Search Documents

By H. W. Mead, C. E. Birchenall

SELF-DIFFUSION in pure gold has been studied by Sagrubsky,1 McKay,2 Gatos and coworkers,3,4 and Okkerse.5 Sagrubsky used a sectioning technique but reported results far lower than any of the others. The work seems to be carefully done, and it appears that a factor of 60 must have been omitted in his calculations or the units misstated by an equivalent amount. McKay used a surface activity method, and Gatos and Kurtz, following Gatos and Azzam, applied autoradiography to the measurement of activity on an oblique section through the diffusion zone. These two investigations agree well with each other but give results below those reported here. Okkerse employed a very careful sectioning technique. Chemical interdiffusion in Au-Ag alloys has been measured under several concentration conditions. Average values of the diffusion coefficient for the range of 0 to 18 atomic pct Au were obtained by Braune.6 since the diffusion coefficient probably varies markedly over this range, the values may not be too useful. Also, a plot of these data suggests that grain boundary contributions may have been appreciable at the lowest temperature employed. Ebert and Trommsdorf7 give average values for 0 to 9 atomic pct Ag, and Johnson8 reports average values for 45 to 55 atomic pct Au. Johnson also measured silver and gold self-diffusion coefficients in 49.2 atomic pct Au alloys, and self-diffusion in pure silver. The self-diffusion of gold in pure silver has been determined by Jaumot and Sawatsky.10 Other measurements which do not cover a range of temperature or are of low precision are not mentioned in this account since a review by Kubaschewski is available." This contribution reports diffusion coefficients for self-diffusion in gold, self-diffusion of gold in Au-Ag alloys, and chemical diffusion in Au-Ag alloys. Although it had been intended to obtain silver self-diffusion data in the alloys it now appears unlikely that these measurements can be done soon, so a table has been worked out for a self-consistent scheme of diffusion coefficients which should not be too far from the true values. Experimental Details Experiments on pure metals were conducted using fine gold of 99.99+ pct Au and silver of the same purity. Alloys were prepared by melting the two metals together in a graphite crucible in vacuo and allowing the slug to solidify in the crucible. After machining to a cylinder about 0.85 in. diam each slug formed one half of a diffusion couple. Compositions were determined later by analyzing chips taken from the extremities of the diffusion zones. The gold used in the preparation of alloys was sometimes pure gold but was normally either in the form of clean pickled alloy from previous experiments or gold recovered by oxalic acid precipitation from warm aqueous solution. Chips from the various stages of experimentation were dissolved in aqua regia and the solution taken to low bulk, diluted with water, and again taken to low bulk before diluting for the precipitation. This precipitated gold contained a small amount of silver as the only impurity detectable by spectrographic analysis. Disks for use in diffusion couples had opposite plane faces abraded on emery paper as far as zero grit, were annealed for 12 hr at 900°C in argon, and had one face of each disk polished to 000 emery paper. Radioactive gold was plated at about 2 ma per sq cm from a small volume of cyanide solution containing 1 mg of inactive gold as a carrier. Specimens , were freshly abraded on 4/0 emery paper immediately prior to plating. In the case of the active couples disks of a similarly prepared but unplated alloy or pure metal were placed on top and welded to the active disk. With the concentration couples disks of different compositions were welded. Welding was performed after a pressure of 5,000 lb had been applied at

