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By N. E. Holden, R. R. Goodrich

TheRe is a small area about Murray where bedded gold quartz veins occur in Prichard slate. The ore taken from the upper levels, during the early days, was free milling and was treated by stamp milling and amalgamation. There was likewise a considerable placer working. The report is current that tungsten (scheelite) was encountered, which interfered with the amalgamation in the stamp mills and which, in placering, collected in the riffles in the sluice boxes and clogged them. Consequently, in the quartz mines, the scheelite, when encountered, was rejected, being thrown into the waste, sometimes inside the mine and at other times outside on the dump. The free surface ores became worked out and as the ore in depth became pyritic and rebellious to amalgamation the mines closed down. Last spring tungsten ore brought a high price, near $80 per unit, 60 per cent. W03 and up. This so stimulated the output of tungsten ore that old dumps were explored and waste stored in the mines was gone over. Tungsten was likewise mined from virgin ground. So the district produced quite heavily for a time. The condition now is different. The price is not so high, about $20 per unit WO3, which makes profits questionable when mining in new ground. The accumulations from early day mining have been exhausted and the output has greatly declined. The Golden Chest mine was the heaviest producer of tungsten. The months of June and July were spent at this mine studying the problem. Since the mine had produced both gold and tungsten, we looked forward to the problem of recovering both from what might be called a gold-tungsten ore. A study of the Golden Chest vein showed this was not to be the case. While gold ore and tungsten ore come from the same vein, the tungsten ore is confined to a more or less disturbed or distorted portion

Jan 1, 1918

By Klaus Schwerdtfeger

Activities of lead in Pt-Pb and Pd-Pb melts in the temperature range of 800° to 1200°C have been detev-mined from electromotive-. force measurements 202th the cells Both systems display strong negative deviations from Raoult's law. The data obtained with cell [1] were combined with available data on the activity of PbO in silica-satuvaterl PbO-SbO2 melts to calculate the standard free cnergy of formation 01- liquid PbO. FREE energies of formation of oxides and activities of components in metal and oxide melts can be determined with galvanic cells consisting of a metal phase, an electrolyte containing the oxide of one of the components of the metal phase, and an oxygen electrode. This technique has been used previously to measure the standard free energy of formation of solid sio2, 1 and activities in Fe-si, CO-si,2 Ni-Si,2 and CaO-P2O5 3 melts. The present paper reports activities in Pt-Pb and Pd-Pb melts as measured with the same experimental technique. EXPERIMENTAL METHOD General Considerations. The following cells were used: Pbl (PbO-SiO2)liquid, SiO2 Pt-Pb 1 (PbO-SiOz)liquid, SiO2solidO2 [2] Pd-Pb (PbO-SiOz)liquid, SiO2solid O2 [3] Liquid alloy and' oxide melt were contained together in a silica glass crucible of essentially the same design as described previously.1'2 The PbO-SiO2 melts are ionic conductors.' During the experiment, the silica glass crystalizes in a layer adjacent to the electrolyte. The electrolyte equilibrates with solid silica and hence attains the composition of the Si02-liquidus curve in the system PbO-SiO2 at any particular temperature. Molybdenum wires were used to establish contact with the liquid metal. The oxygen electrode, which reaches the surface of the PbO-SiO, electrolyte from above, consists of a platinum wire inserted into a ceramic tube and provided with a 2-mm-diam platinum bead at its end. Gas of known oxygen partial pressure (pure oxygen of 1 atm: air, or N2 with 1.04 pct 0,) is blown through the ceramic tube onto the surface of the electrolyte. The cell reaction is Pb (metal) + 1/2O2 (gas) = PbO (electrolyte) [4] No oxidation of platinum or palladium ("displacement reaction") occurs. This is to be expected from the noble character of platinum and palladium, but was also shown experimentally, as described in the next section. The galvanic electromotive force of the cell is given by where AG is the change in free energy for Reaction [4], E(=2) is the number of electrical equivalents necessary to form 1 mole of PbO, and F is the Faraday constant. Formula [5] is valid only if no junction potential exists within the electrolyte. Junction potentials occur only when the compositions of the electrolyte are markedly different at the electrodes. Such differences are negligible in the PbO-SiO, electrolyte, as shown in the next section. Since molybdenum contact leads are used, appropriate corrections were made on the measured electromotive forces to account for the thermoelectric effect of the Mo-Pt couple. The thermoelec-tromotive forces were measured separately with a Mo-Pt couple, and were found to vary linearly from 19 mv at 740°C to 40 mv at 1310°C with molybdenum being positive and platinum negative (cold junction at 25°C). Extrapolation of these values to higher temperatures yields values which are in satisfactory agreement with those obtained previously in the temperature range 1440° to 1630°c.1,2 The change in free energy for Reaction [4] is expressed as where chemical potentials of the species. The value of constant for a given temperature because the slag composition is fixed. Inserting [6] into [5] and using appropriate expressions for upb and uO2 the relation

