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By G. L. Oldright, Henry de Rycker, S. F. Ravitz

The upper limit of richness of concentrates that can be smelted by means of the blast furnace without added diluents is fixed by the operation of sintering. A sinter feed with normal gangue constituents, containing more than about 50 per cent of lead, tends to fuse; as a result, air does not come sufficiently into contact with the sulphides at roasting temperatures, and sulphur elimination is poor. Since most lead concentrates now contain 55 to 80 per cent lead, it is necessary to add diluents to lower the grade of such sinter feed to about 50 per cent or less. This not only entails the expense of providing barren diluents when adequate diluents containing precious metals are not available but also appreciably lowers the capacity of the blast furnace to produce lead and increases slag losses. Attempts to desulphurize rich lead concentrates by methods other than sintering have not proved successful. Flash roasting, for example, converts much of the lead sulphide to lead sulphate rather than to oxide. However, this suggested the possibility that deliberate flash roasting of the concentrates to sulphate, followed by sinter roasting of the resulting product, might prove promising, particularly inasmuch as the elimination of sulphur from lead sulphate requires heat alone and not contact with atmospheric oxygen. The sintering of lead sulphate products has additional interest because important amounts of such products are now treated by lead smelters. Considerable quantities of lead sulphate are present in rich lead flue dusts and other by-products; lead-chamber sulphuric acid plants and other

Jan 1, 1944

By F. V. Lenel, G. S. Ansell, E. C. Nelson

IRMANN'S' discovery that extrusions of fine alumi-num-flake powders possess remarkable high-temperature strengths has led to the production of a new class of engineering materials whose properties are derived from a fine dispersion of oxide particles in a metallic matrix. A fundamental study of such materials and elucidation of the mechanism whereby the oxide parti-

Jan 1, 1958

By B. J. Jody

At Argonne National Laboratory, we have been developing a potentially economical process to recycle automobile shredder residue (ASR). We identified three potentially marketable materials that can be recovered from ASR and developed technologies to recover and upgrade these materials. We built and tested a field-demonstration plant for recycling polyurethane foam and produced about 2,000 lb (907 kg) of recycled foam. Several 300-lb (I36-kg) samples were sent for evaluation and were found to be of marketable quality. We are also preparing for a large-scale test in which about 200 tons (181 tonnes) of ASR-derived fines «0.25 in. [<0.62 cm]) will be used as a raw material in cement making. A major cement company has evaluated small samples of fines prepared in the laboratory and found that they meet its requirements as a substitute for iron ore or mill scale. We also produced about 50 lb (23 kg) of recycled acrylonitrile butadiene styrene (ABS) from obsolete automobiles and found that it has properties that could be readily upgraded to meet the specifications of the automotive industry. In this paper, we briefly discuss the process as a whole and summarize the results obtained from the field work on foam and fines recycling.

Jan 1, 1996

By Jacques B. Wertz

Although fracture intersections and "domes" seem at a number of places to be the basic structural combination for the occurrence of a mining district, of the porphyry-copper type particularly, this situation is, of course, not always to be expected. For instance, the group of mines comprising Superior, Ray, Miami, Globe, Christmas appeared from the beginning of these structural studies as typical exceptions, and there are others. One had to expect additional parameters to allow for any mineral concentration to occur. One of these apparent parameters is here considered. From the result of stratigraphic studies related to ancient formations in Southeast Arizona, the Martin limestone (Devonian in age) was retained as having a possible relationship with the structure-economic studies in progress, as evidenced for instance by the mineralized O&apos;Carroll bed located at the base of the Martin. This limestone formation has been rather extensively investigated in the past and there are many known sample localities. For this work, the isopach map was drawn by computer to insure more objectivity and, in addition to the available data points, a number of dummy points with a zero value were added around the assumed form-

