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By L. C. IlsLey

"There is an old saying that ""It is too late to lock the stable after the horse is stolen"". Is not this just what is being done by many mine operators today when it comes to buying safe electrical equipment for gaseous and dusty coal mines?The ""open type"" of electrical equipment or even the ""half safe"" type represents the unlocked stable. After the mine disaster, and after men have lost their lives, the lock is put on - that is, safer equipment is installed.For example, an open type of electric coal drill was used in a gaseous mine in West Virginia, This was the probable cause of the death of 27 men. A half safe type of electric coal-cutting machine was used in a gaseous mine in Pennsylvania. This was likely the cause of the death of 36 men. An unapproved, unsafe type of flame safety lamp was used in a gaseous and dusty mine in Utah. This was the all¬eged cause of the death of 171 men. All three disasters happened within the last six months, and seem to have been avoidable if proper equipment had been used.It is understood that more rigid requirements will be enforced in West Virginia. The committee of State mine inspectors made definite recommendation for im¬proving the conditions in the given mine in Pennsylvania. The Industrial Commission of Utah have already issued new orders which will remedy the use of unsafe lamps in that State.These acts and recommendation are all good and will help prevent accidents in those States in the future. Is it not a pity that such recommendations and order were not made a little earlier before the tell of life had been exacted? Is it not a pity that other States will not take these lessons to heart and safeguard their mines before and not after disasters take place?Electric current can cause accidents in five general ways as follows: (1) By shock to persons; (2) by igniting powder; (3) by igniting gas; (4) by igniting coal dust; and (5) by setting fire to inflammable material such as timber and coal. A great many accidents from these causes are preventable if proper care is taken. Most of the accidents caused by sparks and flashes from electrical apparatus would not take place if approved electrical equipment was used. By approved equipment, the writer means equipment that has been tested and formally approved by the Bureau of Mines. So far as known, up to the present time, no disasters have been caused by sparks or flashes from equipment having the Bureau's approval."

Jul 1, 1924

By N. Damiano, J. Noll, C. Zhou, J. DuCarme

"Preventing machine-related injuries is one of the major safety concerns in underground coal mines. Severe injuries and fatalities occur when a miner is struck, crushed, or pinned by mining equipment such as a continuous mining machine (CMM), shuttle car, or a scoop. Proximity detection systems (PDSs) have been applied in mining to reduce these types of injuries and fatalities. All of the PDSs that are currently approved by the Mine Safety and Health Administration (MSHA) for use in underground coal mines are magnetic-field based and could be affected by metallic objects such as trailing cables. Researchers from the National Institute for Occupational Safety and Health (NIOSH) investigated the influence of trailing cables on the performance of PDSs. In particular, the magnetic field coupled from proximity system generators to a de-energized trailing cable were characterized. The results show that significant energy can be coupled from the proximity system generators to a trailing cable when there is a closed loop in the cable. The effect on PDS performance from the magnetic field radiated around an energized trailing cable was also quantified for different current amplitudes in the cable. It is shown that the magnetic field caused by the electric current in the trailing cable mainly consists of a 60-Hz signal and its harmonics which cause little interference to the PDS. The results presented in this paper can help PDS manufacturers to design better systems that are more immune to these effects. INTRODUCTION An average of 250 injuries occur every year during operation of Continuous mining machines (CMMs), and 43 miners have been killed by striking or pinning accidents involving CMMs in the U.S. from 1984 to 2015 (Mine Safety and Health Administration, 2015). In addition, there have been 10 fatal accidents involving mobile haulage equipped with trailing cables from 2000 to 2015 (Noll et al., 2017). In response to these fatalities and injuries the Mine Safety and Health Administration (MSHA) promulgated a regulation in 2015 requiring the use of a proximity detection system (PDS) on all CMMs except full-face machines and proposed a regulation in 2016 which would require a PDS on other mobile underground equipment. Current PDSs approved for underground use are magnetic-field based. The PDS contains machine-mounted magnetic field generators that create fields around the machine. The other part of the PDS is a miner-wearable component (MWC) that reads the flux density of the generators. These systems use the magnetic field strength readings from the MWC to determine whether a miner is at a safe distance from the machine. A stable magnetic field is essential for the accuracy of the system."

