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By R. J. Wysor

CHARLES H. RICH, Conshohocken, Pa. (communication to the Secretary*).-Mr. Wysor has certainly covered his subject in the most thorough and able manner and his paper will no doubt result in enlarged effort toward the conservation of this important byproduct. Not all furnace burdens are as rich in alkalies as those noted by Mr. Wysor. In our own experience we have never gone into any extended examination of the materials entering the furnace burdens, but have made a number of determinations of the water-soluble alkalies of our flue and boiler dust and found maximum of about 4 1/2 per cent. K20-too small for profitable reclamation. We have, however, frequently encountered the smoky gas described by Mr. Wysor. Such gas carries heavy fume, and buds with a fitful flame difficult to maintain. So pronounced was the inhibitory effect of the fume that, in extreme cases, the flame of a lighted match was extinguished by the current of gas and it was found impossible to conduct calorimeter tests without preliminary washing of the gas. When the gas was led through a washer filled with distilled water and pieces of coke, the fume was absorbed and the gas burned without difficulty. Careful analyses conducted on the water solution from the washer showed cyanides in increasing amounts in proportion to the difficulty experienced in burning the gas. We, note Mr. Wysor's statement that he has never found evidence of cyanides in their gas, ascribing the difficulty of burning such gas to the presence of chlorides. Our determinations were conducted in such manner as to preclude possibility of interference by chlorine.

Jan 3, 1917

By R. S. Dean

True careful work of Gross and Zimmerley1 has established the fact that the energy actually used in grinding is proportional to the new sur-face produced. This confirmation of Rittinger's law was made by crush-ing quartz in a frictionless drop-weight machine and determining the surface of the quartz by its rate of solution in hydrofluoric acid. The details of this procedure have been described adequately elsewhere and need not be repeated here. The resultant data furnish the only available basis for comparing accurately the efficiency of grinding machines. This method is so cumbersome experimentally that it has been little used. As an alternative all sorts of approximations have been proposed. The best of these is complete size analysis by sieving and elutria-tion. Such procedure is very lengthy and difficult to carry out accurately. Furthermore, any sizing method becomes very inaccurate for determining surface with very fine sizes where the ratio of surface to volume becomes very large. To avoid the lengthy and difficult technique of elutriation it has been proposed to estimate the size distribution below 200 mesh from various probability formulas. Such a procedure is at best an engi-neering approximation; at worst it is a mere guess. Some time ago Dr. V. H. Gottschalk2 found that the coercive forces of magnetite powders were directly proportional to the surface area, regard-less of size distribution. It was at once apparent that this furnished a method for determining grinding efficiency quickly and accurately. The only requirement was a single determination of the relation between the work input of the Gross-Zimmerley drop-weight machine and the coercive force of the resultant crushed magnetite.

Jan 1, 1936

By Adolf Gurlt

It has long been known that minute quantities of foreign substances, when alloyed with steel, are capable of materially altering its physical properties. Thus, half a century ago, Faraday and Stodart, in England, discovered in the famous Indian steel, known as " wootz," small quantities of aluminum, from 0.0728 to 0.693 per cent., and attributed its extraordinarily good quality to the presence of such minute quantities of that metal. Since aluminum is now produced by electrolytic means on a large scale and at low cost, its addition to cast-steel has been frequently recommended of late. Chromium was alloyed with steel fifty years ago by the celebrated French metallurgist, Berthier, of Paris, and has recently been successfully applied to the same purpose by Holtzer, of Terre-Noire. In 1860 titanium was alloyed with crucible steel by Robert Mushet, of Coleford, the alloy containing up to 0.50 per cent. of titanium, which was extracted from Norwegian ilmenite. The titanium-steel was much vaunted by him for its excellent qualities. Rhodium, a very rare metal of the platinum series, was maintained by Berthier to improve steel materially in strength and hardness. Manganese has always been held by Sheffield steel-melters to provide steel with excellent qualities, and this influence was quite recently investigated by H. M. Howe and L. Campredon. Nickel was tried as an addition by Berthier, not to speak of gold, silver and platinum ; and nickel-steel has recently been brought into prominence by J. Riley and others, who recommend it for its great strength and toughness, particularly as material for armor-plates.

Jan 1, 1894

"Coulter's Rainbow and Crooked Falls are situated about five miles below the City of Great Falls. Coulter's, the first of the series in the course of the river, is unimportant and has been submerged by the Rainbow dam. Next below Coulter's is the Rainbow Falls, 47 feet in height. Following Rainbow Falls is the Crooked Falls, 21 feet in height. The power developed at this point is such that the one clam, power house and tail-race utilize the power from all three of the above falls.The development at Rainbow was started October, 1908, and completed July, 1910. It has a total capacity of 21,000 k-w. in generators, and 36,000 h-p. in waterwheels, and operates at 105 foot head. The general scheme of development is typical of what may be called standard practice in the west for plants of medium head, and consists of a low diverting clam, a double pipe line feeding into a balancing reservoir near the plant, and individual pen-stocks supplying the turbines from this reservoir.The dam is a rock-filled crib structure 1,146 feet long and 29 feet high, the up-stream side of which slopes at such an angle that the stability of the clam is assured even under the greatest floods, the weight of the water acting to hold it down, so that the higher the flood the greater the stability. The down-stream side is also sloping and tapers off into a long apron so designed as to take care of any overflow which may occur without shock or commotion. The clam is founded on solid rock throughout its entire length."

