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By C. T. Holland

This discussion is concerned with those com-J- paratively infrequent bumps that eject material from the failed mass with enough energy to wreck heavy machinery and seriously injure or kill people. In such cases there is a loud report, and the pressure waves set up in the mine atmosphere wreck ventilation controls several hundred feet from the site of the failure. Vibrations are induced in the earth's crust which may be detected several miles from the point of origin, and explosive gases may be released in large quantities." Usually a dense suspension of dust is produced from the failed mass, together with dust placed in suspension by the resulting air blast. These rock bursts or bumps have also been called mountain shots, bounces, pillar bursts, and crumps. Such occurrences, when extensive, are serious catastrophes, and may force abandonment of the mine.' CAUSES OF ROCK BURSTS Rock bursts in coal mines have occurred in sev-eral places under diverse geological conditions, mining methods, and/or practices. A study of many such occurrences indicates that they depend on the following conditions: 1) cover thickness of 500 ft or more, 2) cover composed of strong members and having a strong member lying close to or on the coal bed, and 3) a floor that does not readily heave. The minimum thickness of cover under which coal mine rock bursts occur is based on observation. Under unusual circumstances involving very strong roof members and/or mining systems, and/or practices especially likely to induce bursts, a burst conceivably could occur under less roof. Under special circumstances rock bursts have occurred in marble quarries almost at the surface.' Furthermore, under very heavy cover it is likely that controlling roof members need not be as strong and as close to the coal bed to cause bumps. Just what constitutes a strong roof or roof member is open to question. Obviously the strength of a roof member is determined by its thickness, the distance between bedding planes across which little or no bond exists, the spacing and development of joints, and the inherent strength of the rock material. Strata sections showing roofs under which rock bursts in coal mines have developed are illustrated in Fig. 2. In several instances the strength of rocks composing the roof of mines developing bumps has been tested. The tests (Table I) show that these rocks develop considerable strength in compression, bending, and shear and that in some cases the strengths are very high. No quantitative data are available concerning joints in roof members over coal beds where rock bursts have occurred, but the author has examined many mines subject to bursts and has received the impression that joints in the shales immediately over the coal beds are always present and well developed. In the main sandstone or conglomerate members themselves, however, where observed, he has yet to see a fracture system indicating well developed joints. Undoubtedly joints are present, but the evidence indicates that they are few, poorly developed, and widely spaced. In a mine subject to bumps, moreover, actual measurements of roof spans up to 225 ft between supports under a cover of about 800 ft have been made before roof failure occurred. Such spans signify strong roof. In coal beds subject to rock bursts, the bottom rock is usually a sandy shale. A few tests (Table I) have been made on the floor rock of coal beds. Observations in mines indicate that they are usually weaker than roof rocks and that under load they show more plastic effects. Observation in ground subject to bursts invariably indicates a relatively strong floor highly resistant to heaving, although some heaving may occur. Other factors listed as favorable to rock bursts are: 1) mountainous surface; 2) steeply dipping beds; 3) proximity of faults, folds, and other similar geologic structures. Many bursts have occurred in mines under mountainous country, although many bursts in mines under a surface with little relief indicate that thickness of cover, not relief, is the essential factor. In steeply dipping beds, many bursts occur in mines that are essentially flat, and rock bursts have been recorded in beds dipping as much as 35o Most rock bursts in the U. S. occur in beds that dip less than 10 pct. It is also true that most U. S. coal is produced from beds dipping less than 10 pct. Geologically, faults are regarded as providing stress relief, but in the vicinity of faults, as well as sharp folds, it would seem that residual stresses could be present. The fact that rock bursts occur in areas remote from faults and sharp folds suggests that their presence is not necessary for this phenomenon to take place. There have been many bursts close to faults and folds, and it may be assumed that occasionally such structures accentuate their occurrence3 The conditions and circumstances under which they occur, coupled with the effects produced, leave In the Crowsnest Pass coalfield, British Columbia, a rock burst is estimated to have released 1.8 million cu ft of methane.

Jan 1, 1959

By E. B. Hunt

Paraffin deposition has been studied in the laboratory under conditions simulating deposition in well tubing. A theoretical analysis has been made of the cooling of the oil and the precipitation of paraffin from the oil as it flows up the well tubing and through surface flowlines. It is proposed that paraffin deposits are initiated by the precipitation of paraffin directly on or adjacent to the pipe wall and grow by diffusion of paraffin from solution to the deposit. This mechanism is consistent with laboratory and field observations, and has proved useful in the design and interpretation of laboratory paraffin-deposition tests. Tests have been made of the effect of plastic pipe coatings and chemical additives on paraffin deposition. INTRODUCTION Paraffin deposits which form in well tubing and surface flowlines interfere with production and must be removed. Over the years much progress has been made in developing and improving methods of removing these deposits after they form. Much less progress has been made in developing methods of preventing or inhibiting the formation of paraffin deposits. This is due, it is believed, to the lack of knowledge of the mechanism of paraffin deposition, the absence of satisfactory laboratory testing methods and the difficulties in evaluating the results of field tests of preventive treatments. The present investigation was undertaken to elucidate the mechanism of paraffin deposition and to develop suitable laboratory tests for studying the inhibition of paraffin deposition in well tubing and surface flowlines. Current theories on the mechanism of paraffin deposition have been evolved from field observations, from laboratory studies of various factors which might be involved in paraffin deposition, and from laboratory paraffin-deposition tests.1-9 Paraffin deposits have been formed in the laboratory by immersing a cold finger into a hot wax-oil solution and by flowing hot wax-oil solutions through cooled pipe or over cooled plates. These laboratory conditions differ in important features from field conditions, and the observed deposition behavior is not entirely field-like." Thus, there is reason to question the field applicability of the results of these tests. The present investigation was undertaken to determine how to perform and interpret laboratory paraffin-deposition tests to obtain information on the inhibition of deposition in the field. The paraffin problem in the broadest sense encompasses the formation of any predominantly organic deposit in well tubing, surface flowlines and other equipment in contact with crude oil or gas. The present investigation was limited to paraffin deposition involving the precipitation of paraffin wax from solution by cooling and its concentration in a deposit on a cooled surface. This probably excludes its applicability to those problems arising from asphaltic-base crudes, but not those arising from paraffin-or mixed-base crudes. This also excludes its applicability to emulsion and congealing oil problems which are often included as part of the paraffin problem. The phenomenon of cooling appears to be the controlling factor in paraffin deposition involving the precipitation of paraffin wax and its concentration in the deposit. Deposits of this type are usually found in the field only where cooling occurs. Early in this laboratory investigation, it was not found possible to form deposits under constant temperature conditions from a wax-oil slurry, either by steady flow through pipe or by gas-lift up a pipe. Thus, the investigation was limited to situations involving cooling. THEORY The relationships involved in establishing the temperature profiles in an oil stream as it flows up well tubing with a linear (geothermal) pipe-wall temperature distribution or through surface flowlines with essentially constant pipe-wall temperature are presented in the Appendix. The relationship between radial distance in the pipe and the rate of cooling of the oil is then combined with a relationship between cloud point and rate of cooling to develop the pattern of formation of a wax cloud in the oil. The following discussion of paraffin deposition under various laboratory and field conditions is based upon this development which is presented in the Appendix. PARAFFIN DEPOSITION IN SURFACE FLOWLINES The average temperature of the oil coming out of a well is somewhat higher than the ground temperature. Thus, the oil continues to cool on its trip through the surface flowline, and wax deposition can occur. The temperature distributions calculated from Eq. A-4 are given in Fig. 1. As can be seen, almost all the cooling occurs in the first 500 ft from the wellhead. In addition, the radial temperature gradient near the wall decreases rapidly with distance and becomes very small after a few hundred feet. Thus, growth of a paraffin deposit would be expected to decrease rapidly with distance from the wellhead and become negligible after a few hundred feet, since growth is dependent on concentration gradient. Wax precipitation and diffusion of wax to the already

