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By M. B. Standing, D. L. Katz

Equilibrium data are reported on the composition and densities of coexisting vapor and liquid phases as a function of Pressure and temperature for four hydrocarbon systems prepared from crude oil and natural gas. The data were observed over a range of pressures from 1000 to 8220 Ib. per sq. in. and at temperatures ranging from 35' to 250°F. The compositions of the hydrocarbon systems were such that the critical temperatures of the mixtures were lower than the range of the investigation. Under these conditions, it is shown that the composition of the systems has a marked effect upon both the absolute value of the equilibrium constants and the change of the constants with pressure for the several components comprising the system. From weight-balance considerations, it has been possible to construct the partial phase diagram of a mixture of a 49.9" A.P.I. crude oil and natural gas having a gas-oil ratio of 3660 cu. ft. per barrel. Descriptions of the apparatus used, the analytical procedure, the material used, and the equilibrium measurements are included. A knowledge of the physical behavior of naturally occurring hydrocarbon mixtures is fundamental to the treatment of many problems in the production, transportation and rehing of petroleum. The recent discoveries of pools having formation pressures up to 7500 lb. per sq. in. and higher, and the development of full-scale equipment to operate at pressures of 5000 lb. per sq. in. or more have greatly increased the need for knowledge of the composition, temperature, pressure and density relationships of coexisting vapor and liquid hydrocarbon phases. The following paper presents the results of investigations upon 22 mixtures of natural gas and crude oil of known com~o~itio~ that had been brought to equilibrium under controlled conditions of temperature and pressure. Data are presented upon the densities and compositions of the coexisting vapor and liquid phases for four different systems containing hydrocarbon material having boiling points from minus 2 5S°F. to well over I000 F. The data were observed Over a pressure range from Iooo Ib. per Sq. in to 8220 lb. Per sq. in. and a temperature range from 35' to 2 50°F. The accepted method of computing the physical relationship between two coexisting phases of a hydrocarbon mixture is by use of the "equilibrium constant" K as proposed by Souders, Selheimer, and Brown. definition,

Jan 1, 1944

By M. B. Standing, D. L. Katz

Equilibrium data are reported on the composition and densities of coexisting vapor and liquid phases as a function of Pressure and temperature for four hydrocarbon systems prepared from crude oil and natural gas. The data were observed over a range of pressures from 1000 to 8220 Ib. per sq. in. and at temperatures ranging from 35' to 250°F. The compositions of the hydrocarbon systems were such that the critical temperatures of the mixtures were lower than the range of the investigation. Under these conditions, it is shown that the composition of the systems has a marked effect upon both the absolute value of the equilibrium constants and the change of the constants with pressure for the several components comprising the system. From weight-balance considerations, it has been possible to construct the partial phase diagram of a mixture of a 49.9" A.P.I. crude oil and natural gas having a gas-oil ratio of 3660 cu. ft. per barrel. Descriptions of the apparatus used, the analytical procedure, the material used, and the equilibrium measurements are included. A knowledge of the physical behavior of naturally occurring hydrocarbon mixtures is fundamental to the treatment of many problems in the production, transportation and rehing of petroleum. The recent discoveries of pools having formation pressures up to 7500 lb. per sq. in. and higher, and the development of full-scale equipment to operate at pressures of 5000 lb. per sq. in. or more have greatly increased the need for knowledge of the composition, temperature, pressure and density relationships of coexisting vapor and liquid hydrocarbon phases. The following paper presents the results of investigations upon 22 mixtures of natural gas and crude oil of known com~o~itio~ that had been brought to equilibrium under controlled conditions of temperature and pressure. Data are presented upon the densities and compositions of the coexisting vapor and liquid phases for four different systems containing hydrocarbon material having boiling points from minus 2 5S°F. to well over I000 F. The data were observed Over a pressure range from Iooo Ib. per Sq. in to 8220 lb. Per sq. in. and a temperature range from 35' to 2 50°F. The accepted method of computing the physical relationship between two coexisting phases of a hydrocarbon mixture is by use of the "equilibrium constant" K as proposed by Souders, Selheimer, and Brown. definition,

Jan 1, 1944

By Carle R. Hayward

GENERAL conditions in the lead industry have registered a distinct improvement. The first signs of a strengthening market were found in an increasing demand for scrap. There is keen competition for old battery plates both by large and small dealers. The large operator smelts them either alone or in combination with ores or other lead-bearing material, giving an antimonial lead for which there is brisk demand. The small operator usually has three alternatives. He may simply melt out the metallics in a kettle at low temperature, giving an antimonial lead and a pulverulent lead oxide; he may fuse under oxidizing conditions, giving a soft lead and lead-antimony slag; or he may fuse under reducing conditions, giving a relatively low-grade antimonial lead and a low-antimony slag. In each case the metal product is used or sold, and the dross or slag sold to a large smelter. It will be interesting to see what the final outcome will be of this situation which is generally conceded to be unsatisfactory.

