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By Hans-Jürgen Schaller, Horst A. Brodowsky

Activity coefficients of boron in palladium were determined at concentrations up to PdB0.23 by reducing B2O3 between 870" and 1050°C in a controlled H2-H2stream and measuring the resulting weight gain. The deviations from ideal behavior closely resemble those of the system Pd-H and are interpreted in terms of three principles: 1) The solute atoms occupy octahedral interstitial positions. 2) They donate their valence electrons to the 4 d and 5s bands of palladium, raising its Fermi energy. 3) The lattice strain energy is lower for two nearesl -neighbor interstitial particles than for two farther separate ones. SOLID solutions of hydrogen in palladium are a useful subject for studying thermodynamic aspects of the formation of alloys and of nonstoichiometric systems.1-3 The activity of hydrogen is readily measurable to a high degree of accuracy,4'5 even at low temperatures where the deviations from ideal behavior are more pronounced, and its simple structure facilitates an interpretation of these deviations in terms of a detailed model. Two effects are discussed to account for the non-ideal properties:3 An "electronic" effect, connected with the rise of the Fermi energy, as electrons of the interstitial hydrogen atoms enter the electron gas of the metal, and an "elastic" effect, due to an interaction of the regions of strain around each interstitial atom. The electronic effect is based on the idea that the lowest energy levels of the dissolved hydrogen atoms are higher than the Fermi energy, so that the electron will not occupy a localized state but enter into the electron band of the metal.6 The elastic effect is based on the observation that dissolved hydrogen distorts and expands the palladium lattice. The hypothesis is put forward that the elastic strain energy is lower for two adjacent dilatational centers than for two separate ones; i.e., they attract each other. The resulting pair interaction can be used to calculate an elastic contribution to the thermodynamic excess functions by means of one of the statistical methods. This model permitted a detailed description of the solution properties of hydrogen in palladium3 and in palladium alloys.798 An extension of the approach to describe the excess functions of substitutional palladium alloys is possible.9 In order to further test and refine the model, an investigation of other interstitial alloys was started. Palladium dissolves considerable amounts of boron in homogeneous solid solution.10 The palladium lattice expands linearly up to nB = 0.23 (nB = B/Pd atomic ratio), the highest concentration studied." The expan- sion, extrapolated for 1 mole of interstitial per mole of palladium, is 17 pct of the lattice constant of pure palladium vs 5.7 pct in the case of hydrogen.12 The fact that the lattice expands rather than contracts is a strong indication that interstitial positions are occupied. According to neutron diffraction experiments, hydrogen occupies the octahedral sites of the fcc lattice.13 Unfortunately, this direct evidence is not available for the Pb-B system, mainly because of the high-reaction cross section of boron with thermal neutrons. However, by way of analogy and on the grounds of the rather close similarities between the two systems to be reported here, it seems safe to attribute octahedral positions to the dissolved boron, too. At higher boron contents, compounds of stoichiomet-ric compositions are reported such as Pd3B, which has the structure of cementite,14 so that a close structural relationship seems to exist with the system r Fe-C. In their study of hydrogen absorption in Pb-B alloys, Sieverts and Briining noted that alloys with an atomic ratio of about nB = 0.16 are no longer homogeneous15 This observation was confirmed in an extensive X-ray investigation.11,16 The phase boundaries of two miscibility gaps were established. One two-phase region was stable below a transition temperature of about 315°C and extended from nB = 0.015 to 0.178. The other one extended from nB = 0.021 to 0.114 slightly above the transition temperature and had an apex at nB = 0.065 and 410°C. All phases involved have the fcc structure of pure palladium with lattice expansions proportional to their boron contents. The occurrence of miscibility gaps, i.e., the coexistence of dilute and concentrated phases, points to an energy of attraction between the dissolved particles, in the Pb-B system as well as in the Pd-H system. The filling up of the electron bands seems to be analogous, too, in the two systems, as indicated by the hydrogen absorption capacit15,17,18 and by the suscepti bility of Pd-B alloys.l8 In both types of experiments, boron acts as an electron donor. A chemical method was used to measure the activity of boron in palladium. Boron trioxide was reduced in a moist hydrogen stream: B2O3 + 3H2 = 2B + 3H3O [l] At known activities or partial pressures of boron trioxide, hydrogen, and water, the activity of boron could be calculated from the law of mass action. The equilibrium concentration of boron corresponding to this activity was determined as the weight gain of the sample. EXPERIMENTAL The samples consisted of small pieces of foil of 0.1 mm thickness and about 100 mg weight. The palladium was supplied by DEGUSSA, Germany, and stated to be

