Search Documents

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By Strathmore R. B. Cooke

On the basis of experiments con- ducted on quartz using a bubble pick-up method, it was shown in an earlier paper1 that this mineral will preferentially adsorb hydrogen, calcium, or sodium ions, depending on the relative concentrations of those ions in the solution in which the quartz is immersed. For quartz particles ranging in size from 0.2 to 1 mm, it was demonstrated that the concentration of calcium in solution (assumed present as ions) necessary to completely activate quartz for flotation is given by the expression: In this expression, ionic concentrations are in mols per liter. It was further shown that the pick-up method is apparently more sensitive to changes in reagent concentration than the standard captive-bubble method, and that induction times are apparently much reduced. Since completing these earlier tests, a new type of cell has been constructed; this is shown in Fig 1 and 2. In Fig 1, A is a ground joint, B is a ceutral tube reaching to within a few millimeters of the bottom of the cell, and C is a stopper which may be removed for re- agent addition, and serves the further purpose of excluding carbon dioxide from the air during the test. The entire cell is constructed of Pyrex glass, and does not give the trouble experienced with the earlier cell, in which activating ions were released from the glass at high pH values. The only critical factor in the construction of the cell is the clearance between the central tube and

Jan 1, 1949

By Keats, J. L.

IN THE literature on the elimination of metalloids in basic open-hearth practice, there are a great many heats recorded in which excellent data on changes in slag and metal composition during refining are given, but in almost all of these heats either temperature data or weights and analysis of charge are unrecorded and observations on the physical charac- teristics of the slag are almost always lacking. With these points in mind, a test heat was made in which as complete as data possible on all the factors that affect the elimination of metalloids were obtained.

Jan 1, 1957

By David B. Reger

Wildcat drilling for new supplies of gas and the expansion of previously discovered oil and gas pools were the principal petroleum activities in West Virginia .during 1942. Much of the new gas exploration is still uncompleted and still indecisive but various wildcats made substantial extensions to existing pools. Out of 53 wildcats drilled 27 resulted in commercial gas and 6 in commercial oil. Four of the oil discoveries also had commercial gas. No strictly new pools of oil or gas can safely be described as discovered but several scattered oil and gas wells previously drilled have been confirmed as the openers of definite pools; also, various completions closed wide gaps between apparent gas pools already discovered. The proved oil territory of the state was increased about 4850 acres and the proved gas territory about 51,000 acres. The new proved oil reserves should about balance withdrawals and the new gas may represent a substantial increase. Aside from the drilling in four rather lively pools, oil activity was slight because of unfavorable operating conditions and prices. Gas drilling also declined for reasons beyond the control of the operators. The account of operations, as gathered from trade journals and other reporting services, shows that 797 new wells were drilled, providing 119 new oil wells with 2762 bbl. of daily new production; 536 new gas wells with 1,228,501,000 CU. ft. of daily open flow: and 142 dry holes. Also... 76 old wells were drilled to deeper sands, with 71 bbl. and 26,034,000 cu, ft. of added production. On the new wells the oil average was 23.21 bbl. per well per day; and the gas average was 2,270,406 CU. ft. per well per day. On new wells the ratio of dry holes to completions was 17.82 per cent. On deeper drilling the ratio of failures was 21.05 per cent. Production of oil for the year was estimated by the Oil ad Gas Journal as 3,492,000 bbl., as compared with 3,378,000 bbl. in 1941. Production of natural gas for the year is estimated by the author as 220,000,000,000 cu. ft., as compared with the U. S. Bureau of Mines final figures of 207,000,000,000 cu. ft.* in 1941. General State op Industry Leasing of wildcat acreage increased considerably. The total land of all classes under lease may now exceed 5,000,000 acres. Taking into consideration completions, abandonments and corrected figures or estimates, Table I shows cumulative and late annual statistics. New Pools and Extensions Table 2 shows the principal areas of drilling activity during 1942. Various consolidations of territory, hitherto treated as separate pools, have been made. in addition to these active pools, extensive drilling was done in numerous other areas where pool boundaries can hardly be defined. Summary or Exploration Table 3 gives a summary of important wildcat or exploratory wells drilled during

