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By D. G. Swarthout, J. W. Savage, R. W. Guard

The Nb-N constitution diagvam has been examined from 1100° to 1450°C at 1 atm N2 pressure. On the basis of- our work plus that of Brauer and coworkers the stable nitvide Phases are: a) a solid solutlion, basic niobium (bcc) with nitrogen contained interstitially; NbN,, x = <0.40; b) ß NhNx,x = 0.39 to 0.45; hexagonal (W2C type) (NbzN); a =3.058A,c = 4.961 + 0.001A c) y NbNx x = 0.75 to 0.80; tetragonal (distorted NaCl type) (Nb4N3); a = 4.386A,c = 4.332 + 0.001A; d) 6 NbN,, x = 0.88 to 0.91; cubic (NaCl type); a = 4.3885 + 0.0007A; e) E NbNx x = 0.92 to 1.00; hexagonal (Tip type); a = 2.958A, c = 11.272 * 0.0015A. In addition, a metastuble transition phase 6&apos; has been observed and occurs only during the transition 6 — E. 6&apos; NbN has these distinguishing parameters: NbNx,x = 0.96; hexagonal (anti-NiAs type); a = 2.94A, c = 5 .46A. The high-temperature phase fields in the system are governed by two reactions: a) 6 + Y + E, a entectoid reaction occurring at 1270" ± 20° C; b) o + N2 = E, a 2 012 1 reaction occurring at 1370" ± 20° C. As part of a study of the electronic low-temperature. properties of transition metal nitrides, a number of specimens of niobium nitride were prepared. Preliminary observations on these specimens showed several points of disagreement with data already in the literature. It was, therefore, decided to determine the constitution diagram for the Nb-N system between 1100" and 1450°C. The objective of this research was to define the temperature and composition regions of stability of the various phases and to explain the differences among previously proposed diagrams. Review of Previous Literature. The research on the Nb-N system to 1964 has been summarized by storms.&apos; Although he does not present a phase diagram, his review covers the research on the system thoroughly. One of the earliest works on NbN is that of Ascher-mann and coworkers2 who studied the superconductivity of the cubic 6 NbN. Subsequent work by Horn and ziegler,3 Cook, Zemansky, and Boorse,1 Rögener:5 Schroder6 and sellmaier7 has qualitatively confirmed the first results on superconductivity, although their methods of preparation differed considerably. The constitution diagrams proposed for the system by Brauer and Esselborn8 and Elliott9 are shown in Fig. l(a)and (b). The diagram in l(a) has been modified by more recent results in Brauer&apos;s laboratory (private communication). Although 6&apos; is shown on this diagram, Brauer has indicated that he now believes 6&apos; to be a metastable phase in the temperature range shown. The diagram of Elliott, Fig. l(b), is based primarily on the results of Elliott and Komjathy10 on ni-trided niobium strip or rod specimens examined by X-ray diffraction and metallography. It will be noted that these proposed diagrams are in conflict with respect to the temperature and composition ranges of

Jan 1, 1968

By Kurt Kennedy

A method is described by which three elements can be condensed simirltaneously on a common substrate in such a way that the composition varies with position on the substrate. Almost all possible combinations of three solid elements can be formed in a single evaporation. The three elements are heated by magnetically deflected electron beams. The alloys and cornpounds formed by this method generally correspond to those trade by other methods; however, many exceptions exist. Simple symmetric crystallographic phases tend to form in preference to more complex phases. The Nb-Sn. Cr-Fe-Nt, and other systems of alloys made by this method will be discussed. Phases that form very slowly, such as the o phase in Cr-Fe alloys, may be formed rapidly by this method when certain substrate temperatures are used. STUDYING all the mixtures and compounds of two or more elements by the preparation of individual samples forces the investigator to make sampling sufficiently close together so that the properties of the intermediate compositions can be inferred. A completely unknown system will require a dis c our aging ly large number of preparations in order to fully know all its properties. For the purpose of expediting this type of investigation, methods have been devised to prepare samples that have a continuous variation in composition over some predefined area. The code-position of two elements onto suitable substrates has been used to produce alloys or compounds that have variable compositions depending on their positions on the substrates Composition gradients have been formed by depositing a wedge-shaped layer of one element and then depositing a second wedge-shaped layer on top of it such that the total film thickness is kept constant. Concentration equilibrium perpendicular to the surface is then established by annealing.4 This paper describes a method for the simultaneous condensation of three volatile components on a substrate such that there is a regular variation of composition with position on the substrate. The arrangement of the evaporation sources and the substrate is shown schematically in Fig. 1. Materials to be evaporated are placed in three water-cooled crucibles located at the corners of a 10-in. equilateral triangle. Electron beams from cathodes located below the crucibles are bent 180 deg by magnetic fields and focused on the material to be evaporated. The cathodes are connected in parallel to a constant-current 12-kv power supply. The distribution of emission current from each cathode is controlled by filament temperature. When materials that sublime are to be evaporated, the electron beam is deflected by an auxiliary ac magnetic field so that the beam moves over the surface of the evaporating material rather than digging a hole in one spot. The substrate is a 10-in. triangle of 2-mil stainless steel or molybdenum which is stretched against a slightly curved heat sink by a frame as shown in Fig. 2. This frame and heat sink are located so that each corner is directly above an evaporation source. The heat sink has three radiant heaters at each corner that can be separately controlled permitting the