By D. H. Desy, L. C. Fincher

The magnesium-rich end of the Mg-Ti phase diagram was investigated. The liquidus, solidus, and solvus boundaries to 1 pct Ti were established. All alloys were prepared by saturating molten magnesium with titanium in a consumable titanium crucible under inert gas maintained at 230 psig. The liquidus of the Mg- Ti system was determined by analysis of dip samples taken from 700° to 1300°C under equilibrium conditions in a pressurized inert atmosphere furnace and by analysis of small ingots rapidly poured and quenched from 1400° to 1500°C. The solubility of titanium in magnesium ranged from 0.018 wt pet Ti at 700°C (0.012 wt pet at 650°C by extrapolation) to 1.035 wt pet Ti at 1500°C. The solidus for compositions ranging from 0.03 to 1.00 wt pet Ti was determined to be 650° ± 1°C by thermal analysis. The titanium solid solubility values ranged from 0.08 wt pet at 350°C to 0.19 wt pet by extrapolation to 650°C. The freezing reaction is peritectic. No intermetallic compounds were found in the system; the phase in equilibrium with molten magnesium saturated with titanium was found to be titanium with magnesium in solid solution. Solid titanium will dissolve at least 1.32 wt pct Mg. PREVIOUS investigations of the Mg-Ti system have shown considerable disagreement on the solubility of titanium in liquid magnesium. Furthermore, the solid solubility of titanium in magnesium has not been well established. Liquidus curves for previous work and for the present investigation are shown in Fig. 1. Aust and Pidgeon1 used a dip-sampling method on molten magnesium held in equilibrium with solid titanium under a protective atmosphere to determine the solubility and found that it ranged from 0.0025 wt pet Ti at 651°C to 0.015 wt pet Ti at 850°C. Eisenreich2 introduced titanium into molten magnesium by means of TiCL4 adsorbed on BaCl2. Ingots were then cast at various temperatures. Making the assumption that only the titanium dissolved in magnesium at the time of casting was soluble in H2SO4, Eisenreich determined the solubility of titanium in molten magnesium to range from 0.003 wt pet at 655°C to 0.115 wt pet at 800°C. Eisenreich also determined the solid solubility of titanium in magnesium to be 0.015 wt pet at room temperature and 0.045 wt pet at 500°C. Since the solid solubility just below the freezing temperature for the bulk of the alloy was much larger than the liquid solubility just above the freezing temperature, Eisenreich concluded that the freezing reaction was peritectic. Obinata et al.3 equilibrated molten magnesium with titanium in hermetically sealed titanium containers which were then furnace-cooled. The titanium content of the magnesium was then determined and found to range from 0.170 wt pet at 700°C to 0.85 wt pet at 1200°C. No intermetallic compound was found in the system. The Armour Research Foundation4 determined two points on the solvus by electrical resistivity methods: 0.00057 wt pet at 200°C and 0.0008 wt pet at 300°C. At higher temperatures, data were meaningless with no trends observable. The authors of this report believed that the lack of significant data at the higher temperatures was due to variations in specimen geometry, although there was no positive evidence to verify this supposition. The present investigation was undertaken to clarify the uncertainty in both the liquidus and solvus of the magnesium-rich end of the Mg-Ti system. EQUIPMENT AND MATERIALS The equipment used in this investigation, with some modifications, was essentially that used by Crosby and Fowler5 in their determination of part of the Mg-Zr phase diagram. The equipment, as modified for this work, is shown in Fig. 2. It consists of a sealed furnace chamber which can be pressurized with inert gas so that melts can be made above the boiling point of magnesium at atmospheric pressure. Melts are made by induction heating in a titanium crucible which, after diffusion of sufficient magnesium into the walls of the crucible to saturate the titanium at the sampling temperature, comprises the solid phase in equilibrium with the molten magnesium. Dip samples may be taken with the sampling tube, or the entire furnace may be tilted so that ingots may be poured into a mold in the side chamber. The principal difference from the earlier apparatus is in the thermocouple, which in the present equipment is enclosed in a protection tube and immersed directly in the melt. The tips of both the thermocouple protection tube and the sampling tube, which dip into the melt, are made of high-purity titanium. The 4 1/2-in.-long titanium tip of the sampling tube is threaded into a steel tube, O in Fig. 2, which extends through the top of the furnace. To determine whether the temperature at the tip of

