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By Carl G. Hogberg

DURING recent months, the acute shortage of steel scrap has necessitated the use of higher percentages of hot metal in the open-hearth charge. With these higher percentages, the sulphur content of hot metal has become an increasingly important factor in the control of the quality of steel. Thus, the blast-furnace operator is faced with a demand not only for more output but for a higher quality of product. More than go per cent of the sulphur charged into the blast furnace is contained in the coke. With the tremendously increased demand, the trend of coke quality has been toward higher sulphur, higher and more variable ash, and poorer physical characteristics. This has been brought about by less selective coal mining, increased production rates in coke plants and resumption of operations of many beehive ovens. In a single month last year, one blast-furnace plant in the Pittsburgh district operated with coke obtained from 52 sources. The effect of variability and quantity of coke ash on blast-furnace operation is well known. The improved results obtained with furnaces operating on coke made from washed coals compared with results on coke made from raw coals is ample proof of the effectiveness of low and uniform ash. Coal-washing plants, however, require a large capital expenditure, and are impractical for most of the large number of small producers, whose operations are confined chiefly to periods of abnormally high demand. Furthermore, not all coals are physically adaptable to washing. PRINCIPLES OF IRON DESULPHURIZATION IN FURNACE Although investigations of the blast-furnace process have not clearly revealed the detailed mechanism of iron desulphurization within the furnace, they have been sufficiently extensive to permit a postulation of the following general principles: I. Iron, in its travel from furnace top to hearth, continues to pick up sulphur until it has reached tuyere level. The zone of iron desulphurization is relatively narrow, being confined to a vertical distance extending approximately from tuyere level to the iron-slag interface in the hearth.1 2. Combustion of coke is confined to spherical zones extending approximately 40 in. from the nose of each tuyere.2 Coke ash is released as the coke burns in these combustion areas. 3. With a constant amount of sulphur in the charge, the sulphur content of the metal product is a function of hearth temperature, final slag analysis, slag viscosity, and slag volume. Both hearth temperature and slag analysis affect slag viscosity. For a slag of constant analysis, viscosity always decreases with an increase in temperature;

Jan 1, 1943

By Thomas O. Ziebold, Robert E. Ogilvie

Experimental analysis of diffusion samples covering the entire Cu-Ag-Au system at 725°C has been carried out. Experimental coefficients are computed at twenty-eight points in the lermary system. It is found that the direct coefficienl for copper is nearly independent of the silver, content for 1ow-silver alloys and that the cross coefficient for silver correlates with the ther-nzodynatnic properlies. This lalter observalion leads to the conclusion that the mobililies of copper and gold are nearly equal. Thermodynarmic actiuilies for Cu-Ag-Au were computed from binary data and adjusted to be consistent with neasured tie lines across the two-phase region which extends into the ternary diagram at 725°C. Application of these therknodynarnic calculaliorls to the dijftcsion data terifies the Onsager reciprocal relations to the extent that experimental uncertainlies will allow. It is jound that diffusion neav the critical point of the 1200-phase field in the isothermal section at 725°C causes the composition gradients for copper and silver to approach infinity while the direct and cross coeficients become equal. From the standpoint of experimental Procedures, it has been shown that microanalysis of ternary samples may be carried out using a simple expression for the conversion of X-ray zntensily to composilion. The accuracy of' this method has been demonstrated by the analysis of standard alloys and by the reproducibility of composition determinations using differed X-ray lines. DIFFUSION in a ternary alloy system is basically and significantly different from diffusion in binary alloys. When only two elements are present there is just one independent composition variable, and the diffusion profile of composition vs distance across a sample must change monotonically through all solid solutions bracketed by the terminal alloys. If two-phase regions are stable for compositions between the terminal values, these must appear as planar interfaces in the diffused sample, with the composition profile exhibiting sharp discontinuities. Adding a third element may alter this picture completely. Because of the additional degree of freedom in the composition, we may see composition profiles which do not change monotonically through solid-solution ranges, and stable, nonplanar phase interfaces. Even though two-phase regions may lie between the terminal compositions of a diffusion sample on the constitution diagram, they will not necessarily appear in the diffusion profiles. In binary diffusion only one coefficient is needed to describe the interdiffusion process. From Fick's law this coefficient relates the diffusive flux of one component to its own composition gradient. In ternary diffusion we must allow for cross interaction between the two independent species. By a linear extension of Fick's law we introduce "cross" or "off-diagonal" diffusion coefficients which relate the flux of one component to the composition gradient of the other independent constituent. Thus, we require four interdiffusion coefficients to describe the transport process in a ternary system. In its most general form,1,2 the rate equation for mass transport by isothermal diffusion in a system of s components states that the diffusive flux of component i, Ji, is a linear summation of all driving forces, Xk, each force being multiplied by an appropriate compliance coefficient:

Jan 1, 1968

By A. P. Svenningsen

DURING the work at the test mill in Morenci, it was determined that a suitable feed for the ball mills could be made by a single pass through a short-head cone crusher. These crushers did not require a closed circuit delivering only a screen product to the mills, such as is the practice in some concentrators. By no means does this mean that the practice in these other concentrators is wrong, but just that the Morenci ore can be most economically crushed and ground in this manner. Therefore, the design of the secondary crushing plant was simply a problem of taking 25,000 tons of ore per 16 hour day from the primary crusher, this ore ranging in size from fine particles to 10 or 12 in., and reducing it to minus 3/4 in. Inasmuch as outages must be contended with in any crushing plant, it was assumed that the crusher would operate at full capacity for approximately only twleve hours per day, which is three-quarter capacity for the 16-hour shift. With this in mind, it was necessary to design a crushing plant which would average approximately 1600 tones per hour for the 16-hour day, or 2000 tons per hour for slightly over 12 hours per day.

