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By Jerry R. Johanson

The practical application of rolling theory to the design of roll presses is reviewed along with aspects of plant operations which must be considered to produce the required product economically. Appropriate parameters to scale up from laboratory tests to full- scale press operation and improvements possible in existing operations are discussed.

Jan 1, 1977

By Lawrence H. Van Vlack

The energy of the y-iron grain boundary was determined to be 850 ergs per cm2 at 1105°C. The a/a and the a/y boundaries possess somewhat less energy. The microstructures of several iron alloys are discussed in terms of the interfacial energy relationships. THE dependence of the shape of liquid interfaces upon their energies has been studied for some time.1"3 Recently, Smith' concluded that many of the microstructures observed in metals may be attributed to the energies of the interfaces between the grains and phases. While the energies of liquid surfaces have been measured by numerous different methods: only two attempts have been made to determine experimentally the energy of surfaces involving crystalline solids. Udin, Shaler, and Wulff8 used a procedure introduced by Berggren7 to measure the surface tension of solid copper. It consisted of determining the load required on a thin copper wire so that the surface tension was counteracted, and no net strain resulted. Bailey and Watkins8 sed a different technique and were able to determine both the surface tension of copper and the tension of the copper grain boundary. They measured the contact angle which liquid lead makes against a copper surface. They then calculated the above energies from the surface energy of liquid lead by using the Pb vs. Cu/CuY dihedral angle and the surface groove angle formed during thermal etching. They obtained a value of 1800 dynes per cm for the surface tension of clean copper and approximately 640 dynes per cm for the tension of copper grain boundaries. The former value was somewhat higher than Udin's value of 1500 dynes per cm. This paper includes a determination of the energy of the y-iron grain boundary. In addition, the micro-structural relationships of several other metallic and nonmetallic phases with iron were examined and an attempt was made to interpret the observed structures in terms of interfacial energy relationships. Theoretical Considerations In a three-phase material containing a solid and two liquids, there may be two solid/liquid interfaces, one liquid/liquid interface and one inter- granular interface. Liquid/liquid interfacial energies can be measured directly. Therefore, by determining the energy of such an interface and by measuring the required interfacial angles: the energies of the interfaces involving solids may be obtained.10 They may be shown schematically as in Fig. 1. The above procedure requires the following assumptions: 1—The interfacial energies are, in general, unaffected by boundary orientation, and 2— the shapes of the interfaces are unaltered between annealing and sectioning for microscopic examination. The first assumption is good to a first approximation as shown by Dunn and Lionetti11 except for a few critically orientated boundaries. Two conditions may alter the shape of a boundary upon cooling: 1—Precipitation of dissolved material upon one side of the interface, and 2—a change in volume during the transition from one phase modification to another. The former must be detected by microscopic observation. The latter may become appreciable in systems containing an interface between two liquids which solidify after annealing. However, possible movement of the two-liquid interface may be checked in the system diagrammed in Fig. 1 by measuring 8, for example, and comparing it with its value as calculated from the other interfacial angles by: tan8, C11 05 COS- o- + cos 8, cos- The choice of a suitable pair of liquids is limited by several factors. The relative values of the several

Jan 1, 1952

By R. P. Steijn

IT has been observed by a number of investigators that under certain conditions metals freeze into an aggregate of small hexagonal strands, parallel to one another and with their axes approximately in the direction of growth.'" This structure has been termed "cellular structure" and is explained in various ways by different workers, notably by Rutter and Chalmers." These investigators attribute the phenomenon to the presence of minute quantities of solute atoms which induce constitutional supercooling. However, if this is true, observations of the cellular structure in extremely pure substances, like frozen distilled water' and germanium of less than 0.0001 atomic pct metallic solute,' are difficult to comprehend. The purpose of this communication is to describe several observations made of the prismatic structure in zinc of 99.99 pct purity. Zinc single and bicrystals grown in a constant gradient electrical resistance furnace exhibit the cellular structure after etching in 15 pct HC1. (See Figs. 1 and 2.) It is noticed that the hexagonal substructure sometimes continues unbroken across the bicrystalline grain boundary.