Jan 1, 1969

By M. T. Simnad, G. Derge, I. George

Measurements of current efficiency on iron-silicate slags in iron crucibles showed that conduction is about 10 pct ionic in slags with less than 10 pct silica and about 90 pct ionic in slags with more than 34 pct silica, increasing linearly in the intermediate range. The balance of the conduction is electronic in character. Silicate ions are discharged at the anode with the evolution of gaseous oxygen. Transport experiments show that the ionic current is carried almost entirely by ferrous ions, which may be assigned a transport number of one. THERE has been increased evidence in recent years that the constitution of liquid-oxide systems (slags) is ionic.1-3 The principal studies designed to establish the structure of liquid slags have been by electrochemical methods', " and conductivity measurements1,6,7 which also have indicated the presence of semiconduction in several silicate systems1,4-0 and in pure iron oxide.' It is well known that many slag-forming metallic oxides have an ionic lattice type in the solid state, and their properties are determined to a large extent by the lattice defects and ion sizes. As Richardson8 as pointed out, the detailed models of liquid slags cannot be found on thermodynamic data only but "must rest on a proper foundation of compatible structural and thermodynamic knowledge, combined by statistical mechanics." A careful thermodynamic study of the iron-silicate slags has been carried out by Schuhmann with Ensio9 and with Michal.10 They obtained experimental data relating equilibrium CO2: CO ratios to slag composition and made thermodynamic calculations of the activities of FeO and SiO, and of the partial molal heats of solution of FeO and SiO2 in the slags. It was found that the activity-composition relationships deviate considerably from those to be expected from an ideal binary solution of FeO and SiO2. However, the partial molal heat of solution of FeO into the slags was estimated to be zero. Their experimental results were correlated with the constitution diagram for FeO-SiO2 of Bowen and Schairer,11 with the results of Darken and Gurry" on the Fe-O system, and with the work of Darken"' on the Fe-Si-O system. All these studies were found to be consistent with one another. The variation of the mechanism of conduction with composition in the liquid iron-oxide-silica system in the range from pure iron oxide to silica saturation (42 pct SiO2) in iron crucibles was reported in a preliminary note." The current efficiency, or conformance to Faraday's law, showed some ionic conductance at all compositions, the proportion increasing with the concentration of silica. The current-efficiency experiments since have been extended. Furthermore, transport-number measurements have been completed in silica-saturated iron silicates to determine the nature of the conducting ions. Experimental Current Efficiency in Liquid Iron Oxide and Iron Silicates using Iron Anodes: This study was carried out by passing direct current through slags in the range from pure iron oxide to iron oxide saturated with silica (42 pct silica), using pure iron rods as anodes and the iron container as the cathode. A copper coulometer was included in the circuit to indicate the quantity of current passed during electrolysis. Assuming that the cation involved is Fe-+, the theoretical quantity of iron lost from the anode according to Faraday's law may be calculated and when compared with the actual loss observed, gives an indication of the extent to which Faraday's law has been obeyed. It also gives an indication of the presence and extent of ionic conduction in the melt. Preparation of the Slags: About 100 g of chemically pure Fe,O, powder is placed in an iron pot which is heated by induction until the contents liquefy. In this way, FeO is produced according to the reaction Fe2O3 + Fe = 3 FeO. More Fe2O3 or SiO, powder is added and, when a sufficient quantity of molten slag is obtained, the induction unit is turned off, the pot withdrawn, and the molten slag poured on to an iron plate. Homogenization and Electrolysis of the Slag: Apparatus—After considerable development, the setup illustrated in Fig. 1 proved to be quite satisfactory. A is an Armco iron cylinder, 1 in. ID and 1/8 in. wall, consisting of three sections placed one on top of the other. The bottom section is a pot about 5 in. long with a small hole drilled in its bottom to allow withdrawal of gases during evacuation of the apparatus. The middle section is 6 in. long and consists of a pot which serves as the slag container, while the top section is a hollow-cylinder continuation of the slag-container pot. The height of this latter section is about 5 in., giving an overall length of approximately 16 in. The iron cylinder is constructed in this way for ease of fabrication, the individual sections becoming welded together after the

Jan 1, 1955

By C. W. Kovach, A. Moskowitz

Studies were undertaken to investigate the effects of manganese content on the machinability and other Properties of a free machining martensitic stainless steel (AISI Type 416). Machinability was found to be significantly improved in steels of high manganese content, and a direct relationship was obtained between machinability and steel Mn:S ratio. As the manganese content of the steel increases, the sulfide Phase present changes from CrS to (FeMn)Cr2S4 to (MnFeCr)S, and finally to MnS. The average sulfide inclusion hardness decreases through the same range of increasing manganese content. The mechanism for machinability improvement is discussed in terms of a soft ductile sulfide affecting deformation in the secondary shear zone. Type 416 containing relatively high manganese for improved machinability shows good general properties. The effects of increasing manganese content on mechanical properties, cold formability, and corrosion resistance are described. THE addition of sulfur is commonly used to improve the machinability of stainless steels. However, little attention has been paid in the past to the composition and characteristics of the sulfur-containing phase or phases present in these resulfurized steels. Recent information on the properties of sulfide phases, and their role in metal cutting, suggests that variations in these phases could have critical effects on machin-ability, as well as important effects on formability and other properties such as corrosion resistance. Manganese, chromium, and iron are strong sulfide forming elements present in stainless steels! of these, manganese has the greatest sulfide forming tendency and iron the least.1"1 The manganese content of resul-furized 13 pct Cr steels, often about 0.5 pct, can be insufficient or only barely sufficient to combine with the sulfur that is present; thus, the precise level of manganese can strongly influence the nature of the sulfide phase. Sulfide phases which may be present in stainless steels have been reported to include CrS, a spinel-type sulfide, chromium-rich manganese sul-fide, and manganese Sulfide.5,6 Detailed phase relationships for the Fel3Cr-Mn-S system have been reported by the present investigators,7 and a portion of this work will be referred to subsequently in this paper. Recent work by Kiessling6 and Chao et a1.8 has shown that sulfide phases can display wide variations in hardness, and may undergo considerable plastic deformation under isostatic loading.9-12 Early theories of metal cutting attributed the influence of sulfur to a lubricating effect. It is now apparent that the influence of the nonmetallic inclusions and their properties on crack initiation, deformation in the shear zones, and boundary films must also be considered in relation to the machining process. This paper presents the results of studies conducted to relate machinability to the various sulfide phases which occur in stainless steels. This work has led to the development of alloys with improved machinability, and has generated information on the effects of inclusions on metal cutting processes. Effects of sulfide inclusions and steel composition on other important metallurgical properties are also discussed. MATERIALS For drill machinability and inclusion studies, 10 lb laboratory heats were melted in an air induction furnace. These heats were made with sulfur contents be tween 0.10 and 0.50 pct and manganese contents be tween 0.05 and 3.0 pct. Residual elements were added to the heats in amounts typical for commercial steels. The typical compositional range covered by the heats is shown below: C Mn P S Si Ni Cr Mo Cu N 0.10 0.05 0.007 (M0 0.40 0.40 13.0 0.20 0.10 0.03 3.0 0750 The laboratory ingots were forged in the temperature range of 1800" to 2100°F to 3/4-in. sq bars, and all bars tempered to a hardness aim of 200 Bhn prior to testing. Because of differences in composition and tempering response, the tempered bars showed some variation in hardness (175 to 275 Bhn) as well as variations in delta ferrite content (0 to 50 pct). Composition, hardness, and delta ferrite content were considered in the analysis of the machinability data. Additional tests involving tool-life evaluation and determination of other properties were conducted on materials from commercially melted and processed 15-ton electric furnace heats. TESTS AND PROCEDURES Machinability of the laboratory heats was evaluated in a drill test. In this test, 1/4-in. diam holes, 0.4 in. deep, were drilled alternately in a test bar and in a standard bar for a total of four holes in each. This sequence was repeated three times using a freshly sharpened drill each time. The average time required to drill a hole in the test bar was compared to that for the standard bar. A drill machinability rating was assigned to the test bar relative to a rating of 100

