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By L. W. Rowe, S. S. Cole

A laboratory bench scale unit is described whereby finely divided chlorinatable residues are held for a short period by a restraining bed of a coarse-grained ore of comparable composition to permit 'flash' chlorination of the high surface area powder. Results on chlorinating a finely divicled titania residue using rutile sand as the restraining bed showed that 92 pct utilization of chlorine and equivalent conversion of TiO2 in the fine residue to Ticl4 were attained with a dust loss of about 3 to 4 pct and an equivalent amount of ch1om'nation of the titanium values in the restraining bed. THE chlorination of coarse grain titaniferous ores; i.e., 20 to 150 mesh sizes in fluidized beds is practiced commercially.' One effective method found for the chlorination of a very fine material in a fluidized bed is the "flash" chlorination technique.' By charging the finely divided charge material into the bottom of an established bed of optimum sized rutile, ilmenite, titanium beneficiate, or even an inert material such as sand, chlorination occurs before the dust can pass through the bed. The major requirement is that the bed be less chlorinatable than the charge. In this process, the charge consists of a finely divided (between one and 50 µ) titania residue obtained from a titaniferous ore beneficiation process. The charge is blended with a 20 pct wt basis addition of 20 to 60 .mesh size low volatile coke (to minimize hydrogen chloride formation) and fed to the bottom of the bed with the chlorine gas stream. A ball check device is used to permit entry of the charge and prevent the bed from discharging when the gas flow is cut off. The coarse pieces of coke serve to reduce compaction in the charge mixture and permit sat]sfactory feeding without plugging or jamming. Feed and gas rates are adjusted to provide for complete reaction of the charge material, with 90 to 95 pct chlorine efficiency, and maintain a gas flow in the range of 0.4 to 0.6 ft per sec. The equipment consisted of a 3-in. diam mullite tube enclosed in an electric furnace. A bow-shaped 3/4 in. Saran tube fed the charge from an air lock type of feed hopper (to prevent the escape of the chlorine gas into feed bin) to the bottom of the bed. The charge rate was set by providing a small awiliary hopper below the feed hopper where a weighed portion of the charge could be discharged in a specified time interval into the main chlorine stream. The chlorine rate was measured by a flowmeter. The reaction tube was filled with a bed of Australian rutile ore, this restraining bed serving two purposes; i.e., it rapidly heated the fresh charge to the reaction temperature and retained the particles in the bed for a sufficient time for selective chlorination to proceed. Due to the fine particle size and open, porous structure of the charge, this reaction was almost instantaneous, and, with proper adjustment of feed and gas rates, very little fine material passed through the bed without reacting and only a very small fraction of the restraining bed was chlorinated. A typical reaction procedure was to fill the bench scale fluidized bed unit with a 1 kg charge of Australian rutile ore analyzing 95.5 pct TiO2, 0.6 pct FeO, a beach sand deposit 40 to 150 mesh size. When fluidized, the bed was approximately 2 ft in depth. The ore was fluidized with a 1:l mixture of chlorine and nitrogen at a rate of 0.40 ft per sec. This gas mixture was necessitated by the comparatively short bed depth; a larger unit, with a deeper bed, could be fluidized with chlorine alone without significant free chlorine loss. Feed rate was 8.0 g per min of beneficiated ilmenite analyzing 85.0 pct TiO2, 2.6 pct FeO plus 1.6 g per min of 20 to 60 mesh petroleum coke. The

Jan 1, 1962

By John D. Price

R. W. Campbell (Jones and Laughlin Steel Carp., Pittsburgh)—As usual John Price has presented an excellent paper. I know of no one who has devoted more time and conscientious thought to this subject than he has, and his efforts have produced scientific data and conclusions of real value. Results of similar studies made by the Jones and Laughlin Steel Corp. on the blending of Pennsylvania coals may be of interest. During 1935 the late F. W. Wagner and the present writer developed an empirical physical fuel value formula for evaluating the combined physical tests of metallurgical coke, see Table IV. In the development of the formula, the tumbler test, shatter test, screen test, and porosity of coke have been taken into consideration. Each of these tests brings out some physical property not expressed by the others, and in estimation of the importance of these tests as a medium for evaluating coke for the blast furnace, their worth has been graded as follows: It was thought that some additional penalty should be applied to cokes that do not show a uniform screen size, assuming that coke larger than 4 in. was not desirable and that this size was an indication of irregular size. Therefore the screen test factor is further corrected by applying a penalty of 1 pct for each 1 pct material greater than 4-in. size as shown by the screen test. The physical fitness of coke for blast furnace use depends upon four fundamental characteristics: l—gen-era1 strength, as indicated by the shatter test; 2— abradability, or the resistance of cell walls to reduction in size by attrition, as indicated by the tumbler test; 3—porosity; and 4—size and uniformity. Each of these characteristics is not of equal importance, but surely, in an attempt to determine an accurate physical value, the individual value of each should be taken into consideration. The formula is used as a yardstick, so to speak, in determining variations in the normal production of metallurgical coke and in making comparisons between normal coke and experimental blends with other coals. Table IV gives results of coking tests on raw and washed high volatile coals and these same coals with blends of coke breeze, anthracite coal, char and low volatile coals, all from Pennsylvania. The table also gives the source of the coals and coke breeze, as well as their proximate analyses. It will be noted that the washing of the raw high volatile coal increased the physical fuel value from 26.17 to 39.16, showing the effect of removing shale and slate which produces a detrimental fracturing and weakening of the coke. It is a well known fact that many Pennsylvania high volatile coals contain an excess of resinous material or binder which has a tendency to weaken the coke, owing to its high evolution of gases during carbonization. Tests were therefore made with coke breeze, an inert material, in an attempt to alleviate this condition. Blends of washed coal with 5 pct and 7.5 pct coke breeze collected from the coke plant quenching sump (82.9 pct through 1/8-in. screen) resulted in cokes with a physical fuel value of 20.75 and 16.73 respectively, lower than results obtained from 100 pct raw high volatile coal. It will be noted that the percentage of + 4-in. coke increased but that the tumbler test was very low. Undoubtedly better results could have been obtained if the coke breeze could have been crushed extremely fine. During World War II the government asked the coking industry to consider the use of anthracite coal as a substitute for high quality low volatile coal, which was extremely scarce at the time. The next series of tests was made with blends of raw and washed high volatile coals and 5, 10, and 15 pct Pennsylvania No. 5 buckwheat anthracite (100 pct through l/8-in. screen). It was necessary to use some raw high volatile coal in these blends because of insufficient washer capacity at the time. It will be noted that the physical fuel values

