Search Documents

By Frank Foote, E. R. Jette

In recent years the constitution of the high-silver aluminum-silver alloys has been extensively investigated. Hansenl has reviewed the literature to 1935. More recently, Obinata and Hagiya,2 Hofmann and Volk,3 Taziri4 and Tishchenko5 have confirmed the general features of the phase diagram in the region around 25 atomic per cent aluminum. In this paper we present the results of high-precision measurements of lattice constants of the silver-rich alpha solid solution in the homogeneous range and the neighboring two-phase regions. These results are used to establish the nature of the solid solution, the identity of directly measured densities with those calculated from lattice constants and the homogeneity limits of the alpha solid solution with respect to three different neighboring phases. A study of the earlier investigations indicated that the last two subjects in particular required new and accurate data. Experimental Procedure Preparation of the Alloys.—The alloys were made from high-purity silver and aluminum. The silver was "Proof Silver," 99.999 per cent pure, supplied by the U. S. Metals Refining Co. The aluminum was 99.97 per cent pure (contained Si, 0.009 per cent; Fe, 0.0016 per cent; Cu, 0.004 per cent) and was supplied by the Aluminum Company of America. The lattice constants of these two materials have been reported by Jette and Foote.6 Weighed amounts of the two metals were placed in alundum crucibles and melted in vacuo in a high-frequency induction furnace. The melts were allowed to cool in the crucible, the ingots thus obtained weighed about 10 grams. These ingots were then filed clean, hamered, again cleaned and given a homogenizing anneal in vacuo of from 6 to 15 days at temperatures ranging from 500" to 695°C. The ingots were air-cooled from the annealing temperature. Lattice-constant Measurements.—Carefully prepared filings for X-ray analysis were sealed into evacuated quartz or Pyrex tubes and annealed for various periods of time at suitable temperatures. The furnaces used were vertical, rapid-quenching furnaces, the samples being quenched by crushing the sample tube under water by means of a heavy plunger. The general X-ray technique has been previously described6 The cameras were of the symmetrical, back-reflection, focussing type. Ka, radiation from a cobait-nickel alloy target was used. The wave-length values were taken from the second edition of Siegbaum's book.7 A correction for the index of refraction was applied and the lattice constants were calculated by the method of Cohen.8, 6 The lattice constants were calculated to a common temperature of 25°C., using the value of the linear expansion coefficient of pure silver as 18.9 X 10-6. Presumably the expansion coefficient for

Jan 1, 1941

By Frank Foote, E. R. Jette

Precision lattice-constant measurements have been widely used in the study of cubic solid solutions but as yet have been rarely applied to noncubic solid solutions. (See, however, references I and 2.) With the high precision at present attainable in the measurement of lattice constants, the X-ray method should be readily applicable to noncubic solid solutions. In the work reported here, hexagonal close-packed magnesium was used as the solvent and either lead, bismuth or gold as the solute. In the magnesium-lead and magnesium-bismuth systems the a and c lattice constants were determined as a function of composition, densities were calculated from these lattice-constant data, these theoretical densities were compared with those directly measured and the solid solubility limit was determined on quenched specimens over a considerable range of temperature. In the magnesium-gold system, the solid solubility is very small but we have obtained an indirect check on the solubility limit previously reported. Materials and Preparation oF the Alloys The magnesium used was obtained from the Aluminum Company of America and was 99.987 per cent pure. Impurities as reported On the label were: Fe, Al, 0'004 per cent; Si, 0.009 per cent; Zn, trace; Cu, Pb, nil. The bismuth was Merck's analytical grade, minimum purity 99.95 per cent. Maximum impurities as listed on the label were: Fe, 0.008 per cent; Pb, 0.010 per cent; Ag, 0.010 per cent; Cu, 0.005 per cent; Sn, 0.003 per cent; Sb, 0.00; As, 0.000; S, 0.01 per cent. The gold was purified by double precipitation with sulphur dioxide. The lattice constants of these three metals have been previously reported.3 The lead used was test lead, silver free and with a maximum of 0.10 per cent heavy metal impurities. The lattice constant 01 this lead has been measured and found to be 4.94057 ± 0.00016 at 25°C. The alloys were prepared by melting together weighed amounts of the constituent metals in magnesia-lined alundum crucibles under an atmosphere of hydrogen purified by passing over magnesium heated to 500°C. The magnesia lining prevented contamination 01 the alloys with aluminum. Vacuum melting could not be used because of the volatility of magnesium. A high-frequency induction furnace was used for the melting operation and the stirring action of the current resulted in thorough mixing of the constituents. The melts were allowed to freeze in the crucible, the ingots obtained weighed about 10 grams. An extremely thin white film formed on the surface of the melts, sometimes covering only a part of the exposed surface. The ingots were filed clean, placed in small iror crucibles with close-fitting lids and indi. vidually sealed into Pyrex glass tubes Before sealing off, the tubes were alter