Jan 1, 2018

By Debra C. Man, S. Thomas Freeman, F. Wiley Horne

INTRODUCTION The Metropolitan Water District of Southern California (Metropolitan) is the largest water wholesaler in southern California. Its service area spans the major urbanized portions of Ventura, Los Angeles, Orange, San Bernardino, Riverside and San Diego counties. More than 15 million people are serviced by Metropolitan through its 27 member agencies. The primary sources of Metropolitan's water supply are the Colorado River Aqueduct (CRA) and California's State Water Project (SWP). Currently, planning and design level studies are underway by Metropolitan to expand the water storage and conveyance systems within the service area for the purposes of providing increased efficiency and flexibility to manage limited water supplies, improving water quality, and increasing system reliability. The system reliability issue is particularly significant because the conveyance facilities from both the CRA and the SWP must cross the active San Andreas fault. This fault is considered to be the source fault for the anticipated "Big Earthquake" in southern California. To meet these objectives, Metropolitan's expansion plans involve a major new storage reservoir, new large diameter pipeline and tunnel conveyance facilities, more efficient utilization of existing groundwater basins, and an aggressive public awareness and conservation program. This paper focuses on the planning studies that have been carried out for over 50 miles of tunnels being considered for several of Metropolitan's proposed conveyance systems. These tunnels have ranged in length from a few hundred feet to over 42,000 feet, with depths of cover ranging from a few tens of feet to over 3,000 feet, and finished diameters ranging from 10 to 20 feet.

Jan 1, 1993

By Wm. Hamilton Merritt

With the exception of the Vancouver Island coal, all the western coal-fields owe their present development to the completion, in the autumn of 1886, of the Canadian Pacific railroad. While it could not be expected that a very great deal could be accomplished in three years, enough has been done to pretty thoroughly establish the coal-bearing areas and their correspondence with those which have been developed to the south of the boundary along the lines of the transatlantic railroads in the United States. This summer I visited some of the important developments in the coal areas of Washington Territory, largely with the object of being better able to appreciate the corresponding coal-bearing areas in British Columbia to the north. In Western Canada, coal-bearing rocks have been found in three zones: 1. In the plains to the east of the Rocky Mountains and in the eastern flanking ranges, the coal occurs in the Cretaceous formation (including the Laramie). 2. In the interior plateau of British Columbia, the coal is found in the Tertiary formation. 3. On the coast of British Columbia, Cretaceous and Tertiary rocks are found carrying coal, and on the Island of Vancouver the well known Nanaimo coal has been worked for years in the first named formation. In all of these zones, the coals vary from lignites up to higher grades, the factor determining quality being the amount of pressute to which they have been subjected. The intensity of this pressure is generally shown by the disturbance which the coals exhibit, and, in many cases, is almost directly in proportion to the distance of the deposits from mountain ranges. This seems to be also the opinion expressed by Mr. Bailey Willis in connection with his Census Report on the coals of Washington. It has been elsewhere stated

Jan 1, 1890

By R. E. Stiles

The modified perchloric--EDTA method devised by the Bureau of Mines for the determination of copper in high-grade samples gives results that are more precise and more accurate than those from the classical sulfuric-iodometric method. Although the perchloric--EDTA method is more costly than the conventional method, the savings in time alone largely offsets this difference. Specifically, the modifications wade in the more conventional procedure comprise (1) use of perchloric acid instead of sulfuric acid for dissolution of copper minerals, (2) precipitation of copper as copper sulfide from dilute perchloric acid solution, (3) wet oxidation and dissolution of the precipitated copper sulfide, (4) use of larger amounts of indicator than those employed in the Schwarzenbach method of titrating low-tenor copper solutions with disodium ethylenedinitri10-tetraacetate and murexide indicator, and (5) use of refrigeration to partially stabilize aqueous solutions of the indicator.

Jan 1, 1966

By M. A. Raza

Cable shovels are capital-expensive and primary production equipment in many surface mines. The forces acting on the shovel dipper vary as the dipper moves through the muck-pile. The variations in the forces cause stress loading of the components of shovel and dipper resulting in unplanned downtimes, reduced shovel efficiency, and high mining costs. A potential solution to the above problems is the deployment of an intelligent shovel excavation (ISE) technology, with real-time formation identification, recording, and knowledge transmission capabilities. This research advances the ISE technology by developing dynamic model of cable shovel dipper using Newton-Euler techniques. The model includes the dynamic cutting and dynamic weight forces acting on the dipper as it moves through the muck-pile.