Jan 1, 1971

By K. E. Brown, J. P. Brill, T. C. Doerr

A wide range of intermittent gas-lift tests way conducted in a 1,500-ft experimental well through 11/4- and 11/2-in, nominal size tubing. The well was equipped with two gas-lift valves, four Maihak electronic pressure transmitters and surface facilities to measure casing and tubing pressures, temperature, liquid production and the rate and volume of gas injected. For each tubing size, tests were conducted varying the slug length, gas volume injected and liquid viscosity and surface tension. From these tests, an empirical "fallback" or liquid loss correlation has been developed. No general fallback correlation could be obtained, and the correlation is presented in the form of one curve for each slug length of a given liquid and lubing size. A conceptual model has been developed which combines the fallback correlation with equarions which govern liquid slug pow. A mathematical simulation of the model in the form of a digital computer program is used to calculate total recovery, gas volume used and clearance time for a given test. Tubing pressures at the gas-lift valve and at the gm-slug interface are calculated as a function of time. Tubing pressures at the surface during slug clearance ore also calculated. The results compare favorably with the test data and verify the conceptual model. The extent to which the model can be used for other tubing sizes, depths, liquids and gas-lift valves can only be determined with additional experimental data. Data are also necessary so that a fallback curve can be constructed for the particular test conditions studied. INTRODUCTION The flow of liquid slugs in vertical conduits has long been an established production method in the petroleum industry. Under the name "intermittent gas lift", many advances have been made in engineering design. However, the unsteady-state nature of liquid slug flow has discouraged attempts to describe the problem analytically. The result has been that intermittent gas lift is dominated by rules-of-thumb engineering practices developed over many years. The advent of slim-hole completions has increased the demand for a more rigorous solution to the intermittent problem. Small-diameter conduits offer more frictional per intermittent cycle. Small-diameter conduits are defined to be 1%-in. nominal size tubing or smaller. When oil is produced from the reservoir in which it is found, and transported to surface tanks by intermittent gas lift, three separate flow stages are encountered: flow of the fluids to the wellbore through a porous medium, vertical flow of a liquid slug from the point of gas injection to the surface, and horizontal flow of the liquid slug through the surface flowlines from the wellhead to the surface tanks. The three stages are depicted schematically in Fig. 1. The present study deals with liquid slug flow in both the vertical and horizontal conduits, ending when the bottom of the liquid slug reaches the surface. Due to the large number of variables involved, the analytical study of intermittent gas lift is extremely complex. The possibility of flow regimes other than slug type, the nature of the force fields acting on the system, the interfacial instabilities involved, the varying operational principles of existing gas-lift valves and the complete unsteady-state nature of the physical phenomena occurring in an intermittent gas-lift cycle relate some of the difficulties encountered.

By Herbert Pöllmann

Waste disposals are needed for safe deposition of different kinds of materials which can not be used as secondary raw materials. Often high contents of heavy metals must be bonded tightly to cristalline compounds to protect the environment from contamination. Therefore it is important. to find minerals which are capable to incorporate different heavy metals and protect the ground water. The power of resistance against leaching out effects of highly water-soluble salts can be increased. Mineral groups of metal hydroxy salts, ettringites, apatites, sodalites and calciumchlorosilicates and their hydrates are recommended for their formation in mineral reservoirs. Different wastes as red mud, gasification ash, garbage combustion ash and fluidized bed ashes were included in this study. The formation of different new compounds and their properties were determined.

Jan 1, 1991

By Masao Miyake, Eiichiro Matsubara, Tetsuji Hirato, Yasuhiro Awakura

"Zn-Cr alloy coating with around 15 wt% Cr has been found to have much higher chemical corrosion-resistance to steel than conventional zinc plating, while· its structure has not been clarified. The Zn-Cr alloy plating is performed at high current densities around 1 A cm-2 and for 10 to 20 sec using acidic aqueous sulfate solutions with some additives in the iron-steel industry. Due to the high current densities, it seems reasonable to consider that the Zn-Cr alloy plating proceeds under an unsteady-state condition and that the resulting coatings have a non-equilibrium phase and have a structure change in the .direction of thickness. In this research, the crystal structure of the Zn-Cr alloy coating electrodeposited at high current densities and change of the structure in the direction of thickness were examined by X-ray diffraction. The coatings containing under 20 and 35-40 wt% Cr had hcp and bee structure, respectively, while the coatings containing 20-35 wt% Cr comprised two phases with the hcp and the bee structure. The structure of the coating varied in the direction of thickness; both the hcp and bcc phases coexisted in the vicinity of the substrate, while the hcp phase became predominant with increasing distance from the substrate.IntroductionRecently it has been reported that Zn-Cr alloy coating containing around 15 wt% Cr has much higher corrosion-resistance to steel than conventional zinc plating.1-3) The corrosion-resistanc·e of Zn-Cr alloy plated steel sheet with a plating amount of 20 g m·2 is, for example, superior to that of Zn plated steel with a plating amount in the range 60 to 90 g m·2 , which is widely used for automotive bodies today.4l The Zn-Cr alloy plating is obtained by electrodeposition at current densities over 0.5 A cm·2 from a sulfate solution containing zinc and trivalent chromium ions and some additives.5•6) The deposition current densities mentioned above are much higher than those for usual electroplating processes, e.g., Zn, Cu and Ni plating, carried out about 0.05 A cm·2 • Therefore, the time required for plating is very short; around 10-20 sec. Due to the high current densities, it seems reasonable to consider that the· Zn-Cr alloy plating proceeds under an unsteady-state condition and that the resulting coatings do not have a phase expected from equilibrium diagrams; no phase diagram of the Zn-Cr system with a full composition range has been available. 7). In other words, the alloy phase plated would be a non-equilibrium phase with unknown structures."