Jan 1, 1913

Steps were taken for a permanent organization of the scientific and technical employees of the Government at their mass meeting on May 8. This was the result of an informal meeting on Apr. 23 of thirty representative Government scientists and technical men who organized the preliminary committee and called the mass meeting. This subject has been widely discussed during the last year and was brought acutely to the fore by the work of the Joint Congressional Reclassification Commission, because that Commission has stated that it wished to deal with employees only through organizations. Rodney H. True of the Department of Agriculture was Acting Chairman. He pointed out that the principal advantages that were expected to be derived from such an organization were: (1) Improvement of conditions and facilities for more effective scientific and technical work; (2) adequate presentation of the needs. and results of such work to the public and to legislative and administrative officers; (3) -greater freedom in both official and non-official activities; (4) just and reasonable salaries based on service performed and the economic and social conditions which prevail; (5) greater public recognition of the aims and purposes of research; (6) advancement of science and technology as an essential element of national life. Three plans of organization were offered to the meeting, which covered the fundamental principles which could be utilized by these Government employees. The first plan would have permitted the new organization to work only through existing scientific organizations. This is the plan that scientific and technical Government employees in England have adopted and an outline of the English plan was read to the meeting.

Jan 6, 1919

AT the meeting of January 28 which was held too late to be reported in the February MINING AND METAL-LURGY, Messrs. Taylor, Barron, Bassett, DeGolyer, Hutchinson, Norris, Rand, Reynders, Smith, Sweetser and Callow were present. Aside from routine matters, relating to finances and membership,, the Board author-ized establishment of a payroll account and payment by check. It also approved plans for a regional meeting to be, held at Cleveland on April 19 and 20 under the auspices of the Ohio Section and the Iron and Steel Committee. Following a report from the Committee on increase of Membership, Messrs. Barron, Bassett, and Sweetser were appointed as a special committee to con-sider the feasibility of increasing the dues. Mr. Read was made secretary of this Committee. A pleasant feature of the meeting was the presence of past-presi-dent Olcott and the presentation by him to the Institute of an elaborate scrap book, covering the excursion through Mexico made by the Institute in 1901. The meeting was preceded by a dinner at which Scott Turner spoke of the problems of the Bureau of Mines and the large volume of service work for the govern-ment it was now called on to perform. M. L. Requa discussed the need of more exact data covering our national reserve of minerals. E. N. Cooper gave a vivid picture of conditions in Mexico. W. H. Bassett told of the problems before the Institute of Metals, and Zay Jeffries told of the plans for that Division now being formulated. Max W. Ball reinforced what Mr. Requa had said relative to the importance and value of conservation studies as relates to minerals.

Jan 3, 1927

With a mine output as high as 5000 tpd and mill capacity of 7000 tpd, the uranium mining and milling complex owned and operated by Kerr-McGee Nuclear Corp. in the Ambrosia Lake area is the largest in the U.S. and is likely to remain so for some time. Next year, Kerr- McGee expects to have in production another mine in Section 19 of the Ambrosia area-and will begin ore production in 1976 at its new $15-million mine at Church Rock, located northeast of Gallup, N. M., where the company has already completed the shaft work and is in the early stages of project development. Ore from Church Rock will be transported to the company's facilities at Ambrosia Lake for processing. Kerr-McGee's existing eight mines in Ambrosia Lake go to depths of about 800 to 1500 ft to tap the various horizons of uranium-bearing sands in the Westwater Canyon of the Morrison formation.

Jan 8, 1974

By Ernest J. Stocking

ENGINEERS are the key men in our war program today. Upon the technical knowledge and skill of the engineer and upon his administrative and executive abilities rests the entire success for the production of vital materials of the war. Naturally the work load of the engineering examining unit of the U. S. Civil Service Commission has increased greatly since our active participation in the war. At present, over 550 separate requests for certification of eligibles are received by the engineering unit per week. These represent more than a fourth of the total requests received for personnel by the Commission's central office at Washington and represent a recruitment work load of three to four times that carried by the whole Commission previous to January 1940. These requests represent a minimum of a thousand vacancies to be filled each week, while an average week will produce, at present, approximately 1400 vacancies and a weekly maximum may approach well over 2000 vacancies.

Jan 1, 1942

By NEWTON B. KNOX

CHILEAN mining in the public mind is rightly associated with copper. Chuquicamata with its great hill of copper-bearing granodiorite as well as Sewell and Potrerillos with mineralized volcanic necks together can supply a good proportion of the world's normal necessities of that metal. Chile is an extremely long and narrow country, averaging only 109 miles wide. Its eastern frontier is the Andes and it is on the western slopes of these mountains that the great copper deposits have been discovered. West of the Andes a great longitudinal depres sion has permitted accumulation of nitrates and other soluble salts in the arid north; in the north center it is hidden by a series of cross ranges, but in the center a moderate rainfall makes it the country's most important agricultural region. In the south this depression is drowned and gives rise to a series of straits and fiords. This enormous cleft in the earth's crust is separated from the sea by a coast range of moderate elevation which in the south is represented by a series of islands and mushroom-shaped peninsulas