Jan 1, 1970

By McIntosh F. Galbraith

This paper describes the use of the magnetometer, under geological direction, in exploration of the Sudbury nickel district. The writer's experience at Falconbridge has led him to the belief that only through detailed work, and by careful correlation of both geological and geophysical results, can geophysical prospecting methods be applied successfully to mining exploration problems. It is hoped that the basic technique described in the paper will be found to have general application.

Jan 1, 1942

By George W. Orton

i\- number of investigations have established that tungsten monocarbide (WC) forms throughout a wide range of temperatures (800° to 2200°C), but the di-tungsten carbide (W2C) forms only at the high end of this temperature range.1"7 In addition the decomposition of WC into WzC and C at elevated temperatures has been observed.8"10

Jan 1, 1964

By Oswald J. Heinrich

(Supplementary Paper.) IN conclusion of a series of deep exploration-borings with the diamond drill, I beg to submit the following statements, supplernentary to those in my former papers on this subject: Since my communications read at the St. Louis Meeting, in May last, I have finished two more borings, one terminating at the depth of 922 feet 7 inches, the other at the depth of 715 feet 6 inches. The results in regard to time and expenditure have been highly favorable and fully confirmatory of my opinion stated in previous

Jan 1, 1875

Efficient energy utilization in the electrolytic zinc process, relative to other zinc processes, is one of the reasons for its wide adoption in recent years, says John D. Siddle, zinc plant superintendent at the Bunker Hill Co., Kellogg, Idaho. Designers and operators of electrolytic zinc plants have pioneered process improvements, new equipment, and operating techniques to conserve energy. As energy costs increase it the future and competitive pressure mounts against less-efficient producers, these energy-saving improvements will he regarded as necessary for economic survival. Plant designers and operators should not lose sight of the savings in operating costs possible through intelligent utilization of all available forms of energy.

Jan 11, 1977

Jan 1, 1941

By John J. Van den Broek

As the established tailings disposal techniques do not meet the requirements of today, alternative methods of disposal are explored. McIntyre Mines Ltd., Coal Div. found a solution in the construction and operation of a tailings dewatering plant. The solids are recovered from the tailings slurry by means of mechanical dewatering equipment and are then dried in a unique drying system to provide an excellent thermal fuel for a power generating station.

Jan 1, 1983

By G. W. Powell

ACCORDING to crank,' the accumulation equations for inter diffusion in a binary system whose molal volume is a function of concentration are

Jan 1, 1965

By William F. Blake

The discovery of tin-ore in the Black Hills of Dakota dates from June, 1883, and short preliminary notices were published in September of that year.* The discovery-point is known as the Etta Mine, in the central portion of the Hills, about six miles east of

Jan 1, 1885

By Donald A. Dahlstrom

Stronger Than Armies This editorial by Dr. Dahlstrom is based on his acceptance speech of the 1976 Robert H. Richards Award-Ed. Many public figures are saying that the United States is facing the most critical period in its history, and many of us would agree. But people have always been saying this, and all of them were right. They were right two centuries ago when it took a revolution to give birth to the Republic; and they were right during our Civil War, Pearl Harbor, the Great Depression, etc.

