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By Nicholas J. Grant, Chih-Chung Wang

TO phase of the Ti-0 system has the structure of NaCl and has a wide range of solid solubility.' In the course of studying the Ti-Cr-0 ternary system, binary alloys were made of iodide titanium and high purity TiO,. It was found from X-ray studies of the binary alloys that a transformation of the TiO appears to take place at a temperature near 925°C. Evidence of this phase change is best seen in Fig. 1. Fig. 1A shows the X-ray spectrometer pattern (CUKa radiation) of an alloy of 25 wt pct 0 corresponding to the stoichiometric composition of TiO.

Jan 1, 1957

By H. E. Wheeler

THE work described was carried out during 1917 and 1918 at the testing laboratory of Watertown Arsenal at the instigation of the Nitrate Division and later with the concurrence of the Cannon Section of, the Ordnance Department, U. S. A. The experiments follow three principal lines of work: First, the effect of nitrogen under pressure on steel containers of various compositions at a red heat; second, the effect of decomposing ammonia on various alloy steels, iron, and non-ferrous alloys; third, a new theory of the erosion of guns in respect to the effect of nitrogen in steel. PART I In the Haber process for the manufacture of ammonia from its elements, it is necessary to have nitrogen and hydrogen of 1500 lb. per sq. in. (105.5 kg. per sq. cm.) at a temperature of 500 to 600° C. The steel containers for these gases gave trouble by failing without apparent cause. When the General Chemical Co. began to develop its method for the production of ammonia, it experienced the same difficulty and, knowing that the Haber process had solved the difficulty by the use of alloy steels, it made several small steel bottles of different compositions and kept them filled with these gases at this pressure and temperature until they failed. The time of service varied from a few days, for the plain steel casting, to two years for a chrome-vanadium forging. Four of these steel bottles were sent to this laboratory for investigation; they were a plain carbon-steel forging, a nickel-steel forging, a chrome-vanadium steel forging, and a chrome-steel forging. The time of service was as follows: plain carbon steel, 4 mo.; nickel steel, 6 mo.; chrome-vanadium steel, over 2 yr.; chrome steel, 4 mo. When these containers were cut open and the cross-section surface polished, they showed an inside zone with a different luster from the rest of the metal. Upon etching, this zone was almost unaffected while the rest of the steel etched normally.

Jan 4, 1920

By D. E. Thomas

Oxidation rate constants were determined for Cu-Pd and Cu-Pt alloys as a function of alloy composition and temperature. Reaction products were identified. Relationship between oxidation rate constants and diffusion constants in the reaction zones is discussed. THE mechanism of oxidation of alloys is consider--'¦ ably more complex and not so well understood as that of pure metals. The oxidation of a one-phase binary alloy of which one component is a noble metal should logically be the simplest case of alloy oxidation, for in this case one is concerned presumably only with the oxidation of the base metal and the diffusion process by which it reaches the reaction site. This had led a number of investigators to study such systems. Probably the earliest work was that of Tammann and Rienacker' on the tarnishing of Cu-Au alloys at temperatures up to 300°C. These alloys oxidize according to the logarithmic law, that is, the film thickness is proportional to the logarithm of the time. The rate of film formation was found to decrease with increasing gold content. Raub and Engel² investigated the oxidation of Au-Cu, Cu-Pd, Au-Ag-Cu, Au-Pd-Cu, and Ag-Pd-Cu alloys at 750°C in air. These alloy systems form a continuous series of solid solutions at the temperature of oxidation with the exception of those containing silver. Au-Cu alloys oxidize parabolically, the rate constant decreasing slowly with increasing gold content up to about 15 atomic pct* Au, and more rapidly thereafter. An alloy with 14 pct Cu forms only a very thin layer of CuO on the surface and probably also a subscale.† Alloys containing more than 14 pct Cu have scales consisting of CuO and subscales of Cu,O embedded in nearly pure gold. The Cu-Pd alloys obey the parabolic law except for slight deviations for alloys containing 53 and 84 pct Cu. The overall oxidation rate decreases rather smoothly with increasing palladium content. A scale consisting of a thin layer of CuO and a thick layer of Cu²O and a subscale of Cu²O embedded in nearly pure palladium was observed for alloys containing 84, 53, and 30 pct Cu. An alloy with 19 pct Cu formed only a subscale of CuO embedded in nearly pure palladium, and an 8 pct Cu alloy formed only a thin film which was presumed to be PdO. The ternary alloys considered by Raub and Engel oxidized in much the same way as did the binaries. Wagner and Grunewald³ found that Ni-Au alloys, oxidized at 900°C in oxygen, formed a scale of NiO and a subscale containing NiO and gold. The overall oxidation rate increases with increasing gold content, passes through a maximum and then decreases to zero for pure gold. The fact that gold increases the oxidation rate was attributed to "pores" in the scale. Kubaschewski' investigated the air oxidation of alloys of platinum or gold with up to 10 pct Cu or Ni at temperatures in the range 300" to 1550°C. Parabolic behavior was noted for all alloys except Au-Ni, with rates decreasing in the order Au-Cu, Au-Ni, Pt-Ni, Pt-Cu. The diffusion coefficients for the latter three systems are known, and they decrease in the same order. However, activation energies for the oxidation of these alloys do not agree with the activation energies for diffusion in the respective alloy systems. Kubaschewski and Goldbeck7 nvestigated the oxidation of Ni-Pt alloys in air at temperatures of 600"