Jan 1, 1967

By George C. Fryburg

The oxidation of platinum at high temperatures (above 800°C) is controlled by boundary-layer diffusion, except at the lowest pressures. The rate of oxidation is determined by the rate of diffusion of oxide through the boundary layer away from the platinum. This is in contrast to the situation in tungsten and molybdenum oxidation, where the rate is controlled largely by the diffusion of oxygen through the boundary layer towards the metal. The difference in mechanism is a consequence of the much lower rate of oxidation of platinum. Evidence is presented that supports this mechanism for the oxidation of platinum. SOME years ago we reported1 a study of the oxidation of platinum in ordinary oxygen in the temperature region above 800°C, where the oxide is volatile. All the data available up to that time had been obtained with platinum crucibles or plates heated in tube furnaces. The results were widely variant and highly dependent on the flow rate of gas through the furnace: the faster the gas flow rate, the higher the measured oxidation rate. These results indicated to us2 that reaction equilibrium was being approached in the furnace and that the rate was diffusion limited. To minimize these effects, we employed1 electrically heated ribbons placed in a cooled bulb. We were primarily interested in the low-pressure region, but some experiments were performed at pressures up to 1 atm. We found a peculiar pressure dependency which was explained on the basis that the rate of oxidation was proportional to the pressure at all pressures, but that with increasing pressure an increasing fraction of the volatilizing oxide was back-reflected to the ribbon by the surrounding gas molecules. The oxide molecules are not stable at the temperature of the platinum and are decomposed on impact, the platinum being re-deposited on the specimen. Because of the limitations of space, this explanation was offered summarily without detailed support. Recently, Jaffee and associates3, 4 have suggested that the pressure dependency of our data up to 0.5 torr could be explained on the basis of a Langmuir-type adsorption of molecular oxygen followed by dissociation. Since the correct explanation of the effect of pressure on the oxidation rate is a necessary requirement to the development of the basic mechanism of the oxidation reaction, we felt that the back-reflection theory should be presented in more detail. This is the object of the present paper. RESULTS AND DISCUSSION A typical set of results showing the pressure dependency of the oxidation reaction is presented in Fig. 1, where we have plotted, on logarithmic scales, the rate of oxidation, R, vs the pressure, p. For comparison some results of Krier and Jaffee4 and of Raub and plate5 are also shown. These data were taken at atmospheric pressure using furnaces. The effect of reaction equilibrium within the furnace is apparent from the much smaller values that these observers obtained: Raub and Plate In O2 found a rate of 3.1 µg cm-2 hr-1 compared to our value of

Jan 1, 1965

By Robert S. Dewey

More wells were drilled in West Texas† during 1944 than in any year since 1941. As compared with 1943, there was an 82.5 per cent increase in the total number of completed wells. The 1646 wells required an estimated 140,715 days to complete for a total of 7,632,249 ft. An average of 85 completion days was required to drill to an average of 4630 ft. This depth is approximately 100 ft. greater than that of the previous year. It is estimated that $100,000,000 was invested in drilled wells. As of Dec. 31, 1944, there were 270 field and 91 wildcat wells being drilled. While an identical number of wells were drilling Dec. 31, 1943, the proportion of wildcats increased in 1944 from 19.7 to 25.2 per cent. During 1944, oil wells were completed in 103 of the 164 fields in West Texas. Of the 1361 oil wells, 385 were in Slaughter, 116 in Fullerton, 63 in North Cowden, 62 in Fuhrman-Mascho, 59 in Wasson, 52 in Westbrook and 47 in North Ward. Approximately 22 per cent of the wildcat drilling was to pre-Permian formations. Despite the increasing proportion of wildcat wells drilled, the wildcat discovery rate has declined since the year 1942. AS compared with 1943, the number of wildcat wells drilled increased from 11.7 to 12.7 per cent and the footage in wildcat exploration increased from 13.3 to 13.8 per cent of the total. The monthly production of crude continued to increase to a peak of 15,336,000 bbl. in October 1944. As compared with a similar peak production in October 1943, there was a 37.3 per cent increase. The yearly production increased from 98,165,-ooo bbl. in 1943 to 159,943,000 bbl. in 1944, an increase of 62.8 per cent. Based upon an assumed average price of $1.00 per barrel and less 1/8 royalty, the gross return to the producer amounts to $140, 000,000. From 1943 to 1944, the average number of producing wells increased 6 per cent while the average daily production per well increased 53.1 per cent. The average daily production per well increased from 17.5 bbl. in 1943 to 26.8 bbl. in 1944. The proportion of flowing wells decreased from 50.5 per cent in January to 49.1 per cent in December 1944. Drilling With the continued shortage of labor and materials, drilling costs have risen sharply. Just how much is difficult to ascertain. Owing to competition for available drilling rigs, contractors are reluctant to assume drilling risks. In consequence, some contracts are let on a cost plus basis, or day work below some specified depth with the operator furnishing part of the consumable materials, such as mud and drilling bits. Contractors are having difficulty in maintaining full and effective drilling crews with insufficient and inexperienced labor. Service companies have inadequate labor and equipment to meet their appointments promptly. Pipe Lines The Gulf Pipe Line Co. increased the capacity of its 10-in. main line by filling in gaps amounting to 75 miles on the loops between Judkins and Weatherford, Texas.

Jan 1, 1945

By M. Herman, G. J. London

A series of dilute Fe-Co alloy specimens were prepared from zone-melted iron. The iron used was given ten floating-zone passes in purified hydrogen. Alloying was accomplished by plating a gradient of metallic cobalt onto a 1/4-in.-diam bar of material from a pure plating bath. The deposit was radioac-tively tagged by a small addition of co80 to the plating bath. Alloy homogenization was accomplished by passing an additional floating-zone pass through the plated section of the bar. The final concentration gradient achieved was from residual to about 1000 ppm (0.1 pct) added Co. After homogenization, the bar was swaged to 0.057 in. wire and cut to tensile specimen blanks 1-1/16 in. long. Each specimen was counted in a well-type scintillation counter. The concentration of cobalt was computed by combining the normalized specimen counting rate with the known weight (measured to the nearest 0.01 mg) of cobalt added during plating. Fig. 1 shows the cobalt gradient obtained, exclusive of residual cobalt which was estimated by neutron-activation analysis to be approximately 50 ppm. Results of recrystallization for 1 hr at 750°, 700°, 650°, and 600°C with specimens containing 40, 170, 470, and 870 ppm added Co are shown in Figs. 2, 3, 4, and 5. Recrystallization was accomplished in a dynamic vacuum of less than 1 x 10 torr. The specimens were mounted and polished parallel to the swaging direction. The recrystallization re- sults show a radical coarsening of structure with increasing cobalt concentration. The coarsest structure obtained was at the 470-ppm level (at all recrystallization temperatures) with a slight grain refinement at the 870-ppm level shown. A more normal solid-solution effect is seen in Fig. 5 (60OoC, 1 hr) where the only specimen completely recrystallized is the one containing 47 ppm Co. Since the possibility existed that some atmosphere-contamination phenomenon might be responsible for the observed results the recrystallization series was repeated using sealed quartz capsules. These were filled with purified argon which was gettered during heat treatment on metallic titanium included in the capsules. The results obtained were essentially the same as shown. Another identical alloy was made using a 5-mm-diam bar of Westinghouse Puron. Specimen preparation and recrystallization treatment were also as described. The results obtained (see Table I) were somewhat erratic. Some coarsening in structure does appear at the highest cobalt concentrations. There is no apparent relationship between the coarse, columnar, directionally solidified structure of the as-melted bars and any of the recrystallized grain structures observed, all of which are much finer than the former structure. A recrystallization process can be most simply described as one of homogeneous nucleation of recrystallized grains in a cold-worked matrix followed by more or less uniform growth of the strain free grain into the cold-worked material.&apos; An impurity element may influence one or both of these processes. Aust and utter&apos; have shown that impurities strongly influence grain boundary mobility in lead. Moreover, definite recrystallization textures are produced by small concentrations of tin,3 while additions of silver or gold4 produce large boundary in-