Jan 1, 1956

By H. D. Dahl, Roger C. Parsons

In order to improve roof stability, Continental Oil Co.'s research program, initiated in 1969, was directed toward defining the geological parameters that affect the severity of roof conditions in any particular area of the mine. In addition, the program was seeking to define why roof falls in the Humphrey No. 7 mine (and in northern West Virginia-southwestern Pennsylvania coal mining areas) are oriented so that they occur primarily in north-south rooms or entries. Conclusions and recommendations from this study of roof fall orientation are given.

Jan 1, 1973

By Len Ramp

CHROMITE deposits in southwestern Oregon occur along definite zones or horizons in sill-like ultramafic intrusions. These horizons are here referred to as ore zones and are distinguishable only by relatively Shin and scattered, discontinuous chromite occurrences. The zones are tabular in shape but are usually folded and faulted by the intensive post-intrusion deformation the ultramafic rocks have undergone. A single zone may contain disseminated, nodular, banded, or pods of massive chromite. The typical chromite deposit is composed of a series of thin lens-shaped bodies that lie along a definite plane and generally show evidence of magmatic flow with their long dimensions aligned in the direction of flow. A body of chromite often pinches down to a narrow wisp only a fraction of an inch thick. This thin streak of chromite may point to or be connected with another body of chromite. In some deposits the orebodies have a definite rake. The depth at which chromite may be found can be predicted by its position in a folded intrusive, provided that adequate structural evidence is available. Although the ore shoots are characteristically discontinuous, there is theoretically no limit to the depth at which chromite may be found. Origin: All the chromite deposits examined in southwestern Oregon are of magmatic origin, that is, the chromite was an original constituent of the peridotite magma and became segregated in varying degree from the magma to form the ore de- posits. Examples of early, intermediate, and late magmatic chromite have been recognized in the area. Crystallization of the principal minerals (olivine, pyroxene, and chromite) was apparently near completion at the time of intrusion of the peridotite magma. The magma acted as a viscous crystal mush stringing out aggregates of pyroxene and chromite in the direction of flow. These streaky accumulations are termed schlieren.

Jan 8, 1957

By F. D. Rosenthal, F. J. Dunkerley, G. J. Mills

Activities, free energies, and heats and entropies of mixing of liquid Pb-Zn alloys have been obtained by the electrode-potential method between 400° and 650°C. The large positive deviations observed from Raoult's law are in agreement with the phase diagram, which indicates a wide immiscibility field. A vapor-pressure method was used to extend the activity measurements to 900°C, allowing the maximum of the immiscibility gap to be estimated by thermodynamic calculation. Data on the mono-tectic and eutectic points compare favorably with previously existing work. SEVERAL long-standing methods have been in use for the study of phase diagrams from measurement of the activities of the component metals.' The use of thermodynamic analysis for interpreting equilibria data is comparatively recent, however. Such analysis is usually undertaken by first evaluating the principal thermodynamic functions as, for example, the enthalpy, entropy, and free energy of the alloy constituents. These, in turn, quite often can be correlated with the interatomic potential energies and atomistics of the system, from which a clearer understanding of the causes leading to deviations from ideal behavior is gained. The present study of liquid Pb-Zn alloys is concerned with a determination of these quantities by electrode-potential and vapor-pressure measurements, using these values in calculations involving phase equilibria and to obtain a theoretical insight into an alloy system exhibiting strong positive deviations from ideal metallic solution. A considerable portion of the previously reported work is based on thermal analysis. Supplemented by optical studies of solid alloys, these techniques have revealed the essential nature of the immiscible mixtures that are formed. It is difficult, however, using the phase-

Jan 1, 1959

By F. E. Turton

THE town of Rancagua, at the junction of the state and Braden Copper Co. railroads, is located 82 km south of Santiago, the capital of Chile. From Rancagua 70 km to the east, situated in the Andes at an elevation of 7000 ft, is the town of Sewell, the location of a millsite. Two and one half km east of Sewell by underground railroad at an elevation of 7500 to 10,000 ft is the Teniente orbody. The history of El Teniente dates from the eighteenth century, when according to legend a Spanish lieutenant, or teniente, a fugitive from justice, escaped to the Andes and camped at what afterwards became known as the Mineral El Teniente. This man reputedly discovered a vein of high grade copper ore. The first official records date from 1819, when some exploitation was begun, and continue until 1870. The orebody was large and of relatively low grade and was beyond the capabilities of the small groups attempting to operate it. No effort was made to erect a concentrator until William Braden became interested in the property. In 1901 Mr. Braden promoted the necessary capital for the first practical exploitation of the orebody. Barton Sewell and E. W. Nash, both of the

