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By Leslie C. Richards

The competitive position of producers of industrial minerals depends upon the delivered price of their product. Freight charges are a major factor in the sales to consumers. A comparison of freight rates on movements of limestone and silica rock in the Pacific Northwest shows a wide variance in mills per ton mile for like hauls, thereby favoring some localities over others. Introduction: Sooner or later the potential miner of industrial minerals reaches the conclusion that of the various factors he must consider, the marketing of his product is. the most important. The sooner he realizes this the better, as successful industrial mineral producers .will confirm. Herein lies a difference between i.ndustria1 mineral mining and metal mining. Often in the latter, technical problems of mining or concentrating are equal to or even surpass those of marketing. This is not meant to imply that there are no problems in mining and beneficiation of industrial minerals, but these usually are outweighed by the problem of marketing. Recentlv. an official of a nationally known corporation :i the elecl.ro-metallurgical industry made an industrial mineral survey in the Pacific Northwest. In the course of his investigation he interviewed producers and potential producers of the various industrial minerals scheduled for use in the plant now being constructed in this area. He stated that he was interested in only three factors: namely, (1) Can your product meet our specifications? (2) Are you able to supply our tonnage requirements? and (3) What will be the delivered price? If there are several sources of supply of sufficient grade and tonnage, as is often the case in the Northwest, then the third factor becomes the important and deciding one. While industrial minerals are usually sold f.0.b. cars with the freight being paid by the buyer, it is the delivered and riot the f.0.b. price that determines the competitive position of the producer and his industrial mineral product. Unfortunately for both the consumers and producers of industrial minerals in the Northwest, the sources are generally a considerable distance from the markets. This necessitates long rail hauls, for which transportation charges make up the largest share of the delivered cost and the delivered price of the product. Is it any wonder then, that rail rates play such an important part in the marketing of industrial minerals? In order to sell his product, the producer must be able to deliver to the market at a competitive price. It must be remembered that his largest cost factor is rail transportation, and that he is limited to markets that he can reach competitively. Since the cost of rail transportation is so important, let us compare various freight rates in the Northwest and attempt to determine their influence on marketing. A study of all rates on all industrial minerals transported in this area, is beyond the scope of this paper. For the purposes of comparison, let us consider limestone (broken, crushed, or ground), and silica rock. These are widely used industrial minerals, and are carried by several different rail routes from.the sources of supply to the centers of consumption in the Pacific Northwest. Markets and Sources of Supply: Limestone has a number of uses in western Oregon and Washington. Among them are agricultural lime for the soils of the Willamette Valley and southwestern Washington; paper rock for the mills in such cities as West Linn, Oregon City, Newberg, St. Helens, and Salem, Oregon, and Camas and Everett, Wash.; chemical and metallurgical-grade limestone for the metallurgical plants centering around Portland, and the Tacoma-Seattle areas'; and sugar rock for the sugar refineries at Toppenish, Wash., and Nyssa, Oregon. Since limestone for cement manufacture is generally processed near the quarry, transportation

Jan 1, 1951

By Leslie C. Richards

Sooner or later the potential miner of industrial minerals reaches the conclusion that of the various factors he must consider, the marketing of his product is. the most important. The sooner he realizes this the better, as successful industrial mineral producers .will confirm. Herein lies a difference between i.ndustria1 mineral mining and metal mining. Often in the latter, technical problems of mining or concentrating are equal to or even surpass those of marketing. This is not meant to imply that there are no problems in mining and beneficiation of industrial minerals, but these usually are outweighed by the problem of marketing. Recentlv. an official of a nationally known corporation :i the elecl.ro-metallurgical industry made an industrial mineral survey in the Pacific Northwest. In the course of his investigation he interviewed producers and potential producers of the various industrial minerals scheduled for use in the plant now being constructed in this area. He stated that he was interested in only three factors: namely, (1) Can your product meet our specifications? (2) Are you able to supply our tonnage requirements? and (3) What will be the delivered price? If there are several sources of supply of sufficient grade and tonnage, as is often the case in the Northwest, then the third factor becomes the important and deciding one. While industrial minerals are usually sold f.0.b. cars with the freight being paid by the buyer, it is the delivered and riot the f.0.b. price that determines the competitive position of the producer and his industrial mineral product. Unfortunately for both the consumers and producers of industrial minerals in the Northwest, the sources are generally a considerable distance from the markets. This necessitates long rail hauls, for which transportation charges make up the largest share of the delivered cost and the delivered price of the product. Is it any wonder then, that rail rates play such an important part in the marketing of industrial minerals? In order to sell his product, the producer must be able to deliver to the market at a competitive price. It must be remembered that his largest cost factor is rail transportation, and that he is limited to markets that he can reach competitively. Since the cost of rail transportation is so important, let us compare various freight rates in the Northwest and attempt to determine their influence on marketing. A study of all rates on all industrial minerals transported in this area, is beyond the scope of this paper. For the purposes of comparison, let us consider limestone (broken, crushed, or ground), and silica rock. These are widely used industrial minerals, and are carried by several different rail routes from.the sources of supply to the centers of consumption in the Pacific Northwest. Markets and Sources of Supply: Limestone has a number of uses in western Oregon and Washington. Among them are agricultural lime for the soils of the Willamette Valley and southwestern Washington; paper rock for the mills in such cities as West Linn, Oregon City, Newberg, St. Helens, and Salem, Oregon, and Camas and Everett, Wash.; chemical and metallurgical-grade limestone for the metallurgical plants centering around Portland, and the Tacoma-Seattle areas'; and sugar rock for the sugar refineries at Toppenish, Wash., and Nyssa, Oregon. Since limestone for cement manufacture is generally processed near the quarry, transportation

