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Charles H. Fulton, Rapid City, So. Dak. (communication to the Secretary*): Professor Lodge takes issue with Mr. Crawford and myself on results obtained by the scorification-method of assay on " zinc-box precipitates," which we published in a paper on the subject in the publication named below.' In our work we found that the normal seorification-method, employing only test-lead and a very little borax-glass as a flux, gave results on cyanide precipitates which mere invariably very low, loss having taken place by slag-absorption and volatilization, as repeated slag-assays failed to bring up results similar to those obtained by other methods. Professor Lodge anil his students made a large number of what he terms " scorification-assays," but which, I would like to point out, have claim to that name only in that they are made in a scorifier, for the charge consists of test-lead, a very considerable quantity of borax-glass (10 grams), at times also of litharge and even charcoal, so that the assays are in reality crucible assays. A scorification-slag proper is an oxide-slag to all intents and purposes, while the slags made by Professor Lodge are borates, certainly acid-slags. It has been our experience since our paper, The Assay of Cyanide Precipitates, was published, that the nature of the assay slag in the crucible assay has a great influence on the result. A " basic " or oxide-slag invariably causes high slag-losses, while an " acid " slag gives very fair results on material containing much zinc. This has also been the experience of a mellknown cyanide chemist with whom I have corresponded on the subject, who found that acid crucible-slags gave good results on zinciferous material, but that the scorification-method, as ordinarily employed, gave high slag-losses. I believe that if the conditions are such that the zinc can be

Jan 1, 1904

By J. M. Callow

H. A. MEGRAW, New York, N.,Y.-One interesting thing that might be brought out in this connection is the cost of making sulphide gas. I had a communication the other day which suggested that, in view of the high cost of oil, sulphur and sodium sulphide, we might make use of a well-known chemical reaction to form this sulphide gas by the use of aluminum sulphide. It is difficult to see any advantage in this, however, since aluminum has been affected just as much as any other commodity by the rise in prices, due, to war conditions. RUDOLF GAHL, Miami, Ariz. (communication td the Secretary*) Mr. Callow refers to my paper, History of Flotation at Inspiration, which was presented at the Arizona meeting of the Institute. These notes of Mr. Callow's contain much valuable information on flotation practice, as is to be expected from an article written by an author of Mr. Callow's experience in this branch of metallurgy. Nevertheless, I cannot help contradicting a number of the statements made in the references to my paper. In passing, I will also say a word about the reference in Mr. Callow's paper to the article by Messrs. Laist and Wiggin entitled "Flotation Concentration at Anaconda, Mont." Mr. Callow calls attention to the fact that evidently Callow flotation machines are not very sensitive, inasmuch as one man per shift handles four 800-ton sections of Callow machines or 3,200 tons per day at the Inspiration plant. While-it has been the experience of the Inspiration company that the four sections of Callow machines in the Inspiration concentrator are easily handled by one American operator per shift, it is only fair to state that each man operating four sections is assisted by two Mexican helpers who constantly clean the bottoms of the machines. The tonnage per section, by the way, whether equipped with Callow,, Inspiration or Minerals Separation machines, is considerably in excess 4 800 tons.. Mr. Callow further says that local opinion at Inspiration is that, two 800-ton sections consisting of two 10-compartment and four 6-compartment Minerals Separation machines (these machines are of the Hebbard type) is the limit that one man can properly attend. I do not hesitate to say that I consider it perfectly feasible to have four such sections operated by one man, perhaps assisted by "one helper. The Minerals Separation machines of this type have undoubtedly an advantage as far as easiness of operation is concerned,

