a way of checking the inferences from the cooling curves by comparing these waves of hardness obtained in similar speci-mens quenched in different liquids. One would think that there would be great promise in that way. One's first thought is to quench similar pieces of steel, similarly heated, in different liquids and determine their hardness. I suppose many of us have tried that. We then meet the-difficulty that it is not the most rapid cooling that gives the greatest hardness. There is an intermediate rate of cooling that gives maximum hardness so that you can not by any simple method as that check this cooling method. But it seems possible

Jan 12, 1919

By B. Ramaswami, U. F. Kocks, B. Chalmers

The latent hardening of silver and an Ag-Au alloy was investigated by lateral compression, overshoot in tension and cormpression, and the stability of multiple-slib orientations. The latent hardening of a secondary slip systenz depends on its relation to the primary slip system. For most secondary slip systems the latent hardening is larger for Ag-10 at. pct Au than for pure silver. The maximum increase in. flow stress on a secondary slip system over that of the primary slip system was 40 pct. The work hardening during the lateral-compression test on the latent system after prestress on the primary system is iuterbreted in terms of the preferential distribution of barriers to dislocation movement with respect to the active slip system in work-lzardened fcc crystals. The work-hardening in fcc crystals is mainly due to the dislocation interactions and the barriers to dislocation movement formed as a result of reactions between dislocations of different slip systems. The operation of sources on the latent system depends on the flow stress of those systems; hence, the increase in flow stress of a latent system due to glide on an active system, which is called latent hardening, is an important element in understanding the phenomenon of work hardening. The problem of latent hardening has attracted the attention of many investigators in the past. For example, a theoretical study of the elastic latent hardening of the latent systems due to glide on an operative system has been made by Haasen' and ~troh. These calculations, however, neglect the stress required for the intersection of forest dislocations by the glide dislocations, a factor which would be important for producing macroscopic strains on the secondary slip systems. The importance of this factor will become evident from the results presented here. Attempts have also been made to determine the latent hardening of different slip systems by experimental means by the methods summarized in Table I.3-9 The experimental methods used have been subject to certain limitations. For instance, in the method used by Hauser,9 frictional constraints between the specimen and the compression platen were not eliminated by proper lubrication (see Hos- ford10). Secondly, with the exception of Kocks,6 Hauser,9 and Rohm and Kochendorfer,11 latent-hardening studies have been made on only one of the slip systems, i.e., on either the conjugate or the coplanar slip system; hence, extensive results are not available on the latent hardening of different slip systems in the same materials, with the exception of aluminum.6 It was therefore decided to study the latent hardening of the conjugate, critical and half-related slip systems in silver. Similar experiments were done in Ag-10 at. pct Au to study the effect of solute (gold) on the latent hardening of silver. Lastly, indirect evidence can be obtained by a study of the orientation stability of crystals of multiple-slip orientations in tension and compression. This method has been used by Kocks6 to supplement his studies of latent hardening in aluminum. Similar studies were made at room temperature in single crystals of silver. EXPERIMENTAL PROCEDURE The single crystals of the desired orientations were grown and the tensile test specimens were prepared as described in Ref. 12. The compression tests were made on 1/4-in.-cube specimens. The specimens were cut from single crystals, in the Servomet spark-erosion machine.13 The two cut surfaces were planed using the lowest available planing rate in the machine to minimize the deformation layer. A brass strip was used as the planing tool. This method of preparation ensured plane parallel faces for the compression tests. The deformed material was removed by prolonged etching in a weak etching solution. A weak etching solution was used to prevent pitting of the surfaces and to ensure uniform etching. About 25 to 50 µ of material were removed from all faces by the etching treatment. The specimens were then annealed for 24 hr at 940°C in oxygen-free helium and cooled in the furnace to room temperature over a period of 7 hr. After annealing, the orientation of the specimens was determined by Laue back-reflection technique to make sure that no recrystallization had occurred on annealing. The compression-test technique and setup are described in Ref. 14. The Laue back-reflection technique was used to study the overshoot in tension, the overshoot in compression, and the stability of the axial orientation in tension and compression. The tests were interrupted after every few percent strain to determine the axial orientation. In investigating the overshoot in compression, the operative system was determined by studying the asterism of the Laue spots.