Jan 1, 1941

By Frank Foote, E. R. Jette

Precision lattice-constant measurements have been widely used in the study of cubic solid solutions but as yet have been rarely applied to noncubic solid solutions. (See, however, references I and 2.) With the high precision at present attainable in the measurement of lattice constants, the X-ray method should be readily applicable to noncubic solid solutions. In the work reported here, hexagonal close-packed magnesium was used as the solvent and either lead, bismuth or gold as the solute. In the magnesium-lead and magnesium-bismuth systems the a and c lattice constants were determined as a function of composition, densities were calculated from these lattice-constant data, these theoretical densities were compared with those directly measured and the solid solubility limit was determined on quenched specimens over a considerable range of temperature. In the magnesium-gold system, the solid solubility is very small but we have obtained an indirect check on the solubility limit previously reported. Materials and Preparation oF the Alloys The magnesium used was obtained from the Aluminum Company of America and was 99.987 per cent pure. Impurities as reported On the label were: Fe, Al, 0'004 per cent; Si, 0.009 per cent; Zn, trace; Cu, Pb, nil. The bismuth was Merck's analytical grade, minimum purity 99.95 per cent. Maximum impurities as listed on the label were: Fe, 0.008 per cent; Pb, 0.010 per cent; Ag, 0.010 per cent; Cu, 0.005 per cent; Sn, 0.003 per cent; Sb, 0.00; As, 0.000; S, 0.01 per cent. The gold was purified by double precipitation with sulphur dioxide. The lattice constants of these three metals have been previously reported.3 The lead used was test lead, silver free and with a maximum of 0.10 per cent heavy metal impurities. The lattice constant 01 this lead has been measured and found to be 4.94057 ± 0.00016 at 25°C. The alloys were prepared by melting together weighed amounts of the constituent metals in magnesia-lined alundum crucibles under an atmosphere of hydrogen purified by passing over magnesium heated to 500°C. The magnesia lining prevented contamination 01 the alloys with aluminum. Vacuum melting could not be used because of the volatility of magnesium. A high-frequency induction furnace was used for the melting operation and the stirring action of the current resulted in thorough mixing of the constituents. The melts were allowed to freeze in the crucible, the ingots obtained weighed about 10 grams. An extremely thin white film formed on the surface of the melts, sometimes covering only a part of the exposed surface. The ingots were filed clean, placed in small iror crucibles with close-fitting lids and indi. vidually sealed into Pyrex glass tubes Before sealing off, the tubes were alter

Jan 1, 1941

STANDING COMMITTEES. Executive. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, ALBERT R. LEDOUX, BENJAMIN B. THAYER. . Membership. BENJAMIN B. THAYER, Chairman. KARL EILERS, JOHN H. JANEWAY, JR., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG, Chairman. KARL EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman1 JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALEX. C. HUMPHREYS.4 BRADLEY STOUGHTON.

Jan 10, 1913

By H. L. James

This paper presents the results and analysis of field trials of various magnetic instruments over anomalies ranging from 20 to 5000 gammas of vertical intensity. The following instruments were used: Askania vertical magnetometer, Wolfson vertical magnetometer (model M-I), Hotchkiss Superdips (used both parallel to and normal to the magnetic meridian, with several settings of the "sigma" angle), Lake Superior dip needle, and the dipping circle for measurements of inclination. The change in inclination over the measured anomalies ranged up to 4"; this caused pronounced changes in sensitivity of the Hotchkiss Superdip oriented parallel to the magnetic meridian. The variable sensitivity not only gives apparent displacement of crests of anomalies, particularly at high sensitivities, but also makes the data difficult or impossible to use in preparation of iso-anomaly maps. This weakness in field performance of the Superdip is shown to be eliminated by orienting the instrument normal to the magnetic meridian and measuring vertical intensity only, which in the latitude of upper Michigan is equal to 97 pct of the total intensity. The dip needle is seen to be relatively ineffectual for location of anomalies of less than 400 gammas. Introduction The U.S- Geological Survey, in cooperation with the Geological Survey Division of Michigan Department of Conservation, has for the past three years been engaged in a restudy of the Iron River-Crystal Falls iron mining district of upper Michigan. The bedrock in a large part of this area is covered with glacial deposits as much as 500-ft thick, and, inasmuch as some of the rocks have moderate to high magnetic permeability, extensive magnetic mapping has been done to assist in unraveling the complicated structure of the area. Several types of instruments have been used, and the major purpose of this paper is to present comparative data on the field performances of some of these instruments so as to aid others who face similar problems elsewhere to evaluate and choose the instruments best suited for the work. The paper is directed primarily to geologists and engineers rather than to geophysicists, although some familiarity with the instruments is presumed. The geology of the area consists of a complexly folded series of weakly metamorphosed sedimentary rocks, including the iron formation, which rests on older greenstones. Although the iron formation itself is only locally magnetic, some of the beds stratigraphically above the iron formation are rather strongly so. By tracing these hanging wall magnetic anomalies valuable information is obtained from which the structure and distribution of the iron formation can be inferred. Critical anomalies range from 25 to 6000 gammas of vertical intensity. Many anomalies can be traced in part with the common dip needle, but detection of others requires more sensitive instruments.