Jan 1, 2000

Spiral separators have been used to treat heavy mineralsands in Australia for some 35 years. During the last five years the logical extension of this technology has been torecover cassiterite from alluvial deposits. Plants incorporating spirals are already operating in Indonesian andAustralian tin mines. A more fundamental understanding of the design of spiral separators has recently led to their use in other mineral treatment plants.In particular, the treatment of alluvial gold and fine coal has been most successful. The new generation of spirals that has been developed to treat these minerals is more easily operated than other competing processes and is therefore ideal for new mine situations.

Jan 1, 1986

Differences in the assay results of replicate samples engender doubts on the reliability of ore sampling and of assaying procedures. An analysis of variance is a technique to estimate the variability at each level of the procedures. In an example, the variability of one-metre core samples was far greater than that of the assaying technique.

Jan 1, 1976

By L. D. Muller, C. P. Sayles

When minerals are mined in arid or semiarid areas where water is at a premium, dry processing is a natural route to take for concentrating or classifying the values. Until recently though, dry processing technique were limited by the lack of suitable equipment. With the advent of the pneumatic pinched sluice at Warren Spring Laboratory, Stevenage, Hertfordshire, England, a new tool emerged to fill this gap and it has the potential of providing industry with a high output concentrator or preconcentrator for dry natural ores and secondary materials. The pneumatic pinched sluice gives every indication of fulfilling these requirements with the added advantage that with homogeneous materials-such as crushed limestone or quartzose sands-it may alternatively operate as a high throughput dry classifier or sizing device. An industrial version of the equipment is now being manufactured by Dryflow Separators Ltd., as sole licensee for the National Re- search Development Corporation.

Jan 1, 1971

By N. Birtek, R. P. King

The washability characteristics of fine South African coals were measured and were found to be well characterized by an M-curve having the equation Z = aQb exp(cQ) x dQ, where Z is the ash content per 100 units of total feed and 0 is the mass yield. Parameters a, b, c, and d were determined for 23 different samples of coal from important coal seams in the main South African coalfields in the size range 0,0025 to 1 mm. The relationship between ash content and relative density was determined and correlated by means of two linear relationships. This characteristic behaviour was explained in terms of the liberation of macerals and the different association between the mineral mater and the two major macerals vitrinite and inertinite. The results obtained in this study can be used to calculate the expected performance of an ideal separation process, and can also be used as input for the simulation of real beneficiation plants. An example is worked through in detail to illustrate the method of calculation.

Jan 1, 1990

By Lon Santis

This paper analyzes 110 serious accidents that occurred during the use of commercial explosives in mining, construction, and other industries since 1992. Data from the Mine Safety and Health Administration (MSHA), the Institute of Makers of Explosives (IME) members’ reports, and media reports were used. Only accidents that resulted in a fatality, significant lost work time, or injury to the public were considered in this analysis. The accident data were analyzed for trends in frequency, type of industry, cause, type of individual harmed, and geographical region. Although the data showed that explosives accidents are decreasing in frequency, still, 29 people were killed and 134 injured. Eightyfive of the accidents occurred in mining, 17 occurred in construction, and 8 occurred in other industries including oil recovery, seismic exploration, agriculture, logging, boiler cleaning, and avalanche blasting. As other studies have shown, flyrock and failure of blast area security caused over half of the accidents. Mishandling, misfires, or fumes caused just over one-third of the accidents. Lightning and drilling into explosives were responsible for the remainder of accidents.

