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By S. W. Parr

FRom a study of sulfur with reference to its specific combination in coal, published as University of Illinois Bulletin No. 111, 1919, it is now possible to determine the various forms of this constituent with a good degree of accuracy. This fact suggests two questions: (1) Are the same analytic methods applicable to coke? (2) Is there any correlation between the forms of sulfur as it occurs in coal and the residual sulfur found in the finished coke? The answer to the second question might be helpful in answering a still further question as to what chemical route the sulfur travels during the carbonization process. While the special studies along these several lines are by no means complete, a few preliminary statements are herewith presented. They may, at least, prove suggestive of further possibilities from a continuation of research along these lines. There is no reason, chemically, why the analytic methods devised for coal should not apply to coke and a fair amount of experience in connection with such use affords confirmation of this statement. The procedure in the case of coal may be briefly outlined as follows: Combinations of sulfur as sulfate, or sulfides other than FeS2, are readily dissolved without disturbing either the pyrite sulfur or the sulfur that is in organic combination by means of dilute hydrochloric acid— 1 part of concentrated HC1 to 10 parts of water or approximately 3 per cent. acid. Digestion at 60" C. for 24 hr. insures the complete removal of the sulfur thus combined. In freshly mined coal the amount of such sulfur is very small; weathering processes, however, may very materially increase the amount of sulfate present. Sulfur in the form of iron pyrites, or marcasite, may be quantitatively removed without oxidation of the organic sulfur as follows: A dilute solution of nitric: acid is prepared having 1 part of concentrated HNO3 to 3 parts of water or with an approximate specific gravity of 1.12. The coal sample, ground to 100 mesh, is digested with this solution at room temperature for 3 or 4 days, filtered and evaporated to dryness, taken up with water, and acidified with hydrochloric acid. It is now ready for precipitation with barium chloride in the usual manner. If sulfate is present in the original sample to an appreciable amount, it should be removed by the procedure outlined above. It is not necessary here to give the methods for determining the two

Jan 1, 1920

By F. L. Bosqui

A. L. BlomFIeld, Denver, Col. (communication to the Secretary.*) — Mr. Caldecott says on p. 67: "The Dorr thickener shown, while a useful device when crushing with cyanide solution for removing surplus solution from slime pulp prior to air-lift agitation or vacuum filtration, is not adapted to effect as complete a separation of water from settled slime as the ordinary intermittent settlement and decantation." This statement might have passed muster in this country several years ago when. the Dorr thickener was a new device, but its use in hundreds of mills in the United States has demonstrated that as thick a product is being discharged from it as was obtained from the intermittent settling which it has supplanted. • It is interesting to note that recent investigation, especially the work of 11. 6. Coe and G. H. Cleveilger,' in the March Bulletin of the Institute, under the title: Laboratory Method for Determining the Capacities of Slime Settling Tanks, has developed the general theory of settlement and explains the results obtained in practice. Just as free settlement is a function of surface area, so thickening after the zone of free settlement is passed is a function of time. The time required is obtained by the capacity or volume provided in the settler for this thickening zone. Each pulp is a problem in itself, both in regard to free settlement and to time required to reach a commercially finished thickness. Some pulps require 48 hr. and more to reach a density of 40 per cent. solids; others no coarser to the screen test reach a density of 65 per cent.' solids in a fraction of that time. In thickening any pulp a point is reached where the increase in density is so slow as to be commercially unprofitable. When any part of the pulp has reached this point it should pass on for treatment—its place in the thickener should be occupied by pulp which has not yet reached the commercial limit. By doing this the whole volume of the settling tank is kept in active use. Thus the continuous thickener keeps the whole tank at work to its commercial limit, while the intermittent settler has much of its volume occupied at times by pulp which is either quite finished thickening or at least thickened past the commercial point. The mechanical efficiency of the continuous thickener can be the only argument for limiting this statement. In my own experience I have never

Jan 1, 1916

By D. Turnbull, J. H. Hollomon, J. C. Fisher

UNDERSTANDING of the diffusion problem has recently been furthered by the analysis of Birchenall and Mehl.1 They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,2 Jost,3 Dehlinger,4 and Darken,' who assumed the net flux of dif¬fusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's' activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Hargreaves.7 The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinski10 in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitutional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitutional alloys were analyzed on the basis of the concepts of the chemical rate theory. CHEMICAL RATE THEORY According to the theory of absolute reaction rates8 the reaction [A,+A2+ ... +.A;->X,+X2 +...+X; EqI] is viewed as taking place in two steps. First the reactants A1, A2, . . . A[i] combine to form an activated complex M with which they are in equilibrium; [A, + A2 + .. . + Ai = M. Eq 2] Second the activated complex decomposes to give the products X1, X2. . .. X[j]; [M->X1+X2+ ... +.X;. Eq3] It has been shown8 that the number of activated complexes decomposing per unit volume per unit time is given by the expression† [kT]

