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By R. W. Waterfill

MANY existing ore deposits of valuable metals have been worked out in their upper surface levels and the continued productivity of these mines is dependent on their extension to greater depths in the earth. The maximum depths at present reached are about 6000 to 8000 ft. below the surface, with no evidence of an impoverished ore vein. These mines are widely distributed; some of the best known are in South Africa, Brazil, India and in the western sections of the United States. Among the factors which increase the difficulty of working these mines at increasing depths are hoisting, rock pressure and temperature. The manner and effectiveness with which these problems arc met will, no doubt, determine in a large measure the ultimate depths to which any mine can be profitably worked. The most critical of these three factors at present is the increase in temperature with depth. The high temperature and humidity in many of these mines at present are severely detrimental to the health of the workers and greatly hamper their efficiency. Some have almost reached a condition in which the human system cannot survive. The problems involved in the cooling and ventilation of mines have all been ably analyzed and presented in previous articles. For this reason, only a résumé of conditions affecting the cooling and conditioning of deep and hot mines will be given in this paper before attention is directed to possible methods of improving atmospheric conditions in the working levels. Physiological Effects of Temperature, Humidity and Air Motion Many data on the physiological effects of different atmospheric conditions on the human system have been compiled and published through the combined efforts of the American Society of Heating and Ventilating Engineers, the U. S. Bureau of Mines and U. S. Public Health Service. These data were not primarily developed around the conditions existing in deep mines, but the upper temperature limits of the investigations extend into, and are applicable to, mine atmospheric conditions. While the exact values of the standard comfort conditions, established for persons of such habits as those employed in detecting the different degrees of comfort, might not produce identical effects upon persons inured to

Jan 1, 1929

By Eugene H. Dawson

MICA is a mineral that once was a familiar sight as fireproof windows in stove and furnace doors and as lamp chimneys and shades. Since 1878, the beginning of the electrical age, the use of mica for such purposes has gradually declined and its use in electrical equipment and appliances has developed to such an extent that the known sources of supply are scarcely equal to the demand. With the increasing capacity of electric generating units, the size of mica sheets found in nature was inadequate. However, in 1894, a process was developed whereby thin films or splittings cemented with shellac or other binders could be pressed into large sheets. 18 The introduction of radio in the early 1920s created such a heavy demand for the smaller sizes of mica that on March 22, 1938, mica was included among 23 commodities on the list of strategic materials approved by the United States Army and Navy Munitions Board. To be included in this list, the material must be one whereof the domestic supply is not sufficient to meet the demand. COMPOSITION Mica is a complex mineral composed principally of the silicates of potassium, aluminum, and magnesium. Less prevalent species contain, as essential components, lithium, vanadium, and chromium. Iron usually is present either as an essential component or as an impurity. The mica group comprises some nine different species, five of which, muscovite, phlogopite, vermiculite, lepidolite, and biotite, are widely used in industry. Lepidolite and zinnwaldite (lithium micas) and roscoelite (vanadium mica) are sources of lithium and vanadium. Muscovite, "white mica," is potassium mica. Theoretical formulas H2KAl3(SiO4)3. There are two varieties, distinguished as to color, known in industry as ruby and green. In crystals or "books," the colors each range through varying shades of red and green. However, when split into thin films, all micas, except biotite and phlogopite, are colorless and transparent. Muscovite frequently is stained red or black by thin films of iron oxide between the laminae. The staining usually is derived from magnetite, which sometimes is found as unaltered crystals.

Jan 1, 1949

By O. W. Ellis

In view of the extensive use of the brasses and bronzes in engineering practice it is indeed surprising that so little scientific work has been done on the oxides in these alloys. Recognition of the ill effects of these compounds is universally accorded, both in foundry procedure and in such specifications as cover the melting of these useful mixtures. In the latter, limits, for example, are placed on the proportions of scrap metal In the charge, and clauses governing the use of fluxes are included, the addition of fluxes to the charge being made with the object of avoiding oxidation during the process of melting and of subducing and separating non-metal-lic matter from the melt.1 In the manufacture of brass it occasionally, though rarely, occurs that the virgin metals, copper and zinc, alone arc used. In the event of virgin metals being employed, that of the higher melting point is always melted first. If it is melted under suitable conditions, little or no oxidation will occur. Whether oxidation has occurred or not, however, can best be determined by microscopic examination of a sample taken from the melt. Avoidance of Oxidation in Furnace Practice When melting virgin copper in crucible practice, the avoidance of oxidation is not difficult, nor is it hard to forestall trouble in the electric furnace. In gas-fired furnaces of the barrel type, however, the avoidance of oxidation is almost impossible, no matter what the condition of the flame, the flux employed, or the amount of charcoal included in the charge. Copper melted in furnaces of this type is almost invariably so highly oxidized as to requirc very considerable additions of such deoxi-dizers as, for example, silicon copper to render it free from cuprous oxide. As a result,, the castings produced are decidedly inferior, on account of the. large amount of silica which is engendered in the metal as a result of the reaction, Cu2O + Si = SiO2 + 2Cu. The deoxidation of such oxidized copper could, of course, be effected by means of zinc with, however, even more disastrous results.

