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By M. J. Stewart, F. Weinberg

PREVIOUS investigations into convective flow in molten metals have examined systems in which the length-to-height ratio of the enclosure is large, usually using long graphite boats.''2 In normal castings this ratio is generally small and it is not possible to extrapolate the results of previous work to casting configurations. The present investigation was undertaken to examine liquid flow in systems of low length to height ratio. The apparatus used for the experiments is shown in Fig. 1. The molten zone of tin is contained in an aluminum mold of inside dimensions 6.4 by 6.4 by 0.31 cm. A heating block containing a resistance coil is attached to one end of the mold and a cooling block is attached to the other end. These are used to produce a wide range of temperature differences across the mold. The mold is contained in a stainless steel tank which is heated from the outside by resistance heaters to give the required operating temperature during the experiment. Temperature measurements in the molten tin are made with an iron-constantan thermocouple PT equal to 5 atm. The phase diagram derived by us was the same as that found by Krivsky and Schuhmann, except for a similar discrepancy in one boundary line representing the gas composition in equilibrium with SO a. The vapor pressures of the pure components can be neglected at 1700°K, 1 atm and 2500°K, 5 atm. There-fore, in these cases PT is essentially the total pres-sure in the system. This is valid for all the diagrams presented by Krivsky and Schuhmann except for the one at 2500°K and 0.01 atm, where the vapor pressure of silicon is comparable to PT.6 This work was supported in part by the American Iron and Steel Institute. 'C. E. Wicks and F. E. Block: Thermodynamic Properties of 65 Elements, U S. Bur Mines, Bull. No. 605, 1963. R. P. Elliott: Constitution of Binary Alloys, 1st supplementary, McGraw-Hill Book Co., New York, 1965. 3W. A. Krivsky and R. Schuhmann, Jr.: Trans. TMS-AIME, 1961, vol. 221, pp. 898-904. 4M. F. Ancey-Moret, M. Olette, and F. D. Richardson: Mem. Sci. Rev. Met., 1964, vol. 61, pp. 169-76. 5J . F. Elliott and M. Gleiser: Thermochemistry for Steelmaking, vol. 1. Addison-Wesley, Reading, Mass. 1960. 6 J.Drowart, G. De Maria, and M. G. Ingraham: J. Chem. Phys., 1958, vol. 29, p. 1015. probe of 0.4 mm diam inserted into the open top of the mold. Radioactive sn113, in the form of a small sphere, was gently lowered into the molten tin at point A in Fig. 1 THERMOCOUPLE> WATER ARGON END HEATER QUENCH ARGON Fig. 1—Apparatus for detecting liquid flow. Point A indicates position the tracer was introduced.

Jan 1, 1970

By F. S. McNicholas

IN the writer's opinion the term "block caving" has been rather loosely applied to a general principle of mining, and therefore detailed classification of caving methods and draw, together with the characteristics required for each method, will fill a desired need. Selection of caving method should be made only after a study of all governing conditions, such as size of orebody, lateral and vertical extent of ore-body, attitude, treatment demands, possible resultant pressures, and cost and profit comparison of methods. Successful caving methods can be classified under six main headings: (1) Full-protected block caving, (2) semi-protected block caving, (3) unprotected block caving, (4) full-panel caving, (5) half block-panel caving, (6) block-panel caving. The methods and factors governing choice of method are shown in Table I. Full-protected Block Caving Full-protected block caving consists of develop-ing, undercutting, and drawing to exhaustion a block of ore of predetermined size without coordination of mining or draw with adjoining areas. The block is mined and drawn as an independent unit (Fig. 1). Full-protected block caving demands that mining and draw cannot be done against unconsolidated capping in adjoining caved and exhausted blocks. Two sides of block are against solid. Caved capping must be allowed to consolidate for a suitable period, usually not less than one year. Pillars may be left in lieu of consolidated capping (Fig. 2). The advantages of full-protected block, caving are: (1) A definite area is developed, mined, and drawn as a unit so that all work may be completed, the block drawn to exhaustion in the minimum length of time, and the area then abandoned. (? Production is not restrained because of coordina1, on with adjoining areas. (3) Records of draw and caved reserve of ore are good. Upon abanwnment of the block, accountability for production is closed out with no carry-over to adjoining areas. The disadvantages of full-protected block caving are: (1) Side dilution from the draw adjacent to the consolidated capping may be serious, particularly where capping does not consolidate sufficiently in the allotted time. (2) Boundary weakening is needed on the solid sides of the block except in weak rocks. (3) Maximum cantilever and compression effect to aid caving and fragmentation may not be secured since the draw should proceed from the solid to the consolidated capping to minimize side dilution. However, undercutting from the loose (caved capping) to the solid with a slight initial draw in the same manner will develop cantilever effect. (4) A period of at least one year, more is usually desirable, must be allowed for caved capping ,to consolidate before mining the adjoining block, depending upon the characteristics of the capping. (5) Capping may not consolidate sufficiently in the time that can be allowed. Full-protected block caving is indicated where: (1) The ground is weak and heavy and workings