Jan 1, 1943

By David B. Reger

Wildcat drilling for new supplies of gas and the expansion of previously discovered oil and gas pools were the principal petroleum activities in West Virginia .during 1942. Much of the new gas exploration is still uncompleted and still indecisive but various wildcats made substantial extensions to existing pools. Out of 53 wildcats drilled 27 resulted in commercial gas and 6 in commercial oil. Four of the oil discoveries also had commercial gas. No strictly new pools of oil or gas can safely be described as discovered but several scattered oil and gas wells previously drilled have been confirmed as the openers of definite pools; also, various completions closed wide gaps between apparent gas pools already discovered. The proved oil territory of the state was increased about 4850 acres and the proved gas territory about 51,000 acres. The new proved oil reserves should about balance withdrawals and the new gas may represent a substantial increase. Aside from the drilling in four rather lively pools, oil activity was slight because of unfavorable operating conditions and prices. Gas drilling also declined for reasons beyond the control of the operators. The account of operations, as gathered from trade journals and other reporting services, shows that 797 new wells were drilled, providing 119 new oil wells with 2762 bbl. of daily new production; 536 new gas wells with 1,228,501,000 CU. ft. of daily open flow: and 142 dry holes. Also... 76 old wells were drilled to deeper sands, with 71 bbl. and 26,034,000 cu, ft. of added production. On the new wells the oil average was 23.21 bbl. per well per day; and the gas average was 2,270,406 CU. ft. per well per day. On new wells the ratio of dry holes to completions was 17.82 per cent. On deeper drilling the ratio of failures was 21.05 per cent. Production of oil for the year was estimated by the Oil ad Gas Journal as 3,492,000 bbl., as compared with 3,378,000 bbl. in 1941. Production of natural gas for the year is estimated by the author as 220,000,000,000 cu. ft., as compared with the U. S. Bureau of Mines final figures of 207,000,000,000 cu. ft.* in 1941. General State op Industry Leasing of wildcat acreage increased considerably. The total land of all classes under lease may now exceed 5,000,000 acres. Taking into consideration completions, abandonments and corrected figures or estimates, Table I shows cumulative and late annual statistics. New Pools and Extensions Table 2 shows the principal areas of drilling activity during 1942. Various consolidations of territory, hitherto treated as separate pools, have been made. in addition to these active pools, extensive drilling was done in numerous other areas where pool boundaries can hardly be defined. Summary or Exploration Table 3 gives a summary of important wildcat or exploratory wells drilled during

Jan 1, 1943

By FRED T. WILLIANS

INTRODUCTION. THE Park City mining-district is distinctively a camp of few properties, 5,000 acres, or one-third of the entire district, being under the management of but three companies. As a rule, the ore-bodies lie deep, with no outcrop, except where erosion has formed the deeper canyons and gulches. Ontario canyon exposed the famous Ontario ledge, and Woodside gulch showed the first ore of the Silver King Coalition mine. The Quincy ore-bodies were first brought to light in upper Empire canyon, and Thaynes canyon was instrumental in aiding the prospector during the early days of the camp. There are 22 shafts which have reached a depth of at least 500 ft., ten a depth of 1,000 ft., five a depth of 1,300 ft., and two a depth of 2,000 ft. The amount of lateral development has been proportionally extensive, including six long tunnels, four of which are in 3 miles, with a fifth now being driven. The Ontario lower drain-tunnel is now more than 4 miles long. The formations are sedimentary, dipping about 30° NW. and N., and traversed by many fissures, dikes, and faults. The principal ore-bodies are found associated either with the contact of the basal Ontario quartzite and the overlying limes, or on a quartzite stratum within the limes, or in the fissures, or along some of the porphyry dikes. The district covers the intersection of the Uintah and Wasatch ranges, which explains the existence of large folds and faults, and fissures of great length, width, and depth. In a general way, the geology of the district consists of a basal quartzite dome, which has been exposed by erosion at the Ontario property. The Ontario fissure lies entirely within this formation. Flanking this dome on the west, north, and east lie

Jun 1, 1911

By Robert W. Hunt

THE memorable features of American history have been making fast during the last century, and notably so since 1860; and they are by no means confined to political or to any one branch of scientific development. Of all the industrial arts, none show a greater change or a mightier progress than the Bessemer manufacture. And this year, while we are celebrating the first centennial of our national life, we can also celebrate the first decennial of American Bessemer practice. While not forgetting or undervaluing what has been done in other countries, I have thought that a brief history of the introduction and development of the Pneumatic or Bessemer process in America would be of interest. In 1863 the Kelly Pneumatic Process Company was formed and an arrangement entered into with William Kelly, who had taken out letters-patent of the United States, Nos. 16,444 ; 17,628, re¬issued as 505; 18,910, dated January 10th, 1857 ; June 23d, 1857; November 3d, 1857; and December 22d, 1857, respectively. This association was composed of the Cambria Iron Company, E. B. Ward, Park Brothers & Co., Lyon, Shorb & Co., Z. S. Durfee, and, later, Chouteau, Harrison & Valle joined the combination. Not satisfied with possessing the control of the Kelly patent, they sent Mr. Z. S. Durfee to England, to secure for this country Mushet's patent on recarburization, No. 17,389, dated May 26th, 1857, the same having been taken out in England on September 22d, 1856. In this Mr. Durfee was successful. Previous to the application of William Kelly for a patent, Henry Bessemer, of England, had taken out patents dated February 12th, 1856, and August 25th, 1856, in this country. Kelly claimed priority in the discovery of the principles of the process, and the Patent-office allowed his claim by granting him his patents. In the autumn of 1862 Mr. Alexander L. Holley, while in England, was impressed with the importance of Mr. Bessemer's inven¬tion, and so fully foresaw its future, that, upon his return to the United States, he induced Messrs. John A. Griswold and John F. Winslow, of Troy, New York, to join him in endeavoring to possess Bessemer's American patents. Mr. Holley returned to England in