Jan 1, 1958

By J. Lindbo, B. Vigeholm

IN transmission electron microscopy, specimen thicknesses quoted are frequently based upon either traditionally familiar values or a few evaluations representing the whole material. Taking aluminum in 100 kv TEM as an example, average and maximum values are widely accepted as being 2000 to 2500 and 6000 to 7OOOÅ, respectively. It is the purpose of this note to revise these figures and to point out the importance of evaluating individual specimens carefully. All evaluations have been based upon slip trace widths and lattice orientations as determined from diffraction patterns. In many cases where two or more slip systems have been operating the geometrical method described by Crocker and Bevis1 has been applied as a check. The foils were usually oriented to within 2 deg from the exact Bragg angle. Kikuchi patterns were used as indications of correct orientations but not applied in the evaluations. The tilt of the foil surface relative to the beam normal may with certain geometrical relations between the tilt axis and the operating slip plane lead to substantial errors.2'3 Where these geometries were inevitable the samples were omitted in the investigations. Various measures were taken in order to overcome ambiguities, e.g., comparison with neighboring grains, tilts, evaluations based upon two or three slip systems,' and comparison with extinction contour evaluations where s = 0 conditions were obtained. Errors caused by misinterpretation of the slip traces on a micrograph are easily avoided by considering the bright-dark sequence on opposite surfaces and by taking into account the tapering of the foil usually leading to a distinguishable divergence of the pair of traces. In the investigations described here the interpretation was further facilitated as the slip trace formation was observed on the microscope screen and sketches taken down. In a few observations slipping was so violent that the distinction of pairs was considered dubious and consequently given up. To assess average values, thickness evaluations carried out in two independent investigations were analyzed: I) 99.998 pct A1 extruded, cold-drawn, and recrys-tallized to grain sizes between 35 and 500 um were deformed in tension at room temperature. In order to determine the dislocation densities as a function of strain,4 specimens prepared by spark machining and electropolishing in a PTFE holder were analyzed in the electron microscope at 100 kv. Thicknesses were evaluated for 569 selected areas. Histogram I in Fig. 1 shows the results, the average thickness being 4900Å. II) Electropolished specimens prepared from 99.9999 pct A1 with magnesium contents from 0.005 to 0.5 pct rolled to foil and annealed were subjected to fission fragment irradiationa2 For volumetric dose and defect concentration determinations thickness evaluations were performed on 123 areas. Histogram II in Fig. 1 shows the thicknesses of these areas averaging 4250Å. Whereas in investigation I no selection related to thickness has been made, some thin as well as thick areas have been omitted from I1 for experimental reasons. This and the application of two different microscopes although of the same type may account for the difference in average thickness. Assuming a mean error of 10 pct for a single evaluation, the error of the average should be negligible. In order to investigate the maximum transmissible foil thickness in aluminum, specimens were prepared from single crystals with (111) and (110) orientations parallel to the beam, and from polycrystalline material. Maximum values of thickness that could be measured were given by the stopping of the dislocations. The visibility often extended far beyond the end of the slip trace, but with no means of knowing the

Jan 1, 1970

By S. R. Mitchell, M. C. Fuerstenau, A. M. Gaudin

The two principal attributes of a thickener pulp are its settling rate and the ultimate pulp density of the thickened mud. Testing for evaluation of thickening attributes of a pulp has usually been done batch-wise by placing the pulp in a one-liter glass graduated cylinder and noting the position of the boundary between clear liquor and mud as a function of time. Refinements in testing have included repulping a thickened mud to various dilutions and evaluating the settling rate on these various repulped muds. This is considered to make possible an estimate of the settling rate as a function of pulp density and therefore to pinpoint the slowest settling pulp which ought to be critical from the standpoint of thickener plant design. Finally, tests are sometimes made with model-size continuous thickeners of arbitrary size. In batch tests it is generally accepted that the behavior of a pulp is described by a curve such as the one shown in Fig. 1, in which the position of the boundary between clear liquor and mud (the mudline) is plotted against time. It has also been assumed that the initial settling rate (the slope of the line segment AB) is descriptive of the pulp and independent of the size and shape of the container. Where the settling rate is slower and clearly a function of time (portion CD of the settling curve), it has been assumed that the data are not of much use because of the intrusion of compacting phenomena. The next important datum is the height. PE, which is a measure of the so-called ultimate pulp density. This quantity is assumed to be characteristic of the pulp and independent of the container. When actual data are recorded, results are rarely exactly according to this theory and numerous deviations may be noted. For example, some pulps seem to require an appreciable delay before beginning to settle, as in line AF. This is spoken of as representing the need for an induction time for flocculation. It has seemed desirable to explore thickener data with a more sensitive charting tool than is afforded by the coordinates of Fig. 1. Instead of relating the position of the mudline to time, it has seemed desirable to relate the rate of descent of the mudline to time. This, in effect, amounts to charting the slope of the line in Fig. 1, or the derivative of its ordinates, against the same abscissas. Fig. 2 shows the new chart for the curve ABCDE of Fig. 1. When this new tool was applied to data obtained, for example, with sized clay pulps, astonishing differences appeared. Apparently the traditional tool conceals differences instead of revealing them, whereas the new method emphasizes them. It seems, also, that both charting methods have their uses. In this article attention is focused on the effects of pulp density and container height as they affect the settling behavior of flocculated suspensions of a sized kaolin. The thesis by M. C. Fuerstenau' gives more details than this summary, as well as some information about the effect of other variables. Sized fractions of kaolin were used, supplied through the courtesy of S. C. Lyons of the Georgia Kaolin Co. Large batches were made by agitation in a flotation machine and in a glass jar equipped with a mixer. The settling vessels were 2, 4, and 6-in. diam glass cylinders of various heights. Pulp Dilution: The effects of pulp dilution on sedimentation behavior are shown in Figs. 3, 4, and 5. Fig. 3 shows data on pulps ranging from 2.44 to 16.7 pct solids initial pulp density, flocculated with Separan and charted in the traditional manner. At least two of the lines appear nearly straight in their early sections, but neither of the others does. Each of the curves in this figure includes a region labeled

