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By L. Leibowitz, M. G. Chasanov, L. W. Mishler

A drop calorimeter system is described for use in measuring enthalpies to 3600°K. Data are presented for tungsten between 2800" and 3600°K. The enthalpy of tungsten in cal per mole between 2000° and 3600°K can be represented by the equation HºT- Hº298 = - 1.7622 X 103 + 5.7772T + 8.9861 where T is in degrees Kelvin. A tabulation of com -puted values is presented for heat capacity, entropy, and free energy function. A drop calorimeter has been constructed to carry out enthalpy measurements at temperatures to 3600°K. Samples are heated by induction1 and dropped into a commercial adiabatic calorimeter, modified for this purpose. The experimental temperature is limited by the melting point of container materials and compatibility of the container and its contents. Several high-temperature drop calorimeters have been described in the literature1-5 but none has been used at temperatures as high as those in the present work; our measurements of the enthalpy of tungsten range from 2800" to 3600°K. DESCRIPTION OF EQUIPMENT An overall schematic view of the equipment is shown in Fig. 1. Power for the induction coil is supplied by a 25-kw 250 kHz Ther-Monic generator coupled to an iron core RF transformer. The Sample capsule is suspended in the work coil by 10-mil diam tungsten wires which are wrapped around a horizontal 5-mil diam tungsten wire. The horizontal suspension wire is clamped between two massive copper electrodes which are fixed in an x-y motion device that allows adjustment of the position of the heated capsule from outside the vacuum chamber. The copper electrodes are connected by flexible copper straps to a 1250-joule (5 kv, 100 pfarad) condenser bank. When it is desired to release the capsule, the condensers are discharged through the horizontal suspension wire causing it to vaporize rapidly. Very reliable and precise release of the capsule is achieved in this manner. Experiments have shown that no heat correction is required for this discharge energy. As part of the temperature measuring system, two prism holders have been incorporated in the apparatus. The upper prism holder is in the main vacuum chamber itself, whereas the lower one is in a side arm attached to the drop tube below the gate valve. The upper prism is mounted on a rotary vacuum feed-through, and may be moved under a protective shield when not in use. This prevents deposition of vapors on the prism surfaces when temperature measurements are not being made. Similarly, the lower prism is mounted on a push-pull vacuum feed-through, and when not in use may be pulled into its side tube. The prism mountings are fitted with guides and stops so that they may be moved precisely into the desired position. The aim throughout is to minimize the time the prisms are exposed to vapors from the hot samples. At the high temperatures reported in this paper, only the lower prism was used. The upper prism holder in these cases was fitted with an additional radiation shield. By using a prism and viewport, the lower surface of the samples can be observed by an optical pyrometer. The measurements discussed in this paper were obtained with a Leeds and Northrup 8622-C-S series manual pyrometer which is estimated to be accurate to 0.5 pct. Pyrometer calibrations and prism and window corrections were carried out in the conventional manner6 using tungsten strip lamps calibrated by the National Physical Laboratory, Teddington, England. Prism corrections were rechecked after each use. All work to date has been done in vacuum, and no measurable change has been observed in the prism correction below -2300°K for the upper prism and below -2800°K for the lower one. The total time of exposure of the prisms is about 50 sec per run. At high temperature, the final temperature reading is corrected by using the final A value for the prism; see Ref. 6 for details of this procedure. The calorimeter is a modified Parr Instrument Co. (Moline, lll.), Series 1230 adiabatic calorimeter with automatic jacket control. Other authors5 have used a similar calorimeter with good results. The calorimeter jacket cover and calorimeter cover are attached to the drop tube which contains a radiation shield. This shield is a gold-plated copper disc which can be operated manually from outside the calorimeter. The receiver is attached below the radiation shield and is lined with tungsten. In a typical experiment, the calorimeter and its jacket water temperatures were adjusted to 0.000°K temperature difference. The sample was allowed to equilibrate in the furnace at the desired temperature for about 20 min. The initial calorimeter temperature was then recorded, the sample dropped, and appropriate shutters closed. After about 3 min, the drop tube and receiver were filled with helium to 60 torr. The final calorimeter temperature was recorded after it had remained constant over a 5-min period. The equilibration time in the calorimeter was about 25 min. Thermistor probes are used to operate a hot and cold water supply system to maintain the jacket temperature equal to the calorimeter temperature. For actual measurements of the calorimeter temperatures, a quartz thermometer was used (Hewlett Packard Dymec Thermometer, Model #2801A). This thermome-