Jan 1, 2003

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3&apos;4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH&apos;s when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By Nobuhiro Oguma, Yuji Mizuta, Hideya Sato, Shigehiko Iwahori

"Recyclable materials containing copper and precious metals have been treated at the Mitsubishi Process in Naoshima. In 2003, a new incinerating and melting plant (pre-treatment plant) for waste materials, such as shredder residue of automobile and scrapped appliance, was constructed. All of produced slag/metal mixture is treated at the Mitsubishi Process, and which results in the significant increase of recyclable materials treatment. The combination of two processes has realized a highly efficient and environmentally friendly system for recycling valuable metals in the waste which used to be sent to a landfill. Naoshima continues to make efforts to achieve the highly efficient operations of the two processes, and plans to increase the treatment of recyclable materials further. This paper summarizes the recent operations and the various improvements implemented in the pre-treatment plant.IntroductionRecyclable materials containing valuable metals such as copper and precious metals have been treated at the Mitsubishi Continuous Copper Smelting and Converting Process (Mitsubishi Process) since the start-up in 1991. In the early stages, recyclable materials consisting mainly of metal scrap were charged into the process and the treatment had been increased steadily. In order to promote the recycling business, treatment of various kinds of materials including printed circuit boards was started. However, the treatment hit the ceiling due to a limitation of furnace boiler capacity, since they contained large amounts of combustible materials. In addition, severe corrosion of boiler tubes was caused by halogen contained in recyclable materials."

Jan 1, 2012

By Mantsevich M, Ivanov V, Volkov V, Ponomarov G

A new ecologically promising technology for the copper-nickel ore benefication using insert gases and pyrrhotite depression is under consideration. The finely dispersed nickel-containing sulphides and the pyrrhotite are easily oxidised during the process of flotation resulting in deterioration of selectivity and valuable component loss in the tailings. One of the ways to improve the benefication is the flotation of easily-oxidising minerals in an inert atmosphere. In the experiments nitrogen was taken as the inert gas supposing that in the industrial scale operations nitrogen generating, as a by-product of the oxigen production. will be used (Rybas et at, 1989). The most wide-spread mineral in the Norilsk rich sulphide copper-nickel ores is pyrrhotite containing iron, sulphur, nickel and platinum group metals. Up to 30 per cent of the pyrrhotite sulphur is recovered into the nickel concentrate causing the high sulphur dioxide emission in the further pyrometallurgical process of nickel production. This is the reason why the problem of the pyrrhotite removal during the ore concentration should be solved, the critical factor of the problem being the lowest possible nickel content in the pyrrhotite. According to the data of the geological and mineralogical mapping the nickel content in the pyrrhotites of rich ores varies from 0.3 to 1.8 per cent, with the mean value equal to 0.6 - 0.8 per cent. This assures the technological and economical effectiveness of the low-grade pyrrhotite removal during the flotation process.

Jan 1, 1993

By Phillip O. Tyree, R. A. Metz, Joseph W. Mussey

Bio-epigenetic sulphur deposits occur in Pecos, Reeves and Culberson counties of far West Texas. Sulfate reducing bacteria, utilizing hydrocarbons as energy, transformed gypsum into replacement limestone and hydrogen sulfide. Hydrogen sulfide, retained in the pores of the replacement limestone, was subsequently oxidized by highly oxygenated groundwaters, and native sulphur precipitated. West Texas sulphur was first recognized at surface exposures by William P. Blake, a geologist attached to the Captain Pope Military/ Scientific Expedition of 1854. Attempts were made in the early 1900&apos;s to mine these sulphur vent exposures by a retort method, but the ventures met with little success. In 1967, Duval discovered a large sulphur deposit near some of the old sulphur works in Culberson County. Duval also expanded reserves in a small sulphur deposit in Pecos County. The Frasch process, developed for producing sulphur from Gulf Coast salt domes, proved successful in West Texas type sulphur deposits also. However, modifications of the process were necessary to provide economical and efficient sulphur recovery from the varied ore occurrences. West Texas conditions and logistics require the ultimate in productivity to be competitive in the domestic and foreign sulphur markets. Several companies, in addition to Duval, are producing or have produced sulphur in West Texas. As of June 1, 1984, a total of 29.87 million mt (29.4 million long tons) of sulphur had been produced west of the Pecos River. Duval corporation has produced more than 88 percent of that total.

