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By Leonard C. Grimshaw

Diffusion of carbon from gases into iron has been the object of much research, because of its long recognized importance in carburizing processes, but the direct diffusion of carbon from steel into iron has received relatively little attention. Because of the increasing use of clad metals in industry, direct diffusion from steel into iron is becoming of practical importance. Therefore, the object of this investigation was to study the diffusion of carbon from several different kinds of steel directly into relatively pure iron, realizing that elements in the steels other than carbon might influence the rate of carbon diffusion. The previous work on diffusion of carbon into iron has been considerable, and includes many reports in foreign languages. This work has recently been well reviewed by Mehll and Krynitsky12 and the reader is referred to their excellent bibliographies. Methods of Study There are two main methods by which the direct diffusion of carbon from steel into iron may be studied. In one method, steel is first decar-burized in part, and diffusion of carbon then allowed to take place from the steel into the decarburized steel. This method is open to two serious objections: (1) the decarburized steel is not iron, but contains elements such as manganese, silicon, chromium or tungsten, which may be an essential part of the steel under study, and which may seriously influence the diffusion of carbon into the decarburized area; (2) there is from the start of diffusion an unknown carbon-concentration gradient between the steel and the decarburized area. Another method, which possesses neither of these disadvantages, is to study diffusion from steel into a thick plating of electrolytic iron. Herc the chief difficulty is to secure an electrolytic deposit of iron upon steel without introducing an oxide film at the interface that will interfere with diffusion. The author is able to deposit iron upon any kind of steel without introducing an oxide film at the interface, so that diffusion of elements from the steel into the iron is free to proceed unhindered.

Jan 1, 1938

By W. N. Poundstone, P. C. Thakur

Introduction Horizontal drilling in coal mines is a relatively new technology. The earliest recorded drilling in the United States was done in 1958 at the Humphrey mine of Consolidation Coal Co. for degasification of coal seams. Spindler and Poundstone experimented with vertical and horizontal holes for several years. They concluded in 1960 that horizontal drilling in advance of underground mining appeared to offer the most promising prospect (for degasification) but effective and extensive application would be dependent upon the ability to drill long holes, possibly 300 to 600 m, with reasonably precise directional control and within practical cost limits (Spindler and Poundstone, 1960). Mining Research Division of Conoco Inc., the parent company of Consolidation Coal Co., began a research program in the early 1970s to achieve the above objective. The technology needed to drill nearly 300 m in advance of working faces was developed by 1975 and experiments on advance degasification with such deep holes began in 1976. Preliminary results of this research have already been published (Thakur and Davis, 1977). To date nearly 4.5 km of horizontal holes have been drilled for advance degasification and earlier results were reconfirmed. In summary, these are: • The greatest impact of these boreholes was felt in the face area where methane concentrations were reduced to nearly 0.3% in course of two to three months from original values of nearly 0.95%. • The methane concentration in the section return reduced to 50% of its original value immediately after the boreholes were completed, indicating a capture ratio of 50%. • The total methane emission in the section (rib and face emission plus the borehole production) did not increase but rather gradually declined with time. • Initial production from 300 m deep boreholes in the Pittsburgh seam varied from 3 m3/min to 6 m3/min but then slowly declined as workings advanced inby of the drill site (well head) exposing a larger surface area parallel to the borehole. Encouraged by these results, it was decided to design a horizontal drilling system that would be mobile and compatible with other face equipment. A mobile horizontal drill can be divided into three subsystems: the drill rig, the drill bit guidance system, and borehole surveying instruments. The drill rig provides the thrust and torque necessary to drill 75- to 100-mm diam holes up to 600 m deep and contains the mud circulation and gas cuttings separation systems. The drill bit guidance system guides the bit up, down, left, or right as desired. Borehole surveying instruments measure the pitch, roll, and azimuth of the borehole assembly. Additionally, it also indicates the thickness of coal between the borehole and the roof or floor of the coal seam. Thus, it becomes a powerful tool for locating the presence of faults, clay veins, sand channels, and the thickness of coal seam in advance of mining. In recent years, many other potential uses of horizontal boreholes have come to light, such as in situ gasification, longwall blasting, improved auger mining, and oil and gas production from shallow deposits. The purpose of this paper is to describe the hardware and procedure for drilling deep horizontal holes. The Drilling Rig [Figures 1 and 2] show the two components of the mobile drilling rig: the drill unit and the auxiliary unit. The equipment (except for the chassis) was designed by Conoco Inc. and fabricated by J. H. Fletcher and Co. of Huntington, WV. The drill unit. It is mounted on a four-wheel drive chassis driven by two Staffa hydraulic motors with chains. The tires are 369 X 457 mm in size and provide a ground clearance of 305 mm. The prime mover is a 30-kw explosion-proof electric motor which is used only for tramming. Once the unit is Crammed to the drill site, electric power is disconnected and hydraulic power from the auxiliary unit is turned on. Four floor jacks are used to level the machine and raise the drill head to the desired level. Two 5-t telescopic hydraulic props, one on each side, anchor the drill unit to the roof. The drill unit houses the feed carriage, the drilling console, 300 m of 3-m-long NQ, drill rods, and the electric cable reel for instruments. The feed carriage is mounted more or less centrally, has a feed of 3.3 m, and can swing laterally by ± 17°. It can also sump forward by 1.2 m. The drill head has a "through" chuck such that drill pipes can be fed from the side or back end. General specifications of the feed carriage are: [ ] The auxiliary unit. The chassis for the auxiliary unit is identical to the drill unit but the prime movers are two 30-kW explosion proof electric motors. It is equipped with a methane detector- activated switch so that power will be cut off at a preset methane concentration in the air. No anchoring props are needed for this unit. The auxiliary unit houses the hydraulic power pack, the water (mud) circulating pump, control boxes for electric motors, a trailing cable spool, and a steel tank which serves for water storage and closed-loop separation of drill cuttings and gas.

