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CHICAGO SECTION CHARLES H. MACDOWELL, Chairman, Luther V. DICE, Vice-Chairman, HENRY WT. NICHOLS,. Secretary-Treasurer, 164.5 E. 68 St., Chicago; Ill. ALEXANDER K. HAMILTON-, HENRY P. HOWLAND, GEORGE P. HULST, FREDERICK 1. SNYDER. There were 32 members present at the dinner of the Chicago Section which was held at the Chicago Engineers' Club on Friday Evening, December 22. At the meeting after the dinner, the Chairman called attention to the work of Mr. Hoover in Belgium and spoke briefly of the assistance which' could be given him through the Belgian Kiddies, Ltd. Mr. Alonzo Kinyon read a paper on "Burring Powdered Coal" which so interested the members that many of them participated in the long discussion which followed. Prof. Harry B. Pulsifier then described the metallurgical plants about Chicago. He mentioned briefly the equipment and interesting features of 30 metallurgical plants of importance and stated that there were also 200 foundries in the district. He said that when number, size, quality and diversity of the plants are considered, the Chicago District is justified in calling itself the greatest metallurgical center on earth. The paper was followed by a brief discussion in Which attention was called to some smaller and incipient plants of an interesting character. HENRY T. NICHOLS, Secretary.

Jan 2, 1917

By A. T. Tye

WHEN the roughing tables operated in 1923 were abandoned, all the coarse iron pyrite for-merly removed by the tables had to be ground to flotation size, which caused an increased power con-sumption of 2 kw.-hr. per ton. Recently, by increasing the tonnage, this has been reduced to a total of 16.6 kw.-hr. per ton. The cost of repairs has been slightly reduced by using an alkaline circuit instead of the acid mine water used in 1923. Other economies from elim-inating roughing tables and the finishing tables have more than compensated for the extra grinding and the total costs have remained practically the same, until the first part of 1927, when, with increased tonnage, the total cost has decreased to 72 cents and the repair cost to 9 cents. In 1923, with a combined gravity and bulk flotation flowsheet, the grade of concentrate was only 4.38 per cent copper. With preferential flotation this has in-creased to over 17 per cent copper. The tailing has decreased from 0.29 per cent -copper to 0.18 per cent. The copper recovery, instead of decreasing; as might be expected, has increased from 87.4 per cent to, 91.5 per cent. The silver recovery has also increased from 88

Jan 8, 1927

By J. Kent Smith

Vanadium is generally spoken of as a rare element; but, even in the light of our resources as known a couple of years ago, this description could be accepted in a qualified sense only. In fact, vanadium is very widely distributed, being a constituent of most clays, while even caustic soda has been shown to contain almost regularly a minute proportion of it, although the quantity in each case is so small as to render impracticable the extraction of the metal therefrom with profit. The opening-up of a large deposit of vanadium sulphide ore in South America has put a new phase on the commercial outlook of vanadium, the technical value of which for the improrement of steel has been proved by rigorous scientific investigation. This sulphide ore has the following analysis: Per Cent. Vanadium sulphide,.39.84 Molybdenum sulphide,.1.57 Nickel sulphide,.........1.49 Iron sulphide,.........4.07 Arsenic sulphide,.. nil. Copper sulphide,.. nil. Manganese sulphide,..nil. Free sulphur,..30.57 Phosphorus,...nil. Silica,....13.60 Alumina,..........2.46 Combined water, 5.00 Carbonic acid, Lime, magnesia, potash, soda and unaccounted for, 100.00 Being a free-burning ore it is calcined with ease, losing 45 per cent. of its weight in the process. The calcined ore has the following analysis:

Jan 1, 1908

By the courtesy of Sir Robert Hadfield, we have received the fol¬lowing communication relating to the development and encouragement of science and research in Germany at present. These statements have been translated by Sir Robert from various German sources, and are presented here as an indication of what Germany is doing not only to further her military power, but also to prepare for the period of trade rehabilitation to which she is looking forward after the close of, the war. KAISER WILHELM TRUST FOR PROMOTION OF WAR SCIENCE The Kaiser has approved the foundation of a Trust with the name given above. The aim of the Trust is to further the development of scientific and technical aids to warfare, by uniting the scientific and the military forces of the country for work together. The scientific Work is to be carried on by the following technical committees (or commissions) (1) Committee for the chemical raw materials, for the production of munitions-manufacturing materials. (2) Committee for chemical war materials (powder, explosives, gas, and the like). (3) Committee for physics, including ballistics, telephony, telegraphy, determination of targets and distances, measurements, and the like. (4) Committee for engineering and communication. (5) Committee for aeronautics. (6) Committee for obtaining and preparation of metals.

Jan 8, 1918

By W. J. C. Venter

The use of activated carbon to improve the selectivity in the separation of base metal minerals from bulk concentrates played an important role in the development of separation techniques employed at Tsumeb and Kombat mines. The Kombat mine, owned and operated by Tsumeb Corp. Ltd., is located in the Otavi Valley in the northern part of South West Africa, approximately 213 air miles north of Windhoek and 38 air miles south of Tsumeb, at latitude 19° 43'S and longitude 17º 41'E. The mine is linked to all major centers by both national railroad and tarmac highway systems which pass right through the town. The Otavi Minen- and Eisenbahn-Gesellschaft (OMEG) mined ore on the farm Asis from 1908-1925. Tsumeb Corp. Ltd. acquired the mineral rights in 1947, started diamond drilling in 1954 and commenced mine development in 1960. The mill started production in 1962 when proven ore reserves were 3,378,084 st containing 2.85% Cu and 2.90%Pb. Annual production of 248,411 st was increased in May, 1967 to the rate of 422,990 st, which was still being maintained in 1971, when ore reserves stood at 3,054,701 st of grade 1,91% Cu and 2.5% Pb.

