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By R. H. Olds, B. H. Sage

The transient flow of gases in long pipe lines is a problem of industrial interest. The present discussion deals with the application of the conservation of momentum and material to the transient flow of gas in conduits which are long with respect to their diameter. Solutions of the resulting equations include consideration of variations in friction and specific volume of the fluid as functions of time and position along the conduit. The changes in state along the pipe line are established as a function of time. The methods proposed may be extended to other situations. The flow of compressible fluids under steady conditions' has been considered in detail. Primary emphasis was placed on the development of simple means of taking into account the non-uniform flow' realized in long conduits under such conditions. Binder2 discussed the essential differences between the flow of compressible and uoncompressible fluids. Bonilla" proposed direct methods of solution for equations describing isothermal flow in long pipes. Similar considerations limited to steady flow have been discussed by Ruth.' Palsgrove 5 sugrested a graphical means of solving specific problems relating to the flow of gases in conduits of uniform section. Some of the basic concepts of the flow of a compressible viscous fluid in straight tubes have been described by Kuo.6 Problems of this type require knowledge of the equation of state of the fluid. In many cases it liar been convenient to assume that the fluid follows the relationship ascribed to a perfect gas. The treatment of unsteady flow of compressible fluids is less complete. This state of affairs result* from the fact that the differential equations relating pressure and flow rate with time and position for unsteady flow are nonlinear in character.' Muskat and Wyckoff presented an excellent treatment of the situation in laminar Bow where inertia forces were not of controlling importance. Somewhat earlier Hurst9 discussed the uncteady flow of fluids in petroleum reservoirs. Helhering-ton. MarRoberts. and Huntington'" established experimentally the pressure distribution and accumulative flow rate of natural gas through an unconsolidated sand. Recently Joffe11,12 conhitlcretl the specific problem of the flow of natural gas in relatively long.,. pipe lines for unsteady conditions with emphasis upon the economic feusibility of the storage of gas in such a reservoir. These discussions were based upon approximations of the partial differential equations applying to the condititons of flow. The results were descriptive of the physical situation and indirated the effertiveness of large pipe lines as cyclic storage facilities for natural gas. The advent of analog computers" has increased materially the practicality of solving nonlinear partial differential expressions. Several iterative numerical and graphical methods14,15,16 have been developed to solve nonlinear equations. However, it appears that the pair of simultaneous nonlinear partial differential equations involved in problems of this nature are not directly susceptible to solution by presently available analog computer or formal iterative numerical techniques. Nevertheless. graphical analyses afford a means of obtaining data of engineering value without special equipment. MATHEMATICAL CONSIDERATIONS Since the length of the conduit is large in comparison to the cross section in the cases to be considered, it is possible to treat the characteristics of the flow as independent of position in the cross section of the conduit. This possibility follows since the energy- connected with the velocity profile is small compared to that required to overcome the friction associated with its movement throughout the length of the line. Average values of the pressure. velocity. kinetic energy. momentum, and specific volume may he assigned to the fluid at any particular cross section. From a mathematical viewpoint this may be expressed in the following way for velocity: µ = µ(?X)..........(1) The uncertainties introduced by such assumptions usually are negligible when the ratio of length to diameter is greater than the order of 1.000. On this basis a volume element ma!. be considered to occupy the entire cross section of the conduit. Such an element is presented in Fig. 1.

Jan 1, 1951

By R. H. Olds, B. H. Sage

The transient flow of gases in long pipe lines is a problem of industrial interest. The present discussion deals with the application of the conservation of momentum and material to the transient flow of gas in conduits which are long with respect to their diameter. Solutions of the resulting equations include consideration of variations in friction and specific volume of the fluid as functions of time and position along the conduit. The changes in state along the pipe line are established as a function of time. The methods proposed may be extended to other situations. The flow of compressible fluids under steady conditions' has been considered in detail. Primary emphasis was placed on the development of simple means of taking into account the non-uniform flow' realized in long conduits under such conditions. Binder2 discussed the essential differences between the flow of compressible and uoncompressible fluids. Bonilla" proposed direct methods of solution for equations describing isothermal flow in long pipes. Similar considerations limited to steady flow have been discussed by Ruth.' Palsgrove 5 sugrested a graphical means of solving specific problems relating to the flow of gases in conduits of uniform section. Some of the basic concepts of the flow of a compressible viscous fluid in straight tubes have been described by Kuo.6 Problems of this type require knowledge of the equation of state of the fluid. In many cases it liar been convenient to assume that the fluid follows the relationship ascribed to a perfect gas. The treatment of unsteady flow of compressible fluids is less complete. This state of affairs result* from the fact that the differential equations relating pressure and flow rate with time and position for unsteady flow are nonlinear in character.' Muskat and Wyckoff presented an excellent treatment of the situation in laminar Bow where inertia forces were not of controlling importance. Somewhat earlier Hurst9 discussed the uncteady flow of fluids in petroleum reservoirs. Helhering-ton. MarRoberts. and Huntington'" established experimentally the pressure distribution and accumulative flow rate of natural gas through an unconsolidated sand. Recently Joffe11,12 conhitlcretl the specific problem of the flow of natural gas in relatively long.,. pipe lines for unsteady conditions with emphasis upon the economic feusibility of the storage of gas in such a reservoir. These discussions were based upon approximations of the partial differential equations applying to the condititons of flow. The results were descriptive of the physical situation and indirated the effertiveness of large pipe lines as cyclic storage facilities for natural gas. The advent of analog computers" has increased materially the practicality of solving nonlinear partial differential expressions. Several iterative numerical and graphical methods14,15,16 have been developed to solve nonlinear equations. However, it appears that the pair of simultaneous nonlinear partial differential equations involved in problems of this nature are not directly susceptible to solution by presently available analog computer or formal iterative numerical techniques. Nevertheless. graphical analyses afford a means of obtaining data of engineering value without special equipment. MATHEMATICAL CONSIDERATIONS Since the length of the conduit is large in comparison to the cross section in the cases to be considered, it is possible to treat the characteristics of the flow as independent of position in the cross section of the conduit. This possibility follows since the energy- connected with the velocity profile is small compared to that required to overcome the friction associated with its movement throughout the length of the line. Average values of the pressure. velocity. kinetic energy. momentum, and specific volume may he assigned to the fluid at any particular cross section. From a mathematical viewpoint this may be expressed in the following way for velocity: µ = µ(?X)..........(1) The uncertainties introduced by such assumptions usually are negligible when the ratio of length to diameter is greater than the order of 1.000. On this basis a volume element ma!. be considered to occupy the entire cross section of the conduit. Such an element is presented in Fig. 1.