Jan 1, 1964

By J. S. Fulton

Those who live in steel-mill towns are so accustomed to the sight of flames spouting from the mouth of a Bessemer vessel that they seldom pause to think of the amazing process behind it. Actually cold air is being blown through a hot liquid and, instead of cooling it, raises the temperature of the liquid. When coffee is too hot to drink, we know that blowing on it will cool it, so it was no wonder that when Henry Bessemer (or William Kelly, as your patriotism chooses) first proposed this cycle of steel production, he was considered mad. When Bessemer and Kelly started their investigations around 1852, there was not much practical knowledge of metallurgy and, in consequence, there was wide variation in the product made by their process. It was appreciated that the silicon, carbon and iron were all potential fuels, but not until Mushet discovered the beneficial effects of having manganese in the pig iron did the process really become commercial. Bessemer&apos;s patent of 1855 covered a crucibleful of liquid iron into which a refractory tuyere was lowered and the blow started. Since that time virtually every conceivable form of vessel, bottom arrangemerit, tuyere size and location have been suggested or tried. There have been stationary vessels with fixed bottoms, that were side, top or bottom blown; tilting vessels with two sets of side tuyeres at different elevations; vessels like a three-compartmerit septic tank; vessels of a cylindrical form supported on the long axis with tuyeres along the side submerged by a partial rotation of the vessel (this type continues in copper refineries); portable vessels to make the blow in a ladle over a mold in a foundry; a combination of a cupola and converter in one shell, and various other arrangements. But in all these experiments, compressed air for the blast was presupposed and there was little discussion of the quantity or quality of the air delivered to the tuyeres. At one time or another various practices that now are forgotten have been tried or suggested: for instance, the use of inert gas at the end of the blow; the addition of fuel to the blast; the use of hot-blast stoves; the drying of the air to a minimum moisture in the blast. Except in the last-named method little attention was paid to the quality or quantity of the air blown. Phases Of the many Papers published On various phases of the Bessemer process, nearly &apos;7&apos; according to one bibliography, Over go per &apos;ent were concerned with the metallurgical phase and less than &apos;0 per cent discussed various sections of the pneumatic phase. Since the two phases are coincidental, apparently nine times as much thought has been given to the result as has been given to One of the causes of the Bessemer process. IS it not possible that if more attention had been paid to the pneumatics so many papers would not have had to be written on the troubles in the metallurgical phase? A study of published papers and conversation

Jan 1, 1941

By E. B. Hughes, F. G. Norris

Oxidation is characteristic of all processes for making steel from pig iron. This thought has been aptly expressed by H. W. Graham13 in the recent Howe Memorial Lecture, "The process of steel-making consists of using iron oxide to reduce the carbon content of the pig iron to the desired level." Direct oxidation refers to the reaction that results from introducing oxygen either alone or mixed with other gases directly into the steel bath. In working a heat, oxygen in some form is added to the steel to remove the undesirable constituents as oxides. There are two general methods of supplying this oxygen to the open hearth bath. The method in which the oxygen is added as a compound such as Con or iron ore is designated an indirect method because the steel bath must first decompose the compound to attain oxygen in a usable form. The other method in which oxygen is added to the bath in the elemental or gaseous form, more or less diluted by other gases such as nitrogen, is a direct method because no decomposition is necessary before the oxygen reacts with iron to form FeO which is dissolved in the bath in a usable form. Bubble formation (at least of a macroscopic size) presents no problem in case of direct oxidation because the reacting agent (oxygen) is in the form of bubbles when entering the metal. Regardless of whether oxygen is intro- duced into the bath directly or indirectly, several reactions proceed concurrently. In the presence of the bath of molten iron, FeO is formed either by oxidation of iron by oxygen or reduction of oxides by iron. This FeO dissolved in the molten iron is the source of oxygen for the oxidation of manganese, carbon, silicon, and phosphorus if these are present. The oxidation of carbon from steel is the controlling steelmaking reaction. The introduction of oxygen into the bath, its reaction in the elimination of impurities, and its control by the use of de-oxidizing additions have been subjects of importance since steel was first made by the bessemer process. Direct oxidation is, in a sense, an application of the bessemer principle to the open hearth process. Graham13 states: "The use of oxygen or air jets introduced into the metal bath is essentially an effort to approach in the open hearth the turbulence, rapid interface reaction, and high production rate per hour that exists in the bessemer process." The general subject, "Oxygen in Steel-making," was given new life by the studies of Herty and associates starting about1925. The current interest in elemental oxygen is intimately related to the large scale production of oxygen developed during the war period. Some of the first applications were made during the early summer of 1946 at the Steel Co. of Canada using oxygen with the fuel. Such a use is of considerable interest and importance in contributing to faster heats but is not the subject of the present discussion which deals entirely with the introduction of elemental oxygen directly into the open hearth bath.

