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By R. L. Smith, I. G. Greenfield

The binary system Ga-Sb has been investigated by thermal, X-ray, and metallo-graphic methods. 'The intermetallic compound GaSb melts at 705.9OC and forms a eutectic with antimony at 11.8 atomic pct Ga. This eutectic melts at 589.8OC. A eutectic appears to be formed at 29.8°C but is too close to the composition of pure gallium to be detected. IN the course of an investigation of the semiconducting properties of the intermetallic compound, GaSb, the phase equilibrium between gallium and antimony has been investigated. Recently, the phase diagram of similar systems, such as In-Sb,' In-AS,' and Bi-As3 have been determined. These diagrams have the same general appearance in that an intermetallic compound is formed at 50 atomic pct and a eutectic is formed on both sides of the intermetallic compound. Jenny,& who has been investigating the semiconducting properties of intermetallic compounds, has concluded from thermal data of several alloys that the phase diagram of the Ga-Sb system resembles those mentioned previously. This paper represents a more detailed study of the Ga-Sb equilibrium. Experimental Procedure The gallium that was used to prepare the alloys was obtained from A. D. Mackay Inc. and the Aluminum Co. of America; the latter reported the purity as 99.95 pct. The antimony was obtained from Bradley Mining Corp. who specified a purity of 99.997 pct. Since the intermetallic compound of GaSb was prepared primarily to be used for further studies of the semiconducting properties, additional purification by a standard zone-melting technique under an atmosphere of hydrogen was performed. Hall-effect measurements on this material indicated an impurity content of less than 3 ppm.5 The antimony also was purified by zone melting and used in conjunction with the compound GaSb to make the necessary alloys for the determinations of the antimony-rich side of the phase diagram. The antimony-rich alloys were chill cast in Vycor tubes which were evacuated to a pressure of less than one micron. Since these alloys expand on freezing, precautions were taken to prevent oxidation of the ingot in the event the tube fractured. To insure homogeneity, the brittle alloys were ground and then placed in the furnace for the thermal-arrest determinations. Since the cost of gallium is high, the experimental procedure was complicated somewhat because of the necessarily limited sizes of the melts. In order to economize, the gallium-rich side of the diagram was determined by using a 35 g ingot of pure gallium initially and adding increasing amounts of antimony in order to obtain additional alloys. The furnace used in the determination of the cooling curves is illustrated in Fig. 1. A 2¼ in. quartz tube, sealed at one end, was fitted with a brass flange which was attached with DeKhotinsky cement. The brass collar was water cooled to prevent the cement from softening. An "0" ring was used to provide a seal between the brass collar and the furnace cover. Nichrome ribbon was wound around a 2 ½ in. asbestos-covered copper core which was used to reduce the thermal gradient in the furnace. The insulation consisted of alternate layers of asbestos and aluminum foil surrounded by sil-o-cel refractory and

Jan 1, 1956

By Charles W. Merrill

Obsolescence in the mineral world is virtually nonexistent if the term is taken to mean that a mineral commodity, once established in commerce and industry, subsequently has fallen into disuse. We are living in an age of minerals. Each generation puts an increasing array of mineral-based commodities, in larger quantities, to more uses than ever before. Bastnasite, a museum mineral and a collector's item a few years ago, is now produced in quantity at Mountain Pass, Calif. Uranium, a minor byproduct of vanadium mining in the Rocky Mountain plateau area before World War 11, has grown to be a leading mineral product in several western States. And finally the total quantity and value of minerals both in the United States and in the World establish new records almost yearly. Surely the mineral industry as a whole is not obsolescent in our economy. Nevertheless, there are particular uses for particular minerals that are obsolescent and some applications have been supplanted entirely. Tin does not occupy the prominent place in foil manufacture that it once did, and the schoolboy's slate left most classrooms before the oldest of us were born.

Jan 9, 1964

By A. G. Suydam

Ancient as is the art of producing copper, so ancient is one of its eternal problems: refractories. Looking backward, in the light of present knowledge, clouded though it be, one cannot avoid a sense of profound respect for the patience, acumen and courage of those who have wrought so successfully despite difficulties, a more accurate understanding of which seems merely to accentuate. The problem of refractories arises from the necessity for constructing containers in which to bring natural ores into thermal solution in order to effect reduction and separation of the valuable metal content and free it of undesirable contamination while producing a waste slag. The very forces known to produce thermal solution of sufficient liquidity are necessarily destructive of exposed refractory linings in proportions varying inversely with thermal conductivity, directly with the porosity and ease of fluxing of the refractories used, and directly with the temperatures employed. Beyond this, mechanical forces are set up within the refractory lining incident to rapid heating or cooling, shrinkage at high temperatures, and unequal or excessive loading, that frequently pass the elastic limit, causing spalling or distortion. The effects of these forces are often accentuated by the necessity of providing at the same time as hot a bath and as cool a container as are consistent with fuel economy. Evolution in the Use of Refractories Clay Brick.—Fireclay and clay refractories had to yield wherever they were in contact with slags rich in basic oxides, first because of the combining power of those oxides with free silica and secondly because of the tendency of alumina to form either aluminates or alumina-silicates of varying complexity. Of no less importance, the incipient fusion point was low as compared with good clay brick of today, while the brick lacked strength at high temperatures. Expansion was slight, therefore it was difficult to make and maintain tight walls, roof, or bottom. However, the spalling tendency was low because of some of these properties and clay brick have retained their place in roasting furnaces, boiler furnace linings, and in the upper walls of some of the reverberatory types such as some refining, anode and wire-bar furnaces. They have served often and most efficiently for hot patching.