Jan 1, 1877

By Robert D. Pehlke, Arden L. Bement

A mass transfer coefficient for the removal of hydrogen from liquid aluminum by inert flush degassing has been determined experimentally at 700°C. A mathematical model has been derived, assuming transport control, which adequately describes the experimental data. The removal of hydrogen is shown to increase with decreasing bubble size, and with increasing flow of flushing gas. The presence of hydrogen in liquid metals in amounts which exceed the solid solubility at one atmosphere hydrogen pressure is highly undesirable, causing unsound ingots or castings, or resulting in difficulties during further fabrication. The removal of hydrogen from liquid metals can be accomplished by several methods, the principal two being vacuum treating and inert flush degassing. The design of a process involving either of these techniques is based on the mass transfer coefficient for hydrogen between the liquid metal and a hydrogen-dilute gas phase. In an effort to extend our knowledge in this area, an investigation of the rate of removal of hydrogen from liquid metals by inert gas flushing was undertaken. In view of the difficulties encountered with gas porosity in the casting of aluminum and aluminum alloys, and because of certain experimental advantages, liquid aluminum was selected for the study. PREVIOUS INVESTIGATIONS The removal of gases from liquid metals, particularly steel, has received considerable attention in recent years, The first definitive work of a theoretical nature was presented by Geller1 who considered the case where equilibrium exists between purging gases and metal bath during flushing, and also deviations from this ideal case. Hulme2 has surveyed a number of experimental studies and discussed some of the practical limitations of removing dissolved gases from molten metals. More recently a number of studies have been reported on degassing of steel melts by flushing with an inert gas.3'4 Considerable work has also been reported on aqueous and organic liquid-gas systems, and an excellent summary prepared by Hovis.5 The treatment of liquid aluminum by a flushing gas to remove dissolved hydrogen has been known for several decades.6 A number of gases have been used for this purpose, including nitrogen, argon, and chlorine, or mixtures of these gases. Tikkanen and Erkko7 have studied the relative density changes of aluminum castings poured from melts degassed with chlorine, nitrogen, and mixtures of the two gases. Their

