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By D. H. Baldwin, R. E. Reed-Hill

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By Joseph A. Cavallaro

This report describes the timed release analysis technique that was developed to serve as a tool for assessing the froth flotation cleaning potentials of fine-size coals. Using this developed technique, 16 coals from 10 different coalbeds were tested. All of the coals included in this study were quite amenable to froth flotation with float coal yields ranging from 80.7 to 99.5 percentage points. Float-and-sink analyses of the coals tested are shown to be of limited value in predicting froth flotation cleaning potential. Generally the float-and-sink analyses indicated a better product could be obtained than froth flotation could provide; although, in four of the coals tested froth flotation results were superior to those expected from the gravimetric analysis. The fixed carbon content of the samples collected was found to correlate with the floatability of the coals. The higher rank coals were the most readily floatable coals while the lower rank coals did not respond quite as well to flotation.

Jan 1, 1965

By Frank A. Jerabek

Problems of mine backfilling and fill material deposited underground, the characteristics and relationship between the deposited fill material and overlying ground, and the practical applications and limitations of hydraulic backfilling as ground support are discussed. A great variety of materials ranging from coal washery refuse to concentrator tailings is used as hydraulic fill. Some materials will solidify and cement; others will resemble quicksand, Hydraulic fill as ground support is more efficient in inclined mine openings than in horizontal mine openings, where it cannot be placed tightly to the back. This and other deficiencies of hydraulic backfilling led to the development of pneumatic stowing. Research work in hydraulic backfilling at the Pennsylvania State University is also discussed. This research work includes the investigation of segregation in the discharged fill slurry, the quantity of solids escaping in the drain liquid, the relationship of escaping solids to slurry concentration and discharge rate, and the compressibility of fine fill material.

Jan 1, 1965

By B. B. Letson

The heats of formation of lithium chloride and lithium oxalate were determined with the aid of a Bureau-developed, glass Dewar-type solution calorimeter which uses thermistors as its temperature sensing element. Values obtained at 298.15° K were -98.38 ± 0.54 kcal/mole for lithium chloride and -329.02 ± 0.79 kcal/mole for lithium oxalate, using graphite as the standard state for carbon.

Jan 1, 1965

By I. R. Kramer

In his technical note entitled "Specimen Temperature During Electropolishing of Aluminum Crystals" Dr. Nakada 1 reported that the temperature of his aluminum specimen increased 65°C when it was polished electrolytically; he therefore concluded that the temperature of the specimens used in our work (Nakada's Refs. 4 and 5) similarly increased by this amount. From this he further concluded that the change in plastic-flow characteristics associated with the removal of the surface by electropolishing during deformation were due solely to a temperature effect. We believe that these conclusions are not justified. It is, of course, realized that the amount of the temperature increase is associated with the total heat transfer of the entire system, including the efficiency of the stirring action, heat flow through the grip on the specimen, and so forth. Of great importance is the type of electrolyte used for polishing. For example, in Dr. Nakada's experiment a methanol-perchloric acid solution was used. This solution has a relatively low conductivity and for the current densities of 0.3 amp per sq cm the electrical input appears to be 30 to 40 w. In our research a methanol-nitric acid solution was employed and for the size of specimen employed by Dr. Nakada the power never exceeded 7 w. There are major differences in his test apparatus which also appear to affect the temperature rise. In our case a steel specimen holder was used in order to provide a good heat sink and conduction path. The cathode was a coiled aluminum tube through which a coolant was passed to provide additional cooling capacity near the specimen. The stirrer was placed in a position to obtain maximum cooling efficiency. On the other hand Dr. Nakada used a teflon grip to support the specimen at one end only and a flat copper cathode, thus providing a much less efficient heat sink as compared with the metal grips used in our studies. The relationship between current density and the temperature increase for two sizes of aluminum crystals tested in our tensile apparatus is shown in Fig. 1. The temperature measurements were determined from a thermocouple spot-welded to the surface of the specimen. The thermocouple was protected from the acid by means of a thin film of stop-off lacquer which covered just the outer surface of the thermocouple junction. Whereas Dr. Nakada reported a time delay of 8 min to obtain thermal equilibrium, our temperature change occurred in less than 15 sec. This emphasizes the importance of the heat transfer in the entire system. However, readings were taken over a period in excess of 5 min to assure thermal equilibrium. The data given in Fig. 1 were also confirmed by determining the thermal expansion of the specimen in a sensitive creep apparatus. As may be seen, for the smaller specimen the increase in temperature is 8°C for a current density of 1.5 amp per sq in. The majority of our data on the effects of surface removal on the plastic behavior of aluminum were obtained at current-density values at or below this value. Above 1.5 amp per sq in. the temperature rise is uncertain; for under certain conditions, especially in the vicinity of 2 amp per sq in., the anode can become polarized and the current flow is erratic. This condition is easily recognized because wide fluctuations in the creep and stress-strain data make it virtually impossible to obtain reliable results, a condition which was always avoided in our work. The temperature increase for the larger specimen is less than that of the smaller specimens below a current density of 1.5 amp per sq in. At a current density of 2 amp per sq in. the temperature increased 13°C. The above temperature data are in accord with observations made during creep experiments. Using a transducer capable of detecting strain in the order of 10 -6, temperature changes in excess of 8°C were not detected when the current density was increased to as high a value as 1.5 amp per sq in. Finally we wish to point out that our experimental data cannot be explained solely in terms of a heat effect. For example in Fig. 1 of Ref. 2, the change in slope of Stage II as a function of the rate of re-