Jan 1, 1948

By Tasuku Fuwa, John Chipman

Equilibrium data on the reactions of gases with carbon and oxygen dissolved in liquid iron are reviewed and correlated. A source of error in oxygen analysis of graphitic samples is exposed. New experimental data on the oxygen content of high -carbon iron in equilibrium with carbon monoxide indicate that the activity coefficient of oxygen is decreased by additions of carbon. The carbon-oxygen product decreases slightly with increasing carbon content. In recent years a number of investigations have been reported dealing with the equilibria between carbon and oxygen in liquid iron and gases containing carbon oxides. The laboratory study of these reactions dates back to 1931 with the publication of a paper by Vacher and Hamilton' on "The Carbon-Oxygen Equilibrium in Liquid Iron". The principal object of this study was to obtain data on the reaction shown by Eq. [3] below; their data and others by vacherZ permit evaluation of the other equilibrium constants as well. Subsequent studies have been reported by Matoba, Phragmen and Kalling and by Marshall and Chipman.5 The equilibria may be expressed by the following three equations: C + CO,= 2CO;Kl = Pc° [1] 0-+CO = CO,;K2=-P co, "0.PCO c + O = CO; K3 = In the equilibrium constants, ac and a0 are taken as equal to [% C] and [% 0] respectively in the infinitely dilute solution. At finite concentrations an activity coefficient is introduced such that ac =fc [%C], and so forth. It is to be noted that these equations represent only two independent relations, the third being derivable from any two. Richardson and Dennis have determined the conditions of equilibrium in reaction [I] at temperatures of 1560" to 1760°C. Their results have been confirmed by Rist and chipman7 who have shown how the data may be extended to cover the entire range of liquid compositions at temperatures from the eutectic up to 1760°C. An approximate confirmation has been reported by Fuwa and chipman.' These investigations also established the activity coefficient of carbon which was shown to increase rather rapidly with increasing concentration. For the very dilute solutions the value of Kl is expressed in the equation: log^i = - 7280/T+ 6.65 This equation leads to a value of Kl = 430 at 1540° C in excellent agreement with the average value of Marshall and Chipman.5 It is shown as line 1 in Fig. 1 together with the experimental observations. In the case of reaction [2] the direct experimental results can be supplemented by observations on the corresponding reaction with hydrogen, namely reaction [4]:

Jan 1, 1961

By W. A. Koehler, M. E. Hinkle

INTRODUCTION THE oxidation of pyrites and marcasite in coal-mine strata to produce discolored acid mine drainage has long been explained by chemical reactions occurring in three stages: I. The iron sulphide minerals are oxidized by air in the presence of water to produce a nearly colorless solution of fer¬rous (iron) sulphate and some sulphuric acid. 2. The ferrous sulphate and part of the sulphuric acid combine with additional oxygen to form ferric (iron) sulphate. 3. The ferric sulphate hydrolyzes to form a reddish-brown precipitate and additional sulphuric acid. Nevertheless, chemical data alone are not sufficient to explain all observed facts. The first stage seems to proceed more slowly in the chemical laboratory than in nature. The second and third stages nor¬mally occur to a marked extent within a few days with raw mine water. However, the visible discoloration that characterizes these latter stages will not develop for months if the mine water is sterilized. By means of bacteriological techniques, two organisms have been isolated from acid coal-mine drainage. These are believed to have a part in promoting the chemical reactions summarized above. One organism is considered to be Thio¬bacillus thiooxidans, which is known to be able to convert elementary sulphur or sodium thiosulphate to sulphuric acid. Its relation to the formation of acid mine drainage has not yet been established. Apparently it does not promote the oxida¬tion of ferrous iron compounds in mine, drainage to the ferric state. The second organism has not been identi¬fied by name but is described as "Gram negative, non-spore-forming rods approxi¬mately 0.4 micron wide by o.8 to 1.0 micron long." A pure culture of this when added to sterile mine water will cause the latter to become amber and develop the typical rusty precipitate. However, it has not been found to convert sulphur com¬pounds to sulphuric acid. Further research is planned to determine whether or not these microorganisms play a significant part in the first stage of oxidation whereby pyrites and marcasite minerals go into solution. Some of the conditions found in abandoned sections of coal mines, such as a reduced percentage of oxygen and increased percentage of carbon dioxide in the air, as well as the existing temperature and acidity ranges, will be tolerated by and may even be favorable to these organisms. ACID COAL MINE DRAINAGE Acid coal mine drainage has been the concern of coal mine operators, industrial¬ists, sportsmen and public officials for many years. The amount of acid flowing into our streams in the coal-producing areas varies considerably from mine to mine and from