Jan 1, 1981

PRESIDENT SAMUEL A TAYLOR, District 3 PITTSBURGH, PA PAST PRESIDENTS WILLIAM KELLY, District 5 IRON MOUNTAIN, MICH J V W. REYNDERS, District 0 NEW YORK, N Y FIRST VICE-PRESIDENT E DEGOLYER, NEW YORK, N Y TREASURER CHARLES F RAND. . . NEW YORK, N Y

Jan 1, 1923

By Paul T. Allsman

Recently the U.S. Bureau of Mines completed organizational changes that, for the first time since the beginning of World War 11,. re-emphasize mining research as an important part of its responsibilities. A progress report follows on the Bureau's improved program for mining research. During World War II the Bureau's mining research lapsed in favor of short-range, more urgent activities. Since the end of the war mining has grad- ually returned to an economy where reduced costs and increased efficiency are essential to a vigorous industry, and demand for improvement through expanded research is again pre-eminent. In recognizing this situation, the Bureau is again emphasizing mining technology and has reinstituted some of its earlier mining research activities. Recent research, however, follows a more scientific approach in solving mining problems because new technology, particularly new instrumentation, has developed rapidly during the past decade.

Jan 7, 1960

By T. L. Joseph

Blast furnaces are most efficient thermally when the CO2 in the top gas is highest. Oxygen introduced in the air blast is converted to CO in the combustion zones. The extent to which CO, generated in front of the tuyeres, is converted later to CO2 depends upon the ratio of ore to coke in the charge and the degree to which CO2, formed by reduction of iron oxides with CO, reverts to CO by the secondary reaction C + CO2 = 2CO. About 300 to 400 lb. of carbon' per ton of pig iron is normally involved in the solution-loss reaction or direct reduction of FeO with carbon, which produces the same over-all results; that is, lower CO2 in the top gas. Rich2 has recently reported a reduction in fuel consumption at slower rates of blowing on two furnaces in spite of higher heat losses per ton of iron. Lower fuel consumption at slow operating rates was due to more complete reduction of the ore that resulted in higher CO2 in the top gas and consequently more efficient use of carbon. Kinney3 has reported substantial savings in fuel as a result of crushing and sizing the ore charge. Improvements in practice brought about by sintering magnetite concentrates, flue dust and fine ores have been due to the establishment of conditions favoring more complete reduction of the ore in the upper part of the furnace. The extent to which oxides and fluctuations in composition in pig iron affect the quality of steel and finished product needs further study. There is evidence that more thorough preheating and reduction of the ore in the upper part of the furnace tend to give a better quality of iron. Bogatzkii4 found from laboratory work that the amount of oxygen entering electrolytic iron, melted under various slags, was directly proportional to the concentration of free FeO in the slag and inversely proportional to the basicity of the slag. Herty and Gaines5 concluded that the silicate content of open-hearth steel before deoxidation is related to the concentration of silica in the pig-iron charge, indicating that most of the persistent inclusions are silica from the iron. They also found that