Jan 1, 1949

By H. L. James

This paper presents the results and analysis of field trials of various magnetic instruments over anomalies ranging from 20 to 5000 gammas of vertical intensity. The following instruments were used: Askania vertical magnetometer, Wolfson vertical magnetometer (model M-I), Hotchkiss Superdips (used both parallel to and normal to the magnetic meridian, with several settings of the "sigma" angle), Lake Superior dip needle, and the dipping circle for measurements of inclination. The change in inclination over the measured anomalies ranged up to 4"; this caused pronounced changes in sensitivity of the Hotchkiss Superdip oriented parallel to the magnetic meridian. The variable sensitivity not only gives apparent displacement of crests of anomalies, particularly at high sensitivities, but also makes the data difficult or impossible to use in preparation of iso-anomaly maps. This weakness in field performance of the Superdip is shown to be eliminated by orienting the instrument normal to the magnetic meridian and measuring vertical intensity only, which in the latitude of upper Michigan is equal to 97 pct of the total intensity. The dip needle is seen to be relatively ineffectual for location of anomalies of less than 400 gammas. Introduction The U.S- Geological Survey, in cooperation with the Geological Survey Division of Michigan Department of Conservation, has for the past three years been engaged in a restudy of the Iron River-Crystal Falls iron mining district of upper Michigan. The bedrock in a large part of this area is covered with glacial deposits as much as 500-ft thick, and, inasmuch as some of the rocks have moderate to high magnetic permeability, extensive magnetic mapping has been done to assist in unraveling the complicated structure of the area. Several types of instruments have been used, and the major purpose of this paper is to present comparative data on the field performances of some of these instruments so as to aid others who face similar problems elsewhere to evaluate and choose the instruments best suited for the work. The paper is directed primarily to geologists and engineers rather than to geophysicists, although some familiarity with the instruments is presumed. The geology of the area consists of a complexly folded series of weakly metamorphosed sedimentary rocks, including the iron formation, which rests on older greenstones. Although the iron formation itself is only locally magnetic, some of the beds stratigraphically above the iron formation are rather strongly so. By tracing these hanging wall magnetic anomalies valuable information is obtained from which the structure and distribution of the iron formation can be inferred. Critical anomalies range from 25 to 6000 gammas of vertical intensity. Many anomalies can be traced in part with the common dip needle, but detection of others requires more sensitive instruments.

Jan 1, 1949

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 Charles White Merrill

Mankind's progress is measured in minerals. Man's emergence from prehistory is marked by passage through a Stone Age and a Bronze Age and into the present era, sometimes called the Iron Age or the Age of Metals. With the evolution of civilization and the development of a modem industrial economy, minerals become more and more important. Structures, roads, and machines are built largely of minerals; the energy to heat the structures and to drive the machines is mostly mineral; agricultural fertility is maintained by mineral fertilizers and water; and military strength is provided by fortresses, armaments, and munitions, largely of mineral origin. Thus in the material world, in the productivity of the economy, access to minerals has paramount importance. Every evidence indicates increasing dependence on minerals in the modem economy, particularly on the mineral fuels as energy sources to provide the power base for advancing industrialization. Both the total and the per capita consumption of almost every mineral is increasing in the industrialized nations. Moreover, nations with predominantly agrarian economies call themselves underdeveloped and universally strive to industrialize. Most mineral consumption trends in the more advanced economies have been greatly exceeding population growth-which itself has been advancing at an accelerating rate-and sometimes have surpassed the growth in real income. Some minerals have only recently been adopted or grown to importance in use. Titanium metal did not appear as a commercial product until 1948, and even coal seriously displaced wood as a source of heat less than two centuries ago. On the other hand, minerals have always played an important role in construction. The prehistoric megaliths that form the dolmens of Salisbury Plain are stone; the pyramids are andesite faced with limestone; and many other ancient structures are built of mineral materials. In modem times the whole course of architecture has been redirected by new building materials, mostly mineral. Most conspicuous is the sky-