Jan 1, 1970

By R. L. Moment

The anisotropic elastic behavior of rolled beryllium sheet has been measured, using a pulse echo technique, and compared with X-ray diffraction data. Calculated elastic stiffness constants compared favorably with published values for beryllium single crystals which were attributed to the strong (0002) rolling plane texture. Variations of Young's modulus in the yolling plane could be associated with the velative distribution of (0002) planes out of their ideal position in the rollitzg pkule. WHEN a metal is subjected to cold working such as drawing, forming, or rolling, a crystallographic texture develops which can significantly alter its physical properties. One method for detecting this texture is X-ray diffraction, but Alers and Liu' have recently pointed out how the prediction of anisotropic physical properties from pole figures alone is not always accurate due to differences in interpretation. Variations in Young's modulus with orientation or, more completely, the values of the effective elastic constants of the worked metal, also serve to indicate the presence of a texture. In fact, as Alers and Liu' pointed out, calculated variations in Young's modulus for assumed orientations, when compared with experimental data, can be used to eliminate some of the uncertainty in interpretation of X-ray pole figures. Thus, elasticity measurements can serve not only to clarify any unusual elastic behavior of worked metal, but also to detect and in part determine the nature of its texture. X-ray determination of the texture of rolled beryllium has been reported by Smigelskas and Barrett,2 who found a strong texture of (0002) in the rolling plane with (1070) planes normal to the rolling direction. In the case of metal rolled at room temperature, they reported that [1010] directions also appeared at positions 60 and 120 deg from the rolling direction in the rolling plane, while in more recent work Keeler3 found these directions were also tilted towards the rolling plane. The texture for beryllium rolled at 80O0C, however, only showed (1010) planes normal to the rolling direction and the spread of (0002) planes out of the rolling plane was less. In looking for elastic anisotropy one might consider unidirectional rolling of a metal as introducing an or-thorhombic symmetry through reorientation of the grains, since the three deformations, compression, extension in the rolling direction, and extension in the cross direction, are orthogonal to each other and unequal in magnitude. Thus the rolled sheet could be treated like an orthorhombic single crystal and the nine stiffness constants of the elasticity tensor used to calculate the anisotropy of Young's modulus, the shear modulus and Poisson's ratio. In this case we could write: which is symmetric about its diagonal. Borik and Alers4 have recently used this approach on rolled die steel with very good results. They found, however, that instead of displaying orthorhombic elastic symmetry their specimens could be considered tetragonal in which case Cr1 = c22, c13 = Ca, and c44 =cjj. This conclusion was made solely on the basis of the measured tensor elements, and serves to point out the advantage of this method for studying the anisotropy of rolled metals. Their calculated values for Young's modulus as a function of angle in the rolling plane also checked very well with direct measurements made on different specimens using the resonance technique. In the present study, cross-rolled beryllium was used which had been unidirectionally rolled about 11 pct for the final reduction. This imparted a slight anisotropy in the rolling plane which was detected both by X-ray techniques and elasticity measurements. For purposes of discussion in this paper, the rolling direction is that direction in which the most reduction passes were made and cross direction is the normal to the rolling direction in the rolling plane. It was also decided to consider the rolled sheet as displaying orthorhombic symmetry for the purpose of obtaining elasticity samples with the direction defined as in Table I. Any change in the final symmetry attributed to the sheet would then be made on the basis of the measured elastic stiffnesses. The final data would then be compared with that expected from the X-ray study and that reported for beryllium single crystals. EXPERIMENTAL PROCEDURE Rolling Schedule. The samples used in this study were taken from a large sheet which, because of its size, had to be unidirectionally rolled for the final reduction. The resulting texture was that of cross-rolled metal with a slight unidirectional texture superimposed. A cast beryllium ingot, 9.500 in. sq by 3.325 in. thick, was cross-rolled to 81 pct reduction followed by unidirectional rolling for an additional 11 pct to give a total reduction of 92 pct. The thickness of the final sheet ranged from 0.265 to 0.280 in. Reduction up to 67 pct was done at 980°C and the final 25 pct at 870°C. Analysis for metallic impurities showed aluminum 0.06 pct, iron 0.19 pct, and silicon 0.11 pct, giving a beryllium purity of 99.64 pct.

Jan 1, 1968

By B. E. Terkelsen, B. J. Piearcey

A study has been made of the effect of unidirectional solidification on the creep behavior, stress-rupture properties, and thermal shock resistance of four nickel-base superalloys. The alloys Mar-MZOO, B-1900, IN 100, and TRW 1900 show improved rupture ductility and thermal shock resistance when tested with the columnar grains parallel to the major stress axis during test. The relative improvement in creep-rupture properties depends on the intrinsic strength of the alloy, a property which depends on composition, heat-treatnient, and crystallographic orientation. The data clarifies some of the factors affecting the properlies of the cast nickel-base superalloy. COMPONENTS designed for high-temperature use have, in recent years, been fabricated by precision casting techniques using nickel-base alloys developed specifically for use in the conventionally cast condition. This development was a result of both the increasing complexity of the component and the recognition that high-temperature strength was incompatible with workability. The use of castings can be economically favorable, but, more important, the recent complex designs of air-cooled gas turbine blades and vanes in alloys which possess the necessary high-temperature strength cannot be forged. Common modes of failure of high-temperature components are excessive creep, creep rupture, and thermal fatigue. If rupture occurs then the mechanism is usually by inter crystalline cracking along those grain boundaries oriented transverse to the major stress axis. In the stronger alloys, rapid propagation of intercrystalline cracks result in apparent premature failure demonstrated by the absence of third stage creep in a creep-rupture test and low rupture ductility. Tensile ductility shows a similar trend, that is, decreasing ductility with increase in strength. It is not surprising, therefore, that increases in creep strength have only been obtained with a loss in resistance to thermal shock, a property which shows a dependence on tensile ductility. VerSnyder and ~uard' showed that the application of unidirectional solidification to a brittle Ni-Cr-A1 alloy both improved the rupture life of the alloy and increased rupture ductility. Since this casting method results in columnar grains, it appeared that the solution to the lack of ductility in nickel-base alloy components was the elimination of the source of failure, namely the transverse grain boundaries. This concept was recently developed2 to produce cast-to-size gas-turbine blades and vanes consisting entirely of columnar grains oriented parallel to the major stress axis of the component. Not only did the process impart increased rupture life and ductility to the components, but it also increased their resistance to thermal shock. During this development, the effect of unidirectional solidification on the properties of several alloys was investigated. The resulting data allows certain conclusions to be drawn regarding the factors affecting the creep and stress-rupture properties of the cast nickel-base superalloy and also its resistance to thermal shock. Detailed information was obtained on the alloys Mar-MZOO, B-1900, In 100, and TRW 1900. The composition of the alloys studied are shown in Table I. MATERIAL PREPARATION AND TESTING The conventionally cast alloys are cast as +-in.-diam bars in innoculated shell molds under conditions designed to maintain control of grain size. Unidirec-tionally solidified casting were produced in the form of 3-in.-diam ingots. Specimens from the latter were machined such that the axes of the columnar grains were parallel with the axis of the test bar, except in certain cases where the transverse properties of the material were being evaluated. The specimens were tested in an axial loading creep machine.' Temperatures were measured with thermocouples, attached just outside each end of the gage length, to assure uniform temperature along the entire specimen. Chromel/alumel thermocouples were used up to 1800"F and Pt/Pt-10 pct Rh thermocouples above 1800"F. The specimen temperature was recorded and maintained within i2"F throughout the test. Creep extensions were measured automatically with extenso-meters attached to ridges on the specimen and recorded continuously using linear variable differential transformers and multipoint recording equipment. MICROSTRUCTURE The microstructures of transverse sections of the four alloys studied are shown in Figs. 1 and 2. Fig. 1 shows optical micrographs of the alloys, both in the conventionally cast and unidirectionally solidified conditions. Each alloy displays a cored dendritic structure, a distribution of MC carbide, and the presence of the y — y' eutectic constituent.~ In the case of IN 100 and B-1900, Fig. 1 indicates that in these specimens the eutectic is degenerate. That is, it consists only of y' pools indicating that the y constituent has been solutioned during the cooling period after solidification. The major effect of unidirectional solidification on the microstructures of the alloys is a tendency to promote a more dendritic form of MC carbide and an increase in dendrite arm spacing, both effects being a result of the slower solidification rate in the unidirectional solidification technique. V, lec tron micrographs of transverse sections of the four alloys in the two cast conditions are shown in