Jan 1, 2011

By O. A. Ojo, R. G. Ding, M. C. Chaturvedi

In this study, the fusion zone microstructure of tungsten inert gas weld of a directionally solidified NhAl-base alloy was examined by the standard metallographic techniques involving the use of optical, analytical scanning and transmission electron microscopes equipped with energy dispersive spectrometer. Fusion zone cracking was observed to be closely associated with interdendritic secondary solidification microconstituents identified as consisting of y, y' and NiMo (Y) phases. Depression of solidification temperature to the terminal ternary eutectic reaction temperature of the system during cooling is suggested as an important factor contributing to the fusion zone cracking.

Jan 1, 2006

By Emil H. Geus

A process has been developed to recover aluminum from dross which does not require the use of salt flux as commonly employed, This results in a salt-free residue which has potential industrial uses or alternatively can be safely land-filled. The dross is first heated by an air-fuel or oxy-fuel burner in a sealable rotary furnace. At a suitable temperature the burner is turned off and the temperature of the dross thereafter controlled by means of an atmosphere of oxidative and inert gases. When the free metal has agglomerated it is first discharged from the furnace, followed by the residues.

Jan 1, 1995

Exposure to respirable contaminants in mine atmospheres has long posed a serious hazard to miners. The control of these hazards, some of which can have sudden and catastrophic effects and some others, slow and long enduring consequences, has been a major concern for labor, management and government alike. This concern has manifested itself in four primary mechanisms of control -- (1) regulatory control through minimum standard setting by the passage of mine health and safety laws, (2) engineering control through design and operation of mines according to the best recommended practices, (3) medical control through periodic physical examinations, wearing personal protection devices, etc., and (4) legal and social control through workmen's compensation laws for occupation related health rleterinratinn_

Jan 1, 1988

By Jean Dugas, Roger Sirois

The Mineral Deposits Service of the Quebec Department of Natural Resources is engaged in the preparation of metallogenic maps as a contribution to the Canadian Sub-Committee of the Metallogenic Map of North America. The preliminary work is being done on large-scale maps. The main objective is to clearly represent information on ore deposits in a suggestive way. The design of the legend to meet these requirements is discussed. As these maps are still only descriptive, a further step will be the interpretation of data into metallogenic maps with Jess emphasis on the individual deposits and more on the metallogenic factors. Both types of map should prove useful in the search for ore deposits; the first by providing at once a large amount of information, the second by suggesting the ore controls.

Jan 1, 1967

The latest outcome of science is that aII bodies are composed of vibrating atoms or molecules. In almost all mineral bodies when changing from the gaseous or liquid condition to the solid, if the vibrating molecules are allowed free play, they arrange themselves in a symmetrical manner, and at a definite angle to each other: This angle varies with each system of crystallization. In a great many bodies this process may be brought about artificially, and the growth of the crystal watched. The most common method is to dissolve some substance in water or some other liquid, on slowly evaporating the liquid, the substance dissolved will solidify and the molecules will arrange themselves in their particular crystalline form.The element carbon crystallizes in two forms; as graphite in the form of a short six-sided prism', and in the diamond generally as the octohedron in the cubical system of crystallization. Orystalline bodies, as a rule, have plain faces but what is remarkable in the diamond is that in a great many cases the faces are rounded. Its great beauty as a gem when cut, and the high artificial value placed upon it by fashion, as well as its value as a cutting and boring instrument-it being the hardest body in nature-has caused many attempts to be made to form it artificially. These attempts have met with fair success as a scientific experiment, but as a commercial speculation they have been a complete failure. The most noted of these experIments was carried out by Mr. Hannay, of Glasgow.Paraffin spirit with lithium was submitted td prolonged heating in strong wrought-iron tubes securely welded. In most of the experiments the tubes exploded; but in a few cases the experiments were successful, and on cutting open the tubes small crystals of diamonds were found embedded in a black mass.Despretz produced minute diamonds under the influence of a powerful electric current from coal.