Jan 1, 1936

By T. L. Joseph

Blast furnaces are most efficient thermally when the CO2 in the top gas is highest. Oxygen introduced in the air blast is converted to CO in the combustion zones. The extent to which CO, generated in front of the tuyeres, is converted later to CO2 depends upon the ratio of ore to coke in the charge and the degree to which CO2, formed by reduction of iron oxides with CO, reverts to CO by the secondary reaction C + CO2 = 2CO. About 300 to 400 lb. of carbon' per ton of pig iron is normally involved in the solution-loss reaction or direct reduction of FeO with carbon, which produces the same over-all results; that is, lower CO2 in the top gas. Rich2 has recently reported a reduction in fuel consumption at slower rates of blowing on two furnaces in spite of higher heat losses per ton of iron. Lower fuel consumption at slow operating rates was due to more complete reduction of the ore that resulted in higher CO2 in the top gas and consequently more efficient use of carbon. Kinney3 has reported substantial savings in fuel as a result of crushing and sizing the ore charge. Improvements in practice brought about by sintering magnetite concentrates, flue dust and fine ores have been due to the establishment of conditions favoring more complete reduction of the ore in the upper part of the furnace. The extent to which oxides and fluctuations in composition in pig iron affect the quality of steel and finished product needs further study. There is evidence that more thorough preheating and reduction of the ore in the upper part of the furnace tend to give a better quality of iron. Bogatzkii4 found from laboratory work that the amount of oxygen entering electrolytic iron, melted under various slags, was directly proportional to the concentration of free FeO in the slag and inversely proportional to the basicity of the slag. Herty and Gaines5 concluded that the silicate content of open-hearth steel before deoxidation is related to the concentration of silica in the pig-iron charge, indicating that most of the persistent inclusions are silica from the iron. They also found that

Jan 1, 1936

By Clement K. Chase

The ammonia leach for copper recovery is discussed from historical and current practice standpoints. The chemistry of the system is presented together with Eh-pH and copper-ammonia solubility curves. A list of metals forming ammine complexes is presented. The advantages and disadvantages of the ammonia leach as applied to copper recovery in conjuction with modern liquid ion exchange techniques are compared.

Jan 1, 1980

By Garfield Schnee

MACHINERY has not taken the place of manual labor in steep pitch coal in the anthracite field and there is a shortage of miners experienced in this type of work. To overcome these difficulties several coal companies have resorted to different types of mining such as the diamond or zig-zag method, the slant method, long hole drilling, and several other variations. For the past 5 years the diamond shape method has been used extensively in the heavy pitching beds of both the Knickerbocker and Yatesville basins at Knickerbocker colliery of the Philadelphia & Reading Coal & Iron Co.

Jan 10, 1950

OFFICERS OF THE WOMAN'S AUXILIARY AIME President-Mrs Robert D Coombs, 375 Paramus Road, Paramus, N J First Vice-President-Mrs W McG Peirce, Troy Court 73 F, New England Avenue, Sum¬mit, N J Second Vice-President-Mrs Andrew E Beer, Richardson Avenue, Sea Cliff, Long Island, N Y Third Vice-President-Mrs Ira T Hook, 494 Norton Parkway, New Haven, Conn Fourth Vice-President-Mrs John R Kenney, 427 W Wrightwood Avenue, Chicago 14, Ill Fifth Vice-President-Mrs Alfonso Ballon, Montero Rosas 115, Barranco, Lima, Peru Recording Secretary-Mrs Arnold H Miller, 601 West 115th St, New York 25, N Y Assistant Recording Secretary-Mrs R J Mechin, 66 East 79th Street, New York 21, N Y Corresponding Secretary-Mrs Theodore Nagel, 76 Remsen St, Brooklyn 1, N Y Treasurer-Mrs Robert W Rowen, 116 East 68th St, New York 21, N Y Assistant Treasurer-Mrs Samuel H Dolbear, 11 Broadway, New York 4, N Y Assistant Treasurer-Mrs H A Kursell, 12 Murray Hill Road, Scarsdale, N Y