Jan 1, 1951

By S. R. Goodman, Hsun Hu

The rolling texture transition in copper as a function of deformation temperature is found to be quite similar to that in high-purity silver. The ordinary copper type texture changes gradually to the brass type, accompanied by an increase in the stacking fault frequency, as the temperature of deformation decreases. The rolling textures obtained at low temperatures and the corresponding annealing textures compare remarkably well with the ordinary rolling and annealing textures of low-zinc brasses. Furthermore, it is also found that the observed stacking fault energies of copper specimens deformed at low temperatures correspond closely with those of low-zinc brasses, as deduced from measurements of the dislocation nodes. These results are consistent with the idea that texture transition may be significantly dependent on the stacking fault energy. It was shown in a series of previous publications1"3 that the rolling texture of high-purity silver changes gradually from the common silver type (or the brass type) to the copper type* with increasing temperature *The silver or brass type rolling textures are commonly described as (110)[112],4,5 whereas the copper type rolling textures are mainly (123) [a121 and (146)[211].5 Other ideal orientations have been used by various investigators for the copper type rolling textures, but the actual difference among these ideal orientations is rather small. of deformation, and that such texture transition can be correlated with the change in stacking fault frequency as a function of rolling temperature. Furthermore, it was shown that the formation of annealing textures in high-purity silver from the various rolling textures obtained during the course of texture transition depends entirely upon the deformation texture. From a common silver type or brass type rolling texture (such as produced by rolling at 0" or at 50° C) the recrystallization texture is mainly (120)[211], which is quite different from the recrystallization texture of brass.* However, for both ma- terials the orientation relationship between the rolling texture and the recrystallization texture can be expressed in terms of similar rotations around [Ill.] axes of approximately 30 or 35 deg. They differ in that the [Ill] rotational axes are different. In the case of high-purity silver, the axes of rotation are the two (111) poles near the plane normal of the deformed specimen with a (11l)[112] type rolling texture, whereas in brass, they are the (111) poles near the direction of rolling. For high-purity silver with a predominantly copper type rolling texture (such as produced by rolling at 150° or 200°C) the recrystallization texture is mainly (100)[001], or the cube texture, plus its twin orientations. It was shown previously6 that such reorientation observed in copper or aluminum can be described as [Ill] rotations of 30 to 40 deg. For intermediate cases, i.e., when the rolling textures are composed of a

Jan 1, 1963

By F. J. Haller

IN 1943, we found, in the new Mather operation, a very unusual and disappointing condition in the footwall rock where all of our main haulageways were to be located. With the exception of a few hundred feet out of the thousands then planned and since driven, all of the openings require support. In general, the ground is not particularly heavy, at least by our standards, but it must be supported and the back carefully covered. Also, our operations require rather wide plat openings (16 to 18 ft) and rather flat curves at the turn-outs, all of which adds to the problem. When this completely unforeseen condition was discovered, ordinary timbering was the only answer, because of the impossibility of obtaining adequate steel supplies in time due to war shortages. Then by the time steel supplies were obtained and a practice developed, we found ourselves with between four and five miles of main haulage drifts and plat openings of a permanent nature, all of which were supported by hardwood timber, some of which had already rotted to an unsafe degree. Also, our drifting program was adding some two miles per year to the above figure. F. J. HALLER, Member AIME, is Superintendent, Mather Mine, Cleveland-Cliffs Iron Co., Ishpeming, Mich. AIME Columbus Meeting, September 1949. TP 2840 A. Discussion (2 copies) may be sent to Transactions AIME before May 31, 1950. Manuscript received Aug. 22, 1949. Revision received Jan. 17, 1950. To give all of the details of our experiments, studies, and experiences would fill a large book, but we were satisfied that our organization had done an excellent job, starting from scratch. You can appreciate our surprise when we discovered that we had added very little to an existing record. Attention was called to a footnote in a copy of "Carnegie Pocket Companion" year 1923. The note read: "Full information as to uses of H-Beams is given in pamphlet entitled 'Steel Mine Timbers.' " A search of our Engineering Library brought to light a pamphlet printed in 1911 showing extensive use of steel for this purpose. Except for welding in place of riveting, we have added very little to the designs in that book. We have, however, developed an experience which proves, at least to our own satisfaction, that steel mine supports pay off under the proper conditions. We are now convinced, in spite of the relatively high initial cost of materials, that steel sets, because of comparatively low installation cost, are actually cheaper than either treated or untreated wood sets, if they are properly designed and adapted. Several Sections in Use: Convenience guided our first experiments in steel sets, since for a number of years, we had used the 4-in. WF, 10 lb per ft section in 10-ft lengths as safety forepoles along with wood forepoles. This section replaced the 40-lb rail which had formerly been used for the purpose. Having the 4-in. WF sections on hand, it was natural that our first experiments in steel sets involved their use. Later, the rolling of the 10-lb section was discontinued in favor of the much stronger 13-lb section, which is now standard for both legs and caps in areas of no particular weight, but which, none the less, require permanent support. Our experiments involved the use of the 10- and 13-lb sections as legs and 6- and 8-in. I beams, 16 and 23 lb per ft, respectively, as caps. Experience soon indicated that, if the ground were heavy enough, and the opening wide enough to require a cap stronger than 13-lb, the 8-in, 23-lb should be used, eliminating the 6-in. I beam. We now know that the 8-in. WF section of the same weight, which we propose to use in the future, is considerably stronger for the amount of money involved. Comparative Strengths: Tables I to IV giving strengths of several species of timbers as compared with the structural sections that we now use have been prepared in accordance with accepted practice. Experience indicates that failure due to compression perpendicular to the grain of the wood does not destroy the effectiveness of a wood set frequently enough to be a practical factor. Therefore, no table of these values is included.

Jan 1, 1951

By G. R. Speich

A cellular precipitation reaction in which cells consisting of an Ni3Ti (DO24) phase and austenite are formed has been studied in an austenitic Fe-30 Ni-6 Ti alloy. The variation of the growth rate and interlamellar spacing of the Ni3Ti cells with temperature has been determined m the range 400" to 975°C; the interlamellar spacing is proportional to the degree of undercooling; the growth rate can be expressed by an equation of the form G = K?T)2 exp(-Q/RT). The habit of the Ni3Ti lamellae is (001)Ni3Ti (111)y;[010]Ni3T2 [010]y. An almost perfectly coherent interface is formed between Ni3Ti lamellae with this orientation rela -tionship and the intervening austenite. This first Ni3Ti cellular product is subsequently consumed by a second cellular reaction of much coarser spacing. CELLULAR precipitation reactions have been studied in copper-base,1,2 Au-Ni,3 pb-sn,4 and iron-base ferritic5,6 solid solutions, and this mode of precipitation has been treated theoretically by smith," Turnbull,8,9 cahn,10 and more recently by bohm.11 In the case of substitutional austenitic iron-base alloys little or no data are available, Cellular precipitation reactions are well known in austenitic nickel-base alloys12,13 but usually these reactions do not proceed to completion because of general precipitation occurring in the matrix, and they have not been studied in detail. Precipitation from an austenitic Fe-30 Ni-6 Ti alloy was studied as part of a larger investigation of the mechanisms of precipitation from substitutional iron-base alloys. This alloy, austenitic at high temperatures, decomposes at lower temperatures by a double cellular precipitation reaction. The first decomposition product consists of alternate lamellae of an Ni3Ti(DO24) phase and austenite. The reaction proceeds to completion, consuming all of the original austenite. This first cellular product is subsequently consumed by a second cellular reaction of much coarser spacing. The first cellular reaction was studied in detail by light and electron microscopy, hardness measurements, and by X-ray and electron diffraction. Interlamellar spacings and growth rates were measured during isothermal aging in the range 400" to 975°C. The orientation relationship between the Ni3Ti and austenite lamellae was determined and indicates that an almost perfectly coherent interface exists between the two phases. This first Ni3Ti cellular reaction is of particular interest because it occurs over such a wide temperature interval. This allows cellular growth rates and interlamellar spacing data to be obtained for much larger degrees of undercooling than reported hitherto. MATERIALS AND EXPERIMENTAL PROCEDURE The Fe-30 Ni-6 Ti alloy was prepared from electrolytic iron, Mond nickel shot, and sponge-purity titanium* by vacuum melting in a zirconia crucible

