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By Cyril S., Smith

THE phenomenon of air-hardening is well known in connection with special steels. It occurs when the rate of decomposition of austenite to marten- site is so retarded that it takes place on free cooling in air rather than on more rapid cooling in a quenching bath. If an air-hardening steel is quenched sufficiently rapidly it will remain in the soft austenitic state, while if it is cooled very slowly it will again become soft owing to growth of the carbide particles. It depends on a critical adjustment of the decomposition velocity and diffusion rate, and such alloys are rather rare, especially in the non-ferrous field. In carrying out some experiments on some copper- rich copper-cobalt alloys, the author found that these possess very marked air-hardening properties. The alloys are covered by a patent issued to M. G. Corson (1,723,022-1919), which states that an alloy containing between 2 and 5 per cent cobalt is hardened by simple quenching from above 850° C.

Jan 1, 1930

By P. J. Connors, William J. McCormick, F. B. Olender, Jerome F. Sheldon, Donald T. Mylar, Edgar T. Gregory, Owen S. Roberts, H. Colijn

A quiet revolution has taken place in the conveyor belt industry. Man-made materials, improved production facilities, better splicing techniques and emphasis on repair and maintenance have all contributed substantially to lowering material handling costs for the mining industry. Formerly the rubber industry had only cotton for a belt carcass and tree grown rubber for the protective cover. Monofilament rayon, with desirable elongation and elastic properties, was the first synthetic fiber to be used in place of cotton. But wet strength and other limitations restricted its use, and the conveyor belt industry turned to nylon.

Jan 3, 1972

By H. O. Hofman

Lime-roasting is a term proposed by Ingalls' for the operation of forcing air under pressure through a mixture of galena and lime at the kindling-temperature with the object of oxidizing lead and sulphur and of fritting or fusing the charge. If finely-divided galena were treated in this manner without the addition of lime, the heat set free by the oxidation of part of the lead and the sulphur would be sufficiently great to fuse un-decomposed sulphide, and thus stop desulphurization. Besides the chemical action that the addition of lime, limestone or gypsum to the charge may have, the admixture has the physical effect that it keeps the particles of galena separated from one another and accessible to the oxidizing effect of the air. At present, three methods of lime-roasting are carried out on a working-scale,—the Huntington-Heberlein, the Carmichael-Bradford and the Savelsberg2 processes. In the last, which interests us here, an 8-ton charge is made up of galena, limestone and perhaps some siliceous or ferruginous flux; the whole is crushed to pass a screen with 3-mm. holes and moistened with 5 per cent. of water. It is fed gradually into a bowl-shaped converter, 6.56 ft. in diameter, supported by trunnions attached to a truck. On the bottom the converter has a grate with blast-inlet beneath. In starting, the truck with the converter