Jan 1, 1954

Edward Dyer Peters, the only child of Henry Hunter Peters and Susan Barker Thaxter, was born in Dorchester, Mass., June 1, 1849. From his father he was a descendant of the Peters family of Ipswich and Andover, Mass., whose earliest ancestor settled in Essex County in 1659; while upon his mother's side he descended from several old Hingham families, as well as from the Quineys and from Governor Bradford. Between the ages of fourteen and sixteen he was a student at the Episcopal School for boys in Cheshire, Conn. Near the school was an old tin mine, and he used to spend his Saturday afternoons exploring it. When Edward was sixteen, his father sold his property in South-borough, and for the next three years lived in Europe. Sept. 26, 1865, Edward entered the Royal School of Mines at Freiberg, Saxony. In the summer of 1867 he joined his family on Lake Geneva, and spent a part of the season in that vicinity, going to Chamounix and taking other trips. Extract from a letter to his father: Elbingerode, Harz, Aug. 30, 1868: I left Freiberg with my friend Lilienthal, on Wednesday the 19th of August, reached Leipzig in the evening and spent the night in that city: the next morning we took the cars and in the afternoon reached Eisleben, in Prussia, which was to be our first stopping-place; there are immense copper-mines and smelting-works at this place, and the method of working the mines is very peculiar ... The next morning we got up at five and spent the whole day in the smelting-works where I obtained a number of drawings of the furnaces they use here and a good many valuable data. Saturday morning we got up at four o'clock, and descended a mine about three miles from the town; the Director of this mine was one of the most intelligent and agreeable men that I ever met; he accompanied us in the mine and explained everything that was new to us. The system of mining at Eisleben is peculiar to this town, and is not used at any other place in the world; the copper ore comes in narrow, flat veins eighteen inches high, at the utmost, consequently the men work lying flat on their left side and using the pick with both hands: the ore is carried out of the side passages into the main ones, in very low waggons about twelve inches high, and four by two feet; the boys who pull these waggons have a board buckled to their left thigh and their left arm; they pass their bare foot through a strap in the waggon and wriggle along on their side dragging the waggon after them, with their foot, almost as fast as a man can walk above ground. In the afternoon we walked over to Hittstadt, about twelve miles, and remained there Sunday and Monday. Monday night, at ten o'clock we went out to one of the smelting-works, to see the refining of the copper; this is only done at night, so we worked there from ten in the evening till eleven the next morning, and came home all blackened up and with blistered hands, for our skin was not quite so tough as that of the workmen: at noon the same day we took the stage to Ascherls-leben, and then the train to Stassfurt, where there are immense salt-mines, as well as factories for the manufacture of bromium, which latter process is, however, kept a profound secret, so we had very little hope of seeing anything but the salt mines; we were talking with our landlord about our disappointment, that evening, when he told us that the director of the Bromium works was sitting in the next room with no company but his glass of beer, so we went over to him, introduced ourselves as Americans, and actually succeeded in persuading him that it could do his business no earthly hurt if he showed us his works; at last he consented, after making us give our word of honor

Jan 1, 1919

By R. M. S. B. Horta, W. T. Roberts, D. V. Wilson

Evaluation of results obtained by the Harris method for inverse pole figures is discussed. Two existing analyses and a new approach are compared. In the most frequently used analysis, different reflections are accorded equal weight. A second method involves area-weighting of reflections, mainly to take account of nonuniformity of Pole distribution. In the new method, reflections are weighted according to their multiplicity factors. Intensity ratios obtained from a sample of steel sheet by the three methods are compared. INVERSE pole figures offer a convenient method of depicting the proportions of material with various orientations referred to a unique specimen axis. The technique was first applied to fiber textures, but it is now frequently used as a description of texture in sheet metal, the unique axis in this case usually being the sheet normal. The Harris method' for the determination of inverse pole figures has the great merit of simplicity. It suffers certain intrinsic limitations, but provided that these are borne in mind, the results allow useful conclusions to be drawn regarding the effects of texture components on certain mechanical properties. Much thought has been given to alternative methods of texture description, aimed at eliminating the ambiguity in the simpler methods.2"6 Refinements in the method of description are obtained at the price of increasing complexity, and it seems clear that a simple method, such as that of Harris, will continue to find application. The original derivation by Harris1 has been corrected by Morris7 and later by Mueller, Chernock, and Beck.2 Since the latter reference is more accessible, it is referred to more frequently than the work of Morris. Most users of the inverse pole figure method present their results on the basis of the treatment by Mueller et al., and it is the purpose of the present communication to comment on this treatment and to suggest a simple modification to the method of presentation which enhances the meaningfulness of the results. It will be convenient first to summarize the Mueller analysis as follows: The intensity Ihkl of a hkl reflection from a textured specimen is: Ihkl=CI0AL\Fhkl\2NhklPhkl [1] where C is a constant for a given sample I, is the intensity of the incident beam A is an absorption factor. With usual diffrac-tometer geometry and a flat specimen, A is inversely proportional to the density of the specimen. L is the Lorenz polarization factor Fhkl is the structure factor for the hkl reflection Nhkl is the multiplicity factor phkl is the fraction of crystals in the polycrystal-line aggregate with any particular (nkl) plane parallel to the surface. The corresponding equation for a specimen with randomly oriented grains is lR,hkl=CRl°ARL\fnkl\2Nnklk [2] the subscripts R indicating the factors that are different for the random sample, which will, in general, have a density different from that of the textured one. The intensity ratio is hkl , c A Phkl [3] IR,hkl CR AR PR The constants are eliminated by summing over all the measured reflections ^iRMi °R AR PR ljPkkl and from Eqs. [3] and [4] T IR,hkl The only unknown in Eq. [5] is Yj phkl and before this can be evaluated, it is necessary to adopt some form of normalizing procedure. Mueller et al. assume that when a large number, n, of reflections is used, the average value of p as defined by Eq. [6] below will be unity ? = £j**l3l [6] and the final result of their analysis follows: hkl Pkkl = i I&Jf~ [7] ±y* Ihkl ^ in,hki The normalizing procedure used by Mueller et al. involves an unrealistic assumption since it gives equal weight to each of the hkl reflections. Other normalizing procedures can now be examined with a view to selecting a more appropriate one. For an infinite number of reflections, the function p can be averaged over a continuous range of orientations covering the complete solid angle 4p by the integral relation: p =1 jp(a)dQ = l [8] This is the only exact procedure, but in practice a

Jan 1, 1970

By B. Yarar, J. Kaoma

[Introduction The critical surface tension of wetting of hydrophobic materials has been investigated extensively by Zisman et al. (1973) and relates the spreading of a liquid on a solid to the surface tension of this liquid. Thus, the Zisman ap¬proach shows that a plot of Cos 0 versus ?LV where, 0 is the contact angle and ?LV is the surface tension of that liquid in contact with its own vapor at equilibrium, produces a straight line which can be extrapolated to Cos 0 = 1. The intercept corresponds to a given ?LV, termed the critical surface tension of wetting. In instances, however, Cos 0 - ?LV plots show deviations from linearity. Alternative approaches have also included the plotting of adhesion tension (YLV COs 0) versus ?LV that can be interpreted in terms of critical surface tension data (Lucassen-Reynders, 1963). It has, on the other hand, been customary to correlate contact angle (0) with flotation data, although it is recognized that surface inhomogeneities and related contact angle hysteresis limit the interpretations pertaining to solid surface structures purely based on contact angle measurements. It is nonetheless true that 0 = 0, when the liquid is water, corresponds to a hydrophilic solid. Determination of ?c by contact angle measurements in conformity with the Zisman approach can encounter experimental difficulties, especially when solids are in a powder form. Following the reasoning that 0 = 0 corresponds to the hydrophilic state of a solid, froth flotation experiments can be expected to produce critical surface tension of wetting values for powders. The technique that consists of plotting recovery (% R) versus YLV data and extrapolating the linear part of the curve to % R = 0, has been described elsewhere (Yarar and Kaoma, 1984). This paper describes some of the results obtained by the extrapolation technique mentioned above, using various sulfide minerals. Experimental Materials Molybdenite (MoS2), sphalerite (ZnS), chalcopyrite (CuFeS2), chalcocite (Cu2S), and galena (PbS) were handsorted from massive samples and ground by mortar and pestle, and the -147 Fan fraction used in experiments; sulfur (S) was a C.P. Fisher Scientific Co. product. Method One gram powder samples were conditioned for three minutes in methanol-water solutions of predetermined surface tension values and the percents recovered by flotation using a Partridge-Smith Cell (Partridge and Smith, 1972), were plotted against each ?LV value. Results and Discussion The percent recovery versus ?LV for two naturally hydrophobic solids, i.e., natural molybdenite, MoS2 and sulfur are given in Fig. 1 where it is seen that ?c for sulfur is obtained as 31.5 mNm-1 whereas for MoS2, it is 26 mNm-1. Figure 1 also shows that the new flotation technique described, for estimating ?c is in good agreement with the Zisman method. Curves obtained by the same method for the minerals Cu2S, PbS, and ZnS are given in Fig. 2, where it is seen that for Cu2S, ZnS, and PbS, the extrapolation to % R = 0 produces ?c values of 36, 39, and 49 mNm-1, respectively. CuFeS2, on the other hand, gives a curve that does not permit such an extrapolation to obtain a ?c value with certainty. Nonetheless, treatment of the powder with 8.95 X 10-5 molar Na2S solution followed by washing with distilled water prior to flotation effects the curves as shown in the insert of Fig. 2. The type of curves given in Fig. 1 appear to be typical of hydrophobic solids as can also be observed in Fig. 3. The composition of solid and minute quantities of inclusions seem to play an important role as regards the surface properties of solids as reflected by the slope of the linear part of the % R - ?LV plot and thus the value of ?c obtained by this technique. For example, MoS2 of three different stoichiometric compositions produced the data given below. [MoS2MoS2.14Mo1.002S2 ?c mNm-126.029.031.0 dR/d?8.95.23.0]]