Jan 1, 1952

The San Manuel district of Arizona was first prospected prior to the Civil War, but there was little or no production until 1881. Small operators tried to develop ore bodies from time to time after that without success. Then, in 1917, a drilling program was carried out; but it did not indicate a copper content of interest. Finally, in the 1940s, the U. S. Geological Survey drilled the property and obtained indications of a mineralized area. At that time, Magma Copper and its principal owner, Newrnont Mining Corporation, drilled many deep holes through the gravels and conglomerates and in 1948 proved an ore reserve of 367 million tons of 0.785% copper sulfide ore. Underground exploration and development were started in early 1948, and in 1953 design and construction of the surface facilities commenced. By the end of 1955 plant construction was completed. The ore deposit of disseminated pyrite, chalcopyrite, chalcocite, molybdenite, silver, and gold is in quartz monzonite porphyry gangue. Mine production, which is entirely underground, is by full-gravity block-caving. Initially, ore mined at a rate of 36,000 tpd was hoisted through two identical shafts. From the 5,000 ton coarse ore bins located at the collar of each shaft, the ore was hauled by a shuttle service rail- road in 100-ton bottom-dump rail cars a distance of seven miles to the rail bin. Fragmentation from block-caving supplemented by underground grizzlies at the loading stations controlled the oversize material to give a feed size acceptable to the two 7 ft standard Syrnons crushers. During operation, however, it became evident that a large amount of secondary breaking in the grizzlies was necessary to produce a suitable feed for the standard crushers. The decision was then made to install primary gyratory crushers on the surface adjacent to the shaft site ore bins. Under each 5,000-ton coarse ore bin, an 8ft by 20 ft (2.44 m by 6. 1 m) apron feeder transfers the ore to a 13 ft 6 in. by 10 ft (4. 1 m by 3. 05 m) grizzly set at 6 in. (152 mm) and sloped at 45 degrees. About 65% of the ore passes the grizzly and thus bypasses the 42 in. by 65 in. (1.07 m by 1. 65 m) Allis -Chalmers gyratory equipped with a Hydroset mechanism and having an open side setting of 5 ½ in. (140 mm). Grizzly undersize and crushed ore drop onto a 6 ft by 30 ft (1. 83 m by 9. 14 m) variable- speed apron feeder for transfer to a 54 in. by 90 ft 5 in. (1.37 m by 27.6 m) inclined conveyor equipped with a tramp iron detector. Indication of tramp iron automatically stops the conveyor and both apron feeders. When the iron is removed from the belt by the operator,

Jan 1, 1978

By Martin T. Broome

INTRODUCTION The Luanshya Mine is situated in the southern part of the Zambian Copperbelt. The copper ore deposit is stratiform, and is preserved in a synclinorium known as the Roan/ Muliashi basin. Roan shaft (formally called No.14 shaft) is located at the eastern end of the syncline and is theoldest of the presently operating hoisting shafts, being sunk during the 1930's. It presently hoists some 45 per- cent of the total Luanshya Mine production. A cross-section through the shaft is shown in figure 1. The ore formation on the south limb is unmined on this section because until recently it was believed that such mining might cause damage to the shaft. This paper examines the influences of adjacent mining on this so-called 'shaft pillar', and describes the mechanics of subsidence of the pillar itself. GEOLOGY AND STRUCTURE Figure 1 shows the general form of folding in the vicinity of Roan shaft. The north and south limbs of the main syncline approach parallelism, with the bottom of the trough fairly smoothly rounded. The axis of the - trough plunges to the west-north-west at 6° - l0°. A brief summary of the major lithologies present in the Roan basin is given in table 1, however, the performance of the overall structure during progressive mining of the ore horizon is controlled by the following features in addition to the mining method. Intraformational Contacts These are characteristically weak in most geological environments. The BC/RL7 contact is an unconformity between moderately weak quartz-biotite schists below (unconfined compressive strength 40 - 80 MN/M 2), and strong quartzites above (U .C .S. 170-200 MN/M2) Subsequent formations are conformable, and planes of weakness are generally the result of contrasting lithology (see below). Weak Interbeds The Rt7, RL6, RL5, RL3 and RU2 horizons consist predominantly of quartzitic rocks, i.e. conglomerates, quartzites and argillites, and as such are generally strong and considered suitable for the positioning of development. Between these however, lie two much weaker dolomitic horizons, the RL4 and RU1. The Rt4 is the main hangingwall aquifer, and must be drained prior to mining. Drainage results in an extremely weak, blocky cavernous horizon which usually requires support if exposed by development. Similarly, the RU1 formation is comprised mainly of dolomites and dolomitic arqillites which are weak and cavernous. In the eastern part of the Roan/

