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By L. L. McMurray

Ilmenite is the most important raw material for manufacture of titanium dioxide.' Industrially, several other products are made from ilmenite, the most important of which are: ferro titanium, ferro carbon-titanium, copper-titanium, titanium carbide and titanium nitride. The production of titanium metal is still in the laboratory stage because of the difficulty of extraction and as yet no important application for the metal has been found. Ilmenite has received considerable attention as an industrial raw material. Imports of ilmenite concentrates for the first nine months of 1941 were 156,737 short tons, the chief source being Travancore, India.2 Domestic produttion of ilmenite has heretofore been confined to Amherst and Nelson Counties, Virginia, where a complex rutile, ilmenite, and apatite ore is mined and treated to utilize all three of these minerals. A recent report3 has described development of the large titaniferous magnetite ore body at Tahawas, New York, where it is expected that 800 tons of ilmenite concentrates, containing 48 per cent TiO2 will be produced daily. Additional domestic production is expected from a large ilmenite deposit recently opened in caldwell county, North carolina. Flotation tests indicate that a high-grade concentrate containing 53 per cent TiO2 can be made from the North Carolina ore. Prospecting of domestic ores in other areas has been reported.' It appears that increased domestic production of ilmenite may well save considerable shipping space so vitally needed in these times. The composition and chemical structure of pure ilmenite is given by Dana as: FeO, TiO2; Ti, 31.6 per cent, Fe, 36.8 per cent, O2, 31.6 per cent. This composition is variable in that some iron or titanium may be replaced, giving a variable iron-titanium ratio. As an example, the iron-titanium weight ratio of ilmenite in Caldwell County, North Carolina, has been determined to be 0.94 (using 97.1 per cent ilmenite concentrate obtained by heavy liquids on minus Iso-mesh ore) compared with theoretical 1.16. No rutile was noted in this ore to account for the low value. This North Carolina ore is free of magnetite, which is a common associate of ilmenite ores. In view of a large potential production from North Carolina, the Tennessee Valley Authority conducted a study of methods of concentration of that ore, of which the results are reported herein. The Ore Five samples of Ore were taken from the deposit at various exposed locations and were mixed for the study and testing. An attempt was made to proportion the amount of weathered and unweathered portions in making the composite sample, so as to approximate actual operating conditions. An examination of representative specimens of the sample showed the following general facts: 1. The black mineral comprising nearly 70 per cent of the ore is ilmenite.

Jan 1, 1948

By P. M. Kelly

TWO analytical methods for calculating the positions of matrix and twin reflections on electron-diffraction patterns of a twinned cubic crystal have recently been published.1,2 Meieran and Richman1 considered the case of twinning on (1 12) in a bcc structure, while a more general treatment, capable of analyzing twinning on any plane in a cubic crystal, was developed by Johari and Thomas.2 The latter authors applied their general rotation matrix to both (111) twinning in face-centered crystals and {112} twinning in body-centered crystals and they derived separate expressions for these two cases. This separate treatment masks the fact that in a holosymmetric cubic crystal a (111) twin is crys-tallographically equivalent to a {112} twin.3 This is analogous to the crystallographic equivalence of rotation and reflection twins in centrosymmetric crys tals. A particularly simple example of this equivalence occurs when the two twin planes are perpendicular to each other—for example (111) and (112). Then, if twinning on (111) moves a point P to a new position P1, and twinning on (112) moves P to P2, P1 and P2 will be related to each other by a 180-deg rotation about [110]— the direction normal to both (111) and (112). Since there are diad axis axis along (110) direction in a holosymmetric cubic crys tal the two positions P1 and P2 must be crystallo-graphically equivalent. In other words if a particular pole (hk l) is in a position P1 after twinning on (Ill), then after twinning on (112) a pole of the type {hkl}—but not the particular pole (hk1)—will also be in the position P1. As a result, when only the general (as opposed to the particular) indices of poles after twinning are required, twinning on (111) gives the same results as twinning on (112). To convert the results for a (111) twin to those applicable to a (112) twin, when the particular (as opposed to the general) indices of poles after twinning are required, all that is necessary is to multiply the indices of the twin poles by the matrix for 180-deg rotation about [lie], i.e., The analytical methods suffer the disadvantage that a new set of calculations must be performed for each different diffraction pattern or, as is done in the Meieran and Richman treatment,1 a lengthy list of the location of the twin spots in reciprocal space must be prepared. All the tedious computation involved in these analytical approaches can be avoided by simply plotting, on tracing paper, a stereographic projection of a crystal twinned on say (112). By superimposing this twin stereogram on a standard (001) projection (preferably with the points and indices in a different color from those on the twin stereogram) the relative positions of both matrix and twin reflections can be determined by inspection. Alternatively, a composite projection can be

