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By A. L. Holley

The occurrence of this gas, in quite appreciable quantities, has been observed for many years in its escape along the creeks of Western Pennsylvania, and more recently, in much larger quantities, from the oil wells in and near Venango County. Within about five years several gas wells have been struck, from which the gas has escaped continuously in prodigious quantities and at great pressure. During the last year a systematic attempt has been made to utilize the flow of gas from one of these wells, and results have been reached which were quite unexpected. This well, near Leechburg, Armstrong County, is about twenty miles northeast of Pittsburgh, on one of the side tributaries of the Alleghany River. It had been drilled in search of oil to a depth of 1250 feet in 1871, but none was found. A great flow of gas was developed, however, accompanied by a slight spray of salt water, and this has continued with little or no diminution to the present time. The gas in its escape has been discharged through a 5-inch pipe, and at a pressure of from 60 to 80 Ibs. per square inch, but no exact determinations, either of the pressure or quantity, have been made. The rolling mill of Messrs. Rogers & Burchfield is on the opposite side of the river, and it has been for some years devoted to the production of fine grades of sheet iron from charcoal pig metal, by puddling and in knobbling fires. The usual weekly product of the mill has been 30 tons of No. 30 tin plates, and 50 tons of No. 24 to 28 sheets. The well was bought by this firm for $1000, and the gas is led across the river, a distance of about 500 feet, through a 3-inch pipe. It is distributed through half-inch pipes, and at a pressure of about 45 Ibs. per square inch, to several of the furnaces, but a large fraction of the total flow of gas is still wasted at the well. No essential alteration in any of the furnaces has been found necessary in the use of the gas fuel, except to brick up the firebridge and to put in the gas and air pipes. The old grate used for coal is loosely covered with bricks and cinder, so that a slight percolation of air may take place through them. The gas is admitted through a half-inch pipe, and blows toward the fire-bridge through 18 or 20 one-eighth inch jets. The air is blown in at about 2 lbs.

By W. T. Thom

ALL engineering education is faced by certain basic problems, three of which seem to have particular present importance in geological engineering training in general, and in respect to training for oil field geoexploratory work in particular. PROBLEM I The first of these problems has to do with present and future educational objectives and with the numbers and qualities of the men who should be coming out of our geoexploratory training programs. Before the war we needed ever-increasing numbers of graduates at the Bachelor's level and a very much smaller number of men who had reached the Doctorate degree. Now, with more difficult, more extensive, and more costly exploratory work; with a rapid expansion of company "staff" activities, and with the initiation of many new research organizations and laboratories; it is clear that men of exceptional ability will be more and more in demand, and that the schools will need to carry a greater proportion of their students through to the Ph.D. degree. PROBLEM 2 Assuming that the mineral industries will need an increasing supply of well-qualified Ph.D.s for future geoexploratory work (staff, line and research), can the schools expect to provide this supply of able Ph.D.s merely by expanding the proportion of B.S. and B.A. majors who go on through to the doctorate stage of training? And the answer is definitely "No "-as the situation stands at present. Most A.B. graduates are years short of the preparations in basic science and elementary engineering prerequisite to effective graduate study in the geoexploratory fields (paleontology excepted), and similarly many of the annual crop of B.S. graduates lack adequate training in English; in ancient and modern history; and in the modern principles of labor and public relations. Indeed, several basic problems of undergraduate curricular organization and integration remain to be solved before most recipients of a Bachelor's degree will have that sound and broad educational foundation prerequisite to graduate training on a really effective basis. It is for these reasons that we have continued to experiment with our geological engineering program at Princeton, in an endeavor to provide a pilot-plant demonstration of a suitably broad and flexible undergraduate curriculum. PROBLEM 3 But assuming that the schools can and do get undergraduate curricula set up in proper phase and scale to meet needed enrollment quotas for graduate training, what about the most urgent part of our whole mineral-industry educational problem? What about finding and bringing into mineral-industry training those youngsters of superior ability who are, by potential or known inclination, especially well-qualified for geoexploratory work?

Jan 1, 1947

By M. G. Cheney

THE production record of the Sinclair-Moren pool, in southeast Young County, Texas, demonstrates that under efficient operating methods a single well may obtain normal oil recovery from an area of 100 acres or more. This record is the more surprising in view of relatively adverse reservoir conditions such as lack of water drive, moderate initial reservoir pressures and a consolidated sandstone reservoir with original permeability greatly reduced by processes of lithification. This case history is considered worthy of special study in view of the ever present problem of proper spacing of wells. Cupidity, abetted by the unrestrained law of capture, has in too many instances guided development and production methods without regard for sound economic and engineering principles. Largely as a result of ill advised spacing of wells, many oil fields have brought financial losses instead of deserved profit to those using capital, time and energy in this important business of adequately meeting the petroleum requirements of what is known as our modern civilization. In March 1923, the Sinclair Oil and Gas Co. obtained initial daily production of about 12,000,000 cu. ft. of gas and 1100 bbl. of oil in its first well near the center of a 372-acre lease on the L. P. Moren land, James Rose survey, Abstract 245. This exploratory test was drilled as a geological prospect of average promise, on a plunging anticline with possibly 10 ft. of closure as mapped on the outcropping limestone of upper Canyon (Pennsylvanian) age. In subsurface, the top of the producing res-ervoir is 16 ft. lower in this well than in the highest wells but probably 25 ft. above lowest closing contour. Wells No. 2 and 3 were drilled about 1/4 mile west and southwest near a normal fault with some 30 ft. of downthrow to the southwest. The producing sand was reached at a depth of 2512 ft. and drilled to 2529 ft. in the first well. This sandstone reservoir is of Millsap Lake (middle Strawn, upper Cherokee) age. It was absent in the second and third wells, which were abandoned at the depths of 3725 or more. In April 1925, a fourth well was drilled 600 ft. east and 24 ft. lower for top of sand than No. I. Production of about 100 bbl. daily was reported from 2521 to 2562 after an 80-quart shot. This well was drilled to 4560 ft., plugged back to 2575 and shot again; but was abandoned soon thereafter because of small production.

Jan 1, 1940

By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O'Neill1 observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in intergranular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by 10 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle' in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. [ ] In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1941

By W. C. Hagel

Previous inuestigators have repovted unusually low H* and Do values for self-dzf@szon in certazn bcc metals, e.g., chromium nnd y -uvanium. It has been postulated that this is nn experimental crl -tetion for the existpnce of a four -atom ring meclzanzsm, mid there could be. zmpovtant theoretrcal Implicatlons. By utilizing a precise sectioning technique with Cr51 as the tracer, self-dzffi-lsion measurements in large grains of 99.99-pct Cr were extended from 1200° fo 1600"C. A least- squares analysis of the data yields that D 0.280 exp (-73,20U/RT) cm2 sec-'. These AH* and Do unlues are not anomalous; there is little reason to believe that n vacancy mechanism is not opevatiue. Apparent differences at lower temperatures may result from preferential diffusion along short-circuititing paths and/or sample contamination. WITH continued technological effort, chromium and chromium-base alloys should ultimately become useful high-temperature structural materials. Accurate measurements of self-diffusion coefficients in the pure metal are necessary for a quantitative understanding of sintering, grain growth, creep, and other related rate processes. However, two conflicting determinations have been reported.* Using an Since careful diffusion studies normally yield Do values ranging from 0.1 to 10 cm2 sec-l, the Paxton-Gondolf results require independent experimental corroboration before an undue amount of speculation arises to explain the apparent anomaly. As discussed by Nowick6 and clearly shown by Hoffman and Turn-bull7 for self-diffusion in silver, a low AH* and Do can arise from preferential diffusion along grain boundaries or other short-circuiting paths. The most reliable data come from high-temperature measurements where volume effects predominate. Following a precise sectioning technique developed for determining silver diffusion in the intermetallic compound AgMg8 and cation diffusion in the corundum oxide Cr2O3,9 the purpose of this study was to measure true volume diffusion in high-purity, large-grain samples at higher temperatures than considered previously. Another point of interest is the frequent proposal10-12 that chromium undergoes an allotropic transformation between 1375" and 1800°C where the diffusion data might then show a discontinuity. I EXPERIMENTAL 1) Sample Preparation. The highest purity (99.997 pet) Cr currently available is produced by reduction of chromium tri-iodide. Three pounds of the resulting crystal bar were shipped in a sealed container with a complete chemical analysis from the vendor.* In conformity with the procedure used for