Jan 1, 1970

By S. Feuerstein

THE influence of environment on the mechanical properties of metals has been extensively studied and documented.' Most investigations have dealt with an interaction between a particular environment and a specific metal surface and the concomitant change in bulk mechanical behavior. Typical contributing media are oxide and metal film:;, electrolytes, and other surface-active agents. In the last category fall controlled gaseous environs (i.e., pressure or vacuum). Most vacuum exposure experiments prior to 1963 were conducted at pressures s>10-6 torr and elevated temperatures, or in such a manner as to prolong the exposure (e.g., by stress-rupture, creep, and fatigue). Little attention has been given to vacuum environment effects on the mechanical behavior of metals subjected to simple uniaxial deformation at room temperature. Test times and temperatures were assumed too ineffective as far as bulk changes were concerned. Further, the contribution of surface effects to the bulk mechanical behavior of metals was considered minimal. Under vacuums of the order of 1.0- 8torr and higher, molecular densities and, consequently, the rate of monolayer formation are such that exposures from seconds to days would be required for complete gas coverage. Thus, atomically clean surfaces created under ultra-high vacuum could conceivably maintain their cleanliness for time intervals orders of magnitude greater than at higher pressures. The influence of this unusual type of environmental surface phenomenon on the short-term bulk mechanical behavior of aluminum was first observed by Krame and Podlaseck in 1963.' kin equivalent effect was reported for magnesium by Williams and Nelson.3 It was concluded from these studies2,3 that vacuum and, consequently, the monolayer formation rate of the oxide, were responsible for the described changes in flow behavior. The presence of an oxide layer impedes dis- I) EXPERIMENTAL DATA: MOLYBDENUM The tensile behavior of molybdenum was investigated by the author4-6 at ambient temperature over a range of pressures from 760 to 10-10 torr. These studies revealed that the flow behavior of the bulk specimens (0.200 in. diam by 2 in. gage length) was independent of pressure on sintered (0.062 mm grain size) and arc-cast polycrystals (0.012 to 0.149 mm grain sizes) and single crystals. Since the specimens were relatively large in size, it was assumed that any flow behavior effect would be surface-limited because of the short-term deformation procedure. Strain-rate-change experiments performed to determine the activation volumes for individual specimens at 760 to 10- 10 torr further indicated that the surface flow contribution was either minimal or zero, contrary to the findings of Shen el a1.7 on aluminum. Although the flow behaviors did not change, specimen ductility did change. For the sintered material at a strain rate of 4.2 x 10-4, specimen ductility was -9 pct higher at l0- 10 torr than at atmospheric pressure (dry nitrogen). A more comprehensive investigations on this same material revealed a distinct pressure dependence, Fig. 1. Intermediate and atmospheric pressure tests were obtained by backfilling the system from l0- 10 torr with extra dry, prepurified nitrogen. Other environments (air and purified argon) were also utilized for the 760 torr experiments; the results were essentially the same as those for dry nitrogen atmospheres. Departure from the fracture strain values obtained at 760 torr takes place in the vicinity of l0-6 torr, as indicated by the scatter band; a noticeable ductility increase is apparent at l0-8 and 10-10 torr.

Jan 1, 1970

By M. C. Irani

This study is a survey of supply and demand for minerals, metals, alloys, and compounds used by the chemical industries in the Ohio River Basin (ORB) area of Ohio, Pennsylvania, and West Virginia during 1967. Data for the study were obtained from completed questionnaires received from chemical manufacturers and from interviews with officials of chemical companies and mineral producers and distributors. The information includes kind, quality, quantity, values, sources, specifications, uses, and methods of transportation. Results of the study show that of the total value of mineral materials consumed by the chemical industry, manufacture of inorganic chemicals consumed 46 percent; fertilizers, 22 percent; and soaps and detergents, 19 percent. Fifteen commodities accounted for 91 percent of the total value of mineral materials consumed. Five of these--phosphates, potash, salt, sulfur, and titanium dioxide--accounted for 59 percent of the total.