Jan 1, 1908

By V. Kondic, W. M. Rumball

HUNT and Jackson' have recently suggested that binary eutectics might be classified according to the entropy of fusion of the component phases. Such a classification was in fact proposed2 some time ago by the authors and the purpose of this communication is to present some supporting evidence. As pointed out by Hunt and Jackson' typical metals of low entropy of fusion, ?S, tend to form normal eutectics (using Scheil's terminology3). Where one phase is metallic (low ?S) and the other nonmetallic (high AS) then anomalous structures are formed. These anomalous structures may either be regular (e.g., Bi-Sn)or irregular (e.g., A1-Si). Finally Hunt and Jackson suggest that where both phases are of high ?S regular faceted structures are formed. In the proposed classification2 the ratio of the entropies of fusion is taken as the quantitative parameter, i.e., ?Sa/?SB = E, where e > 1.0. An extensive literature survey has been carried out2,4 for reliable photomicrographs of eutectic structures. The structures, numbering 151, have been classified into two classes, viz., normal (i.e., lamellar and rodlike) and anomalous. The latter group has been arbitrarily subdivided into regular and irregular anomalous eutectics. Details and sources of the structures are given elsewhere.2,4 In the absence of better thermodynamic data the value of E has been determined for each of the systems making the following assumptions and approximations: l) The entropy of fusion of solid solutions may be calculated additively;5 ii) Inter metallic compounds are treated similarly but with the addition of the following term for fully ordered structures.5 -4.573(Ni lOg10 Nl + N2 log10 N2) where Nl and N2 are the atomic fractions. It might be argued that the entropies of fusion are meaningless as the eutectic phases form at some temperature (T,°K) below their true melting point (Ta or Tb). As AS, = Lo/To if La the latent heat of fusion of a, is assumed independent of temperature, the actual entropy change AS& is given by La/Te. The ratio of entropies of fusion then becomes Fig. 1 shows E' plotted against cumulative totals for normal and anomalous systems from which it is seen that normal eutectics predominate at low values of E'; e.g., some 90 pct of normal systems lie below E' = 1.5 with 65 pct of anomalous systems above this value. Fig. 1 also shows that the regular anomalous structures occur mostly at low values of c' possibly suggesting growth more akin to normal than anomalous growth. The choice of c as a classification parameter was based on nucleation concepts, it being observed that metals widely separated in Sundquist and Mondolfo's8 nucleation series were anomalous and those close together normal. The basis of these classification views is really outside the intended scope of this communication but it is hoped to explain them fully in the near future.7 Having arrived at this entropy of fusion classification by nucleation considerations it is interesting to note that Hunt and Jackson's ideas are based on growth considerations. Elsewhere one of the authors4 has shown that an even better classification of the metallographic structures reviewed is obtained from purely conventional heterogeneous nucleation concepts. It has been found that systems having a value of the parameter +b less than 0.28 are almost certainly normal and above this anomalous: V, is the gram atomic volume. This parameter is nevertheless closely related to c and c', these being an approximation of p. The parameter is also related to the other classification3,8,9 which have met with any success in the past. All these classifications are to be reviewed shortly by the authorsU7 A significant thing about the classifications based on

Jan 1, 1968

Secondary blast holes are now being pierced in quartzite and sandstone quarries, using multiple hand-operated Jet-Piercing units supplied with oxygen, fuel and water from a compact mobile carrier. A unit of this type, operating in a Canadian quarry, enabled four Jet-Piercing blowpipes to pierce blast holes for two hours without shutdown. The piercing blowpipes used were developed by Linde Air Products Co., a division of Union Carbide and Carbon Corp. The mobile supply carrier was constructed by the quarry from specifications supplied by Linde and modified by the quarry operators for their particular use. Employment of the new self-contained unit, which allows up to four operators to pierce approximately 450 ft of blast hole without shutdown, accelerates rock removal operations. Normally, only two blowpipes are in operation at one time. Large boulders or ledges, which sometimes remain after primary blasting to hamper loading operations, can, in the case of certain hard rock, be prepared for reduction more rapidly with these new units than by any other means. A special feature of the new manual Jet-Piercing unit is the mobile gas and fluid supply carrier. It consists of a standard truck chassis fitted out with four banks of large standard-capacity oxygen cylinders, a steel-holding tank for fuel oil, and a gasoline-driven air compressor and tank for pressurizing the fuel oil tank. Cooling water for the blowpipes is supplied to the unit from a hose extension to the quarry supply line. Feeder lines from the oxygen cylinder manifolds and the oil and water tanks terminate in four sets of take-off stations on the control panel at the rear of the truck. As many as four hand Jet-Piercing blowpipes can be connected to the take-off panel by high-pressure rubber hoses. The hand Jet-Piercing blowpipe used with the mobile supply carrier is a highly portable device which can be manipulated comfortably by one operator. The blowpipe can pierce blast holes at rates up to 60 ft per hour, depending on the properties of the rock. Blast holes can be pierced at any angle from the vertical to the horizontal, making it necessary for the operator to drill from the top of the boulder. Hole diameter is held to approximately that which allows the use of a standard 11/8-in. diameter dynamite. The manual Jet-Piercing blowpipe has these important design features: a burner from which the combustion gases emerge at supersonic speeds (in excess of 6000 ft per sec); a hole-sizing shell which controls the minimum size of the hole and protects the copper burner; and a sliding shield which protects the operator against the steam and spallings ejected from the hole during the piercing. The Jet piercing process has been applied successfully in United States and Canadian quarries within the last several years as an advanced method of "drilling" blast holes.