Jan 1, 1952

By Geo. W. Bain

PRODUCERS of building stone have had to seek new and attractive uses for their output to supplement the diminished orders for standard products. Lunar is the direct result of the need of new outlets for marble and is. probably the most ingenious and attractive type to reach the market in a quarter of a century. It is a highly translucent stone which retains the same glistening sparkle in transmitted light that marble exhibits by incident rays. This sparkle sets it apart entirely from translucencies made of glass or even onyx, alabaster, and the distinctive exceedingly fine textured calcite marbles produced in Alabama and quarried formerly in northern Vermont and Quebec.

Jan 1, 1936

By George B. Clark

COMMERCIAL strip mining of coal was first begun in the state of Illinois in 1911.1 The annual tonnage of coal produced from coal strip mines in the state was very small until 1924, when the strip mines shipped 1.68 pet of the total state shipping mine tonnage. Since then, strip mines have gradually come into their own by producing a sizable percentage of the coal produced in the state. Table 1 shows the coal tonnage shipped from both underground and strip coal mines in the state of Illinois for selected years. The table illustrates the major role that strip mines play in the state's coal industry. Today, strip mining is generally conducted in areas where the coal seams lie so close to the surface of earth that a stripping method of mining the coal seam is cheaper than an underground method. Strip mining not only recovers 100 pct of the coal deposit, but may also be used as a method of mining large acreages of coal abandoned by the closing of underground mines.

Jan 1, 1949

By AIME AIME

The following changes of address of members have been received at the Secretary's office during the period of Mar. 1 to May 1, 1908. This list, together with the list in Bi-Monthly Bulletin, No. 20, March, 1908, therefore, supplements the annual list of members corrected to Jan. 1, 1908, and brings it up to the date of May 1, 1908. The names of Members who have accepted election during March and April, 1908 (new members), are printed in italics., By a simple method of cutting out these names and addresses, and pasting them directly over the corresponding names in the annual list of members, the record can be kept practically up to date and the value of the list correspondingly increased. For this purpose the changes of address have been printed only on one side of the page. The names of new members, being in italics, are readily distinguished from the others, and can be pasted in approximate alphabetical order on the margins of the pages of the list.

Jan 5, 1908

The resignation of Herbert Hoover, Director General of Relief in Europe, from his post as Chairman of the Board of Directors of the Food Administration Grain Corporation, in which capacity he had served for nearly two years; and the reorganization of the corporation under the name of the United States Grain Corporation, with Julius Barnes, United States Wheat Director, as its new head, took place at the annual meeting of the stockholders, held in New York, July 1. This action on the hart of Mr. Hoover is believed to be one of the first steps in his intended withdrawal from public service upon the conclusion of the war service of the various departments of the Food Administration, or as soon as they shall have been absorbed by other agencies. The Grain Corporation has been, for the past two years, a vast collection and distribution agency. Its function has been to assist in supplying to the Allies and the American Army and Navy large quantities of wheat, wheat flout, and other foods, with very little disturbance of American prices, and with such an even control of American distribution that reserves from one crop to another have been brought down to the lowest possible compass and without the dvelopment of actual scarcity anywhere in the United States. In the year just past, it carried on all the buying and the shipping for, the Belgian Relief Commission, until the commission retired on May 1 and the Belgian Government itself undertook its own overseas supplies. During the twenty-two months of its existence the corporation had disbursed $3,500,000,000 and collected an equal amount, selling for over-seas shipments commodities valued at $1,800,000,000, at an operating expense of about $3,250,000, or one-sixth of 1 per cent. During this time it has not lost a single dollar through fire loss.