Jan 1, 1934

C. A. HANSEN (communicated appendix*).-Since the above paper was written, tests have been conducted with a view to securing a sounder basis for discussing the effects of temperature on the behavior of the zinc cell. The following data, while making no pretense to great accuracy, are still reasonably close. Cells were operated with the same feed solutions, but at varying temperatures, the latter being controlled by means of immersed steam coils. Current efficiencies obtained indicate that the corrosion rate

Jan 11, 1918

By E. H. Crabtree

IN an ideal mill, with perfect milling operations, the mineral extraction would be 100 per cent, the, concentrate would be 100 per cent mineral, the tailing would assay zer.0 mineral and the milling cost would be zero dollars. Such an operation can, of course, never be attained. We can only strive to approach it as nearly as possible and in doing so most recognize .the fact that the three primary factors in milling: assay of concentrate, assay of tailing, and cost of operation bear a definite economic relationship to each other. This relation will change from time to time and will be different for different mills, depending on milling equipment, character and quality of feed, market conditions, and other factors. It is granted that for a given operation there is an economic point, but the location of this point is difficult. It is for the purpose of making some of these economic points a little more tangible that this paper has been prepared.

Jan 1, 1930

By James W. Malcolmson

This paper treats of the history and development of the Sierra Mojada mines in the north of Mexico, the character and extent of the ore-deposits, and the methods of mining the ore. The growth of the smelting industry in Mexico in recent years is, to a large degree, due directly to the output of the lead-bearing ores from the Sierra Mojada mines, and at the present time (1901) new smelters are being built, looking to this district for their supply of lead-ores. These mines are located in the southern part of the State of Coahuila, in the Republic of Mexico, in latitude 27 24' N. and longitude 103O 43' W. of Greenwich. The last account of the Sierra Mojada published in our transactions was contributed by Mr. Richard E. Chism, in October, 1886.* Since that time some 3,000,000 tons of ore have been extracted from the mines, and much additional information has been developed regarding the mineral deposits. Since 1886, the Mexican Northern railroad, 78 miles in length, has been built from Escalon, connecting the camp with the Mexican Central railway, a trunk-line from El Paso, Texas, to Mexico City. The distances by rail from Sierra Mojada to the principal smelting-centers are as follows : To Torreon, Coahuila, Mex., 179 miles; to Monterey, Nuevo Leon, Mex., 422 miles; to El Paso, Tex., U. S., 494 miles; to Aguas Calientes, A. C., Mex., 522 miles; to San Luis Potosi, 8. L. P., Mex., 644 miles; to Pueblo, Colorado, U. S., 1158 miles; to Argentine, Kans., U. S.,

Jan 1, 1902

By L. A. Willey

Although the interierometric method for the determination of length changes was devised by Fizeau more than three quarters of a century ago, it has not achieved the widespread use in the metallurgical field that its precision and simplicity would seem to warrant. The interferometer and the basic principle are both very simple. When optically plane surfaces held at a very slight angle to each other are illuminated by monochromatic light, rectilinear, equally spaced interference fringes arc formed. Each fringe corresponds to a defiuitc thikness of the wedge formed by the optical flat.;. The difference in wedge thickness between two consecutive fringes is cqual to one half the wave length of the illuminating light. Instruments for vicwing the intertero~ncter have passed through a number of modifications. Outstanding among the improvements were those Abbe. in 1884. His improved instrument permitted micrometric mcasurements to the order of one-hundredth of the width of an interference fringe (i.e., lengths were measured to the order of one two-hulldredth of the mave length of light ). It also permitted the consecutive use of light of several wave lengths. which made possible the determination of the order number of any fringe and therefore the absolute thickness of the wedge at any point. The Abbe dilatometer and methods of measuretment, including corrections to he applied for the change of index of refraction with change in tempcrature and barometric pressure in an air wedge, have been thoroughly described by Pulfrich.' Pulfrich2 made further improvements in the interference measuring apparatus. His instrument embodied all the features of the Abbe dilatometer but was made more versatile by its complete mechanical separation from the interferorneter. The introduction of an Amici prism in the piece permitted the simultaneous observ tion of the whole set of fringe systems developed in the interferometer from the visible light of a geisler tulle. .Also, the introduction of a direct-vision, reflecting prism made it possible to set the fringes parallel to the two vertical fiducial line. of the instrument without the necessity of rotating the interierometcr. Interferometric methods employed ill this country have been developed and dcscribed by Priest, Pelers and Cragoe," Austin,5 Merritt,= Saunders,? and Nix and MaNair. Since none of these authors used the type of instrument that was employed in the present investigation, they Will not be discussed here. This paper will be limited to the description of the interfernmetric apparatus and method used at the Aluminum Research Laboratories and to the presentation of data so obtained. Apparatus and Procedure A general view of the dilatometer, not including equipment for controlling and