Jan 1, 1985

By executive order of the President, dated June 25, 1918, the investigation of matters relating to gas warfare, which had been initiated by the Director of the U. S. Bureau of Mines early in 1917, and had been continuously maintained and improved since, that time, was transferred to the recently created Division of Gas Warfare of the War Department. On the occasion of this transfer, both the President and the Secretary of War took occasion to speak most highly of the efficient service that had been rendered by the Bureau of Mines. It gives us great pleasure to reproduce here a letter from the President and from the Secretary of War, bearing on this subject and also to append a brief review of the work of the Bureau of Mines, prepared by its Director, Mr. Van H. Manning. The White House, Washington. June 26, 1918. MY DEAR MR. MANNING: I have had before me for some days the-question presented by the Secretary of War involving the transfer of the chemical section established by you at the American University from the Bureau of Mines to the newly organized Division-of Gas Warfare in which the War Department is now concentrating all the various facilities for offensive and defensive gas operations. I am satisfied that a more efficient organization can he effected by having these various activities under one direction and control, and my hesitation about acting in the matter has grown only out of a reluctance to take away from the Bureau of Mines a piece of work which thus far it has so effectively performed. The Secretary of War has assured me of his own recognition of the splendid work you have been able to do, and I am taking the liberty of enclosing a letter which I have received from him, in order that you may-see how fully the War Department recognizes the value of the services. I am to-day signing the order directing the transfer. I want, however, to express to you my own-appreciation of the fine and helpful piece of work which you-have-done, and to. say that this sort of team work by the bureaus outside of the direct war-making agency is one of the cheering and gratifying evidences of the way our official forces are inspired by the presence of a great national task. Cordially yours, Dr. Van. H. Manning, WOODROW WILSON. Chief, Bureau of Mines, Department of the Interior. War Department, Washington, June 25, 1918. MY DEAR MR. PRESIDENT: In connection with the proposed transfer of the chemical section at. American University from the Bureau of Mines to the newly constituted and consolidated Gas Service of the War Department, which you are considering, I am specially concerned to have you know how much the War Department appreciates the splendid services which have been rendered to the country and to the Army by the Department of the Interior, and especially by the Bureau of Mines under the direction of Dr. Manning. In the early days of preparation and organization, Dr. Manning's contact with scientific men throughout the country was indispensably valuable. He was able to summon from the universities and the technical laboratories of the country men of the highest quality and to inspire them with enthusiastic zeal in attacking new and difficult problems which had to be solved with the utmost speed. I do not see how the work could have been better done than he did it, and the present suggestion that the section now pass under the direction and control of the War Department grows out of the fact that the whole subject of gas warfare has assumed a fresh pressure and intensity, and the director of it must have the widest control so as to be able to use the resources at his command in the most effective way possible. The proposal does not involve the disruption of the fine group of scientific men Dr. Manning has brought together, but merely their transfer to General Sibert's direction. Respectfully yours, NEWTON D. BAKER.

Jan 9, 1918

By Antoni Kidybinski

Mechanical properties of the nether roof rocks play a substantial role in maintenance of mine openings. On longwall faces too low strength is a cause of rock- falls which bring about delays in face advance, and hazard to the miners, while too high strength may result in over hanging of roof rocks in gobs, sometimes over a large area, initiating dynamic periodical pressures. Hence, efforts have been undertaken to develop methods of caveability evaluation for proper selection of roof control system and of longwall-face supports. DESCRIPTIVE CLASSIFICATIONS One of the basic qualitative criteria for classification of roof types with different caveability is the criterion of geological structure. The 26-stages scale worked out for conditions of Donetz Coalfield. USSR, by E.T. Proyavkin et al.(l) may be an example of that type of classification. This scale is presented graphically in Fig. 1. The first types of roofs according to this scale are easily caving immediately after exposure of a small surface, while the last be- long to the strongest roofs which over-hang in waste and require artificial fracturing. Observations and measurements carried out also in Donetz mines lead W.T. Davidyanc (2) to following classification: Class I - weak and densely bedded rocks very easily caving after each advance of supports. The roof subsidence over a waste edge is: [ ] where: h is roof subsidence, m M is thickness of the seam being mined, m S is width of an opening, m Class II - medium caveability and small main roof movements [ ] Class III - hardly breakable rocks, thicker beds with higher strength: caving by large blocks. After exposure of larger roof surfaces the movements of the main roof strata may affect an opening. [ ] Class IV - very hardly breakable rocks - thick, monolithic sandstones: they cause considerable difficulties in working with caving. [ ] Class V - thin-bedded rocks featured by the capacity of a smooth subsidence without disintegration into loose blocks with keeping contact between the particular blocks in a bed. In this classification mining with full roof caving is recommended for class I-III and only exceptionally for class IV. In many coal fields, qualitative and quantitative observations of roof rocks behavior have been carried out: as a result relations and characteristics found in certain mines are given. As an example, Kizielov Coalfield data in the USSR given by B.S. Vinokur (3) may be mentioned. In working thin pitching seams man- less system of undercutting the seam by means of rope saw is used there. The author separated four classes of roofs and gave, for every class, the empirical relation between the extracted area and the time of roof stability. The size of the stable area of exposed roof for particular classes is as follows: 120 to 150 m2 (1291 to 1614 ft2 ), 170 to 200 m2 (1829 to 2152 ft2), 250 to 280 m2 (2690 to 3013 ft2 ) and 350 to 400 m2 (3766 to 4300 ft ). For Kuznetz coalfield in the USSR the following classification of roofs was developed at the WIMI Institute in Leningrad: Class I - completely unstable: impact strength in- dex of rock f = up to 1.5 - the strip of roof 1.4 to 2.0 m (4.59 to 6.56 it) wide, exposed after shearer's cut holds stable during the time not longer than 5 min. Class II - low stability: f = 1.5 to 2.5 - the strip of roof 1.4 to 2.0 m (4.59 to 6.56 ft) wide and up to 4.0 m (13 it) long, exposed after shearer's cut holds stable during 5 to 20 min. Class III - medium stability: f = 2.51 to 3.5 - the strip of roof 1.4 to 2.0 m (4.59 to 6.56 it) wide and 4.0 to 25 m (13 to 82 ft) long, exposed after shearer's cut holds stable from 20 min. to 2 hours. Class IV - stable: f = 3.51 to 4.5 - the strip of roof 1.4 to 2.0 m (4.59 to 6.56 ft) wide and 25 m (82 it) long exposed after shearer's cut is stable during the time longer than 2 hours. Class V - entirely stable: f = over 4.5