Jan 1, 1937

By Robert C. Meaders, Arthur R. MacPherson

Many attempts have been made to eliminate most of the crushing plant and all the grinding plant in the process of ore beneficiation by substituting a combined crushing and grinding unit which could take coarsely crushed ore and reduce it to a fine size in one unit. This unit normally would have no other grinding media than the ore itself. This is true autogenous grinding, as we understand it today, and should be clearly distinguished from pebble mill grinding, where pebbles are substituted for steel balls to grind a ball mill size feed. To compete in efficiency with normal methods of crushing and grinding, the autogenous mill must use less labor and steel to produce an equivalent product at equal or lower power consumption. In general terms, a unit to perform these functions must have means to crush the ore to fine sizes and to then further reduce the crushed pieces by grinding. In other words, to do efficient autogenous grinding, there must be a proper balance established between crushing and grinding rates. There is not much point in crushing at too fast a rate if the grinding means are not present to reduce the small particles to the required product size. The crushing means used in an autogenous mill are impact forces of two kinds, namely, (1) the rock travelling at high speeds striking the shell, and (2) the lifters travelling at high speeds striking the rock. Grinding is probably effected in a manner equivalent to pebble milling.

Jan 9, 1964

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

All the TECHNICAL PUBLICATIONS and CONTRIBUTIONS published in 1940 are available at Institute headquarters, unless otherwise noted. They are also on file in many public, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS. TECHNICAL PUBLICATIONS in Classes A-Metal Mining, B-Milling and Concen-tration, H-Industrial Minerals, and I-Mining Geology are distributed in MINING TECHNOLOGY, which is issued every other month. Technical Publications in Classes C-Iron and Steel Division, D-Nonferrous Metallurgy and E-Institute of Metals Division are distributed in METALS TECHNOLOGY, which is issued twice quarterly. TECHNICAL PUBLICATIONS in Class G-Petroleum Division are distributed in PETRO-LEUM TECHNOLOGY, which was issued quarterly in 1940 but will be issued every other month in 1941. TECHNICAL PUBLICATIONS in Classes F-Coal Division, J-Mineral Industry Education Division, K-Mining Administration, and L-Geophysical Methods of Exploration are issued as separate pamphlets. An Institute member is entitled to one copy of any TECHNICAL PUBLICATION or CONTRIBUTION. Copies of TECHNICAL PUBLICATIONS listed have been mailed to members of the Institute accord-ing to their registration by classes. CONTRIBUTIONS and other TECHNICAL PUBLICA-TIONS will be sent upon request. A member may purchase an additional copy of a TECHNICAL PUBLICATION or a CONTRIBUTION at one cent a page; minimum charge, 25¢. Nonmembers may purchase any CONTRIBUTION or a TECHNICAL PUBLICATION of the F, J, K, or L classes at the same rate, but the nonmember price per copy for METALS TECHNOLOGY, MINING TECHNOLOGY or PETROLEUM TECHNOLOGY is $1.25 domestic, $1.35 foreign countries. TECHNICAL PUBLICATIONS (separate pamphlet form), $2 per annum domestic, $2.50 foreign. METALS TECHNOLOGY, $7 per annum domestic, $7.80 foreign (Iron and Steel Division and Institute of Metals Division ferrous and nonferrous papers). MINING TECHNOLOGY, $6 per annum domestic, $6.60 foreign (metal mining, milling and concentration, Industrial Minerals Divi-sion, and mining geology papers.) PETROLEUM TECHNOLOGY, $6 per annum domestic, $6.60 foreign. Bound volumes have been mailed to members that have requested them, and MINING and METALLURGY is mailed each month. A member is entitled to one volume a year on his membership and he may purchase for $2.50 one copy of a volume not already received; additional copies of the same volume, $5. Nonmembers may pur-chase the volumes listed, at $5 each, plus 60 cents for Canadian or foreign postage. Extra single copies of MINING AND METALLURGY, 25¢ current issue, back numbers 50¢ each to members; to nonmembers 506 current issue and $1 each, back issues. Subscription price to nonmembers and to members for extra copies, $3 per annum domestic, $4.00 foreign.