Jan 1, 1945

By Sherman L. Pease

An inexpensive and relatively rapid method that can be used by field crews is described. Fluid movement is determined by releasing a tracer (dye) in the well at a predetermined level and, after an interval of time, sampling the well fluid at another level. The testing equipment consists of a combined crusher and sampler unit that is run into the well on a wire line. The rate of movement can be calculated from time-volume relationships. Description of Method It is often desirable to determine whether there is occurring any transfer of fluid from point to point in a shut-in well, and, if so, to measure the rate of movement. When it is desired to examine a large number of wells for possible "thief" sands, the time and expense will be considerable unless the method used is inexpensive and rapid. After experimentation with several possible solutions to the problem, the Production Department of the Shell Oil Co., Inc., developed the apparatus described herein, which has proved satisfactory. Routine operations with it can be carried out by field production crews with a minimum of technical supervision and with negligible investment in equipment. The method is based upon releasing a suitable tracer in the well fluid at a known level, and recovering a sample of well fluid at another level after a measured interval of time. Repetition of this process with different time intervals between release and sampling gives the necessary data. For purposes of illustration, the setup for measuring migration of fluid in an upward direction is described in the following paragraphs. The arrangement of equipment is shown diagrammatically on Fig. I. The elements of the combination unit are the tailpiece, the crushing device, the spacer and the sampling device. The lengths of the tailpiece and spacer are varied to place the crushing and sampling devices in the desired positions in relation to the sands being tested. The crushing device breaks the glass bottle containing the tracer when the tailpiece strikes the bottom of the well and the tension on the sand line is slackened. Because of the open construction of the crushing device, the tracer is quickly and completely disseminated in the well fluid. The sampling device is a suction bailer, which obtains a sample of the fluid surrounding the perforated nipple just before the unit is picked up off bottom. The sample is retained in the barrel by the ball valve for examination at the surface. Normally, on the first run into a well, the sample is obtained near the releasing point of the tracer, and thereafter samples are taken near the base of the upper sand if migration is indicated by the dilution or absence of the tracer in the initial sample. The length of the time interval between the releasing of the tracer and the sampling of the well fluid is varied for successive runs, attempting first to establish the rate within limits and then to define it more accurately by additional runs if necessary.

Jan 1, 1946

By Sherman L. Pease

An inexpensive and relatively rapid method that can be used by field crews is described. Fluid movement is determined by releasing a tracer (dye) in the well at a predetermined level and, after an interval of time, sampling the well fluid at another level. The testing equipment consists of a combined crusher and sampler unit that is run into the well on a wire line. The rate of movement can be calculated from time-volume relationships. Description of Method It is often desirable to determine whether there is occurring any transfer of fluid from point to point in a shut-in well, and, if so, to measure the rate of movement. When it is desired to examine a large number of wells for possible "thief" sands, the time and expense will be considerable unless the method used is inexpensive and rapid. After experimentation with several possible solutions to the problem, the Production Department of the Shell Oil Co., Inc., developed the apparatus described herein, which has proved satisfactory. Routine operations with it can be carried out by field production crews with a minimum of technical supervision and with negligible investment in equipment. The method is based upon releasing a suitable tracer in the well fluid at a known level, and recovering a sample of well fluid at another level after a measured interval of time. Repetition of this process with different time intervals between release and sampling gives the necessary data. For purposes of illustration, the setup for measuring migration of fluid in an upward direction is described in the following paragraphs. The arrangement of equipment is shown diagrammatically on Fig. I. The elements of the combination unit are the tailpiece, the crushing device, the spacer and the sampling device. The lengths of the tailpiece and spacer are varied to place the crushing and sampling devices in the desired positions in relation to the sands being tested. The crushing device breaks the glass bottle containing the tracer when the tailpiece strikes the bottom of the well and the tension on the sand line is slackened. Because of the open construction of the crushing device, the tracer is quickly and completely disseminated in the well fluid. The sampling device is a suction bailer, which obtains a sample of the fluid surrounding the perforated nipple just before the unit is picked up off bottom. The sample is retained in the barrel by the ball valve for examination at the surface. Normally, on the first run into a well, the sample is obtained near the releasing point of the tracer, and thereafter samples are taken near the base of the upper sand if migration is indicated by the dilution or absence of the tracer in the initial sample. The length of the time interval between the releasing of the tracer and the sampling of the well fluid is varied for successive runs, attempting first to establish the rate within limits and then to define it more accurately by additional runs if necessary.

Jan 1, 1946

By P. A. Beck, L. J. Demer

As reported in a previous publication,' isothermal grain growth in high purity aluminum and in an aluminum alloy with 2 pct magnesium can be adequately described by means of the empirical relation: Here, D is the average gain size after an annealing period 1. The annealing period includes the time for complete recrystal-lization R, and the time for gain growth 1,. D, is the pain size as recrystallized, n is a parameter depending on the temperature and on the material. The effect of 2 pet magnesium in solid solution was to decrease D, and to increase R, A and n at a given temperature. The present work was undertaken in order to investigate the above listed-effects of magnesium in solid solution, as functions of the magnesium content. The work also includes the study of certain anomalous effects observed in the recrystal-lization and grain growth of the 2 pct magnesium alloy at 350°C. Experimental Procedure The method of producing the ingots used in this work was described in detail1 and need not be reproduced here. The materials used were high purity aluminum, furnished by the Aluminum Co. of America, of lot analysis shown in Table r and magnesium from a high purity distilled stock of magnesium crystals. Table i—Lot Analysis of High Purity Aluminum Per CeNt Si.................................... 0.00~ Fe.................................... 0.002 Cu................................... 0.002 Mg................................... 0.003 Mn................................... o. oox Ingots were prepared for a series of binary aluminum-magnesium alloys of increasing alloy content. The numbers used to designate these ingots and their magnesium contents by chemical analysis are given in Table 2. Table 2—Ingot Numbers and Magnesium Contents Ingot Number Pct oa Magnesium aI 2.05 22 1.80 24 0.12 26 0 02s The analyses showed no difference in composition between the top and the bottom of the ingots. Spectrographic analysis of the ingots for elements other than magnesium showed, within the limits of accuracy of the method, no increase in impurities over the amounts given in the lot analysis for the high purity aluminum in Table I. Careful microscopic study of ingot 21 in the as-cast condition, at magnifications up to I 500X, revealed a cer-