Jan 1, 1948

By Herbert M. Wilson

We of the employer class represent labor in the social organization and in industry just as truly as do those who labor only with their hands, and, because our labor is chiefly with our brains, the duty is all the more imposed upon us to use those gifts in which we excel in helping steer a clear course through the turbulent waters in which we are now enmeshed. Only their selfish engrossment in the daily tasks they were employed to perform could possibly have permitted the great majority of the intelligent and industrious German people to become terrorized by a handful of the idle, the vicious, and the criminal, whom the elections to the National Assembly showed to be in as pitiful a minority as they are in Russia, in this, and in other countries. It is the leisure unemployment of the I.W.W.'s, the Bolsheviki, and the Sparticans that has enabled them to devote their whole time to a concerted and aggressive struggle against the great majority of those of the world's workers who are unorganized, and who are therefore even in opposition one to the other. In union there is strength, and this was never better illustrated than by these conditions. The great fallacy of our previous attitude toward social and industrial problems has been the belief that labor, by which we commonly mean organized or physical labor, is something antagonistic to and having a different object in life from that great body of unorganized laborers who work with their brains. Our difficulty has been our lack of will or opportunity to think. The hurry of our daily struggle to earn our livelihood under the nerve-racking pressure of modern civilization has left us no opportunity for quiet thought and study. The physical laborer, and above all the laborer in the mines, on the other hand, has all his hours of toil in which to think over, in all their varied aspects, those problems that concern his immediate, personal well-being. As a result he has arrived at perhaps a more true appreciation of the facts of life in their relation to social and industrial conditions than we. Have we not too readily adopted the view that, as the managers of industry under the direction of capital, it has been our duty to think and act in opposition to labor, rather than to realize that we also are laborers, have like aspirations, and should participate in a free and aggressive solution of these problems rather than leave their solution

Jan 1, 1919

By J. R. Cahoon, W. V. Youdelis

FOR the diffusion of copper in silver-rich alloys, there have been only two previous investigations, that of Seith and Peretti in 1936, and that of Sawatzky and Jaumot2 in 1957. Seith and Peretti obtained a value of 24.8 keal per g-atom for the activation energy of diffusion whereas Sawatzky and Jaumot obtained a value of 46.1 keal per g-atom. Admittedly, Seith and Peretti used relatively high concentrations of 2 at. pet Cu and polycrystalline diffusion couples, while Sawatzky and Jaumot investigated tracer diffusion in single crystals of silver. The difference in the results, however, seems too large to attribute solely to solute concentration, as a change of over 20 keal per g-atom in the activation energy suggests a change in the mechanism of diffusion. Therefore, in the present investigation the diffusion coefficient for copper in polycrystalline Ag-2 at, pet Cu alloy is re-established using conventional sandwich-type diffusion couples and electron-probe microanalyses, and the results are compared with those of the previous studies. The diffusion couples were prepared from high-purity silver (99.999 pet) and high-purity copper (99.999 pet). The silver disks, 1/4 in. long and 4 in. in diam, were machined from an ingot which had been solidified in a dynamic vacuum of 10-3 mm of Hg to eliminate oxygen absorption which otherwise would result in copper oxide precipitation in the weld zone. The alloy disks of similar dimensions were machined from an alloy ingot (nominal composition 2 at. pet Cu) which had been unidirectionally solidified to obtain a predictable solute concentration,3 and homogenized for 1 week at 800°C. Sandwich diffusion couples were made by pressure welding an alloy disk between two silver disks in an induction heating coil. The couples were diffusion-annealed at temperatures of 800°, 756°, 699°, and 630°C in tube furnaces in which the temperature was controlled to better than ± l°C. The diffusion couples were examined metallographically for weld defects, and couples showing even minute defects at the weld interfaces were rejected. Concentration penetration curves were established using an A.R.L. Microprobe analyzer. CuKO radiation was counted and converted to concentration using 0.5 and 1.0 wt pet Cu chemically analyzed standards. Initially, four continuous profiles were obtained, and averaged to obtain the final diffusion curve. The initial analysis was performed commercially and the welds were not located with respect to the profile. Therefore, the results were rechecked by the authors using the Mellon Institute A.R.L. probe. In the latter case, concentrations were obtained at 10-µ steps for four different traverses, and then averaged to obtain