Jan 8, 1919

By P. J. Burkhardt, L. V. Gregor

The oxidation kinetics of single-crystal silicon has been investigated using extremely dry oxygen as the oxidant. Two techniques were used. The first involved a flow system with which incremental thickness measurements were made. This sytem provided an oxygen ambient at atmospheric pressure which had a moisture content of less than 0.1 ppm of water. The second technique involved measuring the change in volume of oxygen with time in a closed system. A temperature range of 900O to 1200 "C and a pressure range of 20 to 760 Tory were covered. Both techniques showed that a simple parabolic rate law holds only at the higher temperatures. At lower temperatures, the data up to 5000Å can be fitted well to a linear-parabolic equation. The two constants in this rate equation are examined in terms of a physical model. The parabolic portion of the low-temperature oxidatLon fits along the high-temperature curve of an Arrhenius plot. The parabolic rate constant for the flow-system technique can be expressed by k = 2 x 10-9 exp (L 31 kcalRT) sq cm per sec. The manostatic technique gave k = 1 x 10-exp (- 23 kcalRT) sq cm per sec. By extending the thickness range to over 104. a rate law of X = At seems to fit all of the data better than the linear-Pavabolic law. Here the exponent n increases from 0.518 at 1150 V to 0.637 at 900°C. PASSIVATION of silicon planar devices through thermal oxidation is of such great importance that considerable effort has been devoted to the study of the process.17 Much of this work involves hydrothermal oxidation, in which H2O is the oxidant: whereby H2 is produced. It has been proposed that the reaction proceeds by the formation of Si-OH groups and hydroxyl diffusion through the film to react with the silicon surface. Thus, the silicon oxide layer probably contains residual hydrogen in some form after oxidation in H2O and it has already been established that hydrogen has a marked effect on the electronic properties of oxide-passivated silicon surfaces. Silicon is oxidized by oxygen at elevated temperatures; but the rate of oxide formation is considerably lower than that for 0." By using dry O2 as the sole oxidant, the presence of residual hydrogen is presumably avoided. At present, the mechanism of thermal oxidation by dry O2 is a matter for conjecture, and the presence of small amounts of H2O was reported to have a marked effect on the rate of oxide formation10 (perhaps on the electronic properties of the surface, as well). Hence, this study of the kinetics of silicon oxide growth in 0, was undertaken: 1) to determine the oxidation rate at atmospheric pressure in a system designed to exclude rigorously all traces of H2O in the ambient 0,; 2) to obtain oxidation-rate data in situ in dry O2 by means of a continuous monitoring of the amount of 0, consumed during oxide growth. These objectives are complementary—the first assesses what effects (if any) are obtained by excluding H2O from the reaction, and the second expands this information while at the same time avoiding the uncertainty inherent in relying upon incremental measurements of oxide growth to furnish kinetic data. EXPERIMENTAL PROCEDURE The conventional silica open tube in a resistance-heated oxidation furnace is subject to sources of trace H2O, even after the input O2 is thoroughly dried and the outlet gas stream is passed through a trap to prevent