Jan 1, 1930

By G. R. St. Pierre, L. M. Adelsberg, R. Speiser

The rate of scale fot'~I~ti0n on tantalum held in H20-Hz-Ar gns mixtures at temperatures between 840" and 1250°C is related to gas composition and ternpevature. It is found that water vapor partial pressure determines the oxidation rate at a given temperature and that the oxygen potential as fixed by the water vapor to hydrogen ratio Ins no significant effect on the oxidation rate. The Ta205 scale formed during oxidation is composed of an inner lattice-dijf~ision barrier and an outer layer of- cracked/porous oxide 1 HE oxidation of tantalum at temperatures less than 800°C is characterized by solution of oxygen into the metal,'-' the formation and growth of suboxides into the metal,')2~10-15 and the delayed nucleation of the highest oxide, Above 800°C, Ta205 is found to nucleate rapidly10, 11, 15, 16 except at low oxygen pressures:15 however, there is uncertainty regarding which does not retard the oxidation process. For each gas con~position and temperature investigated, the oxidatioz rate becomes constant after a short adjustment period. It is shozm that a constant oxidation rate nzay pre~?ail even though the tlzickness of the inner lattice-dijjitsion layer of Ta205 is clanging. TFze initial czcrz!ature of the typical 'Paralinear" oxidation curve may result froprz causes other than an increasing thickness of tlze inner protective layer. the detailed mechanisms of the high-temperature oxidation. Peterson, Fassell, and wadsworth17 observed linear oxidation behavior for tantalum in oxygen at temperatures between 600" and 1000°C. They reported that equilibrium adsorption of 0, occurs on a surface prior to the rate-deter mining step of the reaction. Cowgill and stringer1' confirmed the observations of Peterson and his coworkers. They stated that the rate-determining step of the reaction could be either the incorporation of adsorbed oxygen into the anion lattice or the dissociation of 0, at the gas-oxide interface. The relative rates of the two surface reactions were proposed to be dependent upon the reaction temperature and the oxygen pressure. stringerlo subsequently reported that the reaction surface is located somewhere

Jan 1, 1968

By Donald F. Irwin

Amid the violent economic changes of recent years that have affected Canadian gold-mining operations so deeply, the discovery and early developments of Kirkland Lake might easily be overlooked. There was more than one "false dawn" for the district before developments finally established the fact of a superb mineralized zone extending through the present operating properties. Never far from the railway, Kirkland Lake has had the benefit of direct rail service for many years. The pioneer discovery on which the first mill and cyanide plant was erected was the "Tough-Oakes," this property being on what is now the eastern end of the producing area; some time later, the "Lake Shore" was discovered at the present center of the district, and a small plant was built upon it also. Both of these early treatment plants were of pre-war design. Progress in gold metallurgy has caused a gradual change in cyanide practice since the early days at Kirkland Lake, which may be observed in the various plants now operating there. From the beginning, it was recognized that Kirkland Lake ores were more responsive to cyanidation than to alternative recovery methods, and that their mineralization contained gold in very finely divided form. Although sulfides and tellurides are present, the quantity is small, being in the order of 1 or 2 per cent by weight, so that gravity concentration is undesirable, since gold is not confined to the sulfides. Some complication is offered by the presence of tellurides, which have caused lengthy controversy over their importance in recovery methods, but which are now generally regarded as less harmful in the light of increasingly high recoveries being obtained. Nevertheless, finely divided gold intimately associated with sulfides in the presence of tellurides; and occurring in the hard Kirkland Lake porphyry ore, substantially free from natural slime-forming constituents, indicates fine grinding. This has been the universal practice although the degree of grinding has varied a little among the different mills and is considerably finer now than formerly. The natural condition as outlined caused the establishment of fine grinding at an early stage in the development of Kirkland Lake, during the period of valuation of gold at, $20.67 per ounce. With the arrival

Jan 1, 1935

By F. W. Miller

A brief history of byproduct coking in Alabama with short general descriptions of plants and the state's production of beehive and byproduct coke. PRIOR to the Civil War, there were several small charcoal furnaces for smelting the brown limonite ore that is found, in comparatively small bodies, throughout the central and north-central portions of the state. During the Civil War, these furnaces furnished charcoal iron to the Confederate Government. No attention was paid to the large bodies of lime-bearing hematite ore that now supplies the bulk of the ore used in the various blast-furnace plants of this district until the latter part of the 19th century. Red Mountain, which is the southernmost and one of the smaller ranges of the Appalachian Chain, lying immediately south of the Birmingham and Bessemer, is the principal source of this ore. The orebody outcrops on the northern face, extends through the mountain, and underlies Shades Valley on the southern side. When it was found that these ores could be worked satisfactorily in the blast furnaces, there was a comparatively rapid growth in the blast-furnace industry in the Birmingham district. As these ores are far more refractory than the limonite ores, this blast-furnace development was accompanied by the construction of beehive ovens to carbonize the coal, in order to supply the necessary fuel. The state's production of bee-hive coke in 1880 was 60,781 tons; ten years later this had increased to 1,072,942 tons; and, in 1897 the production had reached 1,443,017 tons. In 1898, the first byproduct oven built in the state was put in operation. This plant consisted of 120 horizontal-flue Semet-Solvay ovens, three flues in height by thirty flues in length with an average width of 16 in. The plant was constructed by Semet-Solvay Co., for the Tennessee Coal, Iron & Railroad Co., and was located adjacent to the blast-furnace plant of that company at Ensley. Coal was delivered from the Pratt mines, by gravity tracks, directly into bin's of the ovens after having

Jan 9, 1924

By C. G. Dunn, J. L. Walter

SILICON-iron .under certain conditions of processing and annealing will form a cube texture. The occurrence of this texture in thin tapes of silicon iron was first reported by Assmus, Detert, and Ibe.' They concluded that the cube texture in their material formed by a secondary re crystallization process. In the course of present investigations on the development of the cube texture and the mechanisms involved in its formation by secondary re-crystallization it was found that under certain conditions the cube texture was replaced by a cube-on-edge or (110) [001] texture. We call this phenomenon tertiary re crystallization since it follows secondary recrystallization. The secondary recrystallization occurs after primary recrystallization and a substantial amount of normal grain growth. It is the purpose of this paper to describe briefly the occurrence of tertiary recrystallization and the structure and texture prior to and after tertiary recrystallization. The primary and secondary recrystallization structures and textures are the subject of another study and will be referred to briefly in the discussion of results. Evidence will be presented for the view that the dominant driving force for tertiary recrystallization is derived from the surface free energy which depends on the crystallographic planes presented to the gas-metal interface. In the absence of boundary restraining forces (dispersed phases, thermal grooves, and so forth) a sufficiently large difference in surface free energy across a grain boundary would produce boundary migration away from the center of curvature of the boundary intersection line in the surface of the sample according to risher.2 Therefore, particular attention was paid to observation of the direction of motion of these surface boundary lines. Furthermore, measurements of the actual boundary curvatures could be used to estimate the driving force supplied by surface free energy. EXPERIMENTAL PROCEDURE Samples were prepared by hot and cold-rolling vacuum-melted ingots of iron containing 3 pct Si to strips 0.012 and 0.006 in. thick. The ingots contained less than 0.005 wt pct impurities. The rolled strips were cut into samples approximately 1 in. wide by 3 in. long and were electropolished to remove surface imperfections. All samples were annealed in a vacuum at a pressure of approxi-

