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By N. S. Kenny, A. A. Burr

THE purpose of this note is to present evidence that vacancies, which have been produced by quenching from a high temperature, alter the rate of strain-hardening of an hep single crystal. The majority of investigations of the effects of quenched-in vacancies on the yield stress of metals have been made using fee samples in the form of thin wires. However, there is an inherent disadvantage in using such wires to study the effects of vacancies on the rate of strain-hardening of metals because fee wires begin stage II slip either immediately upon yielding or very shortly thereafter. When stage II slip occurs, very rapid strain hardening also occurs, masking the effects of vacancies on the rate of hardening. In this investigation single crystals of magnesium hep were studied since magnesium has only one slip plane at low temperatures and has, therefore, an extensive easy glide region. In addition, the effect of both static and dynamic recovery on the rate of hardening were eliminated by testing in liquid nitrogen. Both forms of recovery occur in hep metals by dislocation climb, which is a diffusion controlled mechanism and is negligible at liquid nitrogen temperatures. Finally, the dependence of the strain-hardening rate on the crystal orientation was eliminated by using the equations of Schmid and Boas.' Variations in the strain-hardening rate could, therefore, be attributed to the presence of vacancies. Single crystals in the form of rods approximately 5 mm in diam and 6 cm long were grown by a modified Bridgman technique from commercial high-purity magnesium (99.97 pet) supplied by the Dow Chemical

Jan 1, 1962

By S. Wiederhorn

The energy and force of interaction between a crack and a slip band have been calculated. When the distance between the crack and the slip band is greater than the dislocation spacing of- the slip band, the force on the cgrack is perpendicular to the slip band. The energy needed to propagate a crack against this force can be lawe enough to pevmit crack propagation parallel to noncleavage planes. SEVERAL recent experiments have demonstrated the occurrence of crack-slip band interaction in ionic crystals having a NaC1-type structure. Stokes, Johnston, and Lil have studied the nucleation and growth of cracks in MgO. From their observations, they conclude that slip bands have the ability to halt and stabilize cleavage crack nuclei. Gilman2 has shown that a crack, propagating along a (100) cleavage plane in a previously deformed LiF crystal, tends, at certain points within the crystal, to switch to (110) planes. He reasons that plastic deformation reduces the cohesive energy of the (110) planes below that of the (1130) planes, making possible (110) crack propagation. Keh3 has demonstrated that when indentations are made in MgO, crkcks form along (110) planes at the indentations. Gilman2 attributes the formation of these cracks to plastic cieformation. There is some doubt as to the formation of cracks on (110) planes. Kuznetsov4 in his discussion of crack propagation in rock salt, shows that splitting along (110) planes requires 1.76 times as much energy as splitting along a stepped (100) surface. Therefore, the observed (110) cracking in LiF and

Jan 1, 1962

Jan 1, 1964

By John Gross

The building of reverberatory furnaces (Fortschaufelungsofen) where ordinary brick, fire-brick and iron are comparatively cheap, is quite a different matter from the building of such furnaces in isolated camps, where proper material is only to be obtained at high cost and with long delays. Time is always a large factor in metallurgical operations, and the metallurgist may find himself in a position where it becomes necessary to erect apparatus and have it running in less time than it would take to obtain material from outside. It is here that he must make use of makeshifts. In Mexico, one of the most important of these is the alluseful adobe. Employed from prehistoric times, it still has its sphere of application in a surprisingly large number of instances requiring an article that can be quickly and cheaply produced. It is quite possible to erect serviceable reverberatory furnaces with no other materials than adobes, stone and wood. The old Mexican smelting shaft-furnace was an example of what can be done with adobes, and the large number of ruins of this class of furnace scattered through the mining districts of Mexico are silent testimony to the genius of a people who demonstrated their capability of adapting material at hand to their needs. The present paper will describe briefly the construction of an adobe reverberatory furnace which is giving good results, can be quickly erected at a low cost, and, if properly built and handled, will last a long time. The material being simply sun-dried, it naturally follows that the construction must be quite heavy. The adobes should be evenly made, with just sufficient straw to hold them together, and not too large in size (9 in. wide, 18 in. long and 4 in. thick