Jan 1, 1940

By W. B. Gogarty

The reported decreases in water mobility do not seem unusual in view of non-Newtonian fluid properties. Shear stress vs shear rate diagrams have been reported for other solutions of water-soluble polymers. Some of these polymers are similar to the type mentioned by the author. Generally, the shear stress-shear rate is a non-linear function for these solutions. Data for plotting apparent viscosity vs shear rate can be obtained from this function. Apparent viscosity is defined as the ratio of shear stress to shear rate at a given shear rate. When plotted, the apparent viscosity decreases with increasing shear rate. This behavior is typical of a pseudoplastic fluid. For some water-soluble polymer solutions, the apparent viscosity decreases more than 50 times while the shear rate increases 1,000 times. Thus, viscosity of a pseudoplastic fluid only has meaning at a specified shear rate. Results of Fig. 1 could be explained in these terms. Viscosities measured in the Ostwald viscometer represent values at a given shear rate. Some average shear rate is affecting the polymer solutions while flowing through the core. This average value fixes the apparent viscosity as long as the flow rate remains constant. Viscosities measured by the two methods will be equal if shear rates are the same. The results indicate that shear rate in the core is lower (higher apparent viscosity) than in the viscometer. In the paper by Johnson, Bossler and Naumann, the relative permeability is independent of viscosity ratio. Thus, the relative permeability with respect to water flow at residual oil should be independent of the flowing phase viscosity. Polymer solutions will appear as Newtonian fluids The discussion emphasizes the nature of the "resistance factor effect" as discussed in the paper. Repeated anomalies arising in hundreds of experiments led us to the conclusion that non-Newtonian flow is not the only factor. Several of the key anomalies are as follows: 1. Measured viscosities over a range of shear rates from <1 sec-&apos; to 1,000 sec-&apos; do not account for but a minor fraction of the R observed in cores when compared in similar shear-rate ranges. 2. The slope of R vs flow rates in cores is always different from that expected from viscometer shear-rate measurements as shown in Fig. 2. in a core, the level of viscosity being fixed at a given flow rate. With these conditions, the definition of resistance factor R by Eq. 2 is simplified to Since , is constant with rate, R becomes a measure of the apparent viscosity in a core at a given flow rate. Variation in flow rate could easily account for the changes of R shown in Fig. 5. Also, this points to the fallacy of assuming R to be a unique parameter. The constant resistance factors at different flooding velocities appear to be in disagreement with the above discussion. The author furnishes Fig. 2 to support his arguments. As shown, the resistance factors remained substantially constant in the two cores over a considerable range of flooding velocities. However, in the 73-md core, the factor increases at lower rates. This behavior agrees with known characteristics of some pseudoplastic material. These materials act both as Newtonian and as non-Newtonian fluids in different regions of shear rate. Some exhibit first Newtonian, then non-Newtonian, finally, Newtonian character. Others are first non-Newtonian and then Newtonian. This latter type would explain the results with the 73-md core. The Fann-instrument results are not significant since shear rates in the core may be much different than with the viscometer. The higher resistance factor at high rates in the 150-md core is more difficult to explain. The greater resistance at increased flow rates could be attributed to what might be termed temporary bridging. As envisioned, changes in polymer configuration occur at the higher energy associated with the increased flow rate. These changes could cause less effective passage of polymer through the core. Correspondingly, increases in pressure drop will occur. These will be interpreted as higher resistance factors. 3. Most polymer solutions are non-Newtonian and many are more shear-rate sensitive than the polymers in question, yet only a very few polymers demonstrate useful R values. Gogarty&apos;s assumption that viscosities in cores and vis-cometers will be the same if measured at the same shear rate is only valid if non-Newtonian rheology is the only parameter. The experimental evidence does not validate this assumption. The anomalies observed in the equilibrium displacement experiment shown in Fig. 5 are not explained on the basis of varying flow rates since the rates were held constant. M

