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By K. Narayana Swamy

Experimental results of 3-phase mixing in a physical model of a CCRL for metals refining, at high levels of bottom gas injection (up to a superfIcial gas velocity (Us) of 12.5 cm/min), are presented. A thermal tracer technique was used to elucidate both longitudinal mixing and interphase heat transfer. The results indicate that even under conditions of significant bottom gas injection, it should be possible to maintain acceptably low longitudinal mixing (D. < 20 cm2/s and D/uL < 0.1) in the CCRL. Interphase mass-transfer coefficients of the order of 0.02 cm/s and higher, are predicted from the measured interphase heat transfer coefficients using the mass and heat transfer analogy. Adequate performance is likely to be possible for an industrial CCRL, based on extrapolation of these results to full-scale conditions.

Jan 1, 1996

By Fan Xiao-Hui, Jiang Li-Juan, Chen Xu-Ling

"In order to solve air leakage of sintering testing cumbersome, inaccurate results, and other issues, the sinter machine air leakage characteristics were studied, and combining the mathematical modeling and the field detection. The temperature before air leakage was calculated by mathematical model, energy balance equation was established according to sintering process, using Adams prediction correction method which has stronge stability and high precision, to solve hyperbolic partial differential equation with astringency problem. The temperature after air leakage is detected by instruments, according to energy conservation calculation the sintering air leakage rate. According to the sintering continuity and periodicity, sintering air leakage location diagnosis expert system was established to judge specific air leakage locations.IntroductionStrengthening of modern blast furnace production depends on the quality of the raw material preparation to a large extent [1]. Technical and economic index of modern blast furnace production is advanced; the most important reason is the use of concentrated feed. Sintering plant is the ""kitchen"" of blast furnace’s concentrate. As we all know, sintering plant is major energy consumption of steel plant, in sinter process energy consumption, the solid fuel consumption of total energy consumption is 75%~80%, power is 13%~20%, ignition and combustion is 5%~10%. To reduce the air leakage of sintering plant is an effective measurement to save energy consumption. At present, our air leakage of sintering compared to the other developed countries is still a long way to go. Japan’s air leakage rate is about 30%, and 35%~60% air leakage of sintering machine at home, a big gap exists between the plants. At present the determination of air leakage is all for manual operation, long measuring period, considerable manpower and resources, and the results are significantly affected by operation. For air leakage of sintering control lag issues, research and development of diagnosis expert system for on-line monitoring model for air leakage and, through this research can reduce the use of detection equipment, detect sintering air leakage, improve the yield and quality of sintering production, reduce energy consumption, and extend equipment life span."

Jan 1, 2012

By Charles Catlett

(Chattanooga Meeting, October, 1M.) THE terms " developed " and " undeveloped " are necessarily relative and cover a wide range; but the latter is here applied to cases in which the information at hand falls short of a clear demonstration of values, and conclusions must be reached from a study of the geological conditions of the particular deposit, interpreted in the light of similar and closely related deposits. Such an inquiry might be characterized as an effort to reach reliable conclusions from insufficient data. But the engineer engaged in commercial work finds himself often face to face with apparently such problems; and while he may realize with regret that a small amount of intelligent development would add enormously to the value of his conclusions, he is compelled to recognize the demand of a business situation for a prompt decision as the basis of immediate action. In a case within my knowledge, the question involved was the purchase of 50,000 acres of coal-land, and 10 days was the limit within which this question must be decided. Of course, it was impossible to make a satisfactory examination within that time; but the &apos;instructions were "to make the most complete examination and the most positive recommendation possible." Such instructions are often given; for, no matter how much time an investor may have, he is likely to put of his decision until the last moment, and then discover that he needs more light and advice. It does not follow that engineers, after full explanation and mutual understanding of the situation, should decline to undertake examinations thus limited. In the case just mentioned, while only the broadest view was possible, half the time available was sufficient to show that the property was a good purchase. The timber alone was subsequently resold for more than the entire purchase-price of the