Jan 1, 1952

By Jei Y. Choi, Paul G. Shewmon

The surface self-diffusion coefficient of copper (D,) has been measured between 847° and 1069 "C for six different orientations. These were the(111), (110, (100, and three higher index surfaces. The activation energy for Ds (designated Q s) was found to be about 49 kcal per mol for all six surfaces, and Do about 2 x 104 sq cm per sec. At any temperature Ds varied by no more than a factor of three over these orientations. It is shown that, if the free energy of a surface atom is uniquely determined by its number of nearest neighbors, it follows from the Principle of microscopic reversibility that Qs should have the same value for all surface orientations, and Ds should vary little with orientation. This model also suggests that for clean fee metals Qs ~ 2/3 AH, (heat of vaporization). This is true for copper. ALTHOUGH it has been appreciated for several decades that atoms can diffuse more rapidly on a surface than through the bulk of a crystal, it has only been in the last few years that reliable values of the surface self-diffusion coefficient (Ds) have become available. Tracer studies of Ds had been attempted prior to this period, but when a tracer is placed on a surface, an ever increasing fraction of it is drained off into the lattice. The correction for this loss involves a very difficult, and as yet unperformed calculation. Those who have worked with tracers have not corrected for this loss.1, 2 Thus their results indicate that Ds is greater than the self-diffusion coefficient in the lattice (Dl), but it has not been established that they give quantitative data on Ds. A procedure which avoids the problem of tracer loss is to study the rate of mass-transfer under the effect of surface tension. If the surface asperity being studied is very small, the mass transfer occurs entirely by surface diffusion. The kinetics at which a grain boundary groove forms on an initially plane surface is a well-studied case of this type. The smoothing of a slight scratch in an otherwise flat surface is another procedure that has been studied. If these grooves are up to 20 to 30 µ in width, the dominant mechanism for mass transfer is surface diffusion (at least in the case of metals with low vapor pressures), and the widths can easily be measured with an interference microscope. Of these two, mass-transfer techniques only in the case of grain boundary grooving has a rigorous mathematical treatment been given. This was done by Mullins.3,4 His analysis predicted that in the case of copper in an atmosphere of an inert gas, surface diffusion should be the dominant transport mechanism. This analysis gave an equation for the groove profile and predicted that the width of the groove would increase as (time)1/4. Mullins and Shewmon showed that both of these predictions agreed with experiments.5 Thus the validity of the values of Ds given by this procedure seems to be well established. Gjostein has used copper bicrystals and the grain boundary grooving technique to determine Ds and the activation energy for surface selfdiffusion (9,) in the [001] direction on surfaces ranging between the (100) and (110) planes.= He reported that Qs = 41 kcal per mole and Do = 6.5 x 102 sq cm per sec for all orientations studied. Since the results did not change with the dew-point of the dry hydrogen atmosphere or the type of refractory tube used, he concluded that the surfaces were clean, or at least that the results were not influenced by any impurities chemisorbed from the atmosphere. The work reported here reproduces and extends Gjostein's study in that D s and Q s were determined for copper over a wider range of orientations. To study the effects of impurities, two purities of copper were used as well as cathodic etching to remove any possible electropolishing film. Gjostein postulated that the diffusing atoms on a surface near a low index plane are the few atoms which are adsorbed on the smooth region between ledges or steps in the surface. A more rigorous derivation of the equation relating Ds to the concentration and jump frequency of these adsorbed atoms is given here. Using this treatment, our empirical observation that Q s and D s are essentially the same for all surface orientations can be shown to follow from the assumption that the free energy of a surface atom is uniquely determined by its number of nearest neighbors. The studies of D s using the scratch technique have been carried out by Blakely and Mukura on nickel,' and by Geguzin and Oveharenko on copper. The latter study using copper gives values of D s roughly