Jan 1, 1967

By M. L. Hammond, G. M. Bowers

Silicon dioxide films have been prepared on silicon wafers by the oxidation of SiH, near 400°C. Results previously reported by Goldsmith and Kern7 have been qualitatively corrobovated using a system of different geometry, and significantly greater deposition rates have been achieved. The deposition rate is independent of thickness and nearly independent of the O2/SiH, ratio over a wide range; however, the rate is strongly temperature-dependent. The structure of the deposit depends upon the cleanliness of the substrate, and the electrical field strength of the deposited oxide depends upon the nature of the electrodes. MULTILEVEL interconnects in integrated circuits using aluminum metallization require an insulator that can be deposited at low temperature. Because the A1-Si eutectic is only 577°C, the maximum deposition temperature must be below about 500°C to prevent reaction of the aluminum with the silicon and with other materials in the integrated circuit. Many methods of depositing insulating films of SiO, and other dielectrics have been reported'-6 but the technique described by Goldsmith and Kern7 offers the simplest method of preparing SiO, films. The technique involves the reaction of SiH, and 0, to form SiO, films in the 300" to 500°C temperature range. Previous work using this gas system has been reported8 and the initial development work at Philco Microelectronics was done at the East Coast R&D Laboratories. 9 This paper corroborates some of the results of Goldsmith and Kern,7 shows that much higher deposition rates can be obtained than previously reported, and presents some observations on the structure of deposited SiO, films. EXPERIMENTAL CONDITIONS Fig. 1 is a schematic drawing of the apparatus used in this study. It differs from that of Goldsmith and Kern in that 1) the gases are mixed before they enter the reaction chamber, 2) there is no fritted glass diffuser, and 3) the wafers are stationary during deposition. The control thermocouple was in a well located 0.06-in. from the substrate, and three gas supplies were used: 1 pct SiH4 in N 2, O 2, and N 2. Water vapor must be excluded from the plumbing to prevent the formation of colloidal SiO, and the SiH4 must be diluted with an inert gas because SiH4-0, mixtures are extremely flammable above about 4 pct SiH The wafer temperature was determined by attaching a thermocouple to a test wafer and the temperature was maintained to +5 C. The conditions used in this investigation are listed in Table I. The temperature range was chosen for compatibility with the A1-Si system. The volume ratio of 0, to SiH4 is the actual volume of 0, delivered to that of SiH4, taking into account the initial dilution of the SiH4. This ratio, which was used by Goldsmith and Kern,7 is a useful indicator of the experimental conditions. The active/inactive ratio is the ratio of the volume of active gases, SiH4 and O2, delivered to the volume of dilution gas. The active/inactive ratio is an important parameter to specify for deposition rate determinations since it determines the amounts of reactants that arrive at the sample per unit time. Fairly high dilution ratios were necessary to achieve uniform deposits of SiO,. Most of the process characterizations were performed on the polished (111) face of 3 to 5 ohm-cm, n-type silicon wafers which were 0.009 in. thick; but the data approximately apply to deposition of SiO, on thin films of aluminum. It is difficult to obtain accurate deposition rate data over aluminum films because of coarsening the aluminum surface during exposure to 300" to 400°C. The deposited SiO, film fol-

Jan 1, 1969

By G. A. Deitz, J. Halpren

The kinetics of dissolution of silver in cyanide solutions under oxygen pressure have been investigated over a wide range of conditions with a view to establishing the reactions involved and the factors which influence the rate. The results indicate that the rate is determined principally by the transport of reactants in solution to the silver surface. The thermodynamic features of the reaction with particular reference to the influence of pH and CN- are also discussed and summarized in the form of potential-pH diagrams. METALLIC silver is readily attacked and dissolved by cyanide solutions in the presence of oxygen. This reaction has long been recognized and extensively applied1 in the well-known cyanide process for the extraction of silver from its ores. While this process has been subjected in the past to a number of investigations2,3 both of a practical and fundamental nature, some features relating to the chemistry of the reactions involved, the role of oxygen, the nature of the rate-controlling step, and the effects of pH and certain reagents such as lime, are still not fully understood. It was felt that this situation justified a further investigation of the reaction, made with a view to obtaining a better understanding of its kinetics and mechanism. In the present investigation rate curves for the dissolution of silver were determined over an extensive range of carefully controlled reaction conditions. By carrying out the reactions in a pressure vessel, the partial pressure of oxygen, and hence its concentration, could be varied widely. The influence on the reaction of other variables including temperature, pH, and the concentrations of cyanide, peroxide, and other salts was also examined. The results of these kinetic studies are presented and discussed in this paper, together with a summary of available thermodynamic information relating to the possible reactions which can accompany the attack on silver by aqueous solutions of cyanide and oxygen. Chemistry and Thermodynamics of the Reaction The chemistry of the reactions of gold and silver with aqueous cyanide solutions has been the subject of several recent reviews.'." It has been proposed' that the following reaction occurs when silver dissolves in cyanide solutions in the presence of oxygen: 4Ag + 8CN- + 0, + 2H.0 -t 4Ag(CN); + 40H- [la] An equation of this form, for the corresponding dissolution of gold, was first suggested by Elsner." Bodlaender5 proposed a similar overall reaction, but suggested that it took place in two steps, 2Ag + 4CN- + O2 + 2H2O ? 2Ag(CN),- + 2OH- + H2O2 [2a] followed by 2Ag + 4CN- + H2O2? 2Ag(CN); + 20H- [3a] On the other hand, Janin- suggested that the dissolution of gold can occur with the liberation of hydrogen, rather than by reduction of oxygen. The corresponding equation for the dissolution of silver is 2Ag + 4CN- + 2H20 -t 2Ag(CN); + 20H + H2 [4a] All these reactions represent oxidation-reduction processes and may be resolved into the corresponding separate oxidation and reduction components. The oxidation step involves the formation of the argentocyanide ion and is the same for all the reactions, i.e., Ag + 2CN? Ag(CN)2 + e [51 However, reactions la, 2a, 3a, and 4a differ in the nature of the reduction steps which are, respectively, O2 + 2H2O + 4e ? 4OH- [lb] O2 + 2H2O + 2e ? H2O2 + 2OH- [2b] H2O2 + 2e ? 2OH- [3b] 2H2O + 2e? 20H- + H2 [4b]