Jan 1, 1963

By G. P. Tiwari

Recrystallization and grain growth in thoria dispersed nickel and nichrome were recently studied by Webster as a function of temperature and deformation. The unexpected part of these results was that specimens which had received heavier deformation developed greater resistance to recrystallization. Retardation of recrystallization was accompanied by the formation of voids around thoria dispersion. To explain these results, Webster suggested that the formation of void around the particles increased the effective size of thoria particles. This resulted in greater impediment to the grain-boundary migration and as a consequence the recrystallization of the matrix is retarded. In the present note an alternative and more probable explanation for the effect of voids on recrystallization is presented. The exact mechanism of void formation in thoria dispersed nickel or nichrome is not known. However, it is reasonably certain that it must be preceded by the stress concentration in the matrix around thoria dispersion during the deformation.'' The resulting stress concentration must be sufficient enough to supply the surface energy for the new surfaces created. Further, the decrease in the strain energy of the matrix surrounding the potential void nucleus must be larger than the surface energy of the newly created surface. The release of strain energy due to formation of crack results in a strain free cylinder of the material around the voids.13 If the void formation is not localized, at few points only (as is the case here), this process may lead to considerable amount of release of strain energy of the matrix. The pattern of recrystallization behavior of single phase homogeneous matrix as well as the matrix having a second phase dispersion is same except for the fact recovery and recrystallization are more clearly delineated.14 In general, the recrystallization temperature is lowered (i.e., recrystallization is easier) with increase in the amount of cold work. This is due to the increase in stored energy in the matrix with increasing amount of deformation. If somehow there is a relaxation of strain energy in the matrix, the recrystallization should become difficult because of the decrease in the amount of stored energy available for recrystallization. Since the formation of voids leads to a decrease in the strain energy of matrix, the recrystallization of the matrix would be inhibited due to the formation of voids during deformation prior to recrystallization. It has been observed by earlier workers15'16 that the presence of preexisting voids in a matrix retards the recrystallization. The essential issue here is how do the voids act to produce this effect. If the voids influence recrystallization only by blocking the grain boundary migration, then the effect should be maximum when they are present almost exclusively along grain boundary. These conditions are obtained during high temperature deformation. However, the voids produced due to creep along grain boundary are not able to prevent recrystallization17 suggesting that they are not effective in blocking grain boundary movement. Recently it was shown by Davies and Williams that the voids can act as sinks for vacancies." As a result the processes dependent on vacancy diffusion like recovery, recrystallization, dislocation climb, and so forth, will be hindered. This fact may be responsible for inhibition of recrystallization during subsequent deformation and annealing cycles. It is to be noted here that there is a large difference between the density of voids in creep experiments and the other experiments where retarding effect of voids on recrystallization is seen. The voids in former may number up to l04 to l05 per sq cm whereas in latter cases the voids density is typically around 1010 to 1013 per sq cm. It appears that the decrease in supply of vacancies in creep is insufficient to adversely affect the recrystallization due to low void population. The author is grateful to P. Das Gupta and S. P. Ray for helpful discussions. Author's Reply D. Webster Tiwari appears to have misunderstood the nature of grain boundary-particle interactions. Tiwari (quoting Cahn) states that second phase particles become more effective as they become smaller, therefore as the voids in TDNiC make the thoria particles effectively bigger their ability to resist grain boundary movement is impaired. This particle size argument was originally proposed in the form of an equation by Zener 20 years agol9 and is not necessarily valid as is discussed below. However, assuming it is valid, it predicts a greater boundary restraining effect by smaller particles simply because their combined cross sectional area is greater at a constant volume. If the number of particles remains the same and their effective size increases, as in the present case, Zener's equation predicts a greatly reduced grain size. This is because the effect

Jan 1, 1970

By Byoung Whie Lee

In order to investigate the change in surface energy as a function of cold work ad environment, the contact angles between a liquid and the surface of elec-tropolislzed aluminum with various degrees of cold work were measured. Specinlens cut from aluminum rod (99.99 pct Al) were annealed at 600°C for 24 hr and then cold compressed parallel to the drawing di-rectzon of the rod in increments of approximately 10 pcl from 0 to 70 pct. The sections, taken transversely to the drawing direction, were mechanically and electro chemically polished. Contact angles between the sessile drop of distilled water, glycerin, and glycol and the specimen surface were measured optically. The differences in interfacial energy were calculated from the contact angle data. The effects of chemical washing and surface roughness of the specimen on the contact angle were also studied. The liquid contact angle was a linear function of the degree of cold working (D) ad changed markedly with differed liquids. THE plastic deformation of polycrystalline metals induces a preferred orientation in crystal structure. A preferred orientation changes the atomic density of a metal surface. This change in surface atomic density brings about the changes in surface interactions of the metals."' Also, the plastic deformation of metals raises the internal energy by increasing the stored energy.' Consequently, the total Helmholtz free energy of the metal increases and, in turn, the surface free energy of the metal. In order to study the effect of plastic deformation on solid surface phenomena, the liquid contact angle of a sessile drop made on cold compressed and elec-trochemically polished aluminum was measured. The preferred orientation in aluminum, due to uniaxial compression, is known to be [110] direction parallel to the compression axis. However, this description is only a first approximation of a rather complex orientation. In actuality, half the crystallites are more than 10 deg from this orientation, regardless of the amount of compression." For randomly oriented fcc crystals, the average surface atomic density can be calculated as follows: The number of atoms in a unit volume is 4/a3, where a is a lattice constant. Hence, the number of atoms per unit surface area is about (4/a3)2/3 = 2.52/a2 However, when the preferred orientation took place along [110] direction, the surface atomic density is as follows: The area of (110) plane of a unit cell, considering ridges and valleys, is BYOUNG WHlE LEE, Member AIME, is Research Metallurgist, Atomic Energy Research Institute of the Republic of Korea, Seoul, Korea. Manuscript submitted May 29, 1968. IMD 2 x J2- a x Ga = 6a2 Since this plane contains 4 atoms, the surface atomic density is 4i6a2 = 2.3/a2 Upon changing from random to preferred orientations, the surface atomic density decreases about 10 pct. The increase in the stored energy and the change in surface atomic density due to plastic deformation would certainly alter the surface tension of a metal. EXPERIMENT High purity aluminum rod of 6-mm diam (99.99 pct Al, obtained from Johnson, Matthey & Co., Ltd, London, England) was cut into sections approximately 1 cm long. The transverse cross section was mechanically polished. Then, the specimens were annealed in air at 600°C for 24 hr. Thus, eight annealed specimens were uniaxially compressed at room temperature from 0 to 70 pct of cold working with an increment of 10 pct. The extent of cold working was determined by the percentage of reduction in axial length to the original length. The specimens were further polished mechanically and, then, electrochemically with the Modern Battelle Type 1 electropolishing solution with a current density of 0.3 to 0.4 amp per sq cm and an electrode potential of 8 to 12 v at the solution temperature of 78" to 82°C for approxirr~ately 5 min. The Modern Whlte Diffusing Screen \t/ --------------- re Goniometer for Mercury Lamp ^-^ Sessile Drop ¦=• Condenser c=> Microscope l_*~_i bJ Mlcromster Filer with Protmcter Fig. 1—Schematic diagram of apparatus set-up for liquid contact angle measurement.