Jan 1, 1970

By M. J. Marcinkowski, D. B. Crittenden, A. S. Sastri

A study co.mbining stress-strain .measurements in conjunction with transmission electron microscoPy has been made with near equiatomic Fe-Cr alloys which were aged for various times at 500°C. Associated with this aging is a marked increase in deformation twinning. The outstanding feature of these twins is that they generate stress fields sufficiently great so as to give rise to spontaneous dislocation loop nucleation nearly normal to the propagating twin. This observation is in agreement with the theoretically predicted elongation of the stress field of a dislocation Perpendicular to its direction of motion as it moves near the speed of sound. Dislocation loop nucleation is more difficult in the longer aged alloys so that this energy absorption mechanism is not effective in hindering twin propagation. Since crack nucleation can readily occur near the tip of a twin, the aged alloys become extremely brittle when deformed in tension. Iron-chromium alloys in the vicinity of the equiatomic compositions become severely embrittled when aged at about 500°C. Fisher et 01.' have shown that this embrittlement is related to the decomposition of the original random Fe-Cr solid solution into a chromium-rich and an iron-rich phase. In addition, Mar-cinkowski et a1.' have shown that twinning becomes an increasingly more important mode of deformation as the aging time is increased. These results have been recently corroborated by the transmission electron microscopy study of Mima and amauchi . The Fe-Cr alloy thus seems ideal for verifying the predictions made in Parts I4 and 115 of this investigation where the behavior of large static or blocked twins and those of large dynamic or propagating twins, respectively, were investigated numerically. It was thus decided to measure the stress-strain curves generated by embrittled alloys that were aged for various times and to examine sections by transmission electron microscopy. EXPERIMENTAL PROCEDURE Electrolytic iron and electrolytic chromium were vacuum-melted and poured into ingot form. The composition of the resulting alloy was found to contain 46.0 wt pct Cr (47.8 at. pct), the remainder being iron. The resulting ingot was swaged above 850°C into 0.250-and 0.400-in.-diam rounds. Compression samples of 0.250 in. diam and 0.400 in. long were cut from the smaller-diameter rounds. These samples were then sealed in evacuated quartz tubes and annealed for 30 min at 1150°C to produce a uniform and equiaxed grain size of mean diameter equal to 1.73 mm. They in turn were rapidly quenched from 850°C so as to preserve the condition of random solid-solution characteristic of the elevated temperature. The samples were then aged for various times up to 300 hr at 500°C in a massive Pb-Bi alloy bath. The samples were next polished and tested in compression at room temperature as described in Ref. 6 using an Instron tensile testing machine. The strain rate used was 0.05 in. per in. per min. The remaining larger round was converted into compression specimens of 0.325 in. diam and 0.500 in. long. This larger diameter enabled wafers of sufficient size to be prepared for examination by trans-mission electron microscopy techniques after subjecting them to a suitable strain. Foil preparation is described in some detail in Ref. 6. All foils were examined in a type HU-11A Hitachi electron microscope operating at 100 kv. RESULTS AND DISCUSSION Fig. 1 shows the effect of aging at 500°C on the room-temperature stress-strain curves of the FeCr alloys. For greater clarity the origin of each curve has been displaced upward. The same origin has been used for both the 0 and the 0.1 curves. It is apparent that with increased aging times a sharp drop in load is observed at the yield stress which becomes more pronounced as aging proceeds. A loud sonic burst accompanies this drop and subsequent metallographic examination shows the sample to contain numerous twins. For intermediate aging times, a number of smaller twin bursts follow the initial large one. The total plastic strain associated with the twinning mode of deformation can be obtained by adding up the contributions AE~ from all i twin bursts, i.e., £,¦££,-, in the manner illustrated schematically in Fig. 2. The contraction of the specimen, as measured from the strip chart of the Instron, after suitably correcting for the elasticity of the machine, was converted into true strain using the assumption that there was no volume change and that the sample remained cylindrical. The dashed lines are all drawn parallel to the

Jan 1, 1970

By K. Shikaze

"For the last three years (1967-9) the value of the output of mineral resources in the Province of Ontario exceeded one billion dollars per year. To produce this great wealth, it was necessary for the mining industry in Ontario to dispose of an estimated 80 million tons of waste mill tailings. Some of these tailings were returned underground but the greater proportion was disposed of above ground in lakes, watercourses, marshy areas and in engineered impoundment basins. This volume of tailings, if accumulated in one location would cover an area of 1000 acres to a height of almost thirty feet. The provision of proper disposal of the waste mill tailings in a manner such that they will not create problems in the environment is one of the costs which must be borne from the extraction of such a wealth from our mineral resources. It is principally the potential water pollution which may occur as a result of the indiscriminate discharges of waste mill tailings which is of concern to the Ontario Water Resources Commission.ONTARIO WATER RESOURCES COMMISSIONThe Ontario Water Resources Commission was formed in 1956 and operates under the Ontario Water Resources Commission Act. The Act has been broadened and amended many times by amendments."

Jan 1, 1970

A new test coke oven of 7 cu. ft. capacity is described. The oven was designed to simulate conditions in a central section of a battery oven and a special feature is the achievement of unidirectional heating from theflues on either side of the charge.The method of charging permits close control of charge conditions such as bulk density and moisture content.These conditions, as well as coking conditions (e.g. flue temperatures and coking time) must be varied to simulate conditions in different batteries. The effects of several variables on coke quality are discussed.Using test oven conditions corresponding to those of Newcastle steelworks batteries, good agreement was obtained between strength indices of test oven and battery cokes. For 17 tests, the average ASTM stability and hardness indices for the test oven coke were 38· 5 per cent and 69·7 per cent, while those for the battery coke were 37· 4 per cent and 67·6 per cent.Observed relationships between coke yield and productivity, and volatile matter and charge moisture are given.The use of a test oven to classify test coals into prime-, medium-, poor-, and non-coking coals is discussed.This may be achieved by observing the effects of the test coal in blends with other coals. The results of a series of blending tests are presented.The dangers of attempting to predict coke quality from a single coal property are pointed out, since this can be done only for very restricted ranges of coals.A diagram is given showing the established trends in the effects of blending various types of Australian coals on coke strength.