Jan 1, 1962

By J. J. Jonas, J. L. Uvira

Equipment was constructed which permitted the hot compression of 99.8 pct Armco iron and 2.8 pct Si steel at constant true strain rates of 0.05 to 1 per sec over the temperature range 600" to 1000°C. A maximum true strain of 1.9 could be attained, followed by immediate quenching or by isothermal annealing. True stress-true strain curves were obtained, and the steady-state flout stress, a, strain rate, i, and temperature, T, were found to fit the following expression: The constants A, a, n', and AH were determined for the two ,materials. The activation energies obtained for Arrnco iron and silicon steel are 66 and 80 kcal per mole, respectively, and approximate those for seu- diffusion and for creep. This indicates that hot compression is a diffusion-controlled thermally activated process. THE hot compression of iron and steel is usually carried out in the austenite temperature range,1"7 as this is the one of greatest interest with respect to industrial hot working. However, a disadvantage of testing in the austenite range is that the hot-worked structure is destroyed by the phase transformations taking place during cooling. The present study was therefore carried out in the ferritic temperature range, and the hot-worked substructures were preserved by rapid quenching after deformation. The substructural results will be described in a separate paper, and the present communication is restricted to the strain rate/stress/temperature relationship observed during hot working. The results of hot-compression testing are usually given in the form of true stress/true strain curves, with a different curve for each temperature/strain rate ~ornbination.',~,~ Sometimes simple algebraic equations are fitted to the curves, so that certain extrapolations or interpolations can be performed.1'2'5 These equations are, however, devoid of mechanistic interpretations. The present study was undertaken to show that hot compression can be described by an equation of the type used in creep studies. That is, it will be shown that the temperature dependence of the strain rate in hot working is well-represented by an Arrhenius term, with an activation energy similar to that for creep. Also it will be seen that the stress dependence of the strain rate is similar to that for creep EXPERIMENTAL METHOD AND MATERIALS The investigation was carried out with the following three ferrous materials: 1) Armco iron; 2) Armco iron with 0.26 pct Mn; 3) 2.8 pct Si steel. The first two materials were utilized for investigations performed in the temperature range 600" to 800°C; the last one was used for tests at temperatures from 600" to 1000°C. The materials were of commercial purity,* as shown in Table I. Cylinders of five different sizes were prepared by strain annealing. The resulting mean grain diameter was 3 mm in the 1-in. Armco iron and 2 mm in the other sizes and grades. Different ratios of diameter/height were used to enable the determination of the coefficient of friction. The specimen faces were provided with concentric grooves, which acted as lubricant holders during compression, as recommended by English and ~ackofen' and others.2'9 Powdered glass lubricants were applied to the samples before hot compression to decrease friction and barreling, following the practice of previous investigator~.~~~~~~~~ Different mixtures of glass powder were used for each temperature, after the determination of suitable compositions by experiment.'' Equipment for Hot Compression. Hot-compression tests were carried out on an adapted 150-ton vertical hydraulic extrusion press and also on a modified high-temperature creep machine. The modified extrusion press was used for temperatures up to 800°C. The following items were added to the press: a) a high-temperature furnace with built-in upper and lower platens; and b) a transmission assembly, which permitted the attainment of logarithmically decreasing crosshead speeds. These accessories are described in detail in Ref. 11.

Jan 1, 1969

By William E. Ford, Edward Salisbury Dana

34. Axial Ratio, Axial Plane. - The crystallographic axes have been defined (Art. 22) as certain lines, usually determined by the symmetry, which are used in the description of the faces of crystals, and in the determination of their position and angular inclination. . With these objects in view, certain lengths of these axes are assumed as units to which the occurring faces are referred.

Jan 1, 1922

By J. W. Spretnak, G. W. King

THE crystallography and morphology of 0-Al,Fe precipitates in an A1 + 0.5 wt pct Fe alloy have been studied by transmission electron microscopy. The alloy was cast in cylindrical ingots, 15 cm in diameter and 60 cm in length, and cooled slowly. The measured composition was 0.527 wt pct Fe, 0.001 wt pct Mg, and 0.003 wt pct Cu. Spectrographic analysis revealed no additional trace impurities. Thin slices were cut from the ingot and reduced by more than 95 pct by rolling to a thickness of 0.1 mm with no intermediate annealing treatments. These thin sheets were then vacuum-annealed for 1 hr at 612°C and air-cooled in their capsules. Thin foils for examination in the electron microscope were prepared by electropolishing. The precipitate is found in the form of oval platelets on the (110) planes of the matrix. The major axes of the platelets are parallel to the (110) directions of the matrix, and vary in length from 1/2 to 2 p. The thickness is about 1/10 p. Examples of platelets, both in the plane of the foil and normal to the foil, are shown in Figs. l(a) and l(b), respectively. lack' found that ?-A13Fe (more correctly All13Fe4) belongs to the monoclinic system. Using Black's structural data and simultaneous electron-diffraction patterns from the matrix and precipitates, the habit planes and directions were determined to be: (00l)? || (110)Al [100]? || [001]Al The orthogonal crystallographic axes of the precipitates are accurately in the habit plane, while the measured coincidences of the directions are only within 10 deg. The major axis of the platelet is parallel to [010] in the 0. This orientation corresponds to the direction of nearest registry of the lattices.