Jan 1, 1965

By T E. Tibbetts

This paper deals with coal sampling in general and with mechanical coal sampling in particular. The necessity of obtaining representative samples is emphasized. Other sections of the paper are devoted to the design and selection of automatic samplers, with a consideration of the three main types, and the testing, operation and maintenance of these samplers. The cost of the installation of an automated sampling system must be related to the value of the material to be sampled, to the volume of coal involved, and to the savings in labour and economy which can be achieved. Introduction T HE Committee?:; on Coal Sampling of the Coal Study Subsection, Thermal Power Section (Eastern Zone), Canadian Electrical Association, was established in November, 1963, to "study the various problem areas of coal sampling." The first undertaking of the Committee was to at-tempt to survey the problem areas of coal sampling through an evaluation of coal sampling difficulties as experienced at both the plant design and operational levels within the electric utilities represented on the Committee. The results of this enquiry indicated that satisfactory answers to almost any conceivable

Jan 1, 1965

The 8 ft by 91/2 ft drive which joined No. 7 Shaft with Browne Shaft on the 1,480 ft level was extended from both ends and met at a point approximately 12,000 ft from No. 7 (2,000 ft from Browne).The surveying required for this 2 1/2 mile haulage drive called for greater accuracy than was obtainable from South Mine standard methods. Procedures and devices from published information were tried and modified as required to suit local conditions. Several new methods were applied and improved as the drive advanced. The control of angular, linear and level measurements was perhaps considerably in excess of the requirements, but this was offset by abnormally large discrepancies resulting from shaft plumbing. The accuracy of the final breakthrough, although not to the standard desired, was sufficient to complete the connection without inconvenience and added cost.INTRODUCTIONThe acquisition of the Browne Shaft leases in January 1962 presented the management of Broken Hill South Limited with the problem of transporting ore from these leases to its mill. It was eventually decided that diesel locomotivehaulage through a 2t mile drive on the 1,480 ft level between the two mines was the best solution. The drive was advanced from both ends after Browne Shaft was deepened by 80 ft to reach the 1,480 ft level horizon. Each end advancedabout 15 ft/day with the miners working three 7 hr shifts. Blasting was restricted to the end of the shift.The survey work involved five shaft plumbings and 78 theodolite stations in a traverse, underground and surface,of more than 5 miles. Because of the exceptional length of the drive, an unusually high degree of reliability was required.The aim was for a maximum error at breakthrough of 1 ft 1 in 30,000, and to secure this, precise methods of linear measurement were necessary. Shaft plumbing in particular posed special difficulties.

Jan 1, 1965

By J. M. Kuchta

Experimental data are presented on the autoignition temperature (AIT) characteristics of the hydrocarbon jet fuel, JP-6, in various oxygen-nitrogen atmospheres under conditions of constant volume and constant pressure. AIT's of this fuel in air varied little with fuel injection pressure but increased greatly with decreasing fuel content at low fuel-air-ratios. They also increased with decreasing oxygen content of the fuel vapor-oxidant atmosphere. Consistent with thermal ignition theory, the ignition temperatures increased with decreasing initial pressure, ignition delay, and vessel radius; expressions are given which define the observed variation of AIT with these variables for JP-6 fuel vapor-air mixtures. The significance of autoignition temperature data obtained using various ignition criteria is discussed to show the usefulness of such data in evaluating fire and explosion hazards. In addition, data are presented on the extent of oxidation that occurs prior to autoignition of this fuel in air at various temperatures.