Jan 1, 1942

By Lawrence Addicks

(San Francisco Meeting, September, 1915) THROUGH the courtesy of Dr. James Douglas I am permitted to give, a summary of some of the results obtained in leaching slimes tailings in a series of experiments conducted under my direction at Douglas, Ariz.. during the past year. While the test run for which the data are given deals with a particular case, much of the work is general in its application and may therefore be of interest. This work was done upon the ores of the Burro Mountain Copper Co. A description of the geology of the district will be-found in the paper by R. E. Somers published in the May, 1915, Bulletin of the Institute. The mineral is pyrite and chalcocite very finely disseminated throughout the gangue and a characteristic of all the ores is the large amount of alumina present. A representative analysis of the particular ore under consideration would be about as follows: Cu, per cent 2.35 S, percent 3.0 Ag, ounces per ton 0.05 CaO, per cent 0.5 Au None K202, per cent 4.0 Fe, per cent 1.5 SiO2, per cent 70.0 A120,, per cent 13.0 The leaching of the ore direct was early dismissed from consideration for the following reasons: 1. The ore would have to be quite finely crushed to liberate the mineral for leaching; concentrating after crushing would cost but a few cents a ton; and a higher total recovery would result from leaching tailings rather than ore. 2. Rough concentration would yield a suitable material for roasting to make sulphur dioxide or sulphuric acid in connection with the leaching scheme. 3. Such a program put the question of cost vs. recovery on a basis where flotation and discarding of tailings were directly comparable.

Jan 8, 1915

By AIME AIME

THE joint symposium on gases in metals on Tuesday: Feb. 16, between the Iron and Steel and the Institute of Metals divisions opened the technical sessions for both of these bodies. After a few words of introduction by P. D. Merica, R. S. Dean presented a paper by V. H: Gottshalk and himself on the solubility of gases in metals.

Jan 1, 1932

By W. H. Bassett

THE modern smelting and refining of copper is distinctly an American development. The present demand for sound and perfect castings for rolling is due to the development of American industry. Prac-tically every article made from sheet metal or, for that matter, from any form of metal is made by mass produc-tion methods. Faulty material disturbs the orderly sequence of operations and in addition requires expen-sive inspection and unbearable rejection of finished product. This demand, therefore, is positive and will have to be met. Some mines produce ore that can be smelted and re-fined without the electrolytic process into satisfactory copper for the wrought metal industry, and some of these ores carry small amounts of impurities that are of use in hardening and toughening the copper. Most of the copper ore mined contains impurities that must be removed and, fortunately, precious metals which are separated at the same time make this re-moval profitable. The modern electrolytic refineries have their methods so well under control that the product meets all re-quirements without question if properly fire refined and cast. The "if" in this case is important, because there is evidence of carelessness or want of control at times in the material from some of the producers. It is nec-essary that the melted cathodes should be saturated with oxide to dispose of sulfur and that the copper should then be poled to the proper pitch or set. Sometimes statements leak out to the effect that it is unnecessary to oxidize completely the molten cathodes and a little less rabbling saves poles, which are expensive. The re-sult is that the rolling mill gets porous castings and produces seamy or slivered sheets or strips. The condition of the molds, their temperature, and the temperature of the metal are all important to good copper cakes, wedges, or wire bars. Cracked, and burned molds leave rough places and porous spots. Molds which are out of shape, or cracked, make shrink-age cracks which gap open when the castings are hot-rolled. Dampness means porosity. Drops of oil mean porous or honey-combed areas. Poor or irregular dress-ing means mold wash in the castings. Cold copper or slow pouring means cold sets.

Jan 4, 1928

By Ramesh Malhotra, Hubert E. (Deceased) Risser

THE WORLD Coal, as a source of energy and as a source of coke for the smelting of iron ore, has contributed significantly to the development of every major industrial nation of the world A number of other materials-oil, natural gas, wood, waste materials, water, and, in some applications, nuclear materials -can be used satisfactorily for the generation of heat and energy, but no generally acceptable and economic substitute has been found to supplant coke in iron ore smelting in conventional blast furnaces. In the development of many nations, coal provided the initial source of energy for industrialization Although coal provided more than 60% of the world's energy each year between 1902 and 1929, oil and natural gas have surpassed it as a source of energy in more recent years (Ref. 38, pp. 439, 441). Despite the rapid rise in importance of other fuels, a considerable amount of the total energy consumed is still supplied by coal. In 1972, coal supplied 32.1 % of the total world energy (Ref. 49, pp. 2-3). To produce this energy, 2.4 billion metric tons of coal were consumed-a 16.0% increase over the amount consumed in 1962. A further worldwide increase in the amount of coal used to supply energy is projected. According to Dr. Karlheinz Bund (Ref. 37, p 145), by the year 2000 world coal consumption could amount to 5 billion mt. Coal Resources and Production The world's coal resources are estimated to be about 10,872 billion mt. Of this amount, 1,297 billion mt are classified as measured reserves (Ref. 50, p. 57). In Table 13.A.1 the estimates of measured reserves and total resources, recent production, and the ratio of measured reserves to production of major coal-producing countries are shown. About 90% of the world's total coal resources are estimated to be in the USSR, the United States, and China. The United States ranks second in the world in coal resources, but in measured reserves, it ranks first. Because of the difference in rate at which available coal resources are being exploited, the ratio of measured reserves to actual production varies widely among areas and countries. France and East Germany have the lowest reserve to production ratios, 49.5 and 60.1, respectively. In Mexico, where currently less than 5 million mtpy of coal are produced, the ratio is 1257 For all countries producing more than 200 million mtpy of coal (except East Germany), the ratio ranges from 350 to 670. For the United States, the ratio is 669.7. In Table 13.A.2, distribution of the world's coal resources by area is shown. More than 97% of the total resources lie in the northern hemisphere, with Asia, including European USSR, having 63.4%. Only 1.9% of the total coal resources are estimat-