Jan 1, 1952

Jan 1, 1954

By Arthur B. Yates

Diamond drilling has advanced and expanded during the past few yean. Along with this increase there has been a marked trend to rely more and more upon drilling for the outlining of ore for reserve purposes. This is especially true underground, where men have not been available for opening up ore by crosscuts, drifts and raises. During the recent heavy call upon known ore reserves, more drilling has been done for exploration and it has become expedient to drill longer lateral holes from underground and deeper holes both from surface and from exploration headings in the mines. Furthermore, these deeper holes have to be drilled closely enough to warrant calculation of "probable" if not "proven" ore, from the results obtained therefrom. Interpretation of diamond-drill results has become more precise and reliable with the growing knowledge and understanding of the geologic structures that control the geometry of ore distribution, and this has broadened the field of usefulness of the drill. All of this has created a necessity and a demand for more accurate control of the hole as to direction, a more precise and reliable method of surveying for position, and a need for better and more complete core recovery, as well as larger cores, to provide an adequate sample. At depth the control becomes more difficult and, at the same time, more important. Control A close study of drilling in various parts of the world for a period of more than 20 years has brought to light one definite rule, practically invariable; namely, that diamond-drill holes tend to deviate into a position normal to any structure existing in the rocks, such as bedding, schistosity, gneissosity, or even parting or jointing— even if the hole is started at almost any angle other than parallel with the structure. It also appears that the better developed the structure is, the more quickly will the hole get into a position perpendicular to it. It has often been said that there is a tendency for holes to "drift" in the direction of rotation. This is obviously untrue, for in a vertical hole the measure of deviation would depend upon the azimuth chosen as zero, and there is an infinite number of choices. It has been proved. however, that in homogeneous rocks there is a tendency for the hole to corkscrew, and that the direction of the spiral is the same as the direction of rotation. This may account for the belief that holes drift in that direction. Some tests have been made using right-hand and left-hand rods, and these show that no matter what the direction of rotation the hole will swing into a position perpendicular to the structure. Methods of Control The foregoing empirical rule may be used as an indirect method of control. If the prevailing structure is known, it may be advantageous to start the hole as nearly normal to it as possible, for the

Jan 1, 1946

By William L. Fink, Kent R. Van Horn

Aluminum forms not only binary compounds with most of the metallic elements but also forms many ternary or more complex constituents. Several of those occurring in the more important alloy systems have been identified under the microscope and the action of various etching reagents has been carefully studied.' The determination of the structure and composition of these complex constituents is a matter of some difficulty and little information is available. X-ray crystal analysis offers a promising method for the study of such constituents. First, and of considerable importance, is the possibility of recognizing the presence of a given constituent by means more positive than microscopic observation. Evidence can also be obtained concerning the nature and composition of the constituent in question and ultimately it should be possible, at least in some cases, to describe the structure including the relative locations of the various atoms. In this paper some results of an uncompleted study of the constituents of the aluminum-iron-silicon system are given and the methods employed are described. Inasmuch as iron and silicon are the chief impurities in aluminum, the constitutional relations of this system are of fundamental importance in the metallurgy of pure aluminum and its alloys; the system has been studied by several investigators and the more important contributions have been reviewed recently.² Fig. 1 shows the structure of the aluminum-rich alloys after prolonged annealing at 560" C., in accord with one of the most recent investigations.3 The ternary alloys examined in the course of the present investigation were all annealed at 550" or 560' C.; in fact, some of the specimens were the identical ones used by nix and Heath, who kindly supplied them for this work. Since the results