Jan 6, 1976

Starting in 1940, national prize-paper contests for Student Associates and members of Student Chapters of the Institute have been conducted by a Sub- committee of the Committee on Student Relations Five cash prizes of $100 each may be given annually To be eligible for the national contest, a paper must have been the prize winner in a preliminary contest conducted by a Local Section of the Institute The money for the national prizes is drawn from the corpus of a special fund begun in 1940 by a contribution of $2,500 made by D C Jackling, and to which others have made substantial contributions since that time Contributions to the fund from members who are interested will be welcome since the original contributions are about exhausted A special committee, headed by Donald H McLaughlin, was appointed in 1952 to obtain further funds

Jan 1, 1952

By AIME AIME

Air transport supplants the old methods. The 3-piece canoe fits in the plane and likewise makes possible not a bad division of labor over a 5-mile portage

Jan 1, 1933

By AIME AIME

Jan 1, 1926

By W. O. Philbrook, K. M. Goldman, G. Derge

T. Rosenqvist—The most interesting point in this paper is the observed transfer of iron into the slag in the initial stage of the desulphurization process, after which the iron again is reduced to the metallic state. The authors interpret this observation as showing that the sulphur enters the slag as an iron-sulphur compound which subsequently is decomposed by the slag. The present writer has previously suggested the following equation for the desulphurization process: S + O2- ? S2- + O For equilibrium in the blast furnace the oxygen potential is defined by equilibrium with graphite and CO of 1 atm pressure: C + O ? CO [2] During the desulphurization process the reactions proceed in the direction of the arrows. If one assumes eq 2 to be significantly slower than eq 1, the transfer of sulphur into the slag, in accordance with eq 1, will build up a local oxygen potential at the metal-slag interface very much higher than that corresponding to the value defined by eq 2. This is possible because the equilibrium oxygen potential in eq 1 is high as long as the sulphur content in the slag is low. This oxygen potential will again be able to oxidize some iron: Fe + O ? Fe2+ + O2- and an increase in the iron content of the slag will be observed. Adding up eqs 1 and 3 one obtains: S + Fe ? S2- + Fe2+ The net effect is thus in harmony with the experimental observation but is obtained without assuming any close ties between the sulphur and iron atoms during the process. Furthermore, it follows from eqs 1 and 2 that when the sulphur content in the slag increases, and equilibrium with C and CO is finally approached, the local oxygen potential at the metal-slag interface will decrease, and the iron in the slag will be reduced back into its metallic state. C. E. Sims-—The data and conclusions presented in this paper are thoroughly convincing in establishing the mechanism of sulphur transfer from iron to slag as in a blast furnace. The evolution of gaseous CO in step 3 of the reactions given on p. 1112 makes the process virtually irreversible. Assuming that the process is similar in slag-metal systems other than in the blast furnace, it is readily seen why free CaO and re-ducing conditions so greatly favor desulphurization. On the other hand, the very effective desulphurization obtained in oxidizing slags when strongly basic, must be attributed to the relatively high stability of CaS as compared to FeS. The ease and simplicity with which the reactions of classic chemistry agree with the experimental data and explain the mechanism is noteworthy. The concept of molecules of FeS, soluble in both phases (metallic iron is not soluble in the slag), migrating from the iron to the slag and there reacting with CaO, which is soluble only in the slag phase, is clear and uncomplicated. This is likewise true for step 3. Those who would deny the existence of molecules or molecular-type combinations in liquid iron, must strain to provide a mechanism so lucid. In the absence of molecules, the Fe and S exhibit a remarkable collusion. L. S. Darken—The investigation and interpretation of rate phenomena in the range of steelmaking temperatures is a difficult task. Most of the laboratory investigations of steelmaking reactions have been concerned with equilibrium. Having determined the equilibrium, our attention naturally focuses next on the mechanism and rate of approach to equilibrium. The authors seem to have contributed substantially to our understanding of these factors for the case of sulphur transfer. I should like to ask the authors whether they consider that the sulphur transfer reaction is diffusion controlled as many high-temperature reactions seem to be. If so, it would seem reasonable to suppose that the slow diffusion step of the process is the transfer across a pseudo-static layer or film similar to that considered in heat flow problems. As the diffusivity and fluidity are smaller for the slag than for the metal, it may tentatively be assumed that the sulphur gradient exists in a thin layer in the slag adjacent to the slag-metal interface and that the metal and the main mass of slag are each maintained uniform by convection. On this basis the amount of sulphur transferred across unit area per unit time is D p (?S%)/100 ?1, where D is the diffusivity, p the density, (?S%) the difference in percent sulphur on the two sides of the layer, and ?l is the layer thickness. At the beginning of the experiment the main body of the slag and hence one side of the layer contains no sulphur; therefore (?S%) may be replaced by (S%), the sulphur content of the slag at the slag-metal interface, which in turn is equal to L[S%] where [S%] is the sulphur content of the metal and L is the distribution coefficient. The rate of transfer thus becomes DpL[S%]/100 ?l, which the authors designate K[S%]. Equating these two quantities and setting D = 10-6 cm2 per sec, p = 3 g per cm3, L = 40, and K = lo-+ g cm-2 sec-1, it is found that ?l, the film thickness, is about 0.01 cm—a value of the order of magnitude of that found in heat transfer problems in liquids. The uncertainty of the numerical values used leaves much to be desired, but at least it can be said that this calculation tends to support the proposed model involving diffusion through a film. Although this does not seem to affect the general argument, I should like to call attention to the fact that the diffusivity3 of sulphur in hot metal is found (on conversion of units) to be about 10-4 cm2 per sec rather than 104 cm2 per sec as stated by the authors. The three equations written by the authors to express the steps in the overall process of sulphur transfer may alternatively be written ionically as only two Fe + S = Fe++ + S-- Fe++ + O-- + C (graphite or metal) = CO (gas) + Fe where the underscore is used to designate the metallic phase; ionic species are slag constituents. After the authors have so neatly demonstrated that iron and sulphur transfer together (at least initially), this fact seems almost self evident; from eq 4 it is seen that if sulphur acquires a negative charge during transfer