Jan 1, 1902

By Henry S. Drinker

THE Butler Mine property is situated in the vicinity of Pittston, in the Wyoming coal-field of Pennsylvania. The coal has been worked out from the fourteen-foot or Baltimore vein for a number of years on part of the tract, the old chambers remaining open as when originally abandoned. This vein outcrops on the Butler property, and is nowhere more than sixty feet below the surface of the ground on the line of the cut-off to be described. Above the fourteen-foot vein and about, say midway, between it and the surface of the ground, there is another small vein or rider of coal, about twelve inches in thickness. The rock between the two veins is a carbonaceous slate, about twenty-five feet in thickness. Above the smaller vein is a bed of sandstone, varying in thickness, but generally not less than from eight to ten feet. This sandstone is also carbonaceous, but the proportion of carbon is much less than in the slate below. Both rocks have been analyzed, and before the next Institute meeting, the writer hopes to be able to furnish the exact proportions. The sandstone is overlaid with debris up to the surface of the ground. Some time during the spring of 1876, it was found that the coal left in the worked-out mine had been set on fire, and that the fire was gradually spreading. Inquiry developed the fact that the fire had originally been started by a woman, who had taken up her abode in an old tunnel leading into the workings. Owing to some delay in the early attempts made to extinguish the fire, it finally gained such headway that no ordinary means were found to be effectual. Finally, Mr. C. F. Conrad, civil and mining engineer, of Pittston, Penna., was called in as consulting engineer. He advised the making of a thorough cut through such portion of the old workings as had not been reached by the fire. It was found by survey that this cut could be limited to a length of about one thousand two hundred feet, as the vein faulted on both sides, and that the greatest depth of the cut would be about sixty feet. Subsequently it was decided to tunnel part of the way, thus saving the deepest portion of the cut. In 1856-7, there occurred a fire in the same mine. Two stone-walls in V-shape running from the apex of the V towards the outcrop, were built to cut the fire off, and these walls were carried as far as the vein had at that time been worked. After the walls were finished

Jan 1, 1879

Theoretically mobile primary crushers at the mine working face can be considered the ideal comminution system. A crusher which follows the ore can reduce materials handling costs because it eliminates about one ton of truck deadweight per ton of ore hauled to the crusher. It also eliminates the backhaul of this same deadweight ton. Development of mobile primary crushers has centered in Germany where many soft iron ore and limestone deposits are flat-lying and thus readily adaptable to the use of shiftable conveyors which easily followed the working face. These ores were easily crushed in impact- type mills which had extremely large receiving openings and therefore large reduction ratios. The feeding of such a unit was done with a front-end loader which dumped its load to an inclined apron feeder, which in turn fed the impactor. Under the crusher was an inclined conveyor which transferred the crushed ore to a belt wagon for delivery to the shiftable overland conveyor. Low headroom overhead eccentric single-toggle jaw crushers and short-shaft gyratories were also used on these units, which generally travelled on tracks. While these early mobile primary crushers were versatile and served their purpose, they generally suffered from low capacities. Manufacturers have quickly responded with larger crusher, feeders, and moveable supports, however; and today mobile crusher s have capacities of up to 1500 metric tons per hour, a figure comparable to the capacity of some 54 in. by 74 in. gyratories. An example of a quarry portable crushing plant is at the Bath cement plant of Canada Cement Lafarge, Limited. Two 12 cu yd front-end loaders are digging the stone and hauling it to the portable crushing plant which feeds a field conveyor system. The crushing plant is moved and the field conveyors extended whenever the length of the haul exceeds 300 ft. At the crushing plant, the loaders discharge the stone onto a pan feeder which feeds into the hopper of a Weserhutte-Hazemag compound crusher which combines primary and secondary rotors in the same housing. These are driven at 1200 rpm by 800 hp and 1,000 hp motors (600 and 750 kw). The maximum 3 ft feed (914 mm) is reduced to 3/4 in. (19 mm) at 800 tph. The Weserhutte steered walking mechanism, operated by hydraulic cylinders, takes five -foot strides. Another example is at Alcoa of Australia's operation at Huntley in Western Australia. At the mine face, front-end loaders load 50 mt rear-dump trucks that transport the bauxite ore to the mobile crusher which follows the mine operation. The crusher can turn 360° within its own length, walk at a speed of 34. 5 ft per minute (10.5 m per