Jan 1, 1956

By David Cole

The appearance of the Wilfley table in 1897 marked an epoch in the art of concentration of ores. The table has merited and received an almost unprecedented measure of public approval, lasting through its whole patent life. It has been very little improved in itself, or improved upon by competitors. The new machines bidding for popular favor have been of the Wilfley family, but without ability to do markedly better work than the parent machine, or to do more work except by the use of superimposed decks, the latter having obvious disadvantages. During the past three years there has been developed at Morenci a new type or arrangement of riffles applicable to the Wilfley type of concentrating table which corrects many of the objectionable features or limitations of the older system and obviates most of the difficulties encountered with it, particularly when handling ores having a low ratio of concentration. The new type is known as the Butchart1 riffle system, and its general arrangement is shown in Figs. 1 and 2. The old system accomplished stratification satisfactorily but has

Jan 1, 1915

By Gail Moulton

THE oilfields in Illinois are located principally along the LaSalle anticline in the southeastern part of the state. The oil produced comes most largely from beds of Pennsylvanian and Mississippian age, but there is an increasing important production from deeper horizons, as will be noted under new development. The oil is largely of paraffin base, and has an average specific gravity of about 35° Baume. The rank of Illinois as an oil producer has dropped from third since 1913, when its production was exceeded only by that of California and Oklahoma, to eighth in 1923. This has been the result of failure to find new pools of considerable size to offset the declining production of the old wells and of the greatly increased production of some of the other states. The noteworthy features of petroleum production in Illinois during 1924 are: the low rate of decline for the state as a whole; the smaller percentage of dry holes; and the larger average initial yield of the new wells.

Jan 3, 1925

By Gail Moulton

THE oilfields in Illinois are located principally along the LaSalle anti-cline in the southeastern part of the state. The oil produced comes most largely from beds of Pennsylvanian and Mississippian age, but there is an increasing important production from deeper horizons, as will be noted under new development. The oil is largely of paraffine base, and has an average specific gravity of about 35° Baume. The rank of Illinois as an oil producer has dropped from third since 1913, when its production was exceeded only by that of California and Oklahoma, to eighth in 1923. This has been the result of failure to find new pools of considerable size to offset the declining production of the old wells and of the greatly increased production of some of the other states. The noteworthy features of petroleum production in Illinois during 1924 are: the low rate of decline for the state as a whole; the smaller percentage of dry holes; and the larger average initial yield of the new wells.

Jan 3, 1925

By Gill Montgomery

The strong upward curve of fluorspar consumption continued through 1968, with domestic producers unable to furnish more than 30% of U.S. requirements. Stocks of all grades were quite short at all points during most of 1968. This resulted in price increases as both domestic and foreign producers sought to cover spiralling labor costs. Further increases are probable for 1969. All Illinois mines were closed by strikes in January and February. The strong trend in metallurgical imports reflects the increased use of fluorspar in steelmaking, as new oxygen process steel plants come into production. The growth of use of all fluorocarbon chemicals continues to require additional acid grade fluorspar, with military uses a major factor. Several new aluminum smelting facilities coming into production are adding to the aluminum fluoride needs, bringing further pressure upon the world supply of acid grade fluorspar. The world-wide consumption pressure on all grades of fluorspar is pushing prices up, and no end to the tight supply is in sight, even assuming that all the new projects cited here are finished on schedule.

Jan 3, 1969

By Robert E. Ennis

This somewhat misnomered "continuous" face section is, in most mines today, still far from perfect continuity. Achieving uninterrupted flow of coal from the mining machine to the outside has been a long sought for goal. Clearly, the largest problem to be solved in continuous mining today is one of increasing the cutting time of the miner. Full machine utilization can never be achieved with the new high capacity miners as long as their performance is tied to that of the shuttle car. A recent development has proven, however, that truly continuous mining and haulage is possible. The Bell & Zoller Coal Co. working with the Research and Development Department of Hewitt-Robins Inc. developed and perfected a new mining system which offers advantages in terms of increased productivity at reduced mining costs and enhances the safety of personnel at the face. This new system involves the use of two pieces of equipment that form an unbroken link between the mining machine and the mine belt haulage system. These pieces are a Mobile Bridge Conveyor and an Extensible Panel Conveyor.

