Search Documents

By A. Satter

Studies of wellbore heat transtnission during the injection of a hot fluid, as either gas or liquid, have appeared in he literature. The present investigation takes into account the effect of condensation, which is of practical sig-nificance when considering steam injection operations. Calculation procedures are given for superheated and for saturated and undersaturated steam. Effects of injection rate, time, pressure, temperature and depth of a well on heat losses have been analyzed. The benefits of using a packer are discussed. Also presented are correlations for estimating heat losses involved during injection of saturated steam. INTRODUCTION Studies of wellbore heat losses during the injection of a hot fluid have appeared in the literature. Ramey' has presented a useful solution for calculating temperature of a heated gas as a function of depth and injection time. Ramey and others have also presented solutions for the hot liquid case.'. ' No method is available to take into account the effect of condensation, which is of practical significance when considering steam injection operations. This paper presents a method of estimating the quality of a condensing fluid as a function of depth and time. The approach is basically the same as that used by Ramey. The following injected fluids and conditions are considered in this study: 1. Injection of superheated steam A. Decrease in temperature until cooled to the saturated state B. Condensation until condensed completely into hot (saturated) water 2. Injection of saturated or undersaturated steam; condensation until condensed completely into hot (saturated) water. Although this investigation does not include cooling of water after steam is completely condensed, Ramey's solution for the hot liquid case can be used for this purpose. The effects of various process variables on heat losses During the injection of steam into a well are investigated. THEORY QUALITY OF CONDENSING STEAM Predicting the behavior of condensing steam flowing down the injection wellbore requires an estimate of the quality of steam, i.e., the mass fraction of vapor in the mixture. Let us divide the total depth of the injection well into several segments which might be, but do not have to be, of equal magnitude. Consider condensation within a given depth interval AZ, the bottom of which is located at a depth Z from the surface (Fig 1). The following equation, derived in the Appendix- relates the quality of steam at the bottom of an interval to that at the top of the interval:

Jan 1, 1966

By Walter Remmers

THE fact that gray iron increases in volume, cracks and distorts upon repeated heating and cooling is rather common knowledge. In ingot molds, Diesel engine pistons, carburizing boxes, continuous furnace parts, grate bars, stoker parts, and all castings that are subjected repeatedly to high and low temperatures, the phenomenon of growth presents a vital problem. Ingot molds distort and produce cracks which result in seams or laps and later appear as defects in the finished product. The heads of Diesel pistons frequently fail by cracking in a stellar shape. This is attributed usually to the result of permanent growth. Distortion and change of dimension of furnace parts frequently renders them entirely unusuable. In chain grate stokers, mechanical difficulties frequently are caused by the growth of the links. In proper operation these links should never attain a temperature sufficiently high to start growth; nevertheless, some have grown 1/8 in. on an 8-in. length when improperly operated. Even though the phenomenon is generally known there still exists a deficiency in the explanation of the mechanism of this growth. The field of investigators of this subject has a decided variation in opinion concerning the causes. The problem is of sufficient importance therefore to warrant further consideration.

Jan 1, 1930

By Segnit ER, Jensen G

The decoppering of soft and hard leads was investigated by stirring in an open pot, using sulfur or sulfur plus pyrites, or sulfur plus pyrrhotite, as reagents. Lead samples taken during the process were analysed for copper. Dross samples were examined by optical micro- scope, SEM and XRD. Soft lead containing silver can be decoppered satisfactorily by stirring with 0.1% S at low temperatures - close to 330¦C. Soft lead, whether containing silver or not, can be decoppered satisfactorily at higher temperatures by stirring with 0.1% S plus 0.4% pyrites. Then CuFeS2, Cu5FeS4 and PbS are formed, instead of Cu2S, CuS and PbS when using S alone. Hard lead containing tin can be decoppered satisfactorily by stirring with 0.1% S at temperatures from 320-400¦C. When stirring with 0.1% S plus 0.4% pyrites, reversion of copper from dross to lead on prolonged stirring does not occur. Hard lead without tin can be decoppered with S plus pyrites better than with S alone, but the presence of antimony hinders the decoppering, which is less effective on lead with 5.5% Sb than with 2.3% Sb.