Jan 1, 1962

By I. R. Kramer

The effect of the specimen diameter, d, on the flow stress, cra of polycrystalline aluminunz (99.997) was studied. The increase in the flow stress could be accountedfor by the increase in the surface layer stress, with decreasing specimen diameter. Both , and a, were found to be proportional to For the smaller-dianzeter specimen (< 0.033 in.) at strains less than aboul 0.1, the work hardening of the surface layer was greater than that associated with the bulk of the specimen. At higher strains the work hardening due to the bulk appears to be independent of the specimen diameter. THE increase in the strength of metals with decreasing diameter is well-known; however, an adequate explanation for the cause of the size effect is still lacking. The earliest systematic investigation of size effect appears to be that of Onol who reported that for aluminum monocrystals the resistance to slip at low strains increased as the specimen diameter decreased. A change in the stress-strain curve beyond 0.001 strain was not found. However, Suzuki et a1 .&apos; reported for monocrystals of a brass and copper having diameters in the range of 2 to 0.12 mm that the entire stress-strain curve was raised as the specimen diameter was decreased. The effect of size was most apparent when the diameter of the specimen was less than 0.5 mm. In the discussion of this paper Honey-combe reported a size effect in copper crystals as large as % in. diam. These results are in agreement with those of paterson3 and Garstone et al.4 While the majority of the investigations on size effects was conducted in terms of the variation in the diameter of the specimen, several investigators studied the influence of the specimen geometry. For example, Wu and smoluchowski 5 reported that in aluminum monocrystals the slip system was a function of the specimen dimension in the slip direction. King-man and Green 6 studied the influence of size on the compressive stress-strain relationship of aluminum monocrystals when the ratio of length to diameter was constant. Their specimen diameters ranged from to & in. For specimens oriented for single slip the critical resolved shear stress for the smaller-size specimens increased with decreasing diameter. No effect was observed in the large-size specimens. Specimens having an orientation near the corners of the stereographic triangle did not exhibit a size effect. Apparently, the increase in strength with decrease in the diameter of the specimen is a general phenomenon and has been observed in a brass |T and cadmium as well as in aluminum and copper.&apos; In a series of investigations (for example Ref. lo), it was shown that during deformation a surface layer was formed which imposes a back stress, a,, on the moving dislocations. It is reasonable to predict that this surface layer stress, as, should be a function of the specimen diameter and could possibly account for the flow stress size effect. In fact, experimental evidence will be presented to show that this is the case; i.e., the increase in flow stress with decreasing size is equal to the increase in the surface layer stress, as, with size. In addition, data will be presented on the variation with size of and a* where is the back stress associated with the generation of dislocation obstacles in the bulk of the specimen and a* is the net effective stress acting on the mobile dislocations. A limited investigation was carried out on gold specimens to determine the influence of an oxide film. EXPERIMENTAL PROCEDURE The aluminum specimens were prepared from -in. bar stock (99.997 pct purity). The 0.350- and 0.150-in.-diam specimens were machined directly from the bars while the specimens having a diameter of 0.033, 0.020, and 0.015 in. were prepared by swaging and drawing to 0.04 in. and electropolishing almost to final size. The specimens were prepared with a 2-in. gage length. The specimens were annealed in vacuum (-10-4 Torr) at 350°C for 8 hr. The grain diameter of the specimens in the various specimen diameter groups was 0.08 ± 0.02 mm. Gold specimens of two diameters, 0.14 and 0.03 in., were prepared in a similar way and annealed at 650°C for 8 hr. The grain diameter of the gold specimens was 0.2 mm. After annealing the specimens were electrochemically polished to the final size and tested in an Instron tensile machine at a strain rate, E&apos;, of 10- 3 per min. While it was possible to determine the surface layer stress, a,, in the larger-size specimens by measuring the difference, Aa, between the stress before unloading the specimens and the initial flow stress after removal of the surface layer as outlined in detail in Ref. 10, this method is not applicable for small wires because of the difficulty in obtaining a sufficiently accurate measure of the diameter. The values at the various strains were therefore determined by measuring after the specimen had been annealed at 35°C for 4 hr. It has previously been shown" that the two methods give the same results for a provided that the annealing temperature is low enough to affect only the surface layer and not the dislocation barriers in the bulk of the specimen. For the gold specimens a treatment at 150°C for 16 hr was found to be satisfactory for the determination of by the low-temperature annealing method. EXPERIMENTAL RESULTS Determination of a,, and a,. The stress-strain curves for the various diameter aluminum specimens, plotted in terms of the logarithms of the true stress, and true strain, are given in Fig. 1. These curves represent the average data taken from at least ten specimens at each size. Over the range of strains investigated the curves follow the empirical equation