Jan 1, 1981

By R. Raring, W. J. Harris, J. A. Rinebolt

The effects of additions of alloying elements on the true-stress, true-strain characteristics of 0.30 pct C, 1.00 pct Mn, 0.30 pct Si pearlitic steel were studied. The alloying elements investigated were C, Mn, Si, P, The alloys are compared on the basis of fracture stress, fracture strain, energy to fracture, rate of strain hardening, strain hardening exponent, height of the flow curve, and lower yield point. IN the past, nearly all studies of the effects of alloying elements on the tensile properties of metals have compared the conventional engineering parameters, namely, tensile strength, yield strength, elongation, and reduction of area. Recently, however, the true-stress, true-strain method of recording results from the tension test has been used; Lacy and Gensamer,' Hollomon," and French and Hibbard- are used this method to study the effects of composition on strength and ductility of metals. In this paper, the effects of certain alloying elements on true-stress, true-strain curves of steels with nearly constant grain size and pearlite spacing are presented. The notation employed in this paper is given in Table I. Since the definitions of stress and strain and the analytical geometry of the stress-strain curve have been explained previously, for example by Gensamer,' they will not be reviewed here. However, the method used for the determination of energy to fracture, E,, requires mention. These energy values were calculated on the assumption that the flow curve followed the idealized equation:' corresponds to the specific energy absorption to that strain value. There is justification for preferring the use of eq 1 for the determination of the energy to a particular strain rather than the area under the experimental stress-strain curve, since Gensamer showed that the use of the Bridgman correctione for stress at the neck of a tensile specimen brought the corrected experimental curve nearer to the idealized power-law curve than to the uncorrected experimental curve. However, it should be noted that the difference between the areas under the idealized curve and the experimental curve is not great for strain of less than 1.0, as can be seen from Fig. 1. In this figure, the true-stress, true-strain curve for a 0.01 pct C, 1.00 pct Mn steel is plotted through the experimental data points. From the value of a,, from this curve and the value of n as determined by the Inm-

Jan 1, 1952

By P. Greenfield, P. A. Beck

RECENT work by J. Darby, Jr. in this laboratory has shown that the reported vanadium-rich limit of the s phase in the Co-V system at 1200°C is in error. The appearance of a second phase in s actually is restricted to alloys containing over 68 atomic pct V. The error in the original value is due apparently to a reaction that takes place along the numerous cracks in the s specimens between the alloy and the impurities present in the He + 8 pct H atmosphere in the annealing furnace. Such a reaction and the consequent appearance of a second phase can be suppressed if the alloys are sealed under vacuum in Vycor tubing. The new value of 68 atomic pct V for the vana-dium-rich limit of the s phase in the Co-V system effects slightly the s compositions calculated from average values of N, and N,. for various s phases. The standard deviation between experimental mean compositions and those calculated from the assumption that s is characterized by a constant number of 3d + 4s electrons per atom (N,), is slightly reduced from 9.1 to 8.8 pct. The maximum divergence for the V-Mn s phase is reduced from 15.5 to 14 atomic pct. The standard deviation calculated from constant electron vacancy numbers given by N.. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2(Fe) + 1.71(Co) + 1.6(Ni) is now greatly reduced, as the maximum divergence for this correlation previously occurred in the V-Co system. This maximum divergence is reduced from 7.6 to 2.3 pct, and the standard deviation for all s- phases is reduced from 4.1 to only 2.9 pct. The correlation for electron vacancy numbers given by N. 5.66 (V when with Ni or Co) + 4.88 (V when with Mn or Fe) + 4.66 (Cr + Mn) + 3.3 (Mn) + 2.66 (Fe) + 1.71 (Co) + 0.61 (Ni) is made slightly worse, and the standard deviation increases from 2.8 to 3.9 pct. These changes, however, do not affect the conclusions of the paper.' The deviation between calculated and experimental s compositions is much less for either one of the electron vacancy correlations than for the correlation with the number of 3d + 4s electrons.

Jan 1, 1955

By R. A. Anderson, T. E. Tietz, J. E. Dorn

Recent investigations1,2,3,4 have conclusively shown that the strain hardened state of metals depends upon the temperature and strain rate of pre-straining as well as on the total plastic strain. A typical example of the effect of temperature of prestraining on the work hardening of metals is reproduced in Fig 1. When pure aluminum is strained at liquid nitrogen temperature the upper solid stress-strain curve (OFGH) is obtained. But when pure aluminum is prestrained to e2 = 0.153 at atmospheric temperature and the test is then completed at liquid nitrogen temperature, the curve OBCD results. Thus a prestrain E2 = 0.153 at atmospheric temperature gives a flow stress C when continued at liquid nitrogen temperature, whereas a higher flow stress G results when the specimen is strained exclusively at liquid nitrogen temperature to the same strain E2. Consequently the metal strain hardens more rapidly at the lower temperature. Obviously the strain alone is not a measure of the strain hardened state in metals. Inspection of Fig 1 reveals that the flow stress at C is identical with that at F. This fact suggests that a strain E2 = 0.153 at atmospheric temperature induces the same work hardened state as a strain E1 = 0.058 at liquid nitrogen temperature. But this concept of equivalent strains is also in error. If curve CD is shifted to the left so that point C falls on F, point D becomes D'. Inspection of the curves reveals that the rate of increase of stress with strain at C is greater than the rate of increase of stress with strain at F even though the flow stresses are identical. Consequently C and F do not represent identical work hardened states. It therefore becomes important to ascer- tain how the strain hardened states at C and F might differ from each other. In a more recent report1 it was shown that straining at higher rates of strain increases the amount of strain hardening in a manner quite analogous to straining at lower temperatures. These observations suggested that the flow stress is not only a function of the strain but also a function of the strain rate-temperature history of straining, perhaps in accord with the Zener- ?H Hollomon parameter p = Ee /RT (where