Jan 1, 1978

By Henry S. Drinker

The Butler Mine property is situated in the vicinity of Pittston, in the Wyoming coal-field of Pennsylvania. The coal has been ' worked out from the fourteen-foot or Baltimore vein for a number of years on part of the tract, the old chambers remaining open as when originally abandoned. This vein outcrops on the Butler prop erty, and is nowhere more than sixty feet below the surface of the ground on the line of the cut-off to be described. Above the four teen-foot vein and about, say midway, between it and the surface of the ground, there is another small vein or rider of coal, about twelve inches in thickness. The rock between the two veins is a carbon aceous slate, about twenty-five feet in thickness. Above the smaller vein is a bed of sandstone, varying in thickness, but generally not less than from eight to ten feet. This sandstone is also carbonaceous, but the proportion of carbon is much less than in the slate below. Both rocks have been analyzed, and before the next Institute meet ing, the writer hopes to be able to furnish the exact proportions. The sandstone is overlaid with debris up to the surface of the ground. Some time during the spring of 1876, it was found that the coal left in the worked-out mine had been set on fire, and that the fire was gradually spreading. Inquiry developed the fact that the fire had originally been started by a woman, who had taken up her abode in an old tunnel leading into the workings. Owing to some delay in the early attempts made to extinguish the fire, it finally gained such headway that no ordinary means were found to be effectual. Finally, Mr. C. F. Conrad, civil and mining engineer, of Pittston, Penna., was called in as consulting engineer. He advised the making of a thorough cut through such portion of the old workings as had not been reached by the fire. It was found by survey that this cut could be limited to a length of about one thousand two hundred feet, as the vein faulted on both sides, and that the greatest depth of the cut would be about sixty feet. Subsequently it was decided to tunnel part of the way, thus saving the deepest portion of the cut. In 1856-7, there occurred a fire in the same mine. Two stone walls in V-shape running from the apex of the V towards the out crop, were built to cot the fire 06 and these walls were carried as far as the vein had at that time been worked. After the walls were finished

Jan 1, 1879

By J. H. Frye, C. P. Sun

A Frimary substitutional solid solution is a solution that has the same crystalline structure as the solvent metal, and in which solute atoms have replaced, solvent atoms at random on the host lattice. This replacement usually results in an increase in hardness as measured by conventional penetration tests. The factors controlling this hardness increase have been investigated in some detail for copper and silver alloys.1-5 It has been shown that at least four factors are involved: (1) concentration of solute, (2) row of the periodic table from which the solute is taken, (3) increase in lattice parameter of the solvent produced by the solute, and (4) work-hardening produced by penetration of the hardness indenter.2,4 The last factor is of the utmost importance. An investigation of the available data2,4 leads to the conclusion that the solutes that produce large hardness increases in copper or silver do so principally because they increase the rate of work-hardening. Furthermore, it is doubtful whether any solute produces appreciable hardening in the absence of plastic deformation and hence work-hardening. Thus it is clear that an understanding of the effect of solutes on rate of work-hardening is essential to an understanding of the hardness of solid solutions. This effect of solutes is also important in forming operations such as rolling or deep drawing. The presence of elements that confer rapid rates of work-hardening will increase power consumption and may well decrease the amount of deformation possible between anneals. This paper is the report of an investigation of the factors that control rates of work-hardening in copper and silver solid solutions. The silver and copper alloys considered are those in which all solutes are from the B subgroups or second short period of the periodic table. Experience with hardness, with structure of alloys, and with electrical conductivity has proved that results of a fundamental nature are most likely to be obtained if alloys are made up on the basis of the positions of the constituent elements in the periodic table. In previous work, Meyer analysis data on high-purity copper and silver solid solutions were obtained through careful measurements with fully calibrated equipment and these data were corrected to correspond to a standard grain size. From these corrected Meyer analysis data rates of work-hardening have now been calculated. Calculation of Rates as Work- HARDENING The Meyer analyses, on which this study of rates of work-hardening is based, consisted in determining impression