Jan 1, 1949

By F. R. Hewitt

The methods of mining talc are simple, and in western North Carolina are almost entirely by open cut and quarry. The larger part of the talc of this section lies in various-sized "veins''. inclosed in quartzitic walls, the majority of which have by folding been thrown into a perpendicular position, or nearly so, and the exposed edges of which have been covered by debris from erosion of the mountain above. This covering of loose rocks and earth is from 5 to 25 ft. thick, and in most cases has to be removed because it is difficult to support. Sometimes the covering is heavy enough to "catch" and timber successfully, and in this case the talc can be worked out by the usual method of following the "vein," using stulls for holding up the walk until the vein is worked out, and then allowing the cut or drift to fall in. In some cases it proves more convenient to sink shafts and run drifts, following the talc "veins" until exhausted. The talc deposits of this section are badly broken and faulted both laterally and perpendicularly, and in some cases are found many feet below the level of drainage, necessitating pumping at considerable expense. My own experience in mining talc has been that the chief point is to get a reliable "vein," and that then the mining is not as difficult, or any more so at least, than that of any common ore. If the "veins" are pure talc it is simple; if the talc is admixed with foreign matter, such as tre-molite in excess, or stains of iron or manganese, as is often the case, one had better abandon the deposit. Methods of Manufacture Talc, being a soft mineral, is not difficult to reduce to the condition desired by the trade. Powdered talc is admitted under low duty from France, Italy and Austria, and some is being imported from Asiatic points. Talc is usually ground and bolted in any simple reduction mill. That mined in this section is hand-sorted and the quality that will make good powdered talc is ground for use in the manufacture of talcum powder, cosmetics, etc., while all that is hard enough and has sufficient strength is used for crayons and blanks for gas burners and electrical work, being sawed into the shapes desired. The rest that is clean and pure is ground

Jan 1, 1917

By John Chipman

THE equilibrium between titanium in liquid iron and titanium oxides has been studied by Hadley and Derge.' They have shown that a minimum occurs in the oxygen content of the metal between 0.1 and 1.0 pct Ti, but its exact level was not fixed. The oxide phase in this minimum range was principally TiO, containing some iron oxide. On the other hand, for concentrations above 5 pct Ti the oxide phase was TiO and the oxygen content of the metal increased rapidly with increasing titanium content. From their observations and the free energy of Ti0 and TiOz reported by Kelley and ah,' it is possible to derive approximate values for the activity coefficients of titanium and oxygen in liquid iron-titanium alloys and the conditions for equilibrium in steel deoxidation. Neglecting possible departures from the stoichio-metric composition, the condition of equilibrium with Ti0 may be expressed as follows: TiO= Ti_ + C) log K = log NTl + log [% O] + log yTi + log fQ Here as a matter of convenience the titanium concentration is expressed in mol fraction while that of oxygen is in weight percent. The activity coefficients are yTi and fo. The value of log fo approaches zero as the concentration of titanium approaches zero, while that of log yTi approaches a limiting value of In Fig. 1 the sum of log NTi + log [% 0] is plotted for mol fractions of titanium between 0.05 and 0.50. The smooth extrapolation gives a value of —4.15 which corresponds to log K — log y:i . We therefore have the equation: According to the data of Kelley and Mah,' the free energy of formation of Ti0 at 1900°K is -82,400 cal. The free energy of solution of half a mol of oxygen in iron, taking 1 pct 0 as the standard state, is -29,300 cal. From these we write: From these equations the activity coefficient of titanium at infinite dilution in iron is found to have a value of 0.011 or log y°. = -1.96. This is only an approximate value but is certainly better than the estimated 0.05 in Basic Open Hearth Steelmaking To obtain approximate values for the activity coefficient at intermediate concentrations, it is as- sumed that log yTi(l is constant and equal to -1.96. This corresponds to a value of E;: = 3 In yTi/aNTi = 9.0 which is not unreasonable We now have the value for the activity of titanium and the percentage of oxygen in equilibrium with TiO. It is therefore a simple matter to calculate the activity coefficient of oxygen which is shown in Fig. 2. The effect of titanium is rather large, being comparable to that of vanadium, but not so large as has been reported for aluminum. The slope of the line at low concentrations corresponds to E: = aln yo/ aNTi=-0.37. At concentrations below 1 pct Ti the deoxidation constant and oxygen content for equilibrium with TiO, can be calculated from the foregoing data and the free energy of formation of TiO,, which according to Kelley and Mah is -144,600 cal at 1900°K. The free energy of solution of oxygen has been given; that of Ti to form a dilute solution with 1 pct Ti as the standard state is RT ln (0.5585 y:i/47.9) = -34,800 cal. From these data we find (for concentrations in wt pct): TiO, = Ti + 2 -0; hFTgO0= + 51,200 cal log if =-5.89 The interaction coefficients, concentrations being expressed as wt pct, are e;: = alogfTi/a[% Ti] = +0.048 and e:' = a logfo,/a[ojTi] = -0.187. The calculation gives the following results which, in view of the impurity of the oxide phase, must be regarded as approximate:

Jan 1, 1961

By Dilip K. Das, Douglas T. Pitman

ONE of the major uses of barium in metallic form is as a getter material in vacuum tubes. Because of the high chemical reactivity of the metal, Ba-Al alloys are extensively used. Numerous methods for the preparation of Ba-Al alloys have been published, a few of which1-4 are cited here. Most of these methods were found to be quite elaborate, involving the reduction of BaO, and not too well adapted for the close control of the final composition of small amounts of alloys prepared for laboratory use. A simple laboratory method for the preparation of Ba-A1 alloys in small batches starting from pure metals was devised, so that it was possible to control the desired compositions to within 1 pct. The pertinent features of the alloy system Ba-Al5 are 1) an intermediate compound BaAl, with the melting point of 1050°C, and 2) a eutectic between aluminum and BaAl4 at 98 pct Al. The accompanying sketch shows the experimental arrangement for the preparation of the alloys. Weighed amounts of aluminum and barium were placed in an alumina and a stainless steel crucible, respectively. According to the supplier's specification, the purity of the metals used in the alloys is as follows: a) aluminum rods—99.9 pct Al, and b) barium rods—99.5 pct Ba. The stainless steel crucible, tapered at the bottom and having a 1/16 in. diam hole, rested on top of the alumina crucible. The assembly was placed inside a graphite sleeve which rested on a refractory platform. The platform moved the assembly up and down through the field of a radio frequency coil. A glass bell jar was placed between the crucible assembly and the radio frequency coil to maintain a steady flow of helium around the melt. A small window was cut out on the wall of the alumina crucible to observe the progress of the re- action and to record the temperature with an optical pyrometer. The platform was first raised high enough to move the barium out of the radio frequency coil field in order to allow only the aluminum to melt. The assembly was then lowered so that the barium began to melt and flow out through the small orifice into the molten aluminum. In order to keep the violence of the exothermic reaction under control, the rate of flow of barium was carefully regulated by raising or lowering the crucible assembly. All the samples prepared by this technique were examined by a Norelco X-ray diffractometer using CuKa radiation, The diffraction specimens were prepared by placing the finely powdered samples in flat specimen holders. The Ba-Al alloys prepared with a high barium content were found to consist mainly of BaAl4. The structure of BaAl4 has previously been reported by Alberti and Andress.8 They found that BaAl4 was body-centered-tetragonal with an a0 = b0 = 4.530Å and c0 = 11.14Å. An alloy whose composition was found by chemical analysis to be almost 100 pct BaA1, was used to determine the relative intensities. The d-spacings were obtained from the same alloy to which a small amount of tungsten had been added as a calibrating material. Accurate values for a, and c, were calculated according to the method proposed by Taylor and Floyd.' The calculated values are: a, = b, = 4.566Å and c0 = 11.250Å. The measured d-values for BaAl4 are shown in Table I along with relative peak intensities above background and hkl indices. Acknowledgment The authors are grateful to L. J. Cronin, the head of the Techniques Dept., for suggesting the problem and for his constant interest. References 1Froges and Camargue: German Patent No. 809107, 1951. French Patent No. 935324, 1949. 2E. Bonnier: Annales de physique, 1953, vol. 8, pp. 259-312. 3M. Orman and E. Zemhela: Prac Institute of Metals; 1952, vol. 4, pp. 437-445. 4E. Fujita and H. Yokomizo: Reports Gov. Chemical Industrial Research Institute, Tokyo, 1952, vol. 47, pp. 291-297. 5E. Alberti: Ztsch. fur Metallkunde, 1934, vol. 26, p. 6. 6E Alberti and K. R. Andress: Ztsch. fur Metallkunde, 1935, vol. 27, p. 126. 7 A. Tnslor and R. W. Floyd: Acta Crystallographica, 1950, vol. 3, p. 285.