Jan 1, 1968

By Sherwin F. Kelly

SINCE we used Chief Buehler's name last year to give our annual report a semblance of respectability, we can follow the good precedent thus established by telling of the work his Missouri State organization has been carrying on, as reported by H. S. McQueen. Considerable value is set upon their magrletorneter working which has covered over 13,000 sq. mi.), for the indications it gives of the major structural features of the region. Numerous geological problems have been tackled Ly resistivity techniques, among which are the locating and outlining of filled sink deposits of sulphides, of iron ore, and of fire clay; tracing of faults and solution channels; mapping of the preglacial structural pattern; measurement of depth of overburden; and

Jan 1, 1937

By Klaus Schwerdtfeger, Leo Zwell

The equilibrium between Ir-Fe or Rh-Fe alloys, iron oxide (wüstite or magnetite), and CO2-CO atmospheres has been determined at 1200°C. The data are used to derive the activities in these binary solid solutions. Both systems show negative deviations from Raoult's law. The lattice parameters are given for the investigated Ir-Fe and Rh-Fe alloys. IRIDIUM and iron form a continuous series of fcc solid solutions at elevated temperatures.' Rhodium-rich Rh- Fe alloys have fcc structure.' In the medium concentration range an ordered bcc phase is stable at temperatures up to about 1300°C. Phase relations in iron-rich alloys are not well-known. No thermody-namic data are available for these alloys. EXPERIMENTAL METHOD The experimental method used was to measure the equilibria between a gas phase of known CO2/C0 ratio, the alloy, and iron oxide (wüstite or magnetite). In one series of experiments the alloys of known composition were heated in CO 2-CO gas mixtures. After treatment (usually 1 day) the sample was quenched to room temperature and its surface examined visually to determine whether an oxide tarnish had formed. The procedure was repeated at slightly higher CO 2/CO ratios until the CO 2/CO ratio of incipient oxidation was found. Subsequently, the CO 2/C0 ratio was lowered again in small increments until the tarnish was reduced. In other experiments mixtures of alloy and iron oxide powders were pressed into pellets and equilibrated with the CO2-CO gas phase. In order to ensure that equilibrium was attained, two specimens with different starting iron content were heated side by side; in most cases, equilibrium was approached in one pellet by reduction of iron oxide and in the other pellet by oxidation of metallic iron. The sample was quenched to room temperature, and the composition of the equilibrated alloy was determined by X-ray measurements of lattice parameters and comparison of these values with calibration curves obtained from alloys of known composition. The oxides present in the specimens were identified by comparison of their diffraction patterns with those in the ASTM Card File. It may be expected from the noble character of iridium and rhodium that no appreciable amount of iridium or rhodium is dissolved in wiistite and magnetite under the present experimental conditions. The activity of iron in the alloy is then equal to that established in the iron oxide by the COrCO atmosphere. The activities of iron in wüstite and magnetite, as a function of oxygen pressure, were taken from the work of Darken and Gurry,