Jan 1, 1960

By Y. A. Chang

Heat content values of tantalum monocarbide and tungsten monocarbide have been determined from 325" to 985°K by means of a drop-type diphenyl ether calorinzeter. Based on the values obtained in the present study and those available in the literature, best values lected and computed from 298. 15°K to temperatures close to their respectiue melting points. At temperatures higher than 1700°Kfor TaC and 27000 K for WC, values of Cp and related thermodynamic quantities were extrapolated based on the two Debye parameters: one corresponds to the metal sublattice and the other to the carbon sublattice. The contrzbutzon In the total specific heat due to lattice dilation was evaluated using the Nernst-Lindemann relalionship. The calculated values of Cp were in good agreement with the In view of their refractoriness, tantalum monocar-bide (TaC) and tungsten monocarbide (WC) are of con- experimentally determined ualues. Furthermore, the calculated values of the absolute entropies at 298.15"K were 5.03 and 4.15 in comparison to the experimental values of 5.05 and 4.15, all expressed in the unit of cal per degg-atom. Using the same Debye parameters, values of the linear coefficients of ther mal expansion for TaC and WC were calculated from absolute zero to their respective melting points using the Grüneisen equation. The calculated values are in excellent agreement with the experimental values available in the literature. Finally, the values of the bulk modulus of TaC from room tenzperature to temperature near its melting Point were also calculated using the equation recently derived by Anderson. No cot~ipari-son between the calculated and experimental values can be made due to lack of experimental data. siderable practical interest. In order to completely define these materials, it is necessary to know their thermal properties as a function of temperature. Tantalum rnonocarbide having a NaCl structure (B-1 type) melts congruently at 4250PK,1 while tungsten monoearbide with a simple hexagonal structure (Bh type) melts per itectically at 3049°K into melt and graphite.2 In the present study, the heat content values (from which

Jan 1, 1968

By H. S. Martin

ALTHOUGH it was known some years ago at the- Utah Copper Co. mills that fine grinding improved flotation recoveries, no accurate data were available until recently as to just how far the grinding could be carried economically. In 1923 the ultimate degree of fineness for flotation feed was supposed to be about 10 per cent. on 65 mesh, with approximately 55 per cent. through 200 mesh, which meant that most of the mineral would pass 100 mesh. At this time Garfield and Wilfley tables were used ahead of flotation and a good deal of the coarse mineral removed prior to the ball mill regrind. Shortly afterwards, mill-scale tests developed the fact that on a feed containing not over 10 per cent. +65¬mesh material flotation alone would give a copper recovery equal to that obtained by the combination of tables and flotation, but that on much coarser feed the recovery with flotation alone was lowered. This was at a time when all the sulfide minerals were floated if possible, so that the only requisite was to grind fine enough to free the mineral from gangue. EARLIEST USE op MICROSCOPIC EXAMINATION OF TAILINGS As early as 1921, the writer had attempted to determine by chemical analysis the relative proportions of copper minerals in tailings from an ore that made extremely poor flotation results. Chemical analysis was not satisfactory or conclusive, and samples of these tailings were sent to the U. S. Bureau of Mines Station at the University of Utah for micro-scopic examination. The question at that time was to determine, if possible, which copper minerals had been lost and why, but R. E. Head, in his report, revealed other interesting data. He said in part: Briefly stated, the mineral particles or grains may be classified into separate groups as follows: 1. Free grains of pyrite, chalcopyrite, chalcocite and bornite, respectively, which contain no other included sulfides; 2. Grains in which all three of the copper sulfides are represented (the core may he of chalcopyrite, partially altered to bornite, these two minerals being entirely surrounded by a shell of chalcocite); 3. Grains composed of equal amounts of bornite and chalcocite or chalcopyrite and chalcocite.

Jan 1, 1929

By Harry V. Welch

Early in the development of the art of metallurgy, it was noted that a distinct difference existed in the character, collection possibility and health hazard of the "smoke" from lead furnaces and those from copper plants. Zinc-plant fumes, although not so detrimental to health, were closely allied in nature to those of the lead works. In Cottrell plants, there are sufficiently distinct differences in operation and amount of construction between those for lead and copper to justify their consideration under separate headings; therefore, while the application of the process at copper-reduction works was covered by the writer some two years ago in the Transactions1,† this discussion will confine itself more distinctly to "fume" collection. General information on the process has been presented in numerous articles and by many authors: Cottre112, Schmidt3, Bradley4, Anderson6, Labbe6, Shiga7, Rathbun8. "Fume" may be defined as material, metal or nonmetal, elemental or compound, evolved as a vapor from a furnacing or chemical reaction and condensing, chilling or reacting within the gas stream to yield a solid form, and in this definition liquid particles are solids in a sense as distinguished from gases or vapors. Such condensed particles are of minute form, on the order of "smoke," and, for example, on the order of a few hundredths of 1 micron (1 micron = 1/25,000 in.) to perhaps 3 microns, with agglomerates, in relatively small proportions of many particles. Metallurgically typical fume products are lead compounds, oxides, carbonates and sulphates; elemental zinc, more commonly encountered as a fume particle of zinc metal with a surrounding "skin" of zinc oxide; arsenic, both metal and oxide and some of its more complex salts such as added sulphates as found in flue dusts; antimony, more particularly its oxide forms; and elemental sulphur, sometimes a troublesome product, in Dwight-Lloyd sintering-plant fumes. These products, particularly the elemental or lower oxide forms, have relatively appreciable vapor pressures at the existing operating temperatures as reported by Welch and Duschak9, Ingold10, Johnstonll, Millar12,13.