Jan 1, 1958

By C. S. Finney, John Mitchell

The decline of the beehive coking industry was inevitable, but it had filled the needs and economy of its day. A beehive plant required neither large capital investment to construct nor an elaborate and expensive organization to run. The ovens were built near mines from which large quantities of easily-won coking coal of excellent quality could be taken, and handling and preparation costs were thus at a minimum. The beehive process undoubtedly produced fine metallurgical coke, and low yields were considered to be the price that had to be paid for a superior product. Few could have foreseen that the time would come when lack of satisfactory coking coal would force most of the beehive plants in the Connellsville district, for example, to stay idle; and if there were those like Belden who cried out against the enormous waste which was leading to exhaustion of the country's best coking coals, there were many more to whom conservation was almost the negation of what has since become popularly known as the spirit of free enterprise. As for the recovery of such by-products as tar, light oil, and ammonia compounds, throughout much of the beehive era there was little economic incentive to move away from a tried and trusted carbonization method simply to produce materials for which no great market existed anyway. With the twentieth century came changes that were to bring an end to the predominance of beehive coking. Large new steel-producing corporations were formed whose operations were integrated to include not only the making and marketing of iron or steel but also the mining of coal and ore from their own properties, the quarrying of their own limestone and dolomite, and the production of coke at or near their blast furnaces. As the steel industry expanded so did the geographic center of production move westward. By 1893 it had moved from east-central to western Pennsylvania, and by 1923 was located to the north and center of Ohio. This western movement led, of course, to the utilization of the poorer quality coking coals of Illinois, Indiana and Ohio. These coals could not be carbonized to produce an acceptable metallurgical coke in the beehive oven, but could be so treated in the by-product oven. By World War I the technological and economic limitations of the beehive oven as a coke producer were being widely recognized. After the war the number of beehive ovens in existence dropped steadily to a low of 10,816 in 1938, in which year the industry produced only some 800,000 tons of coke out of a total US production of 32.5 million tons. The demands of the second World War led to the rehabilitation of many ovens which had not been used for years, and in 1941, for the first time since 1929, beehive ovens produced more than 10 pet of the country's total coke output. Production fell off again after 1945, but the war in Korea made it necessary once more to utilize all available carbonizing capacity so that by 1951 there were 20,458 ovens with an annual coke capacity of 13.9 million tons in existence. Since that time the iron and steel industry has expanded and modernized its by-product coking facilities, and by the end of 1958 only 64 pet of the 8682 beehive ovens still left were capable of being operated. Because beehive ovens are cheap and easy to build and can be closed down and started up with no great damage to brickwork or refractory, it is likely that they will always have a place, albeit a minor one, in the coking industry. The future role of the beehive oven would seem to be precisely that predicted forty years ago by R. S. McBride of the US Geological Survey. Writing with considerable prescience, McBride declared: "A by-product coke-oven plant requires an elaborate organization and a large investment per unit of coke produced per day. Operators of such plants cannot afford to close them down and start them up with every minor change in market conditions. It is not altogether a question whether beehive coke or by-product coke can be produced at a lower price at any particular time. Often by-product coke will be produced and sold at less than cost simply in order to maintain an organization and give some measure of financial return upon the large investment, which would otherwise

Jan 1, 1961

By E. G. Leonardon, C. Schlumberger, M. Schlumberger

Last year the authors presented a paper that discussed the various electrical measurements they perform in drill holes, which they name "electrical coring."' The object of the present paper is to give a brief account of the points of scientific interest that have been elucidated by further field work and laboratory research, as well as the economic results that have been attained recently. The practical examples given in this paper are drawn, for the most part, from the field work performed in Russian oil fields during the years 1931 and 1932. This is due to the fact that, thanks to the comprehensive cooperation of the Russian geologists and scientists, the authors are allowed to make public a large amount of recant information. In other countries in which the authors are engaged in similar work, the competition between private companies makes it imperative, for a considerable lapse of time, to avoid publication of the results obtained. The following points will be discussed successively, under separate headings: 1. Electrochemical phenomena in drill holes. 2. Stratigraphic correlations and tectonic studies. 3. Relations' between the productivity of oil horizons and their electrical resistivity. 4. Location of coal seams. 5. Summary and conclusions. Electrochemical Phenomena in Drill Holes Technical Publication 462l described the author's discovery concerning the existence of important differences of potential spontaneously gener-

Jan 1, 1934

By R. L. Fullman

IN the investigation of metallurgical transformations and the relationships between microstructure and properties of metals, it frequently is desirable to obtain a measurement of the relative amounts of the various phases present and of the mean size of particles into which each phase is dispersed. The relative amounts of the phases can be measured by the classical methods of area, lineal, and point analysis,1-5 in accordance with the principle that the volume fraction of a phase, the fraction of a polished cross section occupied by the phase, the fraction of a random line occupied by the phase, and the fraction of randomly arrayed points occupied by the phase are all equal. The validity of this relationship depends only on the attainment of a truly random sample of area, length, or points, and not on the size, shape, or distribution of the particles constituting the phase. Smith and Guttman8 have derived a relationship between the interface area per unit volume S, and the measurable quantities L., the interface length per unit area on a cross section, and NL, the number of interfaces per unit length intersected by a random line. Their equation, Sv = — L8 = 2NL is also valid regardless of the distribution of particle sizes and shapes. In contrast to the situation concerning measurement of relative fractions of phases and of interface area, the measurement of particle sizes in opaque samples has not been subjected to a complete analysis. It has been common to measure some lineal or area dimension of particles on a polished cross section and to use the mean value as a qualitative measure of particle size. In the present paper, quantitative relationships are established among the various mean dimensions on a polished cross section and the actual dimensions of the particles present. Particles of Uniform Size Spheres: If a metal sample contains particles of a phase a dispersed in the form of spheres of uniform size, a polished cross section through the sample will reveal circular areas of phase a with radii from 0 to ?, the radius of the spheres. Consider a cube of unit dimensions to be cut from the sample. If a cross section parallel to one of the cube faces is examined, the average number of particles per unit area (N,) equals the number of particles per unit volume (Nv) times the probability p1 that the plane would intersect a single sphere positioned at random within the unit cube. Since, of the various possible positions for the cross-sectional plane over the unit length from top to bottom of the cube, only those positions existing over the length 2r would lead to the plane intersecting the sphere, the probability of intersecting a single sphere is just 2r. N8= Nvp1 = Nd-2r [1] Applying the equality of area and volume fractions, the relationship is found between sphere size and average area s of uniform spheres intersected by a random cross section, 4 - f = NV V = Nr . — pra = N s = Nd . 2rs S = —pr2 [2] A similar analysis reveals the average traverse length across spheres of uniform size when random lines are passed through the sample. If a randomly oriented unit cube is cut from the sample and a randomly positioned line is passed through the cube parallel to a cube edge, the number of spheres intersected by the line (Nl) equals the number of spheres per unit volume times the probability p1 of the line hitting a single randomly placed sphere in the cube. Since possible positions of the line occupy unit area, and possible positions for which it will pass through the sphere occupy an area of pr2, the probability of the line hitting a randomly placed single sphere is pr2. NL = Nv p1 = Nvpr2 [3] Combining this relationship with the equality of volume and lineal fraction, the desired relationship is obtained between radius and mean lineal traverse length -i, for spheres of uniform size. 4 - - 3 l=4/3r [4] Circular Plates: Consider a sample containing particles of a phase a in the form of circular plates of uniform radius r and thickness t, where r >> t. If the plates are randomly oriented, as in a sufficiently large sample of a fine grained polycrystalline material, area and lineal analysis may be carried out with parallel cross-sectional planes and lineal traverses. If the plates are not randomly oriented, it is necessary to randomize the orientation of the cross-sectional planes and traverse directions. Let a unit cube be cut from the sample, and a cross-section plane be passed through the cube parallel to one of the cube faces. The number of plates cut by the cross-sectional plane per unit area is equal to the number of plates per unit volume times the probability of a plate intersecting a single randomly positioned and randomly oriented plate in the cube. If J is the component of the plate diameter in the direction normal to the cross-sectional planes, the probability of a plane cutting a single randomly oriented plate is equal to J, the mean value of J for all possible orientations of the plate. Let 4 be the dihedral angle between a plate and the cross-sectional plane, and let p?, d? be the probability that a plate makes an angle between 4 and ? + d? with the cross-sectional plane. Then for ran-