Jan 1, 1964

By C. C. Nathan

Data are resented on the physical properties of five waxes obtained from fields in Texas and Louisiana in which "parafin" troubles are being experienced. The crude parafin was fractionated into three components, voluble in cold acetone, soluble in boiling acetone, and insoluble in boiling acetone. The acetone insoluble fraction was found to consist essentially of straight chain parafin hydrocarbons in the molecular weight range 525 to 700. Solubilities of the purified high molecular weight parafins were determined in a number of solvents. It was found that in hydrocarbon solvents, including crude oil, solubilities could be calculated satisfactorily by use of ideal solubility relations. In chlorinated, and oxygenated solvents, large deviations from ideal behavior were observed. These deviations could be partially correlated with the internal pressure of the solvent. INTRODUCTION A problem encountered in many producing oil fields is that of "paraffin" deposition. The problem refers to the deposition of material from the crude oil onto tubing, pumping rods, flow lines, or other material contacted by the crude. This problem has been recognized for nearly a hundred years, and numerous investigations have been reported on its causes and prevention or alleviation. One of the more comprehensive of such investigations was published by Reistle1 in 1932. A few of the salient findings of his report are briefly as follows: The term "paraffin" as used to describe this problem refers to the deposit of carbonaceous material which is not soluble or dispersible by the crude oil under the conditions where deposition occurs. The "paraffin" normally consists of high molecular weight paraffin hydrocarbons, both straight chain and branched, resins and asphaltic materials of undetermined nature, occluded oil and water, and possibly sand. In consistency, the deposit may vary from a soft, sticky material, to one which is hard and brittle. Deposits are usually black, although lighter colors are sometimes observed. Under the conditions of temperature, pressure, and crude oil composition occurring in the underground reservoir, the paraffin is in suspension or solution in the crude. As the oil flows to the surface, there is generally a reduction of temperature, pressure, and the amount of dissolved gases contained in the oil. Reduction of temperature and gas break-out were shown by Reistle to be factors causing reduced solubility of the paraffin in the crude. Thus, as the crude containing paraffin rises to the surface and flows to storage tanks at atmospheric temperature, the solubility of the paraffin may be exceeded. Deposition will begin at the point in the system where the temperature of the system falls below its cloud point, and continue as long as there is a further drop in the solution power of the crude for the paraffin. The severity of the deposition as well as the location of the bulk of the deposition, i.e., in subsurface or surface equipment, will depend on the amount of paraffin originally in the crude, the manner in which pressure and temperature of the crude

Jan 1, 1956

By Juptner von Jonstorff

A discussion of the paper by Messrs. Jüptner von Jonstorff, Blair, Dillner and Stead, read by title at the Lake Superior meeting, but presented first at the New York meeting of the Iron and Steel Institute (October, 1904), and here published under a mutual agreement between the two Institutes. Correspondence. MR. R. HAMILTON (Glengarnock) wrote to say that it was known for many years, that unless certain precautions were taken in dissolving the sample, there was a liability to obtain a solution from which the ammonium-molybdate solution would not precipitate the whole of the phosphorus. In 1877 Blair and Finkiner independently attributed this interference to the presence of carbonaceous matter in the solution, derived from the action of acids on the combined carbon of the metal, and they directed that the solution should be prepared in such a manner as to destroy these carbonaceous compounds. This was practically effected by evaporating the acid solution to dryness and roasting the residue. Adolf Tamm, in 1884, accentuated the same view. There are methods founded on the above-mentioned observations which leave nothing to be desired in point of accuracy, but the evaporation to dryness with subsequent roasting and re-solution consumes much time, besides the minor inconvenience caused by large amounts of acid fumes. In 1888 P. W. Shinier suggested that the incomplete precipitation of phosphorus was due to incomplete oxidation of -.the phosphorus, and proposed to render all the phosphorus precipitable by oxidizing the solution with potassium permanganate, etc. Experiments were made to test the accuracy of this view (details will be found in the Journal of the Society of Chemical Industry, vol. x., p. 904), and the results obtained seem to-prove that it is the correct one. It was first proved that carbonaceous matter in solution did not prevent the precipitation of properly oxidized phosphorus