Jan 1, 1954

By Vsevolod Krivobok

THE re-crystallization of metals has been the subject of much scientific investigation, some of which has resulted in a better understanding of this extremely important and interesting phenomenon. Unfortunately, while many have propounded theories of re-crystallization, but a few have presented experimental evidence as to how it takes place. If this can be determined the question, why re-crystallization occurs, may be answered more definitely. Re-crystallization in single phase metals consists of a complete rearrangement and re-sizing of the grains, of which the structure is composed, while the type of structure remains the same. That is to say, if the structure before re-crystallization is composed of a number of polyhedral grains of different shape and size, a particular spot after re-crystallization will be seen to consist of grains in no way different from the original except in size and shape. The re-crystallized grains may be smaller or larger, depending on the treatment received; and, while the re-crystallization may be brought about by means of heat treatment only in passing through a critical range, yet it is common knowledge that single phase metals subjected to cold working are possessed of a tendency toward re-crystallization, even if the heating does not reach critical range. The study of re-crystallization would, of course, be much easier if we had single crystals of any metal as the original material with which to study the phenomenon of re-crystallization, since it would permit the observation of structural changes at what amounts to enormous magnification, by changing the scale of the specimen. In metals of more normal grain size the crystal boundaries introduce complications, but the process, it may be assumed, is essentially the same. Such an opportunity

Jan 2, 1926

By Walter E. Mingramm

The construction of rescue-apparatus on the principle of furnishing the wearer with air from a tank containing it under high pressure was given up by inventors about 20 years ago. Such an apparatus must supply continuously, for not less than two hours, nearly 50 liters of pure air at atmospheric pressure per minute, or a total of 6,000 liters (210 cu. ft.); and a cylinder containing this amount of air, under 2,000 lb. pressure, would weigh 180 lb. or more. Although apparatus has been recently constructed utilizing liquefied air, no experiments have been made to determine the regularity with which the air is generated, nor has its chemical composition been determined. Moreover, the chief objection to such an apparatus is the difficulty and cost of keeping on hand a large quantity of liquefied air. The system of furnishing the wearer of a breathing-apparatus with air which has given the best results, and has found

Jan 1, 1909

By Robert A. Bauer

This study showed that diametral point-load testing performed parallel to the bedding planes of highly anisotropic sedimentary rocks produced inconsistent results that cannot be used to accurately estimate uniaxial compressive strength. Axial point-load values from tests performed normal to bedding planes and evaluated by the T500 index produce good correlations with the uniaxial compressive strength values obtained for five different rock types. A strong correlation also existed between the moisture content and the uniaxial compressive strength of the tested lithologies. A combination of axial point-load and moisture content indices produces the best correlation with the uniaxial compressive strength test results.

Jan 1, 1984

By William Kent

More than twelve years were spent by Wöhler at the instance of the Prussian Government in experimenting upon the resistance of iron and steel to repeated stresses. The results of his experiments are expressed in what is known as Wöhler's law, which is given in the following words in Du Bois's translation of Weyrauch:* " Rupture may be caused not only by a steady load which exceeds the carrying strength, but also by repeated applications of stresses, none of which are equal to the carrying strength. The differences of these stresses are measures of the disturbance of continuity, in so far as by their increase the minimum stress which is still necessary for rupture diminishes." A practical illustration of the meaning of the first portion of this law may be given thus: If 50,000 pounds once applied will just break a bar of iron or steel, a stress very much less than 50,000 pounds will break it if sufficiently often repeated. This is fully confirmed by the experiments of Fairbairn and Spangenberg, as well as by those of Wöhler; and, as is remarked by Weyrauch, it may be considered as a long-known result of common experience. It partially accounts for what Mr. Holley has called the " intrinsically ridiculous factor of safety of six." Another "long-known result of experience"—although this has not, as the writer believes, been investigated by scientific experimenters—is the fact that rupture may be caused by a succession of shocks or impacts, none of which alone would be sufficient to cause it. Wrought iron will crystallize by repeated blows in service and become weaker than cast iron. Iron axles, the piston-rods of steamhammers, and other pieces of metal subject to continuously repeated shocks invariably break after a certain length of service. They have a "life" which is limited. Iron rods in bridges sometimes crystallize and break, although the rods in most of our iron bridges