Jan 1, 1980

By Thomas L. Vandergrift

Multiple-scam mining is becoming more common in the United States, especially in the East, where primary reserves arc being depleted, forcing mining companies to develop secondary seams, Although mine engineers and planners are aware of the basic effects of seam interaction and generally follow guidelines for columnizing entries and avoiding load abutments, mine design earn greatly benefit bum more quantitative estimates of scam interaction effects. This paper presents case studies from two eastern mines subject to seam interaction effects where pre-mining stresses were quantified: the Mingo Logan Coal Company's Mountaineer Alma A Mine, and Peabody Group's Lightfoot No. 2 Mine. In each of these mines. mining is being carried out within 60 to 90 ft of overlying longwall and pillar panels under maximum cover of about 1,100 ft As part of overall mine planning and design efforts al these mines. NSA Engineering performed numerical modeling analyses using the non-linear boundary-element code MULSIM/NL Input parameters were calibrated by modeling areas where ground conditions resulting from seam interaction were well documented. By incorporating actual cover loading based on topography and seam dip, and the integrity of remnant, gate road, arid harrier pillars in the overlying mines, the pre-mining vertical stress in the underlying scants was estimated based on the pre-mining stress, plans for mains, gate road, bleeder, and pillar panels were developed. Although mining experience in these areas has beers somewhat limited to date, she designs developed as a result of these analyses have so far proven successful.

Jan 1, 2000

By L. F. Bishop

The ore bodies of the Butte district1 are found in many different vein systems having many different structural characteristics; some are narrow with self-supporting ore but with weak walls; some are wide with weak or strong ore and weak walls; some of the veins dip steeply and others do not; some have well defined walls, and others, in the "horsetail" area, are mined to sample limits. Consequently, many types of stoping methods are used in mining these ores. The stoping methods used in the Anaconda Copper Mining Company's properties are the square-set and cut-and-fill. The square-set method is the principal stoping method used because, generally speaking, the ore and walls are weak, the ore is high grade, and good extraction is required. These square-set stopes may be classified as conventional, vertical slice, slot, timber rill, and Mitchell slice types. The conventional type square sets are those of various shapes and sizes, mined by horizontal slicing to the boundaries of the stopes. The rock is slid to the chute and the filling is moved by gravity. The ore and waste may be handled with a scraper when local conditions require it. The vertical-slice square-set system is the type used in narrow veins that are mined in vertical panels. The slot stopes are stopes in wide veins that employ a slot across the vein instead of a con- ventional chute to handle the ore. The timber rill is a type of square set in which the ore is mined as in inclined cut and fill but the square-set timber is used. The Mitchell slice is the type used for some broken or heavy ore blocks, or for pillar extraction between two converging slot stopes. The cut-and-fill method is used where the ore will stand without much support although the walls may be weak. The principal type of this method is the horizontal cut-and-fill, with mechanical scraping. The inclined cut-and-fill, or rill, stopes are used in some veins too narrow for scraping. The production from the various methods in use for the second six months of 1944 are shown in Table I. This paper deals mainly with the vertical slice and slot types of square-set stoping, because of their effect on production locally and their potential possibilities here and in other districts, with sufficient reference to conventional square-setting for comparison.

Jan 1, 1946

By John S. Johnson, Thomas Fraser

SIZING is the process of separating mixed particles into groups of particles all of the same size, or into groups in which all particles L range between certain definite maximum and minimum sizes. In coal preparation, sizing is generally accomplished by passing the coal over screens. Separation by differential settling in air or water currents has been adapted to the special field of separating very fine sizes, and these processes are in commercial use to a relatively small extent in the coal industry. Separation with screens is a very old industrial practice. Agricola 1 described the use of screens for ore treatment in the middle ages. In the literature of the British coal industry references were made to the screening of coal as early as 1589, but the practice of extensive sizing for the market did not become general until the last half of the nineteenth century. In America, the practice of sizing developed first in the Pennsylvania anthracite region, beginning with the use of rakes2 in the mine working places to recover coarse coal. This mining procedure left the fines in the mine. Preparation outside the mine started with the installation of stationary cast-iron plates with 4 to 6-in. square holes. The run-of-mine coal was dumped upon the platforms, the large pieces of rock were picked out by hand, and the large lumps of coal were broken with hammers. The term "breaker," which still applies to the anthracite-preparation plant, originated with this practice, but the term is no longer descriptive of the entire function of the plant. In 1884, the first power-operated anthracite coal breaker3 was erected by Gideon Bart at his colliery at Wolf Creek near Minersville, Pa. This plant utilized a system of rolls for breaking the coal and revolving screens for sizing. The plant was driven by a steam engine. It could handle