Jan 1, 1965

By C. H. Schack

Extractive metallurgy techniques currently employed to recover silver from primary ores and secondary scrap were reviewed and evaluated to identify and delineate metallurgical problems whose resolution would increase the supply of silver from domestic materials. The survey revealed that practically all primary silver is recovered by froth flotation concentration of various types of ores, followed by smelting and refining of the separate lead, copper, and zinc concentrates. Silver losses during the complex processing are, with rare exception, inconsequential. Furthermore, any silver production gain from base metal ores, which contribute about two-thirds of the total primary silver, is directly dependent no improvement in the market for the base metals. Statistical data on new and old silver scrap are wholly inadequate to make reliable conclusions about scrap processing problems and the possibility of increasing the recovery of silver from the many forms of secondary silver-bearing materials. The available information indicates (1) that efficient silver reclamation practices are employed by the larger users of silver, and (2) that recovery of additional secondary silver involves solution of problems of collection rather than of processing. Several possibilities exist for limited increases in silver production from primary ores by improvement in metallurgical practices. Specifically, research is needed to (1) solve the problem of recovering silver from the copper ores of the Copper Range district, Michigan; and (2) devise economically feasible methods for recovery of silver from presently marginal or submarginal ores char because of grade, location, and frequently complex nature cannot presently be exploited by conventional techniques.

Jan 1, 1965

By H. J. Ramey

Conventional calculation of total system isothermal compressibility for a system containing a free gas phase involves, among other things, evaluation of the change of oil and gas formation volume factors and the gas in solution with pressure. Preferably, this information should be obtained from laboratory measurements made with particular oils and gases. Often, experimental measurements are not available. In this case, it is necessary to obtain pressure-volume-temperature relationships from general correlations such as those of Standing' for California oils. In order to speed estimates of compressibility, generalized plots have been prepared of the change of both oil formation volume factors and gas in solution, with pressure from Standing's correlations. A generalized plot for estimating the change in the two-phase (oil and gas) formation volume factor with pressure is also presented. Usually, the effect of gas dissolved in reservoir water upon the total system compressibility is neglected for gas saturated systems, due to the low solubility of gas in water. Results of this study indicate that the increase in total system compressibility caused by solution of gas in water is often as large as the compressibility of wafer, and can be magnitudes larger for low pressure systems. Generalized results for estimating the change of gas in solution in water with pressure are presented in tabular and graphical form. INTRODUCTION During the past decade, pressure build-up and drawdown techniques have gained an important place in reservoir engineering. Build-up and drawdown analyses are only two special applications of the broad field of transient fluid-flow theory. All solutions of transient fluid-flow problems contain a parameter called the total system isothermal compressibility. This property of fluids and porous rock is a measure of the change in volume of the fluid content of porous rock with a change in pressure, and it may vary considerably with pressure. Evaluation of total system isothermal compressibility is not difficult, but it is tedious and time-consuming. Often compressibilities are estimated roughly, or transient flow methods are neglected completely. The benefits of using accurate system compressibility in properly-executed build-up or drawdown analyses are: 1. Better planning of pressure build-ups may be achieved to avoid unnecessary loss of revenue due to excessively long shut-in periods, or to shut-in periods too short to yield useable data. 2. Better and more reliable estimates of static formation pressures for reserves estimates and rate performance estimates. 3. Reliable information for evaluation of well completion effectiveness, and planning and interpretation of well stimulation efforts. The purpose of this paper is to clarify the nature of the total system isothermal compressibility, and to present useful methods for estimation of compressibility, particularly for systems containing a gas phase. DEVELOPMENT Numerous publications have presented solutions to transient single-phase flow of slightly compressible fluids, stressing pressure build-up applications. In transient flow, a compressibility* term arises to permit volume content of fluids in porous rock to change as pressure changes. The basic nature of the compressibility term is usually taken for granted. Problems arise in practical applications of transient fluid theory because most published works consider only one flowing fluid—in an ideal porous system containing only one fluid. In 1956, Perrine2 presented an intuitive extension of single-phase flow pressure build-up methods to multiphase flow conditions. Later, Martin- established conditions under which Perrine's multiphase build-up method had a theoretical foundation. Perrine has shown that improper use of single-phase build-up analysis in certain multiphase flow situations can lead to gross errors in estimated static formation pressure, permeability and well condition. It is likely that, much pressure build-up data for oil wells should be analyzed on the basis of multiphase flow. For both single-phase and multiphase build-up analysis, the isothermal compressibility term in dimensionless time groups often should be interpreted as the total system compressibility. All real reservoirs contain one or more compressible fluid phases. In addition, rock compressibility can contribute in an important way to the total system compressibility. The proper total system compressibility expression may contain terms for compressibility of oil, gas, water, reservoir rock and terms for the change of solubility of gas in liquid phases.