Jan 1, 1965

By A. A. Bauer, H. A. Saller, F. A. Rough, J. R. Doig

among uranium alloy systems are the U-Zr, U-Ti,and U-Mo binary systems, in that an intermediate phase, of limited solubility range, exists in each system. These intermediate phase alloys offer a promising field of investigation, both as binary alloys and as ternary alloy combinations. While a limited amount of work has been done on the binary alloys, none has been done on ternary combinations of these alloys. As a possible prelude to more intensive investigation of these systems, a study of the phase relationships between the 6 phases of the U-Zr and U-Ti systems was undertaken. The solid-state portions of the binary constitutional diagrams for the U-Ti,1 Zr-Ti,2 and U-Zr3 systems are shown in Fig. 1. The solid to liquid transformations are not shown, as these transformations were not studied in the ternary system. The phase designations employed are based upon those shown in the uranium constitutional diagrams. The crystal structures of the various phases are given in Table I. Experimental Materials and Methods The ternary section presented is based upon the results of thermal, metallographic, and X-ray analyses of a series of alloys ranging in composition between the phases of the U-Zr and U-Ti systems (U-74 atomic pct Zr to U-35 atomic pct Ti). After preparation of the alloys, thermal data were obtained. On the basis of these data, specimens were heat treated and examined metallographically. Specimens were then selected from those heat treated for X-ray determination of the phases present in what were considered critical phase regions. Alloy and Specimen Preparation—Alloys for this investigation were prepared from selected as-reduced uranium and crystal-bar zirconium and titanium. For nominal compositions, see Table 11. Charges were arc melted from five to seven times under a helium atmosphere, finally being cast into wire-bar form for fabrication. A zirconium getter button was used to clean the furnace atmosphere prior to melting. The alloys were homogenized 20 hr at 900 °C and furnace cooled. A portion of each bar was then removed for thermal analysis; the remainder was saved for fabrication. Alloys 8 through 14 were placed in steel tubes along with zirconium getter chips and, after flushing with argon, the tubes were welded shut and rolled at 1500 °F to a 50 pct reduction in diam. The remaining alloys were annealed 24 hr at ll00°F to insure transformation of the ? phase to the 8-U2Ti phase and were then hot rolled from a salt bath. Attempts to roll alloys 6 and 7 at 1100 °F were unsuccessful. Following this, attempts were made to roll pieces of alloys 1 through 5, which had cracked rather severely during casting, at 1200 °F, but these efforts were also unsuccessful. These alloys were, therefore, further treated in their cast and homogenized condition. All alloys were pickled to remove oxide formed during rolling. Thermal data were obtained on these alloys by conventional differential thermal analysis at a heating rate of 30C per min, and by a high-speed heating method at rates of approximately 10°C per sec. For the latter method of analysis, a 36-gage Chromel-Alumel thermocouple is spot welded between two slivers of alloy, the sandwich being en-

Jan 1, 1958

By W. H. Gunniss

When the copper smelters were built, in Montana, all of the refractory products which were used in their construction were shipped in from Eastern factories. It was apparent that if a material suitable for the manufacture of these products could be found within the State, a saving of freight could be effected and a new industry built up. Prospecting for such materials was started and experiments were made with samples from numerous deposits. Considerable effort and funds were expended in an attempt to manufacture silica brick from Dillon quartz, a light colored sandstone that is found near Dillon, Mont., on the Oregon Shortline railroad. As a brick material the Dillon quartz was a failure, but it has proved very satisfactory as a silica cement. It is now being used in laying silica brick and for reverberatory furnace bottoms. A bed of quartzite that is particularly suited to the manufacture of high-grade silica brick was finally discovered at Browns Spur, 6 miles west of Anaconda. The material from this deposit is now being used in the manufacture of the Anaconda silica brick, which have gained a wide reputation for heat-resisting and lasting qualities. The analysis of an average sample of this quartz is: SiO2, 96.7; Fe2O3, 0.3; Al208, 2.5; CaO, 0.3 per cent. The very low percentage of fluxing ingredients makes this a most refractory material. All of the Anaconda silica brick are hand molded. Various types of brick machines have been tried, but the hand-mold process proved the best suited to the manufacture of silica brick from this material. The silica is first put through a jaw crusher and is then dumped into wet pans, where 4 per cent. of lime paste is added, to produce a bond. Without the lime the material would not be plastic enough to mold. After a few minutes&apos; grinding in the wet pans the material is conveyed to the molder, who forces it into the molds by hand. The brick are then dumped on pallets and placed in the drier, where they are left. until dry enough to be set in the kilns. Some of the brick are re-pressed before being dried. They are burned about five days, in round down-draft kilns. It is not necessary to have as much heat in the kilns as the brick will be subjected to when in use in the furnaces. Montana refractories are used in smelters throughout the West. Prospecting for fire clays was also carried on. After experimenting with clays from several different deposits, it was found that a mixture of

Jan 1, 1914

By B. F. Koch

COPPER reverberatories develop large amounts of exit gases of a temperature in the neighborhood of 2000°F. The gases are not only of a noxious nature but must usually be disposed of at considerable heights above the yard level by a stack. Handling these gases at the temperature mentioned would require rather expensive construction of conveying flues and stack. Moreover, wasting such amounts of heat is certainly most uneconomical. Numerous investigations have indicated that waste heat boilers of the water-tube type are the most practical and economical means for utilizing that heat although the gases are heavily laden with rock dust and copper-bearing slag, which upon cooling form hard deposits on the surfaces of dampers or heat absorbing elements placed in the gas stream. Avoiding Slag and Dust Deposits Based largely on the experience of the paper industry in burning black liquor, a waste heat boiler design was developed a few years ago, providing not only extensive water-wall surfaces for cooling the gases below the fusing point of the slag but also settling out, as far as possible, the solidified particles of slag by creating low gas velocity. Matter carried in a stream of gases or air has a tendency to maintain its original direction upon a change in the direction of the flow of the conveying medium. Reverberatory waste heat boilers installed at Hurley and Morenci endeavored to utilize that tendency for the elimination of slagging particles at predetermined places and before they would strike the tube banks of the boilers. Both installations were successful in minimizing the slagging of boiler tubes and thereby minimizing the need for hand lancing. However, the low draft carried at the up-take of the reverberatory furnaces resulted in a positive pressure in the upper part of the furnace of the waste heat boilers, causing the emission of gases from lancing doors and making more difficult the already unwelcome work of cleaning the boilers by handlancing. Attempting to correct this nuisance as much as possible, the overall height of the Chuquicamata waste heat boilers has been reduced to the minimum considered necessary to obtain proper water circulation in furnace walls. Moreover, it is attempted to solidify slag and dust particles by providing large amounts of water-cooled surfaces before the gas stream reaches super-heater and convection banks of the boilers. The furnaces have been made as deep as an economical and practical arrangement of headers for water