Jan 1, 1951

By William Y. Holland, Roger H. Cook

Dexter H. Reynolds (Chapman and Wood, Mining Engineers and Consulting Geologists, Albuquerque, N. M.)—A number of questions are raised by conclusions and inferences made in the above-mentioned paper. The more troublesome of these concern use of the various pozzolans to combat the deleterious effects of the alkali-aggregate reaction. The most alkali-reactive materials listed are opal and rocks containing opaline silica. The pozzolans mentioned specifically for use as amelioratives are opaline shales and cherts. These are stated to retard the expansion caused by the alkali-aggregate reaction. Another well-recognized pozzolan is diatomaceous earth, which consists principally of opaline silica. A pozzolan presumably owes its effectiveness to its high reactivity with the alkaline liquid phase of the concrete mix. It appears reasonable to expect that finely divided opaline silica added as a pozzolan would be more susceptible to reaction with the alkalies present than would larger particles of the same material. The authors report that work with high and low alkali cements indicates that in the presence of alkali-reactive materials, deleterious expansion depends upon the alkali content of the cement. The total effect, therefore, should be more or less independent of the amount of reactive aggregate present, and still more independent of its state of subdivision. The deleterious effects should, if anything, be aggravated by the addition of a finely divided, highly reactive pozzolan. Further, if the alkali-aggregate reaction is of great importance in the long-term soundness of concrete structures, the addition of a pozzolan to a concrete made with aggregate free from known deleterious materials would be a questionable procedure. The benefits reportedly accruing from such use of pozzolans are greater ultimate strength for a given cement content, increased resistance to deterioration by exposure to sulphate solutions and other mineral waters, and greater resistance to damage by wetting and drying and freezing and thawing. In view of the deleterious effects of highly reactive materials are these benefits ephemeral? The same considerations apply to another alkali-reactive material, chalcedony, which appears to consist of ultrafine-grained quartz, with opal absent in detectable amounts. Quartz flour is notably reactive chemically and physiologically (cf. Ref. 11 of Holland and Cook's paper), a fact borne out by its effectiveness as a pozzolan, which presumably might be expected to offset the deleterious effects of the presence of chalcedony in the aggregate. A second question of some importance concerns the reportedly highly deleterious reactivity of acidic and intermediate volcanic glasses, such as rhyolite, perlite, and pumice. Air entrainment is listed as one of the ameliorative measures to combat the deleterious effects of the alkali-aggregate reaction. The alkalic-silica gel formed by the reaction may expand into air bubbles and thus not cause appreciable expansion of the concrete mass. It would appear then that pumice and perlite, particularly perlites of the pumiceous types and other types after expansion, would also tend to counteract the expansion, since these materials consist largely of voids and air bubbles. Certainly this would be expected of structural concrete in which pumice or perlite is used as total aggregate. Finely ground pumice, perlite, and volcanic ash have been demonstrated to be active pozzolans (cf. Pumice as Aggregate for Lightweight Structural Concrete by Wagner, Gay, and Reynolds, Univ. of New Mexico Publications in Engineering No. 5, Albuquerque, 1950). In fact, the term pozzolan was first associated with finely divided pumice or volcanic ash. Such materials were used with hydrated lime as the sole cementitious agent in constructing public buildings, roads, and aqueducts by the ancient Romans. The deleterious alkali reactivity of the volcanic glass, itself