Jan 1, 1944

By J. H. Frye, C. P. Sun

A Frimary substitutional solid solution is a solution that has the same crystalline structure as the solvent metal, and in which solute atoms have replaced, solvent atoms at random on the host lattice. This replacement usually results in an increase in hardness as measured by conventional penetration tests. The factors controlling this hardness increase have been investigated in some detail for copper and silver alloys.1-5 It has been shown that at least four factors are involved: (1) concentration of solute, (2) row of the periodic table from which the solute is taken, (3) increase in lattice parameter of the solvent produced by the solute, and (4) work-hardening produced by penetration of the hardness indenter.2,4 The last factor is of the utmost importance. An investigation of the available data2,4 leads to the conclusion that the solutes that produce large hardness increases in copper or silver do so principally because they increase the rate of work-hardening. Furthermore, it is doubtful whether any solute produces appreciable hardening in the absence of plastic deformation and hence work-hardening. Thus it is clear that an understanding of the effect of solutes on rate of work-hardening is essential to an understanding of the hardness of solid solutions. This effect of solutes is also important in forming operations such as rolling or deep drawing. The presence of elements that confer rapid rates of work-hardening will increase power consumption and may well decrease the amount of deformation possible between anneals. This paper is the report of an investigation of the factors that control rates of work-hardening in copper and silver solid solutions. The silver and copper alloys considered are those in which all solutes are from the B subgroups or second short period of the periodic table. Experience with hardness, with structure of alloys, and with electrical conductivity has proved that results of a fundamental nature are most likely to be obtained if alloys are made up on the basis of the positions of the constituent elements in the periodic table. In previous work, Meyer analysis data on high-purity copper and silver solid solutions were obtained through careful measurements with fully calibrated equipment and these data were corrected to correspond to a standard grain size. From these corrected Meyer analysis data rates of work-hardening have now been calculated. Calculation of Rates as Work- HARDENING The Meyer analyses, on which this study of rates of work-hardening is based, consisted in determining impression

Jan 1, 1944

By Frederic Benard

THIS paper constitutes a preliminary report on experimental work done to date on the anode-furnace treatment of blister copper containing relatively high percentages of nickel. The investigation has not been completed but results obtained to date are considered of sufficient interest to warrant publication. Blister copper treated by the Ontario Refining Co. originates from the Copper Cliff smelter of The International Nickel Company of Canada, of which the former is a wholly-owned subsidiary. The blister as received contains from 0.50 to 1.50 per cent Ni, and in this respect differs from that treated by other refineries on this continent. During the anode-furnace treatment, only a portion of the nickel content is removed, and of the amount remaining in the anodes a varying percentage is found in the anode slimes. This necessitates a more extensive treatment than ordi-nary, nickel-free material. Sometimes it is necessary to repeat roasting and leaching operations several times before the nickel content is low enough to permit the slimes to proceed to the doré furnace. This, besides increasing treatment charges, causes greater selenium stack losses and involves a longer tie-up of precious-metal values. Therefore this investi-gation was undertaken with the aim of determining the factors influencing the diversion of nickel into the anode sludge. From experience it was known that by keeping the nickel content of anodes at 0.55 to 0.60 per cent maximum a relatively satisfactory slime resulted. One avenue of attack therefore was developing improved elimination in the anode-furnace treatment so that the anode content mentioned above was not exceeded. Another angle was to improve the solubility, during electrolysis, of the nickel constituent in the anodes, thus decreasing the percentage diverted to slimes. It may he mentioned here that nickel dissolving electrochemically and entering the electolyte pre-sents no difficulty from a treatment standpoint. Both of these approaches were studied and are discussed sepa-rately below.