Jan 1, 1950

By R. G. Johnson

The prevailing system of locating wells on a rectangular basis, as shown in Fig. 1-A, has developed because of the exigencies of offsetting at boundary lines. When, however, a very large tract is being drilled, it is often possible to abandon this inferior method for the superior arrange- ment known as "staggering," which is illustrated in Fig. 1, B and C. The advantages of the triangular over the rectangular method are evident from Fig. 2, computed on the basis of one well to 10 acres (4 ha.). With the triangular system, no land is more than 409.4 ft. (124.8 m.) from a

Jan 1, 1920

West Virginia University, Engineering Experiment Station, Morgantown, W Va C E Lawall, Director. For copies of Bulletins or other information address the Director Two classes of the Bulletins published by the Engineering Experiment Station are of particular interest in this directory- Research Bulletins, and Extension Bulletins, or bulletins published for use in extension work They are. Research Bulletin 1, The conservation of natural gas in West Virginia (1918), 2, Acceleration stresses in hoisting ropes (1927), 3, Classification of gas wells for operation (1927), 4, Mining methods in West Virginia (1929), 5, The whiteware industry of West Virginia, Extension Bulletin 1, Electricity in mines, series

Jan 1, 1933

For the year ending February, 1920 PRESIDENT HORACE V. WINCHELL.. . MINNEAPOLIS, MINN. PAST PRESIDENTS PHILIP N. MOORE ST. Louis, Mo. SIDNEY J. JENNINGS NEW YORK, N. Y. FIRST VICE-PRESIDENT A. R. LEDOUX NEW YORK, N. Y. TREASURER GEORGE D. BARRON NEW YORK, N. Y SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y VICE-PRESIDENTS CHARLES W. GOODALE,1 . . . . District 5 BUTTE, MONT. MARK L. REQUA,1 District 6 SAN FRANCISCO, CAL. HENRY S. DRINKER, District 2 So. BETHLEHEM, PA. ROBERT M. RAYMOND,2 . . . . District 0 NEW YORK, N. Y. EDWIN LUDLOW,3 District 2 LANSFORD, PA. A. R. LEDOUX,3 District.0 NEW YORK, N. Y.

Jan 11, 1919

[Trans. No,PlaceDate Vol. Page1 1. Wilkes-Barre, Pa*May, '71 13 2, Bethlehem, Pa Aug., '71110 3, Troy, N. Y Nov., '71.. 113 4. Philadelphia, PaFeb,, '72.. 117 5, New York, N, Y.*May, '72,, 120 6. Pittsburgh, Pa Oct,, '72,, 125 7. Boston, Mass Feb,, '73.. 128 8. Philadelphia, Pa,*May, '73., 23 9. Easton, PaOct., '73., 27 10. New York, N, Y Feb., '74,, 211 11. St. Louis, Mo,*May, '74.. 33 12, Hazleton, PaOct., '74., 38 13, New Haven, ConnFeb., '75., 315 14. Dover, N. J,*May, '75.. 43 15, Cleveland, 0Oct,, '75,, 49]

Jan 1, 1928

By Joseph W. Leonard

In a recent publication in the SME Transactions of September, 1975, Volume 258, entitled “Potential for Further Lowering Sulfur in Intensively Cleaned Coal at Mines,” the writer discussed: (1) technical findings useful for the management of reserves to further lower sulfur in intensively cleaned coal and (2) a future coal preparation plant concept for the intensive cleaning of sulfur. The purpose of this technical note is to (1) illustrate the nomographs that can be formed when recovery is phased in with previous work, (2) make note of the powerful potential for predicting future cleaning performance in unmined areas, and (3) discuss resulting mathematical interrelationships.