Jan 1, 1968

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.' is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968

By W. N. Lacey, R. H. Olds, B. H. Sage

Samules of liquid and gas were obtained from the primary separator of a well in the Paloma field. The volumetric properties of the samples and of six systematically chosen mixtures of the samples were experimentally determined at 100°, 190°, and 250°F. at pressures up to 5000 lb. per sq. inch. From these data the influence ,of pressure and temperature upon the composition and specific volume of the bubble-point liquid and of the retrograde dew-point gas was established, The formation volumes and gas-oil ratios of the rnixtures investigated were calculated on the basis of the plant-product oil, which is defined as the isobutane and less volatile portion of each mixture. The results are presented in graphical and tabular form. The volumetric behavior of the mixture corresponding to that produced by the well at the time of sampling was determined for 235ºF., the reported reservoir temperature, by graphical interpolation of the experimental data with respect to composition and temperature. The results indicate that the well-production mixture probably existed as a gas at its retrograde dew point under the conditions of temperature and pressure believed to prevail in the producing zone at the time of sampling. The effect upon the phase behavim occasioned by the omission from the well-production mixture of certain components of intermediate molecular weight was investigated. In the first case, all of the isobutane and 11-butane, and substantially all of the iso-pentane, were removed from the mixture of trap samples corresponding to the well production. In the second case, all the propane, isobutane and n-butane, and substantially all of the isopentane, were removed. Both modifications led to considerable increases in the retrograde dew-point Pressure at 235ºF.; an increase of 558 lb. Per sq. in. above that of the unmodified well-production mixture in the first case, and an increase of 1208 lb. Per sq. in. in the second. It was concluded that the material? remaining after the removal of certain components of intermediate molecular weight could not be injected back into the reservoir in the saqe proportion in which they were produced without entailing appreciable loss of liquid material through condensation within the formation. Introduction Under the usual conditions of production practice, petroleum arrives at the surface of the earth in a physical state considerably different from that in which it existed in the underground reservoir. The relative rates of production and the properties of oil and gas measured at surface conditions do not constitute, in general, even a qualitative description of the fluids existing in the reservoir. The estimation of reserves and the attainment of optimum efficiency with regard to rate, quantity, and cost of production require accurate data concerning the physical properties of petroleum throughout large changes in pressure and temperature. Many schemes have been devised for predicting the behavior of propane, as it is encountered in nature? but the experimental work upon which these predictions are based has not, for the most part, been extended to the higher pressures that occur in practice, nor do these methods permit, as yet, the estima-

Jan 1, 1945

By Robert J. Hite, Samuel S. Adams

Potash, the generic term for a variety of potassium-bearing minerals, ores, and refined products (Table 1), owes its importance as an industrial mineral to the potassium requirement of growing plants. The term potash originally referred to potassium carbonate produced by the leaching of wood ashes. This process, for which the first US patent was issued in 1790, was the basis for the largest United States chemical industry in the early nineteenth century. The agricultural use of potash soon eclipsed the chemical applications following the German discovery in 1840 that potassium is essential to plant growth. The initial discoveries of large deposits of soluble potassium minerals, essential for agriculture applications, were made in 1857 in Germany and in 1914 in the United States. More than 90% of the 27.5 Mt K20 produced in the world in 1980 (Searls, 1981) was derived from marine evaporite deposits and approximately 90% was used in fertilizers. The potassium content of an ore, mineral, or product is customarily expressed as % K20, a unit of measure which is neither a natural nor synthetic compound of potassium (1.0% K is equivalent to 1.2046% K2O). Geology Potassium, the seventh most abundant element in the earth's crust, is present in silicate minerals in igneous, sedimentary and metamorphic rocks. Potassium is also a major constituent of many surface and subsurface brines (Table 2). Economic potash deposits are essentially restricted, however, to widespread, thick accumulations of marine chloride evaporite deposits. These deposits yield high grade, large tonnage ore bodies, many of which are amenable to low cost mining and beneficiation. The products from these deposits are, moreover, ideal for use in fertilizer because of the high relative solubility of the potassium chloride and sulfate evaporite minerals. World potash production and reserves for such deposits so vastly overshadow other sources of potassium that the following discussion will be limited largely to potash deposits in marine evaporites with brief reference to certain potash-rich brines. Approximately 85% of current domestic production is from bedded salt deposits and much of the balance is from brines. Marine evaporite deposits are accumulations of salt minerals deposited in structural sedimentary basins through the evaporation of seawater or mixtures of seawater and other brines. The salt minerals are precipitated in assemblages and sequences of assemblages as determined by the compositions of the brines and the solubility relations in the salt systems (D'Ans, 1933). The evaporation of seawater normally yields carbonate minerals as the first precipitates (Table 3). Further evaporation and concentration of the brine leads to the precipitation, in succession, of sulfate, chloride, and supersaline mineral assemblages including the salts of potassium and magnesium. The common minerals, ores, and products of potassium deposits are listed in Table 1. Many potash deposits contain accessory evaporite minerals together with a variety of detrital and authigenic silicates (Braitsch, 1971). The structural basins within which marine evaporites occur are of two main types: (a) cratonic basins formed by broad epirogenic movements (for example, the Michigan Basin of the midwestern United States and the Permian Zechstein Basin of eastern Europe), and (b) grabens, commonly related to continental