Jan 1, 1938

By M. L. Requa

IN the fall of 1910, the Nevada Petroleum Co., operating in the Coalinga field in California, determined to drill a number of wells with rotary tools, in order to prove conclusively the relative value of the rotary as compared with the standard rig. At that time, the rotary was but little known in California and its proposed introduction met with considerable criticism on the part of the operators and quiet opposition among the standard drilling crews. There were few men available who were competent to handle a rotary outfit, and these few had had but little experience in California fields. Machines as then built were much inferior to those now used, being lighter in construction and of a poorer quality of material. The shells encountered at depths between 1,700 and 2,000 ft. seemed to be too hard to permit of successful drilling, and at these depths the rig was changed over to standard tools and by them completed. Because of the heavy depreciation, the time lost in converting from rotary to standard, and the comparatively small profit, it was concluded that unless in the future there was some material improvement in rotary rigs, nothing would be gained by drilling with rotary tools upon this property. Little or no drilling has been done upon the property since that time, but in the meantime a large number of men have been trained in the use of the rotary; in fact, many standard-tool men have abandoned standard drilling and, starting in as roustabouts, have become thoroughly competent rotary operators. The improvements in the machinery have been such as to remove many of the objections and the rotary drilling of to-day is in every way superior to that of 1910. In contrast, a well drilled recently by the Kern Trading & Oil Co., in the east side Coalinga field may be cited. The first 2,500 ft. was drilled in 24 days and it is confidently expected that the water string will be set with a rotary at 3,400 ft.-a record obviously far beyond that made in 1910 by the Nevada Petroleum Co.

Jan 2, 1915

By M. J. McPherson

Having worked on the thermodynamics of air/liquid-water mixtures passing through the surface fans of deep mines, I find this paper of great interest and congratulate the authors on producing it. There are two matters, however, deserving discussion. First, the authors have described the classical theory of fog formation with fogging occurring at "supersaturation." In fact, the process of fog formation begins well below 100% humidity. The more strongly hygroscopic nuclei in the atmosphere will attract water molecules and begin to grow at a relative humidity perhaps as low as 70%. The process is a dynamic one with both condensation and evaporation taking place throughout the mixture on microscopic liquid surfaces. As saturation is approached, the rate of condensation accelerates rapidly producing the familiar reduction in visibility. Hygroscopic nuclei are present in all natural atmospheres and under the appropriate conditions of pressure and temperature, will produce clean fogs. However, if the air is polluted by particulates from combustion or other processes then the resultant coagulation with growing liquid particles may produce dense (and sometimes photochemical) smogs. It is this process that is likely to occur in underground mines when moist air is cooled below dew point. Second, the authors have summarized very well the individual measures that might alleviate the problem. In particular, I agree that neither heating nor refrigerating the air, by themselves, provides a satisfactory solution. However, there is a combination of these that provides a neat and effective control of fog formation. This involves a small, self-contained refrigeration unit within a duct but without the usual external heat rejection facility. The air is cooled below dew point and, hence, dehumidified on passing over the cold evaporator coils. The heat from the condenser is rejected back into the air down-stream from the water eliminator, as shown in [Fig. 1]. The duct configuration can be designed to create good mixing at the outlet.

Jan 1, 1984

By Norman Brown, Victor V. Damiano

ThE present paper proposes a mechanism of dislocation multiplication at internal inclusions or cavities and presents experimental evidence of such sources in zinc. Using an etching technique recently described by Damiano, Tint, and Herman1 to study the three-dimensional aspects of dislocations in bulk zinc crystals, an investigation was made of helically shaped and closed-loop etch patterns found to be associated with inclusions. Crystals containing 0.1 pet Cd and grown from the melt were deformed slightly by bending and then aged at room temperature to precipitate cadmium at the dislocations. The crystals were cleaved along the (0001) plane and then etched with Gilman's2 etch. Crystals were continuously viewed on the (0001) plane while the etching was in progress and numerous helical and closed-loops etch patterns were continuously recorded as shown in the sequences printed directly from the cine film in Fig. l(a) and (6). These etch patterns are not to be confused with the etch patterns previously reported by Damiano and Herman3 which revealed dissolution spirals on the (0001) plane of high-purity zinc crystals. In the present case, precipitates arranged in the form of closed loops or helicies are progressively uncovered by etching after suitable aging of cadmium doped zinc crystals. Viewed with dark-field illumination as shown in Fig. 2, portions of a helical figure and subboundaries were revealed simultaneously. Continuous viewing while the etching was in progress revealed in Fig. 1(b) that the short line segments observed on single photomicrographs were in fact continuous and described a helix which had its terminus at an inclusion. The observations suggested that a dislocation once nucleated at the interface between the inclusion and matrix may act in such a way as to produce ad-