Jan 1, 1976

By I. E. Campbell, R. I. Jaffe

Oxygen, nitrogen, and hydrogen are known to be absorbed by titanium at elevated temperatures. Ehrlichl reports that about 30 at. pct oxygen can be dissolved in solid solution by alpha-titanium. Nitrogen also has a solid solubility in alpha-titanium, but there is no information as to its extent. The solid solubility of hydrogen in titanium also is high. Kirshfeld and Sieverts2 report 50 at. pct soluble, while Hägg3 reports about 33 at. pct hydrogen to be soluble in alpha-titanium. General statements are made in the literature that oxygen, nitrogen, and hydrogen embrittle titanium, but no quantitative measurements have been made of the effect of these gases on the mechanical properties of the metal. One reason for this is the lack of a source of titanium pure enough to be considered a suitable starting material. Iodide-refined titanium, made by thermal decomposition of titanium iodide vapor on an incandescent wire,4 contains small amounts of carbon, silicon, iron, and aluminum, but is very low in oxygen, nitrogen, and hydrogen content, and, therefore, was used in this work. A further reason for the lack of quantitative information on the effect of these gases, particularly oxygen, is the difficulty of carrying out accurate analytical determinations at the low concentrations of interest in this work. For this reason, the oxygen, nitrogen, and hydrogen were added in measured amounts as gases, and diffused into the titanium, to avoid the necessity of chemical analysis. The purpose of the work reported here was to isolate and measure the effects of oxygen, nitrogen, and hydrogen on titanium of the highest purity available at the time. The concentrations studied were 0.25, 0.5, and 1 at. pct in each case. Experimental Work One-half of a 24-in. hairpin of iodide-refined titanium was available for this work. The rod was approximately 0.25-in. in diam and had a 0.003-in.tung sten core. From chemical and spectro-graphic analyses, the purity of the sample was estimated to be between 99.80 and 99.95 wt pct. The chief impurities (aside from the tungsten core) were iron (0.04 pct), silicon (0.01-0.1 pct), aluminum (0.05 pct), carbon (0.03 pct). The tungsten core constituted 0.05 pct by weight of the sample. Although some alloying undoubtedly took place between the tungsten and the titanium during the deposition reaction, the core remained substantially intact in the deposited metal. The initial average hardness of the titanium as deposited was 105 Vickers (10-kg load). The maximum hardness was 116 Vickers and the minimum 91 Vickers. The metal was somewhat harder than that currently being obtained by the iodide process, that is, 75-90 Vickers. The rod was cold swaged to ¼-in. diam and then cold rolled in diamond shaped rolls to about 0.080-in. square, using reductions of 15 pct in area per pass. The 0.080-in.-square wire was cut into 6-in. lengths for the preparation of the alloys by the gaseous absorption and diffusion method. ADDITION OF OXYGEN, NITROGEN, AND HYDROGEN TO TITANIUM A modified Sieverts' absorption apparatus, shown in Fig 1, was used in