Jan 1, 1970

By E. J. Roberts

F. C. Bond (Allis-Chalmers Mfg. Corp., Milwaukee) —This paper considers comminution as a first order process, with the reduction rate depending directly upon the amount of oversize material present. The data show that other factors should be taken into account, and it is possible that in time these may be evaluated as simultaneous or consecutive reactions: Development of the theory of comminution has been retarded for many years by the assumption that surface area measurements constitute the sine qua non of the work done in crushing and grinding, and it is encouraging to note the belated growth of other ideas. In the Abstract the term "net power" should be changed to "net energy." Throughout the paper the term "hp per ton" should be changed to "hp hrs per ton", or "hp hr t." The term "Probability Theory" in the title does not seem appropriate, since it is not clear how the probability theory is used in developing the ideas in the paper. There seems to be a contradiction between the large calculated advantages of closed circuit operation and the statement following that the closed circuit test results showed no significant change in grinding behavior, when compared with the batch grind curves. Tables I and II show that between 75 pct and 50 pct solids the energy input required decreases with increasing moisture content and may indicate the advisability of grinding at higher dilutions in certain cases. The calculation of the hp-hr per ton factor indicates an input in the laboratory mill of only 7.32 gross hp per ton of balls; this casts some doubt upon the accuracy of the factor used, since the power input in commercial mills at 80 pct critical speed is customarily much higher. The tests show that within fairly wide limits the amount of ore in the laboratory mill may be varied and a product of constant fineness obtained, provided that the grinding time is varied in the same proportion. This has often been assumed, and confirmation by actual testing is of value. The Cavg corrections for differences between the plant and laboratory size distributions do not seem very satisfactory, since in many cases the plant/laboratory ratio is farther from unity after correction than before. The following equation has been derived from the data in Table VI: Relative Energy (log new ball diam in in. + 0.410) Input = --------------—--------------- from which the relative energy inputs for balls of different sizes can be calculated and compared. The relative energy input is unity for balls of 2.715 in. diam. The equation indicates that the work accomplished by a ton of grinding balls per unit of energy input is roughly proportional to the square root of the total ball surface area; provided, of course, that the balls are sufficiently large to break the material. The data in support of this statement are admittedly meager, but are fairly consistent when plotted. The relative grindability values listed in Table VI for 200 mesh multiplied by 4/5 apparently correspond approximately to the A-C grindability at 200 mesh.' It would seem that for open circuit tests comparable accuracy could be obtained much more simply by the old method' of plotting the test grind, extending the mesh grinds to the left of zero time if necessary, and determining from the plot the equivalent time required to grind from the plant feed size to the plant product size, using the average of several mesh sizes. The en- ergy input value of one time interval could be determined by tests on materials of known grinding resistance, and this multiplied by the interval required should give the desired energy input value. The relative grindabilities would be the relative time intervals required for a specified feed and product size. When the plotted mesh size lines of a homogeneous material are extended to the left beyond zero time they meet at one point at zero pct passing. The horizontal distance of this point from zero time indicates the equivalent energy input required to prepare the mill feed. The author's results show that the closed circuit grinding tests give about the same K values as open circuit tests, from which he concludes that open circuit tests are satisfactory in many cases. The value of the closed circuit test is its ability accurately to predict energy requirements in closed circuit grinding for both homogeneous and heterogeneous materials. If the material is homogeneous, the open circuit test gives satisfactory results; but if the material contains appreciable fractions of hard and soft grinding ore, the open circuit tests will not be accurate because of the accumulation of hard grinding material in the circulating load. Since in most cases it is not possible to determine a priori whether the material contains hard and soft fractions, the closed circuit tests are preferable and more reliable. B. S. Crocker (Lake Shore Mines, Ontario)—Dr. Roberts probability theory of grinding is very similar to our log pct reduced vs. log tonnage method of plotting and evaluating grinding tests at Lake Shore. However, although we both seem to start at the same point we finish with different end results. Shortly after publishing our grinding paper (referred to by Dr. Roberts) in 1939, we did pursue the subject of the "constant pct reduction in the pct +28 micron material for each constant interval of time. We ran innumerable tonnage tests on the plant ball mills, rod mills, tube mills with 11/4 and 3/4 balls, and lastly pebble mills, with tonnage variations from 180 tons per day to 950 tons per day. We found that when we plotted the log of the tonnage against the log of the pct reduced of any reliable mesh, we had a straight line up until 90 pct of the mesh is reduced. We have also tested this in our 12-in. laboratory mill with the same results. We have used this method of evaluating grinds for the past 8 years and developed the recent four stage pebble plant on this basis. By pct reduced we mean the percentage of any given mesh that is reduced in one pass through a mill at a given tonnage (or time). For example, if the feed to a rod mill is 90 pct +35 mesh and the discharge at 500 tons per day is 54 pct +35, the pct reduced is 90 — 54/90 = 40 pct. If the feed had been 80 pct +35 the discharge would have been 48 pct +35 or pct re- duced 80-48/80 = 40 pct as long as the tonnage re- mained constant at 500 tons per day. Thus we can easily correct for normal variation of mill feeds. This log — log relationship derived from the tonnage tests of all our operating mills has proved of tremendous help in checking laboratory work and in designing alternate layouts or new plants. The difference between the log — log and the semi-log plot is only shown up when the extremes in tonnages are plotted. When the relationship between the pct reduced and the tonnage was first investigated, we used semilog

Jan 1, 1952

By Voyle R. McFarland, Robert A. Burmeister, David A. Stevenson

The distribution of lead between phases in the Ag-Sb-Te system was studied using microautoradio -graphy. Two compositions were investigated, both containing an intermediate phase Known as silver antimony telluride as the major phase, and one containing AgzTe and the other SbzTes as the minor phase. For both compositions, two thermal treatments were used: nonequilibrium solidification from the melt and long equilibration anneals of the as-solidified structure. For each composition, lead was segregated in the minor phase of the as-solidified structure, but was distributed in the matrix after anneal. The electrical resistivity and carrier type were insensitive to the distribution of lead in the two-phase structure. ThERE has been considerable interest in the Ag-Sb-Te system because of its thermoelectric properties. The major interest has been in compositions on the vertical section between AgzTe and SbzTes, particularly the 50 mole pct SbzTes composition AgSbTez (compositions are conveniently expressed as mole percent SbzTes along the AgzTe-SbzTes section). One of the major problems in the proper evaluation and utilization of this material is the inability to control the electrical properties through impurity additions: all alloys prepared to date have been p-type, even with the addition of large amounts of impurities. It has been shown Wit all the compositions previously studied contain an intermediate phase of the NaCl st'ructure as a major phase (denoted by b) and a second phase, either AgzTe or SbzTe3, as a minor phase.'-3 One explanation for the unusual electrical behavior of this material is that the impurity additions have a higher solubility in the second phase than in the matrix; the impurity would segregate to the second phase, leaving the bulk matrix essentially free of impurity.4 In order to investigate this mechanism with a specific impurity element, the distribution of lead between the two phases was determined using autoradiography. Lead 210 was chosen because of the suitability of its 0.029 mev 0 particle for autoradiography and also because of the interest in lead as an impurity in this system.5'6 EXPERIMENTAL PROCEDURE Two compositions were taken from the vertical section between AgzTe and SbzTes, 50 mole pet SbzTes (Viz. AgSbTez) and 75 mole pct SbzTes, in which AgzTe and SbzTes appear, respectively, as the minor phase. Lead containing radioactive lead (pb210) was added to the above compositions to provide a concentration of 0.1 wt pct Pb. The material was placed in a graphite crucible in a quartz tube which was then evacuated and sealed. The samples were melted and solidified by cooling at a rate of 8°C per min and then removed and prepared for microa~toradiography. After autoradiographic examination of these samples, they were again encapsulated and annealed in an isothermal bath at 300°C for a number of days and prepared for examination. An alternate method of preparation employed a zone-melting furnace; the molten zone traversed the sample at a rate of 1.2 cm per hr and the solid was maintained at a temperature of 500°C both before and after solidification. This treatment had the same effect as solidification at a slow rate followed by an anneal for several hours at 500°C. In order to obtain the best resolution, thin sections of the alloy were prepared by hand lapping to a thickness of approximately 20 p. Other samples were prepared for examination by lapping a flat surface on the bulk sample. The resolution, although somewhat better in the former procedure, was adequate in both instances and the majority of the samples were treated in the latter fashion. A piece of autoradiographic film (Kodak Experimental SP 764 Autoradiographic Permeable Base Safety Stripping Film) was stripped from its backing, care being taken to avoid fogging due to static-electrical discharge. A small amount of water was placed on the sample, the film applied emulsion side down on the surface of the sample, and the sample and the film dipped into water in order to assure smooth contact. After drying, the film was exposed for 2 to 5 days, the period of time selected to give the best resolution. The film was developed on the specimen and fixed and washed in place. Two major factors must be considered in establishing the reliability of an autoradiograph: the in-