Jan 1, 1960

Jan 1, 1936

Jan 1, 1937

By AIME AIME

THE session* on Non-ferrous Metallurgy held Monday morning was conducted in a most satisfactory manner with F. F. Colcord, vice-president, U. S. Smelting Co., in the chair. In spite of the early hour and the fact that members desired to register first, the meeting started quite promptly, with almost every chair in the room occupied. About 65 men were present and during the morning many more came but, not being able to find room, drifted away to other fields of activity. The first paper presented, "Lead Refining Practice of the Bunker Hill Smelter of the Bunker Hill & Sullivan Mining & Concentrating Co.," by Alfred F. Beasley (T. P. 303), was read in abstract by Edward H. Robie, and an animated discussion followed in which Messrs. Johnson (written discussion), Brewer and Jones and Professor Hayward participated. The discussion hinged principally on the liquation of the zinc crusts, but Professor Hayward called attention to the fact that the practice of keeping the gold and silver crusts separate was not new and the present scheme illustrated the axiom that processes based on fundamental principles should not be considered as extinct; one can never tell when it may be found advantageous to make use of them again.

Jan 1, 1930

By G. T. Smith, R. C. Moyer

Cadmium, along with other impurities such as lead, gallium, germanium and indium, is characteristically found associated with zinc ores, the average ratio of zinc to cadmium being about 200 to 1. The increasing demand for cadmium has led most zinc producers to develop a means for its recovery. The separation and recovery of this byproduct constitutes an important development in the metallurgical field. Zinc sulphide concentrates, principally from domestic sources, are processed at Donora Zinc Works and they assay approximately 60 pct zinc, 30 pct sulphur, 0.37 pct cadmium, and 0.8 pct lead. Concentrates are roasted to convert zinc sulphide to zinc oxide. Sulphur evolved as sulphur dioxide is used to manufacture 60º Baume sulphuric acid by the lead chamber process. The roasted calcine is sintered to remove the remaining sulphur and volatile impurities. Fume from the sintering machines is collected by Cottrell pre-cipitators and sent to the Cadmium Department for cadmium removal. The sintered product, a crude zinc oxide, is then mixed with coke and salt and charged into horizontal retorts for reduction to zinc metal. Furnace residues are then passed through a Waelz kiln which recovers practically all of the remaining zinc as an oxide. This oxide is collected by Cottrell precipi-tators and returned to the sintering plant for further processing. The following discussion covers operating procedure, and equipment used in the Cadmium Department for the manufacture of cadmium and its byproducts. (See attached Flow Sheet, Fig 1.) The production of cadmium may be divided into several steps, each of which will be discussed separately. These steps are as follows: 1. Raw Materials—Sinter Plant Cottrell dust, acid sludge and sulphuric acid. 2. Sulphating—Separation of lead. 3. Purification—Separation of impurities other than zinc. 4. Precipitation—Separation of cadmium from zinc. 5. Briquetting—Preparation of sponge for charging to furnace. 6. Smelting—Distillation of cadmium metal. 7. Remelting—Casting into commercial shapes. 8. Recovery of Rare Metals—Separation of germanium, gallium and indium. Raw Materials The raw material, or Sinter Plant Cottrell dust, from which the cadmium is manufactured, is recovered by Cottrell units collecting fume from two Dwight-Lloyd sintering machines. An average analysis of this dust is 36 pct zinc, 1.5 pct sulphur, 17 pct lead, and 5.5 pct cadmium, with associated elements in smaller amounts. A lesser tonnage of material removed from the sintering machine fans, and called fan cleanings, is also treated for cadmium. It is lower grade material and analyzes approximately 41 pct zinc, 1.2 pct sulphur, 14 pct lead, and 4 pct cadmium. Cottrell dust and fan cleanings are delivered to the Cadmium Department by monorail crane in bell-bottomed dump buckets. Acid sludge and 60" Bauine sulphuric acid are received from the Acid Department. The acid sludge is a mixture of lead sulphate, sulphuric acid and zinc sulphate, and is recovered mainly from the floors of the acid chambers or storage tanks. The acid sludge is delivered to the Cadmium Plant in a lead lined bucket. The 60º Baume sulphuric acid is delivered through a lead pipe to a lead lined storage tank. Sulphating Four well ventilated lead lined sulphating tanks, 8 1/2 ft in diam by 12 ft deep, are used. These are steel tanks lined with 20 lb lead on the bottom and 16 lb lead on the ides, equipped with Hastelloy side agitators. 15 hp motors drive 24 in. propellers at 450 rpm. There are water connections to stuffing boxes to keep sludge from entering the bearings. The tanks are covered with removable wooden lids and are connected to marine plywood