Jan 1, 1970

By John B. Pate

In a recent issue of the Mining Congress Journal, J. L. Gilliland discussed the relationship of air quality criteria, standards, and regu¬lations (1). As he pointed out, The Secretary of the Department of Health, Education, and Welfare is charged with issuing "Air Quality Criteria" which are statements concerning the concentration-effects relationship of an air pollutant. These "criteria" provide the states with a basis for their air quality "standards," which may lead in turn to emission "regulations." He further cites a list of major factors described by the National Air Pollution Control Administration, which must be considered in developing criteria. These are: properties of pollution; responses; measurement methods; exposure parameters; and characteristics of receptors. Although we briefly discuss the first two items, the principal concern of this paper is with the third item, the methods of measurements. In attempting to define responses, it has proven surprisingly difficult to establish a clear-cut cause-effect relationship between air pollutants and impairment of health. It is perhaps not too surprising that the ecological approach currently in fashion seems to be a much more powerful tool in defining cause-effects relationships. Without belaboring the point, we would like to point out that establishing such cause-effect relationships have tremendous legal and financial implications e.g., consider the possible establishment of such a relationship between pollution and inadvertent weather modification.

Jan 1, 1970

By H. J. Levinstein, H. J. Guggenheim, C. D. Capio

An optical incestigation of the phase transformations in RbFeF, has been conducted. Details of the ferromagwetic phase transition and the metamagnetic state are disczrssed. The three-dimensional magnetic domain structure existing in bulk crystals of RbFeF3 is described, as well as the effect of the magnitude and direction of the applied magnetic field on the domain struclure. The strong magnetoelastic interaction in RbFeF, is demonstrated. The results of the direct observation of the role of dislocation subboundaries and slip bands as nucleation sites and as pinning sites for magnetic domain walls are reported. THE perovskite compound RbFeF, has recently been shown to exhibit three magnetic states.''' Above 102°K it is paramagnetic, between 102" and 87°K it is antiferromagnetic. and below 87°K it is ferromagnetic (i.e., exhibiting remanence) with a modification of the magnetization occurring at 40°K. The changes in magnetic structure at 102o, 87°. and 40°K are accompanied by shear transformations to successively lower crystal symmetry classes.3 At 102°K a second-order phase transformation to a tetragonal crystal structure occurs. The c/o ratio increases with decreasing temperature to a value of 1.0034 at 87°K where the crystal undergoes another shear transformation to an ortho-rhombic crystal structure. The magnetic modification at 40 K is also accompanied by a shear transformation to a lower crystal symmetry. RbFeF3 is unique in that in the ferromagnetic state it is transparent in the bulk to visible light, has a low saturation magnetization, a large magnetic rotation. and has good optical properties.' All these features make it an ideal material for the investigation of magnetic domain structures in bulk crystals. In addition a dislocation etch has been developed which reveals the point of emergence of dislocations with the (100) surfaces of RbFeF3,5 making it possible to determine the dislocation arrays in the material. As a result domain wall dislocation interactions can be observed in the bulk crystal. In this paper we report on 1) the crystallography of the phase transformations in RbFeF3. 2) the domain configurations as a function of magnetic field and crystal orientation. 3) the interaction of dislocations and magnetic domain walls in RbFeF,. EXPERIMENTAL PROCEDURE Since the temperature range of interest is below room temperature the dewar shown in Fig. 1 was employed. It was designed to fit on the stage of a Leitz panphot metallograph, and permitted examination of the sample at a magnification up to 150 times. The dewar consists of a double-walled glass cylinder bent into an L shape. The space between the walls is evacuated. The viewing wirldows were made of four optically flat quartz discs aligned parallel to each other and sealed to the sides of the concentric cylinders. The specimens were mounted in a holder attached to a flexible plastic shaft. Various holder designs were employed depending upon the type of observations to be made. For studies of the phase transformation between the antiferromagnetic and ferromagnetic state the holder shown in Fig. 2(d) was employed. This holder permitted accurate temperature control at 82" to 88°K by balancing the heat input from the carbon resistance heater against the heat loss to a heat sink immersed in liquid N2. Magnetic field studies were conducted by employing the holders shown in Figs. 2(a) and (b). The holder shown in Fig. 2(n) has a solenoid imbedded in it. such that the magnetic field direction is in the same direction as the incident light. The magnetic field provided by the holder in Fig. 2(b) is perpendicular to the incident light direction. The holder in Fig. 2(r) was employed when observations of the specimen were desired while an elastic bending stress was applied to the sample. The stress was applied to the sample by pulling a wire from outside of the dewar. The wire was attached to a lever pivoted on the holder. which caused the knife edge of the lever to push against the sample. The crystal growth and the sample preparation were described previously.' PHASE TRANSFORMATIONS The first phase transformation in this system is from the cubic perovskite structure to n tetragonal