Jan 1, 1964

By H. E. Lee, P. C. Feddersen

Greenockite is the only known cadmium mineral of importance. It occurs rather universally, in minor concentrations, as a secondary mineral in sphalerite deposits. The world's cadmium output is obtained through the processing of metallurgical by-products, largely from the treatment of residues from electrolytic zinc, retort zinc and lithopone plants. These sources are supplemented by the processing of fumes from lead and copper smelting operations. The development of modern selective flotation practice in the decade 1920-1930, which permitted the economical mining of complex lead-zinc ores, resulted in significant increases in the quantities of cadmium entering lead smelting systems. Being closely related to zinc as to occurrence, properties and production, most detailed description of cadmium recovery methods are to be found recorded in connection with zinc metallurgy. Other than occasional articles pertaining to particular operational procedures, literature offers but little in the nature of a balanced survey of lead smelter cadmium recovery practices. While many of the basic operations described for the recovery of cadmium from zinc by-products are applicable to the treatment of lead plant products, the inherent problems involved differ widely. In general the cadmium content of related by-products from routine lead smelting operations is present in lower concentrations, exists in a less soluble state and is associated with both a greater quantity and a greater variety of detrimental impurities. To cope with these problems, lead smelter practices are found to follow the general outline: Preparatory Processing 1. Concentration operations 2. Sulphation operations Cadmium Plant Processing 1. Leaching operations 2. Purification operations 3. Sponge precipitation operations 4. Metal recovery operations 5. Refining and casting operations As in the case of related zinc plant operations, cadmium recovery practices at lead smelters are not standardized. They not only vary as to type, but also extent. Depending upon prevailing conditions, lead smelter cadmium operations range from simple concentration campaigns, for the purpose of sufficiently "up-grading" products for shipment elsewhere, to complete processing steps for the production of refined metal. Preparatory Processing The cadmium content of lead smelter receipts is low and, as a rule, proportionate to the zinc content; the usual range of cadmium contained being of the order of 0.01-0.05 pct. Were it not for the low boiling point of cadmium, such small concentrations would, no doubt, be lost in the large tonnages of slag, metal and other smelter end products. However, the ready volatility of cadmium and its compounds at prevailing lead smelting temperatures results in its concentration in fractional portions of fume collected. This collected fume comprises a circulating load within the smelter system. Thus, the cadmium content of blast furnace fume* increases with each successive circulation until an equilibrium value is reached when the sum of the cadmium losses, due to handling and in slag, waste gases and other end products, becomes equal to the intake as ore. With ore receipts averaging, say 0.03 pct cadmium, the concentration value obtainable, through fume circulation in a routine manner, approaches 10-12 pct. In such operations, cadmium concentrations in blast furnace fume of from 3-5 pct are readily .attainable. However, the concentration gain beyond this range, with each additional circulation, is progressively decreased as a result of mounting losses occurring through handling and in end products. Therefore, to avoid excessive cadmium loss and to enhance the ultimate concentration anttainable, it is customary practice to isolate blast furnace fume at some intermediate cadmium content for special concentration procedure. The most common type cadmium concentration "campaign" involves special smelting operations wherein a relatively high portion of blast furnace fume at 3—6 pct cadmium is incorporated into the sinter charge. This type practice is roughly illustrated by the diagram on p. 111. Cadmium fume collected from lead blast furnace operations is not amen-

Jan 1, 1950

By N. E. Brown, F. L. Versnyder

THE apparent dependency of the electrical characteristics of hexagonal crystalline selenium on microstructure has aroused much interest in microscopical studies of selenium. Microscopic observations on the crystallization of selenium have been made by Escoffery and Halperin,' P. H. Keck,' and other investigators. It is the purpose of this paper to discuss the microstructural changes observed on polished cross-sections of single layers of selenium after various heat treatments. Observations were also made on crystallization of the free-surface layer of these deposits. In general, all of the transformations studied were either transformations of the vitreous selenium to hexagonal selenium or micro-structural transformation of the hexagonal selenium itself. Procedure The selenium used in this work was obtained from the American Smelting and Refining Co. and was approximately 99.96 pct pure. An intentional impurity of 1 part per 2,000 of bromine was added to the material prior to evaporation. A thickness of approximately 0.002 in. of this selenium was vapor deposited on an aluminum base plate. The maximum plate temperature during the vacuum vapor deposition was 140°C. Mounting of the cross-sectional specimens for metallographic study could not be done in plastic mounting media, as is customary, since temperatures in excess of 50°C would cause unwanted transformations. Consequently, a simple clamp-type device was used to mount the specimens for preparation. All grinding operations were then done carefully by hand in order that the specimen not become heated during this operation. Wet polishing was done on the conventional metallographic polishing laps, using successively finer grinding powders. An extremely careful polish is necessary, since observation and micrography of the specimens are done in the unetched condition under polarized light. The two observations of crystallization made on the free surface of vitreous selenium deposits (Figs. 4 and 5) were made on surfaces which were perpendicular to the cross-sections studied. These free-surface layers were examined directly, i.e., no pre- vious metallographic preparation, as obtained from the vacuum vapor deposition. Microscopic Observations A study was made of polished cross-sections of the vitreous selenium as-deposited. It was noted that in all cases there was columnar crystallization adjacent to the base plate, which appeared to occur during the vacuum deposition process. This observation has also been made by Keck? It also was observed that vagrant spherulitic crystallization occurred in the vitreous selenium. The term "vagrant" is used, since these spherulitic grains appear to crystallize at random throughout the vitreous selenium during the vacuum deposition process. Columnar crystallization at the A1-Se interface and a typical spherulite observed in a polished cross-section of "as-deposited" vitreous selenium may be seen in Fig. 1. Cross-sectional samples of vitreous selenium studied after heat treating individual samples for 20 min in 10" steps from 80" to 220°C revealed that crystallization—in this case, columnar crystal growth —proceeds from the aluminum base plate to the surface of the specimen (Fig. 2). Crystallization was microscopically observed to be complete after the 130°C heat treatment. Visual examination of the free surface of the specimen after the 130 °C heat treatment revealed the readily recognizable grey appearance of the completely crystallized selenium, in corroboration of the microstructural observations. No microstructural transformations then appeared to take place between 130" and 190°C. At 190°C the beginning of recrystallization appeared and proceeded until the columnar grain structure had been completely transformed to equiaxed grains between 210" and 220°C (Fig. 3). Naturally, the grain size of the recrystallized grains at the lower temperatures (190" to 210°C) was smaller than is illustrated in Fig. 3. In addition, polished cross-sections of deposits heat treated at 140°C for 10 min to cause complete crystallization and, subsequently, heat treated in 10" steps from 80" to 220°C for 20 min were studied. As expected, no microstructural transformations took place until the beginning of recrystallization was observed at 190°C. A comparison with the previously studied specimens revealed that recrystallization proceeded almost identically in the two experiments although in the first case the deposits were vitreous prior to the series of heat treatments and in the second case they had been crystallized by a previous heat treatment. By heat treating for longer times (180 min) at lower temperatures, the