Jan 1, 1937

By George Rice

THE subject of dust explosions in coal mines first appears in the Transactions of this Institute following the first great mine disaster that happened in bituminous mines of the United States. This was the Pocahontas explosion, which occurred Mar. 13, 1884, causing the loss of 112 men. The operating company wisely asked the technical assistance of the Institute, requesting that a committee be appointed to investigate and report. This committee consisted of Messrs. Bramwell, Buck, and Williams, who, after careful study, reached the conclusion that the explosion was due "either to dust alone or to dust quickened by an admixture of fire-clamp too slight for detection by ordinary means." This is perhaps the first time in this country that coal dust was considered to be the chief agency in a mine explosion.. The report is given in the Transactions, vol. xiii, p. 237 (1885). It is particularly worthy of note that the committee called attention to "the necessity of full-sized tests and systematic experiments. " In the same volume of the Transactions, there is a most interesting paper reviewing the literature relating to coal dust, by E. S. Hutchinson, entitled Notes on Coal-Dust in Colliery Explosions. Mr. Hutchinson gives a historical account of observations on the part played by coal dust in mine explosions, beginning with Messrs. Lyell and Faraday's report on the Haswell colliery explosion in 1844, in which it is said "much coal gas had been made from this dust in the very air itself in the mine by the flame of the firedamp, which raised and swept it along, and much of the carbon of the dust remained unburned only from want of air." The subject lay dormant until 1875 when William Galloway began some coal-dust experiments in a small gallery at a mine in South Wales of which he was manager. At that time he considered the presence of firedamp necessary for continued propagation of a dust explosion; but in 1884, the year of the Pocahontas disaster, he stated that no earlier author-than himself had credited coal dust with being a principal factor in mine explosions, relegating firedamp to a secondary place.

Jan 10, 1914

By E. L. Mann

Asbestos is the generic name given to a group of fibrous mineral silicates found in nature. They are all incombustible and can be separated by mechanical means into fibers of various lengths and cross sections, but each differs in chemical composition from the others. The commercial grades of asbestos consist of a spectrum of lengths and sizes and are not definitive as are most organic fibers. It is generally recognized that there are two main groups of asbestos. The first only contains the fibrous serpentine called chrysotile and comprises about 94% of the world production of asbestos. The second group contains five minerals in the amphibole series-crocidolite, amosite, anthophyllite, tremolite, and actinolite. The latter two have no commercial importance. Properties Physical The structures of asbestos fibers have been studied intensively over a number of years. X-ray diffraction patterns have been used as a means of identification and classification. Low angle X-ray scattering techniques have shown that chrysotile fibers are "hexagonally close packed" and parallel to each other, having cross-sectional diameters varying from 18Å to 300 Å units, while the amphibole fibers are many times larger in cross section, have considerably smaller surface areas, and the fibers are less symmetrical than those of chrysotile. Electron micrographs of the more common types of asbestos are shown in Figs. 1-4. Fig. 1 illustrates the softness and flexibility of chrysotile which make it suitable for textile-type products. For a number of years there was considerable controversy over the exact nature of chrysotile fiber, but the photographic evidence in Figs. 5-7 clearly show that it is tubular in structure. The curvature is the result of the mismatch in the dimensions of the silica [Si2O5] and brucite [Mg(OH)2] layers which are on the inside and outside, respectively, of a double sheet. This curvature had been predicted by Pauling (1930) years ago based on the molecular dimensions of the two component structures. In contrast to this, the structure of the amphiboles consists of two ribbon chains based on Si4O11 units separated by a band of seven cations with two hydroxyl groups attached to

Jan 1, 1983

By A. B. Parsons

NOT every organization on reaching the relatively ripe age of three score and fifteen can say with truth that its purpose and objects remain precisely the same as prescribed by its founding fathers. Of course, constancy of purpose may be something else than unalloyed virtue. It could merely reflect slavish worship of tradition, intellectual stagnation, or sheer inertia. On the other hand, it could establish the fact that the founders were men possessed of broad outlook, of prophetic vision, and of an acute sense of direction. In addition to charting the course with precision, the founders of the A.I.M.E. surely showed a flair for expressing clearly in a few words what others might say obscurely in many words. To quote verbatim from the "call" for the meeting, in 1871, the proposed organization was to have: "two great objectives: "First, the more economical production of the useful minerals and metals. "Second, the greater safety and welfare of those employed in these industries." This text underwent some refining on several subsequent occasions but today the ultimate product, as set forth in the Constitution reads: "to promote 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 all lawful means." The original call was dated "Wilkes-Barre, Pa., April, 1871," and was signed by Eckley B. Coxe, of Jeddo, and by R. P. Rothwell and Martin Coryell, both of Wilkes-Barre, each of the three subscribing himself as "mining engineer." The authors proceeded to explain briefly just how it was proposed to achieve these objectives: "In European countries, where the arts of mining and metallurgy have long been the subject of the most careful study, no means have been found so effectual in attaining the end above proposed, as the free interchange of experience among those actually engaged in these industries; and this object has been accomplished mainly through the medium of `Institutes,' `Associations,' or `Societies,' composed of those engaged in these occupations, and by the periodical publication of `essays' or `papers' communicated to such societies by their members. "It must be evident to all practical men that the interchange of the varied experience