Jan 1, 1967

By L. E. Young

THE purpose of this paper is to start a discussion on: (1) methods of supporting the immediate roof, particularly of local areas of poor roof, during the mechanical loading of coal; (2) methods of increasing the rapidity of the movement of the mining faces so that, without the use of cribs, jacks, pack walls, and filling, there will be no danger to men, equipment,, and working places from the subsidence of the overlying strata. In the Pittsburgh district the application of mechanical loading devices in mines working in the Pittsburgh seam, has been retarded by the difficulties of holding and handling the draw slate. Normally the thickness of this slate averages about 8 in. but the hardness varies, and a cut of coal cannot always be loaded without placing posts or crossbars to support the slate. Locally, the slate may be thicker and special methods of support may be required. If crossbars are placed to hold the slate when the coal averages 5 ft. in thickness, the standard methods of transporting the coal cannot be followed, and the use of conveyors may be desirable. Very little information is available on the effect of increasing the rate of movement of advancing or retreating break lines or longwall faces. A few British publications have presented some data but all such data relate to longwall faces that have moved not more than 6 ft. a day. The most rapid rate of movement of longwall faces in Germany is 6 ft. per day. In the ordinary hand-loading mine in western Pennsylvania break lines on full retreat will move about 2 ft. per day. If loading machines are used under similar conditions the, rate of retreat may reach 4 ft. per day. In a mine where coal is loaded by hand on conveyors three shifts per day, the rate of retreat has ranged from 11 to 16 ft. per day, with an average of 13 ft. If mobile loading machines could be used to load on con-veyors on break lines, the rate of retreat should be increased substantially.

Jan 1, 1938

By T. D. Yensen, R. K. McGeary

While we have not been primarily interested in the determination of hydrogen in the alloys that we have been dealing with, we arc very glad to cooperate in this symposium on sampling and analysis for hydrogen, as we can never tell when we may find it desirable to perform such analyses. Vacuum-fusion Method Our primary interest has been oxygen and carbon, in the analysis of which we think we have become very proficient. Our oxygen-analyzing apparatus is of the vacuum-fusion type (Fig. I). This employs Dr. Derge's type of graphite cruciblc and slit sleeve, with graphite powder between, for heat insulation (Fig. 2) supported in a clear quartz bulb connected to the Pyrex glass system by means of a carefully made ground joint. The latter is kept cool by means of an air blast from a circular copper tube surrounding the joint. The crucible is heated by high-frequency induction and the 24 one-gram samples successively dropped in from the horizontal tube at the top by means of a magnet. The gases (H², CO, N2) are passed through the CuO catalyst held at 300°C. (converting CO to CO²I, H² to H²O) and the CO² and H2O frozen out in the main liquid air trap, while N2 is evacuated. At the end of the operation, shown by the termocouple vacuum gauge indicating a pressure of 10-4 mm. Hg, the analyzing system is isolated by means of the mercury cutoffs, and the CO² and H2oare determined by transferring first the CO2 and then the HzO to the small trap at the right. This is done by placing liquid air on the small trap, then removing the liquid air from the large trap for one minute, which is sufficient to evaporate the Co2 and transfer it to the small trap. The CO2 is then measured by closing the mercury cutoff at the extreme right, removing the liquid air from the small trap, warming it up to room temperature, adjusting the mercury level to one of the three marks on the glass tube (corresponding to three volumes calibrated so that I mm. Hg of CO² corresponds to 0.001, 0.002 and 0.010 mg., respectively, of oxygen) and finally reading the pressure. Liquid air is now replaced on the large trap, the mercury cutoff at the right opened, transferring the COz back to the large trap. The cutoff to the pumps is then opened, the liquid air removed for one minute, thus evacuating the CO², the pumps again cut off and the H2 O transferred to the small trap as before, except that it is now necessary to warm the large trap with a Bunsen burner in order to evaporate all the H2O. This requires about three minutes, as the inner tube must be heated to at least 100°C. In order to prevent H²O from being adsorbed on the glass walls, the glass tubing beyond the catalyst (i.e., to the right in Figs. I and 3) is kept heated to about 150°C. by means of Nichrome ribbon as shown in Fig. 3. For a I-gram sample the above amounts of oxygen (0.001, 0.002 and 0.010 mg.) 35