Jan 1, 1970

By R. Walker, R. J. Anslow

Today at Tampa we see the end results of a team effort: A vital link in an intermodal transportation system, the link that enables the unit-train concept to be employed with full effectiveness and the link that improves the economics of water transportation systems. Two new phosphate transfer complexes with a multi- million ton annual capacity are in operation in Tampa, Fla. Revolutionary in concept, these companion installations represent a total investment in the Tampa Bay area of $18.5 million.

Jan 1, 1970

By G. H. Gronhovd

This is the final report on a research program to develop a pilot plant gasifier for slagging gasification of lignite at high pressures and to obtain process data under various operating conditions. An operable pilot plant was developed, and the test results show that lignite is well suited for the process. Tests were run at pressures from 80 to 400 psig, and the results indicated that pressure had little effect on gas composition or the material requirements per unit gas produced. Gas production rates as high as 26,000 scfh/sq ft of reactor area were obtained at 300 psig, but limitations on auxiliary equipment prevented full-capacity operation at 400 prig. In several tests lignite having a 37-percent moisture content and 2,500° F ash-fusion temperature was successfully gasified. Refractory materials were found to have a short life in contact with high-temperature slag, and a water-cooled taphole was developed. Exploratory tests with coking coal were unsuccessful.

Jan 1, 1970

By Carlos A. Aranda

The Smelting and Refining Department of Cerro de Pasco Corporation is located at La Oroya at an altitude of 3,720 meters (12,205 feet) in the Peruvian Andes. Producing lead, zinc and copper as well as twelve by-product metals and chemicals, the smelter is among the world's most complex. With the intake of high-bismuth ores in 1934, electrolytic lead refining by a modified Betts process was piloted and the plant went into commercial production in 1937 at a nominal capacity of 100 M.T. per day. After expansions in 1950 and 1963, nominal capacity has increased to 250 M.T. per day. Anodes spaced at 10.8 cm centre to centre and starting sheets are both set into the cells by overhead cranes. The asphalt-lined concrete cells are arranged in a Walker side-by-side configuration, and the electrolyte, circulating at 13 l/min./cell, is a solution of locally-produced hydrofluosilicic acid and lead fluosilicate. The corrosion cycle is limited to four days due to high impurity content of the bullion, which has successfully been treated at contents of up to 9% impurities. The cathodes are melted, drossed, and cast into blocks and pigs assaying 99.997 + % lead. The anodes with the blanket of slime adhering, are washed with electrolyte and condensate makeup water to remove the concentrated lead fluosilicate entrapped in the slimes. The slimes are then removed with high-pressure water sprays, centrifuged and sent to another plant for recovery of silver, gold, bismuth, selenium, tellurium, and antimony.

Jan 1, 1970

By R. B. Schluter, M. M. Fine

Processes for manufacturing prereduced pellets have heretofore required temperatures of 2100°F or higher. Sulfides will accelerate the liquid-phase sintering of metallic iron, yet do not deter the reduction of iron oxides. The sulfides may be introduced as gases to the kiln atmosphere or as solids in the re-ductants. The net result is that well metallized iron pellets with good crushing strength can now be produced at a little over 1800°F. One of the most persistent topics at technical gatherings and in the recent scientific press has been the reduction of iron ore. In May 1960, a symposium on the subject was sponsored by the Electrochemical Society. The proceedings, comprising two dozen papers, were later published.' More recently, in November 1966, a similar gathering took place at Michigan Technological University, Houghton, Mich. The latest meeting was the International Congress on Production and Utilization of Reduced Materials at Evian, France, in May 1967. If the volume of literature, symposia and conferences is a measure of industry concern, then the current interest in reduction must be at a high level. Barrett,2 one of the early pioneers, stated some years ago that "The history of sponge iron has been so discouraging that many men in the iron and steel industry are violently opposed to giving it any further consideration." In spite of the "violent opposition" noted by Barrett, research people in and out of the industry continue to be attracted by the elusive prospect of uncovering a simple, viable means of direct reduction. Wild,3 one of the speakers at Evian, listed no less than 48 direct reduction processes (laboratory, pilot plant and commercial). Some of these were of historical interest only, but many others had resulted from developments within this decade. The previous big thrust into direct reduction occurred under the artificial impetus of a wartime economy (World War 11) and was largely an effort to provide more melting stock without coke ovens and blast furnaces. The present-day inquiry is proceeding at a more leisurely pace and the emphasis is different. For one thing, there is much less anxiety to circumvent the blast furnace. On the contrary, a whole new research endeavor has grown from the discovery that metallized burdens are exceptionally productive.4 Although the search for a melting stock