Jan 1, 1968

By J. W. Cuthbertson, R. A. Cresswell

THE constitution of Cu-rich alloys with 1.5 to 13.5 pct Sn and 0.25 to 3.0 pct Be and the precipitation-hardening characteristics of alloys with 1.5 to 13.5 pct Sn and 0.25 to 1.0 pct Be have been examined. The hardness and tensile strength of the alloys examined increase markedly after solution treatment at 700°C followed by heat treatment at temperatures between 200" and 450°C. By a combination of cold work and heat treatment, hardness values similar to those exhibited by commercial Be-Cu alloys containing 2.25 pct Be can be obtained with ternary alloys containing 9 pct Sn and 0.75 pct Be and containing 10 pct Sn and 0.5 pct Be. Marked hardening effects occur with alloys containing even less beryllium. By heat treatment alone, a hardness value of 310 diamond pyramid hardness can be obtained from an alloy containing 10 pct Sn and 0.75 pct Be. Preliminary tensile tests have shown that an ultimate tensile strength of 110,000 psi with an elongation of 23 pct is obtainable by precipitation hardening an alloy with 8 pct Sn and 0.75 pct Be. The precipitation-hardening process has been followed microscopically for certain alloys and the inference is that, while the initial hardening effect is probably explained by the precipitation of the ß phase of the Cu-Be system, further hardening, proceeding at a much slower rate, also occurs, apparently as a result of precipitation of phases of the Cu-Sn system, particularly precipitation of the 6 phase at temperatures below 350". The presence of the e phase of the Cu-Sn system in certain alloys at temperatures below 350°C has been confirmed. Tin-bronzes are widely used in engineering applications where a combination of high strength and good resistance to corrosion is wanted. The maximum strength is induced in these alloys by cold working, and it would be an advantage for many purposes if high strength could be achieved alternatively by an age-hardening process. While Cu-Sn alloys have a good fatigue resistance they can be surpassed in this respect by Cu-Be, but the use of the latter alloy is limited by its high cost. If, by adding beryllium to tin-bronze, the properties of the respective binary alloys could to some extent be combined, a most attractive alloy should result. As pointed out by Raynor,¹ beryllium is on the borderline of the zone of favorable size factors for copper, and the solid solubility of beryllium in copper is consequently much more restricted than if the size factor were strongly favorable. The size factor is sufficiently favorable, however, to permit an increase in solid solubility with rise in temperature, and there is thus a composition range in which CU- Be alloys are susceptible to hardening by precipitation heat treatment. Although the a phase of the Cu-Sn system is similarly susceptible to precipitation treatment, the time necessary to establish equilibrium in commercial alloys of this type is usually so great that age hardening becomes impracticable. The addition of beryllium to Cu-Sn alloys would appear to offer a means of conferring on the latter useful age-hardening properties. Masing and Dahl² and others have, in fact, shown that the addition of beryllium to Cu-Sn a solid solutions renders these alloys susceptible to precipitation hardening and after such hardening confers on them an encouraging improvement in physical properties. If this improvement could be achieved by the addition of substantially smaller amounts of beryllium than are customarily found in binary Cu-Be alloys, the ternary alloys should possess economic advantages which might make them more attractive than the binary alloy for some applications. Binary Systems Copper-Tin: The constitution of these alloys is now reasonably well known and is summarized in the equilibrium diagram published by Raynor.³ The following observations, due to Raynor,¹ on the structure of those phases of the Cu-Sn system that are likely to be found in the ternary alloy system will facilitate the subsequent discussion on the examination of that system. The ß phase is an electron compound at the electron-atom ratio 3:2 and has a body-centered cubic crystal structure. This phase is stable only down to 586°C, at which temperature it decomposes eutectoidally into the a and y phases. The y phase has a structure that is also based on the cubic system. This phase is stable down to 520°C, at which temperature it decomposes eutectoidally into the a and d phases. The d phase is an electron compound (Cu³¹Sn8) which has a crystal structure analogous to that of 7 brass. This phase is stable from 590" to 350°C; on prolonged annealing at the latter temperature it breaks down into a mixture of the a and E phases. The e phase is an electron compound (Cu³Sn) having the electron-atom ratio 7:4. Its structure may be regarded as a superlattice based on the close-packed hexagonal system. This phase is stable from 676°C to room temperature. The primary solid solubility of tin in copper increases to a maximum of 15.8 pct as the temperature falls from that of the peritectic reaction to 586°C. The solid solubility remains constant from 586" to 520°C. At lower temperatures the solubility decreases progressively. Below 350°C the fall in solubility is pronounced and is associated with the precipitation of the e phase. This precipitation is very sluggish and does not normally occur under service conditions. Copper-Beryllium: The Cu-Be system has been investigated by Borchers&apos; and others. Raynor5 summarized the present state of information on it.

Jan 1, 1952

By H. L. Riley, B. W. Gandrud

AS far as the present writers know, this system of flotation has not been used elsewhere in this country, but in the last couple of years it has been introduced, with minor variations, at one plant in England and one in Wales.&apos; The system has been described and discussed in a number of publications.2-5 The following is quoted from an abstract of the latest of these,5 a paper presented at an International Conference on Industrial Combustion in 1952. On the basis of experience to date with the commercial plants, it is believed that the kerosene-flotation process incorporates all the necessary elements to make it greatly superior to anything else now available for treating of fines in wet processes of coal preparation. Additional study and investigation are still needed, however, to determine if certain phases of the process can be improved to such an extent as to make it generally satisfactory and acceptable to the industry. Further improvements will be needed with respect to the capacities of the flotation cells and the reagent consumption. The situation referred to above explains why an investigation is being made of the possibilities of achieving better cell capacities. Results obtained from this investigation, which is still in progress, are believed significant with regard to both cell capacity in general and the relation of cell design to cell capacity in particular. Commercial equipment now being used in a laboratory-type investigation should have performance characteristics similar to those of the larger machines. Equipment and Procedures: All flotation tests have been made in a standard Denver sub-A 24x24-in. unit cell of 12-cu ft volume. Cell modifications to make it more suitable for the tests were an adjustable front-wall section for varying cell depth and a perforated scraper-drag assembly for removal of the float product. There is also an apron dry-coal feeder, a gravity-feed water supply, reagent feeders, and a centrifugal pump that feeds the mixture of coal, water, and reagents into the flotation cell. A wattmeter connected into the drive-motor circuit records the power requirements of the impeller throughout each run. Dry coal, water, and reagents are all fed through a pan-type intake to the feed pump. A Sturtevant blower was set up to furnish air for supercharging. A centrifugal pump with a garbage-can intake provides for disposal of refuse flow to an outside settling tank. Figs. 1 and 2 show the flotation cell; Fig. 2 also illustrates the blower for supercharging. For purposes of this investigation, the percentage by weight of the feed coal recovered in the float product under a standard set of conditions has been considered as the criterion of cell capacity. The authors realize that such a criterion may be somewhat unorthodox, as the term cell capacity is usually understood to refer to feed input and ordinarily takes into account the ash analyses of the float product and refuse. However, the word capacity is flexible enough so that Webster gives one definition as maximum output, a definition which seems to justify, at least partly, acceptance of the above criterion. It has been the authors&apos; experience in the Birmingham district that the ash-reduction efficiency of the coal-flotation process is generally satisfactory and that the only real problem is to increase the rate of float recovery so that the feed rate to any given bank of cells can be increased without undue loss of coal in the refuse. Originally it was planned to operate the flotation cell to simulate continuous operation during sampling periods. It was assumed that operating for reasonable time with feed coal, water, and reagents turned on would stabilize conditions so that the weight of float coal discharged during a fixed time interval would be an accurate measure of the rate at which the coal was being floated. It developed, however, that this supposition was erroneous. The float coal, caught for fixed time intervals and weighed, gave widely varying results in duplicate runs. Efforts to correct this trouble failed, and it was decided to try to operate on a batch-test basis, whereby all the float coal produced during a run on a known weight of feed coal would be caught in tubs, dewatered, and weighed. This method gives consistent and reproducible results, with total float product weight rarely varying by more than 3 or 4 pct on duplicate runs. The standard test procedure is as follows: A 132-lb sample of dry feed coal is weighed and placed in the feed hopper. The feeder is adjusted for a rate of 800 lb per hr. Feed water and reagents are turned on, and the feed and refuse pumps are started. One minute later the impeller is started. Six minutes are allowed for the cell to fill up with the water-reagent mixture. The feed of dry coal is started at the end of this 6-min period. One minute later the float-coal removal drag is started. The float coal is caught in one tub for the first 6 min after the flow of feed coal starts. Tubs are then changed, and the float coal is caught in a second tub until the feed coal runs out, when the tubs are again interchanged to catch the float coal for the remainder of the run in the first tub. The cell is kept running for 3 min with the water and reagents on after the feed stops to allow residual float coal to be removed. At the end of a test the wet float coal in both tubs is weighed and the total weight recorded. The product in the second tub is used for moisture determination and screen-size analyses. When the