Jan 4, 1917

By G. H. Bishop

The kinetics of the inter granular penetration and embrittlement of [100] tilt boundaries in 99.998 pct pure nickel upon exposure to bismuth-rich Ni-Bi liquids have been determined in the temperature range from 700° to 900°C. The kinetics of penetration are parabolic in time at constant temperature over most of the temperature range. In a series of 43-deg bicrystals the rate of penetration is anisotropic with respect to the direction of penetration into the grain boundaries. In lower-angle bicrystals the penetration rate is isotropic. The rate of penetration decreases with tilt angle at 700°C. The activation energy for penetration in the 43-deg bicrystals is 42 kcal per g-atom independent of direction. It is concluded that the intergranular penetration and embrittlement in the presence of the liquid proceeds by a grain boundary diffusion process and not by the intrusion of a liquid film. This was confirmed by a determination that the kinetics of penetration and embrittlement were the same in the 43-deg bicrystals upon exposure to bismuth vapor under conditions such that no bulk liquid phase would be thermodynamically stable. WhEN solid metals are exposed to a corrosive liquid-metal environment, the grain boundaries are sites of preferential attack. Depending on the temperature, the composition of the liquid, and the composition, structure, and state of stress of the solid, a number of modes of attack are possible. This paper reports a study of the kinetics of intergranular penetration and embrittlement of high-purity nickel bicrystals upon exposure to bismuth which, together with an earlier study by Cheney, Hochgraf, and Spencer,&apos; demonstrates that there are at least two modes of intergranular attack possible in the Ni-Bi system. In the study by Cheney et al., columnar-grain specimens of 99.5 pct pure nickel were exposed to liquid bismuth presaturated with nickel in the temperature range 670" to 1050°C. They found that the majority of the boundaries, which were predominantely high-angle boundaries, were penetrated by capillary liquid films, the attack proceeding by a process which will be termed grain boundary wetting. This process occurs in a stress-free solid when twice the liquid-solid surface tension is less than the surface tension of the grain boundary,* i.e., when 2yLs < YGB In this case the penetration of the grain boundary by the liquid occurs at a relatively rapid rate, resulting in the severe embrittlement of a polycrystalline solid. Grain boundary wetting is a common mode of intergranular attack in systems in which the lower melting component is relatively insoluble in the solid, but the solid has an appreciable solubility in the liquid, for example, the Ni-Bi system, Fig. 1. In systems of this type at temperatures above the range of stability of any intermetallic phases, once the liquid is saturated with respect to the solid so that no gross solution occurs, chemical gradients are small, and surface tensions become major driving forces for attack, provided the solid is stress-free. The results of Cheney et al. appear to be typical of those encountered when grain boundary wetting occurs.&apos; Capillary films were observed in the boundaries after quenching from the exposure temperature. The mean depth of penetration increased linearly with time, and the activation energy for the process was found to be 22 kcal per g-atom. In a study of the Cu-Bi system Yukawa and sinott4 found that the depth of penetration of bismuth into high-purity copper bicrystals of orientations from 22 to 63 deg of tilt about (100) at 649°C ranged from 0.05 to 0.25 in. after a 12-hr anneal. This corresponds to a linear rate of 6 to 15 X 10~6 cm per sec. At the same reduced temperature of 0.68 the rate for the Ni-Bi system&apos; was 7 x lo-&apos; cm per sec. In another study of the Cu-Bi system, Scheil and schess15 determined the kinetics of grain boundary wetting in hot-worked commercial rod. While there were several complicating factors present in this study, there is general agreement with the above results. The kinetics of penetration were linear, the activation energy was 20 kcal per g-atom, and at 650°C the rate of wetting was 2 to 5 x 10-6 cm per sec. The rate of wetting in the A1-Ga system6 is somewhat

Jan 1, 1969

By John M. Gallow

Discussion of the paper of JOHN M. CALLOW, presented at the New York meeting, February, 1916, and printed in Bulletin No. 108, December, 1915, pp. 2321 to 2339. R. H. RICHARDS, Boston, Mass.-I think there is one note which would be interesting to have recorded in connection with this paper, and that is another form of flotation machine. The Minerals. Separation machine has a vortex action, with a vertical shaft and a propeller. This new frother has been developed for the Copper Queen Co. at Bisbee, Ariz. It has a horizontal shaft and a paddle wheel for a frother. It has eight cells, I think, all connected underneath in one continuous tank, and the only separation of the cells is in the upper chambers where the froth is. When this paddle wheel goes around it throws out the froth and the sand goes to the bottom and drifts over from the first to the second cell, where it is paddled again, and comes out with its froth; the sand goes to the third cell where it is again beaten. In that way the sand is continually drifting toward the last cell, while each new froth remains in its own cell. You can see in the working of this machine just the same effect that you see in Callow&apos;s machine, i.e., the earlier cell has the darker or richer froth, and the latter has the lighter or poorer froth until you get to the farthest one-which has very little froth, and is very light. JOSEPH W. RICHARDS, So. Bethlehem, Pa.-Speaking from the metallurgical standpoint, it is quite desirable, in many cases, that the oil be removed from the concentrate in order to facilitate the metallurgical work, and I think attention should be directed to the desirability of removing from zinc sulphide concentrates the oil which interferes with their subsequent roasting. The value of the oil is not large; in Mr. Callow&apos;s plant, for instance, it would be $20 a day, and it may be possible that a process might be developed which, within the limits of the value of the oil, would remove it, and thus facilitate the metallurgical treatment. LEONARD WALDO, New York, ,N. Y.-The question came up about a year ago as to why-Mexican crude was not an admirable oil for flotation. I have never heard any satisfactory answer to the question. The Mexican crude has the peculiar property of comparative freedom from dangers of fire, a very great reluctance to part with its water, and a specific gravity almost identically the same as water.

Jan 5, 1916

Discussion of the paper of CHARLES H. MACDOWELL, presented at the New York meeting, February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 103 to 114. GEORGE S. RICE, Pittsburgh, Pa.-I am especially interested in the mining side of this important question. In 1911, when in Europe investigating mining matters, giving special attention to subsidence clue to mining, for there is a very big problem of that kind, as many of you know, in the Pennsylvania anthracite region, I visited Stassfurt, which is one of the chief centers of potash mining, and which was pointed out as the place to see surface subsidence. We found the town much askewsome of the streets having sunk from 15 to 30 ft., leaving many ancient buildings pitching at various angles. One old church, 500 or 600 years old, has been sunk about 20 ft., cracking it badly. I understand that this condition came about because in early mining clays they were careless about leaving proper supports and used no filling or packing. The Stassfurt mines work along a buried anticline the sides of which pitch at 45° on the average. Through this careless mining they had a break of the hanging wall which let in water from the overlying marls and sands. The water rapidly dissolved the salts in the pillars, and spreading through the entire chain of mines, caused their complete loss, with serious trouble for the old city. They had to start new mines some distance away, and take care to prevent roof caves. The packing system is of interest. They were driving large rooms into the rock-salt foot wall and using the rock salt as dry filling. The application of hydraulic filling, using a saturated solution, was under contemplation at some plant nearby. Whether 6r not the plan was carried out I do not know. I was reminded of the plan by Mr. MacDowell&apos;s remarking on the use of a saturated salt solution in the core drilling. His reference to the apparent breakdown of the potash syndicate raises an interesting question. We have had the German system of syndicates pointed out as perhaps one means of solving our troubles in the soft-coal mining industry due to overproduction. It seems to have worked out admirably in the case of the Westphalian coal-mining syndicate and also in the syndicate of Upper Silesia; but apparently the syndicate plan did not work in the potash industry. .