Jan 1, 1956

By T. G. Nilan

Steels containing 0.4 and 0.8 pet C have been transformed isothermally at pressures up to 34 kbuv. Decomposilion mechanisms are so intimately related to phase equilibvia that, as the equilibria shift under high pressure, the microstruclures of the decomposition producls change, maintaining at pressure the same correspondence between a given phase equilibrium and a given microstructure as a1 1 atm. A bainitic unicvo-structure occurs in these steels at high pressure that IS observed only at 1 aim abole 1.4 pct C. This strrrcl111,e 1s ruliorzalized in terms of the effect of pressure on the transformation to lower bainite. The pressuve depetlderlce of the kinetics of pearlile formation is descrihed by an absolute rule theory amalysis. The activation volume for the transformation is 7 cu cm per mlole, which is indicative of a phase-interface transformation-rate cotntrol mechanism. This fortmulation, when expressed in terms of known solule effects on the energelics of tvansformation, gives promise of explaining the effects of alloying elemenls on hnrden-abilily, particularly that of 'coball. KINETIC processes in solids are functions of the primary thermodynamic variables of state: composition, temperature, and pressure. Until the development of high-pressure techniques' that permitted the generation of sustained high pressure at high temperatures, metallurgical studies of such reactions were largely limited to isobaric conditions at atmospheric pressure. The data so obtained, and theoretical deductions based on these data, were necessarily incomplete For the particular case of austenite decomposition, a knowledge of the phenomenology of the reaction in terms of all the state variables should lead to a clarification of the process. This deeper understanding should facilitate a decision between conflicting theories that have been proposed to rationalize these phe- nomena. An analysis, derived from an understanding of the transformation mechanisms, may aid in the optimization of alloy steel development. The first studies of the effect of pressure on transformations in steel were made by Kulin et al. in 1952.' In a study of the influence of applied stress on mar-tensite formation in a 30 pct Ni steel, they found that the martensite start (M,) was depressed 8°C per kbar* by hydrostatic pressure. Jellinghaus and Friedewold3 were apparently the first to investigate the effect of pressure on isothermal transformations above the Ms. They found that the bainite transformation rate in a 1.2 pct C, 3.8 pct Mn steel was reduced by a factor of 3 by a hydrostatic pressure of 4 kbar. In both of these investigations,2,3 the M, of the steels studied was below room temperature. Austenitizing and quenching were done at atmospheric pressure, followed by the decomposition of the metastable austenite under pressure. The maximum temperature at pressure in the bainite study3 was 350°C. Until the advent of the present high-pressure devices, it was not possible to conduct isobaric high-pressure heat treatments from austenitizing through isothermal decomposition and quenching. The exploitation of high pressure as a variable in metallurgical studies was greatly advanced by the apparatus and techniques developed by Hall4 and co-workers. Utilizing these techniques, Radcliffe et a1.5 and Hilliard6 etermined the pressure dependence of phase equilibria in the Fe-C system. Hilliard and cahn7 examined the pearlite transformation rate in an AISI 1080 steel and also in a high-purity 0.92 C Fe-C alloy at 1 atm and at 34 kbar and found a 700-fold reduction in rate at pressure in the 1080 steel but only a fivefold reduction in the high-purity alloy. In agreement with the shift of phase equilibria under pressure, the microstructures were hypereutectoid at 34 kbar pressure, whereas they are eutectoid at 1 atm. Determination of the effect of pressure on carbon diffu-

Jan 1, 1968

By P. de Vitry, Oliver Bowles

The conventional wire saw, introduced in the slate district of Pennsylvania by the Bureau of Mines in 1927, and used thereafter with remarkable success, consists of a three-strand steel cable having a diameter of 93/16 or 54 in. The equipment, methods used, and accomplishments have been described in previous reports.'-I Similar wire saws have been used extensively in Europe, in quarries and in shaping blocks and slabs. During the period 1932-1937, competition in European marble quarries was keen, prices were declining, and orders were not abundant. When orders were received, there was generally an urgent call for speedy delivery. Because of the diversification of demands, it was impossible to maintain in stock marbles of the color, size, and thickness called for, therefore the material generally had to be fabricated after the order was received. The wire saw enabled stone mills to fill such orders promptly. With skillful handling, 7/8-in. slabs could be cut accurately and rapidly with this equipment. It was found, however, that, as the three-strand wire became worn, the cutting speed dropped rapidly and the cut became less accurate. To overcome these difficulties the junior author of this paper, after much experimentation, developed a new type of wire consisting of a single ribbon-shaped strand, twisted as shown in Fig. I. To ensure straight sawing, the twist of the ribbon is reversed from right to left and vice versa every 25 ft. The reversal of the twist is shown in Fig. 2. This is not a new feature; it has been used to advantage with the three-strand wire both in Europe and America for several years. However, some difficulties arise in splicing the three-strand reverse-twist wire, and the claim is made that cutting is less accurate as the wire becomes worn. To make an endless belt, the ends of the single-strand wire are brazed together with Pyrophyllite is a hydrous aluminum silicate (A1²Si4O10(OH)²)1 that, occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mohs' scale.' The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey12 contain pyrophyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, ('are noticed in but small quantities to the extent they might occur as accessory constituents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 per cent and the alumina from 22 to 33 per cent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent. Sources At present, North Carolina is the only commercial source of pyrophyllite, although the mineral has been found in small quantities in many parts of the world. The North Carolina deposits are in the "Carolina Slate Belt," which traverses the center of the state in a southwesterly direction. This belt varies from 8 to 50 miles in width. Two major deposits of pyrophyllite lie along its eastern boundary, in what is known as the Deep

Jan 1, 1942

By P. de Vitry, Oliver Bowles

The conventional wire saw, introduced in the slate district of Pennsylvania by the Bureau of Mines in 1927, and used thereafter with remarkable success, consists of a three-strand steel cable having a diameter of 93/16 or 54 in. The equipment, methods used, and accomplishments have been described in previous reports.'-I Similar wire saws have been used extensively in Europe, in quarries and in shaping blocks and slabs. During the period 1932-1937, competition in European marble quarries was keen, prices were declining, and orders were not abundant. When orders were received, there was generally an urgent call for speedy delivery. Because of the diversification of demands, it was impossible to maintain in stock marbles of the color, size, and thickness called for, therefore the material generally had to be fabricated after the order was received. The wire saw enabled stone mills to fill such orders promptly. With skillful handling, 7/8-in. slabs could be cut accurately and rapidly with this equipment. It was found, however, that, as the three-strand wire became worn, the cutting speed dropped rapidly and the cut became less accurate. To overcome these difficulties the junior author of this paper, after much experimentation, developed a new type of wire consisting of a single ribbon-shaped strand, twisted as shown in Fig. I. To ensure straight sawing, the twist of the ribbon is reversed from right to left and vice versa every 25 ft. The reversal of the twist is shown in Fig. 2. This is not a new feature; it has been used to advantage with the three-strand wire both in Europe and America for several years. However, some difficulties arise in splicing the three-strand reverse-twist wire, and the claim is made that cutting is less accurate as the wire becomes worn. To make an endless belt, the ends of the single-strand wire are brazed together with Pyrophyllite is a hydrous aluminum silicate (A1²Si4O10(OH)²)1 that, occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mohs' scale.' The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey12 contain pyrophyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, ('are noticed in but small quantities to the extent they might occur as accessory constituents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 per cent and the alumina from 22 to 33 per cent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent. Sources At present, North Carolina is the only commercial source of pyrophyllite, although the mineral has been found in small quantities in many parts of the world. The North Carolina deposits are in the "Carolina Slate Belt," which traverses the center of the state in a southwesterly direction. This belt varies from 8 to 50 miles in width. Two major deposits of pyrophyllite lie along its eastern boundary, in what is known as the Deep