Mar 1, 1909

By M Thompson, N Vines, Z Hearne, S Lam, G A. Gomes-Sebastiaõ, D van der Spuy

Construction and commissioning of the Nova Copper-Nickel project of Independence Group was completed in late 2016. The plant is in the Fraser Range of Western Australia, about 120km east of Norseman and produces separate Copper and Nickel concentrates. Since the early feasibility phases of the project, the importance of automation and control was recognised and planned for to ensure the plant performance meets the design expectations. The site is well equipped with common as well as advanced instrumentation. It currently boasts the largest number of Blue Cube MQi (mineral quantifier inline) slurry grade analysers on a single plant worldwide. It was also decided that 25 Blue Cube TempoTracks would be installed on the flotation cells. The TempoTracks provide information on froth height and velocity, hence giving continuous, quantitative measurements of the froth that is pulled off each cell, rather than relying on infrequent, subjective visual inspections.The Nova concentrator consists of a differential flotation circuit whereby copper bearing mineral are selectively floated prior to nickel flotation. It is imperative that losses of copper to the nickel circuit, and vice versa, are minimised. The plant metallurgical team and Process IQ collaborated to develop and implement the advanced control strategy for the plant. This paper focusses on the optimisation of the copper concentrate that is pulled off the copper rougher and scavengers. This strategy was made possible by the additional measurements listed above. The control optimisation of the copper rougher and copper rougher scavenger circuit was implemented during August 2017 on the StarCSTM advanced control platform. It continuously optimises the level and air setpoints. The control philosophy incorporates several notable techniques which include: a variable mass pull target that is a function of the quantity and grade of material entering the circuit, integrated compensation to prevent inventory build-up in cells, balancing of the froth velocity over the lip of each cell to adaptive, modular system usage and advanced error handling. CITATION:Gomes-Sebastia&#245;, G A, Hearne, Z, Lam, S, van der Spuy, D, Thompson, M and Vines, N, 2018. Nova copper-nickel project optimisation of the copper rougher-scavenger circuit through advanced measurement and control, in Proceedings 14th AusIMM Mill Operators&#39; Conference 2018, pp 77–92 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Aug 29, 2018

By J. Esson, R. A. D. Pattrick, M. K. Nimfopoulos, D. A. Polya, K. M. Michailidis

"Abstract-Economic Mn-oxide ore deposits of commercial grade occur in the Rhodope massif near Kato Nevrokopi in the Drama region, Northern Greece. The Mn-oxide mineralization has developed by weathering of continental hypogene rhodochrosite-sulphide veins. The vein mineralization is confined by tectonic shear zones between marble and metapelites, extending laterally into the marble as tabular, pod or lenticular oreshoots (up to 50 m ?? 20 m ?? 5-10 m). Supergene oxidation of the hypogene mineralization led to the formation of in-situ residual Mn-oxide ore deposits, and secondary infills of Mn-oxide ore in embryonic and well developed karst cavities.Whole rock geochemical profiles across mineralized zones confirm the role of thrusts and faults as solution passageways and stress the importance of these structures in the development of hydrothermal and supergene mineralization at Kato Nevrokopi. Three zones are recognized in the insitu supergene veins: (A) a stable zone of oxidation, where immobile elements form (or substitute in) stable oxide mineral phases, and mobile elements are leached; (B) a transitional (active) zone in which element behavior is strongly influenced by seasonal fluctuations of the groundwater table and variations in pH-Eh conditions; and (C) a zone of permanent flooding, where variations in pH-Eh conditions are minimal. Zone (B) is considered as the source zone for the karst cavity mineralization. During weathering, meteoric waters, which were CO2-rich (PCO2 ~10-3.8 to 10-1.4) and oxygenated (fO2 ~10-17 for malachite), percolated downward within the veins, causing breakdown and dissolution of sulfides and marble, and oxidation of rhodochrosite to Mn-oxides. Karst cavity formation was favored by the high permeability along thrust zones. Dissolved Mn2+ was transported into karst cavities in reduced meteoric waters at the beginning of weathering (pH~4-5), and as Mn(HCO3)2 in slightly alkaline groundwaters during advanced weathering (pH~6-8). Mn4+-oxide precipitation took place by fO2 increase in ground waters, or pH increase by continuous hydrolysis and carbonate dissolution. In the well developed karst setting, some mobility of elements occurred during and after karst ore formation in the order Na>K>Mg>Sr>Mn>As>Zn>Ba>Al>Fe>Cu>Cd>Pb."