Jan 1, 1950

By J. S. Osoba, J. W. Graham, P. H. Monaghan

Of the many factors which affect the productivity of hydraudically fractured wells, the wettability of the propping sand has received little attention in the pas/. This paper shows that the wettability of the propping sand is an important factor which shorcltl not he overlooked. An analysis of relative permeability data shows that fractures packed with water-wet sand should be more permeable to oil than are fracturer packed with oil-wet sand. Laboratory results verify this conclusion. Cnlculations show that higher permeability to oil in the fracture should provide higher well productivity. A method is presented which ensures that the propping sand in an induced fracture is water-we1 even though oil is used as the fracturing fluid. The rnethod has been used in more than 150 field jobs: the field resrrlts are discussed briefly. The fluidized nature of water-wet sand in oil has giver1 unexpected benefits. This characteristic of water-wet sand and how it has been used advantageously in field operations are discussed. INTRODUCTION Hydraulic fracturing of subsurface strata to increase the productivity of oil and gas wells has been practiced for about 10 years. Today, fracturing is used more often than any other method of well stimulation. Basically, the process consists of breaking down (fracturing) a subsurface formation with pressure applied by means of a carrier fluid, usually oil or water, and propping the induced fractures apart by means of an agent, usually sand. suspended in the carrier fluid. Currently about 68 per cent of all fracturing is done with a simple mixture of refined oil or lease crude oil and sand'. The research of other investigators has suggested that dry sand is rendered oil-wet when it is contracted with certain types of crude or refined oils.' Hence, it may be expected that some fracturing operations employing an oil as the carrier for sand leave fractures packed with oil-wet sand. Conversely, those operations which employ water as the carrier for the sand probably leave the fractures packed with water-wet sand. Since the permeability of a sand-packed fracture to a mixture of oil and water is dependent upon the wettability of the fracturing (frac) sand, research was undertaken to determine to what extent the wettability condition (water-wet or oil-wet) controls fracture permeability which, in turn, affects well productivity. Additional research was directed toward the development of a method for obtaining the desired fracture wettability. In this report both theoretical and experimental evidence is presented to show the desirability of employing water-wet sand in fracturing operations. A method to obtain water-wet sand is discussed, and field results are reviewed briefly. DEPENDENCE OF WELL PRODUCTIVITY ON FRACTURE WETTABILITY To determine the dependence of well productivity on the wettability of the frac sand, it is necessary to know, first, the effect of fracture wettability on fracture permeability and, second, the effect of fracture permeability on well productivity. The relationship of these variables is considered separately in the order indicated. Effect of Wettability on Permeability Fig. 1 shows relative permeability relations for 20-30 mesh Ottawa sand. Inspection of these curves reveals that the relative permeability to oil when a small amount of water accompanies the flow is considerably higher when water rather than oil is the wetting phase. For

By Charles E. Mauk, H. William Prengle, Robert W. Legan

A process breakthrough was needed for the complete destruction of total cyanide influent as high as 100,000 mg per 1, or below 1 mg per 1, to produce an influent with total cyanide below the limit of detection. The process uses ozone for the total destruction of cyanide and metal cyanide complexes. It was found that while ozone alone reacted with the iron cyanide complexes too slowly for practical application, ozone at slightly elevated temperature became more effective, and ozone with ultraviolet light became effective enough to permit the design of a successful system.

Jan 1, 1977

By W. C. T. Yeh, T. G. Oakwood, A. A. Hendrickson, R. H. Hammar

The objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for by the influence of the solute addition on the dislocation structure oj- the crystals. The additions of both tin and indium produced only small changes in the dislocation densities and arrangements in silver crystals. However, as found previously, small solute additions have large effects on the tensile properties; the inj-luence of the tin and indium additions on the temperature dependence of the flow stress and the easy-glide range is especially strong; It is concluded that the indirect strengthening effect of the solute due to variations in the dislocation density as proposed by Seeger is of minor importance and that solute atom-dislocation interactions are responsible for the observed strengthenirzg effects. The experimental results were combined with those of Rogausch to test the concenlvatiorz dependence of solute strengthening. Both the first and one-half power dependences of the critical resoleed shear stress on concentratiorz fail in very dilute solutions. THE objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for, at least in part, by the influence of the solute addition on the dislocation structure of the crystals. It is recognized that the addition of solute atoms may influence the strength properties of a metal through both "direct" and "indirect" effects. The former refer to the strengthening mechanisms that result from the interaction of solute atoms with dislocations; in the latter case, the strengthening effects arise as a result of solute's influence on quantities such as dislocation density, dislocation arrangement, stacking-fault energy, diffusivities, the elastic constants, and so forth. It is clear that the correct interpretation of solid-solution strengthening phenomena cannot be given until the importance of indirect strengthening effects is properly evaluated. In the particular case of close-packed metal crystals, Seeger showed that solute strengthening effects in dilute solutions of copper and silver might be accounted for by an increase in dislocation density due to the addition of the solute. Seeger's argument was that the strengthening effects extrapolated from more concentrated solutions indicate that small concentrations of impurities raise the critical resolved shear stress much more than is predicted by a concentration-independent dislocation density. The above idea was a very reasonable one. The dislocation theories of work hardening of Taylor,2 Cot-trell, 3 Mott, 4 and seeger5 had already associated the increased flow stresses with increased dislocation densities in deformed metals; investigations of the dislocation structure of metal crystals had provided a logical basis for expecting an increased dislocation density in crystals containing impurities (see for example, Ref. 6). The numbers involved seem reasonable, too. It can be expected that the flow stress of the crystal would increase as the one-half power of the dislocation density.' Solute additions of 1 at. pct to metal crystals result in strength increases by factors in the range of three to ten. If one assumes that the strengths of the pure metal crystals are determined by their dislocation densities, then dislocation-density increases of one to two orders of magnitude as a result of solute addition would be required to account for the observed strengthening—not an unreasonable expectation. In addition to the effect of the solute addition on dislocation density, one might also anticipate important strengthening contributions to result from the solute's influence on the dislocation arrangement. Parker and washburns have reviewed a number of experimental evidences which show important strengthening effects due to the presence of subboundaries. Further, lattice strains due to impurity segregation would be expected to influence the distribution as well as the dislocation density of the as-grown crystal. As pointed out in the reviews of Chalmers,6 Elbaum,9 and winegard,lo micro segregation of impurities occurs at all interfaces of crystals in cellular growth; the impurity gradient results in lattice strains which can be reduced with the presence of dislocation arrays in the region of the impurity gradient. Hence, one would expect the presence of a solute to favor the formation of dislocation subgrain structures and that the subgrains would have an important influence on the strength of the crystal. The experimental observations that concern the possibility of an important strengthening contribution through the influence of the solute on the dislocation density or arrangement are not in agreement. Haasen has reviewed the observations of Meakin and Wils-dorf,12 Howie,13 and Bocek 36 and concluded that the solute's influence on dislocation density is not sufficient to account for strengthening effects in concentrated solutions but might, as seegerl suggested, make an important contribution in very dilute solutions. On the other hand, Hendrickson and Fine 14 concluded that changes in the dislocation density and dislocation width accounted for the solid-solution strengthening effects observed in silver-based aluminum solid solutions. Goss et a 1.I5 observed dislocation arrays in Ge-6 at. pct Si, Ge-0.2 at. pct Sn, and Ge-0.2 at. pct B crystals that were not observed in germanium crystals of