Jan 1, 1945

By Carl Henrich

In the winter of 1895 to 1896, during the construction of the Jackson and Cincinnati railroad, running from Addison, Lenawee county, Mich., to Jackson, Mich., in a northerly direction, I had occasion to observe some interesting geological features, described below, in a cut of this railroad made through the low ridge of gravel and sand, dividing the valley of Silver Lake and Silver Creek from the Goose Lake and Goose Creek valley, in Lenawee county. The surface-deposits of this part of the county are, as is well known, of glacial origin. Gently rounded, long ridges of sand, gravel and clay intervene between the marshy bottoms and the lakes of the valleys. The nature of the deposits, varying from a sandy clay or clayey sand to fine and coarse gravel and pure siliceous sand on the one hand, and to a very tough, fine, uniform and often indurated clay on the other, as well as the irregular and sudden changes, sharply divided, between these materials composing the ridges, in the cuts made through them by the railroad, would admit of no doubt that this country owes its present surface-configuration primarily to the action of the last glacial period, which covered its surface with an immense ice-sheet. The well-known ice-markings on the huge granite, schist, greenstone and conglomerate boulders found everywhere imbedded and protruding from the surface, add their testimony to the other characteristics mentioned. Most of the cuts made by the railway through the ridges showed in a marked degree the irregular arrangement and the sudden changes of and between the materials mentioned above. One cut, however, known as Kelly's cut, or Kelly's gravelpit, about 4 1/2 miles north of Addison, and about 1 1/2 miles south

Jan 1, 1897

By N. C. Gay, P. J. Van Der Veever

The Klerksdorp gold mining district, South Africa, experiences a relatively high level of seismicity with many seismic events of magnitude greater than 4. These large events appear to have foci close to fault planes, most of which displace the strata by several hundred metres over a wide area. To help understand the mechanism of these large mining- associated seismic events, in situ stress measurements were made at 4 sites using "CSIR doorstopper" strain relief techniques. The sites were chosen close to, or some distance from fault planes and other structures. The results show that at all 4 sites a relatively large horizontal stress is oriented approximately north- west. The magnitude of this stress ranges from 0,78-1,O of the vertical stress. A marked horizontal stress anisotropy, varying from 13-30 MPa is also present. The dominant structural features are large, north-east striking normal faults which extend across the entire length of the goldfield. Displacements across these faults vary from a few centimetres to several hundred metres. Bedding plane faults across which large displacements may occur are also common as are north and north-west striking dykes. The majority of the faults strike at approximately 90º to the maximum horizontal stress and at all sites a large compressive stress plunges in the direction of dip of the strata and fault planes. Thus a significant shear stress may act across suitably oriented planes causing them to be in a state of potentially unstable equilibrium. This abnormal stress situation would exist along the entire length of the fault

Jan 1, 1982

By George Rice

INSTANTANEOUS outbursts of gas in underground workings are similar in effect to great blasts of explosives, but without heat effects. Fortunately they occur only in a few localities in exceptional coal fields of the world and under exceptional geologic conditions. Such violent outbursts should not be compared with the ordinary outflows of gas into coal mines or with explosions of gas and dust. The phenomenon is essentially one of gas held in circumscribed areas under very high pressure and as a mining face or heading approaches such a place and the mining excavation sufficiently weakens the natural surrounding dam or shell, this is burst by the pressure just as by the discharge of a mass of explosives. The outbursts, so far as known to the writer, have been confined to coal beds and have not occurred in other mineral deposits. Hence, as discussed later, he believes that it is the relation of the gases to the coal material that is a factor in conjunction with others in producing conditions which permit the phenomena to occur when mining is done. The gases in most instantaneous outbursts have been hydrocarbon gases but in two coal fields they have been definitely found to be chiefly or wholly carbon dioxide. One of these localities in which CO2 outbursts have been frequent and have caused loss of life is in the southern part of the Gard basin, near Alais, in southern France. In 1919, the writer visited the Fontaine mine in this field the day following the occurrence of an outburst by which two men were smothered by carbon dioxide and fine dust. After 24 hr. the CO2 had not been entirely removed by the ventilating current. Occasional outbursts of CO2 have also occurred in other small basins in France, causing accidents, as in Puy-de-Dome. However, mines in the Gard basin, north of those in which CO2 outbursts have occurred, have experienced hydrocarbon gas outbursts.

Jan 1, 1931

By G. Sachs, G. Espey

SIMPLE methods can be used for the determination of the residual stresses in thin-walled tubing if the stresses consist of high tensile stresses at the one surface and high compressive stresses at the other surface Such a stress distribution is approximated in sunk tubing and in deep-drawn shells It is possible to cut sections from such articles in such a manner that a major part of the residual stress is relieved by a bending of the part that is separated from the adjacent metal The circumferential stress is evaluated from the change in diameter D, occurring on splitting a length of tubing (Fig Ib),1-5 or from deflection resulting from the cutting out of a circumferential tongue (Fig Ia) G The bending moment M released by such a flexure is [ ] The release of this bending moment corresponds to the release of stresses, which, in a thin section, vary linearly from one surface to the other, and have the following value in a particular fiber a certain distance (zx from the surface [ ] where C is the section modulus and d is the thickness of the section, the ratio AI C being d 2 for a rectangular section* The maximum stress values at the surfaces are [ ] For most purposes the simpler equations [ ] will be satisfactory, where Dm is the average of the mean diameters of the tubing

