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By D. H. Baldwin, R. E. Reed-Hill

Six compositions of polycrystalline ZY-0 alloys, containing up to 4.2 at. pct 0, were tested in tension between 77° and 600° K. The data obtained from each of the compositions corresponded closely to a rela-ion between yield stress and absolute temperature of the form In s/so = BT, where oo is the yield stress extrapolated to zero degrees and B is a constant. In agreement with others who have observed this relationship, it is shown that the activation energy may be expressed as Ho In so/s. In the present specimens Ho is approximately 18,000 cal per mole and is apparently independent of temperature and composition inside the limits of the investigation. It is also demonstrated that this form of activation energy cowesponds to a strain rate sensitivity parameter RT/Ho. Oxygen was also noted to have an effect upon the operative deformation mechanisms. With increasing oxygen concentration there was an increased tendency to observe both nonbasal slip and cross-slip phenomena. Oxygen does not seriously inhibit twinning more than it does slip. Twins were observed in all specimens tested. It is becoming increasingly evident that interstitial atoms in solid solution are able to interact strongly with mobile dislocations. Stein, Low, and seybolt,&apos; have shown that, if the carbon concentration in bcc iron is lowered below the solubility limit, its flow stress temperature dependence is markedly reduced. This suggests that carbon atoms in interstitial solid solution may be responsible for the pronounced temperature dependence of the flow stress normally observed in iron. This view has recently been challenged by Leslie and sober2 who observed a strong flow stress temperature dependence in iron to which a trace of titanium had been added in order to remove carbon atoms from solution. Since the interstitial concentration must be reduced below approximately 1 ppm in order to produce a pronounced effect on the flow stress temperature dependence,&apos; studies of the effect of interstitials on the flow stress in iron necessarily involve serious experimental difficulties in alloy preparation. There are other metals, however, in which strong effects of interstitial solutes upon both the flow stress and its temperature dependence are observed. Of particular significance is zirconium which, according to Domagala and Mcpherson, 3 is capable of dissolving 28.6 at. pct O. The O-Zr alloy system is an almost ideal system for studying the interaction of interstitial atoms with deformation modes since it is possible to form alloys capable of study over an extensive range of compositions. Mills has made such a study using single crystals oriented primarily for single prismatic slip4 and has found an effect of oxygen concentration on the flow stress temperature dependence analogous to that observed in iron due to carbon by Stein, Low, and Seybolt. The present paper is specifically concerned with the effect of oxygen on deformation in polycrystalline zirconium. Although plastic flow in this type of specimen is much more complex than that reported for the single-crystal work, and involves both slip (on several different types of planes) and mechanical twinning, the results of this investigation are in general agreement with the single-crystal observations concerning the effect of oxygen on the temperature dependence of the flow stress. In addition, they also demonstrate that oxygen affects the acting deformation systems. This is in contrast to single-crystal results4 that showed only single slip on a prism plane. EXPERIMENTAL PROCEDURE Material. High-purity hot-rolled zirconium strip, 0.2 in. thick by 4 in. wide, of 0.10-mm average grain diameter, was used for forming alloys. It was obtained from the Carborundum Metals Co., Akron, N.Y., whose analysis indicated the major impurities were, in wt ppm: Hf, 540, C, 145; Fe, 100; and 0, <80. The plate texture was similar to a wire texture, with basal planes generally parallel to the rolling direction and basal poles randomly distributed about the rolling direction. The heat treatments described below did not appreciably alter the basic texture. specimen Preparation. Small threaded-end tensile specimens were machined from the plate with axes perpendicular to the rolling direction. These transverse specimens had gage sections 1 in. long by 0.060 in. in diam. The small gage section diameter was dictated by the fact that the alloys were formed by dif-