By B, G Strobos, J P. Maree, N Smit

In mining and processing operations where minerals, high in pyrite and low in calcite/dolomite are processed, acid is generated, which needs to be neutralised. Ticor at Empangeni in South Africa (SA) produces rutile (TiO2), leucoxene (TiO2 plus iron compounds), titanium (Ti), zircon (Zi) and ilmenite (TiO2 plus iron compounds). Neutralisation is required in the processing plant where acid is leached into the wash water. This water needs to be treated to a quality suitable for re-use in the metallurgical process or to a higher quality to make it suitable for discharge into the Empangeni sewage system (SA). For re-use the water needs to be neutral and under-saturated with respect to gypsum while for discharge into the sewage system the sulfate concentration needs to be reduced to less than 500 mg/L (as SO4). Acid mine water is generally neutralised with lime. Disadvantages associated with lime are the costs and maintenance of the slaking equipment as well as hazards, associated with handling of the alkali. The cost of powdered limestone (CaCO3) in South Africa, a by-product, is 50 - 60 per cent cheaper than lime. A technology has been developed where limestone is used for neutralisation of acid mine water instead of lime. This development includes: Limestone handling and dosing system. A novel, robust system has been developed where waste CaCO3 from the paper industry is slurried to a constant density. A full-scale plant was constructed to evaluate its performance (Figure 4). The dosing system consists of an inclined slab onto which the limestone is stored and from where it is slurried into a make-up tank. The density of the slurry in the make-up tank is controlled via a loadcell that measures the weight of the tank (operated at constant volume) and activates/deactivates the spray of the recycle slurry onto the slab. Integrated limestone neutralisation/lime treatment process. In this process powdered CaCO3 is used for neutralisation and partial sulfate removal of acid leached from the coal washing plant. The sulfate concentration can be further reduced to below the saturation level of gypsum (ie 1200 mg/L) through gypsum crystallisation by means of lime treatment, resulting in metal precipitation (eg Fe3+ and Al3+). CO2- treatment for CaCO3 precipitation. The pH of the lime treated water can be adjusted to pH levels of 8.5 and lower using CO2. The CO2, generated during limestone neutralisation (Equation 2), can be captured and used in this stage of the process. The first two stages (limestone- and lime neutralisation) of this technology have been implemented on full-scale at Ticor to treat the effluent of the process. The constructed plant is 80 m3/hr and differs from coal processing plants by way of not containing Fe(II) and Fe(III) in the water. The CO2-treatment stage (Stage 3) will soon be implemented at IHM as part of a program to optimise the technology for maximum benefits.

Jan 1, 2003

By William A. Beck

The K.T. Dome Mine in Owen and Henry Counties, Ky., has been operated intermittently under several different owners since the early nineteen hundreds. No record of total production is available, but it is said that during 1943 and 1944, while being operated by the Twin Valley Mining Co., 30 cars of zinc concentrates and 10 cars of lead concentrates were shipped. The vein can be traced for about 10 miles along the strike from Lockport, Henry County, to Big Twin Creek in Owen County. It pinches and swells both vertically and horizontally and is reported to average 20 inches in width. In order to develop additional reserves on the property, the Bureau of Mines drilled four holes on the south extension of the vein. Drilling disclosed that the vein dips to the west on the south side of the Kentucky River and is continuous along the strike and in depth. However, the extent of mineralization in the vein varies widely.

Jan 1, 1949

By N M. Rana, A Take, N Ghahramani, S McDougall, S G. Evans

A critical issue associated with mining operations has been the stability of tailings impoundments. Some breach events have produced catastrophic tailings flows that have caused significant economic damage, mass casualties and long-lasting environmental impact in the downstream environment. This paper reports independently estimated values of runout distance, inundation area and fahrboschung of 16 tailings flows. The adopted methodology involves the geospatial analysis of satellite and aerial imagery to classify each tailings flow into a primary impact zone (Zone 1: main overland flow) and a secondary impact zone (Zone 2: along-creek diluted flow) to characterise runout. Only Zone 1 runout values are reported herein given the greater significance in relation to downstream impact. The fahrboschung is calculated using elevation data from global 30 m digital elevation models (DEMs) and source literature. The results show that all the selected tailings flows travelled long distances (2.4 km to 98.5 km) and inundated large areas (0.35 km2 to 27.0 km2) over very low fahrboschung values (0.04° to 4.8°). This indicates very high flow mobility that is largely governed by the high water content sourced from interstitial waters and, in many cases, supernatant ponds. Scatter plots display poor correlations owing to the complexity and variability in travel path characteristics (confinement, slope angle and obstructions) and the inherent properties of the flowing mass. The slope angle of the travel path exerts a strong control over the flow velocity which has implications on kinetic energy and downstream geomorphological impact. Mean tailings flow velocities may range from ~6 m/s on near-flat, open terrain to over 30 m/s in relatively steeper, channelised travel paths, indicating that tailings flows fall within the extremely rapid and high mobility spectrum of global mass movements. The presented work forms an inceptive part of the CanBreach tailings project, a major component of which is to develop a comprehensive database of case histories to examine the role of geotechnics, failure modes and downstream terrains in influencing tailings flow behaviour.