Jan 4, 1965

By Robert M. Keeney, Jay Lonergan

The electric smelting of manganese ore and the production of ferro-manganese did not exist as an industry, in the United States or elsewhere, previous to the outbreak of war in 1914. Ferromanganese had been produced, electrically, during times of high prices by two companies at Niagara Falls and by several European companies, but the production was spasmodic, and none was electrically produced when ferromanganese sold at from $35 to $40 per ton. Thus the electric smelting of manganese ore must be considered as a development caused by the high prices prevailing during the years 1916, 1917 and 1918, and the necessity of smelting domestic ore in order to fill the ferromanganese requirements of the steel industry of the United States, which increased from 189,088 tons in 1914 to 356,356 tons in 1918. The electric furnace is well adapted to smelting domestic ore because it can be located in small units near the source of ore supply. In 1918, the ferromanganese production of the United States was 333,027 tons, of which about 7 per cent., or 23,000 tons, was produced in the electric furnace. The electric furnace not only assisted materially in the development of a domestic-ore supply but made a considerable saving of coke, as it requires about 11/4 tons of bituminous or lignite coal per ton of ferromanganese compared with a blast-furnace consumption of 2.9 tons of coke per ton of ferromanganese. Some of the plants in the United States that smelted manganese orc in the electric furnace during the war and in 1920 are listed in Table 1. From early in 1919 to about February, 1920, little ferromanganese was produced in the electric furnace. During this period the price of ferromanganese (78 to 82 per cent. manganese) was about $100 per ton. During the first half of 1920, several plants resumed operation when the price of ferromanganese (76 to 80 per cent. grade) gradually increased to $200 per ton, delivered.

Jan 1, 1922

By Jay Lonergan, Robert M. Keeney

The electric smelting of manganese ore and the production of ferro-manganese did not exist as an industry, in the United States or elsewhere, previous to the outbreak of war in 1914. Ferromanganese had been produced, electrically, during times of high prices by two companies at Niagara Falls and by several European companies, but the production was spasmodic, and none was electrically produced when ferromanganese sold at from $35 to $40 per ton. Thus the electric smelting of manganese ore must be considered as a development caused by the high prices prevailing during the years 1916, 1917 and 1918, and the necessity of smelting domestic ore in order to fill the ferromanganese requirements of the steel industry of the United States, which increased from 189,088 tons in 1914 to 356,356 tons in 1918. The electric furnace is well adapted to smelting domestic ore because it can be located in small units near the source of ore supply. In 1918, the ferromanganese production of the United States was 333,027 tons, of which about 7 per cent., or 23,000 tons, was produced in the electric furnace. The electric furnace not only assisted materially in the development of a domestic-ore supply but made a considerable saving of coke, as it requires about 11/4 tons of bituminous or lignite coal per ton of ferromanganese compared with a blast-furnace consumption of 2.9 tons of coke per ton of ferromanganese. Some of the plants in the United States that smelted manganese orc in the electric furnace during the war and in 1920 are listed in Table 1. From early in 1919 to about February, 1920, little ferromanganese was produced in the electric furnace. During this period the price of ferromanganese (78 to 82 per cent. manganese) was about $100 per ton. During the first half of 1920, several plants resumed operation when the price of ferromanganese (76 to 80 per cent. grade) gradually increased to $200 per ton, delivered.