Jan 1, 1965

By R. C. Ferguson, Harlowe Hardinge

Oscar Johnson—In my opinion, the effect of mill speeds on grinding costs must be studied along with capital investment and dollars gathered together as profits. Comparing the entire groups of operators with those who have had the opportunity to make slow-speed mill studies, I think you will find the latter small in numbers. Most managers want the equipment worked to its maximum output. There are, however, some installations where plant and mill sizes are such that they can do the job with reduction of mill barrel speeds. The past and the present installations of the industry are laid out to get the most capacity for the least capital outlay. This is the case even with the plants of Chile Exploration, International Nickel, Morocco, and Anaconda, now under construction or being changed. The industry recognizes that most all equipment it buys today is good and can be depended upon for efficient performance. Under this scheme of things, I am doubtful that slow-speed ball mill operation will be generally applicable. With reference to the U. S. Bureau of Mines laboratory tests, I think table II could have been omitted. It is inconclusive as to maximum efficiency for the low-pulp level mill on hard ore. There should be no question about this point. However, data on mill speeds can be found to substantiate various theories as well as refute them. Gow, Guggenheim, Campbell and Coghill, in their paper on Ball Milling,' believe their 2 x 2 ft laboratory mill reflects results that can be expected from large mills. If so, then referring to their table 11, they state, "The conclusion to be drawn from this second series is that high speed, not exceeding 72 pct of the critical, favors capacity, as before, but that with proper conditions of operation high speeds may give as good efficiency values as low speeds. In this case the efficiency values are nearly constant. A horizontal curve would indicate that the amount of grinding was directly proportional to the power expended, and these tests suggest that such a coildition can be made to exist in commercial operations." Table II (From Paper by Gow et a1)2 Speed. Pot Critical 32 42 52 62 72 82 Capacity: Surface tons per hr (65- mesh) 266 42.1 54.4 65.9 74.3 74.1 Surface tons per hr (200- mesh) 56.1 87.4 112.7 137.1 154.2 153.0 Efficiency: Surface tons per net hp hr (65-mesh) 35.7 36.3 36.3 35.4 34.3 32.3 Surface tons per net hp hr (200-mesh) 75.3 75.3 75.1 73.7 71.0 66.0 Ore in mill, 1.b. 98 100 100 113 122 165 The field performance data, table 111, represents much effort in its collection and preparation. But, one must realize that there are many variables that effect the efficiency of grinding mill operation, and too much must not be assumed as to the effect of some specific change. Possibly with changes in mill speed, the results might be more consistent by also a change in ball rationing, type of ball, volume of ball charge,. p.ulp level and amount of pulp in the mill, pulp consisting, design of liner, circulating load, etc. Also, changes in ore character must be reckoned with when evaluating grinding performance. At present the Climax Molybdenum Corp. is running at much reduced capacity. Mr. James Duggan informs me that at mill speeds of 17 rpm, they save a $0.025 per ton on liners and $0.025 per ton in power, but, if the demand for molybdenum increased, he would go back to higher speed to obtain maximum tonnage, as the values from the increased tonnage would far more than offset the one half saving at the slower speed. The Jnspiration ran a six months' test between mills running 21 rpm and 23.5 rpm. The slower mills ground 10 pct less ore with a slight saving per ton, but when the reduced plant tonnage was checked back into the actual cost figures of concentration, the high-speed mills with their greater tonnage showed considerable advantage. To be convinced of possible practical results from the predictions in the conclusions, I think we would have to rely on the analysis of expert cost accountants to furnish the necessary proof figures. Hardinge and Ferguson are to be commended for the work in preparing this paper. I am convinced that our Massco engineers should go into higher speeds with our equipment. Harlowe Hardinge (authors' reply)—For one, I heartily agree with Mr. Johnson's opening statement that the effect of mill speeds on grinding costs must be studied along with capital investment and dollars gathered together as profits. It was on this basis and for this reason the paper was written. Mr. Johnson, on the other hand, takes the position that, on the whole, low speeds are not justified from the economic standpoint, basing his principal reason on the fact that lower mill speeds cut mill capacities and hence reduce the gross income from the product produced. There is no denying this point. It is almost axiomatic. It is for this very reason that the overall advantage of lower mill speeds has been discounted and even overlooked. It was for this reason mainly that the paper was written in the first place. It is one thing to plan an efficient operation at the outset, basing one's figures on the tonnage requirements at the time, and it is quite another to be confronted with the problem of increasing the output of an existing installation at a minimum of capital expenditure. Economic consideration of a new installation is greatly influenced by referring to an old one. Too often, the analyst assumes that if this practice is followed in the new installation, one would not go wrong. It is just here that he may be wrong. Past practice and low capital expenditure are all too frequently given priority over the engineer's analysis of operating costs. When we are able to start fresh, we should give proper weight to other economic factors which do not exist in an old installation. It is these economic factors that make it possible to spend at the outset just a little more money and get it back in a matter of months and effect big savings for years to come. F. C. Bond—This paper is of considerable importance in that it emphasizes a modern trend to operate ball mills at somewhat slower speeds than formerly. We have checked the data in the paper with that obtained