Jan 5, 1915

By J. L. Taylor, P. Duwez

PARTIAL phase diagrams of titanium with iron, cobalt, and nickel have been established by previous investigators.1-3 These diagrams seem to be reliable, at least for concentrations of titanium ranging from 0 to about 50 at. pct. More recently, Long and his collaborators have presented a tentative titanium-nickel diagram covering the titanium-rich side.&apos; These various studies indicate that in each system three intermediate phases exist and correspond to the compositions Tia, TiX, and TiX2 (or TiX3). The purpose of this paper is to review the available information on the crystal structure of these phases and to give the results of additional X-ray diffraction studies. Previous Work A summary of the work of Wallbaum and his collaborators"-&apos; is presented in table I. The first intermediate phase on the titanium-rich side of the three systems, with iron, cobalt, and nickel, is of the Ti2X type and has a face-centered cubic structure. Although it is stated that the unit cell contains 96 atoms: no lattice parameters are given. The second phase is centered around the compositions TiX for the three systems. The crystal structure of this phase is mentioned in a short note" as being body-centered cubic (CsCl type), but no parameters are given. The analogy between the three systems, which is perfect as far as the two phases of the type Ti2X and TiX are concerned, disappears at the titanium-poor end of the diagrams. In the system titanium- iron, TiFe2 has an hexagonal (MgZn2 type) struc-ture with the parameters given in table I. The existence of TiFe3 has also been reported8 (table I) but was questioned by other investigators2 and is also refuted by the present study. In the system titanium-cobalt, a phase corre-sponding to the composition TiCo2 has been investi-gated by Wallbaum and Witte6 who claim that the structure is cubic (MgCu2 type) for alloys slightly deficient in cobalt and hexagonal (MgNi2 type) for alloys slightly deficient in titanium. The parameters of the two phases are given in table I. In the system titanium-nickel, the nickel-rich phase corresponds to the composition TiNi3 and has been described as hexagonal7 with the parameters given in table I. The present investigation was initiated for the purpose of filling in the gaps in the knowledge con-cerning the structure of the various phases sum-marized in table I. Since the titanium used by Wallbaum and his collaborators was only 95 pct pure,&apos; it was found desirable to redetermine the lattice parameters of the alloys prepared with a

Jan 1, 1951

By Paul A. Farrar, Felix Ermains, Harold Margolin

The systems Ti-Crand Ti-Vhave been reinvesti-gated in the region up to 40 wt pct alloying addition using both conventional and rapid quenching techniques. The Ti-Cr eutectoid temperature was determined to be at 667° & 10° C and 14.5 wt pct Cr. The solubility of the Cr in a Ti was found to be less than 1 pctat 700"C. The P transus of the Ti-V system was found to be depressed to 510°C at 40 wt pct V and the solubility of V in a Ti was found to be less than 2 wt pct at 700°C. Investigation by a. d. McQuillan1-3and m. k. McQuillan4 on the systems Ti-Co, Ti-Cr, Ti-Cu, Ti-Fe, Ti-Mn, Ti-Ni, and Ti-V has cast doubt as to the position of the ß/a + ß boundaries in many of these systems. Their investigations were carried out using hydrogen pressure and/or rapid quenching experiments, as opposed to the conventional quartz capsule techniques employed by most other investigator.&apos;" By these methods, the ß/a + ß boundary was found to be lower than that obtained by conventional techniques in all except the Ti-Fe system. In the latter, the ß/a + ß boundary was essentially the same as the boundary obtained by conventional technique.7&apos; On the basis of rapid quenching results in the Ti-Cr system, M. K. McQuillan4 placed the eutectoid temperature below 550°C whereas other investigations using conventional techniques had placed the eutectoid variously as between 650&apos; and 700°C,5 between 675&apos; and 700°C,6 between 650" and 675°C,7 at 670°C,8 and above 625"C.la9l3 In order to check these results, a reinvestigation of four of the systems was undertaken using both conventional and rapid-quenching techniques. The Ti-Fe and Ti-Mn systems will be dealt with in anoth er paper, with only the Ti-Cr and Ti-V systems being discussed here. EXPERIMENTAL TECHNIQUES Alloys employed for the delineation of the systems under investigation were prepared from iodide titanium sheet capsules containing the alloying materials,