Mar 1, 1905

By Leonard Bernstein, Harry Bartholomew

MANY of the properties of metals and alloys are structure dependent. Not the least of these is the grain structure. For example, in producing alloy bonds between silicon or germanium and gold-alloy foil at temperatures above their eutectics (which are, respectively, at 370" and 356°C) but below the melting points of the individual constituents, it was found that wetting was more complete with a fine-grain structure than with a coarse-grain structure. In cases where the assemblies were held together for long periods of time at elevated temperatures, wetting was not as critically dependent on the grain structure as was the case for shorter periods of time. When liquid phase forms, it first forms in the grain boundaries due to the fact that most of the impurities are concentrated at the grain boundaries and that most impurities tend to lower the melting point of the gold alloy somewhat. In addition, grain boundaries are at high-surface free-energy levels and are thus in a more favorable condition to initiate good wetting. A fine-grain structure will have more grain boundaries per unit area than coarse-grain structure thereby making wetting somewhat easier. To make the grain structure of an alloy sys- tem visible, a satisfactory method for differentiating between the different grains of which the system is composed must be employed. For the alloy bonding system previously described, the grain structure on the foil surface is of primary interest. Conventionally used etchants for the gold-alloy system will not adequately delineate grain boundaries in their structures. For this reason an alternate method is proposed for those cases where such a determination is necessary. Foil between 0.0005 and 0.005 in. thick has been used in this determination. The equipment used in this investigation was described in a previous publication.' Essentially, it employs a resistance-type filament which can be heated up very rapidly and cooled very rapidly. A thin refractory material is placed on top of the heating element. This refractory material may be molybdenum, tantalum, tungsten, or even ceramic but its thickness should be less than 0.010 in. to minimize the temperature gradient across it. The gold-alloy foil is placed on top of this refractory material. The temperature of the heating filament is raised to 900°C and cooled down to below 100°C in 5 to 10 sec. During this cycle, the foil can be observed to plastically deform due to its own weight. With no further chemical etching, this assembly is then viewed under a standard metallurgical microscope and the grain size measured. Fig. 1 is a Au-1 pct Sb alloy at 400X magnification and Fig. 2 is a Au-1 pct Ga alloy at 130X. This technique has proved to be an adequate means for controlling processing conditions in producing large quantities of gold alloy foil.

Jan 1, 1963

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors1 determined the constitution of copper-silicon-manganese alloys contailling over go per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper.2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 2o c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. 'I'able I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. X few other changes will be noted (No. 138 at 450°C., No. 147 at 550°C., Nos. 153 and 149 at 75o°C.). The change from liquid to beta in equilibrium with kappa in No. 137 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. I to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the K-a + Y change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300' and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 + 0.03 per cent or 2.42 ±. 0.05 per cent were cast in ingots of 3-in: diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 700°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors1 determined the constitution of copper-silicon-manganese alloys contailling over go per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper.2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 2o c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. 'I'able I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. X few other changes will be noted (No. 138 at 450°C., No. 147 at 550°C., Nos. 153 and 149 at 75o°C.). The change from liquid to beta in equilibrium with kappa in No. 137 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. I to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the K-a + Y change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300' and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 + 0.03 per cent or 2.42 ±. 0.05 per cent were cast in ingots of 3-in: diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 700°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By J. W. Fredrickson

VERY little information is available in the literature concerning the solubility of magnesium in titanium. Aust and Pidgeon&apos; report the solubility of titanium in magnesium to be 0.0025 pct at 650°C and 0.015 pct at 850°C. X-ray diffraction studies failed to detect any evidence of solid solubility. Based on the fact that the addition of titanium to magnesium increases the c/a ratio of magnesium, Busk&apos; suggested that the Mg-Ti system, like the Mg-Zr, is a peritectic. Eisenreich- eported the solubility of titanium in magnesium to be 0.003 pct at 655°C and 0.064 pct at 760°C. Removal of hydrogen from the melt increased the solubility of titanium to 0.115 pct at 800°C. Eisenreich proposes a peritectic-type diagram for the high magnesium side of the system. Recent work&apos; with Ti-Mg diffusion couples indicate that the solid solubility of titanium in magnesium is extremely small and that there is limited solid solubility of magnesium in titanium. Experimental work on the Ti-Mg system is complicated by the fact that the boiling point of magnesium is considerably below the melting point of titanium. Consequently, the usual alloying methods are impractical. Alloying was accomplished in this investigation by sheath-rolling compressed compacts." The alloys were made from titanium sponge and high purity magnesium. Chemical analysis of the sponge showed 0.04 pct Mg, <0.005 pct Al, <0.001 pct Cu, 0.05 pct Fe, 0.022 pct Mn, <0.0025 pct Ni, 0.007 pct Si, <0.005 pct V, and <0.01 pct Zn. All heat treating was conducted in a protective atmosphere by encapsulating the specimens in fused silica ampules under a partial pressure of helium. Equilibrium was achieved by holding the specimens at temperature for periods of 24 to 120 hr. The alloys were hot rolled, cold rolled, and annealed prior to solution heat treatment. Fig. 1 shows the constitutional diagram obtained for the Ti-Mg system up to 1.5 pct Mg. Oxygen was known to be present in the alloys; therefore, it is necessary to consider the alloys as ternary rather than binary and the diagram should be viewed as a plot of a section through the Ti-Mg-0 system. Other investigatorso have shown that the addition of oxy- gen to titanium stabilizes the a phase. The data presented in Fig. 1 indicate that the addition of magnesium to titanium tends to stabilize the p phase. Armour Research Foundation7 has shown that the addition of magnesium to zirconium lowers the a transus and is classified as a p stabilizer in that system. Magnesium is soluble in solid titanium to the extent of at least 1.5 pct in both the a and /3 phases. No intermetallic compounds or magnesium-rich phases were observed either by light microscopy or X-ray diffraction. However, this does not negate the possibility that such phases exist at higher alloy concentrations.