Jan 1, 1943

By M. Karmis

mining factors and representative ground movement parameters. Based on this analysis, the previously developed prediction methods were modified and tested for their applicability in the Appalachian coalfield. Finally, in order to facilitate the implementation of the prediction methods, as well as the data processing of the monitoring program, a number of computer software were developed and will be discussed in the paper. Surface deformations above underground mines and their prediction and control have been the topics of an extensive research effort by Virginia Polytechnic Institute and State University over the past few years. During the initial stages of this research, a number of case studies were collected from the literature, the mining industry and various government and state agencies and, based on the analysis of this information, appropriate prediction methods were proposed (Goodman, 1980; Webb, 1982; Hasenfus, 1984; Karmis et al., 1984). Although the prediction methods were based on sound concepts, it became evident that their accuracy and implementation were a reflection of the size and quality of the collected case studies. In this respect, the data bank was rather insufficient and posed certain questions regarding the development of subsidence information due to inappropriate length and spacing of monuments used in subsidence surveys, density and accuracy of such surveys, lack of monitoring horizontal movements, etc. In an effort to alleviate these problems, a comprehensive monitoring program was initiated in the coal mines of southwest Virginia, which included: - Two longwall and five room and pillar mines. - In total, seven longwall and sixteen room and pillar panels. - Monitoring lines in excess of 35,000 feet. - Vertical as well as horizontal measurements. A high accuracy digital computer tacheometer was used in all surveys and the type and spacing of all monuments were in accordance with well accepted guidelines. The data from this monitoring program completed the initially collected data bank and, thus, enabled a much needed statistical analysis between

Jan 1, 1987

By E. L. Jr. Spain

This study was undertaken primarily to determine the reasons for certain varia-tions in the soundness of gravel aggregate taken from a number of widely separated points on the Tennessee River. Under laboratory tests, concrete made with these various aggregates it some cases exhibited marked differences in specific gravity, crushing strength and durability. Gravel was studied in detail from Chattanooga to the mouth of the river and to a lesser extent from Chattanooga to Knoxville. The causes of variation were determined, and variational curves were constructed, which accurately predict the composition of aggregate at any point on the river and therefore its relative suitability for use in concrete. The aggregate at any point is suited for making sound concrete; the variance of suitability is due to varying percentages of sandstone and weathered material, which are less sound than other constituents. INTRODUCTION When it is stated that the aggregate from one point is inferior to that from another, it must not be construed to mean that the gravel is unfit for use. The classification upon which such aggregate ratings are based is largely arbitrary, thus inferiority or superiority is merely relative. Samples of gravel were selected from stockpiles at the dams of the Tennessee Valley Authority under construction, from the stockpiles of private companies along the river, and from samples taken by the gravel-exploration barge of the T. V. A. One hundred or more gravels of each size studied were selected at random by taking small handfulls while walking around the piles. These were separated according to the differ-ent mineral or rock constituents present, and the percentage of each constituent was obtained by counting. At least three such samples were taken from each size, and all checked with one another within a few per cent. The results were then averaged. In order to check on the accu-racy of such sampling, a whole sample was taken from one point after the gravel was thoroughly mixed. The two methods gave approximately identical results.

Jan 1, 1937

By Brian Stump, Chris Hayward

Blasting operations at one copper mine are studied in detail to examine the relation between blast design parameters and near-shot, in-mine, and regional seismic and acoustic observations. Five observational experiments, namely collection of blast design data, near source recordings, GPS synchronized video, near mine recordings and distant regional observations were performed during one week in August. A variety of seismic and infrasound instruments were installed near the shot, on the perimeter of the open pit mine, and at several locations up to 500 km distant. Time tagged video recordings were taken of several shots. Three shots were used in the preliminary analysis, a 350,000 lb pattern with long delays, a 60,000 lb pattern with short delays, and a 256,000 lb pattern with short delays. Maximum peak-to-peak amplitudes of the seismic signals in the mine are not a simple function of the total size of the shot, but are related to the pattern timing. Peak pressures have a less clear relation to peak pressure but match the relative amplitudes of spectra modeled from the pattern design. The predicted spectrum based upon a simple impulse model fits the observed spectrum for ground acceleration measured near the pattern and explains why in this case a pattern of 60,000 lb results in the same seismic disturbance as the 350,000 lb pattern.