Jan 1, 1962

By John W. Weeton, Max Quatinetz, Robert J. Schafer

Nickel powders of 1-, 0.4-, and 0.2- average particle size were combined with 0.05- p MgO powder. Oxide was added in quantities of 4, 12, and 20 vol pct. The mixtures were vacuum hot pressed and extruded at 2100°F. In spite of a general tendency to growth of oxide particles during processing, dispersions of fineness comparable to those of Sintered Aluminum Powder, SAP, were achieved. A small amount of oxide considerably improved 1800°F stress-rupture strength, but further oxide addition resulted in a decrease of strength. RECENTLY there has been much speculation concerning the requisites for strong and stable dispersion-strengthened alloys. The nature of the dispersed phase, the stability of the alloys, and variables influencing the mechanical properties of alloys have been given consideration. Such topics have been reviewed by Bunshah and Goetzel. Of the many parameters related to the mechanical properties of dispersion alloys, mean free path between dispersed particles (a measure of the fineness of the dispersion), particle size, and vol pct of the dispersed phase have been shown to be very important. Generally, strength increases with decreasing mean free path, and there is an optimum vol pct of dispersed phase. Just how fine a dispersion ought to be is somewhat open to debate, but Irmann, Lenel, Backensto, and Rose, Gregory and Grant,4 and others have shown in the original SAP-type alloys, aluminum plus aluminum oxide alloys, that better strength is generally obtained with finer dispersions and the best strengths were obtained when the mean free path was less than . Further, Cremens, and rant&apos; showed that in nickel plus aluminum oxide alloys, stress-rupture strength at 1500°F was definitely increasing with decreasing mean free path. In their investigation, however, the finest dispersions that were produced were about 2.0 mean free path. To determine the potential of the nickel plus oxide type of product, it would be neces- sary to obtain dispersions analogous to those of SAP alloys; namely, ones where the mean free path between oxides is less than . Unfortunately, however, it is very difficult to produce extremely fine dispersions of oxides in metals other than those which naturally form refractory oxide skins. There are several approaches to this problem including such procedures as mechanical mixing, internal oxidation, reduction of mixed oxides, and metal deposition from solution. Work at the Lewis Research Center has shown that metal powders 0.1p or finer could be produced by ball milling, when selected grinding aids were utilized.&apos; Because these unusually fine powders were available, it was an initial objective of this study to determine if by mixing of these fine Ni powders with various amounts of MgO (0.05) a fine dispersion of MgO in Ni comparable to those in Al-Al203 might be achieved. A second objective was then to attempt to relate the parameters of structure to 1800°F stress-rupture strength of the alloys. Nickel powders of 1-, 0.4-, and 0.2-p average particle size were combined with 0.05- average particle size MgO powder. This oxide was added in quantities of 4, 12, and 20 vol pct. The mixtures were hot pressed and extruded at 2100°F.

Jan 1, 1962

By Leland Wemple

PREVIOUS to 1915, zinc refining had not become a general practice among the zinc smelters in the United States. Such refining as had been carried on was confined chiefly to remelting very high-leaded zinc, such as third-draw metal from the retort furnaces, and slab dross, and hard spelter from galvanizing pots. In this remelting operation, the lead and iron were settled out and the refined spelter obtained graded fifth class, i.e., Prime Western. Owing to the presence of lead in most zinc ores, the bulk of the spelter produced by direct smelting is of this Prime Western grade. Careful selection of ores of low lead content gave purer grades of spelter, i.e., Brass Special and Intermediate; and smelters which could secure ores carrying practically no lead produced high-grade spelter. Thus, in general, the grade of spelter produced by any smelter was pre-determined by the purity of the ore it could obtain. The needs of the warring nations of Europe for enormous quantities of cartridge and other high-grade brass resulted in such a demand for the purer grades of spelter that the available supply of lead-free and low-lead ores could not produce the quantity required. Prime Western grades went begging, so to speak, while high grades sold at times from 5 to 15 c. per pound over the Prime Western market. The great demand, coupled with the wide market margin, which permitted the inherent costs and losses, resulted in the conversion of the lower grades into higher grades by processes of refining. These conditions also accentuated the development and size of the electrolytic plants, which were being worked out at the time this increased demand for pure grade of metal occurred. The electrolytic process, where available, produces a higher grade of spelter from impure ores than does the fire process; a large portion of those impurities in the ore, which by the distillation process would be carried into the spelter, are removed in the leaching of the ores and the purification of the solutions. The refining process, adopted at a number of smelters for the purpose of converting low-grade spelter into "grades suitable for brash was that of redistillation.

Jan 11, 1917

By George W. Bain

The good work of the surveys supported by the different branches of the government needs little mention to geologists but is underappreciated by people at large. Geologists and engineers realize their usefulness and yet even from this group one hears occasionally an undercurrent of discontent about their work or the distribution of it. The very fact that discontent arises within and without this group and has drawn attention of legislative bodies of the country in the present time of stress means that a large number of people do not receive or do not realize that they receive benefit from these public works. This seems to be a clear indication that more than the relations between government surveys and the mining industry is involved and that if the mining industry is interested in continuation of the work of these surveys on the past scale they must consider the other survey divisions and their activity. Also, relations between government surveys and certain specialized types of mining have not been as close as they should be. I have been employed in almost the entire range of fields offered to geologists and have studied closely the feeling of people towards geological service. Recently it has been a pleasure to be closely associated with men who were as deeply interested in civic welfare and affairs of state as in the financial success of a large industry developing natural resources. Previously I had seen service in a national survey, a state survey, summer employment by a large mining company exploring new property and detailed geological work for a large corporation. Major responsibility as a college instructor has left me free to view each of these assignments in unprejudiced fashion and at the same time study the relation of government surveys to large natural resource industries, average industrial and construction work and service to nongeologists and laymen. Considerations Governing Geologic Public Service Three groups of people must be satisfied by the surveys if dissatisfaction is to be dispelled. First there is a large group of people who pay taxes to support the government activities and must receive some service