Jan 1, 1979

By Morris E. Fine, Richard A. Kloske

The stress-strain beha1,ior in tension of Au-Ag alloy single crystals containing nominally 1,3, 5, 95, 97, and 9.9 at. pct Ag was studied uS strain role and lektlperalure down lo 4.2K. A slrain aging yield hob lc,rrs observed on aging under stress in the temperature range 30° lo 75°C. The species diffusing to the dislocation is thought to be a divacancy-solute complex wilh /he. solute then pinning the dislocation by short-Range ovdering and possibly Suzuki locking. At room tempevullcve the critical reso1ved shear stress .follo~c.s an empirical equation of the form tc = A +Bc' where A and B are 90 and 420 ,g per sy mm tor gold base alloys and 60 and 510 g p~r sq )11ttz .tor si1ver base alloys. This strengthening was attributed to a long-range size ejtect. The alloy slrenglliening at i.2'K is greafer than at room temperature. The additional atrloutzf was altribuled lo a uwak skovl-range i?~levacIion between the solute and dislocallon cove. The activation energy .tor deformation a/ 4.Z0h7 decreases on alloying. 11 increases irr other fee systetns. hi the 5 at. pcl Air-Ag- alloy in pmvlicular there is very extensive easy glide and lavge overshooting- of the synmetry line at 4.Z°K. There is also u sharp decrease in the vale of. strain hardenitlg near the widdle of stage II with the new rate bezng abold the sarne as tlzal In easy glide. This uws attributed to a sudden reduction of activity on the pvitrrarg sgstertr. In Au-Ag alloys the critical resolved shear stress Tc. at room temperature is essentially a parabolic function of atomic concentration:' the 50 at. pct Ag-50 at. pct Au alloy is about 10 times stronger than the pure metals. This strengthening occurs in spite of the similarity in valence and atomic size. Solid-solution strengthening in fcc metals is characteristically greater at low temperatures than at room temperature. In Ag-10 at. pct Au and Au-10 at. pet Ag; r, (20.4K)/Tc (300°K) is 2.3 and 2.5. respectively.- compared to 1.2 in pure silver.3 Suzuki' and Flinn5 explained the alloy strengthening at room temperature as a combination of Suzuki locking and short-range order hardening. The agreement between the computed and measured strengthening was very good: however, in Ag base-A1 alloys Hendrickson and Fine6 concluded that Suzuki locking resulted mainly in a yield drop effect. Recent reviews of the solid-solution strengthening in fcc metals by Fleischer2 and Haasen8, 9attributed the strengthening at room tenl-perature to the combined effect of atom nlisfit and change in shear modulus 011 the long-range stress field surrounding a dislocation. The parameter used by Fleischer was The shear tnoduli of Ag-0 to 6 at. pct Au alloys were measured by Pur-wins. Labusch. and Haasen.In While addition of 4 at. pct Au caused an appreciable increase in the C,, elastic constant. there was a decrease on increasing the solute to 6 at. pct Au: C,, and C :: were not measured in the 6 at. pct alloy. The greater solution hardening at low temperatures implies the presence of short-range interactions between the solute atoms and dislocations These include size and electronegativity effects. Whether the extra alloy strengthening at low temperatures is due to locking or friction hardening is still a controversy."".' In the present research the stress-strain behavior of Au-Ag single crystals containing 1 to 5 at. pct Ag and 1 to 5 at. pct Au was measured vs strain rate and temperature down to 4.2' K. Particular attention was paid to yield drop effects. These have not been previously reported. PROCEDURES The alloys were supplied by the Engelhard Industries. Inc.. as strips 0.050 by 0.250 by 12 in. The compositions are given in Table I. Single crystals were grown under static vacuum using a traveling molten zone technique. Crucibles shaped to the size of the strips were made of high-purity graphite prebaked for 24 hr at 1100°C in vacuum. The crucible and its charge were placed in

Jan 1, 1970

By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

By E. T. Turkdogan, J. H. Swisher

The solubility of oxygen in zone-refined iron was determined in the temperature range.from 881" to 1350°C. The solubility in a iron at 881°C ms found to be about 2 to 3 ppm; in y iron, the solubility was found to increase from about 2 to 3 ppm at 950°C to about 25 ppm at 1350°C. The permeability of oxygen in an iron -0.1 pct Al alloy was determined in the y iron range, using an internal oxidation technique. By combining the permeability and solubility data, the diffzisivity of oxygen in y and a iron was calculated. The oxygen diffusivity in solid iron may be s~immarized as follows: 8820 For 6 iron and IN a recent paper, Hepworth, Smith, and Turkdogan1 reported on the solubility, permeability, and diffusivity of oxygen in 6 iron, together with permeability data for oxygen in a iron. In the present investigation, similar measurements were made in the ? phase region. In addition, a solubility measurement was performed in the a phase region to permit calculation of the diffusivity of oxygen in a, iron. References to early work on this subject are given in the previous publication.' EXPERIMENTAL Solubility Measurements. The oxygen solubility was determined by equilibrating cylindrical samples 0.3 in. diam by 14 in. long of zone-refined iron in water vapor-hydrogen gas mixtures. The zone-refined iron was prepared by B. F. Oliver of this laboratory, using an apparatus and technique described elsewhere.2'3 Six zone-melting passes were used to achieve a total impurity level of about 30 ppm. Of this 30 ppm, the combined nickel and cobalt content was about 20 ppm, oxygen was 4 ppm, and all oxidizable impurities less than 1 pprn each. A vertical resistance furnace wound with molybdenum wire was used for the experiments. The temperature was measured before and after each experiment with a Pt/Pt-10 pct Rh thermocouple. In the gas train, flow rates of hydrogen and argon were measured with capillary flow meters, and the resulting mixtures were passed through a column containing 90 pct oxalic acid dihydrate and 10 pct anhydrous oxalic acid to obtain predetermined ratios of H2O to H2. The vapor pressure of H2O above this mixture as a function of temperature is well-known.4 The exit gas was ana- lyzed periodically for H2O, and good agreement (+3 pct) with the calculated composition was obtained. The zone-refined iron specimens were held in the furnace for a sufficient length of time for equilibration, e.g., 18 hr at 1350°C and 1 week at 881°C, then quenched in a brine solution. After removing the surface oxide from the samples by machining, duplicate analyses were obtained by a combined vacuum fusion-infrared method; oxygen analysis was reproducible within 2 ppm. Permeability Measurements. The permeability of oxygen in alloys containing about 0.1 pct A1 was determined by internal oxidation and measurement of the subscale thickness as a function of time. The experimental alloys were prepared by adding aluminum to electrolytic iron (grade 104A plastiron) that had previously been vacuum-carbon deoxidized. The resulting ingots contained about 20 ppm O, 100 pprn C, 40 pprn Si, 50 ppm Mo, 20 ppm P, 20 ppm S, and 20 pprn Zr as the principal impurities. After hot rolling the ingots to 1-in.-thick slabs, specimens were machined from the stock in the form of rectangular plates, 4 by 5 by 2 in. The general procedure for the permeability experiments was the same as those for the solubility measurements. The specimens were cooled in a reducing atmosphere rather than quenched, however, in order to maintain a clean surface for measurement of the sub-scale thickness. This measurement was made on a polished cross section of each specimen, using a microscope with a micrometer stage. The inclusions formed at the lowest temperature 1033°C were too small to be seen with an optical microscope. An electron micrograph showing the size and shape of individual particles is shown in Fig. 1. The dark band in the picture is a boundary between two subgrains. The subscale thickness in these samples was measured with an optical microscope after heavily etching in 2 pct nital, which gave contrast between the subscale and the unoxidized zone.