Jan 1, 1983

By E. Stamboliadis

Dithiophosphates are reaction products of phosphorous pentasulfide with various organic compounds such as phenols, alcohols, mercaptans, dioalcohols, amines, and nitrides. The products with alcohols are commercially known as "aerofloats" and these are investigated in this presentation. It appears that the formation of insoluble metal dithio phosphates is responsible for their collecting properties with minerals." In this aspect they are very similar to xanthates.3 The solubility of metal dithiophosphates depends on the number of carbon atoms in the organic chain of the corresponding alcohol. An empirical mathematical model is presented here. It allows one to predict the number of carbon atoms necessary to ensure that a certain metal dithiophosphate will form at a selected pH value of the water solution. The Nature of Dithiophosphates Dithiophosphoric acid is the product of the reaction of phosphorus pentasulfide with an alcohol, as shown in the following equation: [P2S3 + 4 ROH - 2 (RO)2 PS2H + H2S (1)] where R stands for a hydrocarbon chain. The acid so produced can be neutralized by a base to produce the corresponding salt as shown in the following: [(RO), PS2H + NH- (RO)2 PS, NH,. (2)] In this aspect dithiophosphates are similar to xanthates, the only difference being the substitution of the tetravalent carbon atom in the xanthate polar group by a pentavalent phosphorus atom in the dithiophosphate group. This difference implies at least two characteristics: (1) that there are two hydrocarbon chains associated with the polar group so that an increase in the number of carbons of the single chain is expected to have a pronounced effect on the flotation properties, and (2) that the bond between the sulfur and the central atom is stronger than in the xanthate group. This probably leads to a decrease in both the polarizability of the electronic cloud of the sulfur and the interaction with cations.3 However, what is lost in the dithiophosphates by having a weak polar group can be gained by an increase in the number of carbons as will be seen later. Taking into account the size of the atoms involved in a dithiophosphate molecule, as listed in Table 1, It is possible to draw an approximate diagram of its structure as shown in [Fig. 1]. It is assumed here that the length of the single hydrocarbon chain is equal to that of the corresponding alcohol. Preparation and Purification Acid dithiophosphates can be prepared, as previously mentioned, in accordance with Eq. 1. The rate of this reaction is too slow at room temperature and can be improved by increasing the temperature to about 60° or 80°C7 or by evacuating the system. In our investigation evacuation was performed by a water aspiration pump. The dithiophosphoric acid so produced is liquid and dissolves in the alcohol. At the end of the reaction the product is filtered from the remaining P2S3; and dissolved in petroleum ether. By blowing anhydrous ammonia gas into the ether phase the ammonium salt forms as a white precipitate and can be sepa-

Jan 1, 1977

This issue presents the first of several articles making up the Bump Symposium, which was held at the 1958 Annual Meeting of AIME. Other Symposium papers will appear in the September issue of Mining Engineering. THE term mountain bump describes the sudden rupture of one or more coal pillars under excessive stress. These bursts occur with varying degrees of violence and sometimes include adjacent strata, especially the bottom rock. Many failures do not develop enough violence to be dangerous and are regarded as an aid to coal production, but severe occurrences are accompanied by tons of flying coal, dense clouds of dust, and excessive gas emission. Such bursts sometimes throw heavy machinery several feet. Major factors to be considered in the problem are the nature of the strata above and below the seam and the depth of cover. Bumps are classified as to their nature, extent of damage, and point of occurrence, e. g., face bump, coal bump, high side bump, low side pavement bump, and district bump. The problem is extremely complex, and it cannot be over-emphasized that preventive measures, if they are to be successful, must be based on a thorough study of conditions in the individual mine. In western Canada, for example, the McGillivray mine, operating in a 9-ft seam at 2000 ft, has experienced severe bumps, but there have been no occurrences in the International mine, which operates in the same coal seam at 2400 ft, where the coal averages 17 ft thick. Differences in conditions governing the operation of these two mines are described in one of the following articles (see page 883). Again, most bumps in coal mines take place along pillar extraction lines, but at the Sunnyside mine in Utah they also occur a long way from active workings and sometimes in virgin territory. It is usual, too, for such failures to occur under fairly deep cover. But at Sunnyside, to cite only one instance, there have been disturbances along the main fault zone under less than 500 ft of cover. All too often conditions favorable to bumps are revealed only by actual mining—at Springhill No. 2 mine, drilling in roof and pavement strata disclosed a 60-ft sandstone bed after operations had started— and where extraction has advanced too far for preventive measures to be incorporated in the mining plan, districts have had to be abandoned. But in an era when premium ores are being rapidly depleted in the face of rising demands, abandonment is not easily justified. There must be systematic planning to eliminate coal mine bumps, insofar as this is possible. As in the Gary district of West Virginia (see page 888) much has been accomplished by planned operations based on known factors in bump control. But even this is not enough. Precise instrumentation is needed to indicate where bumps are likely to occur, and in both the U. S. and Canada stress analysis studies are being carried out with this object in view. These pages reveal the progress being made.

Jan 1, 1959

By J. C. Allen, E. V. Herring

CHILE EXPLORATION CO's. oxide plant at Chuquicamata, the largest of its kind, started in 1915 with initial operations at the rate of 10,000 tons of ore per day. Anaconda Copper Mining Co. acquired the controlling interest in 1923 and in the next few years modernized the plant and mine, extending operations to a nominal capacity of 490 million lb of electrolytic copper yearly by 1942. Plant production averaging 495.7 million lb of copper per year was maintained for the eight-year period extending from 1941 to 1948 inclusive. During the World War II production reached its highest level when in 1944 the output was 531.8 million lb. The maximum production for any one month was 49.6 million lb, achieved in May 1947. E. A. Cappelen Smith, consulting metallurgist for M. Guggenheim's Sons, worked out the first process for the treatment of Chuquicamata copper oxide ore about 1913, and directed a staff of 20 young engineers operating a pilot plant at Perth Amboy, N. J., on three shifts for an entire year. The copper is extracted from the oxide ore by a hydro-metallurgical treatment described in detail by T. A. Campbell in AIME Transactions, Vol. 106, Copper Metallurgy, 1933. The Oxide Plant is divided into five main operations as follows: (1) Crushing, (2) Leaching, including dechloridizing and sulphur dioxide treatment, (3) Tailing disposal, (4) Electrolytic precipitation, (5) Smelting and melting. Crushing The present Primary Crushing Plant has been in operation 25 years, during which time 4,342,112 cars of 70 tons net capacity have passed through the dumpers. The ore as received from the mine is frequently blocky and up to 5 feet in section. It is reduced to 9-in. size by two 60-in. gyratory crushers, and transported to the east and west ore bins by 60-in. conveyors. In the secondary crushing operation the ore is first reduced to 2 to 3-in. size by five standard 7-ft cone crushers and two No. 10 gyratories. This product is then reduced to 3/8-in. size by fifty-two 48-in. vertical Symons disc crushers and is transported by belt conveyors to the loading bridges from which it is charged° into the leaching vats. Conveyor belt No. 14 which serves the eight vats in the east section of the leaching plant has transported over 125 million tons of ore, which is a record for any type of conveyor. This 60-in. belt travels at a speed of 600 fpm and carries loads up to 5500 tons per hr. Leaching The ore is leached in 14 vats, averaging 13,500 short tons net capacity each. These vats are lined with a natural mastic which adequately resists the sulphuric acid leaching solutions. The leaching process as presently conducted comprises soaking the ore with successive volumes of leaching solution and spent electrolyte and withdrawing successive volumes of enriched solution from the vat to a total of approximately 3.2 million gal. The first 1.6 million gal of this volume withdrawn is called strong solution and contains about 35 parts of copper per 1000. The balance of 1.6 million gal subsequently withdrawn is stored in a