Jan 1, 1951

By Harlowe Hardinge, R. C. Ferguson

Oscar Johnson—In my opinion, the effect of mill speeds on grinding costs must be studied along with capital investment and dollars gathered together as profits. Comparing the entire groups of operators with those who have had the opportunity to make slow-speed mill studies, I think you will find the latter small in numbers. Most managers want the equipment worked to its maximum output. There are, however, some installations where plant and mill sizes are such that they can do the job with reduction of mill barrel speeds. The past and the present installations of the industry are laid out to get the most capacity for the least capital outlay. This is the case even with the plants of Chile Exploration, International Nickel, Morocco, and Anaconda, now under construction or being changed. The industry recognizes that most all equipment it buys today is good and can be depended upon for efficient performance. Under this scheme of things, I am doubtful that slow-speed ball mill operation will be generally applicable. With reference to the U. S. Bureau of Mines laboratory tests, I think table II could have been omitted. It is inconclusive as to maximum efficiency for the low-pulp level mill on hard ore. There should be no question about this point. However, data on mill speeds can be found to substantiate various theories as well as refute them. Gow, Guggenheim, Campbell and Coghill, in their paper on Ball Milling,' believe their 2 x 2 ft laboratory mill reflects results that can be expected from large mills. If so, then referring to their table 11, they state, "The conclusion to be drawn from this second series is that high speed, not exceeding 72 pct of the critical, favors capacity, as before, but that with proper conditions of operation high speeds may give as good efficiency values as low speeds. In this case the efficiency values are nearly constant. A horizontal curve would indicate that the amount of grinding was directly proportional to the power expended, and these tests suggest that such a coildition can be made to exist in commercial operations." Table II (From Paper by Gow et a1)2 Speed. Pot Critical 32 42 52 62 72 82 Capacity: Surface tons per hr (65- mesh) 266 42.1 54.4 65.9 74.3 74.1 Surface tons per hr (200- mesh) 56.1 87.4 112.7 137.1 154.2 153.0 Efficiency: Surface tons per net hp hr (65-mesh) 35.7 36.3 36.3 35.4 34.3 32.3 Surface tons per net hp hr (200-mesh) 75.3 75.3 75.1 73.7 71.0 66.0 Ore in mill, 1.b. 98 100 100 113 122 165 The field performance data, table 111, represents much effort in its collection and preparation. But, one must realize that there are many variables that effect the efficiency of grinding mill operation, and too much must not be assumed as to the effect of some specific change. Possibly with changes in mill speed, the results might be more consistent by also a change in ball rationing, type of ball, volume of ball charge,. p.ulp level and amount of pulp in the mill, pulp consisting, design of liner, circulating load, etc. Also, changes in ore character must be reckoned with when evaluating grinding performance. At present the Climax Molybdenum Corp. is running at much reduced capacity. Mr. James Duggan informs me that at mill speeds of 17 rpm, they save a $0.025 per ton on liners and $0.025 per ton in power, but, if the demand for molybdenum increased, he would go back to higher speed to obtain maximum tonnage, as the values from the increased tonnage would far more than offset the one half saving at the slower speed. The Jnspiration ran a six months' test between mills running 21 rpm and 23.5 rpm. The slower mills ground 10 pct less ore with a slight saving per ton, but when the reduced plant tonnage was checked back into the actual cost figures of concentration, the high-speed mills with their greater tonnage showed considerable advantage. To be convinced of possible practical results from the predictions in the conclusions, I think we would have to rely on the analysis of expert cost accountants to furnish the necessary proof figures. Hardinge and Ferguson are to be commended for the work in preparing this paper. I am convinced that our Massco engineers should go into higher speeds with our equipment. Harlowe Hardinge (authors' reply)—For one, I heartily agree with Mr. Johnson's opening statement that the effect of mill speeds on grinding costs must be studied along with capital investment and dollars gathered together as profits. It was on this basis and for this reason the paper was written. Mr. Johnson, on the other hand, takes the position that, on the whole, low speeds are not justified from the economic standpoint, basing his principal reason on the fact that lower mill speeds cut mill capacities and hence reduce the gross income from the product produced. There is no denying this point. It is almost axiomatic. It is for this very reason that the overall advantage of lower mill speeds has been discounted and even overlooked. It was for this reason mainly that the paper was written in the first place. It is one thing to plan an efficient operation at the outset, basing one's figures on the tonnage requirements at the time, and it is quite another to be confronted with the problem of increasing the output of an existing installation at a minimum of capital expenditure. Economic consideration of a new installation is greatly influenced by referring to an old one. Too often, the analyst assumes that if this practice is followed in the new installation, one would not go wrong. It is just here that he may be wrong. Past practice and low capital expenditure are all too frequently given priority over the engineer's analysis of operating costs. When we are able to start fresh, we should give proper weight to other economic factors which do not exist in an old installation. It is these economic factors that make it possible to spend at the outset just a little more money and get it back in a matter of months and effect big savings for years to come. F. C. Bond—This paper is of considerable importance in that it emphasizes a modern trend to operate ball mills at somewhat slower speeds than formerly. We have checked the data in the paper with that obtained