Jan 1, 1965

By P. D. S. St. Pierre

IN recent years the use of high sulphur fuels and charges in steelmaking has necessitated rapid methods of slag control in order to insure the production of high quality steel. Several systems of control have been discussed in the literature, and of these the method described by Philbrook, Jolly, and Henry' has received the most attention recently. In their process the hydrogen ion concentration of an aqueous slag suspension is determined under controlled, but arbitrary conditions. The basicity of the slag may then be derived from a previously established pH-V ratio curve. Thus, by measuring the pH, some indication of the V ratio is gained, from which significant properties of the slag may be deduced. Philbrook et al. made no claims as to the theoretical justification of their treatment, but simply offered it as a rapid means of slag control. Encouraging results caused others to study the method and publish their findings.2-5 Although there was fair agreement on the efficacy of the method, no common parameter was evolved against which pH readings could be plotted. The results of the various determinations were related to such V ratios as CaO/SiO2 and CaO/ SiO2 + P2O5 by some,'-3 while others" plotted against "excess lime." Rivet,' however, found a simple proportionality between the hydrogen ion concentration and the sulphur content of the molten steel beneath the slag. Since slag control in North American practice is largely directed toward the efficient removal of sulphur from steel, Rivet's approach to the problem had the advantage of connecting directly a property of the slag with the impurity being removed. In view of the diversity of parameters used it seemed probable that some fundamental point was being overlooked in seeking a relationship. Examination of the literature revealed that much emphasis had been laid on experimental detail but scant attention paid to the fundamental aspects of the hydrolysis of the aqueous slag suspension. Consequently the present investigation was undertaken with the object of rectifying this deficiency and deriving, if possible, a parameter of general application. Petrographic studies on several matured Canadian open-hearth steel slags have shown that their major constituents are dicalcium and tricalcium silicates set in a complex matrix of iron oxides and ferrites. These phases are shown in Figs. 1 and 2. Free lime is frequently encountered in slags, but is not an equilibrium phase since on continued heating it dissolves forming silicates or ferrites. Thus, it appeared that a study of the hydrolysis of the major phases in steel slags would be profitable. The experimental technique used in the present work was a modification of that described by the other workers.'- Electrical conductivity measurements were also made on the suspensions, since Smith et al." had claimed advantages for this method in their paper on slag control. Experimental Procedure The compounds studied in this investigation were prepared in the laboratory by heating purified oxides

Jan 1, 1954

By A. W. Schlechten, Ernest J. Breton Jr.

Experiments on the separation of copper and zinc ions by selective action of ion exchange resins showed the carboxylic type to be more effective than the sulphonic resins. The latter demonstrated a greater capacity over a wider pH range. Data show the effectiveness of resins as a means of concentration. IN recent years the restrictions of stream pollution laws and the high price of metals have created an interest in ion exchange as a means for metal recovery. Some applications have proved successful. In Germany during World War 11, 17 tons of copper per day were recovered from rayon mill wastes by means of ion exchange resins;' and for some time in this country a large ion exchange unit has been in operation for the recovery of copper from rayon waste water. The possibilities of applying ion exchange to the recovery of metals occurring in plating rinse water is particularly promising. In most of these applications only the metal being recovered occurs in the waste. The ion exchange resins act merely as a means of concentrating the metals to a point where they can be recirculated. It would be highly desirable to use ion exchange as a means of not only concentrating but also of separating metals. With the exception of the impressive separations accomplished in connection with the atomic energy program, very little has been done on metal separations.' Therefore, an investigation was undertaken at the Missouri School of Mines and Metallurgy to determine if either of the two main types of ion exchange resins could be used to separate metal ions in solution. The selective removal of copper ions from a mixture of copper and zinc on carboxylic and sulphonic-type resins was investigated as a function of flow rate, pH, copper-zinc ratio, and concentration. It was shown that zinc can be separated from copper and that very large ratios of concentration can be obtained using ion exchange resins. Since ion exchange is relatively new to the field of metallurgy, a brief review of the subject will be included. Theory of Ion Exchange A comprehensive theory for ion exchange has not been developed as yet, but the mechanisms are analogous to metathetical reactions: R Na + Cu++ *=? K(SO3)2 Cu + 2Na+ R is the designation for the ion exchange resin. If a copper solution is passed over a resin bed in the sodium form, two ions of sodium will be released for every ion of copper removed. For the most part this reaction follows the laws of mass action and of electrical neutrality. Consequently, if an excess of sodium ions is passed over a bed containing copper, the reactions will be reversed, and the resin will be regenerated to its original form. A few empirical rules governing the exchange reaction have been set forth: 1—In general ions with a high valence will replace ions with a lower valence. 2—Ions having higher activity coefficients have a higher replacement potential. 3—In a series of mono-valent ions, those with the smallest radii of hydra-tion will tend to replace those having larger radii of hydration. 4—Where ions are similar in most respects, those with the higher atomic weight sometimes will take precedence. This last rule is not as definite as some of the others. These rules apply to rather dilute solutions at moderate temperatures and assume all ions to be present in about equal concentrations. Higher concentrations and temperatures may in some cases reverse the normal exchange reactions. Ion exchange materials are unique in that their efficiency increases as the concentration of the solution decreases. For many exchangers, most efficient operation is obtained at concentrations in the order of one thousandths of a percent. Most applications, though, are made in solutions containing considerably higher concentrations than this. Coste9 as shown that ion exchange resins will remove aluminum and iron effectively' from solutions of up to 10 pct chromic acid. Ion Exchange Resins Ion exchange resins are insoluble, porous, resinous structures to which active groups have been attached. Active groups such as (—SO,,)- and (COO)- pick up cations; hence structures saturated with groups such as these are called cation exchangers. Structures saturated with groups such as (—NH,)' which pick up anions, are referred to as anion exchangers. The resinous structure of necessity is resistant to strong acids, bases, oxidizing, and reducing agents, and most of the common organic solvents. An idea of the stability can be gaged from the fact that resins last for many years under constant use without detectable chemical or physical breakdown. The ion exchange reaction is not confined to the surface of these synthetic resins. Its porous structure permits active groups in the center of a particle as well as those on the surface to remove ions. A high capacity resin such as Amberlite IR-120 will remove up to 3.3 lb Cu per cu ft of resin. In this investigation several approaches to the problem of separating copper from zinc by ion exchange were considered. First, if a reagent could be found which would complex one of these metals and not the other, then by passing this reagent through a bed of exchanger containing copper and zinc, the