Jan 1, 1952

By Edna A. Dancy, Ronald L. Pastorek, Gerhard J. Derge

In an earlier study1 in this laboratory, it was found that there is a minimum in the specific conductance of Ni-S melts in the region of the stoichiometric composition, Ni3S2. This and similar observations on other sulfide1 and telluride2 systems suggest that short-range order exists in the molten phase for several hundred degrees above the melting point, and a qualitative energy-band model has been proposed, with intrinsic semiconduction at the stoichiometric composition and degenerate electron and hole conduction at metal- and tellurium-rich compositions. This suggestion has been substantiated for the telluride systems by Seebeck coefficient measurements which showed a change in sign from negative on the metal-rich side to positive on the tellurium-rich side. In the present investigation, in order to substantiate still further the proposed model, Seebeck coefficient determinations have been extended to the Ni-S system over a composition range in the vicinity of Ni3S2. The experimental method was essentially the same as that used for the telluride systems, with minor modifications on cells for high sulfur melts to permit the use of tungsten wires and W— W-Re th~rmocouples instead of the chrome1 or alumel wires and chromel-alumel thermocouples originally used. Chrome1 and alumel both deteriorate very rapidly in atmospheres containing sulfur. The Ni-S alloys were prepared as described in the conductivity paper. Initially, a portion of the solidified melt was analyzed at the end of a run, but after this was found to be inaccurate because of segregation during cooling, the whole sample was analyzed. The nickel content, only, was determined, the sulfur content being obtained by difference. The results are summarized graphically in Fig. 1, and clearly show a change in the sign of the Seebeck coefficient in the region of the stoichiometric composition. This change of sign near Ni3S2, coupled with the minimum in the conductivity, is suggestive of an intrinsic semiconductor at the stoichiometric composition, with degenerate electron and hole conduction on either side of this composition, in keeping with the proposed model. The negative temperature coefficient of conductivity, normally indicative of metallic conduction, is not inconsistent with this model. In the completely degenerate region it would be expected, while in the vicinity of Ni3S2 the suggestion originally made by Argyriades, Derge, and pound3 for the Fe-S system can probably be applied. They proposed that the forbidden gap between the valence band and the conduction band is small, and that the increase in the number of the conducting species with increase in temperature is not large enough to compensate for the loss of mobility through thermal scattering. The research was sponsored by the Office of Naval Research under Contract NONR-760(22) Project NR 039-081. 'E. A. Dancy and G. J. Derge: Trans. Met. Soc. Aime, 1963, vol. 227, pp. 1034-38. 'E. A. Dancy: Trans. Vet. soc. AIME. 1964, vol. 233, pp. 270-77. 'D. Argyriades, G. Derge, and G. M. Pound: Trans. Met. Soc. . 1959, vol. 215, pp. 909-12.

Jan 1, 1965

By J. T. McGrath, G. B. Craig

Tensile tests on aluminum single crystals, grown from the melt, revealed that the yield stress of these crystals was raised as the amount of striation substructure was increased. The number of striation-type boundaries was varied by changing the rate of growth of the crystals. The results are interpreted in terns of a blockage of dislocation movement by striation boundaries. IMPERFECTIONS are known to have a large effect on the mechanical properties of metals. Teghtsoonian and Chalmers 1 studied a block or striation-type substructure in tin and found that the formation of the striations depended upon rate of crystal growth and orientation. They found that the angular misorienta-tion between neighboring striations varied between 15 min and 5 deg. Atwater and chalmers2 investigated striations in tin and lead, and found that purity was another factor which influenced their formation. There was a limiting purity above which the striations were straight and regular. There is little information in the literature concerning how substructures in melt-grown crystals affect strength. washburn3 introduced small-angle boundaries into zinc by a shear process and found a subsequent increase in yield stress which he attributed to the presence of these boundaries. Lauriente and pond4 found the critical resolved shear stress in aluminium crystals grown from the melt, to increase with etch pit density. The etch pits were used as an indication of growth imperfections. In Hibbard's5 work on lineage structure in copper crystals grown from the melt, he tested one crystal containing interlineage boundaries, and found a 50 pct increase in the critical resolved shear stress. Fleischer and Chalmers6, in a recent paper, mention briefly that, in the production of aluminium crystals from the melt when the growth rate was raised from 1.2 to 18 cm per hr, the yield stress increased 50 pct. They felt that the increase in yield stress with rate of growth might be attributed to a higher concentration of impurities in the gage length and also might be affected by the increased number of small-angle boundaries (striations). The present investigation was undertaken to determine the effect of the striation substructure on the strength of aluminum single crystals. EXPERIMENTAL PROCEDURE Aluminum single crystals of 99.9992 purity were grown from the melt using a technique described by Chalmers.7 The growth rate was varied from 0.6 to 20 mm per min, thus producing crystals with varying numbers of striation boundaries. To avoid prior deformation, the crystals were chemically cut to the desired length with a saturated solution of cupric chloride. They were then annealed at 580°C for 24 hr and allowed to cool slowly in the furnace. Finally, the specimens were electropolished using an electrolyte of 5 parts ethyl alcohol and 1 part perchloric acid. Each specimen was approximately 5 in. in length and 0.125 sq in. in cross section. The average orientations of the 5 series of crystals studied are shown on the stereographic projection of Fig. 1. The crystals were strained approximately 2 pct in a soft tensile machine. The strain sensitivity was 3.6 x 10-4 cm over a 5-cm gage length.

Jan 1, 1960

By D. E. Peacock, B. Harris

Thermal-expansion and electrical-resistivity measurements have been carried out below 400°K on niobium and two niobium alloys containing tungsten. For anonaly in the expansion us temperature curve below aboct 300°K. This reslt is consistent with an earlier obsercation that Young's modilus joy Cb-132 lms an unusiully strong -tenperati-e dependence below roon temperature. No anonulous behavior was observed in the resistiuity vs temperature curve for either alloy or in the magnetic susceptibility us tenperature curve for Cb-132. These results are disclssed in terms of various electronic and bonding theories of the transition metals and their alloys, but it has not been possible to reach any definite conclusion as to the cause of the results obtained. ALONG with investigations of the low-temperature mechanical behavior of niobium and its alloys, some of the physical properties of these materials have also been studied. In the work described here, thermal expansion and electrical resistivity were measured below 400°K for niobium and two of its alloys, Cb-132 and D-43. In addition, the magnetic susceptibility of Cb-132 was measured over the same temperature range. The alloys are representative of two distinct tion-hardened alloy such as might find service as a turbine blade, while D-43 (Nb, 5.3 at. pct W, 1.1 at. pct Zr. and 0.08 at. pct C) is a solution- and dispersion-hardened alloy, of considerably lower strength than Cb-132. which is a potential vane material. Their significant common feature is the presence of tungsten as the principal source of solution hardening. EXPERIMENTAL TECHNIQUES Thermal-expansion measurements were made with a quartz-tube dilatometer using baths of liquid nitrogen, liquid bromoethane, and a liquid polyalkylene glycol derivative to cover the range 80 to 400 K. Results are recorded as expansion relative to that of quartz, and the probable maximum error in any value of relative expansion. All, is about il pct. The metallurgical condition of the specimens, which were in rod form. will be discussed in the section dealing with experimental results. Resistivity was measured on recrystallized wires 0.030 in. in diam using a potentiometric technique. The same baths were used for temperatures between 80' and 400°K as were used for the expansion measurements. and in addition the resistance of D-43 and Cb-132 was measured at 4.2 K by immersion in liquid helium. The maximum expected experimental error in any resistivity value is about 3 pct and that in any change in resistivity about i0.05 pct. Temperatures in both sets of experiments were measured with liquid-in-glass thermometers with an accuracy usually better than 1°K. EXPERIMENTAL RESULTS 1) Thermal Expansion. In Fig. 1 is shown the relative linear expansion of recrystallized niobium. D-43. and Cb-132. The curve for Cb-132 is composed of results from several runs on three different samples. Two of the samples were annealed for an hour at 1500°C to cause recrystallization and the third was annealed for an hour at 2000'C to remove some mi-crosegregation of tungsten which was known to be present in the wrought alloy received from the manu-