Jan 1, 1970

Denver, the Mile High, Queen City of the Plains, your host for AIME's 99th Annual Meeting has many exciting and picturesque places for you to visit during your stay. A host of restaurants cater to every taste; supper clubs and theaters provide nighttime entertainment; there are sports facilities and a plethora of shops for the ladies. When it comes to dining out, there are many excellent restaurants within walking distance of the Denver Hilton --among them, three in Brooks Towers: the Gitana, the Boston Half Shell serving the finest seafood, and Marvelous Mary's. In the Larimer Square area there in the Bratskellar with a true Germanic atmosphere and Sperte's Laffite offering a typical New Orleans setting.

Jan 1, 1970

By C. D. Hall

This paper may be divided into two main parts: (1) analysis and data to show that Eq. 6 adequately correlates the authors' experimental data, and (2) the assertion that Eq. 20 "should permit scale-up with data taken from one pipe diameter for Newtonian, inelastic non-Newtonian, and viscoelastic fluids, such as dilute polymer fracturing fluids, which produce considerable pressure reductions." The authors might well recommend that this broad grouping of fluid types could be correlated by using Eq. 6 (requiring data from at least two pipe diameters). On the other hand, Eq. 20 is only shown to be adequate for conditions within the range of the present data set. Specifically, predictions by Eq. 20 for diameter scale-up to casing sizes would give larger deviations than implied in Table 2, and scale-up for some other fluids that give large drag reduction could be grossly in error. The description of a class of fluids "which produce a diameter family of straight parallel lines on a log (d?p/4L) vs log (8 v/d) plot. . ." defines a necessary condition for using Eq. 6; i.e., that s shall be constant for each fluid. The proposal that Eq. 20 is applicable to turbulent flow of such fluids is equivalent to saying that the spacing of these parallel lines, with A being constant, will be found to correspond to m = -1.20 for all such fluids. Table 1 shows the values of m derived from data on 16 non-Newtonian fluids. The key statement of this paper is that the diameter exponents "do not vary significantly from . . . -1.20." In statistical terms, this says that the m value for each fluid, which was obtained from all the measurements made on that fluid. has not been shown to be different from the arithmetic mean of the m values for the 16 fluids tested. This implies that the group mean, -1.20, is a more reliable value to use for an individual fluid than is the m value derived from the data on that fluid alone. No statistical test is described to support the key statement that the diameter exponents do not vary significantly from -1.20. Such a test would have to take into account that each individual m value is shown to correlate the pressure gradients for its fluid, with only about 3 percent standard deviation over the diameter range covered. That is, the m value is not the result of a single independent measurement. Thus, it would not be sufficient, or valid, to compare the deviation of one of the m values with the variance of the 16 values of m about their mean. An alternative interpretation of the key statement is that the diameter exponents do not vary appreciably from -1.20; i.e., that using -1.20 does not cause serious inaccuracy. Table 2 seems to be offered in support of such an assertion. However, such a statistical treatment (1) is unnecessary and (2) cannot lead to any valid scale-up generalization. The amount of error introduced by using a 1"wrong" value of diameter exponent — i.e., -1.20 instead of m — is determined by Eq. 6. The ratio of the pressures predicted by Eqs. 6 and 20 for scale-up from ds in small pipe to d, in casing is The pressure for 30-percent calcium carbonate slurry (m = -1.112) in 10-in. ID pipe would be predicted 30 percent higher by Eq. 6 than by Eq. 20, if based on tests in 0.5-in. ID pipe. The data set tested in Table 2 represents only a limited sample of pipe diameters (ratio of about 4:l) out of the population of diameters that would

Jan 1, 1970

By Mary H. Brown

The heats of formation of oxalic acid and sodium, potassium oxalates, and lithium oxalates were related by solution calorimetry to the heat of formation of (COOH)2.2H20, a value believed to be reliable as reported in the literature. The following heats of formation were determined: (COOH)2(a), -198.1±0.1; (COOH)2(ß), -197.8±0.1; UAW,, -328.7±0.4; Na2C204 -316.2±0.1; K2C204, -321.9±0.2; and K2C204-H20, -393.5±0.2 kcal/mole. The heat of the crystalline transformation (COOH)2(a) ? (COOH)2(ß) was determined to be 0.30±0.02 kcal/mole at 298.15° K.