Jan 1, 1997

By R. W. Thompkins

MINE operators are concerned with temperature conditions in their mines, particularly the effects of high temperatures on the l1ealth and efficiency of tl1eir employees. This paper is written to focus attention on the variables of heat transfer between rock and air. It illustrates the difficulties of predicting the manner, and the extent, of heat transfer from theoretical concepts, prior to actual operation of a mine airway. There are ~1any sources of heat in mines. The most important is that of the rock surrounding the airway. This heat, in turn, is a product of the age of the rock, faulting, proximity to recent igneous activity, oxidation of sulphides, hot ground waters, etc. The sources of heat may be constant for any one mine, but they are far from constant when dealing with various mining districts or e1•en with a number of mines in the same district. A second source of heat is that produced by machinery in operation. Practically all the waste

Jan 1, 1962

By David Forrester

"At the 95th CIM Annual General Meeting in Calgary, 1993, a paper entitled “Progress on Futuristic Mining Technologies” was presented(Matthews and Sarin), in which they outlined the goal of continuous excavation of hard rock and some of the technologies being developed to achieve it. The subject continues to be featured in periodic reviews and articles in the literature, (Gertsch, 1994; E&MJ, 1995). Matthews and Sarin note the considerable success of the development and application of continuous mining technologies in the soft rock under-ground mining industry, especially those in coal and potash, with major benefit to overall production, productivity and economic viability. It is the belief that similar achievements can be realised in the underground hard rock mining which continues to drive the development of hardrock continuous mining technology.This overview has been prepared specifically for this issue of the CIM Bulletin. It attempts to tie together current advancements in continuous mining in soft rock (where remote control and automation are already well established) with the background and status of development in hard rock continuous mining. Following a brief review of key factors and machine types, soft rock aspects are discussed, then a more detailed review is given of hard rock technology, with particular reference to Canada’s HRDK Mining Research Ltd. and their key role.The mining industry has long been at the forefront of technology development, for example, the application of the early steam engine to reach reserves at greater depth for dewatering mines in the industrial revolution. By necessity, the individual characteristics of seams and orebodies dictate the mining method, continually presenting mining engineers with new challenges. One of these is the extraction process itself and the goal of replacement of the drill-blast-muck cycle by continuous excavation. Very soft rocks have always been mineable using some form of cutting, even with primative tools. However, as the challenge has been taken up, technologies have evolved to steadily increase the hardness of rock that can be mechanically excavated. It may surprise some readers that at least three machines have successfully cut and loaded rock with an unconfined compressive strength (UCS) of 250 Mpa to 300 MPa (36 000 to 43 500 psi) in field trials (Table 1)."

Jan 1, 1996

By JOHN HOMER, Jacob L. Carr, Jonathan K. Hrica, Kathleen M. Stabryla, Iman Benbourenane, Jennica L. Bellanca

Given the recent focus on powered haulage incidents within the US mining sector, an appraisal of collision avoidance/warning systems (CXSs) through the lens of the available research literature is timely. This paper describes a rapid review that identifies, characterizes, and classifies the research literature to evaluate the maturity of CXS technology through the application of a Technology Readiness Assessment. Systematic search methods were applied to three electronic databases, and relevant articles were identified through the application of inclusion and exclusion criteria. Sixty-four articles from 2000 to 2020 met these criteria and were categorized into seven CXS technology categories. Review and assessment of the articles indicates that much of the literature-based evidence for CXS technology lies within lower levels of maturity (i.e., components and prototypes tested under laboratory conditions and in relevant environments). However, less evidence exists for CXS technology at higher levels of maturity (i.e., complete systems evaluated within operational environments) despite the existence of commercial products in the marketplace. This lack of evidence at higher maturity levels within the scientific literature highlights the need for systematic peer-reviewed research to evaluate the performance of CXS technologies and demonstrate the efficacy of prototypes or commercial products, which could be fostered by more collaboration between academia, research institutions, manufacturers, and mining companies. Additionally, results of the review reveal that most of the literature relevant to CXS technologies is focused on vehicle-to-vehicle interactions. However, this contrasts with haul truck fatal accident statistics that indicate that most haul truck fatal accidents are due to vehicle-to-environment interactions (e.g., traveling through a berm). Lastly, the relatively small amount of literature and segmented nature of the included studies suggests that there is a need for incremental progress or more stepwise research that would facilitate the improvement of CXS technologies over time. This progression over time could be achieved through continued long-term interest and support for CXS technology research.