Jan 1, 1947

By F. F. Craig

Many full-scale waterflooding operations are preceded by pilot floods, one purpose of which is to provide an estimate of recoverable oil. A laboratory model study was made to determine the influence of the producing wells' effective productivity on the oil recovery efficiency of single five-spot pilots, as well as single injection well pilot floods. The effective productivity is indicated by the value of Condition Ratio, defined as the actual well productivity to that of on undamaged and non-stimulated, normal-sized well in the same formation. The effects of initial gas satrcration and mubility ratio on recovery eficiency were also investigated in this model study. Model test results skowed that at favorable mobiliry ratios, a five-spot pilot flood can provide a direct quantitative estimate of the recoverable oil in the pilot area. If the pilot producer's Candition Ratio is 2.2 or more, upwards of 90 per cent of the recoverable oil in the pilot area is recovered from the inside producer, regqrdless of the mobility ratio or initial gas saturation. This Condition Ratio can be achieved with preyent fracturing techniques. Model studies also showed that over the range of imposed injection pressure differences and regional pressure gradients normally encountered in field operations, there was no effect on the recovery efficiency of a five-spot pilot waterflood. Model studies of single injection well pilot waterfloods showed that with no initial gas saturation, the total oil recovery at the offset producing wells can indicate the oil recovery possible by full-scale waterflooding. It is essential that the Condition Ratios of the offset wells be above 1.4. If an initial gas saturation exists prior to water injection, the recoverable oil cannot be directly evaluated by a single injection well pilot flood. However, the production per formance of such a flood can be used to provide information on volumetric sweep efficiency. INTRODUCTION Oil reservoirs are conlplex structures and cannot always be fully studied in the laboratory. Therefore, many operators consider it prudent to evaluate a waterflood prospect by means of a pilot flood. Pilot waterfloods generally involve one of two well arrangements: a single five-spot pilot waterflood, involving four injectors and an internal pilot producing well; and a single injection well pilot flood (sometimes called an inverted five-spot pilot) having one injector and four sur- rounding pilot producers. Some pilot floods are composed of multiple five-spot pilot patterns. To yield information applicable to field-wide performance, the pilot must be located in a representative portion of the reservoir. Pilot floods generally are conducted for one or more of the following reasons: (1) to determine whether water could be injected at desirably high rates, (2) to determine whether an oil bank or zone of increased oil saturation is formed by water injection, and (3) to estimate the oil recovery by waterflooding. Many of the early pilot water-floods were conducted for only the first two reasons. As soon as a buzz in oil production was obtained in the pilot, water injection was initiated throughout the entire lease or field. A number ot laboratory studies have been directed toward determining conditions under which a pilot flood could yield a quantitative estimate of the oil recovery possible by full-scale pattern flooding. One of the early studies of single five-spot pilot flooding' showed that well damage to the inside pilot producer could reduce the total amount of oil recovered. In a study of the single injection well pilot flood pattern,' the results indicated that if the model boundaries were no closer than a half-well spacing beyond the pilot pattern, the pilot performance in the laboratory is unaffected by these boundaries. In another study,? he effect of initial gas saturation and mobility ratio on the ratio of production to injection rate for various groupings of five-spot patterns was defined by mathematical and analog methods. In a study4 involving both potentiometric and flow model experiments at a mobiliry ratio of unity, four different pilot patterns were studied. These included a single five-spot, a single injection well pilot, a cluster of four single injection well pilots and six inverted five-spots. In this study the ratio of well diameter to the distance between injection and producing wells was held constant at 1:1000. The effect of the 7 ratio-—the ratio of the pressure drawdown at the producing wells to the pressure build-up at the injection wells on the pilot performance-was studied. The values of 7 ratio ranged from 0 to 0.34. Results showed that both the total oil recovery and the total fluid production from the pilot relative to the cumulative injection increased with increasing values of the 7 ratio. The effect of both the ratio of injection to producing rates and mobility ratio on the oil recovery performance of a liquid-saturated single five-spot pilot flood was studied in a series of flow model tests.5 Rate ratios ranged from one to four, and mobility rates ranged from 0.1 to 10. Resulls of these tests showed that at low rate ratios, the pilot producers may recover up to four times the recover-

Jan 1, 1966

By S. D. Dahlgren

ORDERED G.P. zones having the cesium chloride structure were found to exist in the bcc iron-rich grains of an Fe-Au-Cu alloy that had been supersaturated with approximately equal atomic percentages of gold and copper, and aged at 400° and 350°C. Streaks and superlattice spots in electron diffraction patterns revealed the presence of the ordered zones in the aged material. The ordered Ll2 structure is commonly found for precipitates in fcc metals (e.g., Ni3A1 in nickelL7') but it is uncommon to find precipitates in bcc metals having the cesium chloride structure. The formation of the G.P. zones caused age hardening of the grains. Samples containing 3.8 at. pct each of gold and copper (with the remainder being iron) were annealed at 95@ or 1125°C in quartz capsules and were quenched by breaking the capsules under water. X-ray diffraction patterns revealed two solid solutions in the quenched samples. One solid solution was bcc and the other was fcc. The microstructure consisted of iron-rich grains of 0.3 mm diam surrounded by a yellow gold-copper-rich grain boundary network. The Au-Cu phase diagram %hows continuous solid solubility of gold and copper with ordered phases forming below 410°C. None of the ordered Au-Cu phases have the cesium chloride structure. Both Fe-Au and Fe-Cu phase diagrams3 show extended miscibility gaps and only terminal solid-solution phases. Consequently, it is reasonably certain the iron-rich grains consisted of an a-phase terminal solid solution, and the grain boundary network consisted of a gold-copper-rich terminal solid solution. Lattice parameters of the quenched solid solutions were consistent with the suggestion that the quenched phases were terminal solutions. The lattice parameter of the bcc phase (2.879A) obtained upon quenching from 950°C was higher than that (2.866A) for pure iron. The fcc phase in this sample had a lower lattice parameter than that for a 50 at. pct Au and 50 at. pci Cu solid solution, i.e., 3.866 compared to 3.877A. The lattice parameter for the 50 pct Au and 50 pct Cu solid solution was interpolated from data for Cu-Au solid solutions.4 More gold and copper were soluble in iron at 1125°C than at 950°C as indicated by a 0.012A increase in the bcc lattice parameter for a sample quenched from 1125°C. After the alloy had been quenched from 950° and 1125°C, the bcc lattice parameters were 2.879 and 2.891A1 respectively G.P. zones having the cesium chloride structure-which formed during low-temperature aging—were detected by electron diffraction and observed with electron transmission microscopy. In Fig. 1, the asymmetrical streaks parallel to ( 100) directions indicate that platelike G.P. zones had formed parallel to (100) planes of the matrix. The direction of streak asymmetry shows that the bcc unit cell of the G.P. zones was larger than the bcc cell of the matrix. The ordered cesium chloride structure is indicated by low-intensity superlattice spots at 010 positions which are nonallowed for bcc structures. The superlattice spots are streaked; therefore they are from the G.P. zones and are not caused by rel-rod effects of a thin matrix phase. The appearance and size of the zones observed in electron transmission microscopy and the appearance of the asymmetrical streaks in the electron diffraction patterns for the Fe-Au-Cu alloy were the same as those observed for a similarly treated Fe-Au alloy.' Ordered G.P. zones were detected also for an Fe-Au-Cu sample aged only at 400°C. The production of the ordered cesium chloride structure zones by low-temperature aging of super-