Jan 1, 1969

The Library of the above-named Societies is open from 9 A.M. to 10 P.M. on all weep-days, except holidays, from September 1 to June 30, and from 9 A.M. to 6 P.M. during July and August. The Library contains about 55,000 volumes, including sets of technical periodicals and the publications of scientific and technical societies. Members of the Institute, with few exceptions, are forced to spend a portion of their time in localities isolated from sources of information. To these the Library can render valuable service through correspondence; letters requesting information will receive special attention. The Library is prepared to furnish references and copies of articles on mining and metallurgical subjects; to determine the existence of mining-maps, and to furnish general information as to the geology and mineral resources of all countries. All communications should be made as definite as possible so that the information received may be what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will be saved, and the information will be sent more promptly and in more usable shape. The members of the Institute can be of service to the Library by forwarding copies of mining-reports, maps privately issued, and similar material, which will be classified, indexed, and made available to other members. Suggestions for additions to the Library, either by purchase or personal solicitation as gifts, will be welcomed. It is hoped that members while in the city will use the Library freely, and assurance is given that most careful service will be rendered to them.

Jan 3, 1914

The Library of the above-named Societies is open from 9 A.M. to 10 P.M. on all week-days, except holidays, from September 1 to June 30, and from 9 A.M. to 6 P.M. during July and August. The Library contains about 55,000 volumes, including sets of technical periodicals and the publications of scientific and technical societies. Members of the Institute, with few exceptions, are forced to spend a portion of their time in localities isolated from sources of information. To these the Library can render valuable service through correspondence; letters requesting information will receive special attention. The Library is prepared to furnish references and copies of articles on mining and metallurgical subjects; to determine the existence of mining maps, and to furnish general information as to the geology and mineral resources of all countries. All communications should be made as definite as possible so that. the information received may he what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will he saved, and the information will be sent more promptly and in more usable shape. The members of the Institute can be of service to the Library by forwarding copies of mining reports, maps privately issued, and similar material, which will be classified, indexed, and made available to other members. Suggestions for additions to the Library, either by, purchase or personal solicitation as gifts, will be welcomed. It is hoped that members while in the city will use the Library freely, and, assurance is given that most careful service will be rendered to them.

Jan 8, 1915

By Leonard Obert

The structural stability of any mine or under- ground opening in rock is dependent on the stress field, that is, the state of stress in rock before mining, the stress distribution in the rock created by the opening, and the in situ strength of the rock. In the past mine design problems have been considered by assuming that the stress field is due only to the weight of the overlying rock, the stress around the opening can be calculated from elastic theory using laboratory-determined elastic constants, and the in situ strength of the rock can be determined from laboratory tests on small specimens. Solutions to hypothetical problems using this procedure are given in a report by Obert, Duvall, and Merrill.&apos; Because of the uncertainties of these assumptions, this method can give only a rough approximation to the solution of actual structural problems. Obviously, this approach to determining the stability of underground openings would be greatly improved if the rock stress could be measured in situ, and it is undoubtedly for this reason that in recent years many investigators have spent considerable effort on the development of procedures for measuring rock stress. In this report a method is described for determining in situ the absolute stress in rock. The method requires the measurement of the deformation of a borehole before and after the rock is stress-relieved. The magnitude and direction of the applied stresses are calculated from the borehole deformation and modulus of elasticity of the rock. Also, the results of absolute stress determination made in the walls and pillars of underground openings in five rock types are presented. From these results a number of conclusions are drawn regarding the accuracy and limitations of this method and the problem of stress measurements in general.

Jan 8, 1962

By Roger E. Barthelemy

PRIMITIVE mining and metallurgy has today almost disappeared. Probably the only remaining tribal tin mining and smelting is practiced by the Laotian natives in one of the less known tin areas of the world. This district lies almost a thousand miles from the sea along the Mekong River, one of the longest rivers in the world, that marks the border between Siam and Laos, one of the five states forming French Indo-China. Less than twenty years ago it took more than two weeks&apos; travel on elephant-back to reach the spot and today it still takes many days of travel, using all kinds of transportation from automobiles to native