Jul 1, 2021

By Charles E. Mann, Douglas J. Lootens, Rufino B. Bomasang

INTRODUCTION The economy of the Philippines, like that of many other developing nations, has been severely strained by the rapid escalation of imported crude oil prices over the past decade. In an effort to reduce its dependence on imported crude, significantly increased emphasis, both in the public and private sectors, is being placed on the rapid development of Philippine coal resources. This paper is designed to present an overview of the Philippine coal industry, its historical development, present status, and future potential. COAL RESOURCES AND RESERVES In 1977, a British consulting firm collated all available data on Philippine coal resources and estimated the total coals potential at about 0.9 to 1.4 billion metric tons (mt). In 1981, using more recent data the Philippine Bureau of Energy Development (BED) estimated the potential at 1.7 billion mt. The BED estimated the proven coal reserves at 257 million mt. These coal resources are scattered throughout the major islands comprising the Philippine archipelago. However, about 52 percent of the currently proven reserves are located in the tiny island of Semirara between the islands of Mindoro and Panay. About 25 percent is located in the Cagayan Valley in northeastern Luzon while 13 percent is located in Mindanao. The remaining 10 percent is scattered in the islands of Cebu, Samar, Mindoro, Negros, Polillo, Batan, and Catanduanes. The bulk of Philippine coal is sub-bituminous in rank. Some bituminous coal with coking properties has been reported in Malangas, Zamboanga del Sur in western Mindanao, and in Catanduanes, but the exact tonnages have not been accurately established. It is believed, however, to be at most 5 million tons. A little semi-anthracite coal exists in Malangas with the remaining unmined reserves estimated at a little more than one million tons. Table 1 shows the quality ranges of Philippine coal deposits.. Figure 1 shows the distribution of known Philippine coal resources PHILIPPINE COAL PRODUCTION In 1981, total coal production was 330,720 mt. Though modest by world standards, this was the highest production figure in Philippine coal mining history. This came from 25 mines, mainly small scale underground mines of capacities varying from 10 to 100 tons per day (tpd). The actual production capability was about 800,000 mt in 1981, but the producers had to scale down production to the level of local demand. Even then, some 50,000 tons of coal remained unused by year-end. The 1981 production came from the following areas: Cebu 224,751 mt (68%) Zamboanga del Sur 57,095 mt (17%) Semirara 13,222 mt (4%) Polillo 17,132 mt (5%) Cebu has always been the main source of Philippine coal production. Coal mining has been carried out in Cebu for the last 50 years, although it has been characterized by a very crude mining technology. Due to the limited size of coal deposits and complicated geology, however, Cebu's share of the total national production is expected to go down to only 10 percent by 1985. Except for Semirara's open-pit production, the balance of Philippine coal production comes from underground mines. These underground mines generally use room-and-pillar methods, except for those at Zamboanga del Sur and Polillo which use modified longwall methods patterned after those used in Taiwan. Due to the much higher mining recovery, most underground mines are now planning on switching to longwall. At Semirara, an open pit mine is now being developed for a one million ton per year capacity by 1984, and will then be the largest Philippine coal mine. While present earthmoving work is done with bulldozers, loaders, and trucks, the main coal extraction equipment will be bucket wheel excavators imported from Austria. PRESENT COAL UTILIZATION Existing coal production is sold mainly to coal- fired cement plants and power plants. The balance is sold to a sugar central, a coconut oil mill, a food processing plant, and two plants producing carbide and ferro-silicon alloys.