Jan 1, 1962

By A. Alonso, J. Daubenspeck

In the nickel extraction process at Nicaro, Cuba, dried and ground nickel bearing laterites are reduced at 1300-1400F in multiple-hearth furnaces. Nickel is leached from the reduced ore by aeration in an aqueous solution of ammonium carbonate. Nickel carbonate is precipitated from the liquor and calcined to yield nickel oxide. The following are the more important modifications of the Nicaro process since plant rehabilitation and expansion. Ten percent increase in tonnage was achieved without decreasing the fineness of the ore by minor mechanical modifications of the grinding plant. Another five percent increase in tonnage was attained by intentionally overloading the ore prepration and leaching circuits in an effort to control cobalt extraction. Modifications at the sintering plant allowed it to handle the entire output of the expanded plant. A fifty percent increase in leach liquor cooling facilities alone provided an increase in nickel production of five percent. Stronger fresh leach liquor for increased nickel washing efficiency was obtained through improved distribution of water to the ammonia absorption towers. Advantage was taken of the reduced calcine's capability to precipitate cobalt, and modifications in the leach liquor circulation provided controlled cobalt solubility with minimum harm to nickel extraction. Several process changes at the drying plant brought about a ten percent reduction in the fuel oil consumption at this pint. Controlled air addition to the reduction furnaces' upper hearths burned formerly wasted combustibles thereby reducing oil consumption by twenty percent. The nickel extraction process successfully emplayed on the extensive but lowgrade lateritic ores of Eastern Cuba at the U. S. Government owned Nicaro plant, has been previously described in various publications. The large mine and plant operated by the Nickel Processing Corporation, located on the northeastern shore of Oriente Province, have been recently expanded to a yearly capacity of about 50 million pounds of nickel. Essentially, the operation involves open pit mining of a limonite-serpentine ore mixture containing 1.3 to 1.4 percent nickel and 34 to 38 percent iron. The comparatively lumpy, wet (25 to 30 percent moisture) ore is first dried and ground prior to chemical treatment, to which the entire 7,000 tons per day feed must be subjected. In the initial chemical action the dried and ground ore is reduced with carbon manoxide and hydrogen at 1300-1400° in multiple-hearth furnaces. The resulting metallic nickel is selectively leached from the reduced calcine by aeration in an

Jan 1, 1961

By G. Derge, L. D. Kirkbride

In recent years the problem of sulfur elimination in iron and steel-making has been of increasing importance. This interest has been due to the increasing amounts of sulfur coming into the system via raw materials. As a result, many investigations have been directed at obtaining information pertaining to the rate and mechanism of sulfur removal in the blast furnace as well as measuring appropriate thermodynamic quantities. Chang and Goldmanl as well as others2'3 showed that the process of sulfur transfer from molten carbon-saturated iron to blast furnace-type slags could be considered as two opposing first-order chemical reactions. Recently, Ramachandran et al.4 have shown that during desulfurization electrical neutrality is preserved in both phases and iron and silicon are transferred into the slag concurrently with the evolution of carbon monoxide gas. They concluded that the reaction s + c-+ (0)=(S) + CO(g) does not express the stoichiometry of the sulfur transfer process. As in all previous investigations, these authors studied the process of a net transfer of sulfur from metal to slag across a slag-metal interface. However, no experimental data have previously been obtained for the process of sulfurization. It was the purpose of this study to investigate the sulfurization process, i.e., net transfer of sulfur from slag to metal. EXPERIMENTAL PROCEDURE Apparatus—The equipment used in this investiga-tion was typical of that used by others.1-3The furnace was a high-frequency induction unit powered by a 35 kw Hg spark gap converter. Fig. 1 shows a schematic diagram of the apparatus. A two-compartment crucible assembly was employed to melt the slag and metal charges; being similar to that used by Ramachandran,4 in size and design. The atmosphere was that produced by reaction of hot graphite with air. Temperature measurements were made by W-Mo thermocouples which were calibrated against a Bureau of Standards Pt - Pt 10 pct Rh couple. Temperature control was always good to * 5°C and in general was much better than this figure. Raw materials used in the experiments were C. P. reagent grade where possible. The silica used in the preparation of the slags was in the form of highly purified silica flour. Silicon and titanium additions