Jan 1, 1950

By W. W. Mein

IN March 1949 the Calaveras Cement Co. was sued by five landowners whose properties are located in the vicinity of the plant. These landowners—all of them cattle ranchers—sued for dust damages of $120,338 and for an injunction preventing the company from casting dust upon their properties in injurious quantities. The issue was split, the jury deciding the amount of damages and the court handling the injunction features. The action came to trial before a jury in April of that year and resulted in damages being awarded in the amount of $7,508. A month later the court issued its injunction requiring recovery of stack dust to an 87 pct minimum. The Calaveras plant, shown in Fig. 1, is located three miles from San Andreas in the heart of the Mother Lode country, about 45 miles east of Stockton, Calif. Since it is in a small town, the company's responsibilities to its employees and to the community are different from those of plants located in large centers of population. Construction of the plant was begun in 1925, and production was started the following year. Standard gray Portland cement as well as several specialty cements are produced. Production facilities have been continually enlarged so that the present capacity is more than double what it was 25 years, ago. The most important item in the company's expansion program was the purchase in 1945 of an 11 ft 3 in. x 360 ft Allis-Chalmers kiln which had been declared surplus by the Defense Plant Corp. The company is now able to produce about 2,500,000 bbl of cement a year, and employment at the plant is approximately 300. The production of cement has always involved a dust problem, solution of which has been attempted in a number of different ways. By far the most efficient method of catching dust discharge is electric precipitation. Soon after the company went into production in the 1920's, the landowners near the plant began complaining about dust discharge. The company settled the matter by paying them a total of $27,000 for dust damages incurred during the period from 1929 to 1938. In the latter year the two-unit Cot-trell Electric Precipitator shown in Fig. 2 was installed and collected over 85 pct of the dust resulting from operation of the two 11 ft 3 in. x 10 ft x 240 in. kilns. From 1938 until 1946 the landowners registered no objection and were apparently satisfied with that dust recovery. In 1946, however, the substantially higher production resulting from operation of the new kiln immediately overtaxed the facilities of the existing two-unit precipitator. In a short time claims for dust damages were again received from the landowners. The company informed them that because of postwar shortages it would take several years to install a new precipitator. The company stated that it intended to purchase an additional precipitator and offered in the meanwhile to pay the landowners a fair amount to cover their damages. This offer was rejected and the landowners filed suit in the Superior Court of Calaveras County asking for total damages of $120,-338 and for the injunction outlined above. Case for the Ranchers The attorneys for the plaintiffs produced three different types of witnesses: first, the landowners themselves and members of their families; second, other cattle raisers who were sympathetic to the plaintiffs; and third, several types of technical experts: veterinarians, soil chemists, and an aerial photographer. The testimony of these witnesses was designed to establish that the flue dust from the plant had not only damaged the land and the forage, but had also caused fluorine poisoning to their animals. By a combination of these causes, the plaintiffs attempted to prove substantial loss of profits.