Jan 4, 1973

Members whose deaths were reported from Apr. 5, 1920, to Apr. 9, 1921. Elected Died 1916 ALLAN, FERGUS L 1920 1916 ATKINSON, CHESTER 1921 1920 BARBERENA, RAUL R 1920 1918 BARKER, F. L 1920 1914 BELL, D. A. S 1920 1920 BREWSTER, GEORGE AUGUSTUS 1920 1917 BRIGHAM, EDMUND D 1921 1915 CARROLL, D. J 1920 1897 CHAPMAN, ROBERT H 1920 1919 COOPER, W. G 1920 1918 CRITCHLOW, EDWARD B 1920 1917 CURTIS, WILLIAM L 1920 1893 DARSIE, JAMES 1920 1892 DELANO, WARREN 1920 1877 DEWEY, FREDERIC P 1921 1917 ENEBO, BENJAMIN A 1920 1896 FAWCETT, JAMES H 1920 1906 FRASER, A LEXANDER J . 1920 1889 GARLICHS, HERMAN 1921 1893 GILLET, LORENZO M 1920 1886 HALDEMAN, HORACE L 1920 1914 HALL, HARRY E 1919 1905 CHART, C. R 1920 1906 HART, PHILIP E 1920 1877 HARTRANFT, SAMUEL S 1921 1914 HICKMAN, E C 1920 1919 || INMAN, WILLIAM ELLIOTT 1921 1920 JETER, J. TINSLEY 1920 1918 JOHNSON, CHARLES W 1920 1916 JOHNSON, FRANK E 1920 1913 KING, FREDERICK G 1921 1887 KNAPP, GEORGE F 1920 1902 LAMB, RICHARD 1920 1880 LANE, J. S 1920 1920 LECKIE, WILLIAM 1920 1887 LEVAT, DAVID 1921 1882 LAWRENCE, BENJAMIN B 1918 1916 LEYNER, J GEORGE 1920 1871 LYMAN, BENJAMIN S 1920 1903 MCCHRYSTAL, JOHN H1920

Jan 1, 1923

We, the undersigned, being all persons of full age and citizens of the United States and a majority residents of the State of New York, desiring to form a corporation pursuant to the provisions of the Membership Corporations Law for the purpose of incorporating, as provided in Section 5 of Article I of said law, the existing unincorporated association known , as American Institute of Mining and Metallurgical Engineers, Incorporated, do hereby make, acknowledge and file this Certificate for that purpose, and do certify as follows I That the American Institute of Mining Engineers is an unincorporated association organized and existing with the object of promoting the arts and sciences connected with the economic production of the useful minerals and metals and the welfare of those employed in these industries by means of meetings for social intercourse and the reading and discussion of professional papers, and to circulate by means of publications among its members and associates the information thus obtained II That the persons duly appointed or designated to manage the affairs of said association are designated by the rules thereof Members of its Council, that the undersigned are all members of said Council as the same was constituted on the 29th day of December, 1904

Jan 1, 1952

By J. G. Paterson, J. A. Meech

Abstract-Activated carbon is a strong adsorbent for amyl xanthate, capable of removing from solution up to a quarter of its own weight in xanthate. In selective flotation systems where depression is unstable, separation efficiency increases with activated carbon additions. The improvements observed are brought about by two mechanisms. First, by removing stripped and residual collector ions from solution, competition between depressant and xanthate is reduced and depression is stabilized. In addition, the texture of the froth phase at high pine oil concentrations is modified by activated carbon such that better drainage between the air bubbles takes place, alleviating the mechanical entrapment of depressed mineral particles. In treating a bulk copper/lead concentrate produced from GECO ore, selectively between galena and chalcopyrite is increased when activated carbon is used. Although the rate of flotation of galena is marginally lowered by activated carbon, a small extension in the duration of flotation allows the lead recovery to increase by 19% at the same recovery of copper. An addition rate of 0.75 kg/ton (1.5 lb/st) of bulk concentrate is suggested as optimum from this testwork. However, the actual level wed in the mill is dependent upon the residual concentrations of collector and frother in the bulk concentrate Pulp.

Jan 11, 1978

By Lawrence Addicks

F. N. FLYNN, Clifton, Ariz.-As a number-of my associates in Arizona know, for a great many years, I have felt that leaching was one of the coming problems. We are about to start experiments at Clifton, along the idea of leaching wet flotation concentrates direct, without roasting-differing in this respect from Mr. Addicks' suggestion. We are prompted in starting these investigations by the difficulty in. transporting and handling flotation concentrates, and consideration for drying and roasting dust losses. I have had the idea for 5 or 6 years past, that those very fine concentrates could best be treated by leaching at the concentrating plant, thus eliminating our transportation difficulties to the smelter, and dust losses at the smelter. Given flotation concentrate, if it must be dried and roasted, it would, in our case, undoubtedly be cheaper to smelt the calcine, but if it can be leached raw and wet and the drying difficulties- and dust loss eliminated, it would be very advantageous to leach it at the mill. I realize that it will be a difficult problem, and one which may take several years to develop, but if developed, it would pay for many years' expense of investigation, and we have been encouraged by our general manager to investigate its merits.