Jan 1, 1961

By W. Mckewan, W. M. Fassell

The oxidation rates of copper have been determined at temperatures from 600" to 900°C in oxygen from 14.7 to 400 psi total oxygen pressure. The oxidation rate of copper is unchanged by oxygen pressures within the range studied. The observed data extend Feit-knecht's conclusion concerning the pressure independence of copper from atmospheric pressure to 400 psi. All samples studied in the above-mentioned temperature and pressure range have both Cu2O and CuO present in the oxide film. NUMEROUS papers have been published on the oxidation of copper, some of which have noted the effect of oxygen pressure on the oxidation rate of copper. It must be noted, however, that no data on the oxidation rates of copper at pressure in excess of 1 atm have been reported in the literature. (Le Chatelier¹ reported that a black oxide of silver was formed at 300°C and 15 atm pressure.) This is likewise true for the other metals. This investigation was initiated to obtain experimental oxidation rate constants for pure metals at elevated temperatures and high oxygen pressure. Copper was selected as the first metal since probably more reliable data are available on its oxidation rates and related physical and chemical properties than for any other metal or alloy. As a general summary, the following conclusions appear well established for the oxidation of copper: 1—The oxide coating consists of Cu2O with a superficial coating of CuO providing the ambient oxygen pressure exceeds the equilibrium pressure for the coexistence of Cu2O and CuO.² The following sequence of phases is then Cu/Cu2O/CuO/O2 (gas). The Cu2O consists of large crystals that have no relation to the orientation of the metal crystals, except for a very thin layer adjacent to the metal." The CuO consists of very fine crystals randomly oriented. If the oxygen pressure is below the equilibrium pressure for the coexistence of Cu2O and CuO, the coating consists of Cu,O only. 2—The rate-determining factor in the parabolic oxidation of copper is the diffusion of Cu+ ions through the Cu,O layer.4,6,7 The Cu+ ions are accompanied by electrons to maintain electrical neutrality. The mechanism of the reaction at the Cu2O/CuO interface and the method of growth of the CuO is in some doubt. 3—On copper, there are three reported pressure effects: (a) At pressures below 0.3 mm Hg oxygen pressure, the oxidation rate increases directly with pressure.', ' .Vxygen starvation at the surface may account for this effect. (b) At oxygen pressures from 0.3 to 63 mm, the oxidation rate increases as the 7th root of the oxygen pressure providing the temperature is such that only Cu2O is present in the film. (c) At pressures from above the equilibrium pressure for the coexistence of Cu2O and CuO (varies with temperature) to atmospheric pressure, the oxidation rate is independent of the oxygen pressure.' Equipment In order to determine the oxidation rates of metals in an oxidizing atmosphere at pressures up to 400 psi, the equipment is somewhat different than for low pressure work as is shown in Figs. 1 and 2. A Leeds and Northrup Micromax recording controller (A) is used to control the temperature of the Ni-chrome furnace winding in conjunction with a Micromax electric drive unit. The drive unit adjusts a 20 amp Variac (variable transformer) to control the power input into the Nichrome furnace winding. Due to the "self heating" of the sample by oxidation, frequently encountered in oxidation rate studies, it is essential that the sample temperature be measured independently. This is done by means of a series of six chromel-alumel calibrated thermocouples located spirally around the oxidizing metal sample. Each thermocouple is partially shielded from the direct radiation of the furnace wall by

Jan 1, 1954

By Paul R. Wieber, Atam P. Sikri

This paper describes the U. S. Energy Research and Development Administration's (ERDA) program to develop in situ coal conversion processes, especially gasification. The potential of this technology, the technical directions being explored, and the program strategy to carry the process concepts toward commercialization are emphasized. The geographic location of the U. S. coal resources and a market analysis are described. Commercially successful in situ coal processes could add over a trillion tons of coal to the U. S. coal reserves. The economics of these processes is compared with surface gasification. Independent studies show this process to be 25% cheaper than surface gasification for Western coals. The major projects are briefly described. The Linked Vertical Well process is in the most advanced stage and shows great promise. The last test produced a low-Btu gas averaging 171 Btu per standard cubic foot for average production rates of 8.5 million standard cubic feet per day. The other projects are Packed Bed, Longwall Generator, and Steeply Dipping Beds. Unique factors of the process development are discussed which may lead to commercial processes in the near term. A development strategy is proposed by which this technology could be commercialized before 1985 with potentially lower gas prices and lower environmental impacts, relative to mining plus surface gasification.

Jan 5, 1978

By L. C. Skinner

THE Coal Hydrogenation Demonstration Plant at Louisiana, Missouri, was completed early in the year 1949. It has operated more or less continuously since completion except for the time required for making necessary inspections, repairs, and alterations between runs. Operations have included a short vapor-phase run on North Dakota lignite-tar distillate oil in 1949, followed in 1950 by four comparatively short exploratory liquid-phase runs and one vapor-phase run on Rock Springs [ ]