Jan 1, 1968

By D. P. Seraphim

Single crystals of bee Li-Mg solid solution were grown and their internal friction was measured as a function of temperature, A peak of the Zener type was found in the damping spectrum. The activation energy for the relaxation process is 21.5 ± 1 kcal per mole and the frequency factor is 1015.7 ± 0.7 sec-1. ZENER internal-friction peaks which are observed for a wide range of solid solutions are attributed to stress-induced changes in local order.' In the present work a Zener internal-friction peak, the first reported for a solid solution of an alkali metal, is

Jan 1, 1961

By R. Fawley, M. A. Quader, R. A. Dodd

Stacking fault energies and annealing twin frequencies have been measured for austenitic stainless steels having a) constant 20 wt pct Cr and varying nickel contents, and b) constant 20 wt pct Ni and varying chromium contents. The effect of nitrogen has also been studied and, to a lesser extent, so has the effect of carbon. All measured stacking fault energies plot linearly against the corresponding annealing twin frequencies, suggesting that, for constant prior deformation and grain size, twinning frequency can be used to estimate stacking fault energy. Compositions low in nickel possess the lowest fault energy, while the maximum fault energy within the investigated composition range occurs mound 20 pct Cr-20 pct Ni. Nitrogen has practically no effect on stacking fault energy when increased from 0.005 to 0.05 wt pct, although Planar dislocation glide is associated with higher nitrogen contents; this may be a short-range order effect. Carbon may raise the stacking fault energy a little, and causes pronounced dislocation tangling in deformed alloys. The basically different dislocation structures promoted by nitrogen and carbon, respectively, are not associated with large variations in stacking fault energy, and the reason for the difference remains unknown. INTEREST in the dislocation configurations developed in plastically deformed alloys arises principally from a desire for an understanding of mechanisms of plastic deformation and fracture. Comparatively little basic work has been concerned with austenitic stainless steels, although considerable interest has developed in the fundamental aspects of deformation of these alloys since the suggestion that those compositions deforming essentially by planar glide are particularly prone to transgranular stress corrosion cracking.' Certain facts are well-established. An 18 Cr-8 Ni steel (type 304) has a low stacking fault energy which is increased by higher nickel contents, and the structure of these steels when moderately plastically deformed changes concomitantly from planar to less planar to distinctly tangled dislocation configurations. These changes are thought to relate to changes in stacking fault energy, and considerable effort has been expended in measuring stacking fault energies of austenitic stainless steels through the determination of node curvatures2"4 even though the method has limitations due to formula approximations,5 an upper limit of measurement of 50 erg cm-2 at the most,5 and the necessity of an extremely meticulous experimental technique. Therefore, it is not surprising that only qualitative agreement between different investigators is generally to be found.'-' At high energies where node radius measurements are inappropriate, some use has been made of annealing twin frequencies to estimate relative stacking fault energies, although a recent critical evaluation of the method suggests that it should be used cautionsly with due regard to effects of grain size and prior deformation.6 Finally, there is a question as to whether the structures of some deformed steels are due to ordering effects. In particular, the role of nitrogen in promoting planar dislocation motion has been suggested to be due to ordering,' but similar suggestions have been made for steels having low interstitial contents.4 EXPERIMENTAL Small ingots of austenitic stainless steels (-50 g) were prepared from components exceeding 99.99 pct purity, the nickel and chromium being Johnson Matthey "Specpure" metals. Carbon was added as pure graphite, and nitrogen as CrN. The components were accurately weighed, and it was assumed that the final composition was the same as the nominal composition