Jan 1, 1956

By Karl F. Peterson, H. K. Najarian, Robert E. Lund

PRIMARY products of the Josephtown smelter are zinc metal of various grades, lead-free zinc oxide pigments, cadmium metal, and sulphuric acid. Zinc concentrates of domestic and foreign origin are blended and desulphurized at the roaster plant. The equipment includes five, 12-hearth Herreshoff roasters and two modified Trail-type suspension roasters. The sulphur dioxide containing gases from the roasting operation are diverted to a four-unit contact acid plant for the manufacture of sulphuric acid. The roasted calcines are agglomerated by sintering on Dwight-Lloyd-type sintering machines; the sinter is crushed and sized within required limits; and the sized sinter is smelted in vertical shaft-type electro-thermic furnaces. Of the 13 electrothermic furnaces of various sizes now in operation, four are designed to produce American process zinc oxidc of various specifications; and the remaining nine furnaces are equipped with vacuum-type condensers and produce zinc metal. Papers describing the general smelting practice at Josephtown have been published by AIME. Since both High Grade zinc metal and lead-free zinc oxide pigments are produced direct from the electrothermic furnaces without need for subsequent refining, the elimination of impurities such as lead and cadmium has to be accomplished during roasting and sintering operations. To effect the producing of both High Grade and Prime Western zinc products, the roasting and sintering operations are on two separate circuits. A High Grade circuit produces finished sized sinter low in lead, cadmium, etc., for the High Grade furnaces; and the Prime Western circuit produces finished sinter destined for the furnaces producing Prime Western metal. Sintering at the Josephtown smelter differs in many important respects from the sintering practice in smelters operating horizontal retort zinc furnaces. Requirements of the electrothermic smelting furnaces define the physical characteristics of the sinter, while the chemical composition of the sinter is controlled according to the grade of metal and oxide to be made as final products. Three principal objectives in the sintering process at Josephtown smelter are: 1. To transform the zinc calcine from the roasting operations into a hard, yet porous agglomerate that will not crumble in the smelting furnace. 2. Crushing and sizing of the sinter to obtain a proper screen analysis which is normally —% in. down to +1/4 in. particle size. 3. To eliminate, particularly in the High Grade circuit, as much of the impurities such as sulphur, lead, and cadmium as possible. The sintering plant as originally built in 1930 was equipped with three standard 42 in. x 44 ft Dwight-Lloyd sintering machines. Each machine was equipped with a 15x60 in. sintering corporation fan driven by 150 hp, 900 rpm synchronous motor through a magnetic clutch and capable of delivering 30,000 cfm of air at 15 in. of water and 150°F. Each sintering machine was driven by 7½ hp dc motor with controllers for varying the speed of the machine from 8 to 32 in. per min. The pallets were cast iron and the grates of the herringbone type. The charge was mixed in a 4 ft diam x 8 ft Stehli pugmill and transported by belt conveyor, elevator and tripper conveyor to a small bin over each machine. Shortly after the start of operations the following changes were found necessary: 1. The herringbone grates which plugged very quickly and were difficult to keep clean were replaced by straight, narrow cast-iron grate bars running at right angles to the travel of the pallets. These grate bars are held in place by a center bar extending across the pallet on the 24 in. dimension and by removable retaining plates which form the sides of the pallets. 2. Mechanical grate knockers were developed in conjunction with new grate bars for continuously and automatically cleaning the grates. 3. As the cast-iron pallets cracked, they were replaced with cast-steel pallets. In 1938, the capacity of the sinter plant was increased with the installation of two 42 in. x 22 ft machines which were brought from the company&apos;s Herculaneum lead smelter. With a circulating load of some 250 to 300 pct, production of finished sinter on the 42 in. x 44 ft machines at this time amounted to about three tons of sized sinter per machine hour. In 1945, one of the 42 in. x 22 ft machines was replaced by a 60 in. x 44 ft machine of our own design. In 1948, as part of the plant-wide expansion program, the sinter plant not only was expanded but also divided into two separate plants; namely, Prime Western and High Grade circuits. The sinter destined for furnaces producing Prime Western zinc metal is made in a new plant comprising two 60 in. x 44 ft Dwight-Lloyd-type sintering machines, each having a 45,000 cfm Sturtevant fan at 18 in. water static pressure and served by an 8 ft diam x 12 ft long rotary charge pclletizer and auxiliary crushing and sizing equipment. The sinter destined for furnaces producing High Grade zinc metal and zinc oxide pigments is produced in the old sinter plant which was expanded to accommodate four of the 60 in. x 44 ft sintering machines, replacing the old sintering units. In the High Grade sinter circuit, two units of the 60 in. x 44 ft machines are used as preliminary soft sinter machines; and the remaining two units of the 60 in. x 44 ft machines are used to make finished hard sinter. Purification Theory Partial elimination of lead and cadmium in the sintering of zinc ores is common knowledge. However, by some manipulation and by taking advantage of the double circuit, it is possible to make zinc sinter which is nearly free of contaminators. Lead

Jan 1, 1952

By J. Szekely, P. Tarassoff, N. J. Themelis

In a copper converter air enters the bath in the form of turbulent jets. The interaction of these jets with the molten matte is fundamental to the converting process. In the present study, an equation is derived to describe the trajectory of a gas jet in a liquid. Calculated and experimental results for air jets injected into water are in good agreement. The trajectories of air jets in copper matte are predicted. THE air injected through the tuyeres of a Peirce-Smith copper converter emerges into the bath of molten matte in the form of a highly turbulent jet. The air jets affect a number of chemical and physical processes occurring in the converter: i) Converting Rate. It is generally recognized that the production capacity of a converter is limited by the flow of air which can be injected through the tuyeres and by the oxygen efficiency. In turn, the air flow is limited by pressure drop considerations or by the amount of splashing within the converter. ii) Oxygen Efficiency. This depends on the dispersion of the air jet in the liquid bath, and its trajectory through the bath. iii) Mixing. The jets act as mixing devices by transferring momentum energy to the bath; in this way the heat generated by the converting reactions occurring in the jets is distributed through the bath. iv) Refractory Wear. The proximity of the jets, which are centers of heat generation, to the refractories in the tuyere zone may have an important effect on refractory life. Mixing conditions in the bath will also influence refractory erosion. v) Splashing, and Accretion Build-Up. The energy of the jets is not dissipated entirely in mixing the bath. particles of liquid are carried out kith the gas above the surface of the bath in the form of liquid spouts and droplets. These result in the undesirable build-up of accretions on the converter mouth, and dust losses in the flue gas. Despite the importance of the interaction of the air jets and the matte in a converter, very few studies of the fluid dynamics of converting have been reported in the literature. Metallurgists in the USSR appear to have been more concerned with the subject than their Western counterparts. Deev et al.1 studied the interaction of an air jet with aqueous solutions in a converter model and qualitatively determined the tuyere air velocity and tuyere inclination which produced the most favorable results with respect to good mixing in the bath, and minimum splashing. Shalygin and Meyer-ovich2 also examined the air-matte physical interaction both in models and in industrial converters; they concluded that in conventional converting practice, there was no significant penetration of the air jets into the matte layer, and consequently the converting reactions occurred mainly in a zone adjacent to the tuyeres. The behavior of air jets in a converter bath, and the aerodynamic characteristics of tuyeres are discussed at length in a monograph on converting by Shalygin.3 However, the description of the phenomena occurring in the converter bath is largely qualitative. The side-blown Bessemer converter for steelmak-ing is very similar to the Peirce-Smith copper converter. Among the few investigations of the behavior of air jets in the bath of a Bessemer converter are those of Kootz and Gille4 who studied splashing in the course of an investigation on the effect of blowing conditions and converter shape on nitrogen pick-up in Bessemer steel. They found that during blowing standing waves were formed on the surface of the bath; the amplitude of the waves increased with the depth and angle of tuyere immersion until the whole bath moved backwards and forwards causing heavy splashing. Kazanstev5 used a model of a Bessemer converter to obtain correlations between the axial velocity of a gas jet and distance from the tuyere orifice and the Froude number of the jet. shalygin3 used these results to calculate the horizontal penetration of an air jet in a copper converter; the penetration was defined as the distance in which the axial jet velocity decreased to 10 pct of its initial value. However, the rising trajectory of the jet was not taken into account. In the absence of quantitative information on the fluid dynamics of converting, the design of copper converters has been based mainly on operating experience. Such experience tends to vary widely from smelter to smelter., This is reflected in Table I which is based on data compiled by Lathe and Hodnett.6 Aside from a rough, and perhaps obvious correlation between the total air flow and converter volume, Fig. 1, no pattern emerges from the data. For example, tuyere throat air velocities vary from 215 to 465 ft per sec in converters of the same size, for little apparent reason. The air jet energy input per cubic foot of converter volume, which may be taken as a measure of the amount of mixing in the converter bath, also varies greatly. A recent analysis of converter data by Milliken and Hofinger7 has also revealed unexplained variations in operating parameters. It is believed that by gaining a better understanding of the fluid dynamics of converting a more rational basis may be provided for the design of converters. In particular, it is proposed that if one takes into account the desirable criteria of a high converting rate, high oxygen efficiency and long refractory life, there should be an optimum configuration of tuyere air flow for a converter of a given diameter. The present investigation is concerned with the form and trajectory of an air jet in a converter bath. The general theory of turbulent jets has been expounded by Schlichting8 and Abramovich.9 However, most experi-