Jan 1, 1982

By A. H. Daane, B. J. Beaudry

The Sc-Y and Sc-Zr systems were studied by thermal and X-ray methods. Both systems are characterized by complete solid solubility in the low temperature hexagonal form and in the high temperature bcc form. In the Sc-Y system, there is a minimum in the solidus at 50 at. pct and 1365°C, while the solidus in the Sc-Zr system follows a nearly straight line relationship between the melting point of scandium and zirconium. There is a minimum in the temperature of transition from hexagonal to bcc in the Sc-Y system at 43 at. pct Y and 1175°C; while the temperature of transition is raised in the Sc-Zr system to a maximum of 1415 °C at 30 at. pct Zr. INTEREST in the metals of the first transition series has usually stemmed from their useful properties; however, there is now a great deal of interest in determining the fundamental nature of these metals. Since scandium is the first of these transition metals, a study of the preparation and Properties1 and the alloying behavior of scandium2 was initiated. In a continuing study of the alloying behavior of scandium, the systems of scandium with zirconium and yttrium have been established. Extensive solid solubility in both the Sc-Zr and Sc-Y systems was expected from application of the classical rules of Hume-Rothery. Also, the modified Darken and Gurry plot as suggested by Gschneid-ner3 showed ideal conditions for solubility in the Sc-Zr system with less favorable conditions in the Sc-Y system. The effect of scandium on the transformation temperature of zirconium and yttrium was of interest, since a recent empirical observation by Uly and Burr4 predicted that the solute scandium would raise the transformation temperature of zirconium and lower the yttrium transformation. In addition to noting the validity of the above predictions, the SC-Y and Sc-Zr systems were established. EXPERIMENTAL METHODS Materials. The metals employed in this investigation were crystal bar zirconium, distilled scandium prepared by the method described by Spedding, et al.1 and yttrium prepared by the method described by Carlson, et a1.5 The major impurities present in these metals are listed in Table I in ppm. Alloy Preparation. All the alloys examined were initially formed by comelting the two metals in a nonconsumable electrode arc-melting furnace under an atmosphere of purified helium or argon. The buttons were inverted at least five times and re-melted each time to ensure homogeneity. During preparation of Sc-Zr alloys, approximately 1 wt pct was lost which was attributed entirely to the loss of scandium by distillation. When preparing Sc-Y alloys, approximately 1.5 wt pct was lost, but it was assumed that the intended composition was maintained, since the relative weight lost when arc melting the component metals was nearly the same. Samples weighing 15 to 20 g were prepared for time-temperature thermal analysis, while only 1- to 2-g samples were prepared for the optical pyrometer and X-ray diffraction studies. Thermal Methods. The solidus and the melting points of the metals were determined by an optical pyrometer method described previously.2 The temperatures at which the transformation from hexagonal to bcc occurs were determined by differential thermal analysis. Several points on the solidus and liquidus in the Sc-Y system were also determined by this method and are in good agreement with those obtained by the optical pyrometer method. The procedure followed in the preparation of samples for thermal analysis and the furnace used have been described elsewhere.2'6 Since a limited quantity of scandium was available, most of the alloys were not melted during thermal analysis, thus avoiding contamination by the crucible. The alloy could then be reused and the composition changed by adding the desired quantity of solute to obtain the next alloy. Heat Treatment and X-Ray Methods. In order to ensure homogeneity, the "as arc-melted" alloys Were wrapped in tantalum foil, sealed in quartz capsules and heated at 1100°C for 15 hr and then cooled at a rate of 8 deg per min. Samples for X-ray diffraction were filed from these heat-treated alloys, sealed in 1/8 in. by 1/2 in. tantalum capsules under

Jan 1, 1963

By D. E. Wolfson, D. A. Reynolds, F. W. Smith

IN 1948 the U. S. Bureau of Mines began a three-phase program to evaluate the extent and quality of U. S. coking coal: 1) a factual appraisal of known recoverable reserves in beds of mineable thickness, 2) a study of preparation characteristics, and 3) a study of carbonization properties. A previous paper presented the methods used in assessing reserves.' Although this investigation is only partly completed, data on coking properties of the Pittsburgh district coals are now available. The results are presented in this article. When coals are selected for manufacture of metallurgical coke more factors must be considered than for any other major use, as no basic industry requires coal of such high quality and uniformity. This is particularly true in the Pittsburgh district, where blast furnace practice is based on use of cokes from high quality coals. Although it is true that inferior coals are carbonized in other industrial areas, both here and abroad, the Pittsburgh coals are the best economically obtainable in the required tonnages, even though they are not the most desirable for metallurgical use. In the general evaluation of suitability of coals for coke making, particular attention is given to: 1) reserve, 2) ash and sulfur content, 3) inherent properties of forming strong, well fused coke, 4) expanding characteristics, and 5) blending properties. Items 1 and 2 are covered in detail in the first two phases of the survey, and coking behavior is considered in items 3 through 5. Problems is Coal Evaluation: Although not all coal beds of immediate or potential use to the coking industry in the Pittsburgh area have been tested for their coking properties, enough tests have been made to permit certain generalized statements. Virtually all the coals that will be used in this district are from the Appalachian region, and except for high oxygen coals from outcrops or stripping operations, they are coking coals. Hence the evaluation problem is not so much that of distinguishing between coking and noncoking coals as attempting to measure quantitatively differences in the coking and expanding properties of the better coking coals. Quantitative differentiation between good coking coals, is complex, since differences in their coking abilities are frequently of about the same magnitude as the precision of the test. Small-scale tests are generally unsuitable for measuring these slight differences, and there has been gradual acceptance of pilot-scale tests. Test Methods Employed: All the data reported here were obtained in two units known as the Bureau of Mines-American Gas Association (BM-AGA) carbonization apparatus and the sole-heated expansion oven. The BM-AGA unit, which consists essentially of a cylindrical steel retort about 18 in. diam and 26 in. high, carbonizes enough coal (180 lb) to allow evaluation of the coke by standard methods of the American Society for Testing Materials. The BM-AGA carbonization procedure and methods of testing the gas, liquid, and solid products have been described.' Expanding characteristics of the coals were determined in the sole-heated expansion oven," wherein the coal charge, heated from the bottom only, is carbonized under a constant applied force and the linear expansion or contraction is measured. Although results in this oven have never been quantitatively correlated with the expansion behavior of coals in conventional slot ovens, they are useful in assessing expansion behavior. In this report discussion will be confined to results obtained from these pilot-scale units, although the following data are available for most coals: proximate and ultimate analyses, free swelling index, agglutinating value, and plasticity. Sources of Coals Tested: In selection of coals for coke manufacture, economic considerations are as important as quality, and each coke plant balances these two factors to meet requirements of the most satisfactory coke at lowest price. Although these economic factors may in some instances outbalance small differences in coke quality, they are usually specific to each coke plant and cannot be given in any general statement. Recognizing that coal and plant operating costs are beyond the scope of the survey, the USBM evaluates the coking quality of various coals without regard to their competitive economic status. For the purpose of this article, coals of interest to the Pittsburgh district are arbitrarily defined as