Jan 1, 1952

W ho holds title to the continental shelf? As submarine mineral ventures move out into deeper and deeper waters, the dispute over this question is bubbling up with greater and greater urgency. Basically, the forces of disagreement are lined up on two fronts--one nationalist and the other internationalist. The nationalists, or "broad shelf" proponents, view the shelf as a geologic extension of the coastal nations and therefore subject to the sovereignty of these nations. The internationalists or "narrow shelf" proponents, seek to circumscribe the jurisdiction of the coastal nations by a topographic line beyond which all rights would be reserved to an international regime. In the U.S. public sector, three groups----the American Bar Association and International Law Association committees and the National Petroleum Council (NPC) - have taken a stand on the broad shelf. These are joined by AIME, which has consolidated its position in a "Policy Statement on the Outer Limit of National Sovereignty Over Seabed Resources." This statement was adopted by the AIME Board of Directors last October 15 after its submission by Earl Cook, Chairman of the AIME National Affairs Committee, at the behest of the Society of Petroleum Engineers. The main organization holding to the narrow shelf is the Commission on Marine Science, Engineering and Resources.

Jan 1, 1970

By J. S. Ross

OIL-FIELD waters enter into many underground problems with which the petroleum engineer has to deal. Whether the problem is one of infiltration or natural encroachment, it is always desirable to determine the source of the water before commencing repair or remedial work. The usual mechanical tests for determining the source of extraneous water in wells are slow and expensive. An excellent means for the identification of oil-field waters may be afforded by their chemical characteristics when the chemical character of waters from the various sands has been established, by careful sampling and analysis cautiously interpreted. In the Salt Creek field, Wyoming, a fairly high degree of efficiency has been attained in the controlof field operations by utilizing the information afforded by the analysis. All of the operating companies appreciate this means of identifying waters, with the result that water-sampling has become general practice. Most of the chemical work dealing with Salt Creek waters has been done since the laboratories of the Midwest Refining Co. and the U. S. Geological Survey, were established in the field; the former in 1922, the latter in 1924. A spirit of cooperation has existed between the company and the government personnel by which many of the data for this paper were made available.

Jan 1, 1928

PRESIDENT WILLIAM L. SAUNDERS,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES F. RAND,1 NEW YORK, N. Y. BENJAMIN B. THAYER,2 NEW YORK, N.Y. FIRST VICE-PRESIDENT PHILIP N. MOORE,1 ST. Louis, Mo. TREASURER GEORGE C. STONE,' NEW YORK, N. Y SECRETARY EMERITUS ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 6, 1915

[VOL. XXXVI. Page. Line. 155 29 For "Joachimstahl," read "Joachimsthal." 215 Foot-note 2. For " May, 1892," read " May, 1902." 216 21 For " ack-screw," read " jack-screw." VOL. XXXVII. 31 3 For "quantity of tons," read "quantity of slimes." 35 10 Expunge "recorded in Table VII." 37 24 Expunge "to." 38 33 For "page 89," read "page 9." 44 40 For "page 86," read "page 6." 47 In table, third line under heading "Excavators and Conveyors," expunge "per 40 ft. of."]

Jan 1, 1918

By D. H. Newland

CERTAIN observations from the field and laboratory suggest the need for recasting some of our ideas about gypsum as a rock-forming mineral and in relation to supplies for industrial use. Until about 25 years ago, the use of gypsum was confined almost entirely to agriculture. During the past quarter century, though, its usefulness has been greatly developed, particularly in the building trades, which now absorb most of the gypsum produced. In 1919, according to the U.S. Geological Survey, the output of crude gypsum was 2,240,163 tons, a gain of 912 per cent. in 25 years. About one-half of this production was mined in New York, Ohio, and Michigan, where the proved supplies can hardly be regarded as over-large when viewed in relation to the rapid expansion of industrial requirements. The occurrence of gypsum in the United States is treated by R. W. Stone and others.1 The deposits of Canada are described by L. H. Cole.2 Several states, including Kansas, Oklahoma, Iowa, Michigan, and New York, have had special surveys made their of gypsum deposits, but the reports, as a rule, refer to conditions as they existed from 15 to 20 years ago.