Jan 1, 1922

By E. R. Morgan, J. C. Shyne, V. F. Zackay

NITROGEN used as an alloying element in steel has received increased attention in recent years. Its merit as an austenite stabilizer and hot strengthener has long been recojinized, particularly by European investigators.' Recent work' indicates that nitrogen contents of 1/2 pet or more allow the addition of several percent of ferrite-forming hot strengtheners, such as molybdenum, without subsequent austenite decomposition at elevated temperatures. The room temperature properties of such alloys are characterized by high yield and tensile strengths with excellent ductility, even after cold working, as shown in Tables I and 11. The 1350°F creep-rupture properties of Cr-Mn-Mo-N steels are comparable to those of commercial alloys such as Timken's 16-25-6, containing 16 pct Cr, 25 pct Ni, and 6 pct Mo, as shown in Table 111. Cr-Mn steel containing 1/2 pet N must be made under pressure if ingot gassing is to be avoided. However, there are difficulties attendant to this practice. Pressure melting restricts the ingot size, and the equipment required is costlier and more complicated than comparable air melting facilities. An effort was made, therefore, to determine more economical methods of adding nitrogen. The pressures generated in centrifugal casting usually range from 5 to 10 atm and are sufficient to prevent the gassing of high nitrogen Cr-Mn steels. A centrifugal casting was made of an alloy containing 16 pct Cr, 18 pct Mn, 2 pct Mo, and 0.73 pct N. A risk, 8 in. diam and 11/2 in. thick, was cast at 1000 rpm. It has been calculated that a pressure of 9 atm was developed at the periphery of the disk at this speed. Metallographic inspection of specimens taken from the disk revealed no gas holes or other defects. The elevated temperature properties of radial and circumferential specimens taken from this casting are given in Table IV. The creep-rupture life of this cast nickel-free austenitic steel was equivalent to that of the wrought Cr-Mn-Mo-N steels. Although centrifugal casting appears to lend itself to the manufacture of high nitrogen austenitic steels, its applicability is limited to relatively small sizes. A process applicable to the production of large ingots of high nitrogen steels is suggested by low carbon rimming steel practice. Gas holes formed during ingot solidification are not detrimental so long as they weld shut during hot rolling. An economic advantage of gassing ingots is the increased ingot-to-slab yield, especially if the ingots are mechanically capped. Also, it is probable that higher nitrogen levels can be achieved with mechanically capped ingots than with hot-topped ingots. A series of gassy heats was made under both atmospheric and higher pressures, as indicated in Table V. Several of the air melted ingots were mechanically capped by chilling the molten ingot tops with a steel plate. The ingots were allowed to freeze in steel molds without hot-tops unless otherwise indicated. A comparison of Table 111 with Table V shows no significant difference in the creep-rupture properties of the gassy and the nongassy ingots after hot work- ing nor between the gassy ingots produced under different conditions. References 1 F. Rapatz: Application of Stainless and Heat Resisting Steels Alloyed with Nitrogen. Sinhl and Eisen ( 1941) 61, pp. 1073-1078. 'V. I?. Zackay, J. F. Carlson, and P. L. Jackson: High Nitrogen Austenltlc Cr-Mn Steels. Trans. ASM 119551 48, PP. 509-523.

Jan 1, 1957

By Charles A. Kelliher

In November of 1957, the Aliquippa Works started operation of the third basic oxygen furnace shop in North America. This high speed basic steelmaking method provided a very economical increase in capacity at the Works. The success of these two (2) 81-ton furnaces led to the construction of a second B.O.F. shop, producing heats of 230 tons at J&L's Cleveland Works in 1962. The experience gained operating both shops provided the background for the design of the new steelmaking complex at the Aliquippa Works. This new complex consists of a three (3) furnace shop with two (2) furnaces blowing alternately producing heats ranging from 120 to 207 tons. This variation in heat size is predicated on the requirement that approximately 20% of the shop production will be used to supply steel to a six (6) strand casting machine, producing 4' through 7" billets. The new B.O.F. shop has replaced all other steelmaking units including the #1 Shop, where operations were discontinued in September of 1968. With the advent of the strand casting facilities in September of 1969, many of the standard shop practices had to be changed to compensate for higher tap temperatures, longer handling times, and reduced ladle availability. The subsequent changes in these areas led to the evolution of the strand cast ladle practice which is described in this paper.

Jan 1, 1972

By Mark D. Tabak

Measurments of the transient photoconductivity in fillns of amorphous selenium with blocking- contacts haue been used in studying the transport properties. The results shozu that the transport of free carviers cannot be explained in terms of a model using bulk trapping. Measurments of the photocurrent-applied field characteristic as a unction of sample thickness do not pvoduce the scaling lau,s approps-iate lo a range-limited model. THE investigation described here was undertaken to explore the mechanisms of transport in amorphous selenium films. These films are used in xerography, where a photoconductor is charged electrostatically and then exposed to light to form a latent image. The sensitivity that one can expect when operating in this mode is directly related to the transport properties of the photoconductor material. The study of photoconductivity at high fields in insulating materials is often complicated by contact effects. Injection from the contacts can easily mask the fundamental transport processes that are being studied. A technique is described in this paper that allows a study of photoconductivity and transport processes in amorphous selenium films without the complicating effects introduced by contacts. Accordingly, the samples are prepared using insulating films between the sample and the metal electrodes, where the electrodes are capacitively coupled to the surfaces of the sample under study. A transient measurement is performed with pulsed light, and the photocurrent measured near the beginning of the pulse before the field is distorted by polarization at the blocking elec- trodes. A similar method has been described by Manyl using pulsed electric fields in studying the high field transport in insulating cadmium sulfide. EXPERIMENTAL It is possible to eliminate undesirable contact effects and maintain uniform high fields across the sample by using blocking electrodes and measuring the current-field characteristic under transient conditions. The sample configuration is shown schematically in Fig. 1. Each of the gold electrodes is separated from the amorphous selenium film by a layer of insulating plastic (Formvar) approximately 2000~ thick. The electrode on the front surface is semi-transparent to allow illumination of the sample. The whole configuration is mounted on a KEL-F substrate, which is a transparent insulating plastic having a thermal expansion coefficient that allows low-temperature measurements without cracking the selenium film. Fig. 2 shows a block diagram of the measurement apparatus. Light was obtained from a 450-w Xenon arc lamp, the intensity of which was controlled by stainless-steel screen filters and monitored by a pho-tomultiplier which was calibrated periodically against a thermopile. A camera shutter operated at 1/200 sec provided the light pulse and a synchronized signal to the oscilloscope. The photocurrent transient is ob-served with a high-speed picoammeter (response time of 1 msec) the output of which is displayed on an oscilloscope. The applied voltage is constant throughout the transient measurement. The selenium films were prepared by evaporation of four 9's pure selenium shot supplied by Canadian Copper Refiners. Spectrographic analysis showed about 1 ppm of Te and Fe, 5 ppm of C1, and 0.05 ppm