Jan 1, 1951

PRESIDENT Michael Lawrence Haider New York City PAST PRESIDENT Willis McGerald Peirce New York City VICE-PRESIDENTS 0. B. J. Fraser, New York City J. B. Morrow, Pittsburgh, Pa. J. L Gillson, Wilmington, Del. ' L F. Reinartz, Middletown, 0. Philip Kraft, New York City R. W. Thomas, Tucson, Ariz

Jan 1, 1952

By Larry Kaufman

A useful method for estimating the entropy of NaCl type compounds has been developed by combining the Debye theory of specific heat with the Lindemann formula. This method pemnits calculation of the entropy from a knowledge of the atomic weight, atomic volume, and melting point of the compound. Comparison of the calculated and observed entropies of 35 NaCl type compounds over a wide temperature range yields good agreement thus establishing the usefulness of the method. Application of the method to other crystal types is also discussed. KUBASCHEWSKI~ has suggested a useful method of estimating the enthalpy of formation of inter-metallic compounds from a knowledge of the crystal structure, lattice parameter, and heats of sublimation of the component elements. This method is quite valuable in predicting the tendency for compound formation in a given system and is of particular value in considering systems for which no experimental data are available. In order to supplement the enthalpy calculation afforded by Kubschewski's method, it would be of value to be able to estimate the entropy of compounds so that the entropy and free energy of formation could be evaluated. Although a considerable body of such data determined by calorimetric and equilibration techniques exists at present, the difficulty of making such measurements (particularly at high temperatures) and the ever increasing number of new compounds which are of interest make the desirability of such a computational method clear. This paper deals with a method for calculating the entropy of a compound from a knowledge of the atomic weight, atomic volume, and melting point. Since these data are generally easier to determine and therefore more readily available than thermo-dynamic data, they should provide an additional tool in estimating the stability and reactivity of compounds at high temperatures. I) THE ENTROPY OF PURE METALS As a first approximation, the specific heat of a pure metal can be represented by a sum of terms where C,($/tI is the vibrational specific heat calculated on the basis of the Debye theory, lo4 TC, (0/T) is an approximation to the Cp - C, correction. T is the electronic specific heat, and Cp (p) is the magnetic specific heat. Although the Debye theory does not provide a complete description of the vibrational specific heat, i.e., the Debye temperature 0 is not a constant, it does provide a good approximation when used properly. Blackman6'7 has written several reviews on this subject discussing the different values of 0 determined by various methods (specific heat, X-rays, elastic constants, electrical resistivity, and so forth), as well as the observed temperature dependence of 0 with T. In the present case the 0 in Eq. [I] naturally refers to the specific heat 0. The variation of Debye 0 (as determined from specific heat measurements) with temperature is observed to exhibit its most radical behavior at very low temperatures. At higher temperatures the 8 values are observed to become more nearly constant. Blackman6'7 has presented the variation of 0 with temperature for several metals. His tabulation is reproduced in Table I. Reference to Table I shows that above a certain temperature level, 0 remains fairly constant. The value of 0 which is most useful in computing the specific heat, and hence the entropy, is the value of 0 in the range 0/6 « T « 0. In 1910, Lindemann' suggested a relation for estimating Debye 0 values. According to this formula, where V is the atomic volume, T is the melting point in 'K, M is the atomic weight, and CL is a constant. Mott and Jones9 present this formula and state that there is at present no satisfactory theoretical explanation, but that it does have an empirical basis. By using the valuesof 0 in Table I along with known1' values of M, T, and the molar volume VM, where the Lindemann constant can be evaluated. This