Jan 1, 1992

By Ottey M. Bishop, William G. Peryam, Fred E. Johnson

THE Lepanto Consolidated Mining Company is the largest copper producer in the Philippines, and the only one that makes a concentrate valuable principally for its copper; also, it has the only productive copper mine situated at considerable distance from the sea, and is the only one in the islands operating its own smelter. The Lepanto mine is in the Municipal District of Mankayan, sub-province of Benguet, near the heart of the Mountain Province of Northern Luzon. It is 165 km. from its shipping point at San Fernando, Province of La Union, on the shore of the China Sea. Elevations at the property range from 3200 to 4500 ft. The climate is very mild; temperatures are seldom below 50° or above 80°F. Annual rainfall approaches 170 in. and is mainly confined to a rainy season lasting from May to October. The months from December to April, inclusive, are usually extremely dry. This climatic pecularity entails the problems of landslides on the roads during the rainy season and water shortage during the dry season. The Mountain Trail, an improved rocksurfaced toll road maintained by the Commonwealth Government, gives access to the property. The 105 km. over this road may be traveled in about 4 ½ hr. during the dry season. Very few sections of the road are straight for more than 100 meters, and about one third of it is a one-way road controlled by gates. All freight for the property is delivered by the Manila Railroad Company to Bauang, La Union, 45 km. west of Baguio and at sea level, where it is picked up by freight trucks and hauled via Baguio to Lepanto. Granulated matte is hauled in bulk from Lepanto in four-ton lots on freight trucks to the storage bins at San Fernando. Freight rates from Bauang to the property amount to [P]8.oo per ton, and from the property to San Fernando the rate is [P]16.00 per ton. The company pays the road toll, [P] 1.00 per truck, each way. THE CAMP The company maintains a modern camp, well separated from the mine and reduction plant. Comfortable and sanitary living quarters, water, and light, as well as free medical service are provided all employees. A hospital staffed by a doctor and two nurses takes care of all medical treatment. Considering recreational facilities of great importance, the company has provided two tennis courts, two basketball courts, and badminton courts for employees. Bowling alleys and a motion picture theater are operated by the company, the profits being expended for other recreational purposes. A moderate sized recreation hall serves for barrio dances, meetings,

Jan 1, 1942

By S. Sener

In this investigation, the changes in the grindability of both ulexite and colemanite related with the different structural modifications created by the heat treatment were examined with respect to work index (Wi). The effects of the heat treatment temperature and time on grindability index were also investigated. It was observed that, heat treatment significantly affected on the grindability of ulexite. The work index of original ulexite was found 7.11 kWh/shton and decreased to 3.5 kWh/shton level within 200-480°C for 60 minutes. On the other hand, the work index of original colemanite was found as 6.48 kWh/shton and no appreciable change was observed when heated up to 320°C. Thermally assisted comminution can be used to improve the grindability characteristics of ulexite. Besides, the different behaviour of ulexite and colemanite under heat treatment can be used for their separation. The artificial mixture of ulexite and colemanite could be separated with over 90% recovery by utilizing their different grindability characteristics by thermal treatment, semi-autogeneous grinding and screening.

Jan 1, 1999

By W. P. Frey

The briquet plant of the Lehigh Coal and Navigation Co., at Lansford, Pa., has previously been referred to.&apos; It has passed the stage of experiment and now rests on a foundation practically and financially sound. The purpose of this&apos; paper is to explain how success has been attained, and to set standards for the development of hard-coal briquetting which may eliminate future failures. All the conclusions are based on actual results, avoiding speculation and theory. Up to three years ago, the L. C. & N. Co. used coal-tar pitch as a binder in making hard-coal briquets. The plant operated with a monthly output of 300 to 600 tons and was unable to meet its own expenses. Naturally, no one was satisfied, especially as the ideals of a smokeless briquet were still unrealized. Then came the Dutch oil process, introduced in this country by the General Briquetting Co. of New York. This process uses as binder a small percentage of heavy residue of petroleum, which, being liquid, permits great economy of handling; it also did away with the most objectionable fumes of the former briquets. This oil2 is not absolutely smokeless; heating the fresh fuel to red heat liberates some low-volatile hydrocarbons, yielding a white smoke which is not objectionable. On the other hand, this oil adds to the briquet about 7 per cent. of volatile matter, giving the product a heating capacity equal to that of the best free-burning anthracite coal. The average silt used in the manufacture of these boulets averages 16.5 per cent. chemical ash, corresponding to 12,000 B.t.u. per pound of coal. The Hydrolene used as binder runs about 17,500 B.t.u. per pound, and approximately 7 per cent. of it enters into the mixture, hence 12,000 X 0.93..........................11,160 B.t.n. 17,500 X 0.07.......................... 1,125 B.t.u. Total.....................................12,385 B.t.u. per pound of briquets