Jan 1, 1951

By D. E. Mikkola, G. E. Poquette

X-ray diffraction was used to study the growth of antiphase domains in quenched (or "disordered&apos;? Cu3Au annealed in the range 300" to 385°C. Measurements of the long-range order parameter indicate that a high degree of order is established rapidly at these annealing temperatures. Average domain sizes obtained by Fourier analysis of the superlattice peak profiles show that antiphase domain growth is analogous to classical metallurgical grain growth (i.e.,fol-lows a D2 US kt relation). The activation energy for the growth process, 44 kcal per mole, indicates diffusion control. The anisotropy in the observed effective domain sizes from seven different superlattice peaks can be best accounted for by a configuration involving antiphase domain boundaries on {100 } and (111 ) planes, where the (100) boundary is the low-energy type, {lOO} Type I. The disappearance of the (111) antiphase domain boundary during domain growth is dif-fusion-controlled with an activation energy of 48.5 kcal per mole. On the other hand, the behavior of the parameter representing the amount of (100) Type I boundary indicates that there may be a conversion of the higher-energy boundary types to (100) Type I boundary during the growth process. THE order-disorder transformation in the alloy Cu3Au has been the subject of numerous experimental investigations over the past 40 years, most of which have involved measurements of convenient physical properties such as resistivity and hardness as a function of heat treatment. The interpretation of these data is difficult because measurements of this type have the disadvantage that they yield total changes resulting from several different atomic processes which may be occurring simultaneously. The present study was undertaken to establish by means of X-ray diffraction the kinetic behavior of one of these atomic processes, namely antiphase domain growth. In the completely ordered state Cu3Au has an L12 structure which can be described as an fcc type arrangement of atoms in which the gold atoms occupy the corner sites and copper atoms the face-centered sites. Three other equivalent unit cells can be formed by allowing two gold atoms to occupy opposite face-centered sites and copper atoms to occupy the remaining corner and face-centered sites. These four different unit cells are crystallographically related by a shift of 1/2<110>. Quenching from above the critical temperature (392°C) to room temperature retains the "disordered" structure-a "random" arrangement of copper and gold atoms having the fcc structure. Annealing the disordered alloy below the critical temperature causes ordering to occur through the nucleation and growth of ordered regions at different points throughout the crystal. These small ordered regions, each based on one of the four types of unit cell, grow by consuming the disordered material until they impinge to form a domain structure in which the domains are antiphase by a shift of 4(110). The boundaries between domains are called antiphase domain boundaries (APDB) and they have been found to lie primarily on &apos; {100} planes in highly ordered Cu3Au. Two types of APDB can occur on ( 100) planes. An example of an (001)1/2[110] shear type APDB is shown in Fig. I. Because of the layer of copper atoms separating the domains in this case, there are no near-neighbor violations across the boundary and it has a low surface ener This type of APDB will be referred to as {lOO} Type I. Fig. 2 shows an (001): [011] climb type APDB, (100) Type 11. This type of APDB can be described as resulting from removal of a (200) plane followed by a shift of 1/2<110> to bring the separated regions together. Near-neighbor violations across (100) Type I1 APDB make it a high-energy boundary. There are numerous other possible APDB configurations; however, it is only worth noting that shear type APDB can be produced on the (111) plane by motion of a normal fcc dislocation with Burgers vector 1/2<110> through the ordered structure. A (111); [110] shear type APDB is shown in Fig. 3. Again, because of the near-neighbor violations this type of APDB has a higher energy than the (100) Type I APDB.