Jan 1, 1956

By Nicholas J. Grant, H. C. Chang

EMPHASIS on the importance of grain boundary sliding as a mode of deformation at elevated temperatures has been presented elsewhere.&apos; The extent to which boundary sliding occurs under certain creep conditions has been determined for high purity aluminum2,3 and aluminum alloys.&apos; In general, boundary deformation extends quite far into the adjoining grains, resulting in a rather wide band of deformation along the grain boundaries. This has led some investigators to doubt that grain boundary sliding consists of shearing along the boundary surface; it has been contended instead that boundary sliding is a result of concentrated slip in the neighborhood of the deformed grain boundaries."&apos; The purpose of this note is to present evidence that grain boundary sliding takes place by a bulk shear process. gh purity polycrystalline aluminum, wherever and whenever there is grain boundary sliding, boundary migration and concentrated deformation along both sides of the deformed boundary are associated with it. Therefore, it has been rather difficult to obtain unambiguous evidence of boundary sliding. On the other hand, it would be expected in certain alloys of aluminum, when tested under particular conditions. that the severity of the interfering effects of boundary migration and concentrated deformation along the deformed boundary might be reduced. Current research in this laboratory&apos; shows that a 20 pct Zn-A1 solid solution alloy fractures in an intercrystalline manner during creep at 500°F with a small total elongation of not more than about 14 pct, and that it does so with extremely limited grain boundary migration. Accordingly, this alloy was chosen for the present study. The experimental procedure was similar to that used in previous work and has been presented elsewhere.&apos; Two parallel flat surfaces were milled from a round specimen. The gage portion of the specimen was 1 in. x .09 in. x .17 in. The specimens, which were annealed at 1030°F for 24 hr, showed two to four grains across the width of the test bar. The specimens were subjected to creep at 500°F at stresses of 2000 to 5000 psi. The rupture times were from 10 sec to 3 hr. Appreciable boundary sliding occurred in all the tests. A typical example of boundary sliding is shown in Fig. 1. (The tension axis is vertical in the micrographs.) Sliding has taken place along the boundary between grains A and B unaccompanied by important boundary migration. The sharpness of the offset at the triple point can be clearly seen in grain C. As a result of sliding along the boundary between grains A and B, a new boundary surface between grains A and C was created. The offset at the triple point is about 0.07 mm. This boundary sliding is accompanied by the formation of rather sharp kinking bands and, of course, slip on several slip systems in grain C. This type of deformation has been referred to as fold formation&apos; in previous work with high purity aluminum.