Jan 1, 1952

By Leonard A. Wood, A. G. Winslow

Subsidence has occurred in several areas of the upper Gulf Coast region of Texas, although in most cases this is not evident without precise instrumental leveling. As referred to in this report, the region com- prises about 7200 sq miles of the Gulf Coastal Plain and includes all or parts of the following counties: Harris, Fort Bend, Waller, Brazoria, Galveston, Liberty, Chambers, Orange, and Jefferson (Fig. 1 ). Topographic relief is low, ranging from sea level at the Gulf of Mexico to 300 ft or more in northwestern Harris County.

Jan 10, 1959

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

846 . . . Metals Transactions, Vol. 185 T. J. WOODSIDE*—In the paper it was stated that many of the A. S. and R. plants probably used a process patented by Roscoe Teats in 1930. I might describe

Jan 1, 1950

Paralleling recent experiments in the U. S., the Mines Branch of the Department of Mines and Technical Surveys in Ottawa has developed a laboratory process for recovering cell-grade alumina from aluminiferous shale. Mines Branch Research Report R45 (1959) entitled The Alum-Amine Process For The Recovery of Alumina From Shale by G. Thomas and T. R. Ingraham states " . . . With the recent resurgence in Canada, and in the United States, of attempts to recover cell-grade alumina from clays and shales, the Mines Branch undertook to review certain processes that had been tried with marginal success . . . In particular, it seemed quite possible that some recent developments in organic chemistry, relating to uranium technology, might be utilized for the removal of the last traces of iron from intermediate products to permit the attainment of a satisfactory grade of alumina." This introductory paragraph explains the authors&apos; approach toward development of an alumina recovery process from shale. The following is an abstract of their successful laboratory experiments.

Jan 3, 1960

By W. Ivanick, Frank W. Glaser

ORDERING reactions of Fe-Si compositions in the a region have been mentioned in a number of review articles.7-8 However, little is known in regard to the critical temperature, T at which this transformation takes place. Greiner and Stoughton,&apos; in a study of the constitution of iron-rich Fe-Si alloys below 800°C, placed the onset of order at a composition of about 4 to 5 wt pct (7.5 to 9.5 atomic pct) Si. They observed that at this composition the ductility and strength begin to decrease sharply and brittleness develops. During X-ray studies they observed only the appearance of superlattice lines for compositions containing 12.5 atomic pct Si. More recent X-ray diffraction studies- etected the appearance of superstructure lines (corresponding to the calculated positions of [Ill] and [ZOO] reflections) for alloys containing 9.5 atomic pct. This fact confirms Greiner and Stoughton&apos;s original hypothesis in regard to the onset of order at compositions containing about 7.5 to 9.5 atomic pct Si. The physical properties.of Fe-Si alloys containing more than 10 atomic pct Si have been studied only to a limited extent. Their extreme brittleness and difficulties of sample preparation render them of little industrial use in comparison with alloys in the 0 to 10 atomic pct Si range. The properties of Fe-Si alloys reported to date are mostly properties measured at room temperature on ordered compositions It appears that because of experimental difficulties fully disordered alloys could not be produced in the critical composition ranges and their properties could therefore not be reported. In Figs. la, lb, and lc, a summary of physical properties of Fe-Si alloys, measured during recent investigations of the influence of silicon additions to iron, is presented. No mention of determination of the critical temperature, T for disorder could be found in the literature. The following is an account of work done in an attempt to: 1) produce the disordered state of various Fe-Si alloys and establish the critical temperature, T for disordering, and 2) compare the electrical and thermal conductivity characteristics of the ordered and disordered phases as functions of composition. Materials, Preparation of Test Samples, and Testing Methods Fe-Si alloys with high silicon contents (about 10 atomic pct) are usually prepared using powder metallurgy techniques. This method insures accurate compositions and high purity through the use of protective atmospheres during solid state diffusion alloying of the mixed powders."" Iron and silicon powders were mixed in the desired proportions, cold or hot pressed, and then homogenized at 1150°C for periods ranging from 6 to 12 hr under a protective getter and in a hydrogen atmosphere. Fully homogenized samples were quenched in water from various and successively higher temperatures to establish the critical temperature for disorder. Temperatures were determined using Pt—Pt-Rh thermocouples in contact with the test samples. Test bars were approximately 0.6x1.25x7.5 cm. Electrical measurements were made at room temperature by determining the potential drop over a 1.5 cm span for a current of 10 amp. Densities of the samples were determined by immersion. High temperature electrical resistivities were measured using previously described techniques.&apos;" Specific heat conductivity up to 200°C was measured by heating one end of the test bar and water-cooling the other; heat conductivity was then obtained by subtracting the rate at which heat entered the water from the