Jan 1, 1969

By G. B. Craig, G. L. Montgomery

A simple technique has been developed which reveals glide dislocations in zone-refined aluminum as etch pits. The technique has been tested quantitatively by making dislocation counts on aluminum single crystals deformed in pure bending. The method has the advantage of being insensitive to the orientation of the surface under examination. A number of etchants which will reveal dislocations in annealed aluminum have been reported.'-' These etchants apparently depend on decoration of the dislocations by an impurity (probably iron) and cannot, therefore, be used to reveal fresh glide dislocations. In addition, it is unlikely that screw dislocations will be etched because of their small attraction for impurity atoms. Amelinckx6 has reported that glide dislocations located along slip traces can be revealed by fluo-rated aqua regia. This work indicated that dislocations themselves, irrespective of decoration by impurity atoms, are responsible for the etch pits. However, as a result of additional etching experiments, Wyon and Marchin7 concluded that dislocations alone are not sufficient to explain the localization of etch pits on slip lines in aluminum using chemical etch-pitting techniques. In addition, their results show that glide dislocations are revealed only on surfaces approximately parallel to a (100) axis and that not all slip systems are attacked. These observations have been confirmed by the present authors. The technique described in this article is insensitive to the orientation of the surface, and reveals dislocations on all glide systems. Fig. 1 shows a deformed region in the neighborhood of a scratch. Dislocations can be seen along three slip traces. In the present work, single crystals of zone-refined aluminum are polished for from 2 to 5 min in a chemical polishing reagent held at 100°C, as described by Herenguel and second:' H2Sol 60 pct H3PO4 30 pct HNO3 10 pet The samples are then coated with a thin oxide film by annealing in air at 450°C for 1 hr and cooling in the furnace. After deformation, dislocation etch pits are developed by immersing the specimen in the same polishing solution which is now held at a temperature of 50°C. The formation of small hydrogen bubbles indicates that etching has occurred. The sample is immediately removed from the solution. Prolonged etching results in enlargement of the pits and, in regions of high dislocation density, the overlapping and loss of resolution of individual pits. It is the experience of the authors that contact with iron will ruinously contaminate the reagent. With careful etching, dislocations separated by half a micron can be resolved optically and the method has been shown to be sufficiently sensitive to reveal dislocations produced during the pre-easy glide region of deformation, Fig. 2. A few examples of glide-dislocation configurations, as revealed by this technique, are shown in Figs. 1 to 4.

Jan 1, 1964

By Arthur F. Taggart, Nathaniel Arbiter

The fact that the floatability of minerals with fatty-acid collectors changes as the pH of a pulp varies was utilized in the early days of flotation, when sulphuric acid was used with oleic acid to float sphalerite and galena. from gangues which themselves float with fatty acids in alkaline pulps. Gaudin1 showed that this difference in floatability is a regular function of the extent of the change in pH. The present paper offers an explanation of the phenomenon, and on the basis thereof sets up recommendations for control of soap-flotation operations. Experimental Parallelism between floatability of a mineral in a given environment and its contact angle in that environment is so well established,2 and the contact angle is so readily and rapidly measurable, that contact angles have been used throughout the experimental work to indicate relative floatability. Experiments comprised contact-angle measurements on a number of representative minerals and metals, and a variety of subsidiary tests designed to check and to amplify the contact-angle indications. Contact-angle measurements were made by the method described in detail by del Giudice.3 Sequence of procedure for determination of the points of Fig. I was: I. Polish specimen. Most specimens yielded zero contact angle after polishing; a few showed a slight "cling." Cling is characteristic of specimens that pit on polishing; it is due to a residue of organic contamination, originally on the particle surface, which persists in the pits. The cling did not change total contact angle after conditioning, and is not, therefore, additive in the upper part of the curves of Fig. I. It may have broadened the bases of the curves for the affected minerals slightly. 2. The specimen was next conditioned in soap solution for 5 minutes. 3. The conditioned particle was transferred, under conditions that precluded surface drying, to an aqueous solution of the pH desired and contact angle determined. 4. The particle was thereupon transferred, again without surface drying, to water. The confirmatory tests will be described at the places pertinent in the argument. Discussion of Results Gaudin and Vincent4 have shown that contact angles with heptoic acid as a collector decrease for a given specimen when the concentration of collector present falls below a certain value. A similar reduction in angle occurs with collector-conditioned particles that are visibly slime-coated, and varies roughly with the extent of coating. Since in the last case the reduction in angle is certainly due to reduction in the proportion of total conditioned mineral surface presented to the bubble, the authors believe that the same condition prevails in the first case cited, and that similar reduction in angle and floatability will occur whenever starvation quantities of collector are present, whether by design or by reason of excessive consumption.