Jan 1, 1969

By G. H. Ruggles

POPULAR opinion, as it might be termed, has always been of the trend that a flotation reagent added to the ball mill during grinding would be more thoroughly mixed with the pulp and for that reason more effective in the production of low tailing. That there are other effects, inimical to good flotation, when using so-called chemical reagents, is brought out by the series of tests outlined in Table 2. It was defi-nitely proved that if either the T. T. mixture (20 per cent thiocarbanalid-80 per cent orthotoluidin) or po-tassium xanthate were added to the ball mill the result-ing flotation concentrate would be lower in copper and higher in insoluble than the concentrate produced by adding these same reagents without the ball mill cir-cuit. With the T. T. mixture four sets of tests were made. The screen analyses of the flotation feed show that there was very little difference in the original grind-ing. When the T. T. mixture was added to the head of the flotation machine the flotation concentrate had a little over 61 per cent solids -200 mesh. If the mix-ture was put into the ball mill the flotation concentrate had but 40.7 per cent of the solids -200 mesh for one set of tests, and 49.0 per cent for the other set. With the mixture at the head of flotation the total concen-trate was high in copper (34.715 and 36.525 per cent) and low in insoluble (13.20 and 11.61 per cent). The assay of the concentrate when the T. T. mixture was introduced into the ball mill was what might be termed low in copper (29.389 and 30.833 per cent). In one of these 'sets of tests (periods 8 to 11, third column) the insoluble was high, 16.81 per cent. The other run (peri-ods 12 to 15, fourth column) for some unknown reason shows a low insoluble, 12.72 per cent. With similar grinding the addition of potassium xan-thate to flotation produced a concentrate having 62.8 per cent -200 mesh, whereas with the potassium xanthate added to the ball mill the flotation concentrate was very coarse, only 36.4 per cent passing 200 mesh. The difference in the total assay of the concentrate is remarkable ; 35.847 per cent copper when the xanthate went to flotation and 30.44 per cent copper when the xanthate was added to the ball mill; insoluble, 10.94 per cent in the former instance, as 22.15 per cent in the latter.

Jan 8, 1927

By Alfonso W. Ovalle, Héctor R. Albornoz

INTRODUCTION The El Teniente Mine of Codelco-Chi le has extracted 588 mil lion tons of ore in its 77 year history for a total copper output of 8.800.000 tons. The mine production has been obtained mainly by traditional block-caving where grizzlemen using a hand held lever send ore through long-raises to load trains. At present the mine is about to introduce mechanized block-caving using LHD equipment to extract the primary rock. This paper describes this method which will be tested starting next month by caving an 11.000 square meter block. THE PRIMARY ROCK PROBLEM The secondary enrichment sulfides of the El Teniente ore body have characteristics which makes a standard unmechanized block-caving practice very successful. In the 60's parts of blocks encountered primary ow in the Teniente 1 and Sub-13 levels which proved to be extremely hard to extract. These foretold the obstacles that arised in the central part of the Teniente 4 level. Preparation of a completely primary 8.100 square meter block started in 1970. Its undercutting was completed by the end of 1972 and by 1973 the problem of mining the primary rock was clearly visualized. The numbers below describe the difficulties in mining this block: -Long-hole drilling rate is 90 m (270 ft) per shift in secondary rock and 37 m (110 ft) in primary. - Undercutting which is completed in 9 shifts in secondary took 180 shifts in the primary block. - Average grizzlymen productivity in secondary is 250 tons per shift while in primary it is only 25-30 tons, both at 343 mm (13 1/2 in. ) grizzly opening. - Powder consumption for secondary blasting increased from 8 grams per ton in secondary to 84 in primary. - The protection pillar between the under- cutting and the production levels was 60% broken in primary while 20% is usual for secondary. - Extraction advanced 5 cm per day in primary while a 50 cm per day rate is the aver- age in secondary. This is the main reason that after 8 years this primary block has a 20% extraction. Secondary blocks take 1.5 to 3 years to complete their extraction. - 80% of the boulders in primary rock are larger than 343 m (13 1/2 in.) with 10-20 % of them larger than 3 meters. -Direct cost of production (preparation, undercutting, extraction and haulage), using the traditional block-caving design for secondary rock, increased 3.5 to 4 times when used in primary rock. The following indicators of Table 1 show the rock characteristics differences.