Jan 1, 1931

By C. W. Mueller, P. H. Robinson

A technique was developed for depositing single -crystal films of silicon on single-crystal sapphire substrates via the pyrolytic decomposition of SiH4/H2 mixtures. Electron diffraction and X-ray Laue reflection examinations of these films revealed single-crystal patterns. These films were characterized by measuring conductivity type, thickness, resistivity, and Hall mobility. Chemical etching, dislocation staining, and electron-microscopy examination have indicated the presence of low-angle grain boundaries and microtwinning in the silicon films. The role of the sapphire substrate with respect to its quality, orientation, surface finish, and thermal and chemical treatment was investigated. Hall mobility as a function of sapphire orientation was measured. A mobility equal to 88 pct of bulk silicon mobility was attained. Insulated-gate field-effect transistors which have a transconductance of 4000 pmho at 6 ma were fabricated using these films. THE technology of the fabrication of microelectronic circuits with active and passive components directly on a single wafer of semiconductor material has attained a high degree of perfection during the last few years. One inherent difficulty with the single-wafer approach has been undesirable coupling between components arising from the common base material. Several techniques have been developed for minimizing this coupling and obtaining good electrical isolation between components; however, these result in extra capacitance being added to the circuit. The extraneous capacitance of the connecting leads, resistors, and capacitors degrade circuit performance and limit the high-frequency operation of these circuits. Recently there has been considerable interestl-3 in the deposition of silicon films upon insulating substrates. The use of silicon as the semiconductor allows the subsequent utilization of the large amount of technology which has been developed for silicon for the fabrication of good active components. A sapphire substrate supplies an excellent insulating material which at the same time gives a thermal-conductivity improvement of an order of magnitude over glass-type substrates. This paper will describe the results obtained for the deposition of single-crystal silicon layers upon single-crystal sapphire substrates as well as the characterization of these films. I) APPARATUS The 'system used for the growth of silicon films on sapphire substrates by means of the pyrolysis of SiH4/H2 mixtures is shown in Fig. 1. The all-quartz reaction chamber is water-cooled and includes a quartz optical-flat window for use in conjunction with a 5 kw, 2.5 Mc per sec constant-temperature controlled rf generator. The temperature sensor for the rf generator is a thermopile which is focused through the quartz optical flat onto the susceptor surface. With this system the rf generator will hold the temperature of the susceptor to about +0.3°C at 1200°C. The susceptor is supported on a quartz sled inclined to the gas flow to increase the uniformity of the deposition. The water jacket surrounding the reaction chamber is used to keep the quartz wall temperature low enough to limit the decomposition of the silane to the rf-heated susceptor which contains the sapphire substrates. This eliminates the reaction of silicon with the hot quartz to form SiO which deposits out on the apparatus walls, thus obscuring vision, and interferes with the optical measurements of the temperature as well as with the growth process itself. Provision is also made for "n"- and 'p"-type doping by using mixtures of either phosphine or diborane in hydrogen which are added to the silane during the growth process. The hydrogen used is the purest commercially available tank hydrogen further purified by use of a palladium diffuser. The susceptors which were used include 1) spectro-scopically pure graphite, 2) high-purity molybdenum, 3) high-resistivity silicon using a low-resistivity insert to facilitate coupling to the rf generator, 4) silicon carbide-coated graphite. The latter two susceptor materials produced silicon films on sapphire substrates with more reproducible resistivities. Prior to silicon deposition all connecting lines as well as the reaction chamber are thoroughly flushed with argon and then hydrogen. After the hydrogen flow is set, the growth temperature is adjusted to 11009 to 1150°C, and when thermal equilibrium is reached the silane flow is started. The flow rate of the hydrogen must be fast enough so that turbulent flow occurs in the size of reaction tube used, otherwise a streaked nonuniform silicon deposit occurs. After the deposition

Jan 1, 1967

By Paul Weir

Bleaching clays have been used extensively in the oil-refining industries for a number of years. Their use in water purification is relatively recent and less extensive. They are frequently classified as (1) those naturally active and (2) those active after artificial activation with acid. Fuller's earths fall within the general group of bleaching clays and gradually the commercial term "fuller's earth" has been applied to natural clays originating, for the most part, in the southeastern section of the United States. Bentonitic clays are usually classed as activable and are prevalent in the southwestern section of the United States.l Bleaching clays vary considerably in chemical and physical properties throughout the country, or even in different parts of one deposit (Table 1). The fuller's earth type of clay is characterized by a lack of plasticity, relatively adsorbent, foliated structure, and does not swell to form a