Jan 1, 1970

J. E. JOHNSON, JR., New York.-It seems to me that it ought to be somebody&apos;s job to tie these notch tests with the reversed-stress tests, because the thing that causes failures in structures, in a great majority of cases, is where the material is stressed repeatedly up somewhere near the elastic limit, and the repetition of that stress seems to bring about what I suppose you may call a growth of crystals and that eventually develops into a break. It seems to me that it would be of the greatest value if there could be a coordination of the results of a shock test of some kind with the reversed-stress test, so that we could be sure that a material that had shock-test resistance would have reversed-stress resistance. H. F. MOORE,* Urbana, Ill.-The question raised by the speaker concerning the correlation of results from impact tests of notched bars with the results of repeated-stress tests is a very complicated one. Impact on a specimen sends energy into the specimen, and if the specimen absorbs this energy without fracturing there must be developed both stress and elongation. A notch in the specimen allows but little elongation to take place before rupture, and develops the ductility of the

Jan 5, 1919

By W. J. Wrazej

THE measurements on the formation of multi-layered scales on pure iron1 and the metal -lographic examination of the produced layer of FeO, Fe,O,, and Fe2O3 shown in micrographs2 throw much interesting light on this apparently well-known subject. Professor Paidassi announced2 that in a few months7 time further results are going to be published with regard to the growth of Fe2O3 and Fe2O3 layers on an Armco iron as a function of temperature. Because of the very thin layers of Fe2O3 which are shown by Paidassi (Fig. 10 of ref. 2) when samples were scaled in air at 700°C for 4 hr and because this is not in agreement with the present author&apos;s previous observations, the following experiment was recently carried out. Polished cylindrical samples 13/64 in. in diam and 1/4 in. long from electrolytic iron used for spectro-graphic work (Hilger, H.S. Iron rods, F.693) and an Armco iron sample 1/4 in. in diam of the same length were suspended in a muffle furnace on Nichrome wire and annealed in air for 4 hr at 700°C 5OC. Because of the known easy peeling off of the Fe2O3 layer which is mainly in the form of powder (purple red dust on the surface) the samples were protected against any draft and shock. After annealing, the samples were cooled in air and placed in the mount-

Jan 1, 1954

By J. L. Taylor, Pol Duwez

THE present knowledge of the Ti-Al system is limited to the portion of the diagram extending from pure aluminum to the intermetallic compound TiAl3&apos; A preliminary investigation of the titanium-rich Ti-A1 alloys revealed that the solubility of aluminum in titanium is quite extensive and that the transformation temperature of titanium is raised by alloying with aluminum. From an X-ray diffraction study of alloys containing up to 75 atomic pct Al (TiAl3), the phase boundaries at 750°C were located as follows: the a titanium solid solution extends from 0 to about 36 atomic pct Al, a two-phase region exists from 36 to 46 atomic pct Al, and an intermediate phase of varying concentration extends from 46 to 62 atomic pct Al. The purpose of the present paper is to describe the crystal structure of this new phase. The alloys were prepared by melting in a helium arc furnace on a water-cooled copper plate, using a furnace essentially the same as that described in ref. 2. The titanium metal was of the iodide type furnished by the New Jersey Zinc Co., and a piece of pure aluminum (99.99 pct) was obtained through the courtesy of the Aluminum Co. of America. After melting, the samples, weighing approximately 5 g, were sealed in evacuated fused silica tubes and homogenized for 4 hr at 1000°C. The specimens were then held for 10 days at 750°C and rapidly cooled to room temperature. Filings were then taken from each sample, sealed in evacuated vials, annealed at 750°C for 4 hr, and rapidly cooled to room temperature by quenching the vials in water. Powder diffraction patterns were obtained with a 14.32 cm diam camera, using K copper radiation filtered through a nickel foil. Structure Determination The X-ray diffraction patterns of the alloys containing 46, 50, 55. 60, and 62 atomic pct Al were identical, except for a slight shift in the positions of the reflections. The alloy containing 55 atomic pct Al was chosen far structure determination. The powder pattern contained 37 reflections and the a, doublets were well resolved in the back-reflection range. The relatively small number of reflections and the sharpness of the pattern were considered as an indication of a simple atomic arrangement in a relatively small unit cell of high symmetry, and an attempt was therefore made to solve the structure without single crystal work. A satisfactory fit was found on a large scale Hull-Davey tetragonal chart for an axial ratio of approximately 1.45. All the reflections were readily indexed and the tentative unit cell dimensions were computed to be a - 2.81 kX, c - 4.07 kX, and c/a = 1.448. The indices (hkl) and the values of d and sin2 A are given in Table I. The agreement between observed and computed sin2 is quite satisfactory. Once the unit cell was known, the details of the structure were readily found. First, it is obvious that the number of atoms per unit cell cannot exceed two, since more than two atoms would lead to a density greater than that of pure titanium. The next logical step is to assume that the two atoms occupy the corner and center of the cell. If this assumption is correct, the structure may be described as follows: space group D1, - P 4/mmm; one titanium atom in a: 000; one aluminum atom in d: 1/2 1/2 1/2: and no extinctions. Assuming this structure to be the correct one. intensities were computed by means of the usual equation: sin2 0 cos 0 where F is the structure factor; 8, the Bragg angle. and p, the multiplicity factor. The calculated values of intensities are compared in Table I with the visually estimated intensities. The agreement is quite satisfactory and the structure is therefore confirmed. The crystal structure of TiAl just described is the same as that of AuCu ordered. The AuCu ordered