Jan 9, 1921

By Leonard D. Jarrard, Ernest E. Thurlow

THE Boulder batholith of western Montana may be considered a uranium province: a regional geologic environment within which uranium is found in uncommon amounts. Reconnaissance examinations indicated that the Atomic Energy Commission should undertake an evaluation of the potential of this area for uranium production. The AEC has been assisted by the U. S. Geological Survey which has given priority to selected uranium-bearing areas in overall studies of the mineral deposits of the batholith and adjacent regions. Although no out- standing uranium deposits have been discovered, uranium ore has been produced from three widely separated deposits upon which most of the exploration to date has been directed. The intrusive mass referred to as the Boulder batholith occupies a strip of mountainous country about 18 miles wide between Butte and Helena, Mont., covering an area of approximately 1000 sq miles. Elevations range from 3500 ft along Prickly Pear Creek to nearly 9000 ft near Elkhorn Peak a few miles to the east. Except for a few flat-lying valley lands, the region is wooded with lodgepole pine and fir. Though mainly dependent upon mining ventures in the past, the area now is supported, outside of the Butte district, almost wholly by agriculture and some lumbering.

Jan 7, 1954

By Steven Cordiviola, Richard Sergeant

The Kentucky Geological Survey(KGS) was established in 1854 as the official geologic research organization in the Commonwealth. Since that time the Survey has performed basic research in a number of geologic areas such as energy, applied geology, mineral resources, geologic mapping, and hydrogeology. Because of coal's importance to Kentucky, a significant part of the geologic data collected by the KGS is coal related. Coal-related data also occur in a variety of other KGS data sets such as the petroleum and water data files. To adequately respond to coal-related inquiries, the KGS maintains an inter- active, on-line data base in which various types of geologic and hydrologic information can be easily stored, retrieved, and manipulated. The KGS will continue to expand and update this data base through ongoing research, and by cooperating with the Kentucky Natural Resources and Environmental Protection Cabinet, Kentucky Department of Mines and Minerals, U. S. Geological Survey, and University of Kentucky Institute for Mining and Minerals Research. Data in this comprehensive system is available to State, Federal, and local governments; industry; researchers; and the general public. These data facilitate coal exploration, mine planning and permitting, coal production, and research activities in the Commonwealth of Kentucky.

Jan 1, 1983

By Roger M. Nendick

The recovery of precious metals from heap leach solutions can be accomplished by two processes: 1. The Carbon Adsorption Process 2. The Merrill-Crowe Zinc Precipitation Process A brief review of the relative process economics is made. Each process presents certain design considerations that must be addressed during the evaluation and engineering design for the project. Discussion is presented on the design criteria for each process.

Jan 1, 1984

By J. P. Kerr, W. N. Logan

Lack of reliable and detailed information on many of the older fields in Indiana has necessitated the use of x and y in many instances. Even in the younger fields many data were lacking. It was thought that even though much was to be desired regarding the amount and accuracy of the information on the old Trenton field, it was too important to be left out. We trust that we are not perpetuating any of the inaccuracies that are to be found in the data for Indiana.