Jan 1, 1942

By Paul Weir

Bleaching clays have been used extensively in the oil-refining industries for a number of years. Their use in water purification is relatively recent and less extensive. They are frequently classified as (1) those naturally active and (2) those active after artificial activation with acid. Fuller's earths fall within the general group of bleaching clays and gradually the commercial term "fuller's earth" has been applied to natural clays originating, for the most part, in the southeastern section of the United States. Bentonitic clays are usually classed as activable and are prevalent in the southwestern section of the United States.l Bleaching clays vary considerably in chemical and physical properties throughout the country, or even in different parts of one deposit (Table 1). The fuller's earth type of clay is characterized by a lack of plasticity, relatively adsorbent, foliated structure, and does not swell to form a

Jan 1, 1942

By John H. Holloman

In recent papers, O'Neill,' Vivian, and Zener and Hollomon3 have reviewed some of the information concerning the relations between stress and strain during plastic deformation. Since further information has been obtained since these reviews were published, this paper attempts to further coordinate and amplify the knowledge concerning the plastic deformation of metals in simple tension. Ordinarily the results of tensile tests of metals are presented as graphs in which the load divided by the original area is plotted as a function of the percentage of elongation measured over some specified gauge length. The interpretation of graphs of this sort is limited, since the stress required to deform the metal at any stage of the deformation is actually the load divided by the instantaneous rather than the original area. Furthermore, each increment of the deformation is performed on metal that has been previously deformed, and, as pointed out by Ludwik,4 the strain could be more effectively defined: where e is the strain and AO and A are, respectively, the original and instantaneous areas. The results of the tensile tests can be more effectively presented and interpreted if the stress* (load divided by actual area) is .lotted as a function of the strain as defined above. A schematic curve of this type is presented as Fig. I. In a previous paper,6 the concept of Ludwik7 concerning the flow and fracture of metals was successfully employed to explain some of the puzzling results of notched-bar impact tests of steel. It appears that the use of this concept ii; very fruitful and should be kept in mind in any study of the deformation charactcristics of metals. Ludwik considered that a flow stress-strain curve of a metal was essentially a locus of points that described the stress required for plastic flow of an infinite numbcr of specimens, each with a different strain history determined by the preceding part of the flow curve Each of these specimens can also be considered to have a fracture strength. Uniortunately (or fortunately depending upon the point of view), all the specimens, except the one deformed to the fracture strain, flow and do not fracture. Even though the metals do not fracture, the concept of a fracture-strength curve seems

Jan 1, 1945

By D. N. Collins, J. R. Stevens

New expressions in the technical assessment of mineral concentration processes have been defined as Concentration Efficiency: Concentration Index: where h is the percentage of head grade; c, percentage of concentrate grade; maximum percentage of concentrate grade obtainable at 100 pct recovery; and R, percentage of recovery. In developing these expressions, the basic requirements for the technical assessment of concentration operations have been defined and the various expressions suggested by others for asses-sing the results of such operations reviewed and criticized. The derived expression for E, depends on a simple combination of recovery (R) and a new term selectivity (s), where S is (c-h)/(c,,, -h), by definition. Limitations of the new expressions are discussed and examples given of applications to concentration operations. It is also shown that the formulae for E, and I, can be applied to scatter diagrams, multi-component systems, size-assay analyses, and classification data. Many methods of quantifying concentrating operations have been proposed. These include direct presentation of weights and assays together with the derived data for other items such as ratio of concentration, recovery, rejection losses, and enrichment ratio. These terms are now accepted mineral dressing nomenclature, and in the assessment of the results of concentration processes, concentrate grade and recovery are together the most widely accepted measures of concentration efficiency. For practical purposes when the concentrate grade is equal to or greater than a predetermined acceptable value, test or operation results may be assessed by the recovery figures alone. Similarly when recovery is within specification, the operation can be assessed by concentrate grade. The ultimate assessment and selection of a concentration operation is—admittedly with a few ex-ceptions—a matter of economics. There is however an intermediate stage in laboratory and pilot plant testing when evaluations must be made without the assistance of an economic yardstick. Numerous techniques are employed to facilitate such evaluations among which may be mentioned graphical plots of grade vs recovery, cumulative weight vs cumulative recovery, scatter diagrams, etc. The desirability of combining metallurgical results and product weights and assays into a single value has been recognized and discussed by many workers1-" with the resultant suggestion and use of such terms as Metallurgical Efficiency ,' Summation Index,' Selectivity Index,'- and Absolute Efficiency B None of these expressions completely satisfies all the requirements of a selectivity or efficiency formula and it is proposed in this report to define the terms, relating to the technical efficiency of a concentrating operation, concentration index and concentration efficiency. Examples are given of their application and a comparison is made of their use in relation to other formulae. All product grades in this paper will be referred to in terms of mineral percentages and a list of symbols is given in Table I. CONSIDERATION OF EXISTING FORMULAE A number of the existing efficiency and index terms used in quantifying concentrating operations are considered below. Metallurgical Efficiency:

Jan 1, 1961

By C. O. Fairchild

THE meaning of temperature control can be extended to cover not only the control of temperatures' but also the control of processes through a knowledge of the temperatures involved. In this sense it has a very wide interest. A list of the industries in which temperature control is used in one way or another would cover nearly the entire industrial field. This discussion will be confined to the field of high temperatures. In practically all industries involving operations at high temperatures, pyrometers are used or men are paid for their ability either to estimate temperatures or gage an operation by some physical or chemical change or condition dependent on temperatures. As progress is made in the development of instruments and of methods for measuring temperature, some of these highly skilled artisans are learning the use of a new tool. Many processes have been, in recent years, improved by means of exact measurement thus substituted for estimation, but in a great many industries the pyrometer has had practically no opportunity to demonstrate its usefulness. The perfecting of instruments must be accompanied with a dissemination of the knowledge that new instruments are available and can be economically used. The demand at present, however, is ahead of the supply, and many industries are handicapped by the want of pyrometers. One of the highest paid skilled tradesmen of the present time is the man in the steel rolling mill who knows when proper working temperatures are attained. The metallurgist in his development of steels is continually demanding closer adherence to given temperature ranges in the processes, and the pyrometer is rapidly becoming indispensable. Properties of the finished products are being correlated with working temperatures and so closely that in some cases even the pyrometer is taxed to give the required accuracy. The greatest progress has been made in those industries in which the lower temperatures are used, particularly below 500° C. In this lower range automatic control has been highly developed.

Jan 9, 1919

By George Rice

INSTANTANEOUS outbursts of gas in underground workings are similar in effect to great blasts of explosives, but without heat effects. Fortunately they occur only in a few localities in exceptional coal fields of the world and under exceptional geologic conditions. Such violent outbursts should not be compared with the ordinary outflows of gas into coal mines or with explosions of gas and dust. The phenomenon is essentially one of gas held in circumscribed areas under very high pressure and as a mining face or heading approaches such a place and the mining excavation sufficiently weakens the natural surrounding dam or shell, this is burst by the pressure just as by the discharge of a mass of explosives. The outbursts, so far as known to the writer, have been confined to coal beds and have not occurred in other mineral deposits. Hence, as discussed later, he believes that it is the relation of the gases to the coal material that is a factor in conjunction with others in producing conditions which permit the phenomena to occur when mining is done. The gases in most instantaneous outbursts have been hydrocarbon gases but in two coal fields they have been definitely found to be chiefly or wholly carbon dioxide. One of these localities in which CO2 outbursts have been frequent and have caused loss of life is in the southern part of the Gard basin, near Alais, in southern France. In 1919, the writer visited the Fontaine mine in this field the day following the occurrence of an outburst by which two men were smothered by carbon dioxide and fine dust. After 24 hr. the CO2 had not been entirely removed by the ventilating current. Occasional outbursts of CO2 have also occurred in other small basins in France, causing accidents, as in Puy-de-Dome. However, mines in the Gard basin, north of those in which CO2 outbursts have occurred, have experienced hydrocarbon gas outbursts.

Jan 1, 1931

By C. B. Barlow, T. A. Mekelburg

Due to a tight ash constraint on the clean coal product and difficult middlings washability characteristics, a considerable amount of coal was being lost in the jig middlings at the Monterey No. 2 Mine. An investigation was conducted into circuitry to recover this lost coal with minimal effect on the total clean coal ash. A reverse two-stage hydrocyclone system cleaning at low specific gravities was selected. This system is currently recovering approximately 5.8 kg/s (23 stph) of 11.5% to 12.5% ash coal. The specific gravity of separation for the system is about 1.5 and the probable error is 0.13.