Jun 17, 2022

By J. C. White

"This paper was prepared for and presented at a lecture series on ""Materials Randling"" at McGill University. The development of trackless mining at Gaspe Copper Mines, Limited is described, showing the changes in mining method and the part played by the mobile equipment in the evolution of this highly mechanized underground operation. Comparisons of loading and hauling machines are given and an attempt is made to predict some possible future developments.INTRODUCTIONTHE PROPERTY OF GASPE COPPER MINES LIMITED is located in the Gaspe Peninsula of the Province of Quebec, 60 miles west of the village of Gaspe and 25 miles south of the St. Lawrence River. The original discovery of low-grade ore was made at Copper Mountain in 1921. Subsequent exploration revealed the richer Needle Mountain orebodies, and eventually in 1951 the decision was made by Noranda Mines to build the mining, concentrating and smelting complex (Figure 1). Construction and development of the mine was commenced in 1952 and production started in 1955."

Jan 1, 1968

By S. H. Lorain

Tin mining on Seward Peninsula, Alaska, has been intermittently active since the early 1900&apos;s. Most of the recorded production (over 2,200 short tons of metallic tin) has been obtained from placer deposits, but recent production also has resulted from development of lode deposits associated with intrusive rocks occurring in the western part of the peninsula. Generally, the lode deposits containing tin minerals (principally cassiterite) are found in dikes, in granite masses, and in silicate zones in limestone overlying the granite. Both the placer and lode deposits have been of considerable strategic interest to the Government because of the almost total absence of a domestic supply of tin. The most important tin-lode deposit discovered to date is in the Cassiterite dike at the Lost River mine, on Cassiterite Creek about 85 miles northwest of Nome. This highly altered, rhyolite porphyry dike averages 12 feet in thickness, strikes N. 75° to 85° E., and dips steeply to the south; it can be traced on the surface for about 8,000 feet. Throughout its explored length of about 2,200 feet the dike everywhere contains some tin and tungsten in veinlets and disseminations; economic concentration of the are minerals, however, is confined to definite shoots. The ore minerals include cassiterite, stannite, hulsite, paigeite, wolframite, scheelite, and base-metal sulfides; gangue minerals include fluorite, boron silicates, and lithium-bearing minerals. Some ore minerals also occur in the numerous other dikes and in the granite and intruded limestone in and adjacent to the mine.

Jan 1, 1958

By Shigeru Tsutsumi

The rapid development of transportation facilities in Japan focused the attention of this country on the possibility of converting the existing coal resources (of which there was an abundance) into liquid fuels, for which there was a constantly increasing demand. Previous work had indicated that this could be accomplished by utilizing one of two processes - the Bergius process, in which high temperatures and high pressures were employed to effect direct liquefaction of the coal, and the Fischer-Tropsch process, in which an indirect liquefaction of coal was accomplished by the production of liquid hydro-carbons from hydrogen-carbon monoxide mixtures. This report describes some investigations into the latter process, which was first developed by Fischer and his colleagues in the Coal Laboratory in Muhlheim, Germany, in 1923. By 1932, these investigators had achieved a 60-percent theoretical yield (152 ml. of liquid hydrocarbons per cubic meter of 2H2:ICO synthesis gas) by using a precipitated Co-Th02 catalyst.3/ At the same time (1932), Dr. Kita of Kyoto Imperial University and Messrs. Fujimura and Tsuneoka obtained 145 ml. of gasoline (C5+) per cubic meter of synthetic gas by using a Co-Cu-Th-U catalyst. 4/ This report is a description of the experimental results subsequently obtained at the Fuel Research Institute, Kawaguchi City, Saitama, up to 1935.

Jan 1, 1951

By L. Martins Demuner, D. Burzic, V. Cunha Aranda, F. L. Lourenço, G. Romeu Trindade dos Santos, F. Ramstorfer

For many years, Dynamic Soft Reduction has been regarded as a proper method in improving internal quality of slabs. Even though processes models improved significantly over the past years, the efficiency of Soft Reduction was always limited by the discretization error, which inherently exists if segment rollers cannot be positioned individually. The recently developed SRD segment type allows for an individual roller positioning within the mushy zone by avoiding any discretization deviation from the optimal gap. This paper provides a detailed technological overview of the SRD segments as well as operational results at their very first implementation at Ternium Brazil.