Jan 1, 1880

By C. E. Meissner

THE need for a practical method of deciding upon new alloy steel analyses to widen its markets was the problem facing the Chrome Steel Works at the beginning of 1927. In addition to determining the physical properties of the alloys under consideration, it was necessary to test their value in service. Small melts of steel in a crucible, from which test specimens could be made, were insufficient to determine more than physical properties, therefore actual castings and ingots had to be made before the products could be placed in service. Furthermore, to save further experimental work, it was desirable that these heats should be made on a "pilot" basis; that is, actually duplicating regular open-hearth furnace practice. Therefore a one-ton (2000-lb.) acid open-hearth furnace was built. FURNACE DESIGN There are no special features in the design of this furnace. Standard acid open-hearth practice is followed, with the reproportioning of the dimensions necessitated by its small size; notably, a considerably increased length in proportion to width in order to get proper flame propagation. After the first heat was made it was found that the checkers were insufficient. The checker chambers were increased in size and the checker openings were made much smaller. The furnace was started late in March, 1927, and made 65 heats. Experimental work was then stopped until the data accumulated could be worked up and summarized. The run was resumed in November and the furnace is still operating, having made at this writing 60 additional heats. For the last series of runs, there was some rebuilding of both the furnace itself and the checkers. Slag pockets were added. Fig. 1 shows details of construction; Fig. 2, the, general appearance. All designing was done by the operating and engineering staff. Construction materials were those available around the plant. The reversing valve is a standard butterfly type taken from an old furnace.

Jan 1, 1928

By William Bent

MORE than twelve years were spent by Wöhler at the instance of the Prussian Government in experimenting upon the resistance of iron and steel to repeated stresses. The results of his experiments are expressed in what is known as Wöhler's law, which is given in the following words in Du Bois's translation of Weyrauch :* "Rupture may be caused not only by a steady load which exceeds the carrying strength, but also by repeated applications of stresses, none of which are equal to the carrying strength. The differences of these stresses are measures of the disturbance of continuity, in so far as by their increase the minimum stress which is still necessary for rupture diminishes." A practical illustration of the meaning of the first portion of this law may be given thus : If 50,000 pounds once applied will just break a bar of iron or steel, a stress very much less than 50,000 pounds will break it if sufficiently often repeated. This is fully confirmed by the experiments of Fairbairn and Spangenberg, us well as by those of Wöhler; and, as is remarked by Weyrauch, it may be considered as a long-known result of common experience. It partially accounts for what Mr. Holley has called the "intrinsically ridiculous factor of safety of six." Another "long-known result of experience "-although this has not, as the writer believes, been investigated by scientific experimenters-is the fact that rupture may be caused by a succession of shocks or impacts, none of which alone would be sufficient to cause it. Wrought iron will crystallize by repeated blows in service and become weaker than cast iron. Iron axles, the piston-rods of steam-hammers, and other pieces of metal subject to continuously repeated shocks invariably break after a certain length of service. They have a " life" which is limited. Iron rods in bridges sometimes crystallize and break, although the rods in most of our iron bridges * Strength and Determination of Dimensions of Structures. By Dr. J. J. Weyrauch. Translated by Du Bois, New York, 1877.