Jan 1, 1949

By E. B. Hughes, F. G. Norris

Oxidation is characteristic of all processes for making steel from pig iron. This thought has been aptly expressed by H. W. Graham13 in the recent Howe Memorial Lecture, "The process of steel-making consists of using iron oxide to reduce the carbon content of the pig iron to the desired level." Direct oxidation refers to the reaction that results from introducing oxygen either alone or mixed with other gases directly into the steel bath. In working a heat, oxygen in some form is added to the steel to remove the undesirable constituents as oxides. There are two general methods of supplying this oxygen to the open hearth bath. The method in which the oxygen is added as a compound such as Con or iron ore is designated an indirect method because the steel bath must first decompose the compound to attain oxygen in a usable form. The other method in which oxygen is added to the bath in the elemental or gaseous form, more or less diluted by other gases such as nitrogen, is a direct method because no decomposition is necessary before the oxygen reacts with iron to form FeO which is dissolved in the bath in a usable form. Bubble formation (at least of a macroscopic size) presents no problem in case of direct oxidation because the reacting agent (oxygen) is in the form of bubbles when entering the metal. Regardless of whether oxygen is intro- duced into the bath directly or indirectly, several reactions proceed concurrently. In the presence of the bath of molten iron, FeO is formed either by oxidation of iron by oxygen or reduction of oxides by iron. This FeO dissolved in the molten iron is the source of oxygen for the oxidation of manganese, carbon, silicon, and phosphorus if these are present. The oxidation of carbon from steel is the controlling steelmaking reaction. The introduction of oxygen into the bath, its reaction in the elimination of impurities, and its control by the use of de-oxidizing additions have been subjects of importance since steel was first made by the bessemer process. Direct oxidation is, in a sense, an application of the bessemer principle to the open hearth process. Graham13 states: "The use of oxygen or air jets introduced into the metal bath is essentially an effort to approach in the open hearth the turbulence, rapid interface reaction, and high production rate per hour that exists in the bessemer process." The general subject, "Oxygen in Steel-making," was given new life by the studies of Herty and associates starting about1925. The current interest in elemental oxygen is intimately related to the large scale production of oxygen developed during the war period. Some of the first applications were made during the early summer of 1946 at the Steel Co. of Canada using oxygen with the fuel. Such a use is of considerable interest and importance in contributing to faster heats but is not the subject of the present discussion which deals entirely with the introduction of elemental oxygen directly into the open hearth bath.

Jan 1, 1949

By John G. Tate, George W. Nicolson, James L. Bruce

FOR more than 25 years modern mining has been carried on in the Island of Cyprus, Mediterranean Sea, by the Cyprus Mines Corp. of Los Angeles, Calif. The general features of these operations have been described.1 From 1935 to June 30, 1940, top slicing in the Mavrovouni mine produced in excess of 2,000,000 long tons. The rate for the last part of this period was approximately 50,000 tons per month. DESCRIPTION OF ORE BODIES The shape of the ore body now being top sliced in the Mavrovouni mine is an inclined irregular pyritic pipe or chimney of large dimensions, extending from unknown depths below the bottom level at elevation 250 ft below sea level, to the highest level at elevation 400 ft above sea level. The present surface above the ore body lies between 550 and 650 ft elevation. Undoubtedly the ore body extended to surface and was mined by the ancients by opencast and underground methods. The old pits were gradually filled up by erosion until now they show as slight depressions in the topography. The largest area of the ore body is at elevation 170 ft below sea level, where the horizontal section is almost elliptical, with a width of 600 ft and a length of 1000 ft. Below this elevation the shape of the ore body continues to be elliptical but with reduced dimensions. Above this elevation it rises flatly towards the south with a substantial depression in the upperside of the chimney and irregular ridges or wings rising on each side. It gradually grows smaller as it rises. The ore body is a pyritic replacement of andesitic extrusives which occur as flows and pillow lavas. With the exception of the upper portions of one or two small offshoots rising from the main ore body, all ore is completely surrounded by andesite. Most of the andesite lying above the ore body is covered by marl and clay sedimentaries of Miocene and later age. The Miocene is presumed to be older than the ore mineralization. That portion of the andesites which lies between the sedimentaries and the ore body has been broken by slumpage, and weathered, and iron-stained by the descending meteoric waters. It is a mass of crushed material that caves and follows downward readily as the top-slice stopes retreat. The main ore body is a heavy cupreous pyrites mass assaying on the average about 4.0 pct Cu; 48.0, S; and 42.0, Fe. In places the copper drops below 1.0 pct. On the borders of this heavy sulphide ore body lie disseminated cupreous pyrites ore deposits of large dimensions. Some portions of these appear to be closely related to the heavy sulphide ore, as the ratio of copper to pyrite is about the same. The greater part of the disseminated ore, most of which lies immediately to the east of the main ore body, contains less than 0.10 pct Cu and about 25.0 to 30.0 pct S. This probably can

Jan 1, 1947

By J. W. Matousek, C. S. Samis

me thermodynamic properties of the components in the Cu-Ni-S ternary system have been studied by measuring the H2S/H2 ratios in a gas phase equilibrated with the molten matte at 1200°C. The measured sulficr potentials have been extended by extrapolation and combtned with previously published data to permit the thermodynamic analysis of the ternary system by integration techniques. A simplifying assumption of ideality in the Ni3Sz-CuS pseudobinary has been made. SINCE copper and nickel metals were first extracted from their sulfide ores the interaction between the two metals and sulfur has been of industrial and theoretical interest. The processes developed to extract copper and nickel have been reported periodically in the literature. The theoretical studies on the Cu-Ni-S ternary have been restricted to problems directly associated with production. It is only within recent years that the binary systems related to this ternary have been analyzed thermodynamically and mathematical devices developed to permit a corresponding treatment of the ternary system. In 1910 an investigation of the role of nickel in Cu-Ni-Fe-S mattes was reported,&apos; It was concluded from this work that nickel is not an element replacing iron in mattes, but rather that Cu-Ni alloys behave as a single metal during the matte converting operation. The laws which govern the converting of Cu-Ni alloys were found to be the same laws as those that govern the conventional converting of copper alone. Although considerable information has been reported on the theoretical aspects of copper smelting, little data is available on the smelting of Cu-Ni ores except for phase diagrams and process descriptions. The available information on the Cu-Fe-S ternary and related systems prior to 1953 has been summarized by Ruddle.2 Since Ruddle&apos;s publication, Rosenqvist and coworkers have completed phase equilibria investigations of the Fe-S, Co-S, and Ni-S binaries,3 the Fe-S-O ternary,4 and the Cu-Fe-S-O quaternary.4 An extensive investigation of the Cu-Fe-S ternary system at smelting temperatures has been made by Krivsky and Schuhmann.5 At these temperatures, the Cu-Fe-S system is very similar to the Cu-Ni-S ternary with respect to the location of the single-phase and two-phase liquid matte regions. In the former, however, the area of immiscibility is more extensive and the region of liquid matte-liquid metal-solid metal equilibria is much more extensive. Krivsky and Schumann observed that the Cu2S-FeS pseudobinary system is, for practical purposes, an ideal mixture. This investigation has served as a valuable guide in analyzing the Cu-Ni-S ternary. EXPERIMENTAL The experimental procedure employed in this investigation was the conventional technique of equilibration of the sulfide matte with gaseous mixtures of hydrogen and hydrogen sulfide at 1200°C. The thermodynamic properties of sulfur (S2) in the gas phase are determined by means of Eq. [I] and the activity of sulfur in the matte by Eq. [2].