Jan 1, 1938

The Library of the above-named Societies is open from 9 A.M. to 10 P.M. on all week-days, except holidays, from September 1 to June 30, and from 9 A.M. to 6 P.M. during July and August. The Library contains about 55,000 volumes, including sets of technical periodicals and the publications of scientific and technical societies. Members of the Institute, with few exceptions, are forced to spend a portion of their time in "localities isolated from sources of information. To these the Library can render valuable service through correspondence; letters requesting information will receive special attention. The Library is prepared to furnish references and copies of articles on mining and metallurgical subjects; to determine the existence of mining maps, and to furnish general information as to the geology and mineral resources of all countries. All communications should be made as definite as possible so that the information received may be what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will be saved, and the information will be sent more promptly and in more usable shape. The members of the Institute can be of service to ,the Library by forwarding copies of mining reports, maps privately issued, and similar material, which will be classified, indexed, and made available to other members. Suggestions for additions to the Library, either by purchase or personal solicitation as gifts, will be welcomed. It is hoped that members while in the city will use the Library freely, and assurance is given that most careful service will be rendered to then.

Jan 7, 1915

By E. T. Turkdogan, L. S. Darken, R. J. Fruehan

Further consideration is given to the application of the quadratic formalism to evaluate the thermodynamics of binary metallic solutions from experimental data. The use of the thermodynamic relation, in(r1/r2) dN2= 0, in the evaluation of activity data is discussed. The empirical correlations derived previously for enthalpies and entropies of solutions in Part II are shown to be predicted theoretically for a special case. The applicability of the quadratic formalism to the activity coefficients for binary organic solutions is demonstrated. DARKEN&apos; introduced a quadratic formalism describing the composition dependence of the activity coefficient in the terminal regions of binary metallic solutions. In a subsequent paper (Part II) Turkdogan and Darkeen2 extended this formalism to the enthalpy and excess entropy of binary metallic solutions, and showed that the available data for the activity coefficients and heats of mixing of many solid and liquid binary metallic solutions confirm reasonable applicability of the quadratic formalism. Much variation was noted, however, in the extent of the terminal regions from one system to another, commonly from about 10 to 70 at. pct. For the present purpose, equations derived previously need be given only for one of the terminal regions, e.g. region (I), 0 < N2 < N&apos;2: where subscripts 1 and 2 indicate quantities for components 1 and 2 and superscript ° the values at infinite dilution; other terms are: N = atom fraction, y = activity coefficient, = partial molar enthalpy of solution, ?HM = molar heat of solution, ?Sx = excess partial molar entropy, ?Sx = excess molar entropy. The heat and entropy like terms (constants) el, and S12 are defined in the following expression for the temperature dependence of a12, thus a12 £12 — s12 rnl 2.303RT 2.303 R l J Using this formalism, the thermodynamics of binary systems in the terminal regions may be described over a temperature range of experisental interest in terms of eight quantities: Lº1—Lº2, ?Sx1,?Sxº2 , £12 ,£21,fiai, S12, and S21. In the previous paper, these quantities were evaluated for many solid and liquid binary solutions, and two significant correlations were observed between these thermodynamic quantities pertaining to the terminal regions, thus [10] and [11] Combining Eqs. [9], [l0], and [ll] and rearranging gives a12 -a21 = 1.382R log rº2- 0.08(?S2xº- ?S1xº) [12] Since the second term involving entropies is small and Eqs. 1101 and [ll] are empirical relations, the above equation may be simplified to a12 = 2.74 log rº2 [13] Using the values of a&apos;s and y°&apos;s compiled in Parts I and 11, a12 - a21 is plotted against log(rº2/rº1) in Fig. 1; the line drawn has a slope of 2.74. For Hg-K at 300°C, log(yº2 /yº1)= —5.10, not shown in Fig. 1, and from correlation [13], a12 - a21 = -13.97; this is to be compared with -10.76 derived from the activity data (Part II).

Jan 1, 1970

By Edward H. Robie

THE registration badges gave out, there were not enough programs, the Pioneer Hotel&apos;s rooms were insufficient, and some hundred applicants for banquet tickets had to be turned down at the Institute&apos;s Regional Meeting in Tucson, Nov. 1-5. Minor inconveniences these, however, occasioned by the fact that, optimistic as they are in Arizona, about half again as many partook of the week&apos;s activities as were expected. For this, the local program committee can be blamed-both the technical and social features were too attractive in quantity and quality. Seriously speaking, though, the Institute has probably never had a more successful Regional Meeting than this one. It being the first that has been held in Arizona in 22 years, no effort was spared to make it the distinctive gathering that it was.