Jan 1, 1941

By R. J. Sherman, M. R. Achter

Creep rates have been measured for nickel at 1200°F in air and in vacuum, and related to the depth of surface cracks in the specimens tested in the two environments. The surface cracks were observed to grow faster in air than in vacuum in both short-time and long-time tests. Crack depths, however, could be correlated with creep rates only in the short-time tests. Although no cracks were observed in a relatively brittle Ni-Cr-A1 alloy creep tested at 1300°F, the appearance of alloy specimens fractured after interruption in creep indicated that there was a decrease of intergranular cohesion resulting from the diffusion of atmospheric gases into grain boundaries. PREVIOUS investigations1-3 have demonstrated that the effect of atmosphere on the high-temperature strength of nickel and nickel-base alloys may be reversed by changes in the stress or temperature of the test. At high stress and low temperature the creep-rupture life is longer in vacuum than in air, while at high temperature and low stress the relative strengths are reversed. A mechanism to explain this behavior was proposed based on two competing processes. Oxidation hardens and strengthens a metal, but adsorption of gas, by lowering surface energy, reduces the work required to propagate an intergranular crack. The controlling process is determined by temperature and stress. Basic to this mechanism is the concept that environment determines the ease of propagation of intergranular cracks and thus affects creep rate and rupture life. To explore the mechanism in greater detail, this investigation was undertaken to determine the effect of atmosphere on crack initiation and propagation rates in nickel1 and a relatively brittle Ni-Cr-A1 alloy.3 EXPERIMENTAL PROCEDURE The materials were the same as used previously. Nickel of 99.8 pct purity had the following impurity content: 0.02 pct Co, 0.03 pct Fe, 0.02 pct Mg, 0.03 pct Si, and 0.008 pct C. Rods were cold swaged from 1/2 in. to 3/8 in. in diam and machined into speci- mens with gage sections 1/4 in. in diam by 1-1/4 in. long. They were annealed in vacuum at 1600" F for 1 hr to achieve a grain size of 0.07 mm. The alloy was composed of 19.1 pct Cr, 3.6 pct Al, 1.7 pct Si, 0.57 pct Fe, 0.10 pct Mg, 0.027 pct C, 0.004 pct S, and the balance Ni. Sheet specimens of 0.500-in. width and 1.25-in. gage length were machined from 0.033-in.-thick strip and annealed in vacuum at 2000° F for 2 hr, resulting in a grain size of 0.036 mm. Large amounts of an intergranular phase were introduced as a result of the anneal. Creep tests on both materials, using equipment previously described by Shahinian; were conducted in air and in a vacuum of 1 x 10-5 mm Hg. They were continued to rupture and interrupted at various stages of the test. Although extensions were measured from dial gage readings of movement of the lever arm, it is considered that valid comparisons of creep rate may be made in this manner.l Two parameters were measured metallograph-ically* on longitudinal sections of nickel specimens interrupted during creep—the mean depth of surface cracks 2, and the density n as the number of cracks per unit length of surface. They were combined into one parameter by the relation p = n-d [1] As used here, p is equal to the total of crack depths per unit length of surface. RESULTS Nickel. It is well known that the incidence of intergranular cracking is increased with increasing rupture life. Indeed, it is evident in Tables I and I1

Jan 1, 1962

By R. M. Fowler, H. L. Hamner

DURING the last 25 years, there appeared in the literature a number of papers describing equipment and operating techniques for the determination of total oxygen in iron and steel. In the early papers, comparatively little attention was paid to side reactions that occur when iron is saturated with carbon at a high temperature in a high vacuum. As more experience was gained with the new method, the limitations appeared. Metals, with a boiling point lower than iron, distilled out of the crucible, condensed in the cooler part of the furnace, and subsequently reacted with carbon monoxide to form oxides and carbon. Aluminum, manganese, and the alkaline earth metals proved troublesome in this respect. Modifications have been devised to overcome the difficulties due to aluminum and manganese, while the alkaline earth metals are not of too much concern as yet to the steel chemist. The reactions of sulphur have received less attention, although it is generally recognized that some carbon disulphide is probably formed. Liquid air traps have been used in some cases to prevent any carbon disulphide from entering the analytical train. Sulphur was not a particular problem at the Union Carbide and Carbon Research Laboratories until the analysis of the irons of higher than usual sulphur contents became necessary. In order to describe the procedure developed for such irons, it will be necessary to first describe the type of vacuum-fusion equipment employed because the operation of vacuum-fusion equipment is an art to a considerable extent. At the Laboratories, vacuum-fusion equipment has been in daily operation since about 1930. Over the years, the evolution of this apparatus has been governed by the versatility required to analyze a wide variety of materials. Since all types of materials from high purity metals to slags are analyzed and, since seldom more than a few samples of one type are analyzed in succession, the apparatus was designed for accuracy and flexibility rather than for speed. A general view of the equipment is shown in Fig. 1, while Fig. 2 shows the relationship of the various parts. In Fig. 2, A is a vertical double-glazed 24X27/8 in. OD silica tube heated with a 20 kva mercury-arc high frequency generator. The tube is closed with a water-cooled brass head attached with de Khotinsky cement. A turret cap fits on this head and is sealed with a 1/8x3 in. "0" ring. The head contains a sight glass and two 8 in. horizontal glass tubes, for sample storage, cemented in with de Khotinsky cement. B is a four-stage Gaede mercury diffusion pump connected to the water-cooled head with a 11/2 in. copper tube through a flange with an "0" ring. The output of the vacuum pump feeds into an automatic Toepler F pump which compresses the gas sample over mercury in the measuring burettes, G and H. There are bypasses in this line for a McLeod gage C and a Piranni gage D, a manometer E, and for initial pumping out of the system with a Cenco Megavac backing-up pump. The reduction crucible shown in Fig. 3 is machined of Tungar Bulb quality (A.G.K.T.E.-2) graphite. The sample is guided into the crucible with the graphite funnel depicted on this figure. The arrangement of the crucible, radiation screens, etc. in the furnace is as follows: A 1 15/16x61/2 in. Alundum thimble, porosity RA-84, with two 1/8 in. holes near the top and opposite each other which take a pair of special tongs used for lowering it in place, is prepared. A 3/4 in. layer of powdered graphite is placed in this Alundum thimble, and the graphite crucible containing 20 g of ingot iron and 0.5 g of carbon is carefully centered on this bed of graphite powder and graphite powder is packed around it to the top of the graphite cru-