Jan 1, 1945

By W. S. Sanner

Experiments were conducted to determine the quantity and purity of ultraclean anthracite that could be prepared in the laboratory, using conventional separating techniques. A low, a medium, and a high-volatile anthracite were studied. Specific gravity separation followed by grinding, screening, and refloating at lighter specific gravities yielded small quantities of material purified to 1.0% ash, as follows: from low-volatile anthracite, 0.7%; from medium-volatile coal, 1.0%; and from high-volatile coal, 2.3%. The reduction in ash had no appreciable effect on the volatile matter or sulfur content of the coal. The limited quantities of material containing 1.0% or less ash obtainable indicate that if ultraclean coal is desired, a practical approach should include the processing units as an integral part of a convc.ntiona1 dense-media washing plant. Anthracite preparation practices during much of the industry's history were geared to maximum recovery of the larger sizes, pea through egg, which were used in hand-fired, domestic furnaces. Those sizes were cleaned to meet trade requirements, and the smaller sizes were usually higher in ash content. The impression, thus, was that ash content of anthracite always increased as the sizes got smaller. It was presumed that it was impossible to wash the finer sizes to extremely low ash contents. Following World War 11, the classical domestic market began to decline and the finer sizes assumed an increasingly large share of the market. For example, in 1949l 61% of the production was still pea and larger. Fig. l2 shows that -by 1955 these sizes accounted for only 50%, and in 1965, they were only 39% of the total anthracite produced. With the reduction in the market, increased quality was demanded, especially in export markets, and an increasing number of dense-media magnetite washers were installed in new and existing cleaning plants. In 1965, the coarse coal prepared at 59 breakers in the anthracite fields was sampled by the U.S. Bureau of Mines (USBM); approximately 50% of these plants were equipped with dense-media magnetite washers.3 Since 1950, more attention has been focused on the use of finer sizes for numerous industrial uses, including iron-ore sintering, pelletizing, foundry coke-making, cement manufacture, production of calcium carbide, and of carbon electrodes, etc. Most industrial uses require relatively clean anthracite, such as 10 to 11% ash for sintering and foundry coke, 7% for aluminum melting-pot cathode carbon, and 5% for carbide production. Hence, cleaning methods have been improved to the extent that dense-media washers, hydraulic cyclones, and flotation cells have been introduced as fine-coal-cleaning devices. It is now possible to wash the buckwheat, rice, and barley sizes (9116 X 3132-in.) to ash contents as low as 8 to 10% in dense-media devices, but washing the -3132-in. sizes to those limits presents more difficult problems, due mainly to the fineness of the material. This USBM investigation was conducted to determine the amount and purity of ultraclean anthracite that could be prepared in the laboratory, using conventional separating techniques. The goal was to reduce the ash content to a level acceptable for industrial carbon uses, including electrode manufacture, which generally requires an ash content of 1% or less. While low-ash content is of primary importance in selecting industrial carbons, the amounts of other constituents are also important, including iron, silicon, titanium, nickel, vanadium, and sulfur. They were not considered in this work, since their occurrence in deashed anthracite has been studied elsewhere.4 The results of the present investigation were used to design a flowsheet, suggesting a method for producing ultraclean anthracite as part of conventional preparation practice, using dense-media vessels, crushers, pulverizers,

Jan 1, 1970

By T. E. Seidel, A. U. MacRae

The dependence of the electrical and crystalline properties of silicon containing ion implanted boron atoms have been studied as a function of the incident dose, substrate temperature, and annealing tempera-ture. Hall effect studies show that the compensation due to defects is negligible after annealing at and above 500°C for a dose of 1013 ions per sq cm. Steps occur in the isochronal annealing curve for the sheet resistance at 300°C and 800°C and the mechanisms responsible for these steps are discussed. The range of the ions at 150 kev is 3500 * 5001. Electron diffraction studies on samples implanted with 150 ker ions show the existence of damaged (polycrystalline) silicon closer to the surface than the range of the ions. Etching and subsequent annealing of etched and unetched specimens suggest that the poly crystalline silicon is closer to the surface than the bulk of the distribution of ions. THE purpose of this study is to investigate some electrical and crystalline properties of ion implanted boron in silicon. Sheet resistance, Hall measurement, depth distribution by chemical staining, thermal probe and electron diffraction have been used to study the properties of samples implanted in a random direction with ions having energy up to 150 kev. The boron-silicon system has been the subject of considerable study'-7 due to its possible application in the fabrication of electronic devices. The implanted ions produce considerable crystalline damage to the substrate crystal before they lose most of their primary energy and come to rest. Fortunately, most, if not all, of this damage can be removed by subsequent annealing or by holding the substrate at an elevated temperature during the implantation process. Sheet resistivity measurements of the p-type layers produced by boron implantation into room-temperature silicon, reveal that the annealing occurs in a two-step process: the first occurring at -300°C and the second at -800°C.' Electron-microscope and low-angle electron diffraction studies of this damaged material indicate that the bombarding ions produce an amorphous silicon region about the trajectory of each ion.' At high doses, these damaged regions overlap and an amorphous surface layer results. Furthermore, the 800°C annealing step, appears to be associated with the elimination of this gross damage. The depth distribution of the as-implanted and also the annealed samples have been studied by an angle lap and staining technique as well as by Hall measurements.3-7 We find the experimentally determined ranges of the boron are less than those calculated by the Lindhard-Scharff-Schiott theorys (hereafter referred to as the LSS theory). Our results are in essential agreement with pre- vious results. In addition, we have made Hall measurements on samples bombarded with a low dose (2 x 1013 ions per sq cm) to minimize impurity banding effects, and find that deep ionized levels influence the carrier concentration and room-temperature hole mobility until the sample is annealed at temperatures above 500°C. Above this temperature, the data corresponds to that obtained when silicon is doped with boron by conventional techniques. We have also made a depth distribution determination of the crystalline damage due to the implanted boron by using glancing angle electron diffraction techniques. It was found that the gross damage depth distribution of heavily implanted samples is closer to the surface than the depth distribution of the electrically active boron. By removing this gross damage, without affecting the distribution of the implanted boron, we have determined that the 800°C annealing stage is not exclusively due to the improvement in the crystalline perfection of the amorphous material but also appears to be associated with the annealing of some point defects. These results and their relation to previous results are discussed in the following sections. IMPLANTATIONS Boron ions were implanted into silicon samples using an accelerator capable of operating from 10 to 150