Jan 1, 2002

By Arthur West

It is the purpose of this paper to describe briefly some recent large power stations for blast furnaces, where the blast is exclusively supplied by gas engines using furnace gas. The stations are given in the chronological order in which they were designed, in order to indicate the various improvements suggested by experience. Fig. 1 shows the blowing-engine station of the Bethlehem Steel Co. at Bethlehem. Although the picture shows only five blowing engines, the house now contains 11 engines. In the diagrammatic plan the arrow shows the position and direction of camera. This station handles five modern blast furnaces of 450 to 500 ions capacity each. In this, as in all the other stations described in this paper, each furnace is blown by two single tandem gas engines. Ten engines are thus required for five furnaces, leaving one single tandem spare engine. This spare capacity has been shown by several years' experience at Bethlehem to be adequate to insure continuous operation. The engines in the Bethlehem station are right hand and left hand, arranged in pairs. The outboard bearings of each pair are close together so that there is not room for passageway between them. On the right of the picture are shown the inclined drums communicating with the cold-blast lines outside of building, so that any engine may be operated on any furnace. The illustration shows four cold-blast gate valves with pipes passing through wall, but since the photograph was taken the drums have been extended to take care of a fifth valve for a fifth furnace. At the extreme back of the picture can be seen the tubs of three twin vertical-horizontal Southwark steam blowing engines, which, although of modern design and as good as new, are not operated because of the greatly reduced blowing cost shown by the gas blowing engines. The next station built is shown in Fig. 2. This is the plant of the Minnesota Steel Co. at Duluth, Minn., and is at present constructed for five engines, to handle two furnaces, with one spare engine. The engines are of practically the same size as those at Bethlehem. Instead of being arranged in right-hand and left-hand pairs, as at Bethlehem, all the engines are of the same hand; this arrangement has some ad-

Jan 1, 1915

By R. A. Burmeister, P. E. Greene

Two methods for the synthesis and growth of single crystals of B6 P are described: a solution-growth process employing nickel as the solvent, and a vapor-growth process employing BBr3 and pH3 as the reac-tants. Relevant portions of the Ni-B-P phase diagram have been examined and liquidus data are presented for an isobaric section at an equivalent P2 pressure of 3.8 Torr, and an isothertnal section at 1300°C. Solution-growth techniques are described and the purity and crystalline perfection of the resulting material is discussed. Epitaxial growth of BeP on &P substrates has been obtained using the vapor-phase system. Evidence is presented which supports the assignment of the stoichioknetry B6P to boron sub-plwsphide. THE B-P system differs from other III-V systems in that it contains two distinct compounds. The existence of the monophosphide (BP) has been known for some time,' whereas the subphosphide (B6P) was reported only recently.' Both of these compounds are large bandgap semiconductors (Eg = 2.0 ev for BP~ and 3.3 ev for B6P4), and are therefore of interest for optoelectronic applications. The crystal structure of B6P is quite different from those of most semiconductors, being derived from that of a-rhombohedral boron by the incorporation of the two phosphorus atoms in the intericosahedral sites of the a-boron unit cell?76 B6P also exhibits a number of unusual characteristics, including a high degree of chemical inertness, hardness, and high-temperature stability. No information concerning other physical properties is available in the literature. The present study is part of a broader investigation of the preparation and properties of B6P. This paper considers methods of growing single crystals of B6P of suitable size and quality for physical-property measurements. A detailed discussion of the electrical and optical properties of B6P will be given elsewhere.' GENERAL CONSIDERATIONS The method first used to synthesize B6P was the disproportionation of BP' according to the reaction The equilibrium P2 pressures corresponding to this reaction were also determined .'" It is therefore possible, in principle, to apply several of the reactions reported for the synthesis of BP to the synthesis of B6P merely by selecting lower phosphorus pressures or higher temperatures, in accordance with the equilibrium data. Other techniques for the direct synthesis of microcry stalline B8P have also been reported.1°