Jan 1, 1953

By John R. Eckel

A Iaboratory drilling rig has been devised and placed in operation which permits the application of hydrostatic, terrastatic, and formation pore pressures to a rock sample for drilling under controlled conditions. Calibrated rests of this equipment in-dicate qualitative agreerment with field results on the effect of weight on bit, rotary speed, and rate of circ~~lation on drilling rate. Tests under pressure, using water and air as the drilling fluids, indicate that when drilling saturated limestone samples, a pressure differential between hydrostatic and formation pressure is the only pressure which affects drilling rate. A differential in either direction causes a reduction in rate, but the same diflerential from the wellbore into the formation causes the greater reduction. Also, in lime.stone, air favorably affected drilling rote only when compared to water at high hydrostatic pressurre, all other conditions remaining constant. Large increases in drilling rate with air could be obtained in the laboratory only while drilling a shale, which offered a limited permeability to nitrogen and which could be drilled with a differential from the formation into the wellbore. In general, the magnitude of the changes due to the pressure effect were small compared to changes in drilling rate obtainable by changing either bit weight or rotary speed. INTRODUCTION In the course of Humble's drilling research program, the desirability of investigating several factors which lend themselves to laboratory rather than field study became obvious. Principal reasons for this are the expense involved in field studies and the difficulty of exercising the required degree of control. Of primary importance are investigations of the effect of fluid pressure on rock rate, the effect of pressure on rock drillability, and a study of the fundamental mechanics of rock failure and chip generation. Several years ago some work in the laboratory on the effect of mud properties on drilling rate was re- ported to the API', but the completion of this work and the investigation of the other variables affecting drilling rate required equipment somewhat more elaborate than that used on these earlier tests. This equipment has been assembled to form Humble's Drilling Engineering laboratory. To date only the effect of pressure on rock drillability while using water and air has been investigated, and this work is not yet complete. Facilities are available to investigate the effect of fluid properties on rate of penetration, and information is being assembled on a current basis on the mechanics of drilling. The sequence of presentation in this progress report is somewhat different from that in which the data were obtained since the order of ex-

By Paul R. Wieber, Atam P. Sikri

This paper describes the U. S. Energy Research and Development Administration's (ERDA) program to develop in situ coal conversion processes, especially gasification. The potential of this technology, the technical directions being explored, and the program strategy to carry the process concepts toward commercialization are emphasized. The geographic location of the U. S. coal resources and a market analysis are described. Commercially successful in situ coal processes could add over a trillion tons of coal to the U. S. coal reserves. The economics of these processes is compared with surface gasification. Independent studies show this process to be 25% cheaper than surface gasification for Western coals. The major projects are briefly described. The Linked Vertical Well process is in the most advanced stage and shows great promise. The last test produced a low-Btu gas averaging 171 Btu per standard cubic foot for average production rates of 8.5 million standard cubic feet per day. The other projects are Packed Bed, Longwall Generator, and Steeply Dipping Beds. Unique factors of the process development are discussed which may lead to commercial processes in the near term. A development strategy is proposed by which this technology could be commercialized before 1983 with potentially lower gas prices and lower environmental impacts, relative to mining plus surface gasification.

Jan 1, 1979

By Persifor Frazer

It has been the aim of the writer, by measuring his base line on the territory of theoretical chemistry, to attempt to fix by triangula tion certain points within the domain of mineralogy. As the barest first experiment in this direction, a few of the hydrated oxides of iron have been selected, their theoretical construe tion reduced to percentage of the constituents into which the ordinary analytical methods would resolve them, and the results compared with actual analyses compiled from the most reliable sources; the accidental errors being as much as possible eliminated. This method seems to be a simple one and one easily pursued, but, as will shortly appear, it is beset with grave difficulties, all of which the writer does not pretend to have satisfactorily surmounted. In the first place arises the important question, what are we to understand by the hydrated oxides of iron ? In all books of chemistry and lexicons of minerals, the proposition, long ago taught by the earlier chemists, that water might exist in two forms of combination, viz., as water of crystallization or as water of constitution, is tacitly assumed. There is nothing in the principles of the new chemistry which is opposed to this; for (to carry the mind's eye into the process of con struction of the least units into which a definite chemical compound is capable of being divided without losing its characteristic proper ties), however unlikely it may seem, it is, nevertheless, possible that a given molecule of iron may, under certain conditions of heat, pressure, etc., attract to itself as many molecules of the water in which it is natant as: from the relative size, shape, attractive force, etc. of either, it is capable of taking up, and this complex system of associated molecules might oscillate as a physical unit so long as the conditions on which its existence was dependent remained unchanged. Moreover, it is highly probable that the first effect upon such a mole cule produced by physical or chemical forces would be to separate it into two or more simple ones of different kinds, while a further ap plication of these forces might rend asunder the bonds of the simpler compounds themselves.