Jan 1, 1970

By W. G. Pfann

A simple method of obtaining multistage batch separations by crystallization was described recently. Known as zone-refining, it comprises passing short molten zones through a long solid charge. This technique can now be used on a continuous basis by means of the zone-void method described in this paper. Feed enters, at an intermediate point, a column down which molten zones travel, and waste and product leave at the ends. Materials move in the column through the agency of voids, which are introduced at the ends and travel toward the feed inlet. The voids and molten zones are moved by external heaters in a simple manner, and the principle of reflux is utilized. ANEW method of obtaining multistage separations by crystallization was described recently.&apos; Named zone-refinina.,-, the method comwrises slowly passing a series of molten zones through a long solid charge. Solute becomes concentrated at one or the other end of the charge, depending on whether it raises or lowers the freezing point of the solvent. The separation increases with the number, P, of zone-passes, approaching a limit as P approaches infinity. Zone-refining has been highly effective in purifying germanium and other substances.2,3 and new applications are steadily increasing. Zone-refining is a batch method and as such it has certain limitations inherent in batch operation. If it could be made continuous, its scope and utility would be greatly broadened. This end has been achieved by the zone-void method described in this paper. In the zone-void method feed is introduced continuously at an intermediate point in a column down which molten zones travel, while impure waste and purified product leave at the ends. Both the flows of feed, waste and product, and also the travels of the zones, are actuated by external moving heaters in a simple manner; and the system utilizes the principle of reflux. The method provides, in the field of crystallization, the counterpart of the continuous fractiona-tion column in the field of distillation. The following will be discussed: apparatus and mode of operation, fundamental nature of the separation, design theory, and practical considerations. The method will be described in terms of a binary solute-solvent system in which the solute is an impurity to be removed and the solvent is the desired product. The distribution coefficient, k, defined as the ratio of solute concentration in the solid freezing out of a molten zone to that in the liquid in the zone, is assumed to be constant and less than one. The process is equally effective for k&apos;s greater than one and for ternary or higher order systems. Method and Apparatus The essential features of a continuous zone-refining process are represented in highly generalized form in Fig. 1. A series of molten zones, produced by moving heaters, travels slowly down the column or charge (to the left in Fig. 1). If there were no flows of feed, waste, or product, the process would simply be batch zone-refining, the action of the molten zones being to sweep solute down the column, solvent up the column. For the process to be con- tinuous, with stripping and enriching sections in the column, feed must enter, and waste and product must leave, as indicated. The zone-void process accomplishes both objectives, namely, the indicated movements of zones and the indicated flows of material. Zones are moved by moving heaters, just as in batch zone-refining. Materials are made to flow by creating voids at the waste and product exits and causing these voids to move to the feed inlet. Since there must be a net flow of material from the feed inlet to each of the outlets, the indicated movements of voids are in the desired directions, because movement of a void in a given direction corresponds to flow of material in an opposite direction. In order to produce the desired movements of voids, the column is folded into two vertical sections having the feed inlet in common at their upper ends. Voids are displaced upward by the liquids in the molten zones and their travel is actuated by the motions of the zones. Voids travel with the zones in the enriching section and move continuously. Voids travel opposite to the zones in the stripping section and move intermittently. Creation and travel of voids will now be examined in detail. The enriching section of a column in operation, with its void generator, is shown in Fig. 2. The column section is a vertical tube around which a series of closely fitting, regularly spaced heaters travel slowly upward. Each heater produces a molten region, the temperatures of the heaters and the cooling between heaters being controlled so as to maintain the molten zones approximately constant in size. A void is normally present atop the molten zone in each heater. As the heater rises, it continuously melts solid above it, which drips through the void into the molten zone and continuously freezes out solid below it, of concentration k times that of the liquid in the zone. When a molten zone and void reach the feed inlet, which is kept molten, the void is displaced by an equal volume of feed liquid. Generation of voids of controlled size in the enriching section is shown in Fig. 3. The void generator is a tube of small cross-section, provided with lateral heat-conducting fins which sense the position of the heater. Liquid can escape only when the entire outlet tube is within the heater. If any part of the outlet tube is outside the heater, liquid cannot escape,

Jan 1, 1956

By A. U. Seybolt, V. A. Phillips

Binary iron alloys containing 1 pct of Al, Cr, Mn, Mo, Si, Ti, or V, and 0.4 pct C, 1 pct Cr steels with and without 1.2 pct A1 or 2.0 pct Ti additions, were ion-nilrided at 550° to 600° in N-H mixtures. Nitriding increased the inicrohardne ss of all the binary alloys except those containing manganese or molybdenutn, and also hardened the heat-treated steels if aluminum or titanium urns present. Transmission electron microscopy revealed particle formation in all casts where hardening occurred. Electron diffraction gare positive identifications for ALN, CrN, and a, Si3N4 in the binary alloys, and AlN and CrN in the aluminum- cold chromium-bearing steels, respectil&apos;uly. Cubic VN with a, = 4.13A was tentatively identified. Particles, apparently of CrN, also formed in the base steel but did not increase the hardness very much. Chromium and vanadium formed nitride platelets on {001}° matrix planes, while titanium gave clusters <15A diam. Aluminum nitride precipitated at grain and subgrain boundaries, and within the grains. Silicon gave profuse precipitates of several Morphologies at grain boundaries and cubical particles within the grains. No effect of the alloy carbides on nitride precipitation was observed in the heat-treated steels. THE nitriding of steel has been a well-established commercial process for about 40 years, but in spite of this comparatively long period of use there have been few studies aimed at understanding the process. Most studies, like the early but very competent work of Jones and organ&apos; and nones.&apos; were concerned with establishing the pertinent engineering variables of steel composition, gas composition, temperature, and time. As far as the present authors are aware, there have been no studies of the composition, size, shape, or distribution of the nitrides formed in the nitriding of steel. Noren and Kindbom3 did, however, examine a few nitrided steels by surface replica electron microscopy, and were able to show the presence of car-bonitrides and AlN and TiN nitrides. pitsch4,5 and Hrivnak6 examined nitrided pure iron by transmission electron microscopy. Baird7 found manganese nitrides in Fe-1.6 pct Mn when nitrided at 650°C, using the same technique. In the present work, emphasis was placed on transmission electron microscopy because of its inherently better resolution, using principally binary alloys of iron containing 1 pct of alloying element. In addition, a few simple 0.4 pct C steel compositions were examined to investigate possible carbonitride formation. It was not anticipated that all of the added elements would form nitrides under the conditions used, but it was considered desirable to obtain direct experimental evidence on this point. It would be considerably easier to ascertain the presence of alloy nitrides by examining appropriate binary alloys in preference to relatively complex steels. The work reported here could have been done using orthodox ammonia-nitriding procedures, but an operating ion-nitriding equipment was available, and was therefore used for specimen preparation. EXPERIMENTAL DETAILS 1) Materials. Binary alloys were made up from vacuum-melted electrolytic iron with 1 wt pct additions of Cr, Ti, V, Al, Mn, Mo, and Si of about 99.9 pct purity. In addition, three steels were similarly made up—a basis steel with 1 wt pct Cr and 0.4 wt pct C and two steels with further additions of 1.2 wt pct A1 or 2.0 wt pct Ti, respectively. The materials were vacuum-melted and cast as 11-lb heats into tapered square molds of about 2 by 2 in. average cross section. The castings were forged and hot-rolled to 11/4 in. rounds. Discs of 4 in. thickness by about 1 in. diam were machined from the rods. Some of these discs were hot-forged and hot-rolled to about 0.020 in. thick, sand-blasted, and then cold-rolled to about 0.003 in. thick. At this point, the surface was cleaned by light etching with HC1, then washed, dried, and vapor-degreased prior to nitriding. 2) Ion-Nitriding Procedure. The type of ion-nitriding equipment used here is similar to that described by Jones and Martin.8 Briefly, a mixture of nitrogen and hydrogen at 5 mm total pressure is placed in a vacuum chamber with a dc potential of 450 to 500 v applied between the work (cathode) and the grounded metal vacuum enclosure (anode). Nitrogen ions are accelerated to the work where a thin layer of Fe4N forms on the surface and thus sets up a nitrogen concentration gradient. This causes nitrogen atoms to diffuse into the surface layers of the alloy forming a finely divided dispersion of alloy nitrides, causing hardening of the surface. In the work to be reported here. the nitriding was carried out at 550° to 600°C to be consistent with commercial nitriding practice. The temperatures cited are those measured by a thermocouple located under a platform on which the work was sitting. Except where otherwise stated, the mixture used in nitriding the binary alloys contained -2.0 pct N, balance hydrogen. The nitrogen concentration in the nitriding gas mixture used for the binary alloys was purposely kept lower than normally used in nitriding steels. 10 to 20 pct, in order to minimize Fe4N formation. In this way only the alloy nitrides would be present as a second phase. However, in the case of steels which would contain a- carbide phase along with as