Jan 1, 1952

By R. W. Ludt, C. C. DeWitt

The use of froth flotation for the separation of minerals has become one of the most important of ore dressing processes. Its particular adaptability to the enrichment of low grade ores has made the process an important factor in the national economy. The methods have been extended to the recovery of a great number of minerals. Among the few minerals which have resisted efforts toward industrial flotation is chrysocolla, a hydrated partly colloidal copper silicate. Chrysocolla, being a product of natural oxidation, has been found to occur in small quantities with many ores which are recovered by flotation methods. In present practice, these small quantities of copper silicate pass off with the tailings and are lost. The advantages to be gained by a satisfactory process for the recovery of chrysocolla is apparent. Any application of principles which points a way toward the satisfactory industrial flotation process for copper silicate would be of advantage. This paper presents an attack on this problem. Two methods for the recovery of chrysocolla have been developed by the United States Bureau of Mines.1,2 They have been successful on a laboratory scale but have been seriously restricted in industrial application by critical requirements in the procedure. In one of the Bureau of Mines methods,' the ore is activated with sodium or hydrogen sulphide in an aqueous solution at a pH of 4. Amy1 xanthate is then used as a collector with pine oil as a frother in the flotation process. An excess of sulphide acts as a depressant and the state of optimum conditions is difficult to control industrially. In the second Bureau of Mines method,2 soap is used as the collector at a pH of between 8 and 9. The diffi- culties with this process are that soap is not a specific collector, that heavy metal or alkaline earth ions cause the formation of insoluble soaps, and that a more acid solution causes the formation of a free acid which does not act as a collector for chrysocolla. The problem of recovering chrysocolla by flotation involves the selection of a suitable collector. The collector molecule must be composed of an active polar group that has an attraction for chrysocolla, and of a hydrocarbon chain. Certain dyes have been shown to have an attraction for certain minerals. Suida3 found that hydrated silicates are colored by basic dyes. Dittler4 showed that chrysocolla, among other colloidal minerals of acid reaction, preferentially takes up such basic dyes as fuchsin B, methylene blue, and methyl green. Endell5 gave information to show that the colloidal material in clay may be determined by its selective adsorption of fuchsin. A simple experiment, likewise, illustrates the difference in the adsorptive power of chrysocolla and of silica for the basic triphenyl methane dyes. When a mixture of chrysocolla and silica is immersed in a very dilute dye solution, less than 5 ppm, the chryso-colla is rapidly dyed and the silica is dyed more slowly. The difference is substantial but one of degree. Dean2 showed that the dyes, crystal violet and toluidine blue, are taken up by quartz in an adsorption type process. The difference in the adsorptive power, however, offers the means by which a new collector may act. To form such a collector, a hydrocarbon chain must be attached to the dye molecule. This involves a process of organic synthesis. Butyl, hexyl, and octyl hydrocarbon chains were selected for substitution in the malachite green molecule. For the purpose of identification, the alkyl-substituted dyes formed are called: butyl-malachite green; hexyl- malachite green; and octyl-malachite green. An outline of the procedure for their synthesis is given in the appendix. It is generally recognized in the preparation of this type of dye that the chemical structure of some of the dye molecules varies. However, a uniform formula is attributed to the dye. Such a procedure has been followed in specifying the structure of these alkyl-substi-tuted malachite green dyes. The structure is given on the basis of their properties as an homologous series of dyes, on their method of preparation, and on the purity of intermediates used. Structure of substituted alkyl malachite green is: C6H4 N(CH3)2 p-R C6H4 CH C6H4 N(CH)2 Procedure The flotation cell is a Bureau of Mines 100-g, batch unit provided with an air inlet at the bottom above which is a variable speed agitator. The agi-