Jan 1, 1935

By George W. Bain

The good work of the surveys supported by the different branches of the government needs little mention to geologists but is underappreciated by people at large. Geologists and engineers realize their usefulness and yet even from this group one hears occasionally an undercurrent of discontent about their work or the distribution of it. The very fact that discontent arises within and without this group and has drawn attention of legislative bodies of the country in the present time of stress means that a large number of people do not receive or do not realize that they receive benefit from these public works. This seems to be a clear indication that more than the relations between government surveys and the mining industry is involved and that if the mining industry is interested in continuation of the work of these surveys on the past scale they must consider the other survey divisions and their activity. Also, relations between government surveys and certain specialized types of mining have not been as close as they should be. I have been employed in almost the entire range of fields offered to geologists and have studied closely the feeling of people towards geological service. Recently it has been a pleasure to be closely associated with men who were as deeply interested in civic welfare and affairs of state as in the financial success of a large industry developing natural resources. Previously I had seen service in a national survey, a state survey, summer employment by a large mining company exploring new property and detailed geological work for a large corporation. Major responsibility as a college instructor has left me free to view each of these assignments in unprejudiced fashion and at the same time study the relation of government surveys to large natural resource industries, average industrial and construction work and service to nongeologists and laymen. Considerations Governing Geologic Public Service Three groups of people must be satisfied by the surveys if dissatisfaction is to be dispelled. First there is a large group of people who pay taxes to support the government activities and must receive some service

Jan 1, 1935

By N. S. Bornstein, M. A. DeCrescente

ThE nickel and cobalt base superalloys employed in gas turbine engines under some conditions&apos; oxidize at an accelerated rate when exposed at elevated temperatures to atmospheres containing minor quantities of sea salt. It is generally agreed by investigators in the field that the major steps comprising this phenomena of accelerated oxidation, also called hot corrosion or more commonly, sulfidation, are a) a slag composed primarily of Na2S04 is formed on turbine components, b) the protective oxide scale is rendered ineffectual, c) the slag reacts with. the substrate to form metal sulfides, and d) the substrate is rapidly oxidized. Sodium sulfate, a minor constituent of sea salt, is formed within the gas turbine engine from the reactions between NaC1, the major constituent of sea salt, and the oxides of sulfur.&apos; Depending upon concentration, engine compression ratio, and temperature, the Na2S04 will be present in the gaseous or condensed state. It has been determined that in order for sulfi-dation to occur the Na2S04 must be present in the condensed state.&apos; Although a number of sulfidation mechanisms have been postulated, there is no consistent explanation of oxide scale breakdown and subsequent catastrophic oxidation. Some investigators believe that after oxide scale breakdown, the Na2SO4 reacts with the substrate to form lower-valent sulfur compounds. The accelerated rate of oxidation is due to oxidation of a nickel-sulfide phase." Other investigators believe that sulfur from the fused salt reacts with chromium in the alloy to form chromium-rich sulfides; thereby depleting the alloy of an element which imparts oxidation resistance.3,4 This publication will demonstrate that the accelerated rate of oxidation associated with sul-fidation is due to interactions between Na20, a con-stituent of NazSO.,, ancl the substrate. The aim of this study was to separate and determine the effect of compounds of sulfur and sodium on the oxidation kinetics of various nickel-base superalloys, in order to elucidate the sulfidation mechanism. The work reported herein is sponsored in part by the Naval Ship and Development Center-Investigation of EXPERIMENTAL PROCEDURE The nickel base alloys B-1900, U-700, and Waspaloy were chosen for this study. The nominal compositions are presented in Table I. The specimens, approximately 1 in. by 1 in. by 0.060 in. received in the "as cast" condition were polished with 600 grit emery, washed, and rinsed with acetone immediately prior to oxidation experiments. Sulfida-tion attack was duplicated in the laboratory by apply-ing a saturated aqueous solution of Na2S04 onto the al loy substrate and subsequently exposing the specimens in oxygen at elevated temperature. The method of Na2S04 application is described elsewhere in detail.6 In another set of experiments the affected substrate microstructure associated with sulfidation was reproduced free of the normal oxide scale, by reacting and diffusing elemental sulfur into the alloy. The experimental procedure is also described elsewhere in detail. All oxidation studies were performed using an Ainsworth thermobalance type RV-AU-1, which is readable to 0.01 mg and is reproducible to ±0.03 mg. The specimens, introduced into a heated furnace, were exposed in the temperature range 800" to 1000°C