Jan 1, 1970

By K. Takahashi, I. Iwasaki

The methyl stretching vibrations for a series of normal xanthates, isoxanthates and normal amines were determined with the aid of an infrared spectro-photometer, and the results were compared with published information on the corresponding alcohols. The frequency shifts of methyl stretching vibrations may be attributed to the inductive effect of polar groups. The hydrogens in the shorter chain alkyl groups are somewhat polar and can be expected to interact with water molecules by hydrogen bonding. Contact angle, surface tension lowering, solubility, and critical micelle concentration appear to be related to the induced polarity of the alkyl groups. Traube's rule states that in homologous series of compounds solubility decreases and surface activity increases regularly with the size of the hydrocarbon group. Analyzing the work of transfer of a solute from solution to surface, Langmuir' interpreted this rule to mean that each CH2 group added to a molecule produced its effect independently of the others. It is also well known2 that the maximum equilibrium contact angle with sulfhydryl collectors is independent of the polar groups and of the sulfide minerals, and that it increases to a certain limit with the number of carbon atoms in the alkyl group. This observation is thought to demonstrate the orientation of the collector molecules at the sulfide surfaces. The dependence on the hydrocarbon chain length is usually explained as due to the screening of the force field of polar mineral surfaces.3-5 Here again, Langmuir's principle of independent surface action appears to be implied. Heteropolar compounds consist of nonpolar and polar groups, the former being the hydrocarbon group and the latter containing such electronegative atoms as O, N, S, P, or halogens. According to Palit6 the hydrogens in the alkyl groups are more electroposi- tive than in the paraffins owing to the negative inductive effect of the polar groups and a possibility that a hydrogen bond with water molecules ensues. Goto and Takenaka7 provided direct evidence of the inductive effect by measuring the shift of the C-H stretching vibrations of alcohols, acids, and alkyl bromides with an infrared spectrophotometer. Their approach appeared to be directly applicable to the studies of surface activity both at air-water and water-mineral interfaces encountered in flotation systems. The present article attempts to relate the C-H stretching vibrations of alkyl xanthates, alcohols, and amines with such flotation chemistry parameters as contact angle, surface tension lowering, solubility, and critical micelle concentration. MATERIALS AND METHODS Normal xanthates from methyl to octyl inclusive and the isopropyl, isobutyl, and isoamyl xanthates used in this investigation were prepared in the usual manner.8 Normal amine hydrochlorides with carbon chain lengths of 1, 2, 4, and 6 were from Distillation Products Industries, of 8 from Archer-Daniels-Midland Co., and of 10, 12, 14 and 16 from Armour and Co. Normal propylamines, pentylamines and heptylamines from Distillation Products Industries were used both as received and as hydrochloride formed by converting the amines according to the procedure described by Li9 Perkin-Elmer Model 521 and 621 infrared spectro-photometers were used to investigate the spectra in the frequency region of 3050 to 2800 cm-' with frequency scale expansion. The accuracy of the frequency readings was within + 1 cm-1. The KBr micropellet technique was used to prepare the xan-thate samples for measurements, and the halocarbon mull technique was used for amines and amine hydrochlorides. EXPERIMENTAL RESULTS Fig. 1 shows the CH3 asymmetric stretching vibrations as a function of the number of carbons in the alkyl group for normal xanthates, isoxanthates and amines. Also included in the figure are data for normal alcohols and isoalcohols taken from the article

Jan 1, 1970

By Raymond O. Dannenberg

Potential processes for the recovery of precious metals and copper from diverse types of complex electronic scrap were investigated. Leaching-type processes were not successful, and attempts to physically separate the various gangue metals and plastics from more valuable components were also unsuccessful. The most promising approach was a smelting process, followed by electrolytic treatment to separate precious metal from copper. Recovery of precious metals from the anode sludge may follow conventional procedures. An alternative to the above process is incorporation of the scrap with the concentrate fed to an industrial copper reverberatory or converter furnace, possibly preceded by direct melting to form an assayable bullion and dross.