Jan 1, 1950

By F. R. Wadleigh

It is generally realized and very often admitted by both producers and consumers of coal that there is great need for a revision of existing commercial classifications, and this will involve, of course, determination of a standard classification and a constant revision of marketing practices as they are affected by coal classification. I recently sent out some 200 letters to producers and consumers with a request for their views on the subject of commercial classification. Nearly all of the replies from both sides were that there was needed some change in the present method. There were three or four dissenting voices but the great majority of opinion was in favor of the formulation of some standard commercial classification. The classifications in commercial use today can best be described as a hodgepodge. They are made upon different bases, have different names and have different ways. There are, for instance, about 11 single bases of classifications as used commercially and some 17 or 18 combination bases. Then there were the Tidewater Pool Exchanges. The classification which they put in force is still used in the tidewater markets and has several different bases of its own. It will be considerable of an undertaking to bring about a change in marketing methods as affected by coal classification but it is well worth doing and I think the committee which has been appointed under the auspices of the American Society for Testing Materials realizes the importance of the subject and is on the way to at least bring about some provision for adjusting matters. By way of starting, each member of the Committee on Commercial Classification has been assigned to a general market district and each member is now engaged in collecting the commercial market practice data for submission at the next meeting of the Committee. About a year ago I made up a list of the commercial classifications in the different markets and the total was 171. The 11 single bases I found used in commercial practice were:

Jan 1, 1930

CARL A. WENDELL, New York, N. Y. (written discussion*) .-I have never seen in print anything that even remotely has approached this article in clearness and important conclusions in conjunction with work done on the sink-and-float test. I have had many hundreds of these tests made and on different specific gravity solutions and the resultant product analyzed, but I have never grasped nor been able to show what this article sets forth. This article brings out one factor very clearly to my mind; what is to take the place of the solutions of different specific gravities used to obtain the laboratory results, when it comes to washing on a large scale, since water has one constant weight only? The answer is, sizing of coal. And as we know the importance of size versus specific gravity of the material to be washed, perhaps defined (practical) lines can ultimately be gotten up so that the sizing, if any, may be determined at the same time as the laboratory work on the coal is being done. G. R. DELAMATER, ? Steelton, Pa. (written discussion?).-The authors' deductions are well founded and although they disclaim any wide experience in commercial coal washing, practically all of the data presented are applicable to coals of all parts of this country. The paper clearly sets forth the great necessity of careful preliminary investiga-tion of each contemplated washery undertaking and contains the follow-ing very true statements. "It is not safe to assume that any coal which can he successfully washed on coarse coal jigs can be cleaned more com-pletely by washing at a finer size on tables," and "The effect of finer crushing upon the completeness with which impurities may be separated from coal depends upon two opposing tendencies. First, that the more finely a raw coal is crushed, the more completely will the particles of impurities be detached from the particles of clean coal. Second, the finer a coal is crushed the more difficult it becomes to separate the pieces of clean refuse from the pieces of clean coal."

Jan 12, 1919

The following outline has been prepared by request with the help of leading professors, business men, and social workers. It is arranged to cover 64 or preferably 96 class periods-four to eight month's work at the rate of two or three periods a week. More time would be desirable, but less time would be better than nothing. Certain topics must be omitted, especially if the assigned number of periods are lessened, where time is lacking. Many subjects are suggested in order to permit of choice and adaptation to local conditions; this is merely a suggestive outline. The course should be supplemented y engineering trips to study certain industrial conditions and the betterment work of selected companies-and social agencies. It should also be accompanied by brief surveys and practical service by students along the lines indicated. Reports and essays should be written. This is not a regular course in sociology and economics. It is a course in "human engineering" and should probably be directed by an engineering professor of large practical experience. Other members of the faculty, sociologists, economists, selected engineers, employers, labor leaders or others may be requested to lead certain periods, as desired. Care has been taken to avoid biased judgment in selection of topics and references.* * The authors of this outline have compiled an exhaustive list of references to books and periodicals relating to each group of topics. Lack of space prevents the publication of these lists in the BULLETIN, but they will gladly be supplied on request.-Ed.

Jan 12, 1917

By J. R. Lewis

During the past few years there has been considerable interest in the sizing and the preparation of the iron ore fed into blast furnaces. Furnacemen know that proper sizing of ore tends to increase the efficiency of the furnace. It has been shown by Joseph1 and his associates that there is a direct relationship between the porosity of an ore particle and the time required for its reduction in the blast furnace. This relationship may be stated as follows: All other factors remainig constant, the time for reduction of a given sample of ore is inversely propor-tiofid to its porosity. As a consequence, large pieces of very porous ore, say 3 or 4 in. in cross section, will be completely reduced by the time they reach the hot zone just above the tuyeres, while large pieces of dense, nonporous ore may reach the hot zone with their centers unreduced. This means that for the latter complete reduction will be accomplished by the so-called "direct method;" i,e., where carbon reacts directly with the ore. Some recent work by philbrook2 seems to contradict this rule. He found that of two unlike ores he studied, the one with the lower porosity reduced more readily. He explained his results as "possibly due to an apparently greater tendency of the rA, ore (lower porosity) to crack during preliminary dehydration and during reduction." This brings his results in line with the rule stated above. It is not the author's intention to enter into a discussion of the merits of "direct" versus "indirect" reduction. It is enough to Say that, in general, indirect reduction is desirable. For the greatest efficiency, Gruner's theorem3 requires that all reduction in the blast furnace be indirect. Joseph seems to believe this also, because in his recent article on Some Comparisons between Iron Ore, Sinter and Nodules as Blast Furnace Feed4 he concludes that: "In genera', the carbon in blastfurnace coke is used most efficiently when the largest amount of the carbon charged reaches the tuyeres." However, P. V. hlartin,3 in an excellent paper, has shown that some direct reduction may actually increase the efficiency of the furnace; that is, increase its rate of production while maintaining maximum fuel economy. For nonporous ores there is more opportunity to have an excess of direct reduction unless the factors that make for indirect reduction are favored; for instance; the Proper sizing of the Ore particles' Another factor that has an important bearing on the reduction rate, as it is affected by particle size, is the flow of heat into the particle. The ore particle