Jan 1, 1982

By D. Brunner

System simulation is an increasingly popular technique for analyzing and improving existing as well as newly designed underground mining operations. An engineering firm that specializes in simulation helped a major metals producer build a long-range planning model of an existing underground mine. Subsequently the team adapted this model to assess technology alternatives in the design of a new mine. The two models differ in the level of detail used for modeling the development process. This paper discusses the differences in approach between the models along with the experiences gained and challenges faced during the construction and use of the models.

Jan 1, 1999

By Mohamed A. Eliwah

This paper deals with the determination of hydraulic conductivity of the coastal coralline limestone aquifer of Jeddah, Saudi Arabia. This coastal area has witnessed urban development and establishment of towers which requires deep foundations, excavation and dewatering of huge quantities of unconfined groundwater. It is occupied with successive layers of soft detrital and consolidated massive cavernous coralline limestone of the Quaternary age. These layers are encountered at a depth of 1.5m and extend for more than 100m. Hydraulic conductivity values were obtained by analyzing the pumping tests data under steady and transient state conditions. Hydraulic conductivity values help in selecting the proper and safe dewatering system, as well as determination of discharge rates and quantities of groundwater to be withdrawn. Test results obtained from two surveyed sites showed that the values of hydraulic conductivity are greatly variable. It ranges between 118.1 and 1559.6 m/day at the first site, whereas at the second one it ranges between 94.6 and 350 m/day. These high values are attributed to the cavernous nature of the water-bearing formation. Jeddah city could be divided into three different dewatering zones extending from north to south parallel to the coast line. Well point dewatering system could be applied in the first zone while ditches and sumps are the most suitable dewatering method in the second and third zones. Dewatering using deep wells in such highly permeable formation will require withdrawal of huge quantities of water which will be accompanied by washing out fine sediment filling the cavities in the surrounding areas. This will badly affect the nearby buildings through settlement, crakes and other structural damages. Therefore, construction of grouting plug/blanket with thickness of 3.0 m at a depth of 20.0 m is recommended. This depth will be enough to support the plug against the hydrostatic pressure. Moreover, it is highly recommended to transfer the site into closed box, by using diaphragm walls or secant bored piles.

By S. Rash Ahmadi

Welding is highly reliable and efficient metal joining process. In welding the metal adjacent to the weld joint is subjected to severe thermal conditions. As a result, complex changes in metallurgical structure occur in this region. These changes in structure depend on the material and the temperature history experienced. Friction stir welding (FSW) is relatively a new welding process in which, heat is generated by friction between the tool and the workpiece. The amount of heat conducted into the workpiece determines the quality of weld, residual stress and distortion of the workpiece. The objective of the current work is to study the transient temperature in a friction stir welding. So, a three dimensional transient analytical model is used to study the thermal distribution during the welding. Heat input from the tool shoulder alone is considered in the model. The process parameters like axial load, welding speed and tool rotational speed, used in actual FSW process are taken to build the model. This analytical model is very useful for select the optimized affected parameters in friction stir welding. The model illustrates the comprehensive equation including actual affected parameters in FSW and it can be used for different materials. In addition to the above the thermal history finds application in design of welding tools.

Oct 1, 2011

By C. S. Herzig

In the Engineering and Mining Journal of Jan. 27, 1900, there appeared an article by Fred T. Greene, describing a method of measuring stopes by the use of strings, a clinometer and a tape. In the early part of 1899 I had occasion to use a somewhat similar method, for the purpose of accurately ascertaining the volume of a very irregular drift connecting two mines. This drift was an important factor in a lawsuit for $150,000, in which it was necessary to determine accurately the volume originally occupied by the material extracted from the drift. While it is unnecessary to give all details of the controversy, some explanation of the conditions is required for a clear understanding of the following description. This drift was started by the a E." Co. from its workings, in about 7 ft. of ore, and headed toward the " G " property, the plan being to extract all the ore between foot- and hanging-walls, but to take out nothing but ore. As the " G." workings were approached; the ore-body became very irregular and much thinner. It was, however, very closely followed, and where the drift broke through into the " G." workings, the hole was only 11 inches high by 14 inches wide, or just about the size of a man-hole in a boiler.. Thus, this connection-drift tapered sharply; and the very irregular foot-wall sloped toward the " G." workings, and entered them at a place where the stope was only about 3 ft. high, and the ground had already commenced to cave. It may be added that the ore-body was a nearly flat deposit of lead carbonate in limestone, the ore and gangue being quite soft. I was called upon by the " G." people to make the survey