Jan 1, 1968

By F. F. Poland

The purpose of this paper is to describe the recent applications and improvements made in the process and equipment for the recovery of metallic zinc from secondary metals by means of high temperature electric resistor furnace distillation. The process and high temperature furnace, as developed by Revere Copper and Brass Incorporated, Research and Development Department, was described in a previous paper. † Since the publication of that paper the process and equipment have been licensed to others. Consequently its field of application has been expanded, particularly for the treatment of scrap brass, galvanizers dross and scrap zinc. Other applications are being considered, particularly the melting of metallic titanium and special alloys requiring a controlled atmosphere. Consideration is also being given to modification in design that would allow the melting of copper cathodes for the production of oxygen-free and electrolytic tough pitch copper shapes without the necessity of blowing and poling. In the design of a furnace for melting copper cathodes it is intended that the fundamental principle of charging the solid material into a large pool of molten metal through a double door charging vestibule as shown in Fig 3 of the previous paper, † would be adhered to and, in addition, either dehydrated and desulphurized producer gas or commercial nitrogen, that is, approximately 96 pct nitrogen, 2 pct hydrogen 2 pct CO, also dehydrated, would be used to provide a protective atmosphere for the resistors and to flush out more soluble gases from the molten copper. The operation of a small unit producing approximately 1000 lb of copper per hr has shown that the commercial nitrogen will allow the production of tough pitch electrolytic copper when the metal is transferred from the meltdown unit contemplated to a special type induction unit where the oxygen absorption and temperature can be controlled. Standard practice in treating low grade scrap brass has been to oxidize the zinc by blowing air through the molten metal. This operation results in the recovery of approximately two-thirds or less of the zinc content of the brass in the form of an impure zinc oxide having only a fraction of the value of the zinc in metallic form. The balance of the zinc is lost to slag, fume and drosses. Fig 1 shows the revised flow sheet of the process for the treatment of scrap brass. For this application and as shown on the flow sheet a low frequency induction furnace has been substituted for the Wilkins-Poland type as a melting unit. This type of furnace has been found the most suitable for the purpose as will be shown by the following discussion. Serap Brass The melting of refinery scrap brass preparatory to distillation presents a melting problem quite different from the usual melting of brass mill scrap for recasting because refinery scrap is a heterogeneous mixture of alloys each having different melting and boiling points, and coated with a variety of corrosion products and foreign materials. In addition, brass and copper plated pieces of sheet iron, stainless steel, ceramic materials, and others are present that do not melt except at temperatures above the boiling point of the liquid bath. In the previous paper it is noted that difficulty was encountered in the melting of refinery grade scrap brass without excessive loss of zinc by volatilization and that 5 to 10 pct razorite flux was used to alleviate this condition. While this flux was successful in preventing the excessive loss of zinc by volatilization it interposed a low heat conductivity layer between the source of heat and liquid charge and resulted in lowering the melting rate of the furnace. This same problem presents itself in all types of furnaces in which the metal is heated by radiation and conduction from above the charge. It has been found in melting this type material that the melting rate per hour or per square foot of hearth area

Jan 1, 1950

By F. R. Scauzillo

Equilibrium data which should be useful in the design and/or evaluation of glycol dehydration units were prepared from an analysis of various published data and the correlation of these data by the use of the thermo-dynamic equilibrium ratio. The equilibrium ratios of water are used to solve the glycol absorber problem; such solutions are necessary to define the number of trays and the glycol circulation rate needed to meet drying requirements. Activity coefficients were obtained which relate directly to the equilibrium ratios of water in the water-TEG-natural gas system. These activity coefficients have been used to calculate the equilibrium dew points for aqueous TEG concentrations of 60 to 99.9 weight per cent for the temperature range of 40° to 120° F. They also provide a means of calculating equilibrium ratios for water in the water-TEG-natural gas system; this applies to any desired TEG concentration and to the temperature range from 40° to 120°F. INTRODUCTION During the last several years, the drying of natural gas with aqueous triethylene-glycol (TEG) solutions has become very prominent. Most users of TEG as a drying agent have been satisfied with the performance of TEG solutions at the conditions used; however, there always has been some discussion of the drying ability of TEG solutions at conditions not commonly encountered such as temperatures below 50° or 60°F, but more particularly temperatures above 100°F, and pressures above 1,000 psia. Today, when higher wellhead temperatures such as 120°F are more commonly encountered many are skeptical of TEG's ability to dry sufficiently well to provide dew points around 32°F, which is generally the maximum tolerable when attempting to dry a gas to contract specifications of 7 Ib/MMscf. These views probably have evolved to some extent from the days when suppliers would not guarantee dew-point depressions in excess of 65° to 75 °OF. Also, the feelings about TEG drying may have arisen from the lack of information about the equilibrium relation of water in the drying operations. Porter and Reid' have reported equilibrium data for a 95 per cent TEG solution, while Townsend2 reported equilibrium data for 95, 98 and 100 per cent TEG solutions. Townsend also presented a calculational method which obtains activity coefficients in the liquid phase and, subsequently, the equilibrium water content of a saturated gas over glycol from published3 atmospheric dew points. Wise, Puck and Failey' presented activity data for the water-TEG system at atmospheric pressure. In the past, the equilibrium ratios published for water in a 95 per cent by weight aqueous TEG solution have been used indiscriminately by many for all concentrations of TEG encountered in gas drying operations. Since essentially all such gas operations require the use of more concentrated TEG solutions, a study was undertaken to correlate the existing equilibrium data for aqueous TEG and gas systems and to provide some means of calculating the equilibrium ratio of water in the natural gas-water-TEG system where TEG concentrations were other than 95 per cent. The data presented herein consider only the equilibrium drying ability of the TEG solutions and do not consider the effect of temperature and pressure on the tray eficiency of contactors. In other words, this paper is concerned primarily with the development of the equilibrium relationship between water in the dried natural gas and the water in the lean TEG entering the top tray of the absorber. BASIC EQUILIBRIUM RELATIONS A relationship which relates the K value of water in the natural gas-water-TEG system to the vapor pressure of water at the system temperature, the total pressure of the system and the activities of the liquid and gas phases has been evaluated. It is well known that, for any component of a mixture at equilibrium between a gas phase and a liquid phase,