Jan 1, 1948

By J. R. Lewis

During the past few years there has been considerable interest in the sizing and the preparation of the iron ore fed into blast furnaces. Furnacemen know that proper sizing of ore tends to increase the efficiency of the furnace. It has been shown by Joseph1 and his associates that there is a direct relationship between the porosity of an ore particle and the time required for its reduction in the blast furnace. This relationship may be stated as follows: All other factors remainig constant, the time for reduction of a given sample of ore is inversely propor-tiofid to its porosity. As a consequence, large pieces of very porous ore, say 3 or 4 in. in cross section, will be completely reduced by the time they reach the hot zone just above the tuyeres, while large pieces of dense, nonporous ore may reach the hot zone with their centers unreduced. This means that for the latter complete reduction will be accomplished by the so-called "direct method;" i,e., where carbon reacts directly with the ore. Some recent work by philbrook2 seems to contradict this rule. He found that of two unlike ores he studied, the one with the lower porosity reduced more readily. He explained his results as "possibly due to an apparently greater tendency of the rA, ore (lower porosity) to crack during preliminary dehydration and during reduction." This brings his results in line with the rule stated above. It is not the author's intention to enter into a discussion of the merits of "direct" versus "indirect" reduction. It is enough to Say that, in general, indirect reduction is desirable. For the greatest efficiency, Gruner's theorem3 requires that all reduction in the blast furnace be indirect. Joseph seems to believe this also, because in his recent article on Some Comparisons between Iron Ore, Sinter and Nodules as Blast Furnace Feed4 he concludes that: "In genera', the carbon in blastfurnace coke is used most efficiently when the largest amount of the carbon charged reaches the tuyeres." However, P. V. hlartin,3 in an excellent paper, has shown that some direct reduction may actually increase the efficiency of the furnace; that is, increase its rate of production while maintaining maximum fuel economy. For nonporous ores there is more opportunity to have an excess of direct reduction unless the factors that make for indirect reduction are favored; for instance; the Proper sizing of the Ore particles' Another factor that has an important bearing on the reduction rate, as it is affected by particle size, is the flow of heat into the particle. The ore particle

Jan 1, 1948

By Donald B. Evans, Robert D. Pehlke

The solubility of nitrogen in liquid Fe-B alloys has been measured up to the solubility limit for the formation of boron nitride. The activity coefficient of nitrogen increases with increasing boron content in the range 0 to 7 wt pct B. From experimen -tal data, values have been calculated for the B-N interaction parameter e3 at temperatures in the range 1550" to 1750°C. A value of 0.038 has been estimated for the boron self-interaction parameter eg at 1550°C. The standard free energy of decomposition of boron nitride into the elements dissolved in liquid iron has been determined to be: ?F° = 45,900 -21.25T in the range from 1550° to 1750°C. The nitride is assumed to be of composition BN. BORON nitride has an unusual combination of properties which make it appear attractive in a wide range of engineering applications. Some of its more important and most recent applications are in the nuclear area, particularly in connection with the liquid-metal cooled reactor concept now receiving considerable emphasis. Boron nitride has a high degree of stability at elevated temperatures. It also has excellent ma-chinability and the ease with which its crystals deform suggests applications as a lubricant. These properties stem from a hexagonal layer-type structure similar to the structure of graphite. One of its primary uses to date has been for seals in liquid-metal pumping systems. It is also used in nuclear reactors as an insulating layer to separate two solid metals which are not themselves compatible under the conditions of temperature and atmosphere in which they are used. Its inertness to liquid metals has also suggested use as a mold-release agent in casting processes. In addition to its excellent machinability and reported inertness to liquid metals such as iron, silicon, aluminum, copper, and zinc, boron nitride has high thermal conductivity and excellent thermal shock resistance. This combination of properties would make it appear ideal as a refractory crucible material for refining of high-purity liquid metals, for example high-quality steels. However, since it is known that concentrations of boron as low as 50 ppm can have a marked effect on the physical properties of certain steels,' in particular on the creep and stress-rupture properties, an investigation was undertaken to define accurately the chemical equilibrium among boron, nitrogen, and liquid iron in the range of steelmaking temperatures. EXPERIMENTAL PROCEDURE Two experimental approaches to this problem were employed: a Sieverts' method and a quenching method. In the first method, the Sieverts' technique was used to measure the equilibrium nitrogen solubility in liquid Fe-B alloys of 0 to 7 pct B as a function of nitrogen gas pressure over the melt. The solubility limit of the boron nitride phase formed was determined by the point of departure of the nitrogen absorption from Sieverts' Law. This technique has been applied to liquid Fe-Ti alloys by Rao and parlee,' to liquid Fe-A1 alloys by Evans and Pehlke,3 and to solid Fe-V alloys by Fountain and Chipman.4 In the second method a melt of liquid iron was held in a crucible of boron nitride under a known partial pressure of nitrogen gas. After thermodynamic equilibrium was attained, the melt was quenched in a stream of helium and then analyzed by wet-chemical methods for boron and nitrogen. The Sieverts' apparatus used in the first method was essentially of the same design as the one described by Pehlke and Elliott.5 The charge materials were vacuum-melted high-purity iron (Ferro-vac E) supplied by the Crucible Steel Co. and -325 mesh boron powder supplied by Cooper Metallurgical Associates of Cleveland, Ohio. The boron contained less than 0.02 wt pct O, according to supplier's analysis. Recrystallized alumina crucibles were used to contain the melt. Examination of solidified melts showed these crucibles to be satisfactory with no evidence of any reaction or physical penetration of the crucible wall by the melt. The melt temperature was measured by a disappearing filament-type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diam sight hole in the crucible lid. The pyrometer was calibrated against the melting point of pure iron in the same apparatus, taking the emissivity of