Jan 1, 1935

By S. G. Epstein

Electromigration has been measured in dilute liquid alloys of lead in antimony and antimony in lead. In these alloys antimony migrates with the electron current; lead migrates in the opposite direction. These results, which contradict the mass criterion, were predicted by the electron drag model for electromigration in liquid alloys. The existing experimental data are shown to correlate with the difference in electrical resistivities of the alloy components. FOR many years investigators have attempted to relate observed electromigration phenomena in liquid alloys to the physical properties of the alloy components. The most successful correlation was found by Angus et' al.,1 who in 1959 proposed an empirical criterion for predicting the relative direction of motion of the components of a liquid alloy in an electric field: the component with the smallest atomic mass concentrates at the cathode. While this criterion is obeyed in nearly all the alloy systems which had been investigated, the physical basis for such an effect was not understood. It was also disturbing that the mass criterion predicted the wrong sign for the Haeffner effect; observations with pure liquid metals revealed that in every instance the lighter isotope was transported to the anode.2 Klemm3 explained these isotopic separations by suggesting that the lighter isotopes were more mobile and more easily carried to the anode with the electron stream. Additionally, several deviations from the mass criterion have been found in liquid alloys, notably involving transition metals such as chromium, nickel, palladium, and zirconium, which migrate to the anode in liquid bismuth.4'5 Recently, a model has been proposed6 in which electromigration in liquid alloys is attributed primarily to the interaction between the electron stream and the metal ions. In essence, this model predicts that the component with the greater electron-ion scattering cross section will be preferentially transported to the anode, displacing the other component to the cathode. The electrical resistivity of each pure component at its melting point is taken as the measure of its scattering cross section. This model was developed from the results of systematic studies with various solutes in liquid mercury,7'8 bismuth,9 and sodium.10 In every alloy, the component with the greater resistivity has centrates at the anode. Coincidentally, in every instance the component with the greater resistivity has also the greater mass, apparently satisfying the mass criterion. In order to differentiate between electron-ion coupling and atomic mass as the relevant physical prop- erty influencing electromigration, measurements were made with Pb-Sb alloys. Lead has an atomic mass nearly twice that of antimony, but lead has an electrical resistivity of 91 microhm-cm while antimony has a value of 113.5 microhm-cm at their respective melting points. The mass criterion predicts that in an alloy of the two antimony will concentrate at the cathode; the electron drag model predicts that antimony will concentrate at the anode. EXPERIMENTAL To conclusively determine the relative motion of lead and antimony in each other, solute electromigration was measured in dilute liquid alloys of antimony in lead and lead in antimony. Both starting materials were 99.999+ pct pure. The measurements were made with the same capillary-reservoir technique previously used for measuring electromigration in liquid bismuth alloys.11 Several changes in the experimental apparatus were necessary, however, to accommodate liquid antimony, which has a higher melting point than bismuth. The modified apparatus is depicted in Fig. 1. In each experiment four quartz capillaries were filled with the molten alloy. A direct current was passed through two of the capillaries; the electrode in one of these capillaries was made the cathode, and the electrode in the other was made the anode. The remaining two capillaries sampled the alloy in the reser-

Jan 1, 1969

By Robert K. Waits

The resistivity, temperature coefficient of resistance, stability at 200°C, and structure of annealed Si-Cr films have been studied as a function of film cowposition. Colorimetric analyses of the films indicated 20 to 60 wt pct Cr over the resistivity range of 1 to 10-4 ohm-cm. Resistors were delinealed by photolithographic etching, contacted with aluminum, and mounted in TO-5 packages. The average temperature coefjicient of resistance, a, between 50" and 150°C is related empirically to the film resistivity, p, by a (ppm per °C) = -2900 - 1140 log p (ohm-cm). Near a resistivity of 3.5 x 10-3 ohm-ctn (30 at. pct Cr) , the temperature coefficient changes from positive to negative. The temperature at which the resistance maximum occurs increases with decreasing resistivity. The conduction mechanism between —196" and +360 C appears to have two components—an activated conduction dominating a1 lord chromium content and higher temperatures and a linearly temperature-dependent conduction dominating at high chromium content and low temperatures. Electron diffraction patterns showed the films to consist of Cr3Si and amorphous silicon. Resistors thicker than 150A typically drifted less than 0.6 pct after 5000 hr stor-age at 200°C. Resistors as thin as approxinzately 80°A that had a silicon overlayer showed similar stability. Such films had sheet resistivities of 10 kilohm per square and temperature coefficients near —600 ppm per "c. THIN-FILM resistors having sheet resistivities greater than 1 kilohm per square are required in many integrated circuit applications. A process for producing such resistors should be compatible with present circuit fabrication and packaging, including exposure to maximum temperatures of 300° to 570°C during contact alloying, die-attach, and ceramic package sealing. In addition, the resistors should have a low temperature coefficient of resistance and change less than 1 pct during storage at temperatures up to 200°C for 1000 hr or longer. Reports of work beginning in 1949 at Battelle Memorial Institute indicated that, among other materials, the silicides of chromium, Cr-Co, molybdenum, tantalum, and tungsten were worthy of further study as high-stability resistive films. Later work on Si-Cr films vacuum-deposited by flash evaporation from a tungsten boat1 led to the conclusion that Si-Cr had "excellent properties for development into high- stability ... resistive elements". More recently, Si-Cr films have been vacuum-deposited from a tantalum boat,2 from a BeO-coated tantalum boat,3 by flash evaporation from an electron-beam-heated tungsten Source,4 and by triode sputtering.5 This paper describes a study of Si-Cr films vacuum-deposited by electron-beam heating of Si-Cr alloys. Resistivity, temperature coefficient of resistance, stability at 200°C, and structure were studied as a function of film composition. EXPERIMENTAL PROCEDURE Film Deposition. Si-Cr sources were prepared by vacuum-melting pressed pellets of mixtures of powdered chromium (99.9 pct, -100 mesh, Lunex Co., Pleasant Valley, Iowa) and silicon (99.99 pct, -325 mesh, United Mineral and Chemical Co., New York). A permanent-magnet focused electron-beam gun having a water-cooled copper crucible was used to heat the pellet until complete melting occurred. The mixture was then kept molten for an additional 5 min. The alloy thus formed was used as the source material for Si-Cr film depositions using the same electron-beam gun. Pieces of semiconductor-grade silicon ingots were used as sources for silicon depositions. The films were deposited within a standard vacuum evaporator having an 18-in.-diam Pyrex bell jar, a liquid-nitrogen-cooled trap, and a Consolidated Vacuum Corp. 6-in. diffusion pump containing Dow Corning DC-705 pump fluid. The substrates were thermally oxidized* silicon wafers 2 to 2.5 cm in diam. The