Jan 1, 1957

By S. M. Brisbane

THE life of refractory linings in rotary cement kilns can be shortened by uneven or inadequate support of the kiln and its shell and by variations in the conditions of operation. Alteration of these factors may, according to their nature, bring about mechanical deterioration of the lining or promote chemical attack. Chemical attack has been described elsewhere.1-4 The distortion of cement kilns has been discussed in a general manner by Rochow,6 ho indicates the amount of distortion which may occur in an unlined shell, and by Rosenblad: who states that the deformations of the shell are greatest above the trunnions. The present article indicates the extent of the distortion of a kiln to an oval shape in certain selected positions and the deviation from a straight line of the kiln along its length between two supports. The cement kiln is a long, hollow, rotating cylinder consisting of steel plates which may be either welded or riveted together. This shell is supported on tires, frequently 60 ft apart, which roll on trunnions. The large mass of the kiln causes distortion of its cross-section; it becomes slightly oval, i.e., diameters lengthen as they become horizontal and shorten as they become vertical. There is also a tendency for the shell to bow between supporting tires; this bowing may be upwards or downwards depending on the position of the weight forces and the supports. The extent of the deviations from the ideal kiln shape was investigated. Observations described in this paper were made on the shell of the clinkering zone between the first and second tires of two of the kilns at the Geelong works of Australian Portland Cement Pty. Ltd. The kilns were both 400 ft long and 10 ft diam with a welded enlarged burning zone 11 ft 6 in. diam. The shell was fabricated from mild steel and in this section its thickness was 1 in. It was lined with 41/2 in. of chemically bonded magnesite-chrome bricks which were jointed with mild steel plates. The kilns operate on a 4 pct slope and the speed may be varied between 0.75 and 1.68 rpm. The wet process is used; kilns are coal fired and are fitted with integral coolers. Temperatures within the kiln are difficult to determine with any accuracy because of the absence of black body conditions, but surface temperatures are probably in the range 1420° to 1470°C. Average shell .temperatures at the two positions at which the deformation studies were made were 370°C and 355"C respectively. Methods: In determining the ellipticity it was necessary to measure the lengths of the vertical and horizontal diameters while the kiln was in operation; data obtained from a stationary kiln would not have the same practical significance. For this purpose the four points V, W, X, and Y at the ends of two mutually perpendicular diameters were marked on one kiln. The point X is shown in Fig. 1. For the measurement of the length of the vertical diameter a vertical column, to which a horizontally aligned telescope was attached, was placed 10 ft from the kiln. The telescope could be racked up and down in a vertical plane. Two sets of readings were taken, one set when each of the points V, W, X, and Y was at its maximum height above the

Jan 1, 1957

By Keith Leonard Sutherland

THIS paper is a study of the differential flotation of the sulphide minerals in the presence of salts of silver, lead and zinc. In practice, accidental activation due to these salts is more important than their use as reagents to replace copper sulphate. The general method of investigation has been based upon contact tests, the temperature of 35°C. being chosen in conformity with earlier work. Potassium ethyl xanthate and potassium amyl xanthate were selected as collectors and pure sulphide minerals were used. The experimental procedure has been outlined in earlier papers and all solutions were kept carbonate-free.&apos;&apos; Contact, or spreading of an air bubble, at a mineral surface indicates the presence of an adsorbed collector film. PURITY OF REAGENTS The xanthates were purified in the usual manner.1 Neither the cyanide nor the sodium hydroxide solutions contained sufficient carbonate to give a precipitate with barium chloride solution. The silver sulphate was prepared from pure silver nitrate by evaporation with concentrated sulphuric acid until there was no evidence of brown fumes. This solution was diluted and the difficultly soluble sulphate washed with water so that unchanged nitrate was dissolved. The resultant crystal-line powder was pure white. The lead and zinc salts were prepared by dissolving especially pure lead and zinc in C.P. nitric and sulphuric acid solution and the crystals drained. The standard solutions were checked by titration. It was felt desirable to use the sulphate radical wherever possible, but since lead sulphate was insufficiently soluble for the purpose of the experiments, it was necessary to use some other lead salt. A.R. copper sulphate was used without further purification. RESULTS The results are presented in the accompanying figures; the areas of noncontact (nonflotation) are shaded in Figs. 8, 9, 10 and 11; in the remainder they lie to the right of the curve. Zinc Sulphate The curves in Fig. I are to be compared with those for Fig. 2, for which zinc sulphate is absent. This comparison shows that the influence of the zinc ion is usually small. Its influence is more marked, however, for chalcopyrite in the absence of cyanide. The influence of zinc sulphate is also marked for copper-activated sphalerite, for which tests were made only in the absence of cyanide. The results are of importance in the separation of pyrite from copper-activated sphalerite when zinc sulphate is added in the lead flotation section (p. 204 of ref. I). Sphalerite does not adsorb the collector (i.e., become floatable) under the conditions chosen.