Jan 1, 1943

By Nathaniel Arbiter, Arthur F. Taggart

The fact that the floatability of minerals with fatty-acid collectors changes as the pH of a pulp varies was utilized in the early days of flotation, when sulphuric acid was used with oleic acid to float sphalerite and galena. from gangues which themselves float with fatty acids in alkaline pulps. Gaudin1 showed that this difference in floatability is a regular function of the extent of the change in pH. The present paper offers an explanation of the phenomenon, and on the basis thereof sets up recommendations for control of soap-flotation operations. Experimental Parallelism between floatability of a mineral in a given environment and its contact angle in that environment is so well established,2 and the contact angle is so readily and rapidly measurable, that contact angles have been used throughout the experimental work to indicate relative floatability. Experiments comprised contact-angle measurements on a number of representative minerals and metals, and a variety of subsidiary tests designed to check and to amplify the contact-angle indications. Contact-angle measurements were made by the method described in detail by del Giudice.3 Sequence of procedure for determination of the points of Fig. I was: I. Polish specimen. Most specimens yielded zero contact angle after polishing; a few showed a slight "cling." Cling is characteristic of specimens that pit on polishing; it is due to a residue of organic contamination, originally on the particle surface, which persists in the pits. The cling did not change total contact angle after conditioning, and is not, therefore, additive in the upper part of the curves of Fig. I. It may have broadened the bases of the curves for the affected minerals slightly. 2. The specimen was next conditioned in soap solution for 5 minutes. 3. The conditioned particle was transferred, under conditions that precluded surface drying, to an aqueous solution of the pH desired and contact angle determined. 4. The particle was thereupon transferred, again without surface drying, to water. The confirmatory tests will be described at the places pertinent in the argument. Discussion of Results Gaudin and Vincent4 have shown that contact angles with heptoic acid as a collector decrease for a given specimen when the concentration of collector present falls below a certain value. A similar reduction in angle occurs with collector-conditioned particles that are visibly slime-coated, and varies roughly with the extent of coating. Since in the last case the reduction in angle is certainly due to reduction in the proportion of total conditioned mineral surface presented to the bubble, the authors believe that the same condition prevails in the first case cited, and that similar reduction in angle and floatability will occur whenever starvation quantities of collector are present, whether by design or by reason of excessive consumption.

Jan 1, 1943

Electrowinning U.S. 4,066,520 - Recovery of copper from copper sulfide ore. Finely divided ore concentrate is leached with moderately strong sulfurous acid to solubilize copper ions, the leach solution treated with calcium sulfite to reduce the copper ion concentration by forming copper-precipitate solids therein, the solids filtered off, and and the filter cake dewatered to obtain a slurry of copper-precipitate solids amenable to direct electrowinning of copper therefrom using a described electrolysis apparatus which utilizes high current flow with a minimum of mechanical agitation. R. C. Emmett, Jr., J. K. Dicksa. B. C. Wojcik and F. A. Baczek, assigned to Envirotech Corp. Jan. 3, 1978. 14 pp. (204- 108). Filed: 9- 1-76 (7 19,867).

Jan 1, 1979

By H. Shafick Hanna, Carl Rampacek

Wastes generated by the mining, mineral processing and metallurgical industries now total about 1.8 billion tons annually. The wastes include gases, dusts, solutions and a variety of massive solid mineral materials such as tailings and slags all of which now must be disposed of with a minimum of environmental degradation and at an acceptable cost. Some of the metal and mineralconstituents have potential economic value and their recovery can augment our primary mineral and metal resource supply base. The resource potential of wastes generated by the iron and steel, aluminum, clay, phosphate, copper, coal mining and processing, nonmetallic, and selected secondary metals industries is identified. Information on current efforts being made to recover these resources and the technology now employed or under consideration are presented.