Jan 1, 1879

By Persifor Frazer

(Read at the Amenia Meeting, October, 1877.) IT has been the aim of the writer, by measuring his base line on the territory of theoretical chemistry, to attempt to fix by triangulation certain points within the domain of mineralogy. As the barest first experiment in this direction, a few of the hydrated oxides of iron have been selected, their theoretical construction reduced to percentage of the constituents into which the ordinary analytical methods would resolve them, and the results compared with actual analyses compiled from the most reliable sources; the accidental errors being as much as possible eliminated. This method seems to be a simple one and one easily pursued, but, as will shortly appear, it is beset with grave difficulties, all of which the writer does not pretend to have satisfactorily surmounted. In the first place arises the important question, what are we to understand by the hydrated oxides of iron ? In all books of chemistry and lexicons of minerals, the proposition, long ago taught by the earlier chemists, that water might exist in two forms of combination, viz., as water of crystallization or as water of constitution, is tacitly assumed. There is nothing in the principles of the new chemistry which is opposed to this ; for (to carry the mind's eye into .the process of construction of the least units into which a definite chemical compound is capable of being divided without losing its characteristic properties), however unlikely it may seem, it is, nevertheless, possible that a given molecule of iron may, under certain conditions of heat, pressure, etc., attract to itself as many molecules of the water in which it is natant as from the relative size, shape, attractive force, etc. of either, it is capable of taking up, and this complex system of associated molecules might oscillate as a physical unit so long as the conditions on which its existence was dependent remained unchanged. Moreover, it is highly probable that the first effect upon such a molecule produced by physical or chemical forces would be to separate it into two or more simple ones of different kinds, while a further application of these forces might rend asunder the bonds of the simpler compounds themselves.

Jan 1, 1878

By Yoichi Ishida, Ching-Yao Cheng, John E. Dorn

Tile creep behavior of a iron was investigated over the range of temperatures from 375° to 1150°K. Apparent activation energies for creep, obtained by the effect of sudden changes in temperature on the creep rate, revealed the presence of- four distinguishable regions. The creep behavior of a iron in Regions II (480° to 774°K) and 111 (775° to 1045°K) was found to correlate well with a model where the creep rate is controlled by the nonconsevualive motion. of jogged screw dislocations. An anomalous increase in the apparent activation energy fur creep in Region III was found to be in harmony with the known decrease in the free activation energy for self-diffusion over the Curie transformation range. Furthermore, the creep rates in Regions II and III were found to increase with stress due not only to the effect of stress on the activation energy but also to an increase in density of mobile dislocations. The evidence suggests that pipe diffusion along moving dislocations could be a significant factor over the lower temperatures of Region II. ALTHOUGH the creep properties of iron and steel have been of interest to metallurgists for some time and an extensive literature is now available, most of the published information has not produced much toward understanding the fundamental dislocation processes controlling the creep behavior of these materials. Whereas the activation energy for high-temperature creep of metals usually agrees well with that for self-diffusion, Sherby, Orr, and Dorn1 deduced from the data of Tapsell -and c1enshaw2 that the activation energy for creep of Armco iron is about 78,000 cal per mole and more recently Lytton and sherby3 reviewed the data of Jenkins and Mellor4 and found an activation energy for creep of a iron of 80,000 cal per mole. Both values are substantially greater than the activation energy for self-diffusion in a iron. Because of the limited data suitable for purposes of identifying the controlling dislocation mechanisms of creep and the unusually high activation energies for creep quoted above, it was considered desirable to reinvestigate in detail the creep of a iron by more reliable techniques which would provide sufficient data for determination of the creep mechanisms. EXPERIMENTAL TECHNIQUE Creep specimens were prepared from 3/8 by 4 in. iron bar stock of the following composition by weight percent: 0.001 C, 0.0120 0, 0.001 N, 0.004 S, and 0.003 P. The as-received bars were cold-rolled to a thickness of 0.100 in., annealed under argon for 30 min at 1113°K, cold-rolled to a final thickness of 0.063 in., and machined into tensile specimens having gage section 0.250 in. wide and 1.70 in. long. Finally they were recrystallized under argon at 1113°K. Specimens to be crept above 1060°K were recrystallized at 1173°K. Both recrystallization treatments gave the same reproducible equiaxed ASTM No. 4 grain size. Creep testing was conducted in machines fitted with Andrade-Chalmers arms that maintained a constant stress to within ±0.2 pct of the reported values. Deformation over the specimen gage section was sensed with a linear differential transformer and recorded auto-graphically as a function of time. The strains deduced from these measurements were sensitive to ±5 x 10-5. During creep the specimens were contained in an argon-filled chamber which was immersed in a temperature-controlled molten tin bath. Creep temperatures, as measured by thermocouples attached to the specimen, were maintained to within ±10.25°K of the reported values. For activation-energy determinations rapid changes in temperature of about 12°K were obtained within 30 sec by direct resistance heating of the creep specimen, and maintained to ±1°K of the reported values. Observations of structural details of specimens before and after creep tests were made by electrolytic polishing and etching in acqueous ammonium persulfate. EXPERIMENTAL RESULTS A typical example of the determination of apparent activation energies, Q, by the effect of small changes in temperature is illustrated in Fig. 1. Q is defined by