Jan 1, 1880

By Frank Haas

Many articles on the physical properties of fire damp have appeared in the Transactions and elsewhere but practically nothing has been written in regard to its occurrence or fluctuation in quantity in an ordinary mine. After the Monongah explosion in 1907, with the loss of 361 lives, the Consolidation Coal Co. sought a method by which such catastrophes could be prevented. While the cause of this particular explosion was attributed to coal dust, some of those acquainted with the mine thought that fire damp was involved, if it was not the initial cause. So the literature on the subject was studied and mines where similar conditions prevailed in this country and Europe, were visited, with the view of establishing some system by which gas could be more easily detected and controlled. The results of this study were disappointing for no method was found other than the time-honored fire boss with his safety lamp, with some variations in the rules and regulations governing his inspections and reports. Duties of the Fire Boss Pending the development of a better method, it was decided to standardize and perfect the duties of the fire boss and the reports based on his observations. Those who were then in service were closely examined, various lamps were experimented with and the lamps and individuals tested under known conditions. It was found that a fire boss could tell whether gas was present but his estimate of quantity was not even an approximation; therefore, while the services of fire bosses were indispen-sible there was need of additional information by which the quantity of gas could be estimated with some precision in order to determine its variation from time to time. Chemical Process for Determination of Methane After considering all methods known at that time a chemical process was adopted. The principles involved in the process are that in an enclosed receptacle, in the presence of excess air, methane will be completely burned by means of a hot platinum wire to carbon dioxide and

Jan 1, 1927

By Michael Hoch, Walter C. Wyder

The isothermul section of the Nb-Ti-Zr-O system at 1500°C was investigated using X-ray dzffraction and metallographic techniques. UP to 66.7 at. pct 0, the system contains nine four-phase regions. Tsopleths at 10, 20, 30, 40, 50, and 55 at. pct 0 weye constructed. The purpose of this investigation was to determine the general shape of the quaternary equilibrium phase diagram of niobium, titanium, zirconium, and oxygen at 1500°C. The system was truncated at 66.7 at. pct. O., PREVIOUS INVESTIGATIONS The Ti-Zr-O system was investigated in this laboratory.' The binary systems of interest have been compiled and discussed by anssen2 and Levin, McMurdie, and Ha11. Elliott4 has determined the Nb-O system by metallographic and X-ray diffraction techniques. He shows the existence of three oxides, namely NbO, NbO2, and Nb2O5. At 1500°C the solubility of oxygen in niobium is about 4 at. pct. No solid solubility region is shown for either NbO or NbO2. EQUIPMENT The same equipment as that for the study of the Ti-Zr-O system was used. The X-ray diffraction patterns were analyzed with the help of the ASTM card set5 and NBS circulars.6 MATERIALS The niobium powder (99 pct pure), the titanium powder (99.6 pct pure), the niobium pentoxide, and the zirconium dioxide used in this study were purchased from the Fairmount Chemical Co., Newark, N.J. The zirconium powder (99.4 pct pure) was obtained from the Charles Hardy Co., Inc., N.Y. Reagent-grade titanium dioxide was purchased from the Matheson Co., Inc., Norwood, Ohio. The oxides were dried in air at 700°C for 24 hr before use. Though the materials used were not "hyper-pure," the impurities present do not affect the results (lattice parameters, phase boundaries), within the experimental accuracy. PROCEDURE Samples of the desired compositions were made up, in mole pct, from the materials listed above. In some cases the intermediate binary compounds, such as NbO and TiZrO4 were prepared beforehand and used in the preparation of the samples. This technique enabled equilibrium to be reached from two sides. The components of each sample were mechanically mixed in a mortar and pestle and pressed into 3/16-in. diam pellets. The pressures used in compacting were of the order of 50 to 100 x 103 psi. Sintering was accomplished by heating the samples in a tungsten crucible (3/4-in. high, %-in. diam, 1/8-in. wall, lid with XB-in. hole). The pellets were separated from each other and from the crucible by means of small spiral coils of tungsten wire placed between the stacked pellets and on the bottom of the crucible. The sintering time was from 4 to 12 hr at 1500°C under a vacuum of 6 x 101-5 to 1 x 10-6 mm of Hg. All samples were reground after the first or second heating repressed, and reheated. In most cases: equilibrium was obtained after the first heating, as the X-ray diffraction pictures after each heating remained unchanged. Quenching of the samples from 1500°C was at first only possible by allowing the crucible and its contents to lose heat by radiation. The temperature dropped from 1500° to 900°c in approximately 1 1/2 min, which was considered adequate when compared to the times used by other investigators to reach equilibrium in the temperature range of 1000°c and lower. Later, a new technique for faster quenching of the samples was cleveloped. This technique involved the removal of the samples from the crucible, whereupon they were quenched by coming in contact with the water-cooled copper base of the furnace. This manipulation was performed without breaking the vacuum. The sample pellets were placed on a tungsten wire rack inside the crucible. The wire rack passed through the hole in the crucible lid, where it was connected to a small nonmagnetic chain. The chain was fed to the side of the furnace by means of a brass rack which fitted between the body and lid of the furnace. Suspended at the end of the chain, near the furnace wall, were three magnetic washers. With the use of a strong