Jan 1, 1968

By J. P. G. Farr, R. Brownsword

THE role of solute segregation in the formation of cellular solidification substructures in tin and its dilute alloys is well-established, see, e.g., Ref. 1. Segregation has been shown to persist during cooling, enabling solidification structures to be studied from sections taken at some distance behind the interface. In the present work, a single crystal of commercial nickel, 99.965 pct, was examined in this way. The crystal was cut from the center of a rod given a single pass in an electron beam floating zone melter. Polished sections of a nickel specimen taken normal to the growth direction showed a very fine precipitate phase, the distribution of which varied over the section. The identification of the phase proved difficult because of the small amount present and the small particle size, about 1 p: but it was shown by probe microanalysis to contain only nickel and oxygen in detectable concentrations and was probably nickel oxide, NiO. Bulk analysis of the material before melting showed there to be only 3 to 4 ppm of oxygen present, thus demonstrating a very considerable segregation concentration effect. In some areas of the section the precipitate formed a discontinuous hexagonal network suggesting decoration of the cellular boundaries known to be present in the sample2 whereas in a restricted region the precipitate formed small clusters. Occasionally it could be seen that the clusters were at the intersections of an hexagonal network of cellular dimension. It was suggested3 that this was the result of enhanced segregation to the cell boundary intersections whereas general cell boundary segregation was insufficient to give a precipitate. Enhanced nodal segregation has since been demonstrated in a number of systems.1, 4-8 The development of a suitable electrolytic etching technique (perchloric acid 20 pct v/v; ethyl alcohol 70 pct; glycerol 10 pct; current below electropolishing plateau; 1 to 2 sec etching) suggested the association of the phase with regions of solute segregation (where ko < 1); in these regions anodic attack produced grooves or depressions. In a study of the variation of solidification substructures with degree of constitutional supercooling, Biloni et a1.&apos; appear to have used standard growth conditions and varied the solute concentration. They were able to produce in a series of individual tin crystals examples of substructure ranging from planar interface through various cellular structures to den- Fig. 1—Electroetched section taken normal to the rod axis; the center of the rod lies to the left and the periphery to the right of the micrograph. The variation of structure across the section is evident. Magnification 60 times. drites. It was possible in the present nickel crystal to observe a continuous range of substructures varying with degree of supercooling across a single section as shown in Fig. 1. Growth rate, 13 mm per min, and temperature gradient were essentially constant; the variation in structure is thought to be due to a radial gradient in solute concentration ahead of the solid interface. The liquid at the interface is likely to have been richer in solute toward the periphery of the zone, the result of curvature of this interface. The type of substructure was seen to vary with increasing constitutional supercooling as follows: a) region free of precipitate. top left, Fig. 1: 6) region of nodal precipitates which became arranged in hexagons on passing from the center of the rod: c) irregular hexagonal cells with incomplete boundary precipitation; d) regular hexagonal cells of decreasing size with complete boundary precipitation. Fig. 2 shows the transition from stage 6 and Fig. 3 shows the structure in stage d. Within stage 0, the range of conditions over which irregularly positioned nodes occur appears to be small and the nodes are soon recognizable as taking up positions at the intersections of an hexagonal network as the supercooling increases.

Jan 1, 1970