Jan 12, 1916

WE the undersigned, being all persons of full age and citizens of the United States, and a majority residents of the State of New York, desiring to form a corporation pursuant to the provisions of the Membership Corporations Law for the purpose of incorporating, as provided in Section 5 of Article I. of said law, the existing unincorporated association known as American Institute of Mining Engineers, do hereby make, acknowledge and file this Certificate for that purpose, and do Certify as follows: I. That the American Institute of Mining Engineers is an unincorporated association organized and existing with the object of promoting the arts and sciences connected with the economic production of the useful minerals and metals and the welfare of those employed in these industries by means of meetings for social intercourse and the reading and discussion of professional papers, and to circulate by means of publications among its members and associates the information thus obtained. II. That the persons duly appointed or designated to manage the affairs of said association are designated by the rules thereof Members of its Council; that the undersigned are all members of said Council as the same was constituted on the 29th day of December, 1904.

Jan 1, 1923

CERTIFICATE OF INCORPORATION [AMENDED Nov 22, 1912, AND JUNE 27, 1919 ] WE the undersigned, being all persons of full age and citizens of the United States, and a majority residents of the State of New York, desiring to form a corporation pursuant to the provisions of the Membership Corporations Law for the purpose of incorporating, as provided in Section 5 of Article I of said law, the existing unincoiporated association known as American Institute of Mining Engineers, do hereby make, acknowledge and file this Certificate for that purpose, and do Certify as follows I That the American Institute of Mining Engineers is an unincorporated association organized and existing with the object of promoting the arts and sciences connected with the economic production of the useful minerals and metals and the welfare of those employed in these industries by means of meetings for social intercourse and the reading and discussion of professional papers, and to circulate by means of publications among its members and associates the information thus obtained II That the persons duly appointed or designated to manage the affairs of said association are designated by the rules thereof Members of its Council, that the undersigned are all members of said Council as the same was constituted on the 29th day of December, 1904

Jan 1, 1923

By J. H. Swisher

HIGH-temperature anneals in wet hydrogen are widely used in research as a technique for decarburiz-ing Fe-C alloys. This technique is also used commercially in processing low-carbon steels for magnetic applications. The results of some calculations to be presented show that for temperatures up to 1100°C there is a critical temperature for maximizing the decarburization rate of alloys containing about 0.1 pct C. The low-temperature portion of the iron side of the Fe-C phase diagram1 is reproduced in Fig. 1. Preliminary calculations show that the critical temperature is between 727" and 905°C. In this range, the alloy contains two phases during heat treatment, ferrite and austenite. Decarburization therefore occurs by a process termed "diffusion accompanied by a phase change".' For intermediate stages of decarburization, the carbon concentration profile in a flat plate is shown in Fig. 2. The carbon content increases linearly from zero at the surface to a value, cB , at the two-phase boundary. cB is known from the phase diagram, see Fig. 1. At the interface where x = 5, the carbon content increases to ci, the initial concentration in the alloy. smith3 has derived an equation which describes the rate of movement of the boundary. With a rearrange-

Jan 1, 1969

By Louis D. Huntoon

The Hammond Mining and Metallurgical Laboratory is the gift of Prof. John Hays Hammond to the Sheffield Scientific School of Yale University. Professor Hammond was graduated from this school in the class of 1876, and has always shown great Merest in its welfare and progress. In 1903, he offered to build and equip for it a mining and metallurgical laboratory. This offer was gratefully accepted by the trustees; and in October of the same year the architect, W. Gedney Beatty, and I were employed to draw up plans for the building, which is the largest of its kind in this country. The Treasurer's report shows the total gift of Professor Hammond, including land, building, and equipment, to have been $128,741.53. This does not include $5,000 given by Professor Hammond to defray incidental expenses. The detailed cost of the machinery and installation, included in the above sum, is as follows: Macbinery,.......$9,846.00 Pipe and fittings,......925.05 Hangers, shafting, pulleys, belts, etc.,.. Steel-work, tanks, launders, etc.,...272.19 Screens for sizing ore,.....411.37 Lumber,.......1,896.36 General Supplies : Hardware,......$135.96 Tools,.......263.66 Paints,.......204.63 Electric and incidental,.... 439.57 ----------1,043.82 Machine-shop material, . 259.44 Labor,.. 722.29 ----------981.73