Jan 1, 1954

By H. A. Deans

A three-parameter mathematical model for one-dimensional flow in porous media is developed. The objective of the model is to predict accurately the longitudinal dispersion associated with the flow of either gases or liquids over a wide range of Reynolds number. A qualitative analysis of the model parameters is given. Published experimental pulse-response curves are compared with results predicted by the model. Several general types of problems are given for which the model can be used. INTRODUCTION The problem of multicomponent single-phase flow through porous media is encountered in the study of petroleum reservoirs, gas chromatographic and ion-exchange columns, industrial fixed-bed con-tacters and elsewhere. These particular examples span the wide range of flow conditions possible; Reynolds numbers of less than l0-4 are not unusual in oil-production problems, while values in excess of 103 are common in large fixed-bed operations. The study of flow-dependent transport phenomena is complicated both by the changes in the character of the flow over this range, and by the irregularity of the flow boundaries inherent to porous media. Dispersion is one of the important phenomena known to depend fundamentally on flow conditions as well as on fluid and medium properties. As used in this paper, the term "dispersion" refers to the observed mixing of fluid elements of different composition which occurs in flow systems. The actual mechanism may be one or more of a number listed below. Only dispersion in the direction of the mean flow (referred to as axial or longitudinal dispersion, or mixing) is considered here, although lateral dispersion arises as part of certain coupled mechanisms. MECHANISMS FOR LONGITUDINAL DISPERSION A number of distinct mechanisms are known3,5,7,8 to contribute to the phenomenon of longitudinal dispersion. The more important of these are as follows. 1. Molecular diffusion in the flow direction. 2. Turbulent (cell) mixing. 3. Lateral transport processes coupled with velocity and/or residence time distributions, including: (a) "Taylor" diffusion caused by the interaction of velocity profiles in individual voids with lateral molecular diffusion; (b) separation and remixing or interdiffusion of streams having different velocities around particles; and (c) the couplipg of gross velocity profiles, caused by viscous instability or inhomogeneous porosity, with lateral dispersion. 4. Finite mass-transfer rate between a porous matrix and the flowing phase, and finite diffusion rate inside elements of the porous matrix. It is a well documented fact that these mechanisms, whether acting individually or in combinations, produce essentially similar integral effects. The observed dispersion can be described approximately by solutions of the diffusion equation with a properly chosen dispersion coefficient. Necessary conditions for equivalence between dispersion and diffusion are discussed by Klinkenberg and Sjenitzer.7 Apparently these conditions are not satisfied exactly in many real systems. "Best fit" solutions of the diffusion equation often depart appreciably from measured breakthrough curves for the usual pulse- or step-forced experimental systems. In particular, pulse response curves usually show some degree of asymmetry and "tailing" which cannot be reproduced by the one-parameter diffusion model. The three-parameter model proposed herein attempts to produce these effects in a realistic manner. Asymmetry and tailing are predicted for certain sets of parameter values, while for other sets the new model agrees with the diffusion model. VELOCITY DEPENDENCE OF DISPERSION Molecular diffusion apparently controls at sufficiently low Reynolds number in both gas and liquid systems.*l3 At Re > 20, turbulent cell mixing is dominant for gases flowing at low pressure; the data of McHenry and Wilhelm8 show that the mixing cell is approximately 1 particle diameter long in random sphere packs. on the other hand, the data