Jan 1, 1953

By S. F. Shaw

IN 1913, the Tiro General mine, at Charcas, S.L.P., Mexico, which had been making from 125 to 150 gal. of water per min., was allowed to become flooded, after all the pumps had been removed, and in 1918 the problem of unwatering it came up for solution. There are two vertical shafts, the Tiro General, 1390 ft., and the San Fernando, 1225 ft. in depth, with five connecting levels between them. The San Fernando shaft had been partly retimbered, while the Tiro General had been newly timbered from the collar to, 1090 ft. in depth. It had been possible to place guides in only one compartment of the Tiro General, from the collar to the seventh or 850-ft. level, to which it was necessary to lower the water before station pumps could be installed. Soundings indicated that compartments in the Tiro General were open to 1082 and 428 ft., and in the San Fernando shaft to 471, 488, and 586 ft. The water had risen to a point 140 ft. below the collar of the Tiro General shaft. PUMPING EQUIPMENT The steam plant at the Tiro General shaft includes one 300-hp., one 150-hp. and one 100-hp. Erie City water-tube boiler, and two 160-hp. Heine water-tube boilers. All but one of these boilers were supposed to be in good shape, but it was soon discovered that six years of idleness in a climate that is foggy for several months of the year had left them in poor condition. The compressed-air plant comprises one Nordberg cross-compound compressor with piston displacement of approximately 2500 cu. ft. of free air compressed to 96 lb. per sq. in.; and another Nordberg cross-compound with piston displacement of 1235 cu. ft. of free air, to the same pressure.

Jan 2, 1920

By S. H. McFarlane, K. H. Zaininger, G. W. Cullen, C. C. Wang, G. E. Gottlieb

Heteroepitaxy of silicon on stoichiometric spinel has been studied. Both boron-doped (p-type) and arsenic-doped (n-type) single-crystal silicon films have been grown by the pyrolysis of silane on sioichiometric spinel (MgAl2O4) substrates prepared by a flux technique. The spinel crystals are free from strain and subgrains, and exhibit no thermal instability at temperatures employed for silicon deposition. The growth parameters of epitaxial silicon have been studied. Effects of substrate orientation, surface preparation, and growth conditions on the silicon Properties have been determined. The silicon-spinel composite was characterized by X-ray diffraction, electron diffraction, electron microscopy, and optical techniques. Information on epitaxial orientation relationship, defect structures and film-substrate interface has been obtained. A parallel orientation relationship was found between silicon and spinel. The silicon films exhibit no subgrain structures. However, growth pyramids, microtwins, stacking faults, and dislocations are the prevalent defects. The deformation of epitaxial silicon was measured by an X-ray technique. It was found that the epitaxial silicon is strained under compres-sive stress due to the thermal expansion difference between the film and substrate. The stress was estimated using the classical plate theory and beam equation. Electrical properties of the epitaxial silicon have been measured, including resistivity, carrier concentration, and Hall mobility. MIS and vertical through diffused junction structures have been fabricated wing silicon-spinel composite. Information on MIS characteristics, minority carrier life time, and junction properties has been obtained. THE achievement of single-crystal growth of large area silicon semiconductor films on oxide insulating substrates is of technical importance to many solid state electronic devices. The semiconductor-insulator composite structure is also of scientific interest because the heteroepitaxy is determined by the spatial relationship between the atomic arrangement in the substrate and that of the atoms in the appropriate crystallographic plane of silicon. The degree of crystalline perfection of the silicon deposits depends also on the physical condition of substrate surface. Epitaxial growth of silicon on commercial flame fusion Al-rich spinel (MgO:3.3A12O3) has been reported by several investigators.&apos;-4 The lattice of spinel of this composition is distorted. The material cracks and exsolves the excess alumina in the lattice at temperatures (-1200°C) used in fabricating silicon devices. Stoichiometric MgA12O4 spinel exhibits neither lattice distortion nor thermal instability. Results are given on the epitaxial growth and characterization of silicon on stoichiometric spinel. EXPERIMENTAL Fabrication of Silicon-Spinel Composite Structures. The MgA12O4 spinel substrate wafers were prepared from bulk single crystals grown at about 1200°C by a flux technique5 using a PbF2 flux. The crystals are free from strain and subgrains, and exhibit a typical dislocation density of less than 50 lines per sq cm. The crystals are thermally stable without cracking and exsolution of alumina to at least 1500°C. The spinel crystals were oriented for cutting by the Laue X-ray back-reflection method.6 Substrate wafers (about 25 mil thick) of (Ill), (loo), and (110) orientations have been obtained bu cutting the X-ray oriented crystals using a standard type diamond wheel. An accuracy of better than 1/2 deg is maintained throughout the operation. The spinel substrate wafers were mechanically lapped and polished to produce the flat and smooth surface which is required for silicon epitaxy. Lapping was carried out with about 30-µ boron carbide abrasives to obtain a flat coplanar surface. The lapped surface was further polished using successively finer grades of alumina, ending with the 0.3-µ grade. After polishing the wafers generally have a flatness of ±0.4 µ per cm, as revealed by interferometry. Fig. 1 shows (111) oriented MgA12O4 spinel wafers of various shapes.