Jan 1, 1962

By R. L. Skaggs, D. T. Peterson

The effect of carbon in solid solution on the plastic behavior of thorium was studied by measuring the flow stress of Th-C alloys from 4.2" to 573°K and at several strain rates. Carbon was found to strengthen thorium primarily by increasing the thermally activated component of the flow stress. The strengthening due to carbon was directly proportional to the carbon content and decreased rapidly with increasing temperature up to 423" K. The flow stress also increased with increasing strain rate. The strengthening appears to be due to a strong short-range interaction between carbon atoms and dislocations. A yield point was observed in the Th-C alloys which increased with increasing carbon content. JTREVIOUS study of the mechanical properties of thorium has been confined largely to the measurement of the engineering properties. Work prior to 1956 has been summarized by Milko et al.1 who reported that additions of carbon to thorium sharply increased the room-temperature strength. In addition, the yield strength was observed to decrease rapidly over the temperature range from 25" to 500°C. In 1960, Klieven-eit2 measured the flow stress of thorium containing 400 ppm C. He found that over the temperature range from 78" to 470°K the flow stress was strongly dependent on temperature and rate of deformation. A drop in the load-elongation curve, or a yield point, was observed over most of the above temperature range. Above 470°K, the flow stress was nearly independent of temperature and strain rate. This strong temperature and strain rate dependence of flow stress is not generally observed in fcc metals. It is, in fact, more typical of the behavior reported for bcc metals. Bechtold,3 Wessel,4 and conrad5 have pointed out the striking difference between the commonly studied bcc metals and fcc metals in regard to the effect of temperature and strain rate on the flow stress. Zerwekh and scott6 studied the plastic deformation of thorium reported to contain 12 ppm C. They found that this material did not obey the Cottrell-Stokes law as expected for fcc metals. In addition, they found values of the activation volume smaller by an order of magnitude than expected for an fcc metal. They concluded that thorium was strengthened by a randomly dispersed solute. Thorium differs from many other fcc metals that have been studied extensively in that it shows a relatively high carbon solubility at room temperature. Mickleson and peterson7 report the solubility limit at room temperature to be 3500 ppm C. The lowest value reported is that of Smith and Honeycombe8 who report the limit to be 2000 ppm C at 350°C. The pres- ent investigation was a systematic study of the flow stress and yield point phenomenon of thorium over a broad range of carbon content, temperature, and strain rate. EXPERIMENTAL PROCEDURE The thorium used in this investigation was produced by the reduction of thorium tetrachloride with magnesium as described by Peterson et a1.' Chemical analysis of the original ingot after arc melting and electron beam melting is shown in Table I. Alloys were prepared by arc melting this thorium with high-purity spectrographic graphite. Threaded specimens with a gage length 0.252 in. diam by 1.6 in. long were used for the constant stress or creep measurements. These specimens were machined from rod which had been cold-rolled and swaged to % in. diam. Tensile specimens were prepared by swaging annealed 3/8 -in.-diam rod to 0.102 *0.001 in. The as-swaged wire was cut to lengths of 2 in., annealed, and the center 1-in. gage length elec-tropolished to 0.100 ±0.001 in. The specimens were gripped for a length of 3 in. at each end by a serrated four-jaw collet which was tightened by a tapered compression nut. No slipping occurred in the grips and negligible deformation was observed outside the 1-in. gage length. Both the creep and tensile specimens were annealed at 730°C under a vacuum of 1 x X Torr. The resulting structures consisted of equiaxed recrystallized grains with a grain size of 3200 grains per sq mm for the tensile specimens and 2200 grains per sq mm for the creep specimens. After the specimens were prepared, samples were analyzed for nitrogen, oxygen, and hydrogen. The results of these analyses are given in Table 11.