Jan 1, 1980

By Ronald C. Koo

SMALL additions of potassium, aluminum, and silicon as oxides (referred to as dope) to tungsten have been known for several decades to have a very large effect in raising the recrystallization temperature and altering the recrystallized grain morphology of heavily drawn wire. Previous investigations of this doping effect1 6 have led to various speculations but all failed to deduce unequivocally the physical state or the mechanistic influence of the dopant. Recently, walter7 has observed, by transmission electron microscopy, strings of "fine particles" in heavily rolled and annealed doped tungsten sheet and concluded that they were particles of mullite (Al6Si2013). His conclusion was inferred from the electron diffraction patterns of large particles ex-trated by carbon replication of fractured surfaces of slabs rolled from sintered ingots. That the strings of "fine particles" in heavily rolled and annealed sheet were also mullite was an assumption for which no evidence was presented. A similar investigation has been carried out in this laboratory over the past 2 years on a variety of tungsten wire: doped tungsten, and undoped tungsten, as well as 218 doped tungsten purchased from the Lamp Metals and Components Department of the G.E. Lamp Division. Although the electron microscope observations are similar to those reported by Walter, the writer has reached a different conclusion concerning the physical state of the dopant in annealed tungsten. The purpose of this communication is to present evidence that the strings of "fine particles" observed in transmission specimens are not mullite, but are voids. In the present investigation, tungsten wire, 0.88 mm in diam, was rolled into ribbon 0.2 mm by 125 µ thick. The ribbons were annealed in vacuo at a pressure of -1 x 10-5 Torr and then thinned electrolytically in a 2 pct KOH solution. Fig. 1 shows a typical transmissicjn electron micrograph of a sample annealed at 1700°C for 30 min which reveals rows of closely spaced voids having a light contrast (referred to as "fine particles" by Walter) aligned parallel to the working direction. Stereo micrographs (by D. Moon, Westinghouse Research and Development Center) have shown that these voids do not exist on the surfaces of the specimens as a result of thinning but are within the thin-foil specimens. The following experiments have been performed to verify that these are indeed voids. I) Effect of Annealing. Voids are absent in unannealed specimens and appear only after annealing. This behavior cannot be explained if they were solid particles such as mullite. Precipitation (in an unquenched specimen) upon annealing requires solute elements having decreasing solubilities with increasing temperature. Although the solubility of aluminum in tungsten does decrease with increasing temperature, precipitation requires a concentration in excess of 1.4 wt pct,8 which is at least two orders of magnitude higher than the aluminum content in doped tungsten. It is also unreasonable to assume that particles aligned in rows initially present in unannealed specimens were too

Jan 1, 1968

By C. W. Haworth, M. G. Hall

THE diffusion of copper in silver has been studied by Sawatzky and Jaumot1 and Cahoon and Youdelis.2 Sawatzky and Jaumot measured tracer diffusion in single crystal specimens but the 12.9 h half-life of CU64 limited the time of the diffusion anneal to about 50 hr, and in consequence the minimum temperature of the investigation was 716°C. Cahoon and Youdelis employed polycrystalline diffusion couples, and measured the interdiffusion coefficient over the range 0 to 2 at. pct Cu. These experiments were performed at temperatures down to 630°C and a discontinuity in the Arrhenius plot was observed at -700°C. The high D-values at lower temperatures were attributed to the effect of grain boundary diffusion. The present experiments were undertaken to investigate this anomaly and study the low temperature region of the diffusion of copper in silver. The method employed single crystal samples and a plated source of copper. Silver single crystals 2½ by 4 in. sq were grown from zone-refined silver bar (>99.99 pct Ag) by the Bridgeman technique, and $ in. thick slices were cut by spark machining. The specimens were electro-polished, and a 2 µm layer of copper was electroplated on to the planar surface at one end of each specimen using a potentiostatic voltage source. The following solution was used for plating: CuSO4 . 5H2O 125 gm H2SO4 (S.G. 1.8) 53 ml H2O 1000 ml The diffusion couples were sealed in capsules, in an argon atmosphere, and were annealed at either 701, 597, or 498°C. The temperature measurements were made to an accuracy of *l°C After the anneal, the penetration of copper into the silver was determined using an electron probe micro-analyzer. 100 sec scaler measurements of the intensity of Cu Ka! X-radiation were performed at 2 to 5 µm intervals along a line normal to the source, with a beam potential of 25 kv. Allowances were made for the background radiation, and the dead-time of the counting system in the normal way, and the intensity ratios were corrected to weight concentration by the method of Duncumb & de-Casa.3 For the analysis of the diffusion profiles, it was first observed that the copper layer did not completely dissolve in the host crystal for the specimens annealed at 498 and 591 whereas for the specimen annealed at 701°C, a single phase solid solution was formed. For the 498" and 597°C specimens, the concentration of copper in the silver at the interface was therefore constant throughout the anneal and the analysis for a