Jan 1, 1970

By T. G. Nilan

Steels containing 0.4 and 0.8 pet C have been transformed isothermally at pressures up to 34 kbuv. Decomposilion mechanisms are so intimately related to phase equilibvia that, as the equilibria shift under high pressure, the microstruclures of the decomposition producls change, maintaining at pressure the same correspondence between a given phase equilibrium and a given microstructure as a1 1 atm. A bainitic unicvo-structure occurs in these steels at high pressure that IS observed only at 1 aim abole 1.4 pct C. This strrrcl111,e 1s ruliorzalized in terms of the effect of pressure on the transformation to lower bainite. The pressuve depetlderlce of the kinetics of pearlile formation is descrihed by an absolute rule theory amalysis. The activation volume for the transformation is 7 cu cm per mlole, which is indicative of a phase-interface transformation-rate cotntrol mechanism. This fortmulation, when expressed in terms of known solule effects on the energelics of tvansformation, gives promise of explaining the effects of alloying elemenls on hnrden-abilily, particularly that of 'coball. KINETIC processes in solids are functions of the primary thermodynamic variables of state: composition, temperature, and pressure. Until the development of high-pressure techniques' that permitted the generation of sustained high pressure at high temperatures, metallurgical studies of such reactions were largely limited to isobaric conditions at atmospheric pressure. The data so obtained, and theoretical deductions based on these data, were necessarily incomplete For the particular case of austenite decomposition, a knowledge of the phenomenology of the reaction in terms of all the state variables should lead to a clarification of the process. This deeper understanding should facilitate a decision between conflicting theories that have been proposed to rationalize these phe- nomena. An analysis, derived from an understanding of the transformation mechanisms, may aid in the optimization of alloy steel development. The first studies of the effect of pressure on transformations in steel were made by Kulin et al. in 1952.' In a study of the influence of applied stress on mar-tensite formation in a 30 pct Ni steel, they found that the martensite start (M,) was depressed 8°C per kbar* by hydrostatic pressure. Jellinghaus and Friedewold3 were apparently the first to investigate the effect of pressure on isothermal transformations above the Ms. They found that the bainite transformation rate in a 1.2 pct C, 3.8 pct Mn steel was reduced by a factor of 3 by a hydrostatic pressure of 4 kbar. In both of these investigations,2,3 the M, of the steels studied was below room temperature. Austenitizing and quenching were done at atmospheric pressure, followed by the decomposition of the metastable austenite under pressure. The maximum temperature at pressure in the bainite study3 was 350°C. Until the advent of the present high-pressure devices, it was not possible to conduct isobaric high-pressure heat treatments from austenitizing through isothermal decomposition and quenching. The exploitation of high pressure as a variable in metallurgical studies was greatly advanced by the apparatus and techniques developed by Hall4 and co-workers. Utilizing these techniques, Radcliffe et a1.5 and Hilliard6 etermined the pressure dependence of phase equilibria in the Fe-C system. Hilliard and cahn7 examined the pearlite transformation rate in an AISI 1080 steel and also in a high-purity 0.92 C Fe-C alloy at 1 atm and at 34 kbar and found a 700-fold reduction in rate at pressure in the 1080 steel but only a fivefold reduction in the high-purity alloy. In agreement with the shift of phase equilibria under pressure, the microstructures were hypereutectoid at 34 kbar pressure, whereas they are eutectoid at 1 atm. Determination of the effect of pressure on carbon diffu-

Jan 1, 1968

By Morris Cohen, Robert C. Ruhl

Fe-Ni-B alloys were inresligated by X-ray diffraclion after splat quenching. Although this rapid cooling did not produce a measurable supersaturation of dissol1ed boron in either binary Fe-B or Ni-B alloys, a marked increase in dissolved boron was achieved by the splal quenching of lernary Fe-Ni-B alloys. Boron additions up to 2.0 wl pcl to Fe-13Ni and Fe-24Ni alloys cause an increase in retained austenite from 0 to 59 pet and to 92 pet, respectively. The martensitic phase in the Fe-13Ni-9 at. pct B alloy is .found to conlain about 0.6 at. pet interstitial boron, as evidenced by the tetragonality of this phase, and about 3.6 at. pct substilutional boron, us deduced from the lattice paratrieler decrease, the balance of the boron being precipitated as (Fe,Ni)aR. The austenitic Fe-Ni-B plznses also contain both interstitial and substitutional boron. Iron-Boron System. The phase diagram and related information about the solid solutions and intermediate phases in the Fe-B system are given by ansen,' Elliott.2 and Pearson.1 The equilibrium solid solubility of boron in both ferrite and austenite is quite small: the maximum solid solubility of 0.02 wt pct B (0.11 at. pct B) occurs in iron at the eutectic temperature of 1150°C. while the maximum solubility in a iron is less than 0.01 wt pct.l There is disagreement in the literature as to whether these solid solutions are substitutional or interstitial. Based on the measured activation energy of boron diffusion in iron, it appears likely that boron moves interstitially in austenite. 4 However, this observation does not rule out the possibility that some of the dissolved boron may also occupy substitutional sites in this phase. Investigations of internal friction of boron in iron have suggested that boron is interstitial there.' Shevelev, 5 on the other hand, reports a decrease in the ferrite lattice parameter with dissolved boron content, thus indicating a substitutional solution. Unfortunately. Shevelev's methods and analysis are unclear. Goldhoff and spretnak6 have measured the lattice parameters of pure iron and an Fe-0.005 wt pct B (0.027 at. pct) alloy at both room temperature (ferrite) and from 920° to 1200°C (austenite). They reporte: a lattice contraction in the ferrite of 0.0003 ± 0.0002 due to boron, thus indicating a predominately substitutional solution. Appreciable (0.0010 to 0.0060) lattice contractions were found in boron-containing austenites, but these effects were much larger than could be accounted for by the substitutional solution of all the boron present. Nickel-Boron System. Elliott 2 gives a summary of thephase diagram and recent work on this system. The solubility of boron in nickel reaches a maximum of 0.03 wt pct at the eutectic temperature of 1080°C. Iron-Nickel System. ansen' presents the equilibrium diagram for this system and also discusses the metastable austenitic and martensitic phases along with the a=? transformations. The lattice parameters of Fe-Ni ferrites have been recently redetermined by Abrahamson and Lopata.7 Their data, Fig. 1, show an unusual change in slope at about 1.7 at. pct Ni. Very few measurements of the lattice parameters of Fe-Ni martensites are available in the literature. The values of Roberts and Owen8 are considerably higher than those measured in the course of the present work: they find that a, is constant at 2.874? from 8 to 30 at. pct Ni. Both the slope change in the ferrite parameters and the occurrence of a maximum plateau in the marten-sitic lattice parameters vs composition denote the