Jan 1, 1953

By Ö. Valla, A. Muan, K. Grjotheim

The solid miscibility gap between CaO and "FeO" in the system CaO-"FeO" in contact with metallic iron gradually closes as MnO is added as a third component. On the liquidus surface of the system CaO-"FeO"-MnO, this situation gives rise to a boundary curve which originates in the bounding system CaO-''FeO", proceeds a short distance into the composition triangle of the ternary system, and then vanishes. A new approach has been used to follow the course of this boundary curve. It is shown that the curve vanishes at a much lower temperature and at much lower MnO contents than has been inferred previously. The oxides CaO, "FeO", and MnO together with SiO2 are the major components of the slag phase formed in the basic oxygen process. Hence, the system CaO-"Fe0"-MnO is of considerable technological interest. In addition, the system is theoretically interesting. The three oxides above all have sodium chloride structure. The size differences among the cations are such that in the bounding "binary"* systems CaO-MnO and "FeO"-MnO complete solid-solution series are formed,1,2 whereas in the system CaO-"FeO" there is only limited mutual solubility in the solid state,3 see Fig. 1. Hence, a solid miscibility gap exists in a part of the "ternary"* system Ca0-"Fe0"-Mn0, and a liquidus boundary curve originates at the peritectic point, point a in the insert in Fig. 1, in the system CaO-"FeO", extends a certain distance into the ternary system, and then vanishes. Very little quantitative information on the system Ca0-"Fe0"-Mn0 is available in previous literature. Fischer and Feischer4 sketched isothermal sections at 1600° and 1700°C, and estimated that the vanishing boundary curve extends to approximately 1650°C and a composition of 42 wt pct MnO. The work to be described in the following was aimed at locating experimentally the "vanishing" liquidus boundary curve, determining its end point, and deriving representative isothermal sections below and above the temperature of the end point of this curve. EXPERIMENTAL METHODS The phase relations were determined by the well-known quenching method. (For a description of this method as applied to oxide systems, see the original paper of Shepherd, Rankin, and wright.5) Prereacted oxide mixtures of desired compositions were contained in iron crucibles and heated in a vertical tube furnace in an atmosphere of purified nitrogen. After equilibrium was judged to have been attained, the samples were quenched to room temperature, the phases present were identified by microscopic and X-ray examination, and total iron oxide contents were determined by chemical analysis. "Fisher Certified" reagents (MnCO3, CaCO3, Fe2O3, and Fe) served as starting materials. The calcium carbonate and ferric oxide were heated in air at 400° and 800°C, respectively, for 24 hr prior to use. Manganese oxide was prepared by decomposing the carbonate in a graphite crucible in hydrogen atmosphere at 1000°C. The product was ground under acetone to -100 mesh. The iron powder was used directly without any preparation. Dicalcium ferrite was used as a starting material for some mixtures. It was made by mixing some of the above prepared CaCO3 and Fe2O3 in proportions corresponding to the formula 2CaO. Fe2O3. This mixture was then fired in air for

Jan 1, 1969

By Clarence P. Linville

In an article published in the Iron Trade Review,' I gave a convenient arrangement for the installation of wet and dry bulb thermometers for use in making moisture determinations in the air being blown into a blast furnace, and also gave a chart for use in obtaining moisture values from the thermometer readings. The data from which this chart was prepared were obtained from the tables in use by the U. S. Weather Bureau.2 The work of Carrier3 has shown that these tables are somewhat in error. He has recalculated the values for moisture as referred to wet and dry bulb thermometer readings, and he has prepared a psychrometric chart from the values thus obtained. This work has placed the subject of psychrometry upon a correct scientific basis. I think it is proper that we should recognize the importance of his work and give him credit for one of the most interesting and valuable researches that have been published in recent years. Blast-furnace men are not ready to use, as he suggests14 a value expressed in grains of water accompanying a pound of dry air. However convenient this may be for heating and ventilating work and other engineering problems, there are several reasons for preferring the use of a value expressed in grains of water in a cubic foot of mixed air and water vapor, in connection with combustion phenomena and the effects of moisture on blast-furnace operation. Previous papers presented to the Institute have used such values and we have