Jan 1, 1968

By A. J. Kraemer

For a number of years the Bureau of Mines has conducted semi-annual survey to determine the changes in the characteristics of the rotor gasoline being sold in the United States. Certain cities have been decided upon as points of origin of samples. Tare choice of these cities has been governed by their situation as the representative of a more or less definitely bounded marketing territory. Samples have been taken on or about the fifteenth day of January and July of each year. In the collection of the samples an attempt has been made to get a representation of the important types of motor fuel being sold, and also to tame into consideration the proportion of tie total consumption that is supplied by the different marketers. It is therefore felt that the survey affords a reliable indication of the quality of the gasoline being sold throughout the United States at the time of sampling. The figures in Table I, below, were obtained by averaging the end points of the least volatile and most volatile samples of gasoline. For example, of 850 samples analyzed in 1919, the 10 per cent (85 samples) having the highest end points, and the 1C per cent having the lowest end points were averaged. These averages are represented in the table as the "Maximum 10 per cent" and the "Minimum 10 per cent", respectively. The same scheme was used in the succeeding surveys.

Jan 1, 1925

By Sabri Ergun

Previous studies of magnetic separation of pyrite from coals have been reviewed critically. Magnetic susceptibilities of United States coals of differing rank have been measured. The effects of crushing, magnetic mixing, drying, weathering, and heat treatment on the enhancement of the magnetism of pyrite have been analyzed. The importance of size distribution of pyrite in the coal and the necessity of crushing to liberate the pyrite has been discussed. It has been found that the inherent susceptibilities of the carbonaceous, mineral-free portions of coals (? -0.5 X 10-6 in cgs units) and of relatively pure pyrite isolated from coals (? -0.3 X 10-6) do not permit efficient separation of pyrite from coal; the average susceptibility of the magnetic fraction of coal must be raised to 3 X 10-6. Friction forces encountered in crushing sedimentary pyrite embedded in coal do not increase its susceptibility. Subsequent weathering or heat treatment below 400° C leads to the formation of iron sulfate and hence increases the effective paramagnetism of pyrite. Ferromagnetic compounds of iron are not formed in significant quantities at temperatures below 400° C. The degree of liberation and apparent susceptibility of pyrite are the most important parameters in its separation. It is concluded that effective beneficiation of coals can be achieved by magnetic separation. A sufficient increase in the susceptibility can be achieved by converting less than 0.1 percent of pyrite into ferromagnetic compounds of iron. Such conversions occur only at temperatures >500° C. An investigation of the dielectric properties of coals and pyrite in the frequency range 0.1 to 60 Mhz indicates that the imaginary dielectric constant of the pyrite is about 100 times larger than that of coal. Exploratory experiments indicate that pyrite can be selectively heated to temperatures above 500° C without appreciable rise in the temperature of coal. It appears that dielectric heating of coals in the Ghz frequency range is the most feasible method of enhancing the paramagnetism of pyrite.

Jan 1, 1968

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,' Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By Mark Leggett, Kevin Roberts

The need to modernise and increase the safety provision of older road tunnels raises challenges in maintaining the operation of the tunnel during such improvement works. The Mersey Kingsway twin road tunnels located in Liverpool UK, constructed in the late 1960s, have had three new cross passages constructed to allow emergency evacuation from one tunnel to the other tunnel and provide safer access for emergency services. The 3200m long road tunnels are lined with an unusual reinforced concrete steel-faced segmental lining with a paint finish. Construction of the cross passages occurred during night possessions with the tunnels returned to normal operation during the daytime. Constructed through water bearing sandstone and lined with precast concrete segments, the passages required advance ground treatment and support works. This paper presents the historical background to the Mersey Tunnels and describes the procurement strategy, design and construction approach adopted for these important safety improvements.

Jan 1, 2003

By Nickson NM, Lancucki CJ

X-ray diffraction and differential thermal methodshave been used to determine the mineralogy of some clays used by the heavy clay industry in the Adelaide area. A detailed analysis has been made of the mineralogy and. particle size distribution of eighteen samples from beds' in two pits in~the Recent seaiinents in the Adelaide plains, of six white clays.: developed from the weathering of the Adelaide series of `sediments and, of ,four -Recent alluvial clays from a pit in the Mount Lofty ranges south of Adelaide. Structural clay products 'in the Adelaide area are manufactured from mixtures of these clays:, so the mineralogy and particle size distribution have been determined of eighteen clay mixtures used to make red bricks, cream bricks,. facing bricks, pipes and tiles. Knowledge of this mineralogy is important in understanding the ceramic behaviour of the clays.