Jan 1, 1969

HIGH-GRADE manganese ore, from which manganese is obtained commercially, is not found in large quantities in any major steel-producing nation in the free world. The U. S. is a "have not" nation with respect to deposits of directly mineable high-grade manganese ore. Known resources of 48 pct Mn or better grade ore amount to less than 200,000 tons. In 1950 the U. S. steel industry consumed 1.8 million short tons of metallurgical grade manganese ore that contained about 800,000 tons of manganese. About 16 pct of the manganese content was lost in processing, so that about 650,000 tons, or 13 pounds per ton of steel actually entered into steel production. Under present practices use expands directly with steel output, and by 1975 the demand in both the U. S. and the rest of the free world is expected to be roughly 60 pet greater than in 1950. In peacetime about 80 pet of manganese consumption goes into steel production; high-manganese steel, dry cells, and chemicals account for the remainder. The manganese supply problem centers around high-grade ore for ferromanganese production. Use of ores containing less than 35 pet Mn sharply increase the costs of making ferromanganese. Use of ferro-manganese of grade below 70 pet in turn requires changes in steelmaking that increase steel cost. Under normal conditions the present small domestic production cannot be expected to increase. Major resources in the U. S. consist of 12 low-grade deposits. The cost of mining and treating these ores to extract a product as good as that yielded by imported ores is at least twice and in some cases more than four times the 1951 price of foreign ores delivered to the U. S. However, as long as trade relations and overseas shipping are not interrupted, deposits in India, Africa, and Brazil can meet steadily increasing demand at approximately present costs. Cost considerations indicate that the U. S. should continue to rely upon overseas sources for its peace-time supply, and that this situation is satisfactory. But, this does not take into account the question of how the U. S. will be able to meet its needs in war. Position of the Rest of the Free World In 1950, free world steel producers outside the United States, with a steel output of 70 million ingot tons, consumed about 1.3 million tons of metallurgical-grade ore. Their manganese ore demand, expected to increase directly with steel production, will by 1975 be about 2.3 million tons. Russia possesses over half the known manganese ore reserves of the world and is producing twice the tonnage of any other country. It supplied more than a third of the U. S. manganese requirements up to 1938 and again in 1948, but by 1950 Soviet manganese exports to the free world had virtually ceased. The free world&apos;s supply of manganese now comes mainly from India and Africa. Somewhat over 10 pet of U. S. imports came from Brazil and Cuba. Security Considerations In the event of war the U. S. might be substantially cut off from 90 pet of present sources. Reduction in manganese specifications might cut consumption by over 10 pet without seriously affecting steel quality. By elimination of losses in the production of ferromanganese savings as high as 10 pet might be possible. But, wartime manganese requirements cannot be met through conservation alone. To meet possible future emergencies the U. S. should continue its comprehensive security program for manganese, including stockpiling and research on the economic use of low-grade ore, domestic ores, the recovery of manganese from slag and the reduction of manganese requirements in steel production. If this work, including additional pilot plant operation is pursued vigorously, it should be possible in an emergency to get an adequate supply of manganese from domestic sources. The national stockpile then can be looked upon as a source of supply during the period of at least 2 years required to reach full-scale production from low-grade resources. Ferromanganese Smelting In comparison with smelting of pig iron, ferro-manganese smelting is a very wasteful process. Under present ferromanganese blast-furnace smelting practice, about 8 pet of the manganese in the furnace charge is lost to the slag, and roughly the same amount is lost to the stack gases; the total loss approaches 15 pct. Present practice is a compromise between excessive slag loss and excessive stack loss. In fact, it may be seriously questioned whether conventional blast furnace design is suitable for manganese smelting. U. S. Resources The known manganese deposits of the U. S. contain a total of 3500 million long tons of raw material and 75 million long tons of metallic manganese. More than 98 pct of this contained metal is in 12 large low-grade deposits of which the most important are those at Chamberlain, S. Dak; Cuyuna, Minn.; Aroostook County, Maine; and Artillery Peak, Ariz. Reserves of high-grade ore (48 pct Mn) amount to less than 200,000 tons. About 20 million tons of ore average over 15 pct Mn, and when grade is decreased to 10 pct Mn reserves amount to about 100 million long tons. If cut-off grade is decreased to 5 pet Mn, resources amount to 800 million long tons. Many of these low-grade ores may be beneficiated by flotation or other concentration methods. Pyrometallurgical Methods For smelting ferromanganese, it is essential to have an ore containing at least 50 pct manganese, with an Mn:Fe ratio of about 8:1. Direct smelting of 20 pct Mn concentrates is not promising. The only method that offers any promise involves two-step smelting.