Jan 1, 1970

By T. F. Witherbee

On .the 22d of November, 1879, white, iron unexpectedly ap peared while working the Cedar Point Furnace, Port Henry, N Y., on the following burden, calculated to turn out mill and foundry iron: Anthracite coal,. ., .. .. 8000 pounds. Connellsville coke,. ..1500 " Total,..4500 " Old Bed ore,........ 3750 " New Bed fine ore,. ..2000. " New Bed chunk ore,. .. 1000 " Kearnev hematite ore,.750 " Total,..... 7500 " Magnesian limestone,. 1665 " Common limestone,. ...835 " Total,........ 2500 " The production per week since making mill iron-—from September 1st, 1879, to date, seven weeks—was 412 gross tons. Ore was not immediately taken off, as nothing serious was looked for. The iron for the next week graded from No. 4 to white, and in six days the make was 2741/2 tons. At 10 p.m., Friday, the 28th, a slip of -14 feet occurred, and on Saturday, at 5 A.M., another of 3 feet on the south side and 7 feet on the north side took place. At this time it was found that the south side had been hanging for over a week—a fact which had not been reported. Throwing off the wind, to produce slips and reduce pressure, had been tried with no effect. The stock, as seen through the tuyeres, seemed to consist almost entirely of coal, with just enough infusible cinder to cement it into a mass through which the blast could not be forced. At 3.50 A.M., Sunday, the 30th, the first cinder seen in seventeen hours came into tuyeres Nos. 1, 2, 3, and 6. At 9.30 A.M. No. 3 was taken out to see if the stock

Jan 1, 1881

By L. S. Darken

It has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernstl in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and FuossZ with results which have recently been confirmed experimentally by Harned and Nuttall. This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author,4,5 who pointed out4 that "for a system of more than two components it.is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepti- cism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley" in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion of acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 10500 C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1949

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.&apos; At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir&apos;s work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.&apos; Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By D. J. McAdam, G. W. Geil, R. W. Mebs

As shown in previous papers by the authorsg-17t the resistance of a metal to fracture, like its resistance to plastic deformation, is a function of all three principal stresses. A technical cohesion limit is the technically determined resistance to fracture under a specific stress system. The technical cohesive strength thus comprises an infinite number of technical cohesion limits corresponding to the infinite number Of possible com-binations of the principal stresses. The technical cohesive strength, therefore, may be represented by a surface in a diagram with the three principal stresses as coordinates. As shown in previous papers,&apos;-&apos;&apos; the technical cohesive strength increases with plastic deformation, with decrease in temperature, and with increase in the strain rate. The technical cohesion limit, therefore, is affected by the same factors that affect the flow stress,$ namely, the stress system, plastic deformation, temperature, and the strain rate. More- over, the influence of each of these factors on the technical cohesion limit has been shown to be qualitatively similar to the three of the same factor on the flow stress.9-18 Advance of knowledge about the conditions determining fracture of metals has been retarded by the reluctance of some investigators to abandon preconceived ideas about how metals &apos;&apos;should,, behave. The incorrect idea is still prevalent that the conditions determining resistance to fracture are very different from those determining the flow stress. Attempts are still being made to express resistance to fracture in terms of a single parameter, such as a limiting value of the greatest principal stress, the maximum shearing stress, or the volume stress (one-third the algebraic sum of the three principal stresses). In these attempts, a sharp distinction is sometimes made between a ductile or ,plasticdeformation, fracture,, and a "brittle frat-ture.H In making this distinction, however, the meaning attached to the term "brittle fracture" sometimes is not made clear. The term could mean fracture after very little plastic deformation or it could be used to designate the type of fracture. An ordinary fracture of a ductile metal at room temperature starts as a cleavage, generally transverse to the direction of the greatest principal stress, but eventually changes to a shearing fracture&apos; In some conditions, however, the metal fractures entirely by cleavage, with no evidence of plastic deformation during the fracture; the surface of such a fracture may have a