Jan 1, 1969

By D. Havlena, A. S. Odeh

The use of the straight-line method of solving the material balance equation is illustrated by means of six field cases. Also, the application of statistical criteria to arrive at the most probable answer is shown. The theory underlying the straight-line method of solution and the applicability of the statistical criteria was presented in a previous paper.' The field cases include saturated and undersaturated oil reservoirs with and without water drive. The aquifers discussed are: limited radial, infinite radial, very small aquifer and infinite linear. The field cases also include a gas reservoir producing under water drive. INTRODUCTION In a previous paper,' the authors presented the theory underlying the solution of the material balance as an equation of a straight line. The appropriate equations for various material balance cases as well as the methods of analysis and interpretation with comments and discussion were also included. To illustrate the various theoretical cases treated previously, five field cases are analyzed in this paper by employing the straight-line method of solving the material balance equation (MBE) and one example previously published is referred to. The use of statistical criteria to arrive at the most probable answer is also shown. All the field examples presented, except Case 2, are excerpts from complete reservoir studies. To illustrate the method, only sections specifically dealing with the material balance principles are included. Additional geologic information and basic data are reported to better acquire an understanding of the cases and thus to better follow the reasoning that suggested the successful application of the straight-line method of solving the MBE. The six cases are: (1) saturated reservoir, small gas cap, limited aquifer; (2) saturated reservoir, very small gas cap, infinite aquifer; (3) undersaturated-saturated reservoir, very small aquifer; (4) highly undersaturated reservoir, no water drive; (5) high undersaturated one-well reservoir, limited aquifer; and (6) gas reservoir, infinite linear aquifer. THE D4 SAND, GUICO FIELD, VENEZUELA The D, sand, which was discovered in 1943, is presently in a depleted state. Since its discovery it has produced under water drive, gas-cap-gas expansion, and solution gas drive. In Nov., 1947, water injection was initiated to arrest further pressure decline. When discovered, the D, sand was a saturated reservoir with a gas cap /oil zone volume ratio m estimated volu-metrically at 0.0731, an average permeability of 500 md, a porosity value of 25 per cent, and an oil viscosity at reservoir conditions of 0.3 cp. The volumetrically determined stock-tank oil initially in place was 23.1 million bbl. The volumetrically weighted physical data and production data available until Nov., 1953 are reported in Table 1. In Ref. 1, the effects on the straight-line plot of various values of ro/r for a constant ?to, or of various dimen-sionless times for a constant r8/r10 were theorized and were illustrated in Fig. 3A of that reference. In this field case, the previously theoretically predicted effects are established. Thus, the MBE calculations using Eq. 3c of Ref. 1 were performed for various r6/r10 and dimension-less time values. Eq. 3c of Ref. 1 is:

Jan 1, 1965

By Glenn C. Waterman

Richard Strong (Oliver Iron Mining Div., U. S. Steel Corp.)—Mr. Waterman states (p. 59, Trans., January 1954): "Core-sludge combining factors have been calculaied for any combination of core-sludge recovery on the basis of several logical assumptions: 1—The sludge sample loses reliability geometrically as sludge recovery drops. 2—The sludge sample should not be used if the percentage of sludge return is less than the percentage of core recovered. 3—A core sample should receive a weighting at least equal to the percentage of core recovery." Assumptions 1 and 2 seem justified at Chuquicamata and most geologists would agree to the validity of assumption 3. However, contrary to the statement quoted above, the core sample does not in general receive a weighting at least equal to the percentage of core recovery when the Chuquicamata methgd is used. Furthermore, the basic Chuquicamata method is identical to the Longyear or relative volume core-sludge assay combining method. Finally, the Chuquicamata method does not, in its present form, reflect true geometric loss in sludge sample reliability according to the relationship L = AR (N-1) The basic equations representing the two steps of the Chuquicamata method can be combined algebraically as follows (using the symbology of the original article except as noted): Vol A + B Assay 2 = ASA = Assay 1 Vol A VolB Core Assay [I] Vol A CA.F + ASA (100 —F) Combined grade =[21 100 Pct where F and (100 — F) are the core and adjusted sludge assay factors from Fig. 3. Substituting Eqs. 1 and 2 and collecting terms Combined grade = Vol B Vol A + B CAF (100—-F) + Assay 1 (100-F) Vol A Vol A 100 pct Eq. 3 is a unified and general statement of the Chuquicamata method. The true core factor includes not only the factor F from Fig. 3 but also the quantity VolB ------------- (100 — F), which is implicit in the value of Vol A the adjusted sludge assay. This quantity is real and positive for all values of F and core recovery less than 100. Therefore the true core factor is always less than F except when F is equal to 100. If sludge recovery is 100 pct, Eq. 3 can be further simplified as follows: Let F = percentage of core recovered. Let Vol A = Vdh (100 Pct — Pct CR) where Vdh is the total volume of the sampled interval and let Vol B = (Vdh — Vc.) Pct CR where V, is the core volume in the sampled interval at 100 pct core recovery. Then combined grade = Vo V. CA Pct CR- + Assay 1, 100 Pct — Pct CR Vdh Vdh [4] 100 Pct Eq. 4 shows that when sludge recovery is 100 pct the laboratory sludge assay receives significant weight in the Chuquicamata method, even at 100 pct core recovery. The maximum weight assigned to the laboratory sludge assay depends on drillhole size, as follows: Eq. 4, with suitable changes in symbology, is identical to Royce's formula 8,' which is a statement of the Longyear or relative volume method of combining core and sludge assays. If Mr. Waterman's assumption 3 is of paramount concern to the geologist, the Royce method (for core recoveries of 60 pct and above) or a method employing the percentage of core recovered as a core weighting factor are the only recognized methods known to the writer which achieve the desired result. A modification of the latter method embodying Mr. Waterman's assumptions 1 and 2 would result from applying the factors from Fig. 3 directly to the laboratory core and sludge assays.