Jan 1, 1963

By J. Gurland

The wmk is concerned with the estimate of the degee of continuity of a particulate phase dispersed in a matrix. The first section is a verieu: of the parameters nzeasurable by quantitative rnetallogvaphy, namely the contact area and, under certain conditions, the number of contacts between particles of one phase. In the second section, the frequency of particle contacts is related to the degee of continuity of a randomly embedded phase orz the basis of the lattice-percolation model of Hamrnersley and others. THE extent of continuity of the constituent phases may greatly influence the structure-sensitive properties of phase mixtures, particularly if the phase properties differ significantly. An example from the literature1 is shown in Fig. 1. The marked decrease of the electrical resistivity of sintered silver-alumina bodies near 25 pct by volume of silver presumably occurs because the more conductive phase changes from a discontinuous to a continuous structure. Other example of electrical- and thermal-conductivity transitions are cited by kingery In view of these observations, a knowledge and understanding of the connectivity of the microstructure may be of considerable practical importance. This study is concerned with one aspect of the genera1 problem, namely the estimate of the degree of continuity of a particulate phase dispersed in an opaque matrix. The first section reviews the parameters measurable on a polished cross section by auantitative metallography, such as the contact area and under certain conditions, the number of contacts between particles of one phase. In the second section, an attempt is made to relate the frequency of particle contacts to the degree of continuity of a randomly embedded phase. For the purpose of this discussion, the aggregate has two constituents: the particulate phase and the matrix. The latter is considered to be homogeneous. The term "particle" is used with the meaning of "grain", i.e., a minute unit of matter which is usually a single crystal of a readily distinguishable substance within the confines of a simply connected boundary. While many of the concepts which are used here to describe the structural variables characterizing the microstructure of phase mixtures are qualitative and ill-defined, they are presented with the intent of stimulating further work of a more general and rigorous nature. I) PARTICLE CONTACT, CONTIGUITY, AND MEAN FREE PATH 1) Measurement of Contiguity. The fraction of the total internal surface of a phase a shared with particles of that same phase in a two-phase mixture of and $ is indicated by the contiguity ratio:3 whereis the area of the interface between o particles, and Sap is the area of the interface between a particles and matrix P, per unit volume of mixture. The contiguity ratio ranges from 0 to 1 as the distribution of the a phase changes from a completely dispersed to a completely agglomerated structure. The interfacial areas may be obtained from simple intercept measurements on a random plane, after Smith and Guttman where and N are the numbers of intercepts between a random line of unit length on a plane of polish and the interparticle and interphase interfaces, respectively. The equations are valid for any distribution of particle sizes and shapes.

Jan 1, 1967

By John G. Tate, George W. Nicolson, James L. Bruce

For more than 25 years modern mining has been carried on in the Island of Cyprus, Mediterranean Sea, by the Cyprus Mines Corp. of Los Angeles, Calif. The general features of these operations have been described.&apos; From 1935 to June 30, 1940, top slicing in the Mavrovouni mine produced in excess of 2,000,000 long tons. The rate for the last part of this period was approximately 50,000 tons per month. Description of Ore Bodies The shape Of the Ore body now being top sliced in the Mavrovouni mine is an inclined irregular pyritic pipe or chimney of large dimensions) extending from unknown depths below the bottom level at elevation 250 ft below sea level) to the highest level at elevation 400 ft above sea level. The present surface above the ore body lies between 550 and 650 ft elevation. Undoubtedly the Ore body extended to surface and was Mined by the ancients by opencast and underground methods. The old pits were gradually filled up by erosion until now they show as slight depressions in the topography. The largest area of the Ore body is at elevation 170 ft below sea level, where the horizontal section is almost elliptical, with a width of 600 ft and a length of 1000 ft. Below this elevation the shape of the ore body continues to be elliptical but with reduced dimensions. Above this elevation it rises flatly towards the south with a substantial depression in the upper-side of the chimney and irregular ridges or wings rising on each side. It gradually grows smaller as it rises. The ore body is a pyritic replacement of andesitic extrusives which occur as flows and pillow lavas. With the exception of the upper portions of one or two small offshoots rising from the main ore body, all ore is completely surrounded by andesite. Most of the andesite lying above the ore body is covered by marl and Clay sedimentaries of Miocene and later age, The Miocene is presumed to be older than the ore mineralization. That portion of the andesites which lies between the sedimentaries and the ore body has been broken by slumpage, and weathered, and iron-Stained by the descending meteoric waters, It is a mass of crushed material that caves and follows downward readily as the top-slice stopes retreat. The main ore body is a heavy cupreous pyrites mass assaying on the average about 4.0 pet Cu; 48.0, S; and 42.0, Fe. In places the copper drops below 1.0 pet. on the borders of this heavy sulphide ore body lie disseminated cupreous pyrites ore deposits of large dimensions. some portions of these appear to be closely related to the heavy sulphide ore, as the ratio of copper to pyrite is about the same. The greater part of the disseminated ore, most of which lies immediately to the east of the main Ore body, contains less than 0.10 pct Cu and about 25.0 to 30.0 pct S. &apos;This probably can