Jan 1, 1964

By D. S. Hutton, W. C. Leslie

Thermal etch patterns developed on poly crystalline 3.5 pct Si-Fe by heating in hydrogen or in argon have been examined. The most prominent feature of the etching is the development of striations on grains with (100) planes near the plane of the surface. These striations are probably produced by the resoution of a random, high-energy plane into (100) facets of lower energy. THE thermal etching of iron and iron-base alloys has a long history. The phenomenon was observed by Osmondl more than 70 years ago. The literature on thermal etching between that time and 1951 was reviewed by Olney,2 and a briefer review appeared in 1958. 3 The only articles which have been found dealing with the thermal etching of silicon iron are those of Dunn and Lionetti4 and of Dunn, Daniels, and Bolton,5 and they reported only grain boundary etching. EXPERIMENTAL PROCEDURES A cast 3.5 pet Si-Fe alloy was given a metallo-graphic polish and etch, then placed in flowing purified hydrogen for 6 hr at 2200°F. The same specimen was later repolished and etched to remove the thermal etching. The specimen was then held in flowing purified argon at 2200°F for 72 hr. In both instances the specimen was rapidly cooled by being pulled up quickly into the cold zone of the furnace. All photomicrographs shown are of the surface as removed from the furnace. Oblique illumination was essential for observation of the thermal-etching effects with a light microscope and was used for all the photomicrographs. RESULTS AND DISCUSSION Grain boundary etching, grain boundary movement, and contouring within grains are illustrated in Fig. 1. The contours within a single grain followed behind the advancing grain boundary. To determine the average contour interval, or step height, white light was used in an interference microscope. The steps were of the correct magnitude to separate while light into its spectrum of colors. A green light was focused at the top of a contoured area, shifting to red across the field. By using the difference in the dominant wave length of red and green light,6 and counting the number of steps across the area, it was possible to obtain a value of about 80A for the average step height. Laue back-reflection patterns of four grains with contour lines showed that the grains had a (100) plane slightly inclined to the plane of the surface (± 5 deg). Insofar as this could be determined from their irregular traces, the contour lines within a grain had a common direction, <100> ± 5 deg.