Jan 1, 1914

By L. S. Darken

It has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernstl in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and FuossZ with results which have recently been confirmed experimentally by Harned and Nuttall. This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author,4,5 who pointed out4 that "for a system of more than two components it.is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepti- cism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley" in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion of acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 10500 C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1949

By A. S. Michaels, M. C. Porter, A. Stancell

Previous laboratory studies have demonstrated that the injection of small quantities of reverse wetting agents during water displacement can increase oil recovery from unconsolidated porous media.9 In the present investigation, an attempt has been made to determine more fully the effects of reverse wetting treatments and to clarify the mechanism by which increased oil recovery is effected. Water-oil displacements were performed in beds of 140-200 mesh silica sand. Hexylamine slugs (injected after 0.25 pore volume of water throughput), when adequate in size and concentration, were effective in promoting additional oil recovery. Their effectiveness increased with the quantity of amine injected. However, slugs of sufficient size and concentration to stimulate oil production at water flow rates of 34 ft/day did not do so at 4 ft/day. Visual studies in a glass grid micromodel have shown that the stimulation of oil production, via ayueous hexylamine, is a result of transient changes in the oil wettability of the pore walls. if the amine slug is of sufficient size and concentration to induce significant changes in the adhesion-tension, large continuous oil masses will be formed. if the superficial water velocity is high enough to result in rapid desorption of the amine, a favorable "wettobility gradient" may be established across the masses; under such conditions, high oil mobility is observed, and increased oil recovery results. INTRODUCTION It is generally agreed that the efficiency of oil displacement by water in porous media is limited in part by capillary forces which cause the retention of isolated masses of oil — resulting in the so-called "irreducible minimum oil saturation". Recent estimates10 indicate that there are about 220 billion bbl of petroleum in United States reservoirs which are not economically recoverable with present techniques (such as water flooding). This amounts to almost five times the known recoverable reserves. It has been recognized for some time that a suitable alteration in the water-oil interfacial tension and/or the contact angle, as measured between the water-oil interface and the solid surface, should result in better displacement efficiency. Surface active agents can be used as interfacial tension depressants to accomplish this objective,1,2,7 but unfortunately, the additional oil recovery is seldom commensurate with the treatment cost. In contrast to interfacial tension depressants, the effect of contact angle alterations on water-oil displacements has received relatively little attention in the literature. It is known that the wettability affects the displacement process.3,4,11 Displacements in water-wet systems generally result in lower residual oil saturations than those in oil-wet systems. The effect of "'transient" wettability alterations concurrent with the displacement process have been investigated by Wagner, Leach and coworkers,4,11 wherein it has been demonstrated that the establishment of water-wet conditions during water flooding of oil-wet, oil-saturated porous media is accompanied by significant increase in oil displacement efficiency. Michaels and Timminss studied the effects of transient contact angle alterations resulting from chromatographic transport of reverse wetting agents through unconsolidated sand. It was demonstrated that chromatographic transport of short-chain (C4 through C8) primary aliphatic amines can improve oil recovery and that the recovery increases with the quantity of amine injected (i.e., with either the amine concentration or the volume of the slug injected). Circumstantial evidence indicated that the increased displacement efficiency resulted primarily from transient changes in wettability of the porous medium. In the Present investigation. additional information has been obtained on the effects of reverse wetting treatments and the mechanism by which increased oil recovery is accomplished. Hexylamine slugs of varying size and concentration were chromato-