Jan 1, 1949

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

The a-p type alloys are subject to a loss of tensile ductility with increasing hydrogen content. No hydride phase is visible in embrittled a-B type alloys. The embrittlement encountered appeared to be of the strain-aging type. Both compositional and structural factors are shown to influence the hydrogen tolerance of a-B type alloys. IN previous papers by the authors, the effects of hydrogen on the structure and mechanical properties of high-purity and commercial-purity titanium were described. It was shown that the presence of hydrogen in these materials results in a hydride phase having low solubility at room temperature. This insoluble phase had little effect on the room temperature tensile properties, but did decrease the notch-bar toughness to a large degree. The binary Ti-H systemz indicates that hydrogen is much more soluble in £ than in a-titanium. Hence, it is not expected that the embrittling effects of hydrogen in a-fi alloys will be similar to that found in a alloys. Materials of this type studied in the present investigation included two commercial a-/3 alloys, Ti-8Mn and Ti-4A1-4Mn; three high-purity Ti-Mn alloys containing 3, 6, and 9 pct Mn; and four high-purity Ti-Mo alloys, Ti-SMo, Ti-10.9M0, Ti-13.1 M0, and Ti-20M0, of the a-B and B types. Materials and Fabrication—The high-purity base alloys, composed of iodide titanium and high-purity metals, were prepared by double arc melting under argon in a water-cooled copper crucible, using a water-cooled tungsten electrode. Radiographic examination showed homogeneous Ti-Mo alloys. The analyses of the alloys used in this investigation and their as-fabricated hydrogen content, where determined, are listed in Table I. The two commercial alloys were 1/2 and % in. diam bar stock. No analyses other than hydrogen content were made. In order to maintain the a-B relationship existing in the two commercial alloys, vacuum annealing and hydrogenation were carried out in the B field prior to final fabrication. Fabrication then was done by The three high-purity Ti-Mn alloys were forged to 3/4 in. diam rods at 1600°F, and hot swaged to 1/2 in. diam at 1380°F. Machined and degreased bar stock was vacuum annealed or hydrogenated, fabricated to 1/8 in. diam rod by hot swaging, annealed in argon for 1 hr at 1380°F !75O°C), and water quenched. The six yz lb Ti-Mo ingots were forged to Wi in. diam rods at 1600°F and then hot swaged to % in. diam. Machined and degreased specimens were vacuum annealed or hydrogenated in the /3 field, prior to fabrication, by swaging to Y4 in. rod at 1400°F. After fabrication, the 5 and 10.9 pct Mo alloys were annealed in argon for 16 hr at 1290°F and water quenched to give equiaxed a-B structures. The higher molybdenum content alloys were argon annealed 4 hr at 1470°F and water quenched to give all £ structures.

Jan 1, 1957

By D. Geoffry Minnes, Ray Blair, Stanley J. LeFond

Nepheline syenite is a silica deficient crystal-line rock consisting of albite and microcline feldspars and nepheline, together with varying but small amounts of mafic silicates and other accessory minerals. Nepheline-bearing rocks are widely distributed around the world but only in Canada, Norway, the Union of Soviet Socialist Republics, and the United States are deposits worked commercially, Because of its low melting point and fluxing ability, nepheline syenite was investigated in the early 1900s by many students of glass and ceramics. Although the nepheline syenite deposits in Methuen Township, Ont., Canada, were discovered as early as 1897 it wasn&apos;t until 1935 that the first mill was erected to produce nepheline syenite products. In Canada, nepheline syenite deposits are worked by Indusmin Ltd. and International Minerals and Chemical Corp. (Canada) Ltd. who have combined production capacity in excess of 1800 stpd. Between 1935 and 1972 seven million tons valued at $78 million were produced from the Methuen Township deposits. In Norway, the Norsk Nefelin Div. of Elkem Spigerverket has produced nepheline syenite from a deposit on Stjernöy Island in western Finland since early 1960. Production has increased from 8 kt in 1961 to over 200 kt in 1980. Nepheline syenite has been under investigation in the Union of Soviet Socialist Republics (USSR) since at least 1928. In 1951 the first commercial alumina works was brought on stream at Volkhov, near Leningrad, utilizing nepheline concentrates from the Kola peninsula as mill feed. Since then two others have been completed and more are planned. Large quantities of portland cement, sodium carbonate, and potassium carbonate are produced in conjunction with the alumina. A material called nepheline syenite, but actually a pulaskite, is produced in Pulaski County, Arkansas, by the McGeorge Construction Co. for construction aggregates and by the 3M Co. for roofing granules. The Dome Fill Co. purchases the fines and uses them in the preparation of enclosed construction fill. Production is over 2,000,000 stpy. Chap. 16 on "Feldspar, Nepheline Syenite, and Aplite" in the 3rd ed. of Industrial Minerals and Rocks (Castle and Gillson, 1960) and Nepheline Syenite Deposits of Southern Ontario (Hewitt, 1960) contain excellent accounts of earlier commercial development of nepheline syenite as a glass and ceramic material. As in the 4th ed., this chapter deals mostly with the period since 1960 and with matters not previously reported in detail. An English monograph on Nepheline-Syenite and Phonolite (Allen et al., 1968) is a complete survey, at the time, of nepheline syenite which, with its very complete list of references, is an excellent source book. End Uses Nepheline syenite from the Canadian and Norwegian producers finds use primarily in the manufacture of glass and ceramics. One producer also makes several grades of nephellne syenite that are useful as extender pigments and fillers in paint, plastics, and rubber. In the Soviet Union nepheline is used in increasing quantities in the manufacture of alumina, alkali carbonates, and portland cement and to a lesser degree it is used in the manufacture of colored container glass.