Jan 1, 1901

By Barry D. Lichter, Pierre Sommelet

High-temperature heat contents of InSb, GaSb, and AlSb were measured over the temperature range 400" to 1450°K using a diphenyl ether drop calorimeter. Smoothed ualues of the thermal properties, H$ - H:9s, have been derived and are tabulated at even temperature intervals. The heats of fusion of the three compounds were determined as, respectively, 5707 *100, 7780 * 100, and 9800 5 3011 cal per g-atorn at the determined melting points of 797" l°, 985" * , and 1330" * 5°K. The calculated entropies of fusion are, respectively, 7.16 0.12, 7.90 * 0.11, and 7.37 * 0.23 cal per deg per g-atotn. The heat capacities increase substantially on tnelting in contrast to the behauior of structurally related germanium and silicon. Deriations from the Kopp-Neumann rule are negative for solid compounds and positive for the liquid phases. Previously obsevrrd "post melting" in InSb is confirmed. The high-temperature thermal properties of 111-V compounds are presently not well-established, despite the technical importance of these semiconducting cbmpounds. Uncertainties in available heats of fusion and heat contents have seriously hampered thermo-chemical evaluations' and thermodynamic analyses of phase equilibria2"" in these systems. This paper reports results of high-temperature heat content investigations of InSb, GaSb, and AlSb measured in the range 400" to 1450°K employing a diphenyl ether drop calorimeter. Similar measurements for InAs and GaAs will be reported in a following publication.~ EXPERIMENTAL PROCEDURES Samples. High-purity samples of the compounds InSb and GaSb were supplied in the form of crushed crystal fragments by Dr. Carl Thurmond of the Bell Telephone Laboratories and in the form of single crystals by Dr. A. Strauss of the M.I.T. Lincoln Laboratory. Single-crystal samples of semiconductor-grade AlSb were supplied by Dr. W. P. Allred of the Bell and Howell Research Center. Chemical analyses indicated that all compounds were stoichiometric to *0.1 at. pct, which is within the experimental uncertainties of the analyses. Samples were crushed, weighed, and encapsulated in evacuated, thin-walled, fused silica capsules. The capsules were nearly identical in external shape, 2 cm by 2 cm diam, but varied in weight due to differences in wall thickness. One sample of AlSb was contained in a thin-walled, high-purity alumina cup encapsulated in silica and used for heat content determinations of liquid AlSb. The capsule materials showed no visual evidence of reaction with any of the compounds. The sample and capsule weights are given in Table I. Calorimeter. A Bunsen-type calorimeter, similar in design to a previously described instrument6 but employing diphenyl ether (C6H5)'0 as the calorimetric substance, was used for measurements of heat contents above 300.0°K, the melting point of diphenyl ether. Heat input to the calorimeter caused isothermal melting of diphenyl ether, and the resulting increase in volume was measured by displacement of mercury from the calorimeter into a 200 cm horizontal, calibrated capillary, 1.25 * 0.01 mm diam, or into a weighed beaker. The advantages of diphenyl ether over water have been previously pointed out7 and include: i) an increase by a factor of 3.5 in sensitivity as measured by the ratio of the volume change to the enthalpy change on fusion, ii) the smaller required extrapolation from the melting point to the standard temperature of 298.17"K, and iii) the positive volume change on fusion of diphenyl ether in contrast to the contraction which occurs on fusion of ice. Diphenyl ether was purified by fractional crystallization to 99.95 mol pct as determined from the melting point depression with fraction crystallized. During assembly of the calorimeter, the ether was repeatedly outgassed under high vacuum to remove dissolved air. The calorimeter receiving vessel consisted of an 8-in.-long by 1:-in.-diam copper tube with twelve horizontal 3-in.-diam radiator "fins" for dissipating heat to the surrounding mantle of diphenyl ether. Before forming the mantle the chamber surrounding the receiving vessel contained 3300 cu cm of liquid diphenyl ether above 250 cu cm of mercury which was

Jan 1, 1970