By Charles L. Mantell, B. G. Shah

SINCE the beginning of the industry, commercial electrolytic manganese has followed the Shelton patent' among others, which called for the addition of sulfur dioxide in controlled amounts, to a purified manganese sulfate-ammonium sulfate at a controlled pH. Every attempt to eliminate sulfur dioxide additions has resulted in operating difficulties, chiefly solution of the deposited metal and lowered current efficiencies. Many replacements for sulfur dioxide have been proposed and studied, chiefly sulfur compounds, urea, thiourea, and proteins similar to those employed successfully in copper refining. It has been suggested that sulfur dioxide is a re-ductant for higher-valence manganese compounds, or that it is reduced by manganese metal in the deposit to hyposulfites or its compounds, and that these might affect the cathode film or the deposition potential, or the overvoltage of manganese. The additives were studied following the method of Mantel1 and Ferment2 who determined the feasibility of current-potential curves as an analytical tool for monitoring manganese elec trowinning solutions for metallic impurities: nickel, cobalt, silver, copper, zinc, molybdenum, cadmium, magnesium, and sodium. The individual effect of each on the standard polarization was determined for a range of concentrations. Not all affected the polarization curve; cadmium, magnesium, and sodium had no effect. Nickel, cobalt, silver, copper, and zinc yielded a correlation between transition current and concentration of impurity.

Jan 1, 1968

By J. E. Elliott

ALTHOUGH the firm in which the writer is a partner is not exactly the pioneer in the coring of rotary-drilled wells in Southern California, it has taken the lead in bringing coring to its present status. To the Shell Company of California belongs the, honor of having first used the core drill in its endeavors to locate subsurface structures west of Santa Fe Springs. Following those operations, similar work was done near Wasco in the San, Joaquin Valley. Results of the latter core drilling were successful, in that they made it possible to determine the under-ground structure. At, about the same time that the Shell Company was doing the work at Wasco, it was experimenting in the use of the core drill in connection with rotary-drilled holes. The oil sands in its dis¬covery well at Signal Hill were located by means of the rotary core drill. In 1921, in view of the trouble that the operators were having in the fields of Southern California, and particularly at Huntington Beach, R. E. Collom, of the State Mining Bureau, called their attention to the possibilities of the core drill for eliminating many of the serious problems that were facing them. It was this same difficulty encountered by the operator in locating the oil sands that caused the writer to enter into con-tract core drilling; late in 1921 the California operators became converted to the advantages of that method, and in the short space of one year core drilling in rotary-drilled holes has risen from a theory to an established practice.

Jan 10, 1923

By A. Styka, G. Fischer, S. Tour

Described herein are the results obtained during research work involving coating titanium alloys with molybdenum by vapor-deposition methods. Results show that the method can be used successfully to deposit hard adherent wear-resistant coating of methodmetallic molybdenum on titanium or titanium alloys without changing the microstructure of the titanium base. PRODUCTION and use of titanium and its alloys have increased tremendously in the past few years. The physical, mechanical, and chemical properties of this engineering metal have caused considerable enthusiasm among metallurgists and engineers. However, as with all materials, there are some drawbacks. For example, titanium is susceptible to seizing and galling on wearing surfaces. In order to produce a good wear-resistant surface, many investigations have been conducted evaluating oxidizing, carburizing, nitriding, carbonitriding, sili-conizing, and chromizing of titanium. All of these processes require high temperatures for rather extensive periods of time. It has been possible to produce hard surfaces on titanium and its alloys by a number of these processes at the expense of a deterioration of the physical properties of the base material. A practical solution to the problem of providing titanium and titanium alloy parts with a satisfactory wear-resistant nongalling surface must be one that does not involve excessive temperatures for long periods of time. Sam Tour & Co. Inc. has completed a research and development contract for the United States Army Ordnance Corps on vapor deposition of molybdenum on titanium and titanium alloys. On the basis of results obtained from the research program, titanium alloys can be coated successfully with molybdenum to provide a hard wear-resistant surface without harm to their base mechanical properties. The remainder of this article is a description of the techniques used to apply the coating and the results obtained from wear tests on molybdenum-coated titanium. Theory Basically, the technique used was the application of molybdenum by a vapor-deposition method, thermal decomposition of molybdenum hexacarbonyl [Mo(CO)] with hydrogen as the carrier gas. The selection of this method was based chiefly on the following considerations: 1—low plating temperature which would minimize excessive grain growth, 2— low decomposition temperature of the carbonyl, 3— possibilities of controlling the hardness of the plate by adjusting the carbon content using the plating temperature and pressure as the primary variables, 4—use of high vacuum, thereby avoiding unnecessary oxidation and other complex reactions with the atmosphere. Free energy data1 show the strong tendency for titanium to combine with O2 N2 or carbon from normal temperatures to temperatures above its melting point. To maintain the titanium in a film free condition, the use of as high a vacuum as possible is indicated. The literature' indicates that the reaction product of hydrogen with titanium is unstable in vacuum at around 400°C. 5—Although it is indicated from the thermodynamic standpoint that there is little possibility of removing carbon from either titanium or molybdenum, the work of Lander and Germer -ndicates that the use of a suitable H,/CO ratio is somewhat effective in minimizing carbon deposition. 6—Availability of molybdenum carbonyl. In the simplest form, the conditions of equilibrium3 in chemical reactions involving decomposition of carbonyl are as follows: Mo (CO) ? Mo + 6CO 2CO * C + CO,. The plating rate is proportional to the rate of evolution of CO from the decomposed carbonyl, i.e., it is proportional to the pressure of the gaseous decomposition products. Carbon released from CO gas is the significant constituent for the variability of the physical properties of the product. High carbon deposition is favored by increasing pressure. Limitations are imposed in the selection of plating temperature and pressure. Excessive temperature re-

Jan 1, 1956