Jan 1, 1981

By G. N. Goldberg, Robert A. Rapp

The steady-state kinetics and microstructures of simultaneous internal oxidation and external scale formation were investigated for the oxidation of Cb-Zr and Ch-Zr-Re alloys in pure oxygen at 1000°C. For each binary alloy, a constant rate of scale formation was observed at steady state; the internal oxidatton zone reached a steady-state, time-independent thickness. The dependence of the scaling rate on zirconium content exhibited a maximum at a low zirconium colttent; more concentrated alloys oxidized at a slower rate than pure columbium. This composition dependence of the scaling rate may be partially attributed to the effect of the internal oxidation process as an intenla1 sink for oxygen, with the formation of voluminous, and relatively impermeable ZrO2 precipitates. However, the morphologies of the ZrO2 internal oxide precipitates also affected the scaling rate. The internal oxide precipitates were distributed uniformly in the external scale. The steady-state thicknesses of the internal oxidation zones were not in agreement with those predicted theoretically from an idealized simple model. However, in this particular alloy systen1 the ideal model is not satisfied experitmentally. For ternary Cb- Zr - Re alloys with Nr10e = 0.02 or 0.05, the steady-state thicknesses of the internal oxidation zones were less than those for the corresponding binary Cb-Zr alloys. For ternary alloys with NRe(0) - 0.05, a more adherent and much less porous external scale was formed, and a reduction in the kinetics of scale formation was observed. A number of authors'-7 have reported linear oxidation kinetics for the reaction of pure columbium at 1000°C in air or in oxygen of about 1 atm pressure. A thin and tightly adherent oxide layer is found at the metal/oxide interface beneath a porous external layer of scale. Although the suboxides CbO and CbO2 represent thermodynamically stable phases at 100O°C, generally only Cb2O5* is identified as a reaction product in quenched specimens. Studies at 1000°C at lower oxygen pressures8,10 (Po2 - 10-4 Torr) show that both CbO and CbO2 do form and that CbO2 is a protective oxide. The growth of CbO2 results in parabolic kinetics until Cb2O5 is nucleated and grows. Apparently because of the large volume change associated with its formation, Cb2O5 is porous and does not serve as a diffusion barrier; linear kinetics prevail after the surface is covered with Cb2o5. On the basis of these observations, several authors5,9,10 have suggested that the linear oxidation of pure columbium at 1000°C in air or oxygen of 1 atm is limited by a Loriers-type mechanism,11 whereby the total rate or reaction is controlled by ionic diffusion through a thin layer of CbO2 which is maintained at a constant thickness throughout the linear oxidation. However, the concept of a Loriers model for a three-phase CbOlCbO2 Cb2O5 scale, with the only oxygen activity gradient across the NbO2 phase, is not self-consistent. Further, the suboxides CbO and CbO2 were not observed in the high-temperature X-ray diffraction study of columbium oxidation by Goldschmidt.8 From investigations in which the large PO2, dependence of the linear scaling rate was demonstrated, the importance of an oxygen adsorption or dissolution step has been suggested.4,5,7,10,12 Thus the mechanism for the linear oxidation of pure columbium remains quite controversial. Since further insight into the oxidation mechanism of pure columbium is not provided by this investigation, the authors wish to emphasize at the outset that their experimental results are not interpreted in terms of a particular rate controlling step for the oxidation of pure columbium. Previous investigations13-18 of the oxidation of Cb-Zr solid-solution alloys in air or oxygen at 1000°C suggest a remarkable dependence upon zirconium content. For an alloy of bulk zirconium mole fraction, N2r(0) equal to 0.05 or 0.10, the oxygen uptake is reported to be as high as four times greater than that for pure columbium;13,14 for alloys with NZr(0) 0.05 or 0.10 the oxygen uptake is reported to decrease with increasing NZr(0); to a minimum uptake of about one quarter that for pure columbium at NZr(0): = 0.50.13-15Since zirconium forms a more stable oxide (ZrO2) than the lowest columbium oxide (CbO), and since columbium exhibits a high solubility19,20 and diffusivity21,23 for oxygen, the internal oxidation of the zirconium component to ZrO2 is expected at a reaction front ahead of the advancing metal/scale interface. The external scale is then formed at the metal/scale interface by the inward migration of oxygen through the scale, probably through a series combination of molecular and ionic diffusion. Internal oxidation in conjunction with external scale formation has been investigated by Maak24 for the oxidation of dilute Cu-Be alloys in pure oxygen at 850°C. For cu-Be and many other binary alloys,24-27 very small, essentially uniaxial internal oxide particles are formed in the most dilute compositions; for somewhat more concentrated alloys. the internal oxide particles precipitate as platelets or needles. From pertinent solutions to the diffusion equation, Maak28

Jan 1, 1967

By R. E. Crater

Brown, Gaudin, and Loeb in their study of intergranular comminution by heating attempt to find one explanation for all types of rock in terms of the properties of the phases present. The only necessary condition for intergranular cracking by heating is the setting up of high stresses at the grain boundaries. Such stresses may be set up in multiphase isotropic mixtures if the thermal expansions of the phases are different, in non-cubic single phases because of the anisotropy of thermal expansion in the various crystallographic directions, and in materials containing quartz because of the a-ß transformation at 575°C. In addition, for intergranular comminution by heating, the cooling and not the heating is most important.

Jan 3, 1959

By S. J. Matas, R. F. Hehemann, R. H. Goodenow

The hot-stage metallographic method has been employed to determine radial growth rates of upper and lower bainite. Lower bainite appears to grow as individual plates that increase in both length and thickness while upper bainite grows as sheaves of closely spaced plates or needles. A discontinuity in the temperature dependence of the growth rate appears to be associated with the transition from upper to lower bainite and stepped quenching experiments suggest that lower bainite will not continue to grow when the temperature is raised to the upper range. Thus, a single process does not appear to control the growth of both upper and lower bainite. A tentative model based on the forces acting on a dislocation interface is proposed to account for the slow growth of bainite. It has been recognized since the early studies of Davenport and Bain that a close relationship exists between the martensite and bainite transformations in steels. However, diffusion of carbon during the transformation has lead to considerable controversy concerning the reaction mechanism.1-7 Many studies4,5,7-9 have emphasized the structura and kinetic aspects of the bainite reaction and, in particular, the difference observed between the two forms of bainite—frequently termed upper and lower bainite. A kinetic difference between the two types of bainite has been revealed in the activation energy determined from the overall reaction;4,5 however, many difficulties arise in an interpretation of these activation energies since a number of temperature dependent factors contribute to the kinetics of the overall reaction. The displacive surface relief10 accompanying the bainite reaction permits a separation of the nuclea-tion and growth contributions to the reaction and allows the kinetics of the growth process to be examined. Several investigations of this type have been conducted; however, they have been restricted to the low temperature range.3'6'11 Here, bainite plates are observed to grow slowly in both length and width. The present investigation extends such studies to include the upper bainite range. MATERIALS AND PROCEDURE Materials. The composition of the steels studied in this investigation are presented in Table I. The range of composition permitted a study of the effect of carbon content on the growth rate of upper bainite in the 9 pct Ni steels and consideration of both upper and lower bainite in the higher carbon steels. These steels were received as hot-rolled rounds and were forged to approximately 1/2 in. thick plates for preparation of metallographic specimens. In order to produce an essentially zero carbon steel, Steel A was decarburized in wet hydrogen at 1550°F for 15 days with the result tabulated as Steel AD. Experimental Procedure. In order to study the slow growth of the displacive transformation product, a commercially available Leitz hot stage was modified to permit heating of the specimen by its own resistance in a manner similar to that employed by other investigators.6 The furnace chamber was maintained at a pressure of 2 to 3 X 10-5 mm Hg prior to austenitizing at 2000° ± 12° F for 5 min. Samples could be cooled from the austenitizing to the transformation temperature in approximately 15 sec and the progress of transformation was recorded with a 9 cm by 12 cm single frame camera or a 16 mm movie camera. RESULTS AND DISCUSSION Growth Characteristics. The general growth characteristics observed in this investigation were analogous to those reported previously.3,6,11 Typical growth sequences for the high temperature and low temperature forms are illustrated in Figs. 1 to 5. In both temperature ranges, bainite plates increase in length at slow, temperature dependent rates until interrupted by a grain boundary, another plate, or