Jan 1, 1964

By Jerome Alexander

IT is an outstanding fact of Nature that many of the practical properties of substances are dependent, not on their ultimate chemical composition, but on the kind and degree of aggregation of their constituent particles. Thus, a granite boulder is unmoved by wind or water, but if reduced to a fine dust it will be blown about by the wind and washed away by the rain. Carbon in one crystalline state of aggregation (diamond) is the hardest known substance, whereas in another crystalline state (graphite) it is so soft that it is used as a lubricant. Laying too much stress on the mere chemical analysis of substances is apt to obscure the fact that the nature of the aggregation of their particles is always a factor of importance, and sometimes the most important factor. Colloid chemistry deals with matter in. a very fine state of subdivision; its sphere begins with particles just a little smaller than a wave length of light-and extends clown until they blend into molecular dimensions. With particles of this size; such phenomena as surface tension and adsorption, which depend on the development of free surface, become enormously magnified. Thus a cube of 1 cm. edge has a surface of only 6 sq. cm.; but if it is reduced to colloidal dimensions by being cut up into cubes each having an edge of 0.01 , (0.00001 mm.), it will yield one million, million, million (1,000,000,000,000,000,000) such cubes, having a combined area of 600 sq. in., or 21,274 sq. ft. The tiny force with which a drop of rain clings to the window pane becomes a. factor to be reckoned with, if the surface involved is increased millions of times. From the colloid-chemical viewpoint, metals and alloys may be regarded as jellies or sponge-like structures, the viscosity or stiffness of which at ordinary temperatures is exceedingly great; and like all jellies their properties are dependent on the composition and degree of dispersion of their constituent phases. These, in turn, depend on chemical composition, mutual solubility, speed of chilling, subsequent mechanical and heat treatment, etc In fact, in preparing metals and

Jan 2, 1919

By Read Winterburn

This discussion covers only one method of pressure drilling—that developed in the Kettleman Hills field. Thus it is probable that many departures from the procedure herein described would be advisable, and perhaps necessary, in using this method of drilling wells in other localities. Purpose of Pressure Drilling By the early part of 1936, formation pressures in the heavily produced north end of the Kettleman North Dome field had declined to range from 1000 to 1500 lb. per sq. in. This low pressure, combined with the depth of the wells (8000 to 9000 ft.) permitted water to be filtered out of the mud into the producing sands during drilling operations. The loss of water was indicated by loss of fluid from the suction tank while drilling, accompanied by an increase in mud weight. It was found that when water was added to the mud stream at such a rate as to keep the fluid level in the suction tank constant, the mud weight would not vary. This indicates that water only was forced into the sands. The rate of this loss at various wells ranged from 2 to 5 bbl. per hour. At some places complete loss of circulation occurred, and drilling mud to the extent of 200 to 1000 bbl. had to be pumped into the sands before returns were regained. It was believed that these conditions had already begun to harmfully affect production, and that such effect would become more pronounced as formation pressures continued to decline. Pressure drilling with oil was introduced because it eliminated the danger of loading the formations with mud and water. The method also afforded a convenient means of testing as drilling progressed, lessening the amount of formation testing, which had become necessary because of encroaching edge water.

Jan 1, 1938

By M. E. Nicholson

The solubility of carbon in Ni-Cu alloys was determined at 1000°C. The factors which limit solid solubility are discussed with particular reference to the influence of electronic factors. The results indicate the extent of solid solubility is a function of the density of states at the Fermi surface. THE solid solubility of an interstitial element is primarily limited according to Seybolt and Fullman1 and Speiser and Spretnak2 by (a) the strain energy produced when the solute atom takes its interstitial position, and (b) the partial molal free energies of the solid solution and the coexisting phases. In several binary systems of a transition and a noble metal, where there are no abrupt changes in strain energy or free energies of coexisting phases, the solid solubility of an interstitial third element drops abruptly to a negligible value at a composition corresponding to a complete filling of the "d-band." Such a decrease occurs in the case of hydrogen in the Pd-Ag system at 60 pct Ag.3,4 The solubility of carbon in Ni-Cu alloys seems to vary in a similar manner as indicated by the embrittling effect of carbon on these alloys. These al- loys are embrittled by slow cooling due to the precipitation of graphite. This embrittlement can be removed by heat treatment if the carbon content is less than the solid solubility limit at the heat-treating temperature. If the carbon content of the alloy exceeds the solid solubility at the heat-treating given temperxture, the embrittlement cannot be eliminated by solution heat treatment.' Since pure nickel has a carbon solubility of 0.25 wt pct6 at 1000°C, embrittlement is easily removed from commercial nickel and nickel-rich alloys, which may contain of the order of 0.10 wt pct C. Embrittlement due to carbon cannot be removed from Ni-Cu alloys containing 70 to 80 wt pct Cu by annealing unless: the carbon content is of the order of 0.04 wt pct CL or less."' Thus, it appears that the