Jan 1, 1967

By Richard H. Jahns

GRANITIC pegmatite deposits are the chief source of commercial feldspar, sheet mica, beryllium, tantalum-columbium, and lithium minerals, and certain types of kaolin. They also have yielded significant quantities of cassiterite, gems, scrap mica, molybdenite, tungsten minerals, uranium-thorium and rare-earth minerals, and zircon, either directly or as the sources of placer deposits. The output from pegmatite mines in the United States is small as compared to other mineral products in terms of bulk or value, and much of it comprises minor metals and nonmetals. Nevertheless, pegmatite minerals play a vital part in domestic industrial economy, particularly in the ceramic and electrical industries. Numerous special purpose uses also are important, even though they require small quantities of raw materials. Never was United States dependence upon pegmatite mining more clearly emphasized than during World War 11, when greatly expanded demands and uncertainties of foreign sources of supply caused much concern. Such commodities as beryl, tantalite, and sheet muscovite remained high on the critical list for months at a time, and for some minerals there was a real struggle to achieve and maintain a favorable ratio of supply to demand. Satisfactory stock piles of certain sizes and qualities of sheet mica, for example, were not built up until late in 1944, when wartime requirements already had begun to level off or even to decrease. Production of all the strategic pegmatite minerals from domestic deposits during World War I1 constituted only 10 pct or less of the total domestic consumption of these minerals, but the importance of this contribution should not be minimized. Domestic production often represented the difference between increase and further reduction of existing stocks of commodities already in seriously short supply, and in the early stages of the war it was the only assured source if imports were cut off. During the recent war period, the U. S. Geological Survey carried on a program of pegmatite studies in the New England and Southeastern States, in the Black Hills area of South Dakota, in the Rocky Mountain region of Wyoming, Colorado, and New Mexico, and in various parts of Washington, Idaho, Utah, Nevada, Arizona, and California as shown in Fig. 1. Several papers and reports already have appeared as an outgrowth of this work,'-= and others are in preparation. This paper outlines some results of data obtained by the writer during the period 1942 to 1946, when he was engaged in studies of pegmatites in the Southeastern, Southwestern, and Rocky Mountain States. Beryllium Minerals Beryl is the present commercial source of beryllium metal and beryllium compounds, which are used in ceramics, in the preparation of X-ray tubes and fluorescent lamps and screens, in special processes of paint and textile manufacture, and in the optical systems of some electrical instruments. The metal also is used in nuclear physics, chiefly as a source of neutrons. Beryllium is alloyed with aluminum for certain light-metal uses and is a constituent of some nickel and iron alloys. Currently the chief demand, however, is for copper-base alloys, which are exceptionally resistant to fatigue and wear, are responsive to hardening treatments after

Jan 1, 1952

By Leah L. Naugle, H. G. Landau, H. H. Lowry

EVIDENCE has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its "Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,1-12 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends-including coals numbered I to 55b, inclusive -which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or I8-in. cylindrical retorts." In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash; from 2.1 to 15.9 per cent, in moisture from o.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the go coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1941

By J. E. Pavlick, A. G. Guy

The total creep of tin alloys containing antimony in solid solution was observed to decrease with increase in antimony content. However, near the solubility limit an anomalous maximum in deformation was. found, in agreement with similiar observations by Bochvar. IT has long been recognized that alloys may deform more rapidly under stress if there is a tendency for a phase change or other structural change to occur simultaneously. However, the phenomena involved are complex and in some instances the opposite effect, strengthening, may result.' This area of research has not attracted much interest in the western world, and although Russian investigators have studied it for the past 15 years their work has not received due attention here. Recently diametrically opposing views on one aspect of this problem have been espoused by two Russian investigators, Kornilov and Bochvar. The question is this: in certain binary alloys tested in creep at the temperature where the solute is at the limit of solid solubility, does the incipient formation of the second phase strengthen or weaken the alloy? Korni-lov's arguments in favor of strengthening were presented at the 1954 Symposium at the National Physical Laboratory, =Creep and Fracture of Metals at High Temperatures.The most recent statement of Boch-var's theory of weakening is in Oding's new book on creep and rupture.3 Although Bochvar agrees that strengthening occurs in some alloy systems, he argues that in certain alloys an anomalous weakening is observed. However, the extensive work of Korni-lov's group on creep properties of alloy systems has not revealed any anomaly of this type, but instead has tended to refute Bochvar's theory. This clear-cut controversy offered a good opportunity for a simple experiment to resolve the problem. The experiment and its results supporting Bochvar are the subject of this paper. However, it will be helpful first to sketch the present status of the larger question of the effect of a phase change or other structural change on plastic deformation. PREVIOUS WORK One of the first researches in this area was by Pfei1,37 who investigated the creep resistance of an 80 Ni-20 Cr alloy containing varying amounts of titanium. He found that the resistance to creep increased rapidly as the solid solubility limit in the alloy at 775'c was approached and slightly exceeded. With further addition of titanium the creep resistance decreased, presumably because of precipitation effects. Bochvar's first work in this field was a study in 1945 of "superplasticity" in zinc alloys containing 15 to 25 pct Al.4 He found that alloys quenched from about 400 had anomalously low hardness when tested below this temperature. The following year, in a paper on the dependence of mechanical properties on the composition and structure of alloys,5 he extended some observations of Kurnakov to predict that at high temperatures of testing the hardness values for solid-solution alloys might be lower than those for the component metals. He also pointed out the influence of changes in solidus temperature in affecting curves of hardness vs composition, and he

Jan 1, 1962

By H. G. Landua, Leah L. Naugle, H. H. Lowry

Evidence has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its ('Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,l-l2 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends— including coals numbered I to 55B, inclusive —which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or 18-in. cylindrical retorts.13 In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash from 2.1 to 15.9 per cent, in moisture from 0.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the 90 coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1942