Jan 1, 1942

By S. A. Falconer

This paper deals with the practical application of the Dutch State Mines cyclone separator for fine-coal cleaning. The more important operating variables are discussed, and results of a number of continuous-scale tests on various fine coals with a 6-in. cyclone separator are given. Descriptions of the Cyanamid Pilot Plant and the 50 tph Cyclone Separator Plant at the Emma Washery in Holland are included. TODAY, as never before, the coal producers of this country are faced with the necessity for obtaining maximum yield of marketable coal of all sizes down to and including the finest. Particular interest is being displayed in a more effective means of recovering the finer sizes which in the past so often have been discarded to waste or treated by inadequate equipment. The reasons for this interest are easily understood. Rising mining costs have resulted in the increased use of mechanized equipment underground for full seam mining. This, in turn, means more refuse in the run-of-mine and also more fines in the feed going to the cleaning plant. Stringent antistream pollution laws now make it necessary at least to impound the fines, and usually it is a paying proposition to recover the coal from these fines before sending them to the storage area. Finally, the market and price of the finer sizes has increased, but at the same time specifications have tightened and the demand is for higher grade products. During the past four years a great deal of publicity has been given to this new process and apparatus for treating fine sizes of ores as well as coal. Excellent discussions of the apparatus itself and the theoretical aspects of the basic operating principles involved in its operation have been presented by M. G. Driessen,1-3 M. R. Geer and H. F. Yancey,4,5 J. W. Hyer6 and more recently by D. A. Dahlstrom8 as well as others.7,9-11 In view of this, it has been decided to include in the present paper only a brief description of the cyclone separator and its operating principles. This paper deals primarily with some of the more practical commercial aspects of the process and equipment required for its operation; the variables in the operation of the cyclone, their effect and means for control; and the results obtained with a 6-in. semicommercial size separator on a variety of fine coals, bituminous and anthracite, using finely ground magnetite for the separating medium solids. A description is included of the commercial-size cyclone separator pilot plant installed by the Dutch State Mines at its Emma mine in Holland, where finely ground slate is utilized as medium solids. Field of Application: The Dutch State Mines cyclone separator operates most efficiently on ores and coal in the size range of % in. to about 48 mesh. On some types of feed, effective separation can be made on sizes as small as 100 mesh, but up to the present, this may be considered exceptional. Depending upon the type of medium used, the specific gravities of separation can be varied within wide limits, up to as high as 2.70, if magnetite is used as medium. Early Development: The development of the Dutch State Mines cyclone as a separator, or cleaner, was the outgrowth of early experimental work by Dries-sen&apos; and others in Holland, just prior to World War 11, in the course of which was discovered the effectiveness of the cyclone in reclaiming and thickening the dense medium used in the "Loess" process of