Jan 1, 1962

By A. E. Back, S. F. Ravitz

When manganese ores are leached with sulphur dioxide, a large part of any zinc in the ore usually is extracted with the manganese.1 In the dithionate process,2,3 in which the manganese ore is leached with dilute sulphur dioxide gas and the manganese is subsequently precipitated by adding lime to the pregnant solution, the zinc is precipitated with the manganese. These facts suggested the possibility of applying the dithionate process to the recovery of zinc from oxidized ores or calcined sulphide concentrates. Accordingly, an investigation was begun, and preliminary tests were made on several ores and concentrates. The results were encouraging, but the need to devote available funds and personnel to other projects made it necessary to drop the work before the various factors involved in the process could be studied in detail. A brief mention of the process,4 however, elicited a number of inquiries, so that it appeared desirable to report the results of the preliminary work. The dithionate process as applied to zinc may be summarized briefly as follows: The ore or calcined concentrate is leached with dilute SO2 gas to dissolve the zinc, largely as zinc sulphate, in accordance with the following equation in which [ZnO] represents the "oxide zinc" in the ore or calcine: [ZnO] + SO2(g) + 1/2 O2 = Zn++SO4— [1] If, in the leaching step, the ore or calcine is suspended in calcium dithionate solution, the sulphate ion, as it is formed, is precipitated immediately as calcium sulphate, which is subsequently filtered off with the insoluble ore residue: Zn++SO4— + Ca++S2O6— = CaSO4(s) + Zn++S2O6- [2] An alternative procedure is to suspend the ore in water, filter off the insoluble ore residue after leaching, add calcium dithionate to the resulting zinc sulphate solution, and then filter off the calcium sulphate precipitate. In either event the zinc is obtained in the form of a pregnant solution of zinc dithionate, from which it can be precipitated as relatively pure zinc hydroxide by adding milk of lime: Zn++S2O6— + Ca(OH), = Zn(OH)2(s) + Ca++S2O6- [3] The zinc hydroxide precipitate is calcined to form the final zinc oxide product: Zn(OH)2 = ZnO(s) + H2O(g) [4] Theoretically the process is completely cyclic with respect to dithionate ion, the calcium dithionate required for reaction 2 being replaced by that formed in reaction 3. In practice, of course, small amounts of dithionate would be lost in the various filter cakes, depending on the economic washing limits. In the leaching step, however, some of the SO2 is oxidized to dithionale instead of sulphate, accord- ing to the following overall reaction: ZnO + 2SO2(g) + 1/2 O2(g) = Zn++S2O6-, [5] so that the dithionate losses are made up, at least in part. Ores and Concentrates Tested The analyses of the ores and concentrates tested are summarized in Table 1, which also includes the analyses of the calcines produced from the concentrates. The concentrates were roasted in a laboratory muffle furnace at the temperatures indicated until evolution of SO2 could no longer be detected; shallow clay dishes ordinarily were used; but calcines 2a and 2c were prepared in iron dishes, with the result that these two calcines were badly contaminated with iron scale. The "complex" concentrate, sample 1, consisted essentially of sphalerite grains containing inclusions of pyrite and other sulphide minerals too minute to be liberated by grinding within economic limits. In the " marmatitic" concentrate, sample 2, the iron was present largely as marmatite (that is, as iron sulphide in solid solution in zinc sulphide) rather than as pyrite inclusions. The zinc was present largely as the carbonate in the two "oxidized" ores, samples 3 and 4, and as the silicate in the "willemite" ore, sample 5. Leaching Tests The leaching cell was a 3-liter glass beaker placed in an electrically heated water bath manually controlled to maintain a temperature of 35°C in the leach slurry. The slurry was agitated by means of a flat paddle-type stirrer

Jan 1, 1950

By Elliot Rexford

The quality of aggregate materials is of major importance in governing durability and permanence of concrete structures. The problem of selecting suitable aggregate materials is two-fold. Geological factors include the type and character of the aggregate source, presence of known or suspected reactive constituents, and presence of thermally incompatible materials. Laboratory investigations include petrographic studies, soundness and reactivity tests, and tests of thermal properties. The importance of each factor in the selection of satisfactory aggregate material is considered in detail.

Jan 3, 1950