Jan 1, 1910

By M. L. Rudee, R. A. Huggins

Samples of iron containing nitrogen or carbon have been given treatments similar to those used in cold-work peak (CWP) measurements and examined by transmission electron microscopy. It was observed that the unusual and nonreproducible behavior of the carbon CWP can be explained by a strong tendency for carbon to form grain boundary precipitates at temperatures below those used for CWP measurements. These precipitates dissolved at the temperatures used in the CWP measurements. There was no evidence for nitrogen precipitation at grain boundaries. There was no indication of precipitation along dislocations in either carburized or nitrided samples given treatments similar to those of CWP measurements. Although it is possible that subelectron-microscopic clustering had occurred, this observation supports the theories of the CWP that are based on continuous atmospheres rather than on individual precipitates. In an earlier paper,' the present authors developed a new distribution function to predict the occupation of sites for interstitial impurity atoms around a dislocation. When this distribution was applied to the case of carbon and nitrogen in iron, it predicted that, if the temperature dependence of the concentration of solute atoms in the matrix was controlled by the presence of equilibrium carbide or nitride precipitates, the tendency for nitrogen to segregate to dislocations would be greater than that for carbon even though their binding energies to dislocations are identical. The cold-work internal-friction peak (CWP) is considered by most authors to be produced by the interaction of interstitial impurities with dislocations. Many investigators have studied the CWP in iron containing carbon and nitrogen and have observed a significant difference between its behavior in the two cases. In this paper a series of experiments will be reported that were initiated to determine whether the application of the new distribution function would explain the observed differences between the carbon and nitrogen CWP. Although it was found that the distribution function, pev se, did not explain the differences, the differences became clear, and some insight into the mechanism of the CWP was realized. Before reporting the present experiments, the literature pertaining to the differences between the carbon and nitrogen CWP in iron and the various mechanisms proposed for the CWP will be reviewed. LITERATURE REVIEW Snoek2 first observed the CWP in iron specimens containing nitrogen, but also reported a weak and unreliable peak in carburized samples. Later, Ke3 established that the CWP height was proportional to the degree of deformation. The presence of nitrogen alone would produce a peak of the same size as found in a sample containing both nitrogen and carbon, and KG concluded that the CWP was caused by nitrogen. In a discussion of G's paper it was reported that Dijkstra had investigated the CWP in samples that contained only carbon. He found it to be much smaller than the nitrogen peak and "unstable". KG et al.4 charged specimens of iron with both carbon and nitrogen. They observed that the carbon CWP was much smaller than that observed in nitrided samples, but that aging at 300°C caused the carbon peak to increase. A similar treatment produced no change in a nitrogen peak. Annealing at higher temperatures caused the height of the CWP in both the nitrogen and carbon samples to decrease. This behavior was also observed by Kamber et al. 5 who found that the activation energy for the annealing of the CWP was identical with the activation energy for the self-diffusion of iron. They concluded that the annihilation of dislocations by climb caused the reduction in the CWP height. Kamber et al. studied the "unstable" carbon peak in detail. They measured both the Snoek and CWP during various aging treatments. In carburized samples, aging at 100°C caused the Snoek peak to disappear, although the CWP peak remained small. However, a subsequent treatment for 5 hr at 240°C caused the CWP to reach a maximum. They proposed that an additional location for the carbon, other than whatever site produced the CWP, is present. In nitrided samples the CWP was completely developed as soon as a measurement was made; additional sites are not present. No explanation of either the additional site or the difference in the behavior of carbon and nitrogen was offered. petarra5 performed a systematic study of the effect of composition on the CWP. Using three kinds of "pure" iron, he showed that there was a residual CWP when the carbon and nitrogen concentrations had been reduced to less than that detectable by Snoek-peak measurements. He observed the same general annealing behavior and composition dependence as previous investigators, with the following exceptions. On first measuring the carbon CWP, it was found to be identical with the residual peak, and essentially independent of the carbon content. If the CWP was measured a second time in the same sample, it increased in size, but was still only about one-fourth the size of a CWP in a sample of the same iron nitrided to the same composition. On the other hand, a series of annealing experiments showed that the nitrogen CWP was not al-

Jan 1, 1967

By James C. Word, R. M. McLouski

This paper will describe the development and application of large-scale integration techniques employed in the fabrication of a germanium multielement array. The array consists of 100 by 228 PNP bipolar transistors fabricated on 5 mi1 centers. Back-biased p-n junction techniques are used for electrical isolation of the individual elements. The end use of the array is a high resolution, large area IR sensor. The monolithic array is fabricated in 1 ohm-cm p-type germanium epitaxially deposited on 6 ohm-cm n-type substrate. Epitaxy was accomplished through the hydrogen reduction of germanium te trachloride. Di-borane was used as the dopant. Base regions are achieved by the diffusion of arsenic from doped oxide or arsine sources. Oxide-masking of the arsenic im-pzlvity was achieved by the chemical deposition of a boron doped glass. The emitter is formed by an aluminum alloy diffusion technique. Vacuum deposited aluminum is used for the emitter, interconnections, and for the contact and bonding pads. ALTHOUGH a great volume of literature pertaining to the development of large scale integration techniques (LSI) has been published for silicon and in particular silicon imaging applications,' to date only a small number of similar devices have been constructed using germanium technology.' Since the physical and chemical properties of germanium are vastly different from those of silicon, the fabrication technology for integrated structures in germanium is also different from that of silicon. In particular germanium does not possess a stable oxide as can be grown on silicon by heating in an oxidizing ambient for masking of dopants and passivation. This paper describes the application of germanium LSI techniques employed in the fabrication of a multielement infrared sensor array. The array is used in a high resolution, large area infrared sensor for operation in the 0.8- to 1.5-u spectral range. Back biased p-n junction techniques are used for electrical isolation of individual elements. Discrete germanium devices have been fabricated routinely for some time. However, mainly due to the lack of a suitable mask for selective doping and the high current leakages inherent in germanium p-n isolation, few monolithic germanium structures have been constructed. THE INFRARED MOSAIC A cross-sectional view of the array is shown in Fig. 1. The monolithic structure consists of 12,800 PNP transistor elements in a 100 by 128 matrix fab- ricated on 5 mil centers. The emitters of each line of transistors are connected together using aluminum interconnects while the strip collectors are connected together in series at right angles to the emitter lines. The selection of this structure is dictated by the readout technique involved. Access to each element transistor is obtained by applying a bias voltage to a particular collector strip and separately interrogating each emitter row. A charge storage, i.e., an integration mode is used for reading out this particular array Construction techniques available for use with germanium do not include a selective p-type diffusion capability for surface concentrations greater than 10" per cu cm and junction depths greater than about 10 u. This fact limits the type of structure that may be used. Therefore, an array of PNP transistors that did not employ p-type diffusions was chosen. The structure was fabricated by growing a 1 ohm-cm p-type epitaxial layer on a carefully prepared 6 ohm-cm n-type substrate. N-type dopants were used for the isolation and base diffusions and alloyed aluminum was used to form the emitter junctions. The array was then completed by evaporation of aluminum interconnections and contact pads. SUBSTRATE AND SUBSTRATE PREPARATION Germanium substrates of (111) orientation grown by both Czochralski and zone leveling techniques were utilized for mosaic fabrication. Czochralski substrates were preferred because of the lower dislocation densities available in this type of material. Dislocation densities for the Czochralski material were typically less than 3000 per sq cm, while those for the zone leveled material were typically less than 5000 per sq cm. All substrates were uncompensated to minimize thermal conversion problems in subsequent epitaxial and diffusion processing. Both in-house and vendor polished wafers were used. The in-house polishing technique employed consisted of an initial gross chemical etch in CP4 to remove saw damage from both surfaces. This was followed by a chemical-mechanical polishing operation of one side of the wafer. The chemical-mechanical polishing solution used was Lustrox 1000 (Tizon Chemical Co.), and consists of zirconium dioxide, sodium hypochlorite, water and a surfactant. The wafer thickness before and after polishing was typically 0.020 and 0.010 in, respectively. THERMAL CONVERSION The problem of thermal conversion of both the substrate and epitaxial layer was particularly acute because of the relatively low carrier concentrations employed in both regions. This problem has been encountered by other workers in the past.3 Without special treatment before epitaxial growth substrate conversion (n-type to p-type) and changes in the re-