By Thomas E. Garnar

Zirconium and hafnium are curious elements because they are almost always found together in nature. Zirconium was discovered by Klaproth in 1789 and isolated 35 years later by Berzelius. Because hafnium's chemical properties are so close to those of zirconium, it was not discovered until 1923 when Coster and Von-Heresey detected it using x-ray spectrographic analysis. These elements occur most commonly in nature as the mineral zircon (ZrSiO4) and less commonly as the oxide baddeleyite (ZrO2). They also are found as a variety of other silicates. Zircon was identified as a component in alluvial and beach sands in 1895, but it was not produced in any quantity until 20 years later. Zircon is always a coproduct from TiO2 mining and processing. During World War I it was produced as a coproduct of beach sand mining for titanium minerals just south of Jacksonville Beach, FL, and was patented as a refractory. It was not until the 1930s when Zircon Rutile, Ltd. began mining at Byron Bay on the east coast of Australia that zircon was first used as a foundry sand. Later in the 1940s, NL Industries, Humphreys Gold Corp., and E. I. du Pont de Nemours & Co., Inc. began production of zircon sands from fossil beaches in northeast and northcentral Florida. Baddeleyite first became available as a commercial product in 1916, but never in the quantity of zircon. Zircon holds a unique position as an industrial mineral because it is used for both its physical and chemical properties as well as an ore of zirconium and hafnium metals. Australia is the major zircon producer followed by South Africa and the US. Zircon is also produced in India, Sierra Leone, Sri Lanka, Malaysia, China, Thailand, and Brazil. Undeveloped heavy mineral beach sand reserves containing zircon are known to occur in Egypt, Malawi, Senegal, and Tanzania. Locations are shown in Fig. 1. Mineralogy Zirconium and hafnium are always present together in naturally occurring compounds. Most commonly they form as the silicate sometimes containing iron, calcium, sodium, manganese, and other elements. Less commonly they are found as oxides in combination with titanium, thorium, calcium, and iron. Zircon is the most common form. It is extremely resistant to weathering, therefore, often it is present in ancient beach sands and placer deposits. Although resistant to alteration from external sources, it is vulnerable to internal alteration as the result of thorium and uranium substituting for zirconium either in the zircon lattice or in solid solution. Alteration to the metamict state takes place as radioactive emanations from these elements disorder the crystal lattice, accompanied by hydration, reduction in specific gravity, and changes in color. The mineralogy of zircon and baddeleyite and variation of physical and chemical properties are shown in Table 1. The effects of zircon's internal alteration and darkened color can be corrected by heating to 1000°C for 30 min or so. A certain time-temperature relationship makes it possible for decolorization and reordering of the crystal lattice to take place when heating at higher temperatures for shorter periods or at lower temperatures for longer periods. After heating, x-ray diffraction patterns are sharper, the grains may be harder, and except for particles of malacon, the grains will be white or colorless in the absence of grain surface coatings. The color change is only temporary and the particles slowly darken with time. Zircon fluoresces light yellow in shortwave ultraviolet light. If exposed to ultraviolet light for extended periods of time, white (calcined) zircon turns purple. With time the induced color begins to fade and eventually disappears (e.g., calcined Florida zircon exposed to ultraviolet light for 24 hr still retains faint, but discernible, purple color after six months).