Jan 1, 1965

By Luke L. Y. Chang, Bert Phillips

A number of molybdenum oxides have been synthesized and their crystal structures have been described.' No data have been published on the stabilities of these oxides nor on the phase relations in the system Mo-0. It is probable that the tendency toward oxidation of both the metal and the oxides with low oxygen content in addition to the high volatilization rate of the oxides with high oxygen content have precluded accumulation of reliable data for establishing phase relations. These problems make experimentation difficult, but a modifi-

Jan 1, 1965

By Mulligan John J.

The Bureau of Mines investigated lode tin deposits on Potato Mountain, Seward Peninsula, Alaska. Tin was found to occur as cassiterite associated with quartz, tourmaline, pyrite, arsenopyrite, and earthy clays, but the deposits lack the varied accessory minerals commonly found in tin districts. The tin-bearing deposits are in metasediments along minor breaks and bedding planes but not in the crushed earthy filling of major faults. Cassiterite and sulfides occur with quartz in veins, both with and without earthy clays, and disseminated through tourmalinized wall rocks. The deposits are characterized by irregular segregations containing 1 to 10 percent tin within zones averaging not over 0.25 percent tin. The largest segregation exposed is on the summit of a low hill on the east-central slopes of Little Potato Mountain; most of the outcroppings are in an area trending east to west, roughly 10 to 30 feet wide and 300 feet long. Sample values ranged as high as 12 percent tin, but the average grade may be about 1 percent tin. The extreme irregularity of both grade and composition precludes a more exact determination. Similar concentrations are scattered for over 1,000 feet to the west and north, but these are smaller and lower in grade. Elsewhere on Potato Mountain, generally similar deposits occur as clusters of veinlets at widely separated points in the metasedimentary walls of major faults.

Jan 1, 1965

By C L. Briend, O&apos

This paper presents the main features of coal mining in Japan, as determined by the author while attending the International Coal Conference in October of 1963. The general economy of the country is considered, and the requirements for coking coal are outlined. Statistics and comments on production and consumption are then given, with accompanying cost figures, and the characteristics of Japanese coal mining are compared with those of Canada. Mining methods and underground transportation are covered, with emphasis on undersea mining. Finally, a description is given of a visit to the Miike colliery, the largest in Japan. I T was my privilege to attend the International Coal Conference held in Tokyo in October, 1963, to meet many prominent members of the Japan Coal Association and to visit one of the major coal fields. This is probably the reason why I was asked to present this review of the coal situation in Japan. In doing so, it must be pointed out that I am not an expert in coal mining, that my

Jan 1, 1965

By Robert J. Gorney

This paper deals with the actual application of a direct digital control to simple as well as complex industrial process control loops, Fundamental descriptions of preliminary research and design are described briefly, as is the development of the present day controller and control computer. The results and effects of direct digital control in various types of single and cascaded loops as opposed to the use of conventional controls are discussed. Computer supervision of a process and control override are taken into account, in addition to methods of short and long term plant economic optimization.