containing several percent of the alkalies, apparently did not contribute to the remarkable state of preservation of those ancient structures, as exemplified by the Appian Way and the Pantheon Dome. Still a third question involves .the reactivity of constituents of concrete when exposed to various salt solutions. Resistance to. deleterious expansion and cracking as a result of contact with mineral waters and its relationship to the mineral content of the aggregate are not mentioned by the authors. Yet the phenomena pictured in Fig. 1, and especially in Fig. 2, appear very much like those caused by exposure to mineral waters. The deterioration of concretes exposed to sulphate waters is generally considered related to the chemical constituency of the cement itself, particularly to the relative amount of tricalcium alum-inate contained. Could not many of the ill effects presently blamed on alkali-aggregate reaction really have been caused by contact with sulphate or other salt-containing mineral waters? Or perhaps their use as mixing waters? May not the deleterious expansion be as much a function of the chemical makeup of the cement as it is of the mineral constituency of the aggregate? Would it not be just as important to use alkali-free mixing water as it is to use a low-alkali cement? It appears obvious that resistance of cements and concretes to sulphate and other salt solutions cannot be left out of account in discussion of deterioration of concrete structures with time. This factor may be of equal or even greater importance than the alkali-aggregate reaction, particularly for concrete subjected to wetting and drying cycles, such as airstrip paving, water-retaining dams, and highway structures. Another very important factor is called to attention on page 1022 of the article in Mining Engineering, October 1953, in that failure of concrete structures may result from poor construction practices and use of too high water-cement ratios. Both of these can contribute remarkably to decreased resistance to attack by sulphate waters, and presumably could have an equally remarkable effect upon extent of damage resulting from the alkali-aggregate reaction. From the above remarks it appears that while alkali-aggregate reaction may be an important factor in decreasing the useful. life of a concrete structure, it is not the only factor involved, and it may not be even a controlling factor. Likewise, many of the phenomena apparently associated with the alkali-aggregate reaction may have resulted from cond'itions which had little relationship to the alkali-reactivity of a constituent of the aggregate. Certainly if alkali-aggregate reactivity is a major factor in bringing about early failure, one cannot help feeling anxiety concerning the future of the many concrete structures in this country and abroad in which pumice and perlite were used as total or partial aggregates. This anxiety can only be dispelled by calling to mind that among the best-preserved relics coming down to us from ancient times are structures made with mortars containing highly alkali-reactive aggregates.

Jan 1, 1955

Jan 1, 1941

By A. J. W. Schwandt

Magmont is a venture jointly owned by Cominco American Incorporated of Spokane, Washington and Dresser Minerals, Division of Dresser Industries, Houston, Texas. Cominco American assumed direction of the operation in 1961 and completed exploration, preproduction planning and development, and is now the operating partner managing the operations. The plant has a rated capacity of 4200 tpd and produces in excess of 60,000 tons of lead per year. [ ]

Jan 1, 1970

By K. S. Benson

DEPLETION is a subject of vital importance to the mining industry. Yet, in spite of its importance, its significance is not generally understood. The purpose of this discussion is to clarify the main aspects of the subject from the viewpoint of a metal mine taxpayer.

Jan 7, 1951

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Jan 1, 1938