Jan 1, 1970

By John Wulff, David A. Stevenson

The solubility of iron and cobalt in liquid lead, the solubility of chromium in liquid tin, and nickel in liquid silver were determined up to 1300°C in an atmosphere of hydrogen. Liquid samples were taken at different temperatures and analyzed. The data obtained were plotted to show the relationship between log mole fraction of solute and the inverse of the absolute temperature. Resulting values for the differential heat of solution (AH) and the excesspartial molar entropy (S)are: for the iron-lead system = _24,200 cal per mole and AT = 5.0 e.u. for the a phase, and AH = 18,300 and S = -0.1 e.u. for the y phase; for the cobalt-lead system AH = 16,500 cal per mole and AS =0.7 e.u.; for the chromium-tin system AH = 15,600 cal per mole and AS = 8.5 e.u.; for the nickel-silver system AH =18,000 cal per mole and AS = 4.0 e.u. RECENT developments in coating, brazing, and heat transfer have focused attention on specific cases of solid-liquid interaction in metal systems, particularly those involving dilute liquid solutions. One fundamental quantity of interest in such systems is the equilibrium phase distribution between solid and liquid phases. In any effort to fully understand such interactions, one must be able to describe the equilibrium state precisely. Furthermore, in order to develop genera! relations for such systems, one must know the equilibrium state in a number of different cases. This investigation was devoted to a study of the equilibrium phase distribution in four binary systems: solid iron-liquid lead; solid cobalt-liquid lead; solid chromium-liquid tin; solid nickel-liquid silver. The iron-lead system was previously studied by Shepard and parkman' and later by Fleischer and Elliott2 with differing results. Both investigations were carried out by sampling the saturated liquid, and analyzing it chemically. The cobalt-lead system was previously reported by Pelzel,3 who noticed no discontinuity near the transformation. A limited investigation of the chromium-tin system was made by Wlodek and wulff4 using a weight loss method. This work was done in conjunction with the development of a process for coating molybdenum with chromium from tin solutions. To more fully under- stand the kinetics of the process, a more accurate determination of a solubility was desirable. No significant data were found in the literature on the nickel-silver system. Data on the latter system were, however, relevant to the investigation of the corrosion kinetics of copper-nickel alloys in liquid silver as carried out by Harrison and wagner,5 EXPERIMENTAL APPARATUS AND PROCEDURE Of the techniques available for the study of such systems the most effective appears to be that of liquid sampling,2,6,7 which is the method used in the present investigation. A schematic diagram of the sampling furnace is given in Fig. 1. Large pieces of solute metal, in excess of saturation solubility, were added to 200 g of the solvent metal, and the entire charge placed in an alundum crucible. Analytical reagent or materials of chemically pure grade were used in all investigations. The crucible was contained in a zircon muffle tube positioned vertically in the uniform hot zone of a Globar resistance furnace. The tube was provided with a number of ports which permitted sampling at temperature and in controlled atmospheres or vacuum; the ports were also useful for evacuation and introduction of gases as well as for thermocouple measurements. A chromel-alumel thermocouple Sheated in a porcelain tube was used for temperature measurements. A purified hydrogen atmosphere was employed in all experiments reported in this paper. The hydrogen was purified by passing it first over hot copper gauze to remove oxygen and then through a molecular sieve immersed in

Jan 1, 1962

By J. E. Neal, C. T. Naber, O&apos

Silicon thin films were deposited by electron beam evaporation in an ultrahigh vacuum onto (0001) and (1102) sapphire substrates. Attempts were made to correlate the structural properties of the deposited silicon films with the following: 1) substrate orientation, 2) substrate surface condition, 3) substrate temperature, and 4) deposition rate. The substrate temperatures were varied between 500° and 1000°C and the deposition rates were varied between approximately 50 and 700A per min. The following sapphire surface treatments were investigated: 1) annealing in the ultrahigh vacuum at 1200° C; 2) heating in a hydrogen atmosphere at about 1350°C; and 3) etching with silicon by evaporating silicon onto sapphire substrates heated to 1200° or 1300°C. Twinned silicon films were occasionally formed at substrate temperatures between the 800° and 1000°C on unprocessed mechanically polished substrates; however, the reproducibility and crystallinity of these films were generally poor. Single-crystal and twinned silicon films were formed at substrate temperatures between 700° and 1000°C on substrates which were silicon-etched at 1300°C prior to deposition. Fiber texture films were formed at substrate temperatures between 500° and 700°C. The (111) lattice plane of the silicon single-crystal films was parallel to the (0001) sapphire plane and the (100) silicon plane was parallel to the (1102) sapphire plane. TECHNIQUES are well-established for growing single-crystal silicon thin films on sapphire by chemical methods.'-* Vacuum epitaxial techniques have a number of advantages over chemical epitaxial techniques in the fabrication of thin film microcircuits.5 One of the most significant is that vacuum techniques are compatible with well-established procedures for forming vacuum-deposited thin-film resistors, capacitors, and interconnections. Salatna, Tucker, and young6 recently reported the formation of relatively poor crystalline-quality silicon films on sapphire by electron beam evaporation in a vacuum of about 7 x 10-7 Torr. The purpose of the investigation described here is to determine the relationships between the structural properties of silicon thin films deposited on sapphire substrates by electron beam evaporation in an ultra-high vacuum and the following: 1) substrate orientation; 2) substrate surface condition; 3) substrate temperature; and 4) deposition rate. The substrate temperatures were varied between 500° and 1000° C and the deposition rates were varied between approximately 50 and 700A per min. Two orientations of sapphire were used: (0001) and (1102). The thick-nesses of the films were between 8000 and 16,000A. The morphology and crystallinity of the deposited films and substrate surfaces were investigated by optical microscopy, electron microscopy, and electron diffraction. APPARATUS AND PROCEDURE A cross section of the ultrahigh-vacuum thin-film evaporator is shown in Fig. 1. The bell jar is stainless steel and copper gaskets are utilized at all seals. High vacuum is attained by a 6001iter per sec ion pump and a titanium sublimation pump. Sorption pumps are used to rough the system to a pressure of about 10 µ prior to starting the ion pump. Vacuums in the 10- 10 Torr range were attained after baking the system at about 250°C for 8 hr. Vacuums in the 10-8 to 10-9 Torr range were maintained during silicon evaporation. The silicon charges, which were cut from p-type single-crystal boules which had resistivities between 2000 and 4500 ohm-cm, were placed in the water-cooled copper crucible of a 180 deg bent-beam 5-kw electron beam evaporator. During evaporation, a molten zone was formed in the top center of the silicon charge, and the portion of the silicon charge in contact with the water-cooled crucible remained solid. The substrate heater, which has been described