Jan 1, 1958

By R. F. Mehl, C. E. Birchenall

SINCE Maxwell1 first considered the self-diffusion process in 1872 its importance in the kinetic theory of matter has been recognized. Until the discovery of isotopes in 1913, a direct measurement of this quantity seemed impossible. The only information that could be gathered indirectly was for gaseous systems for which the kinetic theory was well developed. When methods of direct observation be-came available, investigations on self-diffusion were carried out in condensed phases. In metals these data are presumably of potential importance in the study of recovery, recrystallization, creep, sintering, and related phenomena. Following the pioneer work of Von Hevesy2 and his collaborators, who determined the rate of self-diffusion in lead with the naturally occurring thorium B isotope, several metals have been investigated. Pb, Ag³, Au.6,5, and Cu6,7,8,9 are examples of isotropic crystals existing in only one phase modification. Anisotropy of diffusion has been demonstrated in Bil6 and Znll. This paper is a study of a single metal in two allotropic forms and also of self-diffusion in a body-centered cubic lattice. Despite the fact that the measurements in each of the papers cited on self-diffusion in copper seem to be internally consistent to about 10 to 15 pet, the curves reported by different authors differ by factors of 2 to 4 at the same temperatures. This uncertainty may account, in part, for the failure to establish a successful correlation between the self-diffusion rates and other physical characteristics of the metals. No satisfactory theory of metallic self- diffusion has as yet been proposed to account for all the existing data and to permit estimation in other metals. Experimental Part: Two units of radioactive iron were used in these experiments, each a mixture of Fe53 and Fe59 (12). Fe53 decays by K electron capture and the emission of an X ray with a half life of about 4 years. Fe59 emits two beta spectra, one with a maximum energy of 0.26 Mev, the other 0.46 Mev, and gamma rays of 1.1 and 1.3 Mev, with a half life of about 44 days. They were present in nearly equal concentration initially. The composite half life started at about 50 days and increased as the Fe59 decayed, leaving Fe55 relatively more abundant. After aging a year, the half life was too long to measure significant decay in a month. The absorption properties also changed with time. Because of the importance of the absorption coefficient in the diffusion calculations, it was necessary to determine this quantity frequently over the period during which these experiments were carried out. This correction was unsuspected at the time of publication of notesl3 on this work and accounts for the discrepancy in alpha iron and for part of the discrepancy in gamma iron.* * The data in the present paper supersede those given in the notes entirely. In one note the scale of log D was inadvertently reversed. In addition to the correction for the drift in absorption coefficient, the D values for gamma iron at low temperatures were high owing to insuficient correction for diffusion occurring during heating and cooling through the high temperature part of the alpha range at a rate much slower than that employed in the runs reported here. The high temperature alpha rates are much higher than the low temperature gamma rates and correspond to large equivalent times at these temperatures. These experiments were discarded and new measurements taken. Independent experiments with the same activity units indicated a radioactive contaminant in the iron, but exhaustive attempts to isolate and identify it chemically failed. These experiments? indicate † These experiments will be discussed in a later publication from this laboratory. that the contaminant represented only a trace of little importance in the diffusion results. The active iron was plated from an iron chloride solution. Enough of the solution was dropped on a 1% in. square of filter paper to wet it thoroughly.

Jan 1, 1951

By F. C. Bond, J. T. Wang

H. J. Kamack (E. I. du Pont de Nemours & Co., Inc., Wilmington, Del.)—Rittinger's law usually is stated to the following effect: "The work (or energy) consumed in particle size reduction is proportional to the new surface area produced." The law has been stated substantially in this way by Taggart20 Berry21 Dalla Valle22 Coghill and DeVaney,23 Richards and Locke," Gross,25 and many others, and, according to Gaudin,26 was originally expressed by Rittinger in the same form. Consequently there can be little doubt that this is the understanding of the law among most workers in the field of particle size reduction. Bond and Wang, however, express the law in the form "the useful work accomplished . . . ." (italics theirs). The distinction is critical, for in the form used by Bond and Wang the law becomes, as they themselves remark "merely a more or less arbitrary definition of useful work," while in its usual sense the law expresses a physical hypothesis which has been verified experimentally within certain limitations. Considering the way the law has been used, it might be stated more explicitly as follows: "In a given machine operating under a given set of constant operating conditions, the work consumed in the particle size reduction of a given material is proportional to the new surface area produced." Or, as Coghill and deVaney have said,27 "the (Rittinger) law holds only when the tests being compared are made under analogous conditions." There are occasions when the law transcends these limitations; for example, the surface area produced per unit energy consumption for a given material in a ball mill does not vary much over a fairly wide range of operating conditions. But by and large, the surface area production per unit energy consumption will vary with the operating conditions, the type of machine, and the material. The essence of Rittinger's law is that the surface area production per unit energy consumption is independent of the particle size, and this has been verified experimentally by numerous workers for numerous materials, within certain limits. An important limitation is that when one grinds to very small particle sizes, agglomerative forces may tend to interfere with size reduction so that the surface area increases less rapidly than Rittinger's law would predict. Within such limitations, Rittinger's law can be regarded as empirically established. The law has, however, certain theoretical implications, and it seems to be chiefly against these that Bond and Wang direct their criticism. Solids are believed to possess surface energy which is proportional to surface area. Thus, Rittinger's law implies a proportionality between surface energy produced and mechanical energy expended (for a particular material in a particular machine). It does not imply that all or most of the mechanical energy is transformed into surface energy; in fact it is known that most of the mechanical energy is transformed into heat. Bond and Wang assert that most of this heat arises from the damping of elastic vibrations of stressed particles. This may possibly be true for crushing (with which they are chiefly concerned), although in grinding it is probable that much of the heat arises from friction between particles. However, the fact that the surface energy is small compared to the heat energy does not invalidate Rittinger's law, which implies merely that they are proportional. The authors also criticize Rittinger's law on the grounds that "this theory cannot be justified mathematically, since work is the product of force times distance, and the distance factor is ignored," and "energy input must be the product of force times distance, and the Rittinger theory completely ignores large variations in the distance (strain dimension or deformation) throughout which a force must act to produce breakage of different materials." However, the quantities force and distance as such are irrelevant to Rittinger's law, which considers energy input as an integral quantity. The fact that different materials require different forces and strains (hence, different amounts of energy) to break them is incontrovertible but again is irrelevant to Rittinger's law, which, as mentioned before, applies -only to a single material. Even in theory, it would not be expected that the surface area produced per unit energy consumption would be the same for different materials, because the surface energy per unit area is presumably specific to each material. Bond and Wang advance another argument of a

Jan 1, 1952

By J. G. Savins

Certain types of macromolecules added to water and salt solutions flowing in turbulent motion can reduce the pressure gradient. Alternatively, the volumetric capacity of a pipe for these fluids is increased by the presence of these materials. Examples presented show that the drag reduction can become significant. Thus, the presence of 0.28 per cent of a gum derivative in a solution of sodium chloride flowing at 200 gal/min in a 1.89-in. pipe yields a pressure drop which is 0.44 of the single-phase drop measured under the same conditions of turbulent flow; the addition of 0.1 per cent of a vinyl derivative to a I-in. water line yields a throughput capacity which is 1.78 of the single-phase capacity at the same pressure drop. It is further shown that these phenomena are distinctly different from previous observations with other classes of non-Newtonian systems. There a simple lowering of friction factors below the levels predicted from the resistance laws for Newtonian fluids is associated with a suppression of turbulent motion. A rational physical explanation for drag reduction is advanced. Briefly, the proposed mechanism is a storage by the molecular elastic elements of the macromolecules in solution of the kinetic energy of the turbulent motion. INTRODUCTION This study was inspired by a recent review of some paradoxical drag reduction phenomena in turbulent pipe f1ow.I Under very moderate conditions of turbulent flow, the pressure gradient necessary to pump solutions containing certain specific kinds of polymers, fibers and metallic soaps may become appreciably lower than that required* to pump the solvent, i.e., water or a low-viscosity hydrocarbon, under identical flow rates in the same conduit. As shown by our review, this phenomenon of drag reduction in turbulent duct flow was first noted during the second world war, apparently arising in connection with the development of flame warfare weapons. Since that time several papers illustrating this phenomenon have appeared: Toms, Oldroyd,3 Agoston et al., Bundrant and Matthews, Robertson and Mason,6 Ousterhout and Hall,7 Daily and Bugliarello~ Lummus, Anderson, and Fox. 9 That there are practical applications for techniques which increase discharge or decrease the pressure necessary to transport a liquid through a pipeline is illustrated in the patents which have issued which take advantage of this peculiar phenomenon, e.g., Mysels,l0 Dever, Harbour, and Seifert.11 One also finds fragmentary evidence of this effect in the data pertaining to a few of the polymeric solutions studied by Shaver12 and Dodge.13 However, these investigators were concerned with the development of friction factor vs Reynolds number correlations for a variety of non-Newtonian solutions and suspensions, rather than in a study of drag reduction-. A similar kind of drag reduction effect has been observed in gases. Sproull, for example, reports that adding dust to air flowing in turbulent motion through a pipe results in a lowering of the pressure gradient at identical flow rates. There are also military applications for reducing the drag on hydrodynamic vehicles. For example, the possibility of injecting a rheologically complex fluid into the boundary layers of bodies to reduce the skin friction has been investigated by Fabulal5 and Granville.16 Along somewhat different lines are the drag reduction studies of Kramer.17118 He has shown that skin friction can be reduced by covering the surface of a vehicle with a flexible skin. The effect is apparently due to the boundary layer being stabilized by the presence of the skin. Drag reduction by means of coexisting gas and liquid boundary layers, e.g., film boiling and continuous gas injection, has been proposed by Bradfield, Barkdoll, and Byrne,19 Cess and Sparrow,20'21 Sparrow, Jonsson, and Eckert.22 Here the skin friction occurs between a vapor and a surface rather than between a liquid and a surface. There are several references in the literature to friction-factor correlations for non-Newtonian solutions and suspensions: Shaver and Merri11,23 Dodge and Metzner, Clapp,25 and Thomas.26