Jan 1, 1964

By A. E. Zawadzki

A progress report is presented on the development of a process for the removal of sulfur dioxide from flue gases. Catalytic oxidation of the sulfur dioxide in flue gases, with the production of recoverable sulfuric acid, has been demonstrated to be technically feasible. Problems associated with the process are discussed. The need for an inexpensive and efficient process for controlling sulfur dioxide emissions from utility plant stacks has been accentuated by the ever-increasing public demand for elimination of all man-made air pollutants. I would like to describe the results of an investigation of the development of such a process; more important, I would like to present a discussion of the problems associated with the process which remain to be solved. The research work on the BCR catalytic gas phase oxidation process has been jointly sponsored by the Association of Edison Illuminating Cos., Edison Electric Inst. and Bituminous Coal Research, Inc., since 1958. However, work on SO2-pollution abatement was initiated by BCR in 1953. Tieman and Clymer,1 working with ozone and simulated flue gases, evaluated a gas phase oxidation process for removing SO2 from flue gases. Their experimental data indicated that the use of ozone to oxidize SO2 in flue gas concentrations, with subsequent recovery of H2SO4, did not appear to be economical due to the large ratio of ozone to sulfuric acid produced (2.6 to 1). The cost of the ozone would be 6 to 10 times the cost of sulfuric acid produced. As a result of the ozone study, work on a catalytic oxidation process was developed. The following reactions are the basis for the catalytic oxidation process Reaction [I] normally occurs in the combustion of sulfur-bearing fuels. At the high temperature found in the combustion chamber, 95% to 99% of the sulfur in the fuel is oxidized to SO2 and 1% to 5% is oxidized to SO3. The concentration of SO2 in the combustion gases depends on the combustion efficiency and the quantity of excess air used. A commonly used rule of thumb is 0.1 percent by volume SO2 in the flue gas for each 1% sulfur in the fuel. Reaction [2] proceeds at a wide range of temperatures. The rate of the reaction is rapid above l,000°F; however, the equilibrium conversion drops rapidly above this temperature. 2 Reaction [3] occurs rapidly to completion at temperatures below 400°F; above this temperature some SO3 exists in equilibrium with H2SO4. Complete dissociation of H2SO4 occurs above 650°F.3 The simplicity of the proposed process provided added incentive to the development and evaluation of the various component unit operations. The advantages of the process were considered to be as follows: 1) no raw materials were required, 2) the unit operations were not radically new; and 3) a salable product, sulfuric acid, would be produced. The successful development of the process was contingent upon the solution of several major problems: 1) The development of a catalyst which would provide high catalytic activity at reasonable conditions of gas flow and temperature without causing an unacceptable increase in pressure drop. 2) The development of a high temperature dust collection system to provide clean flue gases to the catalytic reactor. 3) The complete recovery of the sulfuric acid produced in the process; the effluent gas must contain less than 20 ppm by volume of sulfuric acid. As of this date, the complete solution to these problems has not been achieved. EXPERIMENTAL Catalyst Development: The use of platinum and vanadium catalysts for the production of sulfuric acid by the treatment of dry gases containing 5% to 20% by volume sulfur dioxide has been known for many years. The application of the basic idea of catalytic oxidation of sulfur dioxide in flue gas concentrations was

Jan 1, 1965

By J. Szekely, V. Stanek

Heat and gas flow interactions in nonisothermal packed beds were examined in the paper. A study was made of the response of the system to a step or pulse change in the inlet gas temperature, with a fixed value of the overall pressure drop across the bed. Under these conditions the heat flow and fluid flow transients are coupled because the convective heat transfer rate is alfected by the mass flow rate of the gas which, in turn, for a fixed pressure drop will depend on the temperature profile in the system. The Problem was stated in terms of differential equations, which were integrated numerically. The parameters used in the computation were so chosen to reflect the operation of the stack region of blast furnaces and sinterbeds. The computed results showed that the pressure drop-flou1 relationships and the rate of progress of the temperature fronts (waves) were strongly interrelated and were also markedly affected by variations in particle size and in void fraction. MANY metallurgical processes involve the contact of solid particles with a gas stream in a packed bed arrangement under nonisothermal conditions. Examples are shaft furnaces, regenerators, pebble heaters, and the sinter process. Although the heat and mass transfer aspects of packed bed processing have been extensively studied, the associated flow phenomena and in particular the effects of nonisothermality on the flow, have received little attention to date. :In fact, most of the previous workers considered the flow rate of the carrier gas time invariant and independent of the heat or mass transfer processSzekely and carr2 have shown that the pressure drop-flow relationships in nonisothermal packed beds may be strongly affected by the temperature profile within the system. These authors have devised a method for relating the pressure drop to flow for a given temperature profile. thus providing an extension of the Ergun equation to steady nonisothermal systems. Finally, in a recent paper willmot3 examined the response of regenerators to externally imposed changes in the gas flow rate. Both these investigations were somewhat specialized since, in general, neither the temperature distribution nor the gas flow rate may be regarded as truly independent variables, thus the heat transfer and the fluid flow problems have to be solved simultaneously. The work reported here is divided into two parts: in Part 1 the general formulation is given and a detailed discussion is presented of fixed bed systems. Part is devoted to systems in which a gas and particulate solids are contacted in a counter flow arrangement. FORMULATION Consider a nonisothermal fixed packed bed, extending from through which a gas is flowing. The problem is to develop a relationship between pressure drop and gas flow (with the gas flow being the dependent variable) and to evaluate the rate at which a change in the gas temperature, imposed at the inlet, travels through the system. Let us consider an infinitesimal section of the bed and establish differential heat, mass, and mechanical energy balances over this region. In addition, relationships are needed describing the temperature dependence of gas density (equation of state) and the temperature dependence of viscosity. These may be written as: where c, and are constants. It is noted that in this formulation we neglected any temperature gradients within the solid particles, thus assuming these to be either sufficiently small or of sufficiently high thermal conductivity to meet this condition. The justification and consequences of this assumption will be mentioned in the discussion.