Jan 1, 1983

By R. P. Alger, C. A. Doh, M. P. Tixier

The principle, the equipment and field operation of sonic logging are described. The tfio-receiver system produces logs independent of hole size and mud. Field experience is given and forms the basis for the interpretation of the log. The derivaiion of porosity values from measured velocities is discussed, according to the type of formations (hard formations, compacted sands, and unconsolidated formations). The time-average equation proposed by M. R. J. Wyllie, A. R. Gregory and L. W. Gardner is uscd as a basis for the computation of porosity in limestones, cemented sandstones and compacted sands. Variations in the lithologic character of limestones do not seem to change the porosity calibration markedly. The compaction of sands is related to the compaction of shale adjacent to them; and, thus, the shale velocity is used for the establishtnent of empirical relations for the computation of porosity in un-consolidated formations. Various forrnu.las are tentatively presented to account for shale and fluid content. Field experience demonstrates that considerable attenuation of sonic energy takes place in unconsolidated formations, particularly when gas bearing, and in fractrured formations. Unusually large attenuation produces skipped cycles, a feature easily recognized. The application of sonic logging to structura1 studies is featured, showing its possible integration with the dipmeter. Correlation and its application to the irrterpretation of seisrmic surveys are reviewed. The paper is illustrated with field examples. Sonic logging is the recording of the time required for a sound wave to traverse a definite length of formation. Sonic travel-times are inversely proportional to the speed of sound in the various formations. The speed of sound in subsurface formations depends upon the elastic properties of the rock matrix, the porosity of the formations and their fluid content and pressure. Below the "weathered" or low-velocity layer extending from 50 to 100 ft or so below the surface, sound velocities may range from about 6,000 ft/sec in shallow shales to as much as 34,000 ft/sec in dolomites. In hard formations (well cemented and/or compacted), the sonic log reflects the amount of fluid in the formations; hence, it correlates well with their porosity. In unconsolidated formations, which are usually of fairly high porosity, the sonic log gives an approach to porosity determination, when its readings are corrected for lack of compaction, shaliness, and fluid content. In such formations the sonic log may also indicate the presence of gas and may distinguish between oil- and water-bearing beds. Field experience with the sonic log in soft formations is more limited than that in hard formations. As a result, interpretation in soft formations is not as well developed at the present time. In all types of formations the sonic log is of considerable value for correlation and for the more detailed and accurate interpretation of seismic data. EQUIPMENT AND PRINCIPLE FIELD OPERATION The basic features of the sonic log" are a two-receiver system and two available short spacings. The log is recorded on film using a standard field unit. An SP curve is run along with the sonic curve to give a more interpretable log and to establish absclute depth control for comparison with other logs run in the same well. If desired, a gamma-ray curve may be recorded simultaneously with the sonic curve. Fig. 1 shows the sonic-gamma ray combination sonde. The sonic portion consists of a sound transmitter and three receivers mounted 3, 4 and 6 ft from the transmitter. When the first and second receivers are used, a sonic log of I -ft spacing (distance between receivers) is obtainea. Use of the first and third receivers provides a 3-ft spacing. The transmitter emits pulses at the rate of l0/sec. After the transmission of a pulse the first arrival of sound energy at each receiver triggers its response system. The differ-

By J. G. Patchett, R. W. Rausch

Fresh waters and the presence of clay in many Rocky Mountain and West Coast sands require special methods of log analysis. Archie's saturation equation requires addition of a shale correction term, and the SP equation must also be modified to account for clays. Suitable equations were developed several years ago, but have not been widely used due to the algebraic complexity. A computer-oriented method has now been developed to overcome this problem. The basic shaly sand equations are rearranged in four different ways to permit solution for various sets of available input data. Essential to application of the method is the correction of observed SP values to those that would be observed if the resistivity of the formation waters were exactly interchangeable with the activity. A graphic method for doing this is given. Where conditions require consideration of the effect of clay in the sands, the method presented has been found to improve the accuracy of water-saturation determinations. INTRODUCTION Log interpretation in many Rocky Mountain and West Coast basins is complicated by rapid vertical and lateral changes in water resistivity. Calculation of formation water resistivity from the SP curve becomes difficult in zones that contain clay, since changes in SP deflection may be due to changes in either clay content or water salinity. In hydrocarbon-producing reservoirs, the problem is further complicated because hydrocarbon saturation also reduces the SP.1 A log interpretation system using computers has been developed to provide a solution to this problem, based on equations proposed by de Witte.2 Four different simultaneous solutions of de Witte's equations have been made. Each solution method uses a different set of input data as independent variables. Thus, a choice of solution method is possible, depending upon the logs run and the availability of other data. Two of the solutions do not require a knowledge of water resistivity. This system is intended to be used primarily in multiple sandstone-shale sequences of low and moderate resistivities where the principal contaminant in the sandstones is clay. However, where sufficient regional data are available, interpretation in single-zone sandstone reservoirs can also be improved by using the method. THEORY AND HISTORY OF SHALY SAND ANALYSIS The log interpretation formula originally proposed by Archie3 in 1941 is applicable only to rock-fluid systems wherein the rock has negligible electrical conductivity. In 1949, Patnode and Wyllie4 showed that if the rock itself can be considered conductive due to the presence of clay, a different calculation approach is necessary. During the following years, this problem was investigated at great length, as was the related problem of the effect of rock conductivity on the SP.5-11 These investigations established functional relationships between SP, resistivity, water saturation and water resistivity for such a formation. Refs. 2 and 12 provide summaries of these studies. Unfortunately, practical use of these relationships required that water resistivity be known independently from the SP. Although log interpretation methods for rock systems containing clay were proposed at that time,' they were not generally accepted for routine use. There are three principal reasons for this. First, in many field situations involving high-salinity water, rock conductivity may be neglected (even if present) without introducing appreciable error. This may be seen by considering the following expression for waier-saturated rock.' 1/R2=1/R1+1/FRn....(1) where 1/R, is conductivity due to clay. As Rw becomes small, I/FRw becomes much greater than 1/R, which may be neglected. Where 1/R, may be neglected, the sandstone is called clean. If the term may not be neglected, the sandstone is termed dirty or shaly. For resistivity purposes, the classification between clean and shaly sands then depends not only upon the conductivity due to shale in the sand, but also upon the resistivity of the associated water (shale is used here to mean surface condition due to disseminated clay). A sand of given conductivity might safely be treated as clean in association with high-salinity water, but would require shaly sand methods if associated with fresher waters. Shaly sand methods are not required in many areas having saline waters; but in Rocky Mountain and West Coast sands having relatively fresh waters (often more than 0.3 ohm-m resistivity at formation conditions), the shaly sand methods are needed. Errors Rw calculations from the SP due to the presence of shale are likewise related to water salinity. In saline water formations drilled with fresh mud, the ratio of mud filtrate resistivity to water resistivity is high, the SP is large and the presence of shale can introduce large errors in water resistivity calculated by the conventional method. When the resistivity ratio is low, the errors are smaller. At zero SP, no error would result from shale. Thus, from the SP viewpoint, a given rock could be shaly if associated with a saline water, and clean in association with a fresh water, which is the opposite of the resistivity-oriented definition above.