Jan 1, 1983

By F. F. Aplan, P. H. de Bruyn

The adsorption density of hexyl mercaptan was measured at the gold-solution and the gold-vapor interfaces. This collector is strongly adsorbed at low concentrations, a monomolecular layer being formed at the gold-solution interface at concentrations as low as 2 x 10&apos;6 moles per liter. A maximum contact angle of 83 ± 3° is observed. From a thermodynamic analysis of the experimental data the changes in surface tension at the gold-gas and gold-solution interface are calculated. The data also suggest that the adsorption density of mercaptan at the gold-gas interface exceeds that at the gold-solution interface. In the equilibrium state, a simple flotation system consists of three phases, the solid to be floated, air, and an aqueous solution in stable contact along a line. During the process leading to this final state, a solid-gas interface is created at the expense of a portion of the liquid-gas and solid-liquid interfaces. This change of state is achieved by addition of a collector and, if necessary, suitable modifying agents to the system. By a combined application of the Gibbs Adsorption and the Young Equations, de Bruyn, Overbeek and Schuhmannl were able to show theoretically that the equilibrium distribution of the collector at all three interfaces determines the magnitude of the contact angle. Their analysis led them to conclude that the equilibrium adsorption density of the collector at the solid-gas interface exceeds its density at the solid- liquid interface. This paper succeeded in focussing attention on the neglected role of the solid-gas interface in flotation. In recent years the application of radiotracer, infrared, electrochemical and electro-kinetic techniques to studies of the solid-liquid interface2-5 enhanced our understanding of adsorption processes at this interface. Except for the measurement of contact angles, the solid-gas interface received no attention in fundamental flotation studies. In an attempt to apply the analysis of de Bruyn, Overbeek and Schuhmann to a simple flotation system, an investigation of the adsorption of hexyl mercaptan onto gold was undertaken. Gold was chosen as the solid phase in order to keep the number of dissolved chemical species in the solution phase to a minimum. Hexyl mercaptan (1 - hexanethiol) was selected as collector because its relatively high vapor pressure at room temperature makes it possible to obtain adsorption measurements at the solid-gas interface. This flotation system consists, therefore, of a pure solid phase (gold), an aqueous solution of a weakly dissociated collector (1 -hexanethiol), and a gaseous phase, nitrogen saturated with respect to both water vapor and mercaptan vapor. EXPERIMENTAL MATERIALS AND METHODS Materials: Liquid 1-hexanethiol (C6H13SH) was obtained from Distillation Products Industries and was further purified by double distillation. The purity of the final product was established by boiling point and refractive index measurements. For the adsorption studies from aqueous solution, the radiotracer element, sulfur-35, (half life 87.1 days, 0.169 Mev beta ray) was synthesized into the mercaptan by Tracerlab Inc., Boston, Mass. A close boiling fraction of the synthesized compound was used in the adsorption studies. The specific activity of the radioactive compound was 10 millicuries per gram.

Jan 1, 1963

By A. Brown

RAPIDLY rising world demand for mineral products has accelerated depletion of the more readily accessible ores, particularly those of premium grade. Operations must proceed at a faster rate to deeper horizons, where there are problems of ground control that restrict economic recovery of the mineral and introduce new hazards to mine personnel. For some of the new Canadian mining fields severe problems of ground stress are still in the future, but much of Canada&apos;s mineral output comes from well established mines that have reached considerable depths. It must also be anticipated that the depletion of premium grade ores will eventually necessitate mining low grade material at competitive cost, and unsolved problems of ground control can materially increase costs. Studies of ground stress phenomena in underground workings are therefore considered a present-day necessity, especially since these investigations must be a long-term effort owing to the highly complex nature of the problem and the difficulty of making full-scale observations. In recent years the Mines Branch of the Department of Mines and Technical Surveys in Canada has conducted such an investigation. This report of the work is primarily concerned with stress problems in some Canadian coal mines and, in particular, with mine bumps. Mines Branch investigations of this and related problems are carried out by a small team of mining engineers and physicists who, with assistance from geologists, pool their special skills in an integrated program. These Canadian investigations combine a field and laboratory approach. Since data obtained under contrasting mining conditions allow useful comparisons of ground behavior under stress, this article will present data gathered under a wide range of Canadian coal mining conditions. Two contrasting longwalls in eastern Canada will be discussed and two dissimilar pillar extraction operations in western Canada. Locale of Observations In eastern Canada observations are being made in the collieries at Springhill, Nova Scotia. The district&apos;s No. 2 mine, which has a history of bump occurrences dating back to 1917, is currently being worked at a depth of 4200 ft. The mining method is longwall retreating along the strike and the practice is to retreat three walls in line, each about 350 ft long. There is no machine cutting or shooting—the coal is hand-picked and hand-loaded onto face conveyors. There are three rows of hardwood chock block supports parallel to the coal face. These supports are built during the two daily coal loading shifts, and the rear line is withdrawn during the midnight shift. The goaves are partially packed by stone midwalls 12 ft wide which are built forward daily in step with the face advance. The seam dips at 15° and averages 9 ft of strong, well cleated bituminous coal enclosed in competent beds of shales, sandy shales, and sandstones of Carboniferous age. The bumps rarely disturb the retreating longwall faces but manifest themselves as violent upthrusts of pavement in the levels leading to the walls. Observations have also been made in Springhill&apos;s No. 6 mine, which operated in a 5-ft seam of coal at a depth of about 2500 ft. Although No. 6 mine was

Jan 1, 1959

By H. E. Biber

DURING the production of tin plate a thin layer of FeSn2, is formed at the interface between the steel sheet and the protective tin coating. Because excessive amounts of this alloy layer are undesirable, the kinetics of its formation is a subject of interest in the tin-plate industry. A recent study of this subject at our laboratory uncovered a relationship which should be of general interest to anyone studying kinetics of reactions in metallic systems. It had been previously concluded that, at any given temperature in the range 175" to 330°C, the Fe-Sn alloy layer would have a parabolic growth rate.1,2 However, our studies showed that this rule apparently holds only when the tin plate is heated very slowly to the "reaction" temperature; when the tin plate is rapidly heated, considerably different growth rates occur. An example of this effect of heating rate on growth behavior is contained in the accompanying results of alloy-layer growth measurements at 240°C in oil baths stirred at 10,500, 1800, and 0 rpm. The heating curves for these three conditions are given in Fig. 1, and the growth data are presented in Fig. 2. With the rapid heating rate, provided by the stirring at 10,500 rpm, the alloy layer had three distinct stages of growth. In the initial stage, which persisted well beyond the time required to heat the tin plate to bath temperature, the alloy layer formed very rapidly. The growth followed a rate law of the form w = ktn where n > 1. This initial stage was followed by a growth-retardation stage of about 50-sec duration in which little additional alloy was formed. In the third stage the growth again followed a rate law of the form w = ktn, but here « =0.3. With the intermediate heating rate provided by stirring at 1800 rpm, the three-stage nature was less pronounced and the slope of the third stage increased (i.e., n > 0.3). With the slow heating rate provided by the unstirred oil bath, the alloy layer grew in two stages. The initial rapid-growth stage persisted only until the specimen was heated to bath temperature, no growth retardation was observed, and the slope of the main portion of the plotted data was greater than in the stirred baths, having a value of almost 0.5. Similar results were obtained for other bath temperatures in the range 200" to 300°C. This effect of heating rate on growth behavior may be due to changes in the rate of nucleation of FeSn, crystallites. The iron and tin are in contact from the onset of heating. Thus the initial formation of FeSn, occurs not at the "reaction" temperature but rather while the tin plate is being heated to that temperature. Because nucleation is in general temperature-dependent, different heating rates could cause different over-all nucleation rates, which in turn could cause different growth behaviors. A more detailed discussion of the growth of Fe-Sn alloy layer and the effect of heating rate will be published shortly.