Jan 1, 1970

By K. Brack, G. H. Schwuttke

Annealing properties of subszerface amorphous lavers produced through high-energy ion implantation in silicon are studied. The buried layers are produced through the implantation of ions (nitrogen), ranging in energy from 1.5 to 2 mev. X-ray interference patterns, transmission electron microscopy, and resistivity profiling are used to study the annealing characteristics of the ion damage. The annealing experiments indicate a low temperature (below 700°C) and a high temperature (above 700°C) region. Significant changes occur in the amorphous layer during the high-temperature anneal. Such changes are corre-lated with the re crystallization of the amorphous silicon and the formation of subsurface (buried) silicon-nitride films. TODAY'S main problems in the field of ion implantation are related to the accurate determination and prediction of 1) the distribution profiles of implanted ions, 2) the lattice sites occupied by the implanted ions, 3) the lattice damage produced through ion implantation, and 4) the annealing characteristics of damage centers in the lattice. This paper reports investigations concerned with the problems listed under 3) and 4). EXPERIMENTAL Our investigations cover the energy range of incident ions from 100 to 300 mev and from 1 to 2.5 mev. The emphasis of this study is on the energy range from 1.5 to 2 mev. The experiments are conducted with single charged nitrogen ions. To implant the ions a van de Graaff generator is used as described by Roosild et al.1 Accordingly, a gas containing the desired ion specie is passed through a thermome-chanical leak into a radio frequency activated source. The positive ions are driven into the van de Graaff with the help of a variable voltage probe. Emerging from the accelerator the ions drift into a magnetic analyzing system and here the desired ion specie is bent 90 deg into the exit port. The ion beam leaving the analyzer is defocused and drifts down a 4-ft long tube to hit the silicon target. At this position the 20 pamp ion beam has a circular cross-section of 2.1 cm. N2 is used as a source gas for nitrogen ions. The implantation target is silicon with zero dislocation density, 2 ohm-cm resistivity, (111) orientation, mechanically-chemically polished, and 1 mm thick. The target is mounted on a water-cooled heat sink and kept at room temperature. A fluence of 1015 to 1016 ions per sq cm is used. RESULTS 1) Silicon Perfection after Bombardment. High-energy ion bombardment of silicon has some striking effects on lattice perfection. Some results were reported in detail previously at the Santa Fe conference2 and are here briefly summarized for the benefit of the experiments described in the following. 1.1) Identification of Surface Films on Silicon. After bombardment all samples are found to be coated with surface films. The films on the silicon surface vary in thickness and color; they can be transparent, slightly brown, or opaque. The films are thicker and darker in the high-intensity area of the beam and they delineate the bombarded surface area of the crystal. The films produce electron diffraction patterns characteristic of carbon and of SiO2. Carbon is predominant. The presence of carbon in these films was confirmed by use of the electron microprobe. Formation of the films occurs independently of the ions used and is attributed to a contaminated vacuum of the high-voltage machine. The carbon is most likely the product of the pump oil which is cracked and polymerized under ion impact. The films stick tenaciously to the silicon surface and burn off in a low-temperature Bunsen flame. 1.2) Mechanical Perfection of the Silicon Surface. The mechanical perfection of the bombarded silicon surface was investigated through optical microscopy, electron microscopy in which the replica technique is used, and optical interferometry. No mechanical damage of the surface was visible after bombardment. However, if a bombarded sample is soaked for several minutes in hydrofluoric acid (HF), gas bubbles may develop in certain spots of the silicon surface. It is also noted that in these areas the surface film starts to peel off. Relatively large patches of film come off if the sample is soaked in HF during ultrasonic agitation. After HF treatment, pits may be present on the silicon surface. The pit dimensions are estimated to be as large as 50 µ. The pits appear in the region of most intense irradiation. 1.3) Lattice Perfection After Bombardment. No lattice damage is found on the silicon surface. Electron transmission micrographs and selected area diffraction patterns of the surface show no difference before and after bombardment. Measured approximately 2 µm down from the surface, the silicon lattice throughout this depth is of good perfection. Well-defined Laue spots and Kikuchi lines are obtained from the surface as well as from the indicated area below the surface. However, some radiation damage is dispersed in this top layer. A sharp boundary line separates this surface layer from a highly damaged layer which extends further downward into the silicon. Typical of this