Jan 1, 1948

By R. W. Mebs, G. W. Geil, D. J. McAdam

As shown in previous papers by the authorsg-17t the resistance of a metal to fracture, like its resistance to plastic deformation, is a function of all three principal stresses. A technical cohesion limit is the technically determined resistance to fracture under a specific stress system. The technical cohesive strength thus comprises an infinite number of technical cohesion limits corresponding to the infinite number Of possible com-binations of the principal stresses. The technical cohesive strength, therefore, may be represented by a surface in a diagram with the three principal stresses as coordinates. As shown in previous papers,&apos;-&apos;&apos; the technical cohesive strength increases with plastic deformation, with decrease in temperature, and with increase in the strain rate. The technical cohesion limit, therefore, is affected by the same factors that affect the flow stress,$ namely, the stress system, plastic deformation, temperature, and the strain rate. More- over, the influence of each of these factors on the technical cohesion limit has been shown to be qualitatively similar to the three of the same factor on the flow stress.9-18 Advance of knowledge about the conditions determining fracture of metals has been retarded by the reluctance of some investigators to abandon preconceived ideas about how metals &apos;&apos;should,, behave. The incorrect idea is still prevalent that the conditions determining resistance to fracture are very different from those determining the flow stress. Attempts are still being made to express resistance to fracture in terms of a single parameter, such as a limiting value of the greatest principal stress, the maximum shearing stress, or the volume stress (one-third the algebraic sum of the three principal stresses). In these attempts, a sharp distinction is sometimes made between a ductile or ,plasticdeformation, fracture,, and a "brittle frat-ture.H In making this distinction, however, the meaning attached to the term "brittle fracture" sometimes is not made clear. The term could mean fracture after very little plastic deformation or it could be used to designate the type of fracture. An ordinary fracture of a ductile metal at room temperature starts as a cleavage, generally transverse to the direction of the greatest principal stress, but eventually changes to a shearing fracture&apos; In some conditions, however, the metal fractures entirely by cleavage, with no evidence of plastic deformation during the fracture; the surface of such a fracture may have a

Jan 1, 1948

By R. J. Quigg, G. P. Conard, J. F. Libsch

IN a recent investigation of the Mn-Ge system by Zwicker it was reported that two inter-metallic compounds in this system, Mn,Ge, and Mn,Ge,, exhibited ferromagnetic properties. Of these, Mn,Ge, was reported as "strongly magnetic" and Mn,Ge, was said to be "weakly magnetic" but no actual values were given. In a study of magnetic alloys of nonmagnetic elements sponsored by the United States Army Signal Corps at Lehigh University, test bars having the nominal composition of these compounds were prepared by pressing elemental powders and sintering them in a purified helium atmosphere. Magnetic values obtained on these compounds are reported in Tables I and 11. It should be cautioned that the test bars were somewhat porous and that X-ray patterns run on these materials indicated that the homogenization in the samples was not complete, but that in each case the compound reported on was the dominant phase. The (B-H) max and particularly the Br values for pure dense M&Ge, can, therefore, be expected to be somewhat higher than those reported herein, while those for Mn,Ge, may be in error in either direction. Further details on this investigation are available in previous publications.23

Jan 1, 1956

By E. M. Baroody

MUCH information on intermetallic diffusion has been obtained in experiments in which two volumes, initially at different uniform concentrations, are maintained in contact at an interface which is plane, or nearly so. Concentration-distance curves are obtained after suitable times, and analyzed on the basis of a one-dimensional form of Fick&apos;s law In early work the linear equation to which Eq. 1 reduces when D is independent of concentration was used. However, when the initial concentrations c, and c, are appreciably different this simplification is often unjustified, and the suggestion by Matanol in 1933 of a way of avoiding it was welcomed. Matano&apos;s paper was based on work done as early as 1882 by Boltzmann.2,3 In 1938 Rhines and Meh14 reported an extensive investigation of systems in which the diffusion coefficient depends strongly on concentration, and included a detailed description of the Matano-Boltz-mann method. To a large degree, this description represents the formal method as it is understood and applied today, most later discussions having emphasized thermodynamic and mechanistic aspects of diffusion. Exceptions are the comments of R. V. Churchill, contained in a paper by Ham, Parke and Herzig,5 and the papers by Hall8 and by Kirkaldy.7 More discussion appears necessary since some aspects of the problem remain obscure. Better computational procedures are also needed. The common method, involving graphical determination of slopes and areas, is inconvenient and makes the estimation of errors difficult. Background of the Matano-Boltzmann Method Eq. 1 is to be considered along with initial and boundary conditions. Take the origin of x at the

Jan 1, 1958