Jan 1, 1963

By William A. Johnson

THE fundamental role of diffusion in many reactions occurring in solid metals has long been recognized, and there have been careful measurements of rates of diffusion in numerous alloy systems, but our understanding of the atomic mechanism by which diffusion occurs is scarcely in an advanced state 1-3 It is doubtful that this mechanism can ever he directly ascertained, rather, all imaginable mechanisms must be examined and the one that is in best accord with such data as can be obtained from suitably chosen experiments should be selected Because of its relative simplicity, diffusion in a system containing only one kind of atomic species-commonly called self-diffusion-is of considerable theoretical interest It may be expected that diffusion theory will not be advanced appreciably until a wide variety of diffusion experiments-of which diffusion in a chemical concentration gradient and self-diffusion are two important types-are carefully performed and inter-compared Aside from the purely theoretical interest in self-diffusion measurements, such studies will be of considerable engineering importance The rate of any process in a pure metal requiring the movement of atoms, of which recrystallization and creep are two familiar examples, will be understood more readily with the aid of self-diffusion data † Self-diffusion implies the diffusion of something into its exact counterpart, the detection of such a process is patently impossible, and it is-necessary to substitute for it the diffusion of one isotope (in this case radioactive) into another isotope (in this case stable) of the same chemical element There is, however, no reason to suppose that a radioactive atom will not diffuse at the same rate as its stable isotope, for all of the isotopes of the same element have exactly the same chemical properties, neither the difference in nuclear energy nor the difference in mass would be expected to exercise an important influence in this phenomenon In this sense, self-diffusion may be thought of as the diffusion of radioactive atoms down a radioactivity concentration gradient, just as usual diffusion is the diffusion of one kind of atone down its chemical concentration gradient The first measurements of self-diffusion ii ere made by von Hevesy4-6 using the radioactive lead isotope thorium B in ordinary lead The recent development of means for producing artificial radioactive elements has made possible similar measurements on gold,7,8 copper,2,9 and zinc 10 11 Many of the data that have been obtained are rather poor, and no adequate reason has been given for their poorness, it appears, however, that the unsatisfactory results are characteristic of the particular experimental procedure employed, and not of self-diffusion measurements in themselves The experimental technique that has yielded the poorer results is the deposition of a thin layer of radioactive atoms on the surface of a specimen and the determination of the rate of inward diffusion

Jan 1, 1941

By Frederic L. Kadey

Diatomite is a siliceous, sedimentary rock consisting principally of the fossilized skeletal remains of the diatom, a unicellular aquatic plant related to the algae. Thus, it has-been formed by the induration of diatomaceous ooze, and consists mainly of diatomaceous silica, a form or variety of opal which is first formed in the cell walls of the living diatom. Diatomaceous silica is not generally regarded as a synonym or the equivalent for diatomite, although it has been so used at various times. Accurately, diatomaceous silica is the preferred name for the principal mineral component of which the rock, diatomite, is composed. The terms diatomaceous earth and kieselguhr are used as synonymous with diatomite. The designations tripoli, tripolite, infusorial earth, etc., were used at one time but are now obsolete. With the changing nomenclature, these terms that were at one time correct when proposed and used for generations would be considered incorrect if used today in the light of current knowledge. The designation diatomite is reserved for those accumulations of diatomaceous silica that are of sufficient quality, size, and minability to be considered of potential commercial value. Processed diatomite possesses an unusual particulate structure and chemical stability that lends itself to applications not filled by any other form of silica. Foremost among these applications is its use as a filter aid, which accounts for over half of its current consumption. Its unique diatom structure, low bulk density, high absorptive capacity, high surface area, and relatively low abrasion are attributes responsible for its utility as a functional filler and as an extender in paint, paper, rubber, and in plastics; and as an anti-caking agent; thermal insulating material; catalyst carrier; and chromatographic support; polish, abrasive, and pesticide extender to name a few representative applications. The United States is the principal producing country, although diatomite is found in numerous other locations.

Jan 1, 1975