Jan 1, 1965

By C. O. Tarr, G. V. Smith, R. F. Miller

METALLURGISTS have long recognized that the Fe3C type of carbide is not a stable phase in steel and that, given sufficient time, it will decompose with formation of graphite, at least at temperatures below about 2050°F.1 This slow graphitization has never been of much concern to users of hypoeutectoid steels, for in such steels it occurs only during prolonged exposure at elevated temperature. In 1935, Kinzel and Moore2 reported complete graphitization of the carbide of a 0.1 5 per cent carbon steel that had been in senrice for about 26,000 hr. at a temperature of about 1100° to 1200°F. In discussing this paper, both Mathews and Sauveur reported graphitization of slightly hypereutectoid steels. In an extensive investigation of graphitization of high-purity iron-carbon alloys, Wells1 produced graphite at 7o0°C. (1290°F.) in an alloy containing as little as 0.13 per cent carbon, and showed that graphite may precipitate either directly from austenite or from decomposition of Fe3C, also that the rate of graphitization tends to increase with increase of temperature, at least up to a certain point, and with the presence of graphite nuclei. Jenkins, Mellor and Jenkinson,3 studying the structural changes in carbon steels ranging from 0.17 to 1.14 per cent carbon during stress-rupture tests at elevated temperature, obsenred graphite in an aluminum-killed 0.40 per cent carbon steel after fracture in 4340 hr. under a stress of 17,900 lb. per sq. in. at 840°F. and in many of the steels after stress-rupture test at 1200°F. Unstressed samples of 0.60, 0.86 and 1.14 per cent carbon steels graphitized almost completely in 360 hr. at 1200°F., while samples of 0.90 and 1.10 per cent carbon steels were somewhat graphitized, and steels containing 0.24, 0.40 and 0.57 per cent carbon showed no sign of graphite. Their results indicate that graphite precipitates the more readily the higher the carbon content, though this tendency is influenced to some extent by deoxidation practice, and that graphitization is accelerated by plastic deformation. In a recent study of the graphitization of 0.4 and 0.6 per cent carbon steel strip, made by M. A. Hughes,4 it was found that at 1200°F. graphite appeared after 72 hr. in aluminum-killed but not in silicon-killed steel, and that the rate of graphitization was increased by slow cooling from 1600°F. and by cold-working prior to annealing. In creep tests of normalized o. I 5 per cent carbon steel killed with 2.5 lb. of aluminum per ton, at the U. S. Steel Corporation laboratory at Kearny, spheroidization and some graphitization were found after 3000 hr. at 1000°F. under a stress as low as 15m lb. per sq. inch.

Jan 1, 1944

By H. L. Sheakley, D. J. Coolidge

This paper does not deal with all sands used in the glass industry in Missouri; it covers only that used in the plate-glass factory at Crystal City. However, it is probably safe to say that other sands, pro- duced throughout the state for this purpose, are of identical nature. The glass sand used in Missouri is cornrnonly called the St. Peter deposit, which is ascribed to the Ordovician Rock series in the form of sandstone. This St. Peter deposit, aside from a few small outliers, covers a large area of eastern Missouri. It forms, through a broad curve, the northeast margin of the typical Ozark region between Cape Girardeau on the southeast and Mineola, Montgomery County, on the northwest. The belt is extremely irregular, varying from one to ten miles in width; its length is 150 miles in a straight line. The outcrop near the entrance to the Crystal City mine appears in the form of a sandstone bluff approximately 30 ft. high, running along Plattin Creek (Fig. I). Above the sand rock an overburden of Joachim limestone appears, which thickens to nearly 300 ft. and forms the hill commonly called Buck Knob. Test holes where drilled at various points and the drillers' log indicate that the St. Peter deposit ranges in thickness from 63 to 71 feet. Properties of the St. Peter Sand From an analysis of the glass sands of the St. Peter formation in Missouri, the follow-

Jan 1, 1948

By D. J. Coolidge, H. L. Sheakley

This paper does not deal with all sands used in the glass industry in Missouri; it covers only that used in the plate-glass factory at Crystal City. However, it is probably safe to say that other sands, pro- duced throughout the state for this purpose, are of identical nature. The glass sand used in Missouri is cornrnonly called the St. Peter deposit, which is ascribed to the Ordovician Rock series in the form of sandstone. This St. Peter deposit, aside from a few small outliers, covers a large area of eastern Missouri. It forms, through a broad curve, the northeast margin of the typical Ozark region between Cape Girardeau on the southeast and Mineola, Montgomery County, on the northwest. The belt is extremely irregular, varying from one to ten miles in width; its length is 150 miles in a straight line. The outcrop near the entrance to the Crystal City mine appears in the form of a sandstone bluff approximately 30 ft. high, running along Plattin Creek (Fig. I). Above the sand rock an overburden of Joachim limestone appears, which thickens to nearly 300 ft. and forms the hill commonly called Buck Knob. Test holes where drilled at various points and the drillers' log indicate that the St. Peter deposit ranges in thickness from 63 to 71 feet. Properties of the St. Peter Sand From an analysis of the glass sands of the St. Peter formation in Missouri, the follow-