Jan 1, 1970

The industrial might of the Bowen Basin is primarily the result of Utah Development Co.'s work- which has opened up the Blackwater, Goonyella, Peak Downs, and Saraji mines; built the Hay Point port; and is now developing the Norwich Park mine.

Jan 1, 1977

By A. O. Drysdale

In Canada, the market for cement is not a national one but rather a collection of local or regional markets. Excess capacity on a national basis does not necessarily preclude a shortage on a regional basis. with portland cement selling for less than a cent a pound, the low price-to-weight factor makes transportation to the market a major cost item and thus a small plant can be justified to serve a limited regional market. The Brookfield plant of the Canada Cement Co. is designed to supply the Province of Nova Scotia, a regional market that shows promise of growing to a point where it will support a one-kiln plant. The market is presently being served by boat shipments from the Canada Cement Co. plant at Montreal East, Quebec, and from the North Star Cement Ltd. plant at Corner Brook, Newfoundland, and by rail and road shipments from the Canada Cement Co. plant at Havelock, N. B.

Jan 4, 1965

By W. J. Joslin

The frontal-advance equation can determine how the fluid withdrawal rate and subsurface operating pressure influence oil recovery from pressure-maintained reservoirs having characteristics favorable for efficient vertical segregation. For effective vertical segregation in formations having low dip angles, the requirements are: thick, massive sands, low viscosity oil and high vertical permeability with few discontinuous shale members. This approach has been successfully applied to the LL-370, which is a massive Eocene sandstone reservoir containing crude with an average gravity of 26" APT, a dip of only 3" and vertical permeability of ½ darcy. The average gas cap saturation was calculated for various rates of vertical gas-oil contact movement corresponding to a wide range of reservoir producing rates. This method also evaluated the effect of different pressure maintenance levels on oil recovery. Applicability of this procedure for calculating the present oil saturation in the LL-370 gas cap has been substantiated from field performance, where the oil saturation was computed by comparing oil recovery with the gas cap volume vacated. INTRODUCTION During the natural depletion history of the LL-370 reservoir, located in Lake Maracaibo, Venezuela, excellent vertical segregation resulted in the formation of a thin gas zone over a substantial portion of the oil-productive area. Subsequently, gas injection forced this thin gas-saturated zone slowly downward, reducing the oil saturation in the gas cap to a low value. The oil recovery has been raised considerably above earlier predictions where vertical segregation effects were under-estimated. In order to determine the maximum efficient producing rate and optimum operating pressure for this reservoir, a vertical gas frontal-advance analysis has been made through application of the fractional flow equation. LL-370 RESERVOIR CHARACTERISTICS The reservoir consists of a truncated monocline of massive. highly-permeable Eocene sandstone, called the B-b formation, covering an area of more than 13,500 acres. The original oil in place was 2.17 billion STB. Internal non-sealing faults subdivide the structure into four blocks called the B-6-x.6, 10, 11 and 13, which are effectively bounded by major faulting on the flanks, an unconformity updip to the west, and an immobile aquifer to the southeast. The producing formation occurs at an average depth of 5,250 ft subsea and has a closure of more than 1,500 ft. A typical producing section has a net oil sand thickness of 170 ft. Scattered throughout the section are a few randomly-positioned shale lenses which increase in thickness and areal extent downdip. The reservoir rock and fluid properties vary with depth. The permeability and produced oil gravity are 1600 md and 28" API at the top, compared to 300 md and 18° API at the water-oil contact. The productivity of updip wells is, therefore, much higher than the reservoir average. The reservoir oil was originally saturated at the crest, grading to a slight degree of undersaturation at the water-oil contact. There was no original gas cap; and material balance and the field performance indicate no water influx. Except for the northern B-6-x.6 block, the fluid and rock properties have already been published.' Average LL-370 reservoir properties are shown in Table 1. RESERVOIR PERFORMANCE UNDER NATURAL DEPLETION Fig. 1 shows production performance from 1939 to date. Early development was gradual, with 30 wells pro-