Jan 1, 1938

The Library of the above-named Societies is open from 9 A.M. to 10 P.M. on all week-days, except holidays, from Sept. 1 to June 30, and. from 9 A.M. to 6 P.M. during July and August. The Library contains about 55,000 volumes, including sets of technical periodicals and the publications of scientific and technical societies. Members of the Institute, with few exceptions, are forced to spend a portion of their time in localities isolated from sources of information. To these the Library can render valuable service through correspondence; letters requesting information willreceive special attention. The Library is prepared to furnish references and copies of articles on mining and metallurgical subjects; to determine the existence of mining maps, and to furnish general information as to the geology and mineral resources of all countries. All communications should be made as definite as possible so that the information received may be what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will be saved, and the information will be sent more promptly and in more usable shape. The members of the Institute can be of service to the Library by forwarding copies of mining reports, maps privately issued, and similar material, which will be classified, indexed, and made available to other members. Suggestions for additions to the Library, either by purchase or personal solicitation as gifts, will be welcomed. It is hoped that members while in the city will use the Library freely, and assurance is given that most careful service will be rendered to them. .

Jan 1, 1916

By John J. Egan, A. B. Kinzel, Walter Crafts

The demands of the petroleum and chemical industries for steels to be used in pressure vessels and similar structures at artificially low temperatures are continually increasing, and the writing of proper specifications with suitable tests becomes increasingly important. Likewise, the selection of suitable steels for such applications is of increasing concern to the metallurgist. It is generally recognized that highly alloyed steels of the austenitic stainless type retain their properties even at very low temperatures and represent the best technological solution of the low-temperature steel problem. However, in many instances less expensive carbon or low-alloy steels suitable for service within limited temperature ranges are available. The problem thus becomes one of defining the various factors involved in the production and fabrication of these less expensive steels and determining the temperature ranges in which their properties justify engineering application. Most of the applications involve welded structures, and the heat effect of welding as well as the nature of the weld metal are matters of prime concern. The first problem that the metallurgist faces is the determination of the type of test to be used as a criterion of the performance of the steel in low-temperature service. It has been generally recognized that the static properties of steel as determined in the ordinary tensile test undergo a gradual and relatively slight change as the temperature of test is lowered in the range of current interest; i.e., from room temperature to minus 120&apos; C. It is further generally recognized that the behavior of steel under impact involving notch sensitivity is definitely affected at the lower temperatures. While the major subject of this paper is the effect of grain-refining deoxidizers, of low-alloy additions and of welding on the low-temperature notched-bar impact properties, an inquiry into the general behavior of steel under low-temperature impact testing is included. This is a pertinent portion of the investigation and the results thereof are

Jan 1, 1937

By Leslie F. Tedsen, John E. Dorn, Alan E. Flanigan

It is necessary occasionally to use aluminum-alloy sheet where moderately elevated temperatures are encountered. Considerable attention has been directed toward determining the influence of "artificial aging" on the room-temperature properties of the precipitation-hardenable alloys, as testified by numerous company reports and by references I to 4. Investigations on the properties at elevated temperatures are few, however, and have not always covered the range of times and temperatures of greatest interest. The present investigation was instituted to overcome this deficiency. The work was done for the Office of Production Research and Development of the War Production Board, under the supervision of the War Metallurgy Committee, as a part of the "restricted" Project NRC-548. It has been released for publication by the Office of Production Research and Development. AS is well known, the high-strength aluminum alloys achieve their remarkable properties as a result of precipitation-hardening. In production they are subjected to a solution heat-treatment followed by quenching, to retain the supersaturated solid solution. The solution treatment is followed by "aging" (precipitation-hard- ening) either at room temperature or at a suitable elevated temperature. A considerable increase in tensile and compressive yield stresses results from precipitation at room temperature ("natural aging"). Through the elevated-temperature process ("artificial aging") it is possible to obtain values of yield stress considerably higher than those attainable by natural aging. The increase in yield stress is accompanied by a smaller gain in ultimate tensile stress and by a decrease in elongation. During the first stages of artificial aging the yield stress increases steadily until it reaches a maximum value. In this condition the material is said to be "fully aged." Further exposure results in "averaging," attended by a steady decrease in yield stress. In the production of the artificially aged materials, temperatures and times are selected to achieve full aging. The following important characteristics are associated with the process: 1. The higher the temperature, the more rapidly is the fully aged condition attained. :7