Jan 1, 1968

By Pradeep K. Rohatgi, David N. French, Surendar M. Jain, Clyde M. Adams

The effect of solute concentration and diffussivity on dendritic solidification of dilute binary aqueous solutions has been investigated; chlorides of sodium, potassium, lithiurn, and hydrogen were used as solutes. Dendrite spacings were measured in spherical droplets and in unidirectionally solidified specimens. In the droplets, the freezing rate is uniform over the entire specimen and remains constant from the beginning to the end of solidification. In the unidirec-tionally frozen specimens the freezing rate varies within a given volume of liquid during the solidification cycle; in addition, it varies with location uithin the specimen. Mass transport analysis has been used to calculate the supersaturation, AC, supercooling, AT, and transcerse growth velocity, V , of ice dendrites during solidijication from the dendrite spacings measured in the droplels. The ice dendrite spacing in a given solute increases lineary with the solule concentralion at a fixed freezing rate. The ualues of AC, AT, and V increase with an increase in solule concentration. The value of AT in the aqueous solution is of the same order of magnitude as in Al-Cu alloys of the same concentration; the dendrite spacings in Al-Cu alloys also increase with an increase in solute concentralion. For the jamily of aqueozrs solulions incestigaled, the dendrite spacing increases linearly with solute diffusivity at fixed values of concertralion and freezing ,rate. The values of ?C and ?T decrease, whereas the value of V increases with an increase in solule diffusicity. The measured dendrite spacings , L, can be expressed by the relatiun: L = K;(dfa/db) 4 K2C +K3D - K4 where dfs/d? is-change in fraction solid with time (freezing rate), C is solute concentration, D is solute diffusivit K1 = (14 * 4)pmin1'2, K2 = (70 ± 10) pl (moles)- K3 = (24 r 3) . l05 psec (cm)-~. K. = -132 ± 10) 1. FREEZING of solutions is almost always an ehunmix-ing" process because the composition of crystallizing solid generally differs from that of the parent liquid. " Solute concentration and transport are therefore in]portant considerations in solidification of solutions. The influence of these factors on the dendritic solutions produced from metallic solutions is of practical significance since the properties of the solid aggre-gate are often strongly influenced by dendrite spacing.''' Alexander and Fthines3 found that dendrite spac- ings generally increase with solute concentration in several metallic systems. Michael and Bever1 have observed an increase in a aluminum dendrite spacings in dilute A1-Cu alloys. Rohatgi and AdamsJ have reported a linear increase in a aluminum dendrite spacings with increasing copper contents up to 28 pct in A1-Cu alloys. Bolling and Tiller"' have theoretically examined the effects of solute concentration and diffusivity on the growth of cells and dendrites. Their analysis of dendritic growth assumes a steady-state growth and the maximum possible velocity for dendrite propagation. In addition, the quantitative analysis is restricted to dendrites of rotational symmetry and is therefore not directly applicable to the plate-shaped dendrites of ice obtained in the present study. There are practically no experimental observations of the effect of solute diffusivity on dendrite spacings in metallic systems. The reason appears to be the lack of experimental data on solute diffusion coefficients in liquid metallic solutions. The present work is concerned with the effect of solute concentration and diffusivity on dendritic solidification of dilute aqueous solutions: the solutes examined are potassium chloride. sodium chloride, lithium chloride. and hydrogen chloride. There were several reasons for selecting these solutes. The variation of dendrite spacing with freezing rate in these solutiolls is similar to that observed in A1-Cu alloys.8 These aqueous solutions have almost identical phase diagrams at dilute concentrations. Fig. 1. and the diffusion coefficients show very little variation with solute Concentration.9,10 Dendrite spacings were measured as a function of freezing rate. solute concentration. and solute diffusivity. Dendrite spacings were measured in two different types of freezing systems. droplet and unidirectional, respectively. In the droplet freezing system