Jan 1, 1967

By R. N. Zitter

PRESENT work was done in connection with a program for obtaining a low energy gap semiconductor suitable for photodetection. The inter-metallic compound InSb, which is now being in-

Jan 1, 1959

Jan 1, 1889

By G. P. Gladis, R. H. Atkinson

PALLADIUM has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items-at least 100 times as rare as gold. Although both visual and spectrophotometric examination demonstrated that the color of palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400° to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946

By A. D. Rich

The term "bleaching clay" or "bleaching earth," as used in the oil industries, refers to clays that in their natural state, or after chemical or physical activation, have the capacity for adsorbing coloring matter from oil. There are three common types of bleaching clays: fuller's earth, activated clays, and activated bauxite. Fuller's earth, or naturally active clay, is prepared from bentonites (see Chap. 5) that possess natural activity. It is not activated commercially; in fact, earths of this type ordinarily do not respond satisfactorily to acid activation. Fuller's earth is prepared in pulverized as well as granular form for use in the contacting and percolation processes, respectively. Acid-activated clays also are of bentonitic origin. The basic raw clay, however, is of a type that has a very low natural activity but is highly activable by treatment with mineral acid. Commercial acid-activated clays generally possess several times the decolorizing power (bleaching efficiency) of the best quality of fuller's earth. The former are prepared commercially only in the pulverized grade because of the difficulties in obtaining a satisfactory granular product, and hence are used only in the contact process. Activated bauxite is made by heat-treating bauxite ore, which in its natural state has very little natural activity. The commercial product is prepared in granular form for use in the percolation process on petroleum oils. For the most part, bleaching clay is used commercially in the decolorization of animal, vegetable and petroleum oils, fats and waxes. It is applied in two ways: (1) by the percolation method and (2) by the contacting method. Percolation refers to the passage of oil through a bed of granular clay whereas contacting refers to direct agitation of oil and pulverized clay followed by removal of the clay from the oil by filtration. In either case, the decolorizing effect is obtained by intimate contact between the liquid oil and the solid adsorbent. Petroleum oils are treated commercially by either the percolation or the contact process. Animal and vegetable oils are treated by the contact process only. Composition The raw clays from which both fuller's earth and acid-activated clays are prepared are composed of hydrous aluminum silicates containing varying quantities of magnesium, iron, calcium and other elements. These raw materials are usually nonswelling bentonites derived from volcanic ash or lava by weathering and hydrothermal chemical reactions. The bentonites have as their chief mineral constituent montmorillonite, which has the formula [(OH)4Si6A14O20•nH2O], according to Grim. (See Chap. 5, ref. 6, p. 91.) The underlying reasons are not fully known for the natural activity of the fuller's earth type of clay and its usual failure to further activate with mineral acid in contrast to the natural inactivity of the activatable type of clay. However, it may be said that the bentonites that are responsive to the acid-activation treatment generally have not undergone any drastic metamorphism. The chemical composition is not a reliable means of discrimination between a nonactive, a naturally active, and a nonactive but activable clay, therefore it is not possible to forecast the ultimate quality of a clay on the basis of the raw-clay analysis alone. Table 1 gives typical analyses of representative clays of the foregoing classifications.

Jan 1, 1960