Jan 1, 1942

By R. G. Grieves, G. Thodos

A method is presented for the accurate calculation of the cricondentherm and cricondenbar pressures of multicomponent hydrocarbon mixtures of known composition. The mixtures may contain six and quite possibly any number of components including paraffins, isoparaffins, olefins, acetylenes, naphthenes and aromatics. The approach is similur to that used for calculating critical pressures and cricondentherm and cricondenbar temperatures. The critical pressure, the normal boiling point and the approximate vapor pressure behavior of each component are all that art required. A stepwise culculation procedure is necessary for mixtures containing more than two components. From an analysis of 22 binary systems and 118 mixtures, the average deviation of calculated cricondentherm pressures from reported values is 2.4 per cent. For nine multicomponent mixtures the average deviation is 1 per cent. Considering 19 binary systems and 108 mixtures, the average deviation of calculated cricondenbar pressures from reported values is 1.7 per cent. For 15 multi-component mixtures, the average deviation is 2.2 per cent. INTRODUCTION A knowledge of the phase behavior in the critical region of multicomponent hydrocarbon mixtures is of value both in industrial processing operations and for the optimum operation of gas condensate reservoirs. Accurate methods of calculating the critical temperatures and critical pressures4,6,7,8,9,23 and cricondentherm and cricondenbar temperatures6p10 of multicomponent hydrocarbon mixtures are available in the literature. If the cricondentherm and cricondenbar pressures could be calculated with equal accuracy, the entire phase diagram of a multicomponent hydrocarbon mixture could be well approximated. The work of Etter and Kay6 is limited to systems containing the normal paraffins and has not been tested on systems containing a heavier component than heptane. In addition, the development of their multicomponent equations is based upon a limited number of mixtures containing from three to six components. Silverman and Thodos have considered systems containing both paraffinic and non-paraffinic hydrocarbons, but their correlation is limited to binary systems and is highly inaccurate for methane systems. Eilerts has done extensive work on the cricondenbar pressure; he has produced an excellent correlation for binary systems. However, his procedure for multicomponent mixtures is chiefly useful for highly complex mixtures requiring a knowledge of the vapor-liquid equilibrium behavior of the mixtures; he has not considered the cricondentherm pressure. The objective of this study was the development of an accurate and rapid method for the calculation of the cricondentherm and cricondenbar pressures of multicomponent mixtures containing all types of hydrocarbons and having a wide volatility range. The approach that was adopted is similar to that used by Grieves and Thodos for cricondentherm and cricondenbar temperaturesl0 and for critical pressures.9 However, methane systems had to be considered separately and a modified stepwise calculation procedure was utilized for the cricondertherm pressure. The correlations were developed in a manner similar to those for critical pressures and cricondentherm and cricondenbar temperatures. Based upon binary data reported in the literature it was observed that the ratios of cricondentherm and cricondenbar pressure to the pseudocritical pressure (molar average), pt/ppc and pp/ppc, respectively, in two-component systems depended upon the mole fraction of the low-boiling component and upon the diversity in properties of the two components. A dimensionless boiling-point parameter Tb,/Tb was chosen to represent the diversity in properties of the components. For a binary system, Ti,'is the molar average of the normal boiling points of the two components involved. For a multicomponent system it is either the molar average of the normal boiling points of all of the components involved or the molar average of the normal boiling point of the pure low-boiling component and of the atmospheric boiling point of the low-boiling-free mixture of

Jan 1, 1965

By J. T. Norton, Joseph Gurland

IN spite of the extended use and high state of practical development of the cemented tungsten carbides, the structure of these alloys is still a matter of considerable controversy. The characteristic high rigidity and rupture strength of sintered compacts have been attributed to a continuous skeleton of tungsten carbide grains, formed during the sintering process. This view is based mainly on the work of Dawihl and Hinnuber,1 who reported that a sintered compact of 6 pct Co maintained its shape and some of its strength after the binder was leached out with boiling hydrochloric acid. After leaching, only 0.04 pct Co was reported to remain in the compact. They also showed that the assumed increasing discontinuity of such a skeleton, as the cobalt content is increased, could be made to account for the observed discontinuous increase of the coefficients of thermal expansion, the loss of rigidity, and the impaired cutting performance of alloys of more than 10 pct Co. Contradictory evidence was cited by Sanford and Trent,' who mentioned that a sintered compact was destroyed by reacting the binder with zinc and leaching out the resulting Zn-Co alloy. The skeleton theory also does not account for the observed change of strength of sintered compacts as a function of cobalt content. If the skeleton is responsible for the strength, the latter would be expected to decrease with increasing binder content. Actually, the strength increases and reaches a maximum around 20 pct Co. In addition, tungsten carbide is brittle and undoubtedly very notch sensitive. The highest value found in the literature for the transverse rupture strength of pure tungsten carbide prepared by sintering is 80,000 psi.3 herefore, such a skeleton does not easily account for a rupture-strength value of 300,000 psi and higher, commonly found in sint.ered tungsten carbide-cobalt compacts. In view of the conflicting data present in the literature, experiments were undertaken to determine whether the sintering of tungsten carbide-cobalt alloys leads to the formation of a carbide skeleton or whether the densification behavior and the properties of cemented compacts are consistent with a structure of isolated carbide grains in a matrix of binder metal. The specimens were prepared from powders of commercial grade. Tungsten carbide powder ranged in particle size from 0 to 5x10-4 cm. Mixtures of tungsten carbide and cobalt were ball milled in hexane for 48 hr in tungsten carbide lined mills. After milling, the specimens were pressed in a rectangular die (1x1/4x1/4 in.) at 16 tons per sq in. NO pressing lubricant was used. Sintering of the tungsten carbide-cobalt compacts was carried out in a vertical tube furnace equipped with a dilatometer (Fig. I), by means of which the change of length of the powder compacts could be followed from room temperature to 1500°C. An atmosphere of 20 pct H, 80 pct N was maintained inside the furnace. Decarburization of the samples was prevented by the presence of small rings of graphite inside the furnace tube. The temperature of the sample was measured by a platinum-platinum-rhodium thermocouple, which also was part of a temperature control system able to maintain a constant temperature within ±100C. Pure tungsten carbide compacts were prepared by sintering the carbide without binder or by evaporating the binder from sintered compacts in vacuum at 2000°C. Since complete densification of these samples was not desired, they were sintered only to 60 or 80 pct of the theoretical density of tungsten carbide. The specimens were prepared for metallographic examination by polishing with diamond powders and etching with a 10 pct solution of alkaline potassium ferricyanide. Cobalt etches light yellow and the carbide gray. The amount of porosity is exaggerated since it is difficult to avoid tearing out carbide particles, especially from incompletely sintered samples. Experimental Observations A number of specific experiments were carried out in order to study some particular aspect of the sintering problem. The details of these experiments, together with their results, are as follows: Electrolytic Leaching: The binder was removed by electrolytic leaching from sintered tungsten carbide-cobalt compacts for the purpose of determining the continuity of the carbide phase. The method used was based on the work of Cohen and coworkers4 on the electrolytic extraction of carbides from annealed steels. If the sample is made the anode, using a 10 pct hydrochloric acid solution as the electrolyte, the binder is dissolved, but the rate of solution of tungsten carbide is negligible. A current density of 0.2 amp per sq in. was applied. As shown in Fig.