Jan 1, 1965

By M. R. TECK, N. Rudd, L. K. Thomas, D. L. Katz

The authors are to be congratulated for presenting the first comprehensive paper on the theory and practice of threshold pressure determination in connection with underground gas storage. It is of particular value since most previous experimental work on this subject has been proprietary to the commercial laboratories engaged in such testing and to their clients. This dlscussion is presented in amplification of the subject paper, not in criticism, and is based upon our experience with approximately 5,000 threshold pressure determinations. Our comments are directed primarily to the experimental procedures as described by Thomas et al. It should be noted that, while clay mineral-rich lithologies are the most common caprock materials, the samples used (Table 1) include low permeability sandstones and carbonates, but do not include shales or other formations in which clav minerals exert a dominant effect. While our experience on samples analogous to those investigated by the authors generally confirms their findings, we have found that even more rigorous experimental conditions must be imposed where clay minerals are the controlling factor. These additional conditions result from the well-known molecular character of the clay minerals themselves in which water is interlaminated with, and bonded to, silicate sheets, thus becoming an essential component of the molecule. In many clay minerals the character of the intersheet bonding, and thus the dimension of the lattice, is strongly affected by variations in the identity and concentration of cations present in the intersilicate water. On a supermolecular scale, adsorbed water films on particle or "flakes" of shale provide much of the cohesive force necessary to maintain mechanical strength. The thickness of these films is variable and inversely proportional to intergranular pressure within the dimensional limits involved in caprock investigation. The thickness of the intersilicate water layers may also be subject to pressure under some conditions. These considerations are reflected in several necessary modifications of the experimental procedures described by the authors. Two of these are, in our judgment and experience, of such importance that they cast real doubt on the validity of data obtained on argillaceous materials without their application. The very careful resaturation procedures proposed by the authors should give good results in connection with the relatively "inert" lithologies used in their experiments. Our experience suggests, however, that they would create more problems than they would eliminate if applied to argillaceous materials. 1. Drying of the sample at the temperature and for the duration indicated by the authors not only will dessicate the sample with consequent shrinkage cracking, parting along bedding planes, and even total disassociation in the case of fissile shales, but it may also alter the character of the clay minerals themselves — in some cases irreversibly. 2. Prolonged evacuation to 2 microns Hg further dessicates the sample and is even more effective in reducing the intersilicate water content. 3. Resaturation with water differing in pH or chemical content from that existing originally in the sample also serves to alter the nature of the sample, particularly its structure and strength. 4. Our experience has been that, even with the thorough precautions proposed by the authors, complete resaturation of very fine grained materials is rarely obtained. Yet our experience confirms the

Jan 1, 1969

By Herty, C. H.

No attempt will be made here to review the previous work done by investigators on the general subject of inclusions, because it was discussed sufficiently in an early cooperative bulletin of this series (No. 36, 1928), and reference was then made to general bibliographies. The work described in this present bulletin deals directly with the study of the mechanism of deoxidation of steel with aluminum and the formation of inclusions containing alumina. Unquestion- ably, such inclusions are encountered in most steel-making practices and little has been done to determine their characteristics. Aluminum is used to ensure rapid deoxidation during the solidification stages of the steel. For this reason the possibilities of inclusion elimination are slight and alumina-containing particles will undoubtedly be present in the ingot. Besides this common practice, aluminum is often used in the ladle with other deoxidizing agents such as silicon and manganese. Ladle additions of aluminum are made to rimming steels to obtain the correct partial deoxidation desired in this type of steel. In killed steels the aluminum is added to ensure soundness, as far as blowholes are concerned, in the ingot. In either rimmed or killed steels, alumina or alumina-containing inclusions are found therein, the amount and type depending on the oxidation of the metal, the amount of aluminum added, and the addition of other deoxidizers.

Jan 1, 1957

By AIME AIME

THE convention which met in Washington at the call of the Joint Conference Committee was called to order at ten o&apos;clock on Thursday morning; June 3, by Richard L. Humphrey, temporary chairman, member of the American Society of Civil Engineers, who made a brief statement of the reason for the meeting. Lieut. Col. Charles W. Kutz, Corps of Engineers, U. S. A., and Engineer Commissioner of the District of Columbia, then welcomed .the engineers composing the convention on behalf of the District of Columbia and, the Washington engineers. Although an elaborate program had been prepared on which were many well-known speakers on interesting and important topics, , it was voted to intersperse this to fill in the usual and unavoidable hiatuses in the business program of such a convention[ Calvert Townley, president of the American Institute of Electrical Engineers, was elected permanent chairman, and J. C. Hoyt, of Washington, was elected secretary of the convention. The following committees were appointed: Consti¬tution and by-laws, Richard L. Humphrey, chairman; resolutions, Philip N. Moore, chairman; and program, F. H. Newell, chairman. Then, Gardner S. Williams, member of the, A. S. C. E. and the Grand Rapids Engineering Society of. Grand Rapids, Mich., and one-time member of the American Association of Engineers, offered the following resolutions:

Jan 1, 1920