Jan 1, 1961

Jan 1, 1910

By W. W. Stephen, J. P. Walsted, W. J. Kroll

FOR the production of carbides, various furnace types are available, especially those using arc, resistance, and high-frequency heating. Selection of a specific means of heating depends primarily on the material to be treated and the physical properties of the carbide produced. In the present case, zirconium carbide had to be prepared on an industrial scale as a raw material for the production of anhydrous zirconium chloride. Considering that a rather expensive pure oxide was to be used, the arc-furnace treatment recommended for zircon sands in a previous publication&apos; was ruled out because of the considerable volatilization and dust losses caused by the blast of the arc. For this reason, either high-frequency or resistance heating seemed to offer more promise. Since there was not enough capacity of the former available, resistance heating was chosen. It was first thought that the Acheson silicon carbide furnace would be suitable for the present purpose, but the voltage in such a furnace, in which the current passes through the batch, varies from 220 to 75 v from the start to the end of a run. This variation is so great that a special tap transformer would have been required. Trouble was also expected by local melting of the carbide. Pure zirconium carbide melts at about 3527°C, but the melting point is brought down to 2427°C, according to Agte,2 when an excess of 6 pct C is present in the carbide. This we found confirmed by experiments in a high-frequency furnace. Excess carbon is needed in the batch to obtain a complete reduction. Fusion of the charge would cause great difficulties in an Acheson-type furnace because of the good electrical conductivity of the carbide as compared with that of the loose batch. Also, fused carbide is much more difficult to chlorinate than the spongy product that can be made in the radiation furnace described below. It was apparent that, to obtain a good-qual-ity zirconium carbide, the heat input would have to be well-controlled. The hairpin-resistor principle seemed to offer possibilities in this regard, and a furnace of this type was therefore developed. The advantages of the hairpin-resistor radiation principle have been discussed in previous publications, and a split-tube graphite-resistor furnace," now increasingly used in various laboratories, as well as a centrifugal quartz melting furnace4 of this type, has demonstrated the usefulness of this heating method. The hairpin-heater element has the following definite advantages over a straight resistor of the type used, for instance, by Georges:5 Its resistance is four times greater; it can expand freely; it is sturdier because of the larger diameter, and it has a larger radiation surface; there are no hot contacts that might wear out or overheat; only one clamp is used which permits assembling all electrical leads at one side of the furnace, making the other sides easily accessible to the operator. The shorter element and its larger diameter permit greater concentration of heat. The furnace developed is shown in fig. 1. The box (I), made of 2 1/2-in. graphite plates, has inside dimensions of 23x17x16 in. It contains the briquet-ted batch (2). The box is embedded in lampblack (3) up to the cover plate. The cover plate contains an opening for the gas escape (4) and for the observation hole (5), which permits measuring the temperature with an optical pyrometer. The cover plate is embedded in charcoal (6). The lampblack is contained in the insulating brick lining (7), held in the 1/4-in. sheet steel box (8). The graphite box is set on two rows of triangular graphite bars (9). The hairpin-heater element (10), the dimensions of which are given below the main drawing, extends horizontally in the graphite chamber and radiates freely on the batch. A graphite tube (11) keeps the lampblack from falling into the slot. The split electrode, which in reality is turned 90" against the drawing, is so arranged that the slot is vertical. The water-cooled packing gland (12) is insulated by an airgap from the heater element. A thin pipe (13)

Jan 1, 1951

By Ferit Gurses

EXTENSIVE coal and lignite deposits exist in Turkey. Bituminous coal is the nation&apos;s principal mineral resource; important not only as fuel for the industrial development of the country, but also as a means of obtaining foreign exchange. Of the electrical power generated during 1939, 82.8 per cent was derived from coal.1 It is anticipated that the lignite deposits will be one of the major sources of power for the electrification of the country. BITUMINOUS COAL The locations of the four principal bituminous-coal2 basins are indicated on Fig. 1. The Eregli-Zonguldak basin lies on the Black Sea northwest of Ankara; the Canakkale basin lies near the junction of the Dardannelles; the Trakya basin is in European Turkey northwest of the Bosphorus and the Erzurum basin lies far to the east. The Eregli-Zonguldak basin is the most important of the four. This coal basin was discovered in 1829 but did not arouse interest until 1848; up to 1865, its annual production had not exceeded 50,000 metric tons. In 1865, during the Sultanate, working of coal mines was started by the Navy department, and the annual production was 61,145 metric tons. In 1908, the Minister of Commerce and Agriculture was authorized to develop the whole coal basin. Production reached 264,397 metric tons in 1910, and during 1915-1922, preceding the revolution, the total production of the basin was 2,676,043, or an average of 334,000 metric tons annually. The period of national revolution that followed was marked by a steady increase in coal production in Turkey, although world production decreased, because of the crisis of 1929-1932, about 52 per cent. AREA AND GEOLOGY OF THE COAL BASIN The geology of the Eregli-Zonguldak area is not yet completely known. The basin begins at Gungazi, to the west of Eregli, and extends to Sogutozu, a distance of about 106 miles. The coal beds, however, appear only in places and the overlying Cretaceous strata hide them elsewhere. This area includes the most important centers, such as Kandilli, Alacaagzi, Teflenli, Kozlu, Gelik (see Fig. 2). The geological sequence of the district is correlated with the Cretaceous of the Balkans; which is, in turn, a prolongation of the Alpine zone. Geological surveys made by G. Ralli, R. Zeiller and P. Arni3 show that the Eregli-Zonguldak formations fall into three natural divisions. Series a, The Alacaagzi in the district of that name (Fig. 2), is of the Culm stage. The strata strike generally east-west and dip about 30° south. This series appears also around Kandilli and Camli, with a steeper angle of dip, but the deposits there lack regularity. The Alacaagzi stage appears also farther east, to the south of Kozlu and Gelik. The Alacaagzi series contains 15 seams of an average thickness of 2 ½ ft. of good coal. Series b, the Kozlu, best represented in Zonguldak, Kilimli, Catalagzi, and between

Jan 1, 1944

By Francis M. Walters

IN spite of the war and the preoccupation of many physical metallurgists with work on secret or confidential problems, definite progress was made during 1944 in our understanding of the behavior of steel and of the effect of alloying elements. During the first two years of the war there was much concern over the possible unavailability of certain alloying elements; this period saw the development of the N.E. (National Emergency) steels. However, the measures taken eased the alloy situation and currently, highly practical problems under study are the graphitization of low-carbon steel and weld-cracking, while investigations of more theoretical interest have concerned hardenability, isothermal reactions, the effect of hydrogen and the interpretation of the notched-bar impact test.