Jan 1, 1956

Jan 1, 1969

By C. D. Keen

In the latter part of the summer of 1913 the Conservation Commission of the State of Louisiana, under presidency of M: L. Alexander, decided to stop the waste of natural gas going on at the "burning gas-well," Located about 2 mile southeast of Oil City, La. On several occasions, both in newspapers and in reports, comment had been made on the condition of this well, its harmful effect on the Caddo gas field, and the considerable loss, estimated at several thousand dollars each month, caused by the escape of the valuable fuel., But nothing had been done to bring the well under control and prevent further waste of gas until the State Conservation Commission took the matter in hand. The gas fields of Louisiana are among the greatest in the country. So far most of the gas has been found in the Caddo field proper, although considerable development has been done in and around the city of Shreveport and near the town of Mansfield in DeSoto parish. To extend the life of the gas fields and to prevent the quick exhaustion of the supply of the natural fuel are matters of vital importance for this section of the country. Four gas companies have entered the Caddo field and supply the surrounding towns and cities With gas. The Arkansas Natural Gas Co. has pipe lines to Little Rock, Ark., and supplies gas to the following cities and towns in that State: Texarkana, Hope, Garland, Emmet, Prescott, Boughton, Beirne, Gurdon, Arkadelphia, Gum Springs, Mal-vern, Dsnaldson, Gifford, Perla, Beaton, Beauxite, Mabelvale, Bryant, Sheridan, Pine Bluff, Little Rock, Argenta, Pulaski Heights, and Hot Springs. The Southwestern Gas & Electric Co. transports gas to Mooringsport, Blanchard, Caddo, Rodessa, Oil City, Vivian, Bloomburg, Hosston, Ida, Dixie, Belcher, and Shreveport. The Marshall Gas Co. supplies gas to the town of Marshall, Texas. The Louisiana Co. has a line to Shreveport. In, the oil field the gas is used for drilling purposes, and the operators either have their own gas system or buy from the gas companies. At the present time the surrounding territory depends for its fuel supply on the Caddo field, and the importance of the conservation of the natural-gas

Jan 1, 1915

By E. S. Anolick, Joseph Singer

The magnetic after-effect, in the form of time decay of permeability (l/µ), has been used to obtain independent data on the solubility of' carbon in pure iron. The results differ slightly from the solubilities obtained through internal -friction experiments. The mechanism of the time decay being the magnetic analogue of internal friction, it appears necessary to explain the observed discrepancies, and some suggestions are made. THE purpose of this work was to establish the reliability of the time decay of permeability as a measure of dissolved interstitial in the body-centered-cubic lattice, and further, to establish techniques suitable for such measurements with samples of a form convenient for various other measurements. This particular sample form was the "epstein" strip, i.e., 25 cm by 3 cm by 0.035 cms. While the general conclusions are not limited by this geometry, there are two aspects of the samples that may be relevant: a) texture, and b) grain size, which ranged generally from 1 to 10 mm. Effects due to these two possible parameters were thought to be small and were not investigated. Calibrating the time decay technique and the other experimental procedures by measuring the solubility of carbon in pure iron suggested itself because of the accumulation of data on this subject through the related technique of the internal friction'; The essentials of this report have been published in a somewhat condensed form.5 Since then some additional data have been taken. It is the purpose of this paper to add these data and to provide more complete description of the experimental techniques than was possible then. The time decay of permeability is a form of the magnetic after-effect.6,7 Permeability is measured immediately after demagnetization (µº) and also long after (µ8). The time decay, ?(l/µ), is the difference 1/µ8 - 1/µ0 and has been considered to be proportional to the concentration of a dissolved interstitial6,8,9,12 The relaxation time! 7, is characteristic of a particular diffusion, and affects the permeability as follows: where he being the activation energy for diffusion of the interstitial. Reference is made to the works of snoek6 and Neel7 for a complete discussion. A brief exposition of the principal ideas may be in order here, as follows. On the basis of the simplest model, resistance against domain wall motion increases with time after demagnetization due to the diffusion of interstitials to preferred sites created by the magnetostrictive tetragonolization under the strong magnetic field. Thus permeability, measured with a small field after the abrupt removal of the large field, will continuously fall with the process of diffusion of the interstitials, and the total "time decay" (or "time decrease") should be proportional to the amount of interstitial in solid solution. In the present report, use is made only of the total time decay rather than of the nature of the progress of the decay; the only problem involved in this approach is the need for assurance that only one interstitial is contributing to the effect as used. It is felt that the special use made here of the total time decay warrants the conclusions. Other work has been going on elsewhere on the detailed study of the nature of the time decay.8'9 EXPERIMENTAL A) Materials—12-lb ingots were made in a vacuum furnace from high-purity iron and by a series of hot and warm reductions were brought down to 14-mil strip. This was cut into 25-cm epsteins. The pure iron was decarburized at 750 °C by hydrogen. The time decay measurement for the decarburized iron (see below) indicated a satisfactorily low starting level of interstitials. Grain growth to grain sizes of 1 to 10 mm was produced in the pure iron by a 700" anneal in hydrogen after a critical reduction of about 7 pct as suggested by previous trials. No measurement of texture in the pure iron was made. The grain size was taken to be large enough to be beyond any sharply critical size regarding solubility. B) Infusion of Carbon—Since the permeability measurement required about two dozen epsteins, a special method of carbon infusion had to be developed to ensure homogeneity of infused carbon. This was accomplished by setting the samples edgewise in a