Jan 1, 1969

By Robert C. Collins, Clifford L. Jewett

The development and production of artificially colored roofing granules have been key factors in the success of the asphalt roofing industry. They provide protection for the asphalt from solar radiation and satisfy the home-owner's desire for a wide range of attractive colors. As a result, the asphalt shingle has become the most commonly used roofing material today. In addition to providing a stimulus to the asphalt roofing industry, artificial methods of coloring granules completely changed the nature of granule production from one of quarrying, crushing, and screening to a complex technical operation. Today's roofing granules are the result of many years of research, and they are produced in modern plants to exact specifications. History Asphalt roofing materials available today are the product of a long evolution of technological development. Forerunners of the present bituminous products, appearing as early as 1780, were primitive constructions of burlap saturated with crude tar or pitch. An early improvement to this basic effort was the dusting of talc, mica, or other finely ground material on the coated surfaces to keep the roofing from sticking to itself in storage. At times some pigmentation was added with the dusting material for initial color, but this was far from satisfactory. In fact, this early product possessed none of the qualifications of a good roof surfacing material. It was not economical; it was difficult to handle and apply; it was not attractive; it provided no resistance to fire; and it would not withstand the elements as well as other products then in use. Methods and machines were soon devised to saturate endless webs of felt with asphalt from the fast-growing petroleum industry. Even though saturated felt became available, this product of rags and wood fiber had almost the same limitations as burlap and tar. Even with heavier coatings of asphalt applied to both sides of the sheet for rigidity and longer life, the product still lacked color and fire resistance. Further, it was found that constant exposure to the sun soon caused the asphalt to become brittle, and it eventually cracked and leaked. This led to the first important use for crushed mineral products on asphalt-coated shingles and provided the key to the subsequent growth of the asphalt roofing industry. When a layer of crushed mineral was embedded in the surface exposed to the weather, the asphalt coating was protected from ultraviolet light and retained its elasticity over a much longer period of time. In addition to this protection, the mineral surfacing provided some resistance to fire. Fire resistance in the past had been found only in the expensive slate or tile roofs and the unattractive and expensive metal roof coverings which were then available. The most common mineral granule applied to the early asphalt roofing products as they began to make their first significant advances after 1900 was screened waste from slate quarries. Slate granules being available in dull shades of red, green, black, purple and a few other miscellaneous colors did provide a degree of color. Since slate has a flat platelike cleavage, it provides a cheap protective cover for the asphalt-coated sheets. Records show that coarse slate screenings were used for asphalt roofing as early as 1906. As the asphalt roofing industry developed, many other natural colored rocks and minerals were used to coat the surfaces of the roofing. The list included silica

Jan 1, 1975