Jan 1, 1970

By E. Stamboliadis

Dithiophosphates are reaction products of phosphorous pentasulfide with various organic compounds such as phenols, alcohols, mercaptans, dioalcohols, amines, and nitrides. The products with alcohols are commercially known as "aerofloats" and these are investigated in this presentation. It appears that the formation of insoluble metal dithio phosphates is responsible for their collecting properties with minerals." In this aspect they are very similar to xanthates.3 The solubility of metal dithiophosphates depends on the number of carbon atoms in the organic chain of the corresponding alcohol. An empirical mathematical model is presented here. It allows one to predict the number of carbon atoms necessary to ensure that a certain metal dithiophosphate will form at a selected pH value of the water solution. The Nature of Dithiophosphates Dithiophosphoric acid is the product of the reaction of phosphorus pentasulfide with an alcohol, as shown in the following equation: [P2S3 + 4 ROH - 2 (RO)2 PS2H + H2S (1)] where R stands for a hydrocarbon chain. The acid so produced can be neutralized by a base to produce the corresponding salt as shown in the following: [(RO), PS2H + NH- (RO)2 PS, NH,. (2)] In this aspect dithiophosphates are similar to xanthates, the only difference being the substitution of the tetravalent carbon atom in the xanthate polar group by a pentavalent phosphorus atom in the dithiophosphate group. This difference implies at least two characteristics: (1) that there are two hydrocarbon chains associated with the polar group so that an increase in the number of carbons of the single chain is expected to have a pronounced effect on the flotation properties, and (2) that the bond between the sulfur and the central atom is stronger than in the xanthate group. This probably leads to a decrease in both the polarizability of the electronic cloud of the sulfur and the interaction with cations.3 However, what is lost in the dithiophosphates by having a weak polar group can be gained by an increase in the number of carbons as will be seen later. Taking into account the size of the atoms involved in a dithiophosphate molecule, as listed in Table 1, It is possible to draw an approximate diagram of its structure as shown in [Fig. 1]. It is assumed here that the length of the single hydrocarbon chain is equal to that of the corresponding alcohol. Preparation and Purification Acid dithiophosphates can be prepared, as previously mentioned, in accordance with Eq. 1. The rate of this reaction is too slow at room temperature and can be improved by increasing the temperature to about 60° or 80°C7 or by evacuating the system. In our investigation evacuation was performed by a water aspiration pump. The dithiophosphoric acid so produced is liquid and dissolves in the alcohol. At the end of the reaction the product is filtered from the remaining P2S3; and dissolved in petroleum ether. By blowing anhydrous ammonia gas into the ether phase the ammonium salt forms as a white precipitate and can be sepa-

Jan 1, 1977

By A. J. Lynch, N. W. Johnson, D. J. McKee

The behavior of nonsulfide gangue in chalcopyrite flotation circuits has been investigated. Plant and laboratory tests were conducted on five different ores. Linear relationships between the recovery rates of free nonsulfide gangue and water were observed. From pilot plant tests, there was evidence that the linear relationship was actually a linear approximation to a parabolic relationship. There was evidence that free nonsulfide gangue is transported from the pulp to the froth in the water and that the gangue is subjected to hydraulic classification in the froth column. A classification matrix has been proposed to define this behavior. This matrix is suitable for inclusion in a mathematical model of the process.

Jan 1, 1975

By H. Kobbè William

ARTHUR KNAPP, Ardmore, Pa. (communication to the Secretary*).¬On p. 2275 I find a quotation from Mr. Thompson regarding the fountains of the Baku field. I have seen a large number of these gushers or fountains. In every case where unusual amounts of sand were produced the wells caved in and shut off in a few clays and were an absolute loss Very often the formation had caved so far up as to allow the water to enter the oil strata, and not only was the well lost but the ground for many acres around the well was useless for drilling purposes because the disturbed ground had allowed the gas and oil to dissipate and the water to enter. On p. 2268, Mr. Thompson is again quoted regarding the Balakhany field. If the text is consulted further, it will be found that the oil at Balakhany is heavy only in contradistinction to the Bibi Eibat, field. The gravity of the oil at Balakhany is from 28 to 32. Also, it must be noted that the illustration is taken from the conditions in the older part of the field. This field was first chilled 40 years ago, and was a worn-out field 15 years ago. The wells which produce sand are wells in which the casings are practically gone and the formations are full of water. The sand must be bailed from these wells because the clays from the upper stratum have caved into the wells and are obstructing the passage of oil. On p. 2262 is the statement that the Russian wells cannot be pumped on account of the large amounts of free sand produced. They have never tried pumping in the Baku field to any extent. Wherever tried, it has proven a great success. If we take the author&apos;s theories as correct and wish to put them into practice, it would first be necessary to consider a few figures. Let us assume that we produce oil and sand together in the proportion in which they exist in the productive strata. It is not uncommon to have wells in the California field which are not gushers, but which, by pumping, produce 1,000 bbl. per clay the first 100 clays.