Jan 1, 1969

By A. R. Elsea, E. E. Fletcher

Cast X-40 alloy with the lowest nitrogen content studied had a 100-hr rupture stress at 1500°F about equal to the reported value for the commercial alloy. Increases in nitrogen content progressively decreased the rupture strength, and with about 0.1 to 0.2 pct N a minimum strength was reached, but there was no accompanying change in microstructure. Further increases in nitrogen resulted in the fomzation of progressively increasing amounts of a lamellar, pearlitic-type structure at the grain boundaries, with accompanying increases in rupture strength, and above about 0.25 to 0.33 pct N, the rupture strength exceeded the normally reported values. Two series of melts representing different melting stocks exhibited minimum rupture strengths at different nitrogen contents. This suggests that some unidentwed trace element not removed by vacuum melting has a strong influence on the response of this alloy to variations in nitrogen content. In a series of melts with manganese contents ranging from 0.6 to 3.2 pct, the material with the lowest manganese content had the highest 100-hr rupture strength at 1500°F. The manganese variations had no appreciable effect on the microstructure. CAST cobalt-base alloys such as X-40* exhibit high strengths at elevated temperatures (1500°F and above), but they also show considerable scatter in high-temperature properties. Since the design of parts for critical applications must be based on the minimum expected properties, this broad scatter appreciably lowers the design strength of the alloy. If the relatively poor properties exhibited by a few test parts from any given group could be improved, the spread in properties would be narrowed, and the design stress could more closely approach the average expected properties. The purpose of this research investigation was to learn what were the causes of these erratic properties and, if possible, to find methods for eliminating them. Earlier unpublished work showed that vacuum melting markedly influenced the high-temperature strength of cast X-40 alloy. There were indications that this behavior may have been the result of changes in the nitrogen or manganese content of the castings. Consequently, in the current investigation, the influence of variations in nitrogen and manganese content on the structure and high-temperature properties of cast X-40 alloy was studied. In this program, X-40 melting stock was vacuum melted to produce a base material that was very low in nitrogen content and in volatile trace elements. Additions were then made to this base material to produce alloys of the desired composition. The metal was cast into investment molds producing coupons which were machined into stress-rupture bars. These bars were subjected to stress-rupture tests and me-tallographic study to determine the influence of changes in analyses (nitrogen and manganese content) on the structure and properties. Material—The melting stock used for these experi-ments was in the form of shot from two master heats of commercial X-40 alloy. Only one master heat was used in a given series of melts. Thus, any differences in structure or properties that showed up in the specimens from a given series would be the result only of the intended variations in composition. The certified analyses of the master heats were as follows: C Mn Si Cr Ni Lot No. 2 0.50 0.71 0.66 25.44 10.53 Lot No. 3 0.54 0.73 0.70 25.95 10.00 W Fe Co P S Lot No. 2 7.45 1.34 Bal. 0.011 0.013 Lot No. 3 7.58 1.53 Bal. 0.005 0.016