Jan 1, 1962

By T. L. Chu, G. A. Gruber

Silica films hare been rleposited 011 silicon substmtes at 400° to 600°C by a chemical-transport technique using hydrogen fluoride as the transport agent ill a closed system. This transport takes place from a source materia1 1071: temperature to substrates at higher temperatures, as indicated by the thermochemistry of the transport reaction. The experimental variables of- the transport process, such as the substrate temperature, the pressure pi the transport agent, and so forth, have been studied. The rate -determining step of the transport process appears to he the ),ale of chemical reaction in the source region. The transported films are similar to thermally grown silica films in physical proper-ties with the exception of 'some what higher dissolrrtion rates. SILICA films deposited on suitable substrates serve many purposes in electronic devices. They are used for the fabrication of tunneling devices, the surface passivation of devices, and the shielding of devices from nuclear radiation: and as selective masks against the diffusion of specific impurities into semiconductors. Doped silica films can also be used as sources for the diffusion of impurities into semiconductors. Several oxidation and deposition techniques for the preparation of silica films have been developed to meet the requirements of these applications. The therma1 oxidation of silicon by oxygen or steam at temperatures above 900 C is commonly used in silicon technology. The deposition techniques are perhaps more advantageous since they usually require lower temperatures and are not limited to silicon substrates. Silica films have been deposited on silicon and other substrates by reactive sputtering and chemical reactions. The sputtering of silicon in an oxygen atmosphere is capable of depositing good-quality silica films on silicon' and gallium arenide. Many chemical reactions are known to yield silica at room temperature or higher. These reactions may involve intermediate steps. However, the final step yielding silica should take place predominately on the substrate surface in order to produce adherent films. When silica is formed in the gas phase by volume reactions, no adherent deposit can be obtained. Generally, the experimental conditions of a reaction can be varied so that the surface reaction predominates over the volume reaction. The chemical reactions which have been used successfully for the deposition of silica films are briefly as follows. The pyrolysis of alkoxysilanes in an inert atmosphere or under reduced pressure has been employed to deposit silica films on germanium3 and silicon4 at 650" to 750°C in a flow system. The deposition of silica films from alkoxysilanes has also been achieved at nearly room temperature by a low-pressure plasma. Device quality silica films have been deposited on germanium and gallium arsenide by the deposition of an amorphous thin silicon film followed by oxidation at 600" to 700" . Silica films for high-temperature capacitors have been produced by the hydrolysis of silicon tetrabromide at 950°C in argon and hydrogen atmospheres.7 We have developed a chemical-transport technique for the deposition of silica films on semiconductor substrates at relatively low temperatures. The thermochemistry of the transport reaction, the experimental variables of the transport process, and the properties of the transported silica films are described in this paper. THERMOCHEMICAL CONSDERATIONS The transport of solid substances by chemical reactions in the presence of a temperature gradient has been used for the preparation of films and crystals of many electronic materials. In this technique, a gaseous reagent is chosen so that it reacts reversibly with the solid substance under consideration to form volatile products. Since the equilibrium constants of most reactions are temperature-dependent, the transport of these products to regions of suitable temperature in the reaction system would cause the reverse reaction to take place. depositing the original solid. When the equilibrium is shifted toward the formation of the solid as the temperature is decreased, the solid is transported from a high-temperature zone to a lower-temperature region, and vice versa. This chemical-transport technique can be carried out in a closed or gas-flow system. In a closed system, chemical equilibrium is presumably established in the different temperature regions of the system, and the transport agent regenerated in the deposition region repeats the transport process in a cyclic manner. The local chemical equilibrium may not be approached in a flow system: however, this system offers a greater degree of flexibility. Silica reacts reversibly with hydrogen fluoride and this reaction was chosen for the transport process. The over-all reaction between silica and hydrogen fluoride may be written as: SiO2(s) + 4HF(g-) = SiF4Ur) + 2H2O(^)