Jan 1, 1957

By William F. List, Marvin A. Schuster

Monolithic electrooptical mosaics of 2500 photo-transistor elements with internal row and surface column interconnections have been fabricated by epitaxial-planar diffsion techniques. Unique access to any elemed of the mosaic is provided through one of the fifty X and one of the fifty Y external leads. The sensor mosaic can be used for imaging applications and has a 1:1 aspect ratio, a resolution of 100 lines per in., a dynamic range in excess of lo3, a sensitivity of 0.5 per pw, element response within a 2:l range over 75 pct of the mosaic, and a minimum detectable signal of the order of 10-&apos; w. Design considerations which ilnpose particclar fabrication yequirements are disctussed along with some of the problems peculiar to the epitaxial and planar-dijfision techniqes by which this device is fabricated. The solid-state silicon monolith has an imaging area of 0.5 by 0.5 in. and an element center -to- center spacing of 0.010 in. J monolithic solid-state electrooptical device has been developed as the photon-sensing mosaic for use in an image-converter system.&apos; This system is the solid-state equivalent of the vidicon and can image radiation in the visible and near-infrared regions of the spectrum. The electrooptical image converter has the desirable size, weight, reliability, and low-power characteristics inherent in solid-state devices. It is read out by direct-wire means rather than by beam-scan techniques. The packaged unit is shown in Fig. 1. A selection of material for the sensor was based on considerations of both reliable fabrication techniques and material spectral response. Silicon was selected both for its response from the lower end of :he visible to the long-wavelength cut-off above 11,000A and for its well-developed epitaxial planar-diffused technology. The electrical image is composed of M x N discrete information bits with each bit emanating from one of the individual phototransistor sensors. The interconnected mosaic concept was introduced to provide a structure which is both manageable in its number of leads and compatible with conventional viewing systems which accept XY data. Interconnections along the Y direction are provided by internally diffused strips, while interconnections along the X direction are formed by vacuum-deposited metal surface bars. Unique access to any individual element of the M x N mosaic is available through one of the M and one of the N external leads. PHOTOTRANSISTOR DESIGN A phototransistor structure2 was selected for the discrete photon detectors of which the mosaic is com- posed. Basically, the mode of phototransistor operation is such that incident quanta are absorbed in the base area of the element where they generate electron-hole pairs. If the electrons are liberated within a diffusion length of the depletion region around the collector junction, they will diffuse to this depletion region and be swept across the junction where they account for a small component of the photocurrent. Similarly, the holes which are created within a diffusion length of the emitter junction will diffuse to this region where they forward bias the emitter and so induce injection of minority carriers into the base. This accounts for the substantial transistor photocurrent. This mechanism of operation implies several design and fabrication goals for the individual sensor elements: high electrooptical conversion efficiency, sufficient carrier lifetime in the base regions, and a maximum volume in which photons can be absorbed within a diffusion length from the depletion layer about the junction. Moderately high transistor gain is desirable to permit readout at low light levels; however, very high gain has a deleterious effect on mosaic dynamic range. The mosaic must also be characterized by good uniformity of element response as well as by good isolation between elements. The above set of conditions imply that junction depths must be optimized with respect to photon ab-

Jan 1, 1967

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors&apos; determined the constitution of copper-silicon-manganese alloys containing over 90 per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper .2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 20 c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. Table I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. A few other changes will be noted (No. 138 at 450°C., No. 149 at 550°C., Nos. 153 and 149 at 750°C.). The change from liquid to beta in equilibrium with kappa in No. 139 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. 1 to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the [K = a + ?] change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300° and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 ± 0.03 per cent or 2.42 ± 0.05 per cent were cast in ingots of 3-in, diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 900°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By J. S. Marsh

JOSEPH PRIESTLEY prepared oxygen on Aug. 1, 1774, and noted with great surprise "that a candle burned in this air with a remarkable brilliant flame." On Aug. 2, 1774, some ironmaker possibly began to wonder if this substance could be used to increase his rate of production; at any rate, there is no disputing the fact that the notion of using oxygen for steelmaking in concentrations greater than that available in great abundance-as air-has been in existence for years. Action was delayed by the lack of enough oxygen at a cost within reach of the steelmaker. Within the last several years enough has been available to permit large-scale tests of its use for both combustion, with which this paper is concerned, and for decarburization. The literature is now enormous and easily available; it is sufficient here to cite three items of historic- importance in that all are about 25 years old and in that all are remarkably consistent as far as they go, with what is known today.1,2,3 SIGNIFICANCE OF HIGH-TEMPERATURE HEAT The principal &apos;function of the open-hearth furnace is to supply sufficient, high-temperature heat to melt the charge and then to increase its temperature to a range suitable for tapping, ordinarily in the neighborhood of 2900°F. That heat is required to make steel everybody; however, there seems to be some confusion now and then about the significance of high-temperature heat. Transfer of energy-and heat is energy is always from a point of higher potential to a point of lower potential and, other things being equal, the greater the potential difference, the greater is the rate of transfer of energy. In the open hearth the flame, of course, is the high-potential source. Perhaps the most satisfactory approach is through the notion of theoretical flame temperature; which is the ratio of heat input to the heat content of the combustion products,* the former is composed mainly of heat of combustion of the fuel plus sensible heat of the fuel plus sensible heat of the combustion air. Thus, flame temperature can be increased by increasing the value of the numerator, by decreasing the value of the denominator, or both. The first method is as old as the open-hearth process and, of course, makes use of preheated air; its possibilities have been by no means exhausted. The second method can be put into effect only by changing the composition of the combustion air, since the combustion of a given quantity of fuel produces a definite quantity of product, and since the denominator includes the non-reactive fraction of the air, principally nitrogen. In other words, the denominator consists of the volume of exit gas multiplied by its heat capacity and that volume consists of carbon l is understood by dioxide and water vapor as reaction