Jan 1, 1986

By R. F. Mehl, M. L. Swanson, J. P. Hirth, G. M. Pound

The sorption of zinc in a-brass was investigated. By analyzing the elliPtically polarized light reflected from the surfaces of a-brass solid-vapor couples, their optical constants and surface compositions were determined. It was shown that the surface compositions approached an equilibrium value exponentially with time. The bulk diffusion coefficient, surface diffusion coefficient and condensation coefficient for a-brass solid-vapor couples were calculated near 350°C from the experimental results. It has been assumed during various diffusion experiments with bimetallic solid-vapor couples (Dunn,1 Seith and Kraus,2 Jenkins,3 Balluffi and Seigle,4 and others) that the surface composition of such couples reaches its equilibrium value immediately. Although this assumption is probably valid at elevated temperatures, it is certainly not expected to be confirmed at lower temperatures.* consequently, it was decided that a fundamental experiment, designed to solve this problem as well as to examine all aspects of bimetallic sorption, would be the investigation of the rate of approach to equilibrium of the surface composition of solid-vapor couples. The sorption (i.e., adsorption, absorption, and desorption) of metals is obviously dependent on the state of the metallic surface and substrate. Much recent theoretical8"9 and experimental10-12 work on condensation and evaporation of pure metals has shown that the surface contour in atomic dimensions is a critical factor in sorption, so that any deformation or contamination13,14 of the surface exerts a profound influence. It is also known that absorption or diffusion occurs much more rapidly along grain were and in other deformed regions. Thus an effective sorption experiment must utilize a strain-free and clean surface, or at least a clearly defined and reproducible surface state. A mechanically polished surface is in a highly deformed17-l9 state. Because the degree of this deformation is uncertain, it is clear that for most experimental purposes a strain-free (i.e., etched, chemically polished, or electropolished) surface is desirable. Although adsorbed gas molecules on metallic surfaces are unavoidable even in the highest vacuum,20 oxide films can in some cases be removed by suitable vacuum annealing. Electrolytically polished and annealed surfaces, being relatively without strain, smooth and free of bulk oxides, were considered adequate for the present sorption experiments. Measurement of the surface composition of a solid-vapor couple presents a unique problem. Since experiments to determine the approach to equilibrium of the surface composition must be performed at temperatures where diffusion is very slow, solute penetration is so small that conventional analytical methods are unsuitable. An optical reflectivity method utilizing a polarization spectroscope was employed because of the relatively small penetration (~200A) of visible light in metals. By this method, elliptically polarized light reflected from the metal surface was analyzed and compared with that reflected from samples of known composition. The a phase of the copper-zinc system was

Jan 1, 1962

By Charles Parmelee

When Professor Silliman made his first examination of the newly-discovered Pennsylvania rock oil in 1859, he noted that different rates of heating produced different results in fractionation—longer heating produced larger percentages of light fractions. In 1862, it was found that when petroleum vapors are condensed in the still crown and dropped back into the hot liquid, the result of the distilling operation is materially modified. These early dates mark the beginning of what is called cracking petroleum and is explained as separating the component parts of the hydrocarbon molecules into more and smaller groups of the same elements. The phenomena were utilized for the next 30 years to increase the yield of burning oil. The procedure was that regularly practiced today in dry or destructive distillation. Considerable scientific study was given to the subject from 1862 to 1905, and a number of patents were obtained, but the work done was not continuous or intensive until about 1905, when the increasing demand for gasoline attracted attention of petroleum refiners to the possibilities of cracking. The first equipment built and operated essentially for cracking petroleum on a large scale was placed in successful operation in 1912. The commercial practice is, therefore, less than 15 years old. Comprehensive intense study of the controlling factors during this period has resulted in rapid increase in our knowledge, and material improvement has been made in the practice of the art. It is the purpose of this paper to outline briefly the state of our knowledge and to suggest some of the questions which are attracting attention of researchers at the present time. The major purposes for which petroleum hydrocarbons, including natural gas, are or have been cracked are: 1. To obtain products used to increase the heat value and illuminant content of artificial gas. 2. During the World War, to increase the supply of toluol. 3. To increase the amount of products capable of conversion into industrial chemicals. 4. To produce pure carbon.

Jan 1, 1927