Jan 1, 1970

By H. R. Gardner

The heat treatmmt of plutonium was studied using the Jominy end-quenching technique commonly used for determining the hardenability of steel. Plutonium specimens were end-guenched from temperatures in each of the ß, y, d, d') and E phases. One series of specimens with a low-iron content, 165 pprn Fe, and another gvoup with a high-iron content, 678 pprn Fe, were used in order to study the effect of a Pu-Pu,Fe eutectic network on the hardness and micro-structure. Hardness traverses indicated no significant variations in hardness with either cooling rate or quench temperature. Metallographic studies indicated major effects on microstructure. Grain size was found to vary markedly with quenching temperature and cooling rate. It was determined that the Pu-PueFe eutectic network could be modified extensively by heat treatment, including spheroi -dization in the y phase and 6 phase below 413°C. An unidentified spheroidal inclusion was observed to go into solution in the delta and higher temperature phases. 1 HE element plutonium is unique among metals in that it has six allotropic forms in the solid state.' These have been designated' as the a, ß, y, d, d', and phases. The respective phase transformations occur at approximate temperatures of 122", 210°, 319°, 450°, and 480°C with a melting point at 640°C. With this number of phase transformations it becomes pertinent to consider the effect of heat treatment and cooling rate in the various phases on the microstructure and hardness of plutonium. To determine; the effect of a wide range of cooling rates, the Jominy end-quenching technique was applied to cylindrical plutonium specimens. In addition, since the presence of iron in amounts greater than 500 pprn is common in plutonium and results in a network of the Pu-Pu6Fe eutectic, it was decided to study heat treatment effects on two bomb reduced plutonium buttons with different iron contents. A low iron button containing 165 ppm Fe and a high iron button containing 678 ppm Fe were selected for this comparison. EXPERIMENTAL PROCEDURE Experimental Material. The cylindrical bars for Jominy quenching were cast from button stock in vacuo in MgO coated graphite molds. Metal pouring temperature was approximately 950°C and the molds were preheated to 300°C. The castings were machined to 0.5 in. diam. by 2.5 in. long cylinders. Chemical analysis and density data for the two groups of Jominy specimens containing different iron contents are presented in Table I. Except for iron, heats 19-12-1 and 20-2-1 are comparable within the limits of analytical accuracy. Representative specimens from the low-iron and high-iron bars were taken for metallographic examination. The low iron specimen was found to have extensive microcracking, Fig. 1. In addition, numerous unidentified spheroidal inclusions were present, Fig. 17. The average grain size of the low-iron plutonium is 0.068 mm, Fig. 4. In the high-iron plutonium, a Pu-Pu6Fe eutectic network is prominent, Fig. 7. The average size of the network is 0.100 mm. Unidentified spheroidal inclusions were also common in the high-iron plutonium. The average grain size of the high-iron plutonium is 0.036 mm. Experimental Technique. A Jominy end-quenching fixture was fabricated for glove box use. A 2.5 in. water height was used with an orifice of 0.250 in. ID. The orifice to specimen distance was maintained at 0.5 in. Annealing temperatures of 160°, 265°, 400°, 465°, and 535°c were chosen for the study of the effect of quenching from ß, y, d, d', and e phases on microstructure and hardness. During quenching, cooling curves were obtained from the Jominy specimens at distances from the quenched end of 1/16, 1/8, 3/8, 3/4, 1-1/4, and 2 in. Cooling rate calculations were made from the cooling curves for temperature intervals of 100° to 110° 160" to 170°, 330" to 340°, 420° to 430°, and 490° to 500°c. These temperature intervals were chosen