Jan 1, 1948

By C. R. Boyd

In 1874 I received an appointment in the corps organized by Col. William P. Craighill, U. S. Engineers, to survey the New or Upper Kanawha river for the purpose of ascertaining the practicability and

Jan 1, 1895

By J. L. Huitt, D. K. Lowe

This laboratory flow study covers propping agent transporl in horizontal fractures as influenced by the characteristics of the propping particles, fluid and fracture. Correlations are presented for the transport of particles, deposition and fingering through dunes. For particles moving individually, the article velocity in some cases may be low compared to the hulk average fluid velocity; in other cases, the particle velocity may exceed the bulk average fluid velocity. At high propping agent concentration or low fluid velocity, the likelihood of particle deposition and dune formation increases. Fingering and channeling accompany dune formation. Dune formation can be limited to the outer region of tile fracture by adjustment of pump rate, fluid viscosity and particle concentration. A method is presented by which pump rate and fluid vircosity may he selected to control dune formation for given propping agent concentrations. INTRODUCTION The area and flow capacity of a fracture predominantly control the stimulation derived from hydraulic fracturing. Generation of fracture area exposes the rock matrix to a flow channel; the flow capacity of the fracture controls the flow through the channel to the wellbore under a given pressure gradient. This paper pertains to an important factor that affects the flow capacity of a fracture: the transport of the propping particles in the fracturing during the hydraulic fracturing treatment. With a better understanding of particle transport, fracturing treatments may be designed to obtain more effective distribution of the propping agent. RELATED STUDIES In recent years, the approach to obtaining high fracture flow capacity has been partial monolayer propping. Three papers1-3 have dealt with various facets of this concept. However, in some papers dealing specifically with particle transport, the results generally indicate that packing the propping particles within a fracture is inevitable. In early work&apos; with a sand slurry flowing in a pie-shaped flow cell, qualitative results showed that particle deposition in a fracture during transport should be expected. In other studies"" correlations based on slurry flow in vertical linear flow cells showed particle deposition was primarily a function of fluid velocity. In a recent paper the rate of sand advance (movement of dunes) in a horizontal linear flow cell was discussed. Subsequently, a method was given for designing fracturing treatments, based on the extent of sand advance during a treatment. In this work, particles whose diameter was small relative to the fracture width (i.e., dl W< 0.2) were primarily considered. The particle transport approaches that of sand transport in a stream bed. The industry trend, however, has been to use larger size propping agents. That is, particles with diameters approaching fracture widths predicted by Perkins and Kern.&apos;&apos; This trend has led to generally better fracturing treatments with particle relative sizes in the range 0.2 <d/W < 1.0. In all of the particle transport studies previously cited, the fluid characteristics were discussed. However, little or no attention was given to the parzicle characteristics. In this study the particles. as well as the fluid and fracture, are considered. VARIABLES AFFECTING PARTICLE TRANSPORT In the exploratory work to set LIP a program for this study, it was noted that particles within a batch moved at different velocities in a horizontal linear flow cell. In some cases the particles moved independently. In others there was particle interference. Also, particle deposition and fluid fingering occurred in some cases (Fig. 1). As a result of observing the easily distinguishab&apos;le types of particle movement, the particle variables as well as the fluid variables were included. In addition, the fracture width was included because the fluid velocity profile surely must affect the movement of the larger particles differently than that of smaller particles. Particle variables were density, diameter (based on a sphere of equal volumetric displacement), long and short dimensions, drag coefficient and velocity. Fluid variables were density, viscosity, yield shear strength and velocity. Fracture variables were the width and the angle between the plane of flow and a horizontal plane. Two factors which may prove to be important were omitted because of the complexity resulting from the parameters cited above. These are the fracture-surface roughness and gross irregularities that cause changes in the direction of flow. EXPERIMENTAL EQUIPMENT AND PROCEDURE A linear parallel-plate flow cell (Fig. 2) was used in the study. Lucite plates 1 in. thick formed the test section and permitted a viewing section 11 ft long and 10 in. wide. Spacing between the plates was adjusted with shims to give fracture widths 1/36 to 1/2 in. The model could be tilted to an angle of 45" with the horizonltal plane. Fluid flow was maintained with a Moyno positive displacement pump. Single particles were placed in the flow stream with a particle injector. A .4 - in. diameter plunger moving at a constant rate in a

Jan 1, 1967