Jan 1, 1945

By A. J. Griest, J. C. Danko

IN the course of vacuum evaporation experiments, sublimation figures were observed on the surface of a pure nickel specimen. A cubic figure, typical of those observed on this specimen, is illustrated

Jan 1, 1957

By Robert A. Stansbury

Keeping development ahead of retreat mining is a problem which occurs nearly everywhere longwall mining is used in the United States. As improved equipment technology has allowed the application of longwall mining to more difficult mining conditions, and with higher retreat rates, the problem has become more critical. Many factors determine development speed, including roof and floor conditions, mining heights, seam heights, and the number of entries. In an effort to maximize the rate of development and production from development sections, U. S. Steel&apos;s Gary District has used five entry, three entry, four entry and is planning two entry development panels at its different mines. With the introduction of various types of shield supports, it is now possible to utilize longwall mining in higher coal over 3 meters (10 feet), lower coal under one meter, in difficult roof conditions, and with soft floor. Improved shearers of 300 KW (400 HP) and more make cutting heights over 3 meters (10 feet) possible, and off pan shearers and improved Gleithobel plows make cutting less than 1 meter (40 inches) seam height possible. Longwall mining under these conditions puts an added strain on the ability to develop panels as fast as they are retreated. Poor roof conditions require a substantial amount of additional roof support to ensure that roof control in the head and tall entries will not hinder longwall retreat. The additional measures of longer bolts, resin bolts, point anchor resin bolts, roof mats, roof trusses, steel or wood cross bars, and roof grouting all place an additional burden on man power, installation time, and cost on the mining cycle. Additional roof bolting on development can cut the potential mining rate in half, and any roof falls cause significant delays to mining. Timbers and cribs can restrict ventilation and require more entries. Soft floor conditions can greatly impede development through tramming difficulties with shuttle cars and roof bolters, time required for cleaning and repairing roadways, and maintenance difficulties on equipment. High coal sometimes requires rib support to be Installed during the mining cycle, further cutting the mining rate. Mining low seams requires that roof or floor be mined in the head and tail entries as well as the track or tractor roadway entry to provide clearance of the longwall equipment. Mining this rock slows down the mining rate because of the extra material being mined and the extra wear and tear on equipment. To a large degree these conditions effecting development speed cannot be controlled.

Jan 1, 1981

By L. D. Ricketts

AN older man looks back, perhaps wistfully, on a long and rather active experience, and possibly a popular and brief glimpse of some contrast between past and present may hold your attention for a few brief moments and prove useful. In the late nineties an engineer was .called on to de- sign and build two copper ore concentrating mills of 400 tons average daily capacity. There were larger mills than this at Washoe and elsewhere, but a 400 ton&apos; mill was a large one as mills went over thirty years ago, and one might say a large mill of those days could crush a ton of copper ore in 216 seconds. In the mills I refer to steel construction and the conveying belts were introduced into the copper industry and rein- forced concrete came shortly after. Since then we in the West have ever been faced with a constantly de- creasing tenor in the grade of our copper ores and a constantly increasing demand for our product, and we have therefore been obliged to call for far larger castings and finished machines than were formerly used. The mechanical engineer has also enabled us to accomplish notable economies in power generation and distribution. Ore handling and crushing have been simplified and through the introduction of reagents to induce physical or chemical reactions, or both, our older methods have been vastly improved or even supplanted by new and better ones and our recoveries greatly improved.

Jan 1, 1929

By F. E. Smith, David R. Mitchell, B. M. Bird

DENSE-MEDIA processes utilize the familiar laboratory float-and¬-sink procedure on a commercial scale. Just as wood chips float on water and sand sinks, so coal floats and refuse sinks when placed in a medium intermediate in specific gravity between the coal and refuse. Liquids intermediate in specific gravity between coal and refuse used in commercial plants are of four types: (1) Organic liquids of high specific gravity-halogenated hydrocarbons; (2) dissolved salts in water; (3) pseudo liquids obtained by suspending solids, such as sand, in water, and (4) fluidizing a mass of sand or other solids by air currents. Those most widely used for cleaning coal are solutions of calcium chloride in water and a suspended-sand pseudo liquid. Laboratory float-and-sink testing is an intermittent operation during which every opportunity is given for particles lighter than the medium to float and particles heavier to sink. Commercial processes are con¬tinuous, vertical and horizontal currents of the separating medium occur as either part of the process or unavoidedly produced by the intro¬duction of feed and withdrawal of products, so that the exact separation of the laboratory technique is not duplicated by commercial processes. However, separations close to the theoretical are obtained in commercial machines by careful technical control of the process. Most machines in commercial installations are crowded to get as much out of the equipment as possible, so that careful technical control is necessary to get the recoveries and grade of product desired. Sizes usually cleaned are plus %6-in. or plus 3-in. in the United States and plus 36-in. in Great Britain. Coal as small as 1 mm. has been cleaned in some experimental installations. The separation of coal from refuse in sizes finer than about % in. is made difficult by viscosity effects and hence at the present time cleaning is confined to the coarser . sizes. Technical advances in the art of cleaning coal by dense-media

Jan 1, 1943