Jan 1, 1961

By S. A. Hovanessian

The method of characteristics which reduces the Buckley-Leverett mnlineur, partial differential equation to two first-order, linear differential equations is applied to the solution of a waterffood recovery problem for multiple lines of producing wells and one line of injection wells. The application of the method is described by a numerical example, and a brief theoretical background is given. From the results of this study, it is concluded that the cumulative water injected and oil produced are the same for single and multiple sets of producing wells. INTRODUCTION In this paper, the method of characteristics is applied to the solution of a waterflood recovery problem with multiple lines of producing wells and one line of injection wells. The application of the method to this type of recovery problem considerably simplifies the procedure of obtaining a numerical solution. It differs from the method described by Kern1 because it eliminates the need for integration in obtaining saturation fronts. In addition, the saturation history at any location within the field is obtained from a single diagram (time vs distance with saturation as a parameter)'. The paper includes a brief theory of the method of characteristics and its application to the solution of oil recovery problems. A numerical example is worked out, and the cumulative oil recovery-vs-time curve for a system with multiple sets of producing wells is obtained. This curve is then compared with the recovery curve of a system with only one set of producing wells. From this study, it is concluded that the cumulative water injected and oil produced are the same for single and multiple lines of producing wells. However, the recovery time is considerably longer for multiple sets of producing wells.

By R. K. Dann, L. W. Roberts, R. B. Benson

The mechanical properties of 300-series stainless steels were investigated in both high-pressure hydrogen and helium environments at ambient temperatures. An auslenitic steel which is unstable with respect to formation of strain-induced a (bee) and € (hcp) mar-tensile is embrittled when plastically strained in a hydrogen environment. A stable austenitic steel is not embriltled when tested under the same conditions. The presence of hydrogen causes embrittlement at the mar-lensitic structure and a definite change in the general fracture mode from a ductile to a quasicleavage type. The embrittled martensitic facets are surrounded by a more ductile type fracture which suggests that the presence of hydrogen initiates microcracks at the martensitic structure. If a steel is unstable with respecl to fortnation of strain induced martensile, plastic deformation in a hydrogen environment will produce rapid embrittlement of a notched specimen in comparison to an unnotched one. FERRITIC and martensitic steels can be embrittled by hydrogen that has been introduced into the alloys, either by thermal or cathodic charging prior to testing.1-5 However, conflicting reports exist as to whether austenitic steels that are stable or unstable with respect to formation of strain-induced martensite can be embrittled by hydrogen.8-12 A recent investigation has shown that cathodically-charged thin foils of a stable austenitic steel can be embrittled.13 An earlier investigation of a thermally charged 18-10 stainless steel revealed a significant decrease in the ductility only at the lowest test temperature of -78°C, although strain-induced bee martensite was shown to be present in one specimen tested at ambient temperatures.' When martensitic steels are tested in a hydrogen atmosphere, they are embrittled.'4-'7 It has been observed in this Laboratory that 304L steel, which is unstable with respect to formation of strain induced martensite, forms surface cracks when plastically strained in a high-pressure hydrogen environment. Work in progress elsewhere concurrent with this investigation has also established that 304L is embrittled when tested in a high-pressure hydrogen atmosphere." The objective of this investigation was to study the effect of a high-pressure hydrogen environment on the tensile properties of a stainless steel that contained strain-induced martensite (304L) and one that did not (310). EXPERIMENTAL TECHNIQUES Notched and unnotched cylindrical specimens were machined from 304L* and 310 rods that were heat- treated at 1000°C in argon for 1 hr followed by a water quench. The chemical analyses of these steels are given in Table I. The unnotched specimens had a reduced section diameter of 0.184 & 0.001 in., a gage length of 0.7 in., and were threaded with a 0.5-in.-diam. thread on each end. The notched specimens had a reduced section diameter of 0.260 * 0.001 in. and a 0.75-in. gage length, with a 30 pct 60 deg v-notch at the center. The notch had a maximum root radius of 0.002 in. The tensile bars were fractured in a hydrogen or helium atmosphere of 104 psi at ambient temperatures. The system used for mechanically testing the specimens is to be described in detail elsewhere.19 Several specimens of each type were tested in air using an Instron testing machine. The same yield strength and ultimate tensile strength were obtained in 104 psi helium with the above system as with the conventional testing machine. Magnetic analysis was employed to determine that there was a (bee) martensite in plastically deformed 304L and that it was not present in plastically deformed 310. The magnetic technique depended on allowing the material being studied to serve as the core between a primary and secondary coil. Thus, any change in the amount of magnetic material present between the annealed and plastically deformed steels will be indicated by corresponding changes in the induced voltage in the secondary circuit." The ratio of the output signal of a nonmagnetic stainless steel to a completely magnetic maraging steel was 2000 to I. Several unnotched 304L bars tested in hydrogen were analyzed for hydrogen by vacuum fusion analysis. There was an increase in the hydrogen content to approximately 2 ppm for the specimens tested in hydrogen, as compared to less than 1 ppm for the as-received material. Several thin sections cut from notched areas of 304L specimens tested in hydrogen and containing the fracture surface contained approximately 1.5 ppm H. The accuracy of these determinations was estimated to be ± 50 pct.