Jan 1, 1965

By C. S. Finney, John Mitchell

The introduction of ovens for the production of metallurgical coke is believed to be due to L. L. Norton who operated an iron foundry in the vicinity of Connellsville, Pa. Persuaded by his foreman, an English immigrant named Nickols from Durham, L. L. Norton put up a 12-ft square oven which produced coke in 1833. The coal used was taken from a local mine at Mounts Creek. The oven seems to have been used in conjunction with the customary method of coking in mounds. It was in the Connellsville district also, in 1841, that two carpenters, Provence McCormick and James Campbell, formed a partnership with John Taylor, a stone mason, for the manufacture and sale of oven coke. The task of the mason was to construct the ovens, while the carpenters were to build the arks by which the coke could be taken by water to the market at Cincinnati. The following account of the enterprise was given by McCormick: "James Campbell and myself heard in some way that I do not now recollect that the manufacturing of coke might be made a good business. Mr. John Taylor, a stone mason, who owned the farm on which the Fayette coke works now stand, and who was mining coal in a small way, was spoken to regarding our enterprise, and proposed a partnership-he to build the ovens and make the coke and Mr. Campbell and myself to build a boat and take the coke to Cincinnati, where we heard there was a good demand. This was in 1841. Mr. Taylor built two ovens. I think they were about 10 feet in diameter. My recollection is that the charge was 80 bushels. The ovens were built in the same style as those now used, but had no iron ring at the top to prevent the brick from falling in when filling the oven with coal, nor had we any iron frames at the mouth where the coke was drawn. The top and mouth had to be repaired when they fell in. In the spring of 1842 enough coke had been made to fill two boats 90 feet long-about 800 bushels each-and we took them to Cincinnati down the Youghiogheny, Monongahela, and Ohio, but when we got there we could not sell. Mr. Campbell, who went with the boats, lay at the landing some two or three weeks, retailing out one boatload and part of the other in small lots at about 8 cents a bushel. Miles Greenwood, a foundryman of that city, offered to take the balance if he would take a small patent flour mill at $125.00 hi pay, which Mr. Campbell did. He had it shipped here. We tried it, but it was no good, and we sold it to a man in the mountains for $30.00, and thus ended our coke business." So successful did the coke subsequently prove to be in use that the three partners were asked to deliver more. Evidently they had had enough of the coke business, however, for they refused to have anything more to do with it. Few ovens were built between 1841 and 1855, and it is reported that in the latter year, "there were only 26 coke ovens along the river above Pittsburgh". Successful coke makers of these years included Mordecai Cochran, Richard Brookius, and Colonel A. M. Hill. It was the use of coke in 1859 in the Clinton furnace erected by Graff, Bennett and Co. in a plant on West Carson Street, Pittsburgh, that brought the real beginning of the coke-iron era in America. Here the successful use of Connellsville coke as a blast-furnace fuel was demonstrated beyond all possible doubt, and from the year 1859 the coking industry expanded tremendously. The era of beehive coke ovens During the latter half of the nineteenth century and the early years of the twentieth, the major percentage of metallurgical coke produced in the United States came from beehive ovens. It was not until 1893 that the first battery of by-product ovens came

Jan 1, 1961

By L. S. Allen, R. L. Caldwell, W. R. Mills

Borehole models used in the study of nuclear well logging are reviewed and the merit of heterogeneous us homogeneous formation simulation is discussed. .A heterogeneous model for simulating sandstone formations of variable porosity is described. Simulation adequacy was checked by steady-state and pulsed-neutron measurements. INTRODUCTION In the course of developing new methods of nuclear well logging, the problem of testing new logging instruments under controlled conditions always arises. This testing is usually done in wells of known lithology, porosity and fluid saturation, or in laboratory test facilities which simulate the borehole environment. Although the former approach is possibly more satisfying, it is frequently difficult or inconvenient to find wells with enough variation in the cited parameters for a truly comprehensive study, On the other hand. laboratow- test facilities can simulate a wide variety of formation and borehole conditions if care is exercised to maintain adequate simulation under all conditions. Workers concerned with the development of nuclear well logging methods have reported several types of research facilities in the past. Tittle, et a1 used cubical tanks filled with Ottawa silica sand to study the steady-state behavior of thermal and epithemal neutrons in simulated sandstone logging environments.1 In addition to the effects of fresh vs salt water, a wide variety of casing sizes and compositions were investigated. Tittman also used a large tank of Ottawa sand to measure the slowing down length of sio2;2 for making the same measurement in CaCO3, however, an assembly of solid Vermont marble blocks was used. More recently a very useful and carefully planned test pit for nuclear logs was constructed under the auspices of the API.3 This facility consists of three massive limestone sections, each 6-ft thick and more than 5 ft in diameter. The blocks are buried, one on top of the other, in a concrete- lined pit having a total depth of 24 ft. Each section is made of a different limestone to achieve porosity variation, the selection being Carthage (2 per cent), Indiana (19 per cent) and Austin (26 per cent). The blocks are traversed by a 7 7/8-in. diameter borehole and are saturated with fresh water. Great care was taken to insure total saturation of the stone. Homogeneous mixtures and materials have not been used exclusively for simulating earth formations. Tittle, et a1 4 showed that a heterogeneous lattice of water and graphite could be used to simulate Liquid furfural with very little effecton measured thermal and epi thermal neutron distributions. Subsequently, a lattice-type model for simulating limestone earth formations was designed and built by Berry This limestone model was constructed of 7/8- x 11/4- x 36411. marble rods glued together with a plastic resin to form a 36-x 42- x 42in. cube. The cube was honeycombed vertically with 7/8- x 7/8- x 3641-1. holes for porosity and had a 111/2-in. diameter hole in the center to serve as the borehole. Lower porosities were simulated by placing marble rods in the square holes. The finished cube was used with the borehole vertical and set in a tank to hold liquid for filling the holes in the rock matrix. A second type of heterogeneous borehole model has been proposed by Kukharenko, et a1.6= In this concept the model is composed entirely of solid material. The hydrogen equivalent of formation fluids is simulated by making the model of alternating layers of dense rock and celluloid. Additional hydrogen is included by drilling vertical holes in the rock sections and filling them with solid forms of hydrogeneous material. The volume of the holes is equal to the volume of the celluloid layers, so an axial and radial dispersion of the hydrogeneous material is thus obtained. One such model was composed of alternate 50 mm-thick sand layers and 2 mm-thick celluloid sheets. Approximately 200 appropriately spaced plastic tubes were used in each sand section. The plastic tubes were filled with paraffin for additional hydrogen concentration. This arrangement yielded a model with a water-equivalent hydrogen concentration of 10 per cent. Experimental data taken in this model and in a model consisting of the same material but homogeneously dispersed showed that the heterogeneous system adequately