Jan 1, 1960

By D. E. Baldwin

A method has been devetoped for predicting the produced concentration profile for a miscible slug in a five-spot pattern. The technique consists of dividing the five-spot into radial etements and applying an approximate radial solution of the dispersion equation to each element. To test the method, laboratory experiments were conducted in five-spot models. The models were 2-ft X 2-ft X 2-in. Berea sandstone slabs simulating one quarter of a five-spot. An aqueous system was used with tritiated water as the tracer fluid. Effiuent concentration profiles were obtained for slug sizes ranging from 0.7 to 10.2 per cent of the pore volume. Agreement between predicted and experimental profiles was excellent. A prediction was also made for a field tracer test. For this case the predictive technique was modified to account for stratification by use of a layer cake model. INTRODUCTION Dispersion in porous media is of growing interest to the petroleum industry because of the increasing importance of secondary recovery operations. One of the controlling factors in the recovery of oil by miscible displacement or by the use of waterflood additives is the degree of mixing between the fluids of interest. Consequently, one of the prerequisites of any recovery prediction is an adequate method of predicting dispersion. Also, any quantitative interpretation of waterflood tracer tests is dependent upon the ability to determine the dispersion of the tracer as it flows through the reservoir. During the past few years there have been reported in the literature the results of a large number of investigations, both theoretical and experimental, concerning dispersion in porous media. (An excellent review of these results has been presented by Perkins and Johnston." Only a few of these investigations, however, deal with non-lin-ear flow systems. Raimondi et al.9 have presented an approximate solution of the dispersion equation for radial, diverging flow. Lau et al. 7 and Bentsen 1 have presented laboratory data for radial systems and have shown that the dispersion can be adequately predicted by Raimondi's solution. Bentsen has also presented a small amount of data for a radial, converging system. Brigham and Smith' have applied Raimondi's solution, with approximating assumptions, to a five-spot pattern to predict the behavior of a field tracer test. The afore-mentioned investigations have been concerned almost entirely with radial diverging flow and have neglected the effect of converging flow. For this reason the present investigation was undertaken to develop a method of predicting dispersion in a five-spot pattern including the effects of both diverging and converging flow. The method which was developed consisted of dividing the five-spot into diverging-converging radial elements and applying an approximate solution of the disperson equation to each element. DEVELOPMENT OF PREDICTION METHOD The development of the prediction method consisted of two phases: construction of a radial model of a five-spot pattern and derivation of equations to describe the dispersion in the radial model. FIVE-SPOT MODEL A radial model which simulated the flow characteristics of a five-spot pattern was constructed by dividing the five-spot into diverging-converging radial elements (Fig. 1). Because of symmetry the model represented only an octant of a complete five-spot. Each element had an included angle of l° (making a total of 45 elements) and a radius r, such that the sum of the individual element areas was equal to the area of the five-spot octant. The normal five-spot fractional flow behavior was determined by averaging the experimental five-spot data of Caudle and Witte,' Dyes, Caudle and Erickson 5 and Fay and Prats. 4 The resulting curve is shown as a solid line in Fig. 2. To match this curve with the radial model it was

Jan 1, 1967

By C. N. J. Wagner, E. N. Aqua

Dilute Fe-Si alloys (0 to 5 wt pet Si) were cold-worked by making filings at room temperatuve. The analysis of the broadening of the X-vay powdev pattern peaks yields anisotropic particle sizes normal to the (110), (100), and (112) planes which are a consequence of deformation faults (probability a) and twin faults (probability p). The combined fault probability (1.5a +ß) increases from 0.01 in pure iron to 0.02 in Fe-5 pct Si. The root mean square stvains vary with crystallographic ovientation due to elastic anisotropy of the alloys, and increase from about 0.0035 in pure iron to 0.005 in Fe-5 pct Si measured in the [100] direction. Assuming that deformation and twin faults occur with equal probability, the X-ray data would imply that the stacking-fault energy does not change upon alloying. THE crystallographic aspects of the plastic deformation of dilute Fe-Si alloys has been studied many times since the observation of glide band structures by Barrett et a1.l These glide bands were much straighter than the wavy bands observed by Gough2 in unalloyed iron nearly 40 years ago. This difference in the morphology of the slip band structure has been verified many times, most recently by replication electron microscopy3 and dislocation etch-pitting methods.4,5 These observed differences in deformation behavior have been considered to result from the degree of cross slip that occurs in pure iron and in the Si-Fe alloys. The lowered tendency for cross slip would result from a lowering of the stacking-fault energy of iron by the silicon alloying addition. Experimental evidence for this lowered stacking-fault energy in the Si-Fe alloys, obtained with transmission electron microscopy, is the observation of dissociated dislocations in Fe-6 pct si6 and Fe-3 pct Si alloys,7 and the observation of sharply defined cellular substructures in Fe-3 pct si6,7 compared to the more diffuse substructure in zone-refined iron.' The activation energy for recovery of cold work is greater in the Si-Fe alloys than it is in pure iron, indicating that cross slip has become a more difficult process.9 The purpose of this investigation is to determine the change in stacking-fault probability from the broadening of powder pattern peaks in dilute silicon-in-iron solid solutions, when cold-worked at room temperature. The knowledge of the stacking-fault probability and the dislocation density, both of which can be deduced from line-broadening analysis of two orders of reflections from (110), (200), and (112) planes, will permit us to calculate the change in stacking-fault energy upon alloying silicon into iron. Previous X-ray investigation of cold-rolled Fe-5 wt pct Si (100)[001 ] single crystals did not reveal any line broadening, whereas cold-rolled Fe-3.1 wt pct Si (001) [110] and (001)[100] single crystals10 showed line bro2dening as a consequence of small particle sizes (-200A) and root mean square strains (-0.25 pct), which are comparable to those found in cold-worked iron filings.11 EXPERIMENTAL PROCEDURE A series of five Fe-Si alloys containing nominally 1 to 5 wt pct Si and pure iron were cold-worked by making filings at room temperature. The actual silicon content deviated at the most by +0.1 pct which is of no significance in the present study. The carbon contents of these materials were less than 0.02 pct. The X-ray diffraction patterns were measured with molybdenum, cobalt, and iron radiation using a GE and a Philips diffractometer. The (110)-(220), (200)-(400), and (112)-(224) pairs of reflections were