Jan 1, 1946

By Leslie F. Tedsen, Alan E. Flanigan, John E. Dorn

It is necessary occasionally to use aluminum-alloy sheet where moderately elevated temperatures are encountered. Considerable attention has been directed toward determining the influence of "artificial aging" on the room-temperature properties of the precipitation-hardenable alloys, as testified by numerous company reports and by references I to 4. Investigations on the properties at elevated temperatures are few, however, and have not always covered the range of times and temperatures of greatest interest. The present investigation was instituted to overcome this deficiency. The work was done for the Office of Production Research and Development of the War Production Board, under the supervision of the War Metallurgy Committee, as a part of the "restricted" Project NRC-548. It has been released for publication by the Office of Production Research and Development. AS is well known, the high-strength aluminum alloys achieve their remarkable properties as a result of precipitation-hardening. In production they are subjected to a solution heat-treatment followed by quenching, to retain the supersaturated solid solution. The solution treatment is followed by "aging" (precipitation-hard- ening) either at room temperature or at a suitable elevated temperature. A considerable increase in tensile and compressive yield stresses results from precipitation at room temperature ("natural aging"). Through the elevated-temperature process ("artificial aging") it is possible to obtain values of yield stress considerably higher than those attainable by natural aging. The increase in yield stress is accompanied by a smaller gain in ultimate tensile stress and by a decrease in elongation. During the first stages of artificial aging the yield stress increases steadily until it reaches a maximum value. In this condition the material is said to be "fully aged." Further exposure results in "averaging," attended by a steady decrease in yield stress. In the production of the artificially aged materials, temperatures and times are selected to achieve full aging. The following important characteristics are associated with the process: 1. The higher the temperature, the more rapidly is the fully aged condition attained. :7

Jan 1, 1946

By H. C. Rolseth, J. J. Calaman

6.4-1. Principles of Operation. The jet-piercing process is a patented thermal process which depends upon a characteristic of the rock which is termed spallability. In its simplest terms, spalling is considered as decrepitation resulting from differential expansion of rock crystals due to thermally induced stresses. The number of individual properties influencing the spalling characteristics of rock are so numerous and their interaction so complex that the only truly reliable way to ascertain the spallability of rocks under thermal shock conditions is to expose them to these conditions. However, laboratory and field work have determined the principal thermal, physical, and mechanical properties of rock which affect spallability (10, 18). The approximate relationship between spallability and these characteristics is as follows: [ ] where To is the critical temperature at which, it is believed, a rock becomes elastic or sufficiently plastic to prevent further spalling action. Thermal diffusivity takes into account the amount of heat used in saturating the medium itself during the migration of a heat front. The rate and degree of dimensional changes which influence the spalling tendency of the rock will depend upon the characteristic of the heat gradient in the rock. The greater the spalling tendency, the higher the piercing rate. Those properties most favorable to a high degree of spallability are: 1. Large linear thermal expansion at temperatures below 700°C. 2. High thermal diffusivity at temperatures below 400°C. 3. Equigranular interlocking structure with little or no fine-grained clay or mica alteration products. 4. No significant amounts of soft, low-melting, or elastic mineral or materials which yield after thermal decomposition.