Jan 1, 1966

By D. M. James, J. C. Martin

The results are presented of a study of the application of analytical methods to the solution of two-phase flow into single wells. Approximate analytical expressions for the pressure distribution in two-phase flow are found ;;; a number of conditions. The results obtained from the analytical solutions me found to be in good agreement with results obtained by finite difference techniques using a high speed digital computer. Mathematical solutions for four sets of boundary conditions are presented. All of these solutions are composed of a short-term transient plus a steady or quasi-steady state. The rates of decay of the short-lived transients are analyzed. It is found that the durations of the short-term transients may be characterized by a parameter defined as the time constant which can be determined from simple relations. It is shown also that if the outer radius is much greater than the radius of the well. the short term transients decay at rates which are proportional to the square of the exterior radius, and the rates of decay are only slightly dependent upon the radius ratio. Numerical solutions based on finite difference techniques are presented for a number of conditions. The numerical solutions are in good agreement with the predictions based on the theoretical analysis for small and moderate drawdowns. Examples involving large drawdowns indicate that the nonlinearities in the equations of flow do not appreciably alter the longevity of the short-term transients. In all cases the time required for the short-tern transients to disappear is predicted satisfactorily. INTRODUCTION The mechanism by which oil and gas flow into a single well is of vital interest to the petroleum industry. The fundamental equations of two-phase flow which describe this mechanism are nonlinear partial differential equations. Numerical solutions of these equations describing pressure transients have been obtained with the aid of electronic computers. Although solutions obtained in this manner take into account a large number of effects, the reduction of this information to useful generalities is difficult. One method of obtaining generalities is the use of linearized approximations of the nonlinear equations. Since it is possible to obtain explicit solutions of the linearized equation, general properties of the role of pressure in the flow mechanism may be ascertained. Results obtained from this approach are limited to some extent by the linearizing assumptions. The severity of these limitations may be evaluated by comparing solutions of the linear equation with numerical solutions of the more exact nonlinear equations of two-phase flow. In the past considerable amount of work has been devoted to studying pressure build-up using the single-phase flow theory. Unfortunate1y, most prep sure build-up tests involve multiphase flow. A small amount of work has been done studying pressure build-up where the flow is two-phase. The encouraging results of these studies suggest that useful results may be found from additional studies of not only pressure build-up, but also the rapid transients associated with placing a well on production. This paper presents the basic theory of the pressure transients associated with placing a well on production and with closing it in. The paper is concerned chiefly with two-phase compressible flow; however, the results also apply to single-phase flow. The results are based on analytical solutions of the flow equations, and they are verified by numerical solutions using finite difference techniques. Much of the previous work on compressible flow into wells has been confined to single-phase flow. Some work has been done on compressible two-phase steady state flow, and solutions of the equations of flow have been found by finite difference techniques using high-speed computers. Muskat1 presents some rather general solutions to the equations of single-phase compressible flow into wells. Much work has been done on pressure build-up in wells (see, for example, Refs. 2-6). Almost all of the work on pressure build-up concerns single-phase flow with the exception of Ref. 5 and part of Ref. 2. Some work has been done on pressure fall-off in injection wells.718 Muskat9 presents the solution of the equations for radial steady state two-phase compressible flow. Handyl0 extends Muskat's solution to obtain

By M. A. Grossmann

THE hardenability of most steels can be predicted within 10 to 15 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a ''pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain sue may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter"; namely, the diameter of bar, in inches, that will just harden all the way through (absence of un- hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test. The data bring out certain features rather clearly. For example: I. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals," are known; thus an "incidental" chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybde- num when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful as wouldappear to be common experience; observe that an increase from no manganese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added " 20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the first small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using 1.0 per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost lo per cent in hardenability (in these units); this, however, does not apply to certain steels of high hardenability. It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome- molybdenum and chrome-vanadium steels, undissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum possible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the absence of Cr, and V up to 0.04 per cent), the charts provide reasonable approximations. The precise figures on the charts are suggested as tentative, subject to some modification as more data accumulate, but the fundamental concept appears to be supported by tests made on a wide variety of steels, a few of the correlations being shown in Fig. I.

Jan 1, 1942

By George Krauss, M. Cohen

The reverse martensitic transfomzation (i.e., the conversion of martensite to austenite on heating) was investigated in Fe-Ni alloys containing 30.5 to 33.5 wt pct Ni. The reversed austenite was found to be sufficiently distorted to exhibit marked differences in mechanical properties and to undergo recovery and re crystallization on further heating. In particular, the yield strength of the reversed austenite was as much as 2.5 times higher than that of the virgin austenite: with five cycles of the direct and reverse martensitic transformation, the yield strength was 2.6 times higher. There was an accompanying decrease in strain-hardening capacity and in stable ductility or uniform elongation. The recrystallization was observed to follow sigmoidal kinetics, but was characterized by an abnormal1y large temperature dependence which was evidently due to carbon segregation at the migrating grain boundaries. Upon recrystallization, the strength Properties reverted to those of the virgin austenite, but the ductility did not fully recover until the annealing temperature was further raised to dissipate the carbon segregation at the grain boundaries. The transformation of reversed austenite to produce second-generation martensite resulted in an unusually imperfect structure, thereby leaditg to additional strengthening. Horlleuer, the martensitic phase was much less responsive in this respect than was the austenite. MOST martensitic transformations are capable of undergoing a reverse transformation back to the austenitic phase on heating.&apos; This reaction, like the direct transformation to martensite on cooling, is usually athermal. In analogy with the Ms andMf temperatures for the martensitic transformation (where M, > Mf), the reverse transformation is characterized by the As andAf temperatures (where As<Af). It is well-known that the finish (Af) of the martensite-to-austenite reaction on heating may occur at a temperature where austenite is not stable relative to other phases in the equilibrium diagram.&apos; Reverse martensitic transformations have been found to influence the properties of the parent austenitic phase in a number of ferrous alloys. The austenite thus produced after one or more reversals is significantly altered in strength, microstruc-ture, diffusivity, and annealing characteristics compared to well-annealed, virgin austenite. The first detailed observations of such phenomena were made by Wasserman3 on an Fe-30 wt pct alloy. He found that the reversed austenite (i.e., austenite formed by the reverse martensitic transformation) was much stronger than the original austenite, and the second-generation martensite (i.e., martensite produced from the reversed austenite) was somewhat stronger than the first-generation martensite. On heating the reversed austenite, recrystallization occurred in a manner similar to that of a cold-worked metal; the Laue spots sharpened and the strength decreased.4 In recent years, Russian workers have shown considerable interest in these reverse martensitic transformations. Most of such investigations5-10 have been concerned with the stabilization of reversed austenite relative to subsequent martensitic transformation, and because of its unusual nature, this phenomenon will be discussed in detail elsewhere." On the other hand, the annealing behavior of reversed austenite and the attendant variation in properties have received little attention beyond the experiments of Wasserman.3,4 Gridnev eta1.,8 in one of the few such studies. followed the hardness change of reversed austenite as a function of time at three annealing temperatures. The marked strengthening of austenite achieved by the reverse martensitic transformation has been referred to as "transformation strengthening" by Wasserman3,4 and as "phase hardening" by Malyshev et a1.7,9,10 to differentiate it from hardening produced by cold working. Both groups of investigators noted that further strengthening of the austenite could be attained by repeated or cyclic transformations, but the first cycle resulted in the most pronounced effect. Evidence of the altered microstructure of reversed austenite has been reported by Maximova and Nikonorova6 and by Edmonson and KO.12 The former found that reversed austenite was much more sensitive to etching than the original austenite, and the latter authors observed a (&apos;ghost" structure resembling martensite in certain areas of the reversed austenite. Enhancement of the self-diffusion rate in reversed

Jan 1, 1962

By M. A. Grossman

THE hardenability of most steels can be predicted within 10 to 15 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter"; namely, the diameter of bar, in inches, that will just harden all the way through (absence of unhardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test. The data bring out certain features rather clearly. For example: I. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals," are known; thus an "incidental" chromium content of o.-2o per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful as would appear to be common experience; observe that an increase from no manganese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.2o per cent Mo provides a factor of 1.63, an increase of over 6o per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the first small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater harden ability will be obtained by using, for example, o.5 per cent of each than by using 1.0 per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain steels of high hardenability. It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, undissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum possible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the absence of Cr, and V up to 0.04 per cent), the charts provide reasonable approximations. The precise figures on the charts are suggested as tentative, subject to some modification as more data accumulate, but the fundamental concept appears to be supported by tests made on a wide variety of steels, a few of the correlations being shown in Fig. I.