Jan 1, 1965

By C. F. Jenkins, G. V. Smith

Serrated plastic flow in stable austenitic alloys based on Fe/Ni has been shown to be related to the presence of carbon and/or chromium in the systems. Strength peaks and plateaus in the serrated-flow temperature region for a commercial alloy correlate with an increased dislocation content, arising, presumably, from enhanced multiplication as a result of a strong interaction between dislocations and solute atoms. The data generally support a mechanism controlled by migration of vacancies, with the energy for vacancy motion being modified by the presence of chromium. Chromium atom -dislocation interaction is responsible for effects above 500°C, whereas the defect interacting with dislocations between 200" and 500°C is suggested to be a carbon-vacancy Pair. ThE phenomenon of jerky flow, serrated flow, or the Portevin-le Chatelier (P-C) effect in austenitic stainless steels is usually attributed to substitutional at1,2 mospheres1,2 or to precipitates&apos;-4 which form at dislocations during plastic deformation. On the other hand, evidence exists which supports a direct inter-stitial-dislocation interaction mechanism for serrated flow in fcc Ni-C,5,6 Ni-H7-9 and in nickel-austenites containing carbon." The present work consists in a study of serrated plastic flow in stable austenitic al-loys. The effects of carbon and of chromium were investigated separately, and a commercial stainless steel with different levels of interstitial impurity concentration was studied in an attempt to delineate the combined effects of the alloying elements. EXPERIMENTAL TECHNIQUES a) Materials and Fabrication. A commercial AISI 330 stainless steel and several specially prepared aus-tenitic alloys have been studied. The experimental alloys were prepared by arc melting the constituents under purified argon. Analyses of the materials are given in Table I. The commercial alloy was obtained as 5/8 in. bar stock and rolled to 0.092 in. sq, with several intermediate anneals. At this stage some of the material was annealed in Pd-purified hydrogen at 1100°C to establish different levels of interstitial content. All other heat treatments were in vacuum (10-5 torr). The "pure" alloy ingots were swaged to 0.120-in. rod and annealed in Pd-purified hydrogen at 1100°C. The analyses for these conditions are also contained in Table I. Following the above treatment, the final wire sizes Table I. Chemical Analyses of Test Materials Hrin Hydrogen at Cr, Ni, Alloy 1lOO°C wt pct wt pct C, ppm* N, ppm* Type 330 As-received 14.78 33.25 430 300 Type 330 64 14.78 33.25 40 50 Type 330 200 14.78 33.25 27 21 Fe/35 Ni 72 - 35.10 <10 62 Fe/35 Ni 200 35.10 <I0 44 Fe/35 Nil15 Cr 72 14.95 34.94 <I0 61 Fe/35 Ni/15Cr 200 14.95 34.94 <10 45 Fe/35 Ni/C $ 35.OM 380 *Sensitivity: N t 5 ppm Ct10ppm. f Nominal Ni content. % A master NiC alloy was used in preparation of this material; courtesy of D.E. Sonon. were obtained by either swaging or cold drawing. The test results did not vary with these techniques. b) Specimen Preparation. Two sizes of specimen and two gripping systems were used. i) 0.070-in. wire with a chemically milled gage section: 0.75 in. long, 0.060 in. in diam. These were fastened into grips containing tapped grooves. ii) 0.050 in. wire, gage length 1.5 in. Ball bearings were welded to the ends of the wires and the gage length was taken to include all material between the welds. Socket-type grips were used with these specimens. With specimens of type ii), joining was performed in a specially constructed brass jig, under argon, and automatic timing was utilized in the procedure. No adverse effects of welding were noted. Specimens were encapsulated and solution treated for 1 hr at temperatures selected to produce the same average grain size, -50 µ. Annealing twin boundaries as well as normal crystal boundaries were counted. The temperatures used are listed in Table 11. Table 11. Specimen Size. Temperature of Heat Treatment and Resulting Grain Diameters for Test Materials Recrystallization Resulting Material Condition Temperature Grain Sue AISI 330 Not H purified 0.070 120O°C 45 to 55µ in, wire AlSl 330 H , pure, 0.070 in. 1150°C 45to55µ wire Fc/35Nil15Cr Pure, 0.070 in. wire 1000°C 45tossp Fe/Ni Pure. 0.070 in. wire 775°C 45 to 55µ Fe/Ni/C Pure, 0.050 in. wire 850°C 10 to 20p AlSl 330 Not purified, 0.050 1150CC 45to55p in. wire AlSl 330 ti, pure, 0.050 in. 1150°C 45to55p wire