Jan 1, 1963

[MUNOZ, P.: New Oil Fields in Trinidad, M27, 311 MUNRO, C. H., biography, M84, 354 MUNROE, H. S., biography, M83, 277 Muntz metal (See also 60:40 Brass): corrosion. See Corrosion of Metals. fatigue and corrosion-fatigue, 78, 597 heat-treated: cleavage structure, 83, 498, 505 grain growth, abnormal, 83, 503, 505 machinability, 99, 323 stress-corrosion cracking, 89, 249. 266 MURAKAMI, T.: iron-silicon diagram, 80, 253, 255 MURDOCH, J. A. W., biography, M28, 157 MURDOCK, W. J.: Discussion on Adaptability of Various Coals as Generator Fuel in Manufacture of Water Gas 78, 561, 565, 566, 568 MURPHY. D. W. AND CHIPMAN, J.: Solubility of Nitrogen in Liquid Iron (T.P. 591) 116, 179. Abs., YB35, 33; M35, 114 MURPHY, L. J.: Relative Advantages and Costa of Electric Power in Lease Operations 77, 219]

Jan 1, 1936

The Skorpion process comprises three processing steps-atmospheric leaching in sulfuric acid, zinc solvent extraction and electrowinning to produce special high grade zinc. The major mode of impurity transfer was attributed to crud runs in the solvent extraction circuit. Crud may be described as a heterogeneous, partly inorganic, partly organic mass of material which accumulates predominantly at the interface between organic and aqueous solutions. The paper describes the root causes of the crud formation in the solvent extraction circuit and optimization strategies which are being followed to prevent impurity excursions in electrowinning. Keywords: zinc oxide, solvent extraction, crud formation, colloidal silica.

Jan 1, 2007

By H. Foster Bain

Jan 1, 1910

By N. Albon, J. F. Miller, R. W. Coutant

The deposition of nickel from nickel carbonyl onto amorphous substrates has been studied, with attention being paid to the specific effects of the physical and chemical nature of the substrate and to the effect of oxygen on the crystal morphology. With substrates having microscratches or etch lines, nu-cleation was observed to occur preferentially at these surface features. Flame polishing of the substrate surfaces was found to remove any regularity in preferred nucleation sites. Nucleation was observed to occur less readily on substrates having relatively low surface energies, e.g., Teflon and carbon, than on materials having relatively high surface energies such as fused silica. At low oxygen concentrations [Ni(CO)4/O2 > 54 x 1031, apparently pure and well-formed nickel crystals were observed to nucleate and grow irrespective of the presence of oxygen. At higher concentrations of oxygen, a secondary growth process, dependent upon oxygen concentration and resulting in a gradual change in crystal morphology, was observed. It is concluded that the influence of oxygen on the nucleation and growth of nickel is determined by the relative kinetics of the various possible reactions, and that under the experimental conditions employed the 0-Ni interaction occurs at some nucleation or prenuclea-tion stage. THE purpose of the research on crystal nucleation in chemical vapor deposition as described in this paper has been twofold: 1) to examine some effects arising from the use of amorphous substrates, and 2) to study the specific effects of oxygen on the nucleation and growth of nickel in a nickel carbonyl-carbon monoxide system. The nickel-nickel carbonyl system was chosen for study for several reasons: 1) nickel films are of potential interest in electronic technology, and 2) the deposition can be carried out at moderate temperatures, thus making possible detailed study of the processes occurring and the use of a variety of substrate materials (including some which melt at relatively low temperatures). Fairly well-characterized chemical kinetics and a broad background of information are available on the py-rolysis reactions and on the mechanisms of Ni-O interactions. NUCLEATION AND GROWTH THEORY The theoretical background for the analysis of nucleation and growth by vapor deposition for a one-component system (physical vapor deposition) and the problems encountered therein have been reviewed by Hirth and pound.' More recently Mande12 has indicated the difficulties of applying such theory to chemical systems. One of the major problems involved is the possible multiplicity of chemical reactions and deposition routes. For example, those reactions which are probably of significance in a discussion of the pyrolytic deposition of nickel from nickel carbonyl under the conditions of the present experimental work are illustrated in Fig. 1. As is true with most cases of chemical deposition, many of the quantitative data necessary for a complete analysis of the system are either not available or not directly measurable. However, with the present system, sufficient data are available for a discussion of nucleation and growth on a qualitative basis. Classically, the rate of nucleation of a monatomic species being deposited from a vapor phase is given by

Jan 1, 1965