Jan 1, 1970

By Y. L. Yao

It is suggested that the binary alloy systems of transition metals may be classified into groups according to "excess energy"E. For systems with positive ?E, the Laves phase, the TiNi3-, the TiCu3- and the Cudu-type rich in the smaller atom and the TizNi-type rich in the larger atom may exist. For systems with negative ?E and composed of two components of different crystal structures, the X, the Cr3O and the phase may exist on the side of the phase digrattz rich in the component with the higher "solubility factor" value am! the Cudu-type and the disordered hcp phase on the other side; if the crystal structure of two components is the same, the Cudu-type may exist on both sides. For systems with weakly positive ?E and cotnposed of different crystal structures, the u phase and the MgCd3-type may replace the Laves phase and the other types; the X, the Cr3O and the a phase may also exist. Finally, the equirnolar compounds of the CuAu- and the CsC1-type may exist irrespective of the sign of ?E. THERE are many factors which play a major role in the formation of binary intermediate phases in alloys, such as the crystal structure, the electronic structure, the atomic size and the electrochemical factor. To find the simultaneous effects of all these factors on the formation of intermediate phases of every metal would be a difficult task, especially because only a small fraction of experimental facts necessary for the complete formulation is known at present. Thus the past surveys of intermediate phases have been usually confined to few metals, several types of intermediate phases and some but not all controlling factors. In a previous paper1 the idea of "solubility factor" of metals was introduced. Although the suggested values are tentative and empirical, the formation of a continuous series of solid solutions in metals could be correlated with the interplay among the atomic size factor, the solubility factor and the crystal structure factor. The purpose of this paper is to demonstrate qualitatively the interplay of these factors in the formation of binary intermediate phases among transition metals. FACTORS CONSIDERED The Crystal Structure Factor. With rare earths excluded, the transition metals are classified into three common crystal structures listed in Table I. There is arbitrariness in the present classification of several allotropic elements. However, out of seventy-odd continuous solid solutions formed among transition metals, only six of them, namely, those

Jan 1, 1962

By Marie L. V. Gayler

Without diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange—e.g., of diffusion—is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult—if possible— to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, BFeSi is formed in the solid as the result of the reaction aFeSi + A1 —+ PFeSi. The particles of aFeSi become surrounded with a reaction ring of PFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of aFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By Marie L. V. Gayler

Without diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange—e.g., of diffusion—is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult—if possible— to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, BFeSi is formed in the solid as the result of the reaction aFeSi + A1 —+ PFeSi. The particles of aFeSi become surrounded with a reaction ring of PFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of aFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By D. O. Hobson, J. O. Stiegler, C. J. McHargue

The effects of alloy composition, deformation temperature, heal treatment, ad inlerstilial contamination on the occurrence of deformation twins were studied. The twinning transition temperature varied with composition and was a maximuni of 140°C for the 40 pcl V composition. Tire remperature range of the transition was very narrow. Alloys of 20 to 70 pet V could he cold-rolled and exhibited profuse twinning. The alloys which did not twin at room temperature (10, 80, and 90 pel V) could plot be cold-rolled. Oxygen additions systematically lowered the transition temperatures for all vanadium contents. The transition temperature for a 30 pet V alloy increased with annealing temperature, apparently due to changes in dislocation density and configuration. Twinning did not nucleate fracture in any specimen in the 20 to 60 pet V composition range. THERE is great current interest in the refractory metals and alloys as structural materials. An important factor in considering the ductile-brittle behavior of such materials is the role of mechanical twinning as a deformation mechanism. Mechanical twins have been observed after deformation at low temperatures or at high loading rates in the pure metals iron,1 vanadium,2,3 columbium,4,5 tantalum,6 Chromium,7 molybdenum,8 and tungsten.9 Binary alloys in which mechanical twins have been observed include: iron with silicon,10 phosphorous," or aluminum;12 and chromium, molybdenum, or tungsten with rhenium.13-17 The increase in low-temperature ductility obtained by alloying the Group VI-A elements with rhenium is very important with regard to fabricability, and there has been considerable effort to understand the so-called '(rhenium effect". Factors suggested to explain this effect include:'' 1) increase in solubility of interstitial impurities with alloying (electronic effect): 2) changes in the nature of grain boundary phases; 3) changes in interfacial energies of grain boundaries and stacking faults: and 4) promotion of twinning. Although an outstanding characteristic of these alloys is the profuse twinning that accompanies low-temperature deformation, most studies of the rhenium effect have been concerned with the other factors. During recent studies of refractory-metal alloys, it was noted that solid solutions of columbium and vanadium exhibited high hardness and strength at room temperature and elevated temperature and, surprisingly, also showed considerable ductility at room temperature and below. These alloys deformed by twinning at room temperature when subjected to slow loading rates. It appeared that the low-temperature ductility resulted at least in part from the relaxation of stresses by twinning in a system where slip is difficult. The reason for enhanced twinning behavior in some bee solid-solution alloys is unknown. There have been suggestions18,19 that, as in fee alloys, the

Jan 1, 1965