Jan 3, 1917

By J. Kucera, J. Vreštál

DIFFERENT authors1 &apos; have been engaged in meas-uring the vapor pressure of pure cobalt. The results of their measurements satisfy the expected temperature dependence of vapor pressure and are in mutual agreement, with the exception of the results by De Dyk Man and ~esmejanov.~ The latter authors, by using the effusion method, have achieved considerably higher values than other workers. By using the isotope exchange method they obtained much lower values than other authors. The determination of thermodynamic functions of the binary Ni-Co system was carried out, as far as we know, only by De Dyk Man and Nesmejanov.4 This determination was based on extremely low values of vapor pressure over pure cobalt obtained by the isotope exchange method. Therefore we considered it useful to repeat these measurements. Furthermore, the reliable values of thermodynamic functions should complement the migration characteristics, the inner magnetic field data obtained by Miissbauer effect measurements, specific heat data, and the K effect and positron annihilation characteristics that have been achieved for the Ni-Co system in the Institute of Metallurgy of the Czechoslovak Academy of Sciences in Brno.5-9 The measurements in this paper were performed by the isotope exchange method. In this method, as has been shown by analysis,10-&apos;3 the vaporization rate, w, can be calculated from the relation w = k/1oSw [1] i0Sw) [1] where L, is the activity per unit mass of the source, S is the area of evaporation, k is the tangent at the point t = 0 to the curve giving the radioactivity de-pendence of the target vs annealing time, t, and wis the probability for the tracer atom condensation on the target surface. The value for cc. can be obtained from the equation w = a + 2P(l-a) [2] where P is Clausing&apos;s coefficient and a is the condensation coefficient. In the present work the cylinder shaped containers for annealing the samples were used, characterized by the ratio 1:d = 1.06. Here 1 is the length and d the diameter of the container. For this ratio P = 0.514 and w =0.5, and w is independent of the condensation coefficient. The vaporization rate is related to the vapor pressure p by the relation where R is the gas constant, T is the absolute temperature, and M is the molecular weight of the component investigated. Measurements of the vapor pressure of the i component over the pure metal, p!, and the alloy, pi, at the given temperature and composition enable one to calculate the thermodynamic activity of this component from the equation ai=pi/pi [4] is and the activity coefficient ri=ai/xi [5] xi where xi is the molar fraction of the investigated alloy component. EXPERIMENTAL Evaporization rate measurements were carried out with pure cobalt and eight different Ni-Co alloys, which were kindly delivered by the Centre National de Recherches Me&apos;tallurgiques Liege, Belgium. The composition of the alloys is given in Table I. The cobalt used in these alloys contained the following impurities: 0.016 wt pct Fe, 0.014 wt pct Cu, 0.01 wt pct Mn. Other elements were present in much lower concentrations. From the melts, samples in the form of small cylinders of 12 mm in diam were ma-chined. The thickness of the targets and sources was 2.5 and 1.2 mm, respectively. The lower thickness of the sources was chosen to make their over-all ac-tivity as low as possible. Sources were activated in

Jan 1, 1970

By Joseph J. Yancik

From previous work, it was learned that relative strengths of blasting agents can be reasonably predicted from heats of detonation modified by their (D/D*)2 ratio.(1) Bulk Strength = Q x d x (D/D*)2 x K (1) In this equation Q is the ideal heat released during detonation, d is density, D represents actual detonation velocity while D* is ideal velocity. An energy transfer coefficient, K, was used to account for differences among rock strata in response to explosive loading. This equation gave reasonable, field supported strength values for oxygen balanced blasting agents. For aluminized nitrocarbonitrates and slurries which have high Q&apos;s the rating system predicted better strengths than were shown in the field. This discrepancy was felt to be related primarily to problems in calculating Q and D*. Theoretical calculations cannot take into account varying energy contributions from particulated aluminums whose reactivities vary substantially with physical properties. One approach to circumventing this problem would be to use a characteristic Q that is dependent on mass reactivity of ingredients as components in explosive formulations. Since the underwater testing method is capable of measuring a functional, relative energy release, it was chosen for study.

Jan 1, 1971

By L. O. Howard

R. HATCH, Garfield, Utah.-The object of the meeting, I believe, is to determine the proper chemical composition to insure long wear of a ball in a mill, This might also apply to rods. I feel that there is only one way of determining accurately the wearing qualities of balls in mills, and that is by actually wearing out 400 or 500 tons of different kinds of balls. Two things add to the wearing qualities of a ball: (1) the tenacity, with which the particular particles of iron or steel are cemented together; (2) the individual hardness of each particle. My experience is that a ball that has a Brinell of 550 to 650 will give comparatively long life. There is considerable difference of opinion as to the best steel and iron alloys necessary to produce a satisfactory grinding ball. Some favor chrome, some manganese and some nickel. Personally, I believe cast iron alloyed with chrome makes the best ball for small sizes; for large sizes (3 1/2 in. and up) steel alloyed with manganese is best. L. 0. HOWARD, Pullman, Wash.-How would this method apply to lining? A. KissocK, New York, N. Y.-I do not subscribe to that exactly. As I am connected with the Climax Molybdenum Co. you would hardly expect me to. We have been much interested in trying to work out this grinding-ball problem and have spent a great deal of thought and effort on it. As we are associated with the American Metal Co. and have a number of properties of our own, we are in position to try our ideas on ourselves first. We have tried different compositions, but have not done anything very remarkable with them yet, except that we have been able to say that the combination of chrome and molybdenum has given the best wearing ball. Mr. Hatch feels that iron is the best medium for grinding, but since toughness as well as hardness is a factor in wearability we feel that a well made steel is better for this purpose. Another difficulty with cast, or chilled, iron is lack of uniformity from day to day or from heat to heat and the impossibility of producing balls free from blow or shrinkage holes which materially affect their life. If cast iron is made hard it becomes brittle and lacks stretch or toughness. This prevents its use in the larger sizes, as breakage is a serious handicap to efficiency. We have tried hard and brittle balls and softer but very tough balls and have proved that maximum hardness, with sufficient toughness to prevent breakage, is the most important factor in resistance of a steel to abrasion. It is well known that chromium is one of the best hardening agencies for either iron or steel, and molybdenum is recognized as an element capable of introducing toughness. In other words, the proper combination of chromium and molybdenum permits unusual hardness with still sufficient toughness to stand up under severest impact. It is yet too early to give any actual mill results of this new combination and though we are proving our ideas at our own properties we have to depend on others to help us make the data more general and more worth while and would like to get some tests