Jan 1, 1970

By N. Mungan

Laboratory imbibition and displacement experiments were performed using crude oil and cores drilled with water and preserved under anaerobic conditions. The purpose of these tests was to determine reservoir rock wettability and to find out if more oil could be recovered by use of NaOH solution than by conventional waterflooding. The preserved cores were found to be oil-wet. Contrary to work in the literature, these cores changed to water-wet upon contact with air. After exposure to air for a week, the cores yielded more oil by waterflooding than when preserved under exclusion of air. At reservoir temperature of 160F, flooding the preserved cores with 0.5N NaOH solution recovered more oil than an ordinary wa-terflood, and additional oil when following a waterflood. When the caustic solution was used from the beginning, all the extra oil was obtained before breakthrough; when the caustic followed a conventional waterflood, the extra oil was produced in the form of an oil bank ahead of the injected caustic. The increase in oil recovery resulted from wettability reversal. Also, use of caustic reduced the volume of injection required to flood out the cores. At room temperature, however, the caustic solution did not reverse the wettability and gave no additional oil recovery. Cores which had become water-wet by air exposure or caustic flooding were restored to their original oil-wet state when saturated with crude oil and allowed to equcilibrate at reservoir temperature for two weeks. Therefore, in the absence of preserved cores, it may be possible to restore weathered cores to their original wettability for use in laboratory floods. INTRODUCTION Waterflooding has been in use since 1865, and is by far the simplest of secondary recovery methods. Unfortunately, most waterfloods are inefficient in recovering oil, often leaving half or more of the original oil in place un-recovered. The low oil recovery generally results from low sweep efficiency and low displacement efficiency. Consequently, to increase oil recovery by waterflooding, sweep and displacement efficiencies should be improved. Sweep efficiency is primarily affected by reservoir heterogeneities and mobility ratio, while displacement efficiency is affected by the capillary forces between fluids and rock surfaces. For petroleum reservoirs, the capillary forces are expressed in terms of interfacial tension and wettability. If oil recovery is to be improved significantly in water- flooding, the capillary forces holding the oil in the raervoir porous matrix must be reduced or eliminated. One way to reduce capillary forces is to inject commercial surfactants ahead of the injection water into the reservoir. Laboratory tests of this method have shown no promise of an economical process yet, and no increase in oil recovery was obtained in the field trials which have been reported. Work is continuing in many companies to find surface-active agents which, in workable concentrations, can yield substantial added oil recovery. Another way to change capillary forces operating in petroleum reservoirs is by changing the pH of the injected water. Wagner et al.' showed that change in the pH sometimes activates the surface-active materials natural to some crudes and brings about gross wettability change. Since pH alteration can be obtained with cheap chemicals, such as hydrochloric acid or sodium hydroxide, the process shows promise of being economical in a field application. Pan American Oil Corp. reported oil recovery by use of caustic solution from a flooded-out reservoir.' Their test, conducted at a small additional cost, yielded results which were so sufficiently favorable and encouraging that the wettability reversal flood was expanded to portions of the field not previously flooded.13 It is important to bear in mind that changes in the pH of the water not only can reverse wettability but also can lower the interfacial tension between water and crude oil. Reisberg and Doscher4 have studied the pH dependency of the interfacial tension of Venture crude using sodium hydroxide solutions of various concentrations. Their data show that the interfacial tension was lowered from 23.0 to 0.02 dynes/cm by increasing the NaOH concentration from 0.005 to 0.5 per cent by weight. Thus, the use of NaOH may lead to additional oil recovery due to both wettability reversal and lowering of interfacial tension. Whether alteration of pH results in wettability reversal from oil-wet to water-wet and increases oil recovery depends on wetting properties of the reservoir rock and the crude. This necessitates delicate laboratory experiments, with suitable core and fluid samples from a field. Although many investigators have studied wettability reversal floods in the laboratory,1,2,5,6 these studies have been carried out with synthetic porous media, refined laboratory fluids and surface-active chemicals to simulate the process. The study presented in this paper is the first time that wettability reversal by pH alteration has been accomolished in laboratory core floods using carefully preserved natural cores, live crude and with experiments performed at reservoir pressure and temperature.