Jan 1, 1962

By R. W. Armstrong, P. C. Jindal

The hardness dependence on grain size for polycrys-talline cartridge brass and a leaded brass has been measured by Brine11 and Rockwell B testing. In each case, the hardness, H, depends on the average grain diameter, 1, according to: H =Ho + kHl-1/2 where Ho and kH are experimental constants. Diamond pyramid hardness values have also been measured as a function of the indentation size and grain size to give additional information on the nature of the hardness test and the dependence of hardness on micro-structure. The hardness of polycrystalline brass depends on its grain size. Bassett and Davis' demonstrated this as early as 1919 by making Brinell hardness measurements on cartridge brass. Since then, the hardness of this type of material has been measured as a function of grain size by making Rockwell,2'3 Vickers,4 and Brinell5 tests. he hardness dependence on grain size has also been measured for other materials. Angus and summers6 investigated the grain size dependence of the Brinell hardness of polycrystalline copper and a Cu-4.5 pct Sn bronze. In other studies, nickel,? Armco iron,Big an Fe-0.07 pct C alloy,I0 and an 0.39 pct C-12.45 pct Cr stainless steel" have been investigated. In some of the preceding cases, the hardness results have been analyzed to show that the hardness varies with the average grain diameter, 1, according to an l-l\4, l-1/4 or I-2 dependence,11-13 The studies of the influence of grain size on hardness have not been based on any theoretical model. This may be because the hardness of a material is itself a complicated property. However, attempts have been made to correlate, experimentally and theoretically, the hardness of a material with its unidirectional stress-strain behavior.14-l6 On this basis, Hall" proposed that the polycrystal hardness dependence on grain size might follow directly from the Hall-Petch18,19 relation for the grain size dependence of the yield stress. Thus, the hardness-grain size relation was given as: H = Ho + kHl-1/2 [1] where Ho and kH were taken as experimental constants. The relation was applied to the measurements on brass,' copper,6 bronze,= and Armco iron.' More recently, this relation was shown by Armstrong and jindal20 to adequately describe the measurements on cartridge brass made by Bassett and Davis' and Babyak and Rhines.5 In this case, the relationship was taken a step further by independently relating the values of Ho and kH to the values of oyand ky, previously reported by Armstrong, Codd, Douthwaite, and petch21 from measurements of the yield stress dependence on grain size for this type of material. In the present investigation, new Brinell and Rockwell B hardness measurements have been made as a function of grain size for a cartridge brass and a leaded brass. In addition, diamond pyramid hardness values were measured as a function of the indentation size. All these results are applied to a further analysis of the hardness dependence on grain size. MATERIALS AND EXPERIMENTAL METHODS Cartridge brass and a leaded brass were selected for this investigation for two main reasons: it was anticipated 1) that these materials could be cold-worked and recrystallized to a wide range in grain size and 2) that the results to be obtained on these typical industrial materials could be usefully compared with previous investigations. The chemical analyses of the actual materials which were employed are given in Table I. The as-received 1/2- and 3/4-in.-thick plates were given various reductions in thickness by cold rolling. The rolled material was heat-treated at various temperatures between 330" and 850°C for differing time periods from 5 min to 9 hr to achieve a variation in the average grain diameter between 0.0339 and 0.000543 cm.22 During heat treatment, the brass was protected from zinc loss by packing it in chips or foils of the same composition material. Reasonably equi-axed grain structures were obtained in each case. The metallurgical grain sizes of the specimens were determined from measurements of the average linear intercept on a random line. Annealing twin interfaces were not counted along with grain boundaries. The

Jan 1, 1970

By Luckie. Peter T., Deurbouck. A. W., Harold L. Lovell, E. R. Palowitch, James K. Kindig

PART 1: DENSE MEDIUM SEPARATION by E. R. PALOWITCH and A. W. DEURBROUK INTRODUCTION During 1974, 43.9% of the 603,406,000 tons (549,099,000 mt) of bituminous coal and lignite produced was cleaned mechanically, of which 82,280,000 tons (74,875,000 mt) was cleaned by dense medium processes.l The percentage of bituminous coal and lignite cleaned mechanically by dense medium processes increased from 7 to 31 % between 1938 and 1974. Dense medium separations include those coal preparation processes which clean raw coal by immersing it in a fluid having a density inter- mediate between clean coal and reject. As there is a general correlation between ash content and specific gravity, it is possible to achieve the required degree of removal of ash-forming impurities from a raw coal by regulating the specific gravity of the separating fluid. Dense medium processes offer the following advantages over other coal cleaning processes: 1) Ability to make sharp separations at any specific gravity within the range normally required even in the presence of high percentages of the feed in the range of 2 0.1 sp gr units. 2) Ability to maintain a separating gravity that can be controlled with ± 0.005 sp gr units.

Jan 1, 1979

By Alberto J. Terrones L.

THE classical papers on contact metasomatic deposits by Lindgren on the Clifton-Morenci district,1 by Barrel1 on Marysville, Mont.,2 and by Goldschmitt on the Oslo district, Norway,3 laid the foundation for understanding of the importance of separating the metamorphic process from the subsequent metasomatic stage. Knopf4 made a big step forward by recognizing that sulfide ore minerals are invariably younger than silicates and by further stressing the importance of structural control5 ore finding. Some years later Harrison Schmitt6 fought the idea that contact metasomatic deposits are erratic, irregular, bunchy, economically marginal, and of small size, concluding that these descriptions have little factual basis. He emphasized the importance of detail mapping and careful geological study as fundamental requirements for a better understanding of these deposits. This article presents a comparative description of the structural features at the Magistral, Antamina, Morococha, Vilca, Ferrobamba, Katanga (Quibio), Tintaya, and Huarca contact deposits (Fig. 1). Further, it will describe how these structural features controlled the emplacement of the intrusives, their shape, distribution of metamorphic and metasomatic halos, and sulfide deposition in post-skarn structural channelways. Finally, the modifications introduced by a superimposed hydrothermal stage recognized at some localities will be discussed.

Jan 3, 1958