Jan 1, 1952

By K. F. G. Hosking

I read Professor Gaudin&apos;s paper with great interest and pleasure because for some time I have held that the chemical aspect of comminution is a subject of considerable importance to the mineral dresser and deserves to be thoroughly investigated. It does seem appropriate, however, to emphasize the fact that "fresh" edges and corners produced by the grinding of solids display enhanced reactivity has been recognized and utilized in the development of certain mineral identification techniques. Some of these techniques are worth noting, not only because they might facilitate research in the aspect of mineral dressing under discussion, but also because they emphasize the fact that many mineral species commonly regarded as being very inert can display a surprising reactivity when in the freshly ground state. In 1951 Isakov6 published a number of tests for the components of certain mineral species which depend essentially on grinding in a mortar a mixture of the material under investigation with a solid reagent. Thus when stibnite, 4(Sb2S3), is ground with sodium or potassium hydroxide. the antimony is revealed by a momentary development of a yellow color which changes in air to orange-red. Other antimony minerals need a preliminary treatment before the test can be carried out. This consists of grinding with aluminium sulfate, ferric sulfate or potassium bisulfate, and breathing upon the resultant mixture. I have employed a similar technique to determine the approximate magnesia content of certain limestones.&apos; The method depends essentially on the fact that when a sample of limestone is ground under controlled conditions with solutions of sodium hydroxide and Titan yellow the color of the final product is, within limits, a function of the amount of magnesia present. I have also shown that the components of a wide range of minerals can be identified by applying chemicals to their streaks on portions of vitrified, unglazed floor tiles, etc. Under such circumstances the diversity of the reactions which take place in the cold (because of the reactivity of fresh corners and edges) is surprising. Thus, for example, if a garnierite, (Ni,Mg)3Si2O5(OH)1, streak is treated first with a drop of 0.880 ammonia and then with a drop of a 1 pct alcoholic dimethyl-glyoxime it immediately becomes red, indicating the presence of nickel.&apos; Stevens and Carron9 have evolved a simple field test for distinguishing minerals by "abrasion pH." A soft nonabsorbent mineral is scratched in a drop of water on a streak plate until a milky suspension is formed. A piece of pH indicator paper is dipped into the suspension, after which it is removed and the maximum deviation from neutrality noted. When a hard mineral or one which absorbs water is being tested, fragments are first ground for 1 min with a few drops of water in a mortar to make a heavy suspension. The importance of the findings of such tests to mineral dressing may be judged by the abrasion pH values, Table 11, recorded by Stevens and Carron for certain species usually regarded as comparatively inert. The combined results Of the above researches clearly indicate that comminution is capable of altering the pH of a pulp and of causing the chemical nature of the surfaces of some of the components to be profoundly changed&apos; Depending On circumstances such surface alterations may have a beneficial or an adverse effect if these products are subsequently subjected to flotation. The tests also suggest that by grinding "inert" minerals with appropriate solid or liquid reagents "reactive" surfaces may be developed which might facilitate separations by flotation. It is an interesting and instructive problem to determine the reactions that are likely to take place when dry solid substances are subjected to comminution and to the unavoidable heat liberated during the process. To do this it is theoretically necessary to know the free energy values of the reactants and possible resultants, but unfortunately there is a dearth of such data! However, the heats of formation of many substances are known, and generally speaking, if in a reaction of the type AB + CD = AD + CB the sum of the heats of formation of AB and CD is less than that of AD and CB the reaction will probably proceed to the right. Thus, according to a note I have (the author of which I cannot name) if PbS (black) is warmed with CdSO, (white), PbSO., (white) and CdS (yellow) are formed, and that the reaction does, in fact, take place is indicated by the change in color of the mixture. The reaction is expected, as the sum of the heats of formation of PbS and CdSO, is less than that of PbSO, and CdS (as shown below). PbS + CdSO4 = PbSO4 + CdS 22.2 + 218.0 < 216.2 + 33.9 Finally, certain other aspects of the chemistry of comminution, which are neither mentioned by Professor Gaudin nor referred to by me are to be found in a paper by Welsh" and in the printed discussion thereof. A. M. Gaudin (author&apos;s reply)—The observations contributed by Dr. Hosking are indeed welcome, as they add to our experimental knowledge of a topic which is believed to be of the first importance. In connection with the experiments cited it should be kept in mind that oxidation, hydration, and carbonation at various rates should always be deemed to be possibilities when grinding is done in water or in air, even in "industrially dry" air. Special precautions might lead to sufficient minimizing of these reactions and to the assertion, instead, of deliberately-created reactions. The author wishes to thank Dr. Hosking for his contribution.

Jan 1, 1957

By B. J. Nelson, F. N. Rhines

STUDIES upon the rates of oxidation of copper alloys containing small quantities of the alloying elements1,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidizable alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal subscale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants. Similarly, large volumes of precipitated oxides tend to deposit in various patterns that may be expected to hinder the diffusion of the reactants in the

Jan 1, 1943

By J. E. Burke, Y. G. Shiau

SEVERAL attempts have been made to account for the fact that grains in a fully recrystallized metal will coarsen on annealing Two fundamentally different hypotheses have been advanced; with several variations of each. One school considers that the cause of grain growth is the surface energy of the grain boundary The theory of Jeffries1 that grain size and grain size contrast control growth is an example The second school considers the primary cause to be a difference in the lattice energy on either side of the grain boundary The more perfect grains are considered to grow at the expense of their less perfect neighbors, with a decrease in free energy, and a consequent increase in the stability of the system. Burgers2 presents the case for the strain or lattice imperfection theory of grain growth quite completely The latter theory is attractive, since there is no doubt that differences in lattice energy or lattice perfection can cause grain boundary migration A recrystallization nucleus grows for this reason as was beautifully demonstrated by van Arkel and Ploos van Amstel3 Although it is generally stated that grain growth does not precede recrystallization, several workers4,5 have shown that small strains may induce a single crystal in an aggregate to grow, or at least may cause some&apos; grain boundary migration The origin and nature of the imperfections that are considered to be responsible for normal grain growth have never been clearly described, but it is generally agreed that they are a consequence of the difficulty of atomic reorientation in the solid state, and that they do not seriously differ from the type of imperfection that-can be introduced by mechanical deformation An object of the present work was to determine whether the introduction of mechanical deformation would cause grain growth in a specimen which would not otherwise show it under the conditions used It was also planned to determine the effect of such deformation the rate of growth in a specimen which would show - growth in the unstrained condition Recently Maddigan and Blank6 have indicated that slightly strained specimens of alpha brass can undergo considerable growth prior to recrystallization if annealed at low temperatures French7 has reported that at deformations less than 17 pct it is very difficult to detect the beginning of recrystallization in the same material. It was therefore planned to broaden this work to include a complete study of the microscopic behavior of alpha brass under conditions of temperature, time, grain size and deformation such that recrystallization would not occur or would occur to only a small extent EXPERIMENTAL PROCEDURE The brass was prepared by melting cathode copper and commercially pure zinc

Jan 1, 1947

By E. P. Polushkin, Henry L. Shuldener

This paper describes the results of microscopic examination of a series of brass pipes removed from apartment and office buildings in New York City, adjacent localities on Long Island, and Philadelphia. They were selected as typical of approximately four hundred pipe specimens obtained over a period of five years during an investigation of corrosion in hot-water installations. A part of the investigation is reported in this paper and includes a brief history of the pipes, a description of their inside surface and microstructure, and a study of the effects of corrosion, with particular reference to the structural aspects of local and selective dezincification. Although the bibliography on the corrosion of brass pipes is quite extensive, it refers almost entirely to corrosion in sea water. The authors believe that their examination of this series of pipes, which had been subjected to the corrosive action of fresh water for various lengths of time, may throw some additional light on the problem of corrosion. Pipes Examined The pipes were made by different manufacturers and their sizes range from 3/4 in. to 4 in. nominal inside diameter, the majority being within I to 2 in. They can be divided into two groups according to chemical composition: (I) with a copper content of 60 to 62 per cent and (2) with a copper content of 65 to 68 per cent. The first group (pipes made of Muntz metal) comprises 22 pipes and the second (pipes made of high brass) comprises 18 pipes. The pipes had been in service in various locations in the hot-water systems of the buildings involved. Some were taken from horizontal lines in the basement, some from overhead distributors and some from vertical risers. The distance, in terms of feet of pipe, of the specimens from the hot-water generator was no less than 75 ft. and often IOO to 300 ft. In the majority of cases the water-heating equipment was provided with a regulator to limit the temperature of the hot water supply. The normal range of temperature in pipe systems of this kind is Ioo° to 160°F. Water Supples The average chemical composition of the water supplies carried by the pipes is shown in Table I. In evaluating the corrosiveness of a natural water, four factors are considered of prime importance: namely, hardness, alkalinity, pH and silica content. The waters listed in Table 1 are characterized by relatively low hardness, 10, alkalinity, low pH and low silica content. The waters of lower pH and higher CO2 content are more corrosive. A characteristic of all of these waters is that they do not deposit a protective mineral coating as do waters with high bicarbonate of lime content, which would be reflected