Jan 1, 1953

By B. C. Raynes

IN the early part of 1952, under the auspices of the U. S. Atomic Energy Commission, Horizons Inc. undertook an investigation dealing with the preparation of high purity thorium metal in order to develop an economically competitive production process for this metal based on a recovery of the metal by a fused salt electrolysis, since a survey of the literature of thorium chemistry indicated that electrolytic methods had not received much attention, despite the consideration that electrochemical production methods often offer attractive commercial potentialities. Thorium metal has been prepared by methods which fall into four general categories: 1) reduction of halides or double halides; 2) reduction of the oxide; 3) thermal decomposition of halides; and 4) electrolytic methods. Some of the important results obtained by various investigators since about 1900 in recorded attempts to prepare pure thorium metal are summarized in Table I. A bibliography of pertinent literature is included in this paper. Thorium is strongly electropositive and possesses a great affinity for oxygen and nitrogen. As a result the prospects for the production of high purity thorium from aqueous media or oxygen bearing compounds are remote. The most promising and profitable area of investigation for production of thorium metal lies in fused salt electrolysis. Thorium has been produced previously by this technique from halide salts in fused alkali chloride eutectic mixtures. Until recently, however, the lack of known large uses for thorium has inhibited the investigation of these methods. The basic problem in an investigation into fused salt production methods for thorium is to develop a suitable fused salt system for the economic preparation of thorium. The first portion of the work in these laboratories was a small scale investigation of the electrolysis of potassium thorium fluoride, KThF5, under a variety of conditions. High purity thorium was prepared in this manner, but the process did not appear to offer the simplest and most attractive continuous commercial operation. The work reported here relates to an all-chloride system employing thorium chloride as the cell feed. ThCL4 was produced as an anhydrous material stabilized in molten sodium chloride. This product, further diluted in NaCl, was subjected to electrolysis. The electrolytic process has been studied in cells capable of holding up to 50 lb total salt charge. Ductile, pure thorium metal has been reproducibly obtained in this operation. Considerable experimentation was carried out in the preparation of ThCL as a cell feed free from moisture, oxides, and other impurities. Thorium was cathodically deposited as a coarsely crystalline powder interspersed with residual bath salts. Aqueous procedures for separating and recovering the metal were developed. The thorium metal powder obtained has been evaluated with respect to its hardness, chemical purity, and certain other physical properties. Preparation of ThC1,—Thorium chloride, and the chlorides of some other metals (aluminum, beryllium, tantalum, zirconium, etc.) cannot be obtained from aqueous solution by direct heating and evaporation. Evaporation and heating of a solution of thorium chloride yields a hydrated salt or partially hydrated salt, and finally Tho,. Anhydrous thorium chloride is obtained by forming a hydrated ammonium chloride complex salt in acidified water solution, dehydrating this compound, and finally decomposing the double salt and subliming the ammonium chloride component. Various methods for the preparation of anhydrous thorium chloride, in accordance with this concept, were investigated as indicated in Table I1 from hydrated thorium chloride (ThCl, . 3H2O), and from thorium oxycarbonate (ThOCO,). In the method found most satisfactory for this work, thorium oxycarbonate was dissolved in an excess of concentrated HC1 to give a clear yellow solution. At least 2 mol NH,Cl were added to the solution per mol of contained thorium. Ammonium thorium chloride hydrate was crystallized from solution by cooling and saturation with HC1. The resultant complex, (NH,Cl),ThCl;xH,O, was dehydrated by evaporation at 130° to 150°C and thoroughly dried at about 250°C. The dried ammanium thorium chloride was then mixed with sodium chloride in proportions to form NaThCL or to produce a ThCL4-NaCl mixture with a given thorium content. The ammonium chloride was sublimed off at temperatures above 500°C in an inert atmosphere furnace to give an anhydrous chloride source electrolyte, essentially free of Tho, and of NKC1.

Jan 1, 1958

By C. E. Corson

THE experiments of which the results and significance are set forth in this paper do not by any means cover the whole subject of the heat-treatment of the material referred to, yet they constitute a contribution to that general subject, rather than to the special department of annealing. The material here considered is acid open-hearth steel, containing from 0.50 to 0.80 per cent of carbon, with a nearly uniform percentage of other elements. This class of steel is rapidly increasing in commercial importance. It is even rumored that the rail-specifications of some railroads will hereafter require open-hearth steel. Yet this particular grade seems to have received less study and description from the standpoint of the metallographist than many others. The investigation here described was directed to the following points:-Steel containing about 0.50 per cent, of carbon : 1. The structure as related to the temperature, at the same rate of cooling; 3. The structure and physical properties as related to temperature at different rates of cooling; 3. The structure and physical properties as related to different finishing-temperatures and different rates of cooling; 4. The bearing of these observations upon the statement of Prof. Albert Sauveur.1

Sep 1, 1906

By Zay Jeffries

From the title of this chapter the reader could expect an attempt to outline the anticipated shape of things to come, mineralwise. We have no crystal ball and if we possessed one we could claim no expertness in its use. In the first place no one can tell the future status of man. No one has any way of knowing to what extent peace will prevail, nor to what extent changes may occur in national sovereignties or forms of government or in international relationships. So future man is an uncertainty. Nor can we predict new developments that may result in significant changes in man's status or in the mineral industry or both. If, for example, this chapter had been written in the middle 1930's, nearly everything that has happened since in the field of atomic energy would have been missed. Yet what a vast change this has made in the status of man! Also the changes in the mineral industry have been important. A writer would have been bold indeed had he prophesied that uranium would play such an important role. But we need not confine our foggy vision to the atomic energy field. The steep rise in the use of aluminum, titanium, and germanium reflects the unpredictable in what may be thought of as the more normal pursuits. This should not discourage one from using the past and currently observable trends as bases for limited predictions. To do this, however, it is desirable to make certain assumptions about man's status without even a pretense that these assumptions have a high probability of fulfillment: 1. Only minor changes will occur in the geographical boundaries of the nations of the world. 2. World War III will not take place in the near future. 3. As a consequence of (2), man will not destroy himself by wanton use of atomic weapons. 4. Disarmament will take place, if at all, gradually rather than all at one time. Under the above assumptions the world will enjoy a period of relative peace even though the status may be one of an armed truce. The assump-

Jan 1, 1959

By Zay Jeffries

From the title of this chapter the reader could expect an attempt to out- line the anticipated shape of things to come, mineralwise. We have no crystal ball and if we possessed one we could claim no expertness in its use. In the first place no one can tell the future status of man. No one has any way of knowing to what extent peace will prevail, nor to what extent changes may occur in national sovereignties or forms of government or in international relationships. So future man is an uncertainty. Nor can we predict new developments that may result in significant changes in man's status or in the mineral industry or both. If, for example, this chapter had been written in the middle 1930's, nearly everything that has happened since in the fields of atomic energy and space technology would have been missed. Yet what vast changes these I have made in the status of man! Also the changes in the mineral industry have been important. A writer would have been bold indeed had he prophesied that uranium would play such an important role. But we need not confine our foggy vision to these fields. The steep rise in the use of aluminum, titanium, and germanium reflects the unpredictable in what may be thought of as the more normal pursuits. This should not discourage one from using the past and currently observable trends as bases for limited predictions. To do this, however, it is desirable to make certain assumptions about man's status without pretense that these assumptions have a high probability of fulfillment: 1. Only minor changes will occur in the geographical boundaries of the nations of the world. 2. World War III will not take place in the near future. 3. As a consequence of (2), man will not destroy himself by wanton use of atomic weapons. 4. Disarmament will take place, if at all, gradually rather than all at one time. Under the above assumptions the world will enjoy a period of relative peace even though the status may be one of an armed truce. The assump-

Jan 1, 1964