Jan 1, 1970

By T. Toda, R. Maddin

A study has been made of the microstructure and mechanical properties of splat-cooled aluminum-base gold alloys with gold concentration from 0.25 to 5.0 wt pct. These alloys have been quenched from the liquid state by a torsion-catapult technique, which has made it possible to pepare specimens suitable for mechanical property measwements. From the electron micrographs it has been shown that the solid solubility of gold in aluminum can be extended to 2.5 wt pct (0.35 at. pct) by splat-cooling, while the maximum equilibrium solubility is known to be less than 0.3 wt pct (0.04 at. pct). The very fine grain size (several tenths of a micron), the extended solid solubility, and the fine dispersion of a second phase (AuAl2) contribute concurrently to a substantial strengthening effect. In Al-5 wt pct Au splat-cooled specimens of less than 50 thickness, the yield strength is 17 kg per sq mm or 6 times as large as the strength of bulk specimens. For the Al-1.0 to 2.5 wt pct Au solid solution obtained by splat-cooling, the yield strength reaches 7.5 kg per sq mm after an aging treatment (for 10 hr at 200°C), while it is 3.7 kg per sq mm for the corresponding bulk specimens. A great deal of research has been done in recent years on the structure and the properties of metals and alloys rapidly quenched from the liquid state.' The term "splat-cool" has been used with the meaning of a rapid quenching from the liquid state., The splat-cooling techniques have produced large numbers of new structures, which are expressed in terms of metastable phases,3 concentrated solid solutions,4 amorphous phases,5'6 new phases,7 and so forth. Nearly all previous studies have concentrated on the physical properties; i.e., crystallography, structure, electrical resistivity, magnetism, and so forth, of the splat-cooled metals and alloys. The mechanical strength of splat-cooled metals and alloys has hardly been investigated except for some recent work by MOSS' on A1-V alloys. The principle common to all experimental techniques developed to obtain very rapid quenching rates is based on the heat transfer by conduction. Liquid must be in good thermal contact with a substrate of high heat conductivity. Both of the published devices known as the "gun" and the "piston and anvil" techniques suffer from certain shortcomings. For example, the specimen obtained by the gun technique is very small and flaky, and hence inadequate for mechanical properties measurements. On the other hand if the material is forced to yield a continuous speci- men by the piston and anvil technique, it is probable that some plastic deformation occurs during the quench. A novel method for rapid quenching of a liquid metal or alloy, the "torsion-catapult", has been devised by Roberge and Herman9 at the University of Pennsylvania. In the apparatus the melt is thrown out of a curved furnace by a catapult and impinges on a copper substrate. The apparatus has the advantage of producing a continuous foil which is relatively large in size and of a quality suitable for the measurements of mechanical properties. The quenching rate is estimated to be of the order of l05 to l06 ºC per sec, (comparable to rates achieved by the piston and anvil technique). In selecting an alloy to be studied we were made aware of the fact that gold was believed to be "insoluble" in in and consequently age hardening in the A1-Au system appeared to be interesting. Quite recently Heirnendahl13-15 revealed that the solid solubility, as determined by transmission electron microscopy, was 0.3 wt pct Au at 640°C and 0.25 wt pct Au at 600°C, decreasing with decreasing temperature. In an A1-0.2 pct Au alloy after quenching from a solution treating temperature of 600°C the yield stress was 2 kg per sq mm, and it increased up to 6 kg per sq mm after aging for 1 to 10 hr at 200°C. The precipitation occurred in the form of platelike particles mainly on (100) matrix planes. The intermediate phase n', the equilibrium phase n (AuAl2), and lattice relationships between both precipitates and the matrix were also investigated by electron microscopy. One of the purposes of the present research is to determine whether or not the solid solubility in this system, in which gold has a very small solubility in

Jan 1, 1970

By A. L. Mular

This paper provides a worthwhile contribution to the knowledge needed for calculating and using mathematical models of grinding circuits. The computer search algorithm proposed should remove much of the guesswork as well as reduce computer processing costs and improve the accuracy of estimated parameter values for grinding mill models.

Jan 1, 1970

By C. L. Horn

All the tunneling machines discussed in this chapter are Calweld machines. I have divided the machines designed for soft-to-medium formations into three groups, correlated with typical formations and estimated compressive strengths: 1) Running sand and silt requiring blade cutters. 2) Chalk and clay, requiring drag-type cutters, for compressive strengths ranging from 0 to 2000 psi. 3) Sandstones, hard clays, and limestones, requiring disk cutters, for compressive strengths ranging from 2000 to 20,000 psi. All of the soft-to-medium-formation machines are powered by electric hydraulic or diesel hydraulic pumps. The pumps in turn drive hydraulic motors for the torque reaction. The soft-to-medium-formation machines are enclosed in a 360º shield with a cutting shoe, a center portion of the shield housing the mechanical equipment, and a tail shield. Tunnel supports are usually required, and the supports are normally erected in the tail shield. Our first machine was built in 1963, and all but five of the machines illustrated in the figures with this chapter were built in 1966 and 1967. Some of the machines manufactured will be discussed in the following sections; specific features as development has progressed will be pointed out. HARD-ROCK MACHINE The Calweld hard-rock machine has been designed along basic and accepted principles for a hard-rock mechanical borer. The features of this machine are as follows: 1) Direct electric motor drive through a planetary gear reduction ring and pinion gear, and then to the cutting head through a hollow drive shaft.

Jan 1, 1970