Jan 1, 1928

K. T. Aust and J. W. Rutter (General Electric Research Laboratory)—We find it difficult to reconcile the activation energies determined by Gifkins with his general conclusion that "migration during both creep and grain growth can thus be treated on the basis of the same model" (that of Lucke and Detert). Gifkins finds the activation energy for grain boundary migration during creep to be 24.5 kcal per rnol and that for grain boundary migration during grain growth to be 7.5 kcal per mol. The calculation carried out by Gifkins of the activation energy for grain boundary migration during grain growth, using the Lucke and Detert model, gives a value of 20 to 24.5 kcal per mol, rather than his experimental value of 7.5 kcal per mol. The theory of Lucke and Detert was developed to account for the rates of migration of grain boundaries in the presence of impurities during grain growth. The theory does not take into account the effect on the boundary migration of another, simultaneous process such as creep deformation and would be expected, therefore, to be applicable only to migration during grain growth. The fact that Gifkins measured a different activation energy for boundary migration during grain growth (7.5 kcal per mol) from that during creep (24.5 kcal per mol), although the specimens were of the same composition, shows clearly that such an effect exists under his experimental conditions; the presence of a simultaneous creep deformation markedly affects the boundary migration process in comparison with what would be observed under the same conditions but without the creep deformation. The failure of McLean&apos;s equation (Eq. [4] of Gifkins&apos; paper) to give a satisfactory dislocation density difference for boundary migration during creep is not surprising, since the activation energy which must be used in this equation refers only to the elementary atom transfer process of grain boundary migration. This activation energy value is approximately 6 kcal per mol for zone-refined lead, as determined in both the grain boundary migration experiments of Aust and Rutter31, 32 and the grain growth experiments of Bolling and Winegard.33 Using this activation energy value, McLean&apos;s equation gives reasonable agreement with observed migration rates for grain boundaries moving free of the influence of impurities.31, 32 The value of 24.5 kcal per mol is probably associated with the presence of impurity atoms, as Gifkins suggests. It should be noted, however, that this value was obtained using lead of only one composition and measurements at only two temperatures. The work of Aust and Rutter3"&apos; on the effects of tin, silver, and gold on grain boundary migration in zone-refined lead in the temperature range from 320" to 200°C, as well as the work of Bolling and Winegard34 on the effect of silver and gold on grain growth in zone-refined lead, shows that the measured activation energy is markedly dependent upon the kind and amount of solute present. Gifkins&apos; work does not permit evaluation of the effect of the 8 ppm of impurities other than oxygen present in his specimens. One incidental point: the symbols used to designate the experimental points of Fig. 6 appear to be in incorrect order in the figure caption. As the caption is printed, it would indicate that larger grain sizes were obtained after annealing at 47°C than at 100°C, which does not agree with the text (point M, p. 1019). Finally, it seems clear from Gifkins&apos; results that any serious attempt to determine whether grain boundary migration and grain boundary sliding during creep occur with the same activation energy, as Gifkins suggests and McLean rejects, must take into account the effects of impurities on these two processes, Although the work of Weinberg35 indicated that adding small amounts of copper, iron and silicon to aluminum did not affect the grain boundary shear behavior, it should be noted that his starting material contained approximately 60 ppm of impurities. Gifkins&apos; results indicate impurity effects at an impurity level of 8 ppm, suggesting strongly that the most significant impurity range to be investigated lies substantially below that value. R. C. Gifkins (author&apos;s reply) — As Drs. Aust and Rutter suggest, the results under discussion may have to be reinterpreted in the light of their own work on grain boundary migration, which was not available to me when the paper was written. Because of their work, Aust and Rutter attach more importance than I did to the activation energy for grain boundary migration during annealing (7.5 kcal per mol) obtained from a "direct" plot of log-rate against the reciprocal of absolute temperature. At the time it was obtained, this value seemed rather low, although it was similar to the value obtained by Bolling and Winegard.36 It was then, and still is, difficult to accept this value because of the low value of the index in the power law for grain growth, which seemed to indicate the influence of impurities. It was also concluded that the low value of the activation energy might have arisen from the manner of selecting rates of grain growth which were truly comparable at the two temperatures. There were many other indications in these experiments and those on recrystallization during creep3? that an impurity, probably oxygen, was of importance. The model for grain-boundary migration which Lucke and Detert had proposed was an obvious possibility and its use yielded an activation energy for boundary migration during annealing of 20 to 25 kcal per mol.

Jan 1, 1961

The American Gas Association, 420 Lexington Ave., New York, N. Y. The Proceedings and Reports of the American Gas Association are concerned with the technology and utilization of gas, and research along those lines. A list of publications will be sent upon request. Publications are classified under the general headings: Accident Prevention; Accounting; Commercial; General; Rates; Industrial; Publicity and Advertising; Technical; and Testing Laboratory. As&apos; illustrations of the type of paper presented, the following are cited from the Technical classification: Evaluation of gas oils (1930), 40 cents; Agglutinating value of American coals (1927), free; Composition of coal in relation to spontaneous combustion (1927), free; Physical and chemical

Jan 1, 1933