Jan 1, 1945

By S. W. Poole, J. A. Rosa

THE object of this investigation was to determine the distribution of chemical elements within a large, killed alloy-steel ingot, by sulphur printing and quantitative chemical analysis. With regard to segregation in steel ingots, the factors of melting practice, pouring temperatures, mold design, etc., and the mechanics of solidification and its attendant functions, have been the subject of intensive study over a period of years by many investigators. Notable among these is the Sub-Committee of the No. 5 Committee of the British Iron and Steel Institute. For an exposition 0f the many problems awaiting the researcher on the heterogeneity of steel ingots, the methods of attacking these problems, together with some of the answers, the reader is referred to the nine reports and numerous papers of that committee and its membership. STEELMAKING DATA Melt.-The heat was made in a 70-ton direct arc-type basic electric furnace. Furnace charge consisted of nickel-chromium-molybdenum steel, most of it in the form of heavy mill scrap. All of the scrap was charged cold. The standard double-slag method was employed, the heat being finished under a strong carbide slag. Aluminum was used as the deoxidizing agent. Tapping temperature, as observed with an optical pyrometer, was 3000°F. Detail of Mold and Ingot Size.-Details of the ingot mold and the ingot itself are given in Fig. I. Teeming.-Teeming temperature of the subject ingot as observed with an optical pyrometer was 2830°F. The ingot was top-poured directly through a 1 ½ in. nozzle and required 7 min., 44 sec. to fill up to the hot top. An additional 2 min., 30 sec. were required to fill the hot top. The ingot was stripped hot and charged with the remainder of the heat into an annealing furnace. There it was given the standard annealing cycle used for these ingots. Subsequent heat-treatments are described elsewhere in this paper. SECTIONING AND PREPARATION FOR SULPHUR PRINTING Because of previous favorable experience in sectioning ingots up to 21 ½ in. square with an oxyacetylene torch, it was decided to use this method to section the subject ingot. The ingot was preheated to 900°F. for 12 hr. It was then placed on a steel bed in a horizontal position so that the longitudinal axis was level and parallel to the track of the motor-driven torch carrier. Two cuts were made, one 2 in. above the longitudinal axis and the other 2 in. below. The time required to make each cut was approximately 75 min. The cutting operation is shown in Figs. z and 3. The 4-in. thick slab was mmediately charged into a furnace standing at 1200°F.

Jan 1, 1944

By W. D. Robertson, E. G. Grenier, V. F. Nole

The electrical, mechanical, and corrosion cracking properties of an age-hardenable Cu-Ni-Si alloy have been studied over a range of time, temperature, and deformation states for the purpose of determining the relationship between the properties and the structural state. The precifitate has been identi3ed as and the sites of preferred precipitation have been located by electron microscope studies of the structures developed by various combinations of heat treatment and plastic deformation. An extreme form of deformation banding has been observed in the aged alloy that results in high strain concentration in bands lying parallel to {111} planes. These bands are the structural paths along which transcrys-talline cracks propagate in the deformed alloy. The observations provide a basis for a general mechanism of transgranu-lar corrosion cracking of face-centered cubic alloys in terms of stacking fault probability. AMONG the age-hardening copper alloys the copper-nickel-silicon (Silnic Bronze) type is outstanding in exhibiting a high strength combined with a considerable capacity for cold working, a relatively high conductivity, and a low to negligible susceptibility to stress corrosion cracking. It is not a new alloy and it has been the subject of a number of investigations,1-5 which were made primarily to establish practical composition and heat treatment limits. The structural characteristics of the aging processes in this alloy have not previously been studied in detail. This particular investigation was undertaken to explore, in detail, and over a wide range of conditions, the properties obtainable by various combinations of working and heat treatment and to correlate structural changes with the observed mechanical, electrical and corrosion properties. MATERIAL AND PROCESSING Eight different commercial heats of the alloy were made and used in the investigation. The range of composition among the eight heats is shown in Table I. Billets, 8 by 24 in., were cast into water-cooled molds, extruded to 1.687-in. rod, and quenched in water after extrusion. Extruded material was rod rolled to 0.750 in., annealed at 1450° F for 2.5 hr, and quenched in water. Subsequent working operations were performed by tandem rolling to various sizes depending on the degree of reduction required. Final cold-working operations were performed by drawing to a uniform size of 0.187 in. diam and straightening by a roller straightening machine (Lewis). The combinations of heat treatment, working and aging that were investigated are summarized in Table 11; the various treatments were performed in the order given in each row of the table, and they will be subsequently identified by the symbols shown in the first column. SOLUTION TREATMENT All material investigated in the cold-worked condition, or cold worked prior to aging, was solution

Jan 1, 1962

By J. H. Henderson, T. E. Morrisson

An irvestigation has been made of the production of oil through horizontal fractures of high capacity and large radius placed at the base of producing formations. The specific aitns of the study were to (I) determine by model studies the reservoir performance when gravity drainage is the only producing mechanism, and (2) develop a method of predicting such perfortnance from commonly measured reservoir proper-ties. Although the theoretical approach tailed to develop a rigorous analytic sorution to the transient problem, it (lid lead to a practical method of predicting performance. Predictions (Ire in good agreement with rates and recoveries observed in scaled-model experinzents. Capillary effects and the influence of relative permzenbil-ity are taken into account. The experimental program was mainly concerned with the influenre of fracture radius, fracture capacily and capillary hold-up on the total recovery and the rate of recovery. Much of the experimental work was done on a triangular model which represented one-eighth of a square well pattern, so constritcted that horizontal fractures of varying radii and flow capacity could be studied. An electrolytic model was used to relate the initial production rates to fracture radius, formation thickness and the drainage radius of the well pattern. The conclusions reached as a resrtlt of the work are as follows. I. The production of oil under gravity force alone into a well-propped horizontal fracture, whose radius is of the order of hundreds of feet, is a recovery method which combines high recoveries with very acceptable production rates. 2. The mechanism is effective in "dead oil" reservoirs as well as in reservoirs which possess the energy of solution gas. 3. A method of predicting performance has been developed which gives good agreement with experimental behavior in cases of practicnl interest. Even for very thick beds and large fracture radii, where actual conditions do not conform to the assumptions made, the method gives order of magnitude predictions which would not otherwise be possible. INTRODUCTION Gravity drainage of oil from a formation which has continuous ver- tical permeability over a reasonable depth interval is a surprisingly effective method of recovery. However, for a conventional well the production rates which result from gravity drainage are so low that the economics are seldom attractive. The same formation may produce rapidly and profitably by gravity alone through a high capacity, extensive (i.e., > 100-ft radius) horizontal fracture placed near the bottom of the pay section. Fig. 1 shows a schematic diagram of the plan. Energy in the reservoir gas is not a necessary condition for this recovery process. With a sufficiently large fracture, attractive production rates will result from gravity flow alone, and the producing GOR need only be the solution GOR. It is, of course, necessary to keep the fluid level in