Jan 1, 1942

By S. A. Levy, J. D. Wood, J. F. Libsch

A study of the preparation and characteristics of a sevies of Fe-C-N alloys has been conducted. X-ray, microhardness, and metallographic data from a series of single-phase alloys produced by controlled nitriding of carburized foils are reported. The existence of a, y&apos;, and E carbonitride has been confirmed and it has been found that y&apos; is the hardest of these three phases. These results have been used to interpret the structures observed in nitrided steels. ThIS paper represents the second phase of a three-part study concerning combined nitriding and induction hardening. The first part&apos; reports the engineering properties (depth hardness, fatigue, corrosion, and tempering resistance) obtained when seven different steels were subjected to the combined surface hardening treatment. The present paper concerns the nature of a series of single-phase alloys prepared by controlled nitriding of carburized foils. The objective was to simulate the various layers present in the as-nitrided steels. A third paper will report data concerning induction hardening of the foils and will attempt to set forth a mechanism for the high hardness obtained with the combined treatment. Studies of nitriding generally fall into three categories. The first were performed with bars using conventional nitriding procedures, thus yielding a nitrogen gradient and a series of phase layers near the surface.2-6 Such studies were complicated by the presence of the nitrogen gradient, for it was difficult to correlate microhardness and X-ray data with chemical composition. There were always complications due to penetration of the X-ray beam which yielded data influenced by underlying layers. Similar difficulty was experienced in taking hardness readings on a tapered specimen or in isolating various layers by machining. A second group of investigations was primarily concerned with establishment of regions in the Fe-N7,9,10 or the Fe-C-N phase diagram.8 These were performed with powder specimens which were nitrided in am-monia-hydrogen mixtures to produce a series of single-phase specimens. Unfortunately, the powder specimens were not amenable to either microstruc-ture or microhardness study. The third was essentially a compromise of the first two. Bose and Hawkes," using 0.005-in.-thick iron foils, were able to obtain microhardness, microstruc-ture, composition, and X-ray data on Fe-N alloys of eutectoid composition by equilibration in ammonia-hydrogen mixtures at 1290°F. To obtain a better understanding of the nitriding process and the characteristics of the phases in ni-trided plain carbon steels, the present investigation was undertaken. The investigation was patterned after that of Bose and Hawkes with the exception that nitriding was performed at 930°F (below the eutectoid temperature), as in the case of conventional nitriding. In addition to gaining some understanding of the source of high hardness of nitrided and induction-hardened steels, found in a previous study,&apos; this investigation was concerned with the possibility of controlling the phases present in a nitrided case through the use of ammonia-hydrogen mixtures. Knowledge of the properties of each phase and the conditions necessary for its production could make it possible to avoid undesirable surface layers in nitriding. EXPERIMENTAL PROCEDURE Specimen Preparation. A specimen thickness of 0.005 in. was selected to insure that a uniform nitrogen concentration could be obtained in a reasonable length of time by equilibration in an ammonia-hydro-gen atmosphere. The starting material was a vacuum-cast ingot of pure iron, the major impurities of which were: C, 0.003 pct; 0, 0.014 pct; S, 0.004 pct; N, 0.003 pct.* &apos;Compositions are quoted as weight percent except as noted. The ingot was heated to 1500°F in a nitrogen atmosphere and forged to a slab 0.25 in. thick. The material was then reduced to 0.005 in. by alternately cold rolling and annealing in a nitrogen atmosphere at 1600°F. This material was divided into five groups of specimens which, after carburizing, yielded the following carbon contents: 0.003, 0.28, 0.36, 0.46, and 0.74 pct C. The carburizing was performed by the Leeds and Northrup Research Laboratories, using a controlled "carburizing potential" which yielded a uniform carbon concentration throughout the cross section.

Jan 1, 1970

By William G. Pariseau, H. Douglas Dahl

Recent subsidence legislation indicates that mining engineers would be welt advised to be able to predict and control surface damage caused by mine subsidence. To date, such an ability is practically nonexistent. Model analysis is suggested as one of the alternative paths available which might yield fruitful results. Similitude requirements developed for a self-loaded body in static or quasi-static equilibrium indicate that complete similitude without centrifuging is an impracticability. However, a pilot experimental study which used a simplifying assumption to correctly model mine subsidence has produced results in qualitative agreement with field observations. The purpose of this paper is to present a discussion of the various approaches that can be taken in the study of mine subsidence phenomena. Particular attention is focused upon the rational selection and use of laboratory models. Broadly interpreted, mine subsidence is the deformation of the rock mass enclosing a mine. Depending upon a number of factors, the movement of the subsiding rock mass may disrupt gas and water lines or other buried utilities, damage surface structures such as buildings and bridges, dislocate streams, roads, and rail lines, aggravate acid mine drainage and fire problems, and generally mar the landscape. It is clearly a problem that no mine manager can safely ignore. It is also a problem that will grow with the general population increase. In the following discussion, a summary review of past and present approaches to subsidence studies is given. The possibilities of duplicating subsidence phenomena in laboratory models are examined, and an analysis of a particular type of model is presented. Some preliminary results obtained from a model of the particular type analyzed are then discussed. REVIEW OF PREVIOUS WORK Historically, subsidence investigations have been empirical studies in the field and laboratory or theoretical analyses of mathematically idealized media. Empirical and theoretical work in the United States has generally lagged behind investigations abroad. In the United States, field studies are mostly pre-World War 11. These are summarized in the Mining Engineer&apos;s Handbook. &apos; Field studies in Europe are more recent and more extensive. Those made in Great Britain are summarized in the Subsidence Engineers Handbook2 and represent observations made at 157 different collieries. Such studies by themselves are of limited usefulness as are all empirical studies. One can never be certain that conditions at one mine will be similar enough to those at another to warrant the drawing of like conclusions. European subsidence formulas rely heavily upon the "angle of draw" and "critical area" concepts. The angle of draw is defined as the angle between a vertical line through the face, and another line extending from the face to the surface at the point where movement is zero. The critical area is defined in relation to the least extraction necessary to produce maximum subsidence. Fig. 1 illustrates the angle of draw and critical area concepts. First and second "limits of influence" are also shown. The angle of draw and associated critical area concept are obviously not well defined, being dependent upon the accuracy of the surface survey. In Great Britain, the angle of draw has increased through the years from about 26 to 35°. In the United States, zero and negative angles of draw have been reported. In the authors&apos; opinion, these purely geometrical concepts represent an oversimplification of subsidence phenomena and their use, in the United States at least, should be discouraged. Empirical observations of laboratory models containing layers of earth, sand, clay, and plaster were made by Fayol (cited by Peele) as early as 1885. An outgrowth of his work was the "dome theory," a verbal description of what is assumed to occur in subsiding rock masses. The dome theory has since fallen into disrepute. Theoretical analyses worthy of the name treat a subsiding rock mass as a deformable body. In these analyses, the actual rock mass is replaced by an idealized material that deforms according to a simple stress-strain relationship. The stress equations of equilibrium expressing the Newtonian laws of mechanical action and the geometry of strain furnish additional equations that must be satisfied. A loading criterion-generally understood, and in some cases stated explicitly-completes the theory.

Jan 1, 1969