Jan 1, 1967

By T. B. Massalski, H. W. King

An hcp phase may be induced by cold working the ß&apos; phase of the Ag-Zn system. This phase reverts to ß&apos; on subsequent aging. No phase change occurs on cold working the o phase, but ß&apos; is formed when the deformed alloy is subsequently aged at room temperature. It is concluded that for alloys near 50 at pct Zn the ordered bcc ß&apos; phase is the equilibrium structure at room temperature. WhEN the disordered bcc ß phase of the Ag-Zn system is cooled to temperatures below 258o to 274oC, it transforms to a complex hexagonal phase <o.1,2 The nature of the o ß=o transformation has been the subject of some discussion,2&apos;3 and the structure of o has been described in detail.&apos; The latter phase appears to be stable on aging at room temperature but decomposes following cold work. When alloys containing approximately 50 at. pct Zn are rapidly quenched from the 0 phase field, the ß ? o transformation may be suppressed; but the ß phase undergoes an ordering reaction (ß ? ß&apos;). The ß&apos; structure may also be obtained as a result of cold working and aging at room temperature.4 Kitchingman, Hall, and Buckley4 have suggested that the decomposition of (o following cold work proceeds in two stages, (o ? ß followed by ß ? ß&apos;, but did not confirm this by experiment. When the ordered &apos; phases in the systems Cu-Zn5 and Ag-Cd6 are cold worked, they become unstable and transform to a close-packed hexagonal phase (( ) indicating that when order is destroyed in a ß&apos; structure the close-packed hexagonal phase may in many cases be more stable. It thus became of interest to study more closely the effect of cold work and annealing on the stability of both the ß&apos; and o phases in a Ag-50 at. pct Zn alloy. Predetermined weights of spectroscopically-pure Ag and Zn, supplied by Johnson and Matthey, were melted and cast under 1/2 atm of He in transparent vycor tubing. The ingot was homogenized for 1 week at 630°C and quenched into iced brine. Since mechanical polishing was found to induce a phase change, sections were first polished at room temperature, sealed in tubes under 1/2 atm of He, reannealed for several days at 630o or 200°C and then quenched into iced brine. Sections of the alloy thus prepared were found to be homogeneous when examined under the microscope. The sample quenched from 630°C (ß -phase region) was pink in color, whereas the sample quenched from 200°C (o-phase region) was silver. The latter sample showed the characteristic hexagonal anisotropy when examined under polarized light. Filings of the alloy were examined at room temperature, after various heat treatments, using an RCA-Siemens Crystalloflex IV diffractometer with filtered CuKa radiation. The X-ray reflections from flat powder specimens quenched from 630o and 200°C and sieved through 230 mesh were recorded graphically at a scanning speed of 1/2 deg per min. The resultant patterns are shown in Figs. 1(a) and 1(b) and may be identified as those of the 8&apos; and <02 structures respectively. The lattice parameter of the ß&apos; phase was determined as 3.1566Å.* This value compares very well withthatto be expected for a 50 at. pct Zn alloy from the data of Owen and Edmunds? and indicates that no loss of Zn occurred during casting. In order to study the effect of cold work upon the ß&apos; and o phases, filings made at room temperature and sieved through 230 mesh were mounted immediately in the diffractometer-i.e., without a strain-relief anneal. Changes in structure on subsequent aging were followed by scanning repeatedly over the regions of the low index reflections of the ß&apos; and o structures-i.e. , 28 from 35 to 44 deg. Immediately after filing the 8&apos; specimen, additional diffraction peaks were observed in the low-index region of the pattern, as shown in Fig. 1(c). These additional peaks do not coincide with those of the o structure, Fig. l(b), but may be indexed as the (10.0), (00.2), and (10.1) reflections of an hcp phase (<) with nearly ideal axial ratio. However, this hexagonal phase appears to be very unstable since within a very short time at room temperature it reverts back to the ordered ß&apos; phase, the reversion being complete within seven hours. The 5 ? ß&apos; reversion reaction is, therefore, very similar to those already reported in Cu-Zn5 and Ag-Cd6 7&apos;alloys. The action of filing caused the deformed surface of the originally pink ingot to become silver in color, indi-cating that the ( phase possesses similar reflecting properties to the o phase. Hence, the subsequent

Jan 1, 1962

By M. E. Wadsworth, K. C. Bowles, H. E. Flanders, R. M. Nadkarni, C. E. Jelden

The kinetics of precipitation of copper on iron of various purity were carried out under controlled conditions. The rate of reduction has been correlated with such parameters as copper and hydrogen ion concentration, geometric factors, flow rate, and temperature. The character of the precipitated copper as a function of flow conditions and rate of PreciPitation has been observed under a variety of conditions. ThE precipitation of copper in solution by cementation on a more electropositive metal has been known for many years. Basile valentine&apos; who wrote Currus Triumphalis Antimonii about 1500, refers to this method for extraction of copper. Paracelsus the Great2 who was born about 1493 cites the use of iron to prepare Venus (copper) by the "rustics of Hungary" in the "Book Concerning the Tincture of the Philosophers". Agricola3 in his work on minerals (1546) tells of a peculiar water which is drawn from a shaft near Schmölnitz in Hungary, that erodes iron and turns it into copper. In 1670, a concession is recorded4 as having been granted for the recovery of copper from the mine waters at Rio Tinto in Spain, presumably by precipitation with iron. Much has been published in recent literature on the recovery of copper by cementation, the majority of the articles being on plant practice.5-24 The rest include articles on investigation of the variables involved25-28 and a review of hydrometallurgical copper extraction methods." This literature has established: a) The three principal reactions in the cementation of copper are Cu + Fe — Fe+4 +Cu [ 11 One pound of copper is precipitated by 0.88 lb of iron stoichiometrically. In actual practice about 1.5 to 2.5 lb of iron are consumed. 2Fe+3 + Fe — 3Fe+2 [21 Fe +2H&apos;-Fe+2 + H2 [3] Reactions [2] and [3] are responsible for the consumption of excess iron. Wartman and Roberson&apos;28 have established that Reactions [ I] and [2] are concurrent and much faster than Reaction [3]. b) Acidity control is important in the control of hydrolysis and the excessive consumption of iron. he commercial workable range is approximately from pH = 1.8 to 3." c) Iron consumption is closely related to the amount of ferric iron in solution. Jacobi" reports that, by leaving the pregnant mine waters in contact wi th lump pyrrhotite (Fe7S8) for 3 hr, all the iron was reduced to the bivalent condition and scrap iron consumption was cut to 1.25 lb scrap per pound of copper precipitated. He also reported that SO2 has been used successfully to reduce ferric iron to the ferrous state. d) The ideal precipitant is one that offers a large exposed area and is relatively free of rust. e) High velocities and agitation show a beneficial effect upon the rate of precipitation, as it tends to displace the layer of barren solution adjacent to the iron and also dislodges hydrogen bubbles and precipitated copper to expose new surfaces. Little work, however, has been published on the reaction kinetics of copper precipitation on iron. Cent-nerszwer and Heller20 investigated the precipitation of metallic cations in solutions on zinc plates. They found the cementation reaction to be a first-order reaction. The rate constant was independent of stirring for high stirring rates and they concluded that the rate is governed by a diffusional process at low stirring speeds and by a "chemical" process at higher stirring speeds where the rate reaches a constant value. This conclusion has been challenged by King and Burger30 who could not find any region where the rate was independent of the stirring speed, although the rate constant they had obtained for high stirring speed was greater than the maximum value of the rate constant reported by Centnerszwer and Heller (by a factor of six). King and Burger, therefore, concluded that the rate of displacement of copper was controlled only by diffusion. Cementation of various cations on zinc has been summarized by Engfelder.31 APPARATUS A three-necked distillation flask of 2 000-mm capacity was used as a reaction vessel. A pipet of 10-mm capacity was introduced through one of- the side necks, the sample of sheet iron, mounted in a rigid sample holder, through the other, the stirrer being in the middle as shown in Fig. 1. The whole assembly was immersed in a constant-temperature bath. The stirrer was always placed at the same depth in the solution. EXPERIMENTAL PROCEDURE Reagent-grade cupric sulfate (J. T. Baker Chemical Co., N.J.) was used to make up a stock solution containing 10 g of copper per liter which was then diluted to various concentrations as required. Experimental data were obtained by measuring the amount of copper and iron ions in solution at successive time intervals. The initial volume of the solution was always 2000 ml, 10-ml aliquots being removed each time for chemical analysis. Because the total volume change of the solution was less than 10 pct, no correction was used for solution volume change. Nitrogen was bubbled through the solution before and