Jan 1, 1968

By G. R. Speich

The precipitation of the Feab and Fe,Ti Laves phases (MgZn, type, C14) from Fe-Nb and Fe-Ti solid solutions, respectively, has been studied in the temperature range 500" to 800°C using hardness measurements, light and electron microscopy, and X-ray and electron diffraction. The Fe-Nb alloys contained 0.96, 1.67, and 3.80 pct Nb and the Fe-Ti alloys 3.5, 5.8, and 8.8 pct Ti. In both systems only the equilibrium Laves phase is formed, with nucleation occurring at grain boundaries, at dislocations, and in the matrix. No cellular precipitation or transition phases were observed. The precipitation of the Laves phase in a fine dispersion leads to significant hardening in both systems. The hardness of the aged alloys is proportional to the reciprocal of the square root of the interparticle spacing. The maximum solid solubility of titanium in a! iron is 9.0 pct Ti at 1280°C. THE precipitation of the FezNb and FezTi Laves phases (MgZn2 type, C 14) from Fe-Nb and Fe-Ti solid solutions, respectively, has been investigated as part of a continuing study of the mechanisms of precipitation from ferritic binary iron-base alloys. The iron-rich portions of the Fe-Nb and Fe-Ti phase diagrams are shown in Fig. l(a) and l(b). The Fe-Nb diagram is essentially that given by ansen' with the more recent work of Hume-Rothery and Gibson2 added. Goldschmidt3 indicates that the FezNb Laves phase has a solubility extending from 32 to 55 wt pct Nb. The Fe-Ti diagram is also essentially that reported by Hansen.l The recent results of Nishimura and kamei, Murakami, Kimura, and Nishimura,' indicate that the FezTi Laves phase has a solubility extending from 22.5 to 30.5 wt pct Ti. The L/6 + FezTi eutectic temperature of 1298°C indicated by Kornilov and oriskina' has been adopted. The addition of niobium or titanium to iron lowers the 6 — y transformation temperature and raises the y — a! transformation temperature. This results in a closed y field in the Fe-Ti system, but the lower solubility of niobium in a! (6) iron results in a eutec-toid, 6 — y + FezNb, at 1200°C, and a peritectoid, y + FezNb —-a, at 989°C in the Fe-Nb system. The maximum solubility of niobium is reported to be 4.5 wt pct in 6 iron,' 1.0 wt pct in y iron,7 and 1.8 wt pct in a iron.' Some results from the present work indicate that the maximum solubility in a! iron is actually less than 0.96 wt pct Nb. The maximum solubility of titanium in a! (6) iron is somewhat uncertain since the early work of To faute and Butting-haus indicated a value of 6.0 wt pct while later work of Kornilov and Boriskina6 yielded a value of 14.0 wt pct. The present work indicates that the maximum solubility is actually 9.0 wt pct. In both systems the phase in equilibrium with the iron-base solid solutions is a Laves phase (Mg znztype, C14), FezNb or FezTi. Both of these Laves phases have a wide range of Solubility. The precipitation-hardening behavior of Fe-Nb or Fe-Ti alloys has not been studied extensively. Genders and Harrison' reported that binary Fe-Nb alloys hardened upon aging. Peter and Fisher7 studied the mechanical properties of Fe-Nb and Fe-Ti alloys quenched from different phase fields.

Jan 1, 1962

By W. B. Gogarty

With the use of polymer solutions in secondary recovery operations, the need has developed to understand the mobility control mechanism. This study investigated mobility control by considering both permeability and rheological effects. Experiments used a high molecular weight, partially hydrolyzed polyacrylamide polymer. Flow studies took place in reservoir and Berea cores having zero oil saturation. Effective size of the polymer flow unit was inferred from Nuclepore filter tests. Clay studies indicated the particle size capable of decreasing the core permeability. Flushed permeabilities measured the approximate core permeabilities with flowing polymer solutions. These permeabilities were considerably lower than original values. With mobility data and the flushed permeability, maximum effective viscosities were determined for polymer solution flow in a core. Effective viscosities showed that rheological properties play an important part in mobility control with polymer solutions. The study showed that permeabilities decrease and stabilize with polymer flow. At the lower permeabilities, high shear rates exist in the cores. Because of the pseudoplastic character of the polymer solution, the high shear rates caused low effective viscosities. This condition pointed to the inefficient use of the potentially high viscosity of the polymer solution at low shear rates. INTRODUCTION In the oil industry, a great deal of interest is being shown in the use of polymer solutions for secondary recovery and a number of polymer floods are being performed in the United States.1 Some of these floods have become commercial while others have been reported as failures. A number of floods are still in progress and remain to be evaluated. With the advent of polymer flooding, the need developed to understand the mobility control mechanism in porous media. Rheologically, the polymer solutions behave as pseudoplastic fluids. Investigators have studied the rheology for this type of non-Newtonian fluid in porous media?-6 Results have also been reported on the ability of polymer solutions to decrease mobility.7-10 Some investigators indicated that polymer solutions show a different rheological behavior in cores than on the viscometer.7,8 This study is representative of an initiatory investigation on mobility control with polymer solutions. Some effects are considered on a qualitative basis. Mobility control is considered from the standpoint of both permeability and rheology and, to the extent possible, permeability and rheological effects are considered separately. Results show that mobility control occurs from a reduced permeability caused by polymer retention and an effective viscosity determined by the average shear rate in the core. In this respect, rheological behavior is as important in mobility control as permeability. PROCEDURES A high molecular weight, partially hydrolyzed, polyacrylamide polymer was used in the investigation. Solutions of various concentrations were made with this polymer in different types of water. Some solutions used distilled water and others used tap water. The tap water contained approximately 500 ppm dissolved solids. As used in this paper, concentrations in ppm refer to parts by weight solute to one million parts by weight of solvent. In the tap water, calcium and magnesium accounted for from 60 to 80 ppm of the solids, the remainder being mostly sodium chloride. All solutions contained a bactericide, and anti-oxidants and antiprecipitants were added to the tap water. Capillary and concentric-cylinder* viscometers determined the rheological properties of solutions. The capillary viscometer is described elsewhere.6 Berea and reservoir sandstone were used as core materials for this investigation. Cores were 1 in. in diameter by approximately 2 to 3 in. long. Prior to mounting, the Berea cores were heat-treated for 3 hours at 850F. This treatment decreased the water-sensitivity of the clays in the cores. The reservoir cores were cleaned with solvent and