Oct 1, 2019

By J. D. Davis

THE carbonizing properties of one medium- and and five low-volatile coals from West Virginia and one high-volatile A and two medium-volatile coals from Pennsylvania were determined by 800° and 900° C. BM-AGA carbonization tests and expansion tests in the sole-heated oven. Plastic properties of the coals and the yields and quality of their cokes and other carbonization products were determined. The low-volatile coals comprised a mine and a coke-plant sample of Pocahontas No. 6-bed coal from the. Black Eagle No. 1 mine, Wyoming County, W. Va.; a mine sample of Pocahontas No. 6 bed from the Louisville mine, Mercer County, W. Va. ; Davy Sewell bed was sampled at the Twin Branch mine, McDowell County, W. Va.; and Fire Creek bed was sampled at the Dunedin No. 1 mine, Raleigh County, W. Va. The medium-volatile coals were from the Fire Creek bed, Laurel Creek mine, Greenbrier County, W. Va.; Lower Kittanning bed, Springfield No. 4 mine, Cambria County, Pa.; and Upper Kittanning bed, Springfield No. 6 mine, Clearfield County, Pa. The high-volatile A coal represented the Upper and Lower Freeport beds, Kent Nos. 1 and 2 mines, Indiana County, Pa. In addition to the coals listed, high-volatile A coal from the Pittsburgh bed, Warden mine, Allegheny County, Pa., a standard blending coal, was used in blends in this investigation.

Jan 1, 1950

By B. R. Boardman

Project Environmental Approval is a multi-faceted issue. From a mining perspective, it is a costly item because of avoidable time delay. The government perspective is that the approvals are a necessary part of meeting departmental requirements to ensure that the wellbeing of other uses of the environment is maintained. This paper outlines some of the problems inherent in the environmental approvals process and makes recommendations to both the proponent and government about improving the efficiency of the process.

Jan 1, 1978

By C. H. G. Bushell, G. Brown, C. J. Krauss

1N FLOTATION, copper sulphate is used universally for the activation of sphalerite and marmatite and, to some extent, for the activation of other minerals. The copper activated surface readily adsorbs standard collectors such as the xanthates and dialkyl dithiophosphates whereas untreated zir~ sulphide does not. With the host of reagents available, making a mineral float is seldom difficult. The problem is to achieve selective flotation. In zinc flotation, the great value of copper sulphate results from its ability to activate zinc sulphide preferentially to gangue minerals. At the Sullivan Concentrator of The Consolidated Mining and Smelting Company of Canada Limited, the most abundant gangue mineral in the lead-zinc ore is pyrrhotite, and the zinc mineral is marmatite of somewhat variable zinc to iron ratio. For this Cominco study, selectivity between marmatite and pyrrhotite was therefore the most interesting aspect of copper sulphate activation.

Jan 1, 1961

By Laurance L. Oden

The Bureau of Mines is developing melting data for binary combinations of the alkaline earth fluorides and yttria to facilitate the formulation of slag compositions. The present report deals with the SrF2-Y2O3 system for which liquidus and solidus temperatures and solid solubilities were determined. The information is presented as the phase diagram. The phase diagram was constructed from information obtained by ceramogra¬phy, X-ray diffraction, thermal analysis, and electron probe microanalysis of small specimens encapsulated in platinum-20 percent rhodium or molybdenum ampoules. The data indicate a simple eutectic system with limited terminal solid solubilities. The eutectic temperature is 1,457°±5° C, and the eutectic composition is 4±1 mole-pct Y203. Strontium fluoride containing up to 2 wt-pct 0 2 was studied to determine the effects of oxygen contamination. Oxygen levels in excess of 0.2 wt-pct resulted in eutectic formation between SrF2 and SrO. The eutectic composition is between 0.2 and 0.7 wt-pct 02, and the eutectic temperature is 1,447°±5° C. No intermediate oxyfluoride phases were detected.