Jan 1, 1965

By T. Prof. Egleston

How to interpret the composition of rocks has been a question which has caused a great deal of discussion and investigation among geologists and chemists. It is evident that that analysis will give the clearest results, which will give the relative proportion of the different minerals composing the rock as well as the weight of their different constituents. This, however, is a very difficult matter, and in those rocks which seem to the naked eye entirely compact, like obsidian and other rocks of that class, appears to be impossible. Cordier, in the early part of the century, invented a process which is known as the " mechanical analysis of rocks," which is really a method of mechanical preparation, and consists in crushing the rock to a certain fineness, and then, by virtue of their density, washing out the different minerals, so as to make a mineralogical analysis, separating completely the different constituents of the rocks. In the hands of so skilful a man, this was a comparatively easy matter, and Cordier found no difficulty in ascertaining the mineralogical composition of a rock. The ultimate chemical composition was ascertained from the sum of the elements contained in the different materials. In the light of to-day, it is very easy to see that the complete chemical analysis of the rock does not necessarily lead to the explanation of its character. It has been so difficult, however, to have any other kind of analysis made that most chemical examinations have been made as ultimate, and not as mineralogical analyses. The panning out of the different minerals composing the rock, which are often very nearly of the same specific gravity, is so difficult that a person of ordinary mechanical skill is scarcely able to do it; consequently the mechanical analysis which Cordier proposed, and was able himself so skilfully to effect, has never been practiced to any extent. A school was formed in France consisting of a very small number of Cordier's followers, which, in face of the difficulty of acquiring the method, very soon died out as a school, though some of his most skilful followers are still living. The next important step in ascertaining their composition was to out the rock into transparent sections and examine the minerals with

Jan 1, 1875

By R. W. Raymond

Since the foregoing paper (see p. 387) was printed, I have received the decision of Judge William E. Church, of the first District Court of Dakotah, in the case of Michael Duggan et al. v. John H. and Frank J. Dnvey (Silva Terra—Sitting Bull case), published in full in the Black Hills Weekly Pioneer of August 9th, 1584. The journal mentioned gives also several interlocutory decisions rendered in earlier stages of the case; but I shall quote here only so much of the final decision as bears upon the .construction of the Revised Statutes concerning the apex, the end-lines, and the extra-lateral mining right, together with a sufficient statement of the facts of the case to explain the scope of the decision. " This is an action in equity, brought in the first instance to restrain a threatened trespass by the defendants upon certain mining property in the possession of the plaintiffs, known as the ' Silver Terra' claim ; the allegation being that the defendants were about to enter, through underground workings, the ground of the plaintiffs, and remove therefrom valuable bodies of silver ore. " The answer of the defendants, admitting the acts constituting the alleged threatened trespass, further averred that they had, in fact, at the time complained of, reached and passed, in their underground workings, throngh and beyond the vertical side-line of the Silver Terra claim, and therenpon justified the acts complained of, and claimed the right to pursue their workings into and through the Silver Terra ground, by virtue of their alleged proprietorship of a vein, lode, or ledge of rock in place, hearing silver, having its top or apex within the lines of a certain other mining claim called the ' Sitting Bull,' of which they claim to be the owners, which vein, lode, or ledge extended in a continnons body of mineral-bearing rock from such top or apex to the ground in controversy, and constituted the body of ore in dispute; and that it was in the pursuit of this vein, lode, or ledge in its downward course that they had passed beyond the vertical side-lines of the Sitting Bull claim, and for some hundreds of feet beyond, into the ,ground in controversy " Subsequently, a supplemental complaint was filed, setting up the entry into plaintiffs' ground by the defendants, and their claim of right to do so, and asking fnrther relief by a decree restraining the assertion of such claim, and quieting the title of plaintiffs. "The case was tried before the court without a jnry..... " Custer hill, upon which these claims are located, is situated in the village of Galena, in Bare Butte mining district, in this county. The village lies at the base of the western slope of the hill, which presents a lateral face from south to north

Jan 1, 1884

Jan 1, 1889