Jan 1, 1968

By R. R. Judd, H. W. Paxton

The rate of dissolution of cementite was studied in three low-carbon materials: a zone-refined Fe-C alloy, an Fe-0.5pct Mn-C alloy, and a commercial low-carbon steel. The materials were spheroidized, ad then held isothermally at temperatures above the Al. The isothermal anneal was interrupted periodically by a water quench and the specimens were analyzed by quantitative metallography for the amount of aus-tenite formed during the anneal. The results of this study were compared with an analytical model for the process, which assumes that carbon diffusion in aus-tenite is the rate-controlling step for the cementite dissolution process. The correlation between the model and the experimental data is excellent for the zone-refined Fe-C alloys; however, the Fe-0.5 pct Mn-C alloys and the commercial steel deviate from the calculated model. This deviation is thought to be a result of manganese segregation between the carbide and the matrix. The rate of nucleation of austenite at carbide interfaces was reduced by the manganese addition and enhanced by the presence of ferrite-ferrite grain boundaries. PREVIOUS investigations of the nucleation and growth of austenite from ferrite-carbide aggregates are not entirely satisfying for at least one of several reasons. The most prevalent of these is a lack of quantitative data. Engineering studies have been run on many steels with little control over important parameters such as composition and initial aggregate structure. The data obtained are valid only for material with identical chemistry and thermal history. A more informative approach to the problem of aus-tenitization would be to determine the mechanism that controls the rate of solution of carbide in austenite and how it is modified by alloying elements. This information could then be used to calculate an austeniti-zation rate for any material, provided its composition and structure are known. The object of the present work is to establish the rate-controlling step for cementite dissolution in Fe-C austenite and to investigate the modification of this rate by small manganese additions. The composition and structure of the material used were carefully controlled and all measurements were designed to allow a quantitative analysis of the kinetic process that controls the austenitization rate. A MODEL FOR DISSOLUTION OF CEMENTITE Cementite dissolution has been analyzed mathematically by a model that approximates the material used in the experiments. This model postulates a regular ar-array of identical cementite spheroids with 4 C( diam, embedded in a grain boundary- free ferrite matrix. The analysis provides a detailed description of the dissolution of one carbide spheroid and a generalization of the solution by summation over all the carbides in the material. The carbides may be isolated by defining identical, space-filling cells of ferrite around them. If the cell dimensions are greater than the diameter of the austenite sphere resulting from complete dissolution of the carbide, and no interaction (through diffusion in ferrite) takes place between cells during the dissolution process, the model need concern only one cell, since the solution in each cell is identical. In the experimental material, the dimensions of the cell, the carbide, and the final austenite sphere are approximately 24, 4, and 8 p, respectively; use of the single cell is therefore justified. The experimental observations are made on the austenite nodules that form around each carbide during the dissolution process. The model concerns the growth of these austenite nodules. The attendant shrinking of the carbide can be obtained from the same analysis by an extension of the calculations. Several a priori assumptions are necessary to make the analysis of the growth problem tractable. They are: 1) carbon diffusion through the austenite nodule is the rate-controlling process; 2) local equilibrium exists at all interfaces, 3) the austenite nucleus that forms on each carbide instantaneously envelops the carbide; 4) during the austenite growth process, the diffusion flux of carbon in ferrite is insignificant; 5) a quasi-steady state exists in the austenite concentration field; that is, at any instant during the dissolution process, the austenite carbon concentration gradient closely approximates that for a steady-state solution; and 6) the effects of capillarity on the dissolution rate of the carbides can be neglected. Referring to Fig. 1, a mass balance at the y-a interface for an infinitesimal boundary movement gives: Where rb is the outer radius of the austenite shell, C1 and C are carbon concentrations at the interface in austenite and ferrite, respectively, see Fig. 2, is the diffusion coefficient of carbon in austenite for the concentration of carbon at the interface, and t is time. The fifth assumption permits the austenite carbon concentration to be approximated by the Laplace solution for the spherical case. Therefore, where C(Y) is the carbon concentration at r, and A and B are constants. Local interfacial equilibrium fixes the boundary conditions for the diffusion problem. They are:

Jan 1, 1969