Jan 1, 1969

By Z. Moser, W. Ptak

The experiments were carried out by the method of measuring the electromotive force of concentration cells having zinc as a reference electrode, the second electrode being the liquid alloy Zn-Sn-Cd-Pb. The electrolyte consisted of liquid chlorides and had zinc ions. The measurements were made for seventy -five alloys of different mole fractions within the temperature range of 714° to 877°K. The experimental results enabled the calculation of the activity of zinc in tested solutions. The activities of zinc were calculated by means of Krupkowski's formulas.3 In addition, the formulas for coefficients of activity of zinc, tin, cadmium. and lead as the function of composition and temperature were given. Activity of zinc was compared with the values obtained from experimental results, and good agreement has been observed. On this basis it can be stated that the theoretical formulas are suitable for determining the thermodynamic properties of liquid quaternary metal solutions. IN the metallurgical processes being carried out at present multicomponent liquid metal solutions take part. For the thermodynamic analysis of these processes it is necessary to know the thermodynamic properties of these solutions. Therefore, many experimental and theoretical papers deal with this problem. The theoretical papers are generally based on the assumption that the structure of liquid metals is similar to their structure in the solid state. In this manner the model of liquid solution, consequently described by means of statistical thermodynamics, has been accepted. This method is being lately developed, especially for solid solutions. Statistical thermodynamics was applied among others by Guggenheim 1 for describing the thermodynamic properties. Unfortunately, the formulas of statistical thermodynamics are often not suitable for the interpretation of experimental results. Attention should be drawn to the relations obtained by means of formulas of phenomenological thermodynamics which always have constants derived with the aid of experimental methods. In the case of the multi-component solutions which contain some additions of impurities besides the basic metal, wagner2 introduced interaction parameters. Equations for the relationship between the activity coefficients and composition were also given by Krupkowski." he application of these formulas requires a good knowledge of the thermodynamic properties of the corresponding binary systems. In these formulas, as in Wagner's, there appear constants which should be determined from ex- perimental data. Nowadays, different experimental methods are applied for evaluating the thermodynamic functions of solutions, for instance: vapor pressure measurements, calorimetric methods, and the measurements of electromotive force of concentration cells. In the present paper this last method for evaluating the thermodynamic properties of four-component systems, Zn-Sn-Cd-Pb, was applied. For instance in the case of Zn-Sn solutions Alabyshev and Landratov, 4 Fiorani and Valenti, 5 and ptak6 performed the investigations. The Zn-Pb system was worked out by Kleppa 7 and Cd-Pb and Cd-Sn by Elliot and chipman.' This method was also applied for determining the activity of zinc in ternary solutions. 1) EXPERIMENTAL METHOD The experimental arrangement with detailed description is given in Fig. 1. It consists of resistance furnaces, one serving for melting samples and the other containing the flat-bottomed, measuring quartz tube with the liquid electrolyte. Liquid metals and alloys are in glass supremax tubes, which have an opening in their lower part above the metal level. This opening allows the filling of the tubes by the electrolyte. In these tubes tungsten wires are placed which by means of suitable conductors are connected with a potentiometer. It is assumed that tungsten dissolves Fig. 1—Schematic diagram of the experimental arrangement for the investigation of the thermodynamic properties of liquid metal solutions: 1, resistance furnaces; 2, autotransfor-mers; 3, galvanometers; 4, regulator of temperature; 5, gas purifier with concentrated H2SOP; 6, U-tube with P2O5; 7, thermostats; 8, steel block for thermostating; 9, supremax tubes for alloys; 10, tungsten electrodes; 11, inlet and outlet of argon; 12, measuring quartz tube; 13, tube for melting samples; 14, tube for thermocouple; 15, cover of quartz tube; 16, rubber seal; 17, bottom cover; 18, outlet of electrodes to potentiometer; 19, outlet of thermocouples to potentiometer; 20, upper view of the quartz tube cover; 21, orifices for cover screws; 22, orifice for argon inlet; 23, orifice for thermocouple; 24, orifices for tubes containing liquid metals; 25, inlet for water-cooling system.