Jan 1, 1968

Jan 1, 1930

By James W. Malcomson

The Tigre Mining Co. of Mexico, owned by the Lucky Tiger Combination Gold Mining Co. of Kansas City, decided early in 1910 to enlarge its mill, which consisted of a concentrator milling 3,000 tons of ore per month. The enlarged plant was designed to crush and concentrate 6,000 of ore and to cyanide 7,500 tons per month. The extra tonnage cyanided was to be obtained from tailings which were stored below the old mill. Power was supplied to the old mill from four boilers; a 150-h-p. Corliss engine and two Weber 60-h-p. gas-engines using producer-gas made from charcoal. The total horse-power required, including 60 h-p. used for machine-drills in the mine, was approximately 275. Cord-wood cost $4.32 per cord, 8 by 4 by 3 ft., and charcoal $15 per ton. The fuel supply in the surrounding country was approaching exhaustion; more than 150 mules and 50 men were engaged in cutting and transporting this fuel, and the unsettled political conditions in Sonora were such that it would be practically impossible to keep an organization of this kind together. The price of fuel was steadily rising and at times it became almost impossible to get sufficient fuel to operate. It was estimated that the enlarged plant, together with the mine, would require 750 h-p., as follows: Horse-Power. Old mill, which was left unchanged,..............180 New concentrator,.......................90 Cyanide-plant,........................380 Mine and other requirements,................. 100 Total,........•..................750 In a study of the best manner to obtain power the following alternative propositions were considered:

Jan 1, 1914

By J. A. Herbst, A. L. Mular

Digital simulation is defined and simulation techniques are re- viewed. Typical methodology involves the selection of models, the adjustment of raw data, the selection of a fitting strategy, the assessment of model accuracy in a statistical sense, and the development of an executive simulation structure. Simulations serve as aids for process engineers in evaluating the feasibility of a proposed flowsheet and the effect of a modification to an existing flowsheet. In addition, simulation plays an important role in off-line optimization and in the evaluation of alternative circuit control strategies. Several examples are presented to illustrate these uses for simulation including applications in crushing circuits, grinding circuits, and flotation circuits. It is the opinion of the authors that, within the next decade, mineral processing plants will be studied routinely via digital simulation during the preliminary design stage. Simulation will constitute an important component of the design decision making process.

Jan 1, 1978

By Harmel A. Dawson, Robert A. Wilson

First the basic steps to determine the values present and the minerals involved which are the basis for the metallurgical testing are presented in this paper. Next, choosing the process or processes indicated for treating an ore are discussed. This is followed by the test procedures used, the results of which will indicate amenability to treatment. These test procedures have been developed, used and proven effective in laboratory evaluations relative to plant processing. Special, uncommon processing is beyond the scope of the paper. Evalutation of test results and incorporation into the preliminary and final flow sheet for plant design are discussed. The value of a flow sheet, with material and water balances, to plant design is shown.

Jan 1, 1978

By A. F. Crawley

THIS paper describes part of a series of density measurements on low melting point metals being undertaken at the Mines Branch, Department of Energy, Mines and Resources, Ottawa, Canada. This program has received support from the Canadian Zinc and Lead Research Committee and the International Lead and Zinc Research Organization. Examples of the type of work being done have already been given in earlier papers&apos; , which deal with the densities of lead, tin, and some of their alloys. Densities were measured using a graphite pyc-nometer by a technique which has already been described." The cadmium and indium, supplied by the Consolidated Mining and Smelting Co. of Canada were of 99.999 pct purity. Density determinations on indium, as for lead and tin,1,2 were made under a vacuum of about 5 x 10-6 torr because the oxidation and vaporization characteristics of the metal do not create experimental difficulties. This contrasts markedly with cadmium which, even at the relatively low temperatures of our experiments, has a high vapor pressure and a strong oxidation potential. To suppress the harmful effects of these properties, determinations on cadmium were made with success under an atmosphere of argon, the technique having been previously established in this laboratory for measurements on zinc.3 The densities of cadmium and indium are listed in Table I and plotted in Figs. 1 and 2. From the graphs, it is readily observed that the densities of both metals vary linearly with temperature. This relationship expressed mathematically is of the form:

Jan 1, 1969

By J. R. Spencer

When supplies of high pressure mercury or other liquids are required in analytical work, it is convenient to have the source of supply at a relatively constant pressure and available in sufficient volume to satisfy the requirements of the apparatus in use. It is also desirable that the pressuring device be as simple and as inexpensive as possible and convenient to operate. This pump combined with a small storage reservoir containing gas under pressure has the attributes of (1) positive control of the maximum output pressure through the use of a regulator in the low pressure air supply; (2) an increasing capacity as the rate of withdrawal of mercury from the pressured system is increased; and (3) simplicity, requiring only the use of a lathe, drill press, and welding unit in its construction. DESCRIPTION Essential parts of the pump are shown in Fig. 1. In appearance the unlt is similar to the usual steam pump in common use in industrial applications although considerably smaller in size. The main differences lie in the area ratio of the air and mercury pistons and in the design of the air valve mechanism. Approximate diameters of these pistons are 4.25 in. to 0.375 in. respectively, giving an area ratio of about 130 to 1. The air piston (2) is attached to the end of shaft (4), with the mercury piston being merely a reduced extension of the shaft. Mercury intake and discharge to the pump are controlled by high pressure check valves that screw into the ports indicated at (6). Air supply is controlled by the valve assembly mounted on top of the

Jan 1, 1950

By Henry A. Wriedt, John Chipman

Equilibrium in the reaction of hydrogen gas with oxygen in liquid nickel, iron, and their alloys has been studied at temperatures of 1500° to 1700°C. The equilibrium con^stant, 0/p, [% O], is greater in nickel then in iron by a factor of 45 at 1594 C. In the alloy steel range, the activity coefficient of oxygen is slightly increased by the presence of nickel. NICKEL is more resistant to oxidation than is iron, in both the solid and the liquid state. The solubility of oxygen,&apos; however, is greater in nickel than in iron. The two metals and their liquid alloys constitute an interesting series of solvents in which the chemical behavior of oxygen can be studied by methods similar to those used for liquid iron.&apos; Experimental Method The furnace assembly, including the tube for preheating the entrant gas, was the same as that described by Gokcen and Chipman. " controlled mixture of water vapor, hydrogen, and argon preheated to approximately the melt temperature impinged upon the surface of the liquid metal. The charge, weighing about 35 g, was held in an alumina crucible at constant temperature in the gas stream for a prolonged period, then quenched in a stream of cold helium, sampled, and analyzed for oxygen by the vacuum fusion method. The temperature of the liquid metal was measured by a Leeds and Northrup optical pyrometer which had been checked against a similar instrument certified by the National Bureau of Standards. The freezing point of electrolytic iron in hydrogen, taken as 153j°C, was used for frequent checks. This point and the emissivity determined by Dastur and Gokcen" established the transmissivity of the optical system. The emissivities of Fe-Ni alloys at 1535" are known from the experiments of Smith and Chipman,h nd it was assumed that the variation with temperature is parallel with that of iron. Recorded temperatures are probably accurate within k5"C. Preparation of Gas Mixtures—Since the ratio H,O:H, had to be much higher for nickel than for iron, it was found convenient to construct two separate systems for gas preparation. In both cases, the ratio of argon to the sum of the other two gases was at least 4, the proportion of hydrogen and water vapor being varied to produce H,O:H, ratios from 0.2 to 70. The primary purpose of the argon was to diminish the errors caused by thermal separation&apos; in the gas phase. In addition, its presence lowered the saturation temperature required for a given H,O:H, ratio and minimized the difficulty of preventing condensation. Both systems were modifications of the one used by Dastur and Chipman.&apos; For H,O:HI ratios greater than 2, welding-grade argon purified by passage over magnesium chips at 620°C was mixed with hydrogen produced in the electrolytic cell shown in Fig. 1. The design was based on a cell used by Bodenstein and Pohl," the important features of which area nickel wire cathode and sodium hydroxide solution as the electrolyte. The rate of hydrogen evolution was controlled by a calibrated ammeter and a rheostat in the circuit, the current efficiency being taken as 100 pct. Precise control of the argon flow rate at about 300 ml per min was achieved by means of a capillary flowmeter having a controlled pressure drop. The molar flow rate was measured volumetrically before each run, and a constant flowmeter setting was maintained thereafter. The A-H, mixture passed through a water saturator of the type previously described," the saturation temperature being maintained automatically with a fluctuation of k0.04"C. The tube between saturator and furnace was heated by a resistance winding. The system was of all Pyrex construction with the exception of the stainless steel tube containing magnesium chips. This was connected with the glass tubing at the upstream end by

Jan 1, 1957