Jan 1, 1965

By Jerry B. F. Champlin

NIOSHAn accelerated testing procedure developed by the Bureau of Mines for evaluating commercially available corrosion inhibitors is described. Ultra-sonic agitation of the corrodent solutions and the hot-finished mild steel test coupons was used to evaluate the effects of several variables on the effectiveness of two corrosion inhibitors. Small changes in the weight of the test coupons in both controlled and inhibited corrodents, before and after exposure, affected the precision and accuracy of the results. Minute amounts of oxygen in the systems were found to be causing the relatively large deviations in the corrosion developed in the controlled tests. Microscopic examination of the test coupons revealed that both surface preparation and internal strains resulting from fabrication methods materially affect corrosion behavior.

Jan 1, 1965

By M. F. Corcoran

Rapid advances have been made in the past few years in the application of automatic controls and instrumentation to iron ore pelletizing plants. Present practice in applying instrumentation and control to the Grate-Kiln system of iron ore pelletizing is described. Major control points and loops are tabulated. Future trends in the application of digital control including computer data logging systems are described.

Jan 1, 1965

By Jr. Joyce

This report describes sulfatization of nickeliferous laterites from Puerto Rico and the Philippines for recovery of water-soluble nickel and cobalt sulfates. Temperatures ranging from 665 C to 710 C and a 10-percent sulfur dioxide-air reaction gas were employed during batch-roasting tests and during continuous countercurrent treatment in a 2-inch-diameter shaft furnace. A maximum of 69 percent of the nickel and 76 percent of the cobalt were recovered from one sample of Puerto Rican laterite, and a maximum of 96 percent of the nickel and 91 percent of the cobalt were recovered from the Philippine laterite.

Jan 1, 1965

By Harold N. Miller

Lost time and services caused by electrical equipment breakdown or cable faults can often be substantially reduced by the use of direct-current high-voltage testing as a maintenance tool. This paper discusses the relative merits of alternating-current versus direct-current testing, pointing out the advantages in size and cost of equipment and more definitive results achieved through the use of D.C. General principles of direct-current high-volt-age testing, types of testing, methods of performing the actual test and interpreting the results are explained. ?The value of insulation resistance measurements and their relationship to high-voltage testing is discussed. Pinpointing the physical location of a cable defect using a fault locator or thumper is described. Reference is made to several organizations that have effected considerable savings with high-voltage test programs. Introduction T HE past decades have seen great advances in the field of electrical power distribution and application. Motor generators, power-operated equipment, cables, etc., have all gone through various stages of improvement both in efficiency and reliability. Un-fortunately, however, power failures and equipment breakdown still occur -frequently with disastrous effects in loss of time,

Jan 1, 1965

By Stephen Utter

Stresses induced by block-caving mining were estimated from in-place measurements of strain or deformation in rock and concrete around mine openings. The four types of gages used for measurements in the Climax Molybdenum mine during 1959-61 were Whittemore gage, Carlson strain meter,2 Valore strain cell, and Climax extensometer. Gage performance in the laboratory was evaluated by stressing instrumented rock and concrete specimens in a universal testing machine and by comparing measurements taken by the gages and a standard gage. Gage performance in the mine was evaluated by comparing measurements taken during an 18-month test. The Whittemore gage, Carlson strain meter, and the Climax extensometer proved suitable for the investigation; the Valore strain cell, effective in the laboratory tests, gave erratic measurements in the mine.

Jan 1, 1965

By J. W. Jensen

EXTENSIVE research and development was performed on the manganese-copper vibration-damping alloys to determine the relationship between the properties of the alloys and variations in composition, fabrication, Mid heat treatment. Mn-Cu alloys with unusually high specific damping capacity, 20 to 25 percent at a stress of 5,000 psi, have also the following useful properties: Tensile strength, 90,000 to 110,000 psi; yield strong, 60,000 to psi; elongation, 20 to 25 percent; hardness, 90 Rockwell B; and fatigue limit at, 28,000 to 30,000 psi. Both standard and special methods of testing were employed to obtain data on strength, modulus, hardness, resistivity, dilatation, micro-structure, crystal lattice, and damping capacity. The extensive tabular and graphical data on these properties are presented for alloys containing 50 to 85 percent as quenched d solution) and after various aging treatments. Expansion coefficients for all Mn-Cu solid solutions are graphed and a dilatometer study of contraction during aging is reported. Although high damping capacity is associated with aging to precipitate a-Mn from solid solution, with a cubic-tetragonal transformation and with the occurrence of antiferromagnetic ordering in Mn-Cu alloys, a tenable theory of the damping mechanism has not been reached.

Jan 1, 1965