Jan 1, 1918

By E. R. Dean

A wire-feed mechanism has been employed to fabricute metal alloy film resistors to various sheet resistivities on oxidized silicon substrates. The effect of several thousand hours storage in air at elevated temperatures on the resistance and temperature coefficient of resistance is presented. Unprotected films of- sheet resistivity between 100 and 500 ohms per sq fabricated at 300°C substrate tenzperatures were unstable when stored at 150°Cfor extended periods. The higher sheet resistivity films exhibited the greatest instability; however, even the 100 ohms per sq films drijted excessively for device application. When stored at still higher temperatures, the normalized resistance increases to maximum, then decreases until a minimum value is obtained, then finally increases in resistance until open. The use of a protective overcoating of SiO has had considerable benejicial effects on the film stability, so that 250 ohms per sq films deposited on 300°C substrates are now stable after 1000 hr storage at 250°C and possess a temperature coefficient of resistance less than 200 ppm per C. The use of a low substrate temperature during depositon (100°C) enables the preparation oj resistors with very low tenperature coefficients of resistance (10 to 20 ppnl per &apos;C). However, these films are less stable than their higher substrate temperatuve counterparts. During extended storage, the resistance of the protected films always decreases with lower substrate films exhibiting larger normalized resistance decreases. This resistance decrease is accompanied by a linearly related increase in the temperature coefficient of resistance. The electrical behavior of these films may be explained by postulating That the structure of the films is in the transition region between thick continuous films and ultrathin island structure films so that the conductivity is the restlt of both electron scattering and tunneling-activated charge carrier creation between neighboring grains. The annealing behavior when thermally aged is the result of defect anneal, grain growth, and selective oxidation. TheRE is a considerable interest in thin metallic films for use as resistor elements in microelectronic circuits.1,2 These resistor films must be stable when exposed to elevated-temperature storage or operating ambient, possess low temperature coefficients of resistance (hereafter referred to as T.C.R.), and be of a high enough sheet resistivity to be useful. The resistivity and T.C.R. of a thin metallic film are determined by the structure and thickness of the film. Hence the stability of the film when exposed to stress would depend on the stability of the structure. The resistivity of a thin film is the result of the electrons&apos; interaction with the lattice vibrations (electron-phonon scattering), scattering of electrons due to impurities, defects, and grain boundaries and specula reflection from the film surfaces.3&apos; All of these effects serve to reduce the electron mean free path and result in a resistivity higher than the ideal bulk. In ultrathin films possessing essentially an island structure consisting of a planar array of aggregates separated by a few to a few tens of angstroms, conduction is dominated by a combination of tunneling and activated charge carrier reation. Thin films would be characterized by relatively low resistivity, positive T.C.R., and reasonable structure stability whereas ultrathin films possess unstable structures, negative T.C.R., and exhibit high resistivity. Feldman6 has investigated films intermediate between the two regions and postulates that the resistivity of a film in the transition region is composed of two linearly additive parts: that due to the resistance of the grains and that due to the gaps. The grain resistivity would represent the scattering of the conduction electrons by defects, surfaces, and phonon interaction while the gap term represents the tunneling contribution. For gold and platinum films, he found as the film structure becomes progressively less continuous, corresponding to thinner films, the absolute value of the T.C.R. becomes progressively smaller until negative values are observed with respective zero T.C.R.&apos;s at about 35 and 150 ohm per sq, respectively. Recently the author7 investigated the behavior of a multicomponent alloy of nickel, chromium, and iron and found the T.C.R.&apos;s of these films decrease with decreasing substrate temperature during deposition. The lower T.C.A. associated with lower substrate temperatures was attributed to an increased contribution to the total resistivity from the negatively temperature-dependent gap tunneling since it is well-known that thin films deposited on low-temperature substrates consist of a higher density of smaller grains than the same sheet resistivity films deposited on higher-temperature substrates. Under conditions of thermal anneal, the author found that, when various sheet resistivity films fabricated at 300°C substrate temperature are exposed to extended storage in air at 300°C, the thinner films increase in resistance until open, while the thicker films

Jan 1, 1967