Jan 1, 1948

By J. G. Mravec

The SO-called gas-tube method as developed by Hare, Peterson and Soler for determining the type and content of gases in molten steel is particularly adapted for determining the hydrogen content in molten steel. The development of this method has been quite completely discussed in a paper published by these co-workers in 1937.' The purpose of this paper, therefore, is to familiarize with this method those who arc not well acquainted with it. The principle of the gas-tube method is as fol1ows: One end of an evacuated gas tube is sealed with a very thin copper disk. when this end of the tube is immersed in a test spoonful of molten steel, the copper disk melts almost immediately, allowing a portion of the steel to be drawn up into the evacuated space. Any dissolved gases, and those produced by reactions between the components of the steel during freezing, are liberated into the unfilled portion of the sampling tube. A blob of steel that forms on the immersed end of the tube after the sample is drawn up seals up the end, making it airtight again. The evolved gases are subsequently drawn out of the gas tube through a suitable valve and analyzed by means of an Orsat apparatus. The volume of the sampling tube is sufficiently large so that a pressure considerably below atmospheric is produced after the gas evolution. The low pressure is necessary to effect a nearly complete removal of gases from the steel. Construction oF Sampling Tube The sampling gas-tube apparatus is illustrated in Fig. I. Seamless S.A.E. tubing used for section A is first cut into 7-ft. lengths. Through cxperiencc it was found necessary to use two sizes of tubing for this part, "is-in. and 3/4-in., respectively. The smaller tubing is generally used on the hotter or lower carbon steels. If the inside wall of the tube A is coated with grease or oil, it should be burned out before being machined as follows: One end is machined on the inside diameter to a depth of 34 in., so as to form a seat for a 7/8-in copper disk, which is stamped out from 0.005 to 0.007-in. thick copper sheet. The other end is machined on the outside diameter to a diameter of 1 5/16 in., to take a small reservoir or trap member I?. About 4 in. below the same end, a 1/2-in. hole is drilled to receive the 1/2-in. copper tubing leading to the large reservoir C. The inside of tube A is then thoroughly cleaned with a round wire brush, such as is generally used to clean out shotgun barrels. It is very important that the surface be absolutely free of rust or any nonmetallic coating. Next, the thin copper disk is soldered in place with low-melting silver solder.

Jan 1, 1945

By D. R. Packard, J. D. Verhoeven

The resistivity us atom fraction relationships for dilute solutions of cadmium, mercury, and tin in molten sodium have been determined. With these data and the resistivity capillary-reservoir technique, the electro-transport mobilities, effective valences, and the diflusion coefficients of the three solutes have been determined. The mobilities are found to be higher than in other molten alloys by a factor of around 20. The results are compared to the Mmgelsdorf model for electrotrmtsport. The high values found for the mobility to diffusion coefficient ratio indicate that small quantities of the alkali metals should be susceptible to purification from many solutes by means of electrotransport. PASSAGE of a direct electric current through a liquid metal containing a solute will usually cause a relative motion between the solute and solvent atoms of the alloy. This electrotransport phenomenon may be described experimentally in terms of the mobility of the solute atoms, i.e., the drift velocity of the solute relative to the solvent per unit electric field. In dilute solutions of liquid alloys this relative mobility becomes a measure of the velocity of the solute with respect to the observer since the motion of the solvent is negligible. The mobility is a significant parameter in evaluating the potential usefulness of electrotransport for such things as purification or solute control upon solidification. Prior to around 1958, quantitative data for the mobility of solutes in liquid metals were restricted to some solutes in liquid mercury. Since that time ad- ditional data have been reported for the mobility of solutes in liquid mercury, bismuth, tin, and lead, as shown in Table I. In 1963 Drakin et al.11 reported some values of a transport number for mercury and thallium in molten sodium and potassium. When these values were converted to mobilities, it was found that the mobilities were higher than any of the previously reported values by a factor of around 20, as shown in Table I. Drakin's experimental technique did not eliminate the presence of back-diffusion and consequently his data were expected to be lower than the true values. The purpose of the present investigation was to determine the mobility of a number of solutes in molten sodium with an experimental technique which eliminates back-diffusion errors. EXPERIMENTAL The technique used to determine the mobility was a resistivity capillary-reservoir technique which had previously been used with a high degree of precision on Sn-Bi alloys.4 This technique consists of dipping the vertical Pyrex capillary cell shown in Fig. 1 into a molten bath of alloy while the bath and capillary are under vacuum. The capillary is then filled by intro-

Jan 1, 1969

By David H. Browne

One of the most difficult problems in the chemistry of iron-ore, and one, the solution of which, so far as I am aware, has never been attempted, is the distribution, throughout a given vein, of Bessemer ore, and its relation to the formation of the deposit. In those hematite-mines in which both Bessemer and non-Bessemer ore occur, the sorting of the ore as it lies in the deposit becomes a problem of much economic as well as scientific interest. It would seem, from a superficial examination. or, indeed, from any examination not conducted for this especial purpose, as if high- and low-phosphorus ores were mixed in inexplicable confusion ; and a mining-chemist is very apt to fall into a system of adventitious analyses, taking first-class ore wherever he can find it, and overlooking its relation to the formation and position of the vein. I hope that a few notes which I present on this subject may be found worthy of consideration, as throwing a new light upon this obscure topic. During the last three years, while acting as chemist of the Lumberman's Mining Co., I have made some 3000 analyses of iron-ore from the Ludington mine at Iron Mountain, Michigan. These analyses were necessary in order to separate Bessemer and non-Bessemer ore which occurred intermixed in the deposit. During the last year, I attempted in several ways to find some reason or method in the distribution of phosphorus, and have finally become cognizant of the arrangement herein outlined. I have been obliged to confine my attention to our new mine, and, in that, to that portion wherein

Jan 1, 1889