Jan 1, 1974

By D J. McDougall

Due to changes in the solid-state conditions of minerals in the rocks surrounding hydrothermal, contact meta-somatic or metamorphosed ore deposits, positive or negative thermoluminescent anomalies may be found in their vicinity. Several types of equipment which can be used for both quantitative and semi-quantitative measurements of the emission are discussed and compared. Methods of selecting, preparing and testing samples to ensure reproducible results are outlined, along with the kind of data which can be obtained from different types of equipment. The normal thermoluminescence of rock-forming min~ erals in the common rock types is noted, and variations in the solid-state conditions in the wall rocks which will cause marked increases or decreases of true thermoluminescence are outlined, as well as the thermolum-nescence-like emissions which are present in the vicinity of ore deposits. Introduction T HERMOLUMINESCENCE occurs when certain crystalline materials are heated to temperatures ranging between 180&apos; and 400°C. The light emission can be ascribed to the release of electrons metastably trapped within the crystal lattice, with peak emissions taking place at temperatures which are more or less specific for a particular set of traps; the area under

Jan 1, 1965

By Glen C. Ware

The Bureau of Mines determined the factors involved in the corrosion of starting sheets used in the production of electrolytic zinc with the ultimate purpose of adapting zinc starting sheets to commercial practice . Under present practice , zinc is electrodeposited on aluminum cathodes and subsequently stripped for melting . The use of zinc instead of aluminum would eliminate the need to strip the deposit , thereby reducing the cost of handling and melting it , but zinc has not been suitable because it was too vulnerable to the corrosive attack of the electrolyte . Serious attack was found to be limited to the areas of the cathodes situated immediately above the surface of the electrolyte and to re - entrant corners . It was possible to avoid solution - level corrosion by immersing the starting sheets completely , exposing only a relatively heavy suspension member to solution - level attack . Zinc starting sheets could be made as reliable as aluminum and could be continued in residence for periods up to 39 days . Periods as long as a week were feasible under conditions similar to those found in commercial practice . A test of zirconium as a starting - sheet material showed that it promoted corrosion of the deposit to a lesser extent than aluminum and that the deposit adhered less tenaciously . These two properties lend themselves to the development of ways to strip deposits mechanically from zirconium starting sheets . Titanium was unsuitable for use as a starting - sheet material .

Jan 1, 1963

By Michael Gebman, Jack Gerwick

"With the opening of the new San Francisco-Oakland Bay Bridge East Span, the former bridge and its caisson foundations are being demolished. Caisson foundations are in the path of a future shipping channel and therefore need removal down to the mudline 50 ft below water (MLLW). For the first caisson to be removed (E3) a mechanical demolition was performed above the waterline and an implosion was done for the remaining caisson down to mudline. Mechanical demolition consisted of excavators operating from either on top of the caisson, from work platforms or from barges. The demolition was implemented on a trial basis with a successful implosion on November 14, 2015. The work was conducted in an environmentally sensitive area, with measures taken to protect fish, marine mammals and birds. This demolition technique was cost effective, faster to execute, and had a better environmental impact then an alternative option. The demolition, measures implemented to protect the environment, outcome, and lessons learned are presented.INTRODUCTIONThe California Department of Transportation needed a cost effective and environmentally friendly solution for removal of the remaining San Francisco-Oakland Bay Bridge (former East Span) caisson foundations, starting with caisson E3. This was necessary to clear a future shipping channel. One option was to construct a steel cofferdam around the caisson to allow demolition in the dry down to the mudline. This option would take years to complete, be cost prohibitive, and its noise would disrupt aquatic life and birds throughout the cofferdam construction and demolition. An alternative option was implemented on a trial basis to conduct a mechanical demolition of the caisson above waterline along with an implosion of the remaining caisson down to mudline. This had the clear advantage as a cofferdam was not needed, and the demolition project duration would be approximately 6 months, instead of several years for the cofferdam option. The potential impact on aquatic life and birds from the implosion was a concern, as the location is environmentally sensitive; however, measures were implemented to minimize these impacts. As presented in this paper, this demolition option was implemented on a trial basis for Caisson E3. The technique succeeded and will now be used on the remaining caissons.BACKGROUND INFO ON CAISSON E3The reinforced concrete Caisson E3 is the largest caisson which supported the former East Span of the Bay Bridge. It was constructed in 1934, with the Bay Bridge opening in 1936. Figure 1 shows the project location. The caisson had a cell arrangement of 7 x 2 above the mudline. Below mudline, the caisson had a cell arrangement of 9 x 4. A structural transition was made between the 7 x 2 and 9 x 4 cell arrangements with buttress walls. All cells were flooded, as underwater openings were included in the original caisson walls to equalize the hydrostatic pressure. Figure 2 shows the caisson layout with limits for mechanical demolition and for the implosion."

Jan 1, 2016

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&apos; 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