Jan 1, 1970

By Albert Sauveur

As THE years go by, names of distinguished metallurgists will be added to the list of Henry Marion Howe lecturers, and now and then an illustrious one, for to be chosen to deliver the Howe lecture will be, I do not hesitate to predict, a highly coveted honor. I pray, therefore, your indulgence, if I confess to a feeling of gratification in having been appointed the first of these lecturers. It does not follow, however, that I am losing all sense of proportion and that I have an exaggerated idea of the little I have been able to contribute to our knowledge of iron and steel. Indeed, I fully realize how small were my claims to so great a distinction. I realize, also, that those entrusted with the task of selecting a lecturer were actuated, in coming to a decision, by their knowledge of the long and intimate friendship that had existed between the leader we have lost and myself. For their generous impulse, I thank them from the bottom of my heart; and with becoming modesty, I take up my task as the first Henry Marion Howe lecturer. It would be pleasant and indeed most appropriate to devote this entire lecture to a eulogy of Henry Marion Howe and his work, but how short the time for so large an undertaking and how inadequate my qualifications! On Aug. 28, Sept. 4, 11, and 18, 1875, a series of articles appeared in the Engineering & Mining Journal entitled "What is Steel?" With one exception, these constitute the first professional paper of Henry Marion Howe. That was nearly fifty years ago, three years after graduating from Harvard University. He was then but twenty-seven years old and already his keenly inquisitive mind was actively at work. There is a touch of romance in this young metallurgist who, on entering his. scientific career, destined to be so brilliant and so fruitful, on the very threshold of it, seems to have selected as his motto "What is Steel?" Like a knight-errant of science, he started on his quest for an answer to that question, a quest which was to last forty-seven years and which death only brought to an end. And while thus engaged how many wonderful messages we received from him, each one bringing us nearer to the goal! How illuminating, inspiring and encouraging were those messages! How well-equipped he was to wrench from nature some of the secrets she so jealously guards! How broad his learning and how clear his

Jan 5, 1924

By William E. Ford, Edward Salisbury Dana

IN the representation of crystals by figures it is customary to draw their edges as if they were projected upon some definite plane. Two sorts of projection are use8; the ah- graphic in which the lines of projection fell at right angles and the chirographic where they fall at oblique angles upon the plane of projection. The second of these projections is the more important, and must be tr2atcd here in some detail. Two points are to be noted in regard to it. In the first place, in the drawings of crystals the point of view is supposed to be at an infinite distance, and it follows from this that all lines which are parallel on the crystal appear parallel in the drawing. In the second place, in all ordinary cases, it is the complete ideal crystal which is represented, that is, the crystal with its full geometrical symmetry as explained on pp. 10 to 13 (cf. note on p. 13). In general, drawings of crystals are made, either by constructing the figure upon a projection of its crystal axes, using the intercepts of the different faces upon the axes in order to determine the directions of the edges or by constructing the figure from the gnomonic (or stereographic) projection of the crystal forms. Both of these methods have their advantages and disadvantages. By drawing the crystal figure by the aid of a projection of its crystal axes the symmetry of the crystal and the relations of its faces to the axes are emphasized. In many cases, however, drawing from a projection of the poles of the crystal faces is simpler and takes less time. The student should be able to use both methods and consequently both are described below.

Jan 1, 1922

By Dean, R. S.

THE numerous theories of hardening which have been advanced in recent years are all satisfactory in accounting for some of the phenomena observed in hardening metals, but none so far presented account for all of the facts observed. Some years ago one of the authors, R. S. Dean,&apos; presented a theory to account for some of the properties accompanying work hardening. The present paper develops this theory further in the light of recent experimental work and extends it to other forms of hardening. Many of the ideas included have come from the writings and personally communicated thoughts of others. We have attempted to give proper credit in every case, but it is possible that we have not always done so. As an historical basis it is desirable here to review very briefly the hardening theories which have been current. The first comprehensive theory of work-hardening phenomena was due to Sir George Beilby.2 He contributed the idea that with cold work part of the structure of the metal was rendered amorphous and that-it was to this amorphous material that the cold-worked metal owed its difference in properties. According to Beilby&apos;s theory this amorphous material was a supercooled liquid and, therefore, had the characteristics of a vitreous material. That such a theory is not capable of explaining the property changes in metals has been repeatedly pointed out. This theory also allowed a slip to take place only once on a given plane, which, as has been pointed out by Jeffries and Archer13 is not consistent with the observed length of an, individual slip and the amount of elongation which can be obtained by wire drawing. The modifications, which have been proposed to this hypothesis to make it coincide with the experimental facts, have to a considerable extent robbed the theory of its clean-cut characteristics. The commonest of these modifications replaces the amorphous phase with an

Jan 1, 1927