Jan 1, 1969

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös' law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963

[Admissions: Aurel E. Smith, Chairman Edmond F. Egan Lawrence S. Fennell John S. Fuller Howard J. Ritts, Jr. Gene E. Roark Kenneth W. Robbins Ben M. Gottlieb Advertising: Bernard F. Klein, Chairman Henry N. Lyle R. E. Howard H. M. Krause, Jr. Mrs. Evelyn R. Robertson]

Jan 1, 1961

A High-speed Dilatometer and the Transformational Behavior of Six Steels in Cooling. By Arthur L. Christenson, Edward C. Nelson and Clarence E. Jackson. (With discussion).................................606 Dilatometric Studies of the Graphitization of Cast Iron. By N. A. Ziegler. With discussion) 627 An Interferometer Type of Dilatometer and Some Typical Results. By- L. '4. WIlley and W. L. Fink. (With discussion).........................642 The meeting was held in the Pine Room of the Statler Hotel, Cleveland, Ohio, on Tuesday afternoon, October 17, 1944. The chairmen were F. M. Walters, Jr. and Howard Scott. Introduction F. M. Walters, Jr.—The principal advantages of the dilatometric method perhaps are two, as compared with the method of thermal analysis. One is that the dilatometric method can be applied with a large variety of rates of heating and cooling, whereas thermal analysis—that is, the study of the transformational characteristics by means of heat evolution—is limited to the rates of heating and cooling that reveal the evolution of heat. The dilatometer can be used for the study Of reactions at zero rates of heating and cooling; that is, isothermal reactions. As you will hear this afternoon, the rates have been pushed up as far as 500°C. a second. The other advantage is that the dilatometric method shows that a two-phase region is a two-phase region, whereas the thermal analysis merely reveals the temperature at which the rates of heat evolution are greatest.

Jan 1, 1945

[†AARONSON, ALFRED E., Vice-Pres., Mid-Co. Petroleum Co., Mid-Co. Bldg., Tulsa Okla. '18 ABADIE, EMILE R., Min. Engr Box 927, Porterville, Cal. '76 ¦ABADILLA, QUIRICO A. Student, Colorado School Of Mines, Golden, Colo. '20 ABBOTT, CLARENCE E., Gen'l Supt. Iron Mines Div., Tenn. Coal, Iron & R. I. Co., 1405 Minnesota Ave., Bessemer, Ala. '04] [ ]

Jan 1, 1925

(This list includes only those who have entered military service within the past month, or whose entry has only recently become known to us; it also includes a few names of those whose titles or assignments have been changed within the month. The last complete list was printed in Bulletin No. 131, November, 1917. A complete Honor List is maintained in the reception room at the office of the Institute:) AARONS, J. BOYD, Captain, 4th Reinforcements, 11th Infantry, Australian Imperial Force. AHBE, F. R., Captain, 33d Engineers. AMBLER, HARRY A., 30th Infantry, Camp Greene, Charlotte, N. C. ALFORD, NEWELL G., Sergeant, Headquarters 84th, 9th Division, Camp Zachary Taylor, Ky. ANDERSON, ALEXANDER, Lieutenant, Royal Garrison Artillery. ANDREWS, CLARENCE W., 1st Infantry Co., Officers' Training Camp, 83d Div., Camp Sherman.

Jan 2, 1918

By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.' The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.' The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-' M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"'" due to a

Jan 1, 1971