Jan 1, 1951

By S. A. Falconer

This paper deals with the practical application of the Dutch State Mines cyclone separator for fine-coal cleaning. The more important operating variables are discussed, and results of a number of continuous-scale tests on various fine coals with a 6-in. cyclone separator are given. Descriptions of the Cyanamid Pilot Plant and the 50 tph Cyclone Separator Plant at the Emma Washery in Holland are included. TODAY, as never before, the coal producers of this country are faced with the necessity for obtaining maximum yield of marketable coal of all sizes down to and including the finest. Particular interest is being displayed in a more effective means of recovering the finer sizes which in the past so often have been discarded to waste or treated by inadequate equipment. The reasons for this interest are easily understood. Rising mining costs have resulted in the increased use of mechanized equipment underground for full seam mining. This, in turn, means more refuse in the run-of-mine and also more fines in the feed going to the cleaning plant. Stringent antistream pollution laws now make it necessary at least to impound the fines, and usually it is a paying proposition to recover the coal from these fines before sending them to the storage area. Finally, the market and price of the finer sizes has increased, but at the same time specifications have tightened and the demand is for higher grade products. During the past four years a great deal of publicity has been given to this new process and apparatus for treating fine sizes of ores as well as coal. Excellent discussions of the apparatus itself and the theoretical aspects of the basic operating principles involved in its operation have been presented by M. G. Driessen,1-3 M. R. Geer and H. F. Yancey,4,5 J. W. Hyer6 and more recently by D. A. Dahlstrom8 as well as others.7,9-11 In view of this, it has been decided to include in the present paper only a brief description of the cyclone separator and its operating principles. This paper deals primarily with some of the more practical commercial aspects of the process and equipment required for its operation; the variables in the operation of the cyclone, their effect and means for control; and the results obtained with a 6-in. semicommercial size separator on a variety of fine coals, bituminous and anthracite, using finely ground magnetite for the separating medium solids. A description is included of the commercial-size cyclone separator pilot plant installed by the Dutch State Mines at its Emma mine in Holland, where finely ground slate is utilized as medium solids. Field of Application: The Dutch State Mines cyclone separator operates most efficiently on ores and coal in the size range of % in. to about 48 mesh. On some types of feed, effective separation can be made on sizes as small as 100 mesh, but up to the present, this may be considered exceptional. Depending upon the type of medium used, the specific gravities of separation can be varied within wide limits, up to as high as 2.70, if magnetite is used as medium. Early Development: The development of the Dutch State Mines cyclone as a separator, or cleaner, was the outgrowth of early experimental work by Dries-sen&apos; and others in Holland, just prior to World War 11, in the course of which was discovered the effectiveness of the cyclone in reclaiming and thickening the dense medium used in the "Loess" process of

Jan 1, 1951

By L. R. Blair

Many hydrated silicates have been synthesized and sold for commercial use. However, this paper discusses only hydrated calcium silicates and, to a lesser extent, hydrated magnesium silicates. Synthetic calcium silicates were first formed by man when he found that mixtures of silica or silicates and lime in water set up to form cements. The material which was responsible for the cementing properties was calcium silicate hydrate, although this fact was not recognized until early in this century. In the early 19001s, synthetic calcium silicates, reinforced with fibers and formed simply by reacting calcium hydroxide and silica in water with fiber at atmospheric or under low pressure autoclave conditions, found increased use in thermal insulations and in building products. These insulations were found to have a low thermal conductivity and would withstand temperatures up to 650°C. This, combined with their very low densities (from 8 to 50 Ib per cu ft) and fairly high strength, also made them suitable for use as building products. Following the disastrous Morro Castle fire of the 1930Js, calcium silicate board products were used as partitioning material in all shipboard construction in the U.S. As autoclaving techniques were improved and developed, it was: learned that under hydrothermal conditions new and useful calcium silicates which could be used under more extreme temperatures (up to 980&apos; C) could be prepared. These had high surface areas and other unique properties which suited them for use as fillers, pesticide carriers, low temperature insulating materials, and adsorbents for the removal of fatty acids from various solutions. Hydrated magnesium silicates have not been studied as extensively as the calcium compounds. Their first important use was in the filtration of dry cleaning solutions for the removal of fatty acids. With the introduction of detergents, it was found that these products lost their advantage because of their high affinity for the detergent chemicals. However, in recent years these chemicals are finding increasing use as decolorizing agents for fats and anti-caking agents for resins. Some materials with very high surface are finding new use as adsorbents. CALCIUM SILICATE HYDRATE COMPOUNDS AND THElR CONDITIONS OF FORMATION Within the past ten years much has been done in the field of calcium silicate hydrate chemistry. As a result of this work it has been found that at least 25 different forms of calcium silicate hydrate can either be formed synthetically or found as naturally occurring materials. The stability and composition relationships among these 25 compounds present a very complicated picture, and many of these very closely resemble other forms and are difficult to dis-

Jan 1, 1962

By Keith Leonard Sutherland

This paper is a study of the differential flotation of the sulphide minerals in the presence of salts of silver, lead and zinc. In practice, accidental activation due to these salts is more important than their use as reagents to replace copper sulphate. The general method of investigation has been based upon contact tests, the temperature of 35°C being chosen in conformity with earlier work. Potassium ethyl xanthate and potassium amyl xanthate were selected as collectors and pure sulphide minerals were used. The experimental procedure has been outlined in earlier papers and all solutions were kept carbonate-free.14 Contact, or spreading of an air bubble, at a mineral surface indicates the presence of an adsorbed collector film. Purity of Reagents The xanthates were purified in the usual manner.&apos; Neither the cyanide nor the sodium hydroxide solutions contained sufficient carbonate to give a precipitate with barium chloride solution. The silver sulphate was prepared from pure silver nitrate by evaporation with concentrated sulphuric acid until there was no evidence of brown fumes, This solution was diluted and the difficultly soluble sulphate washed with water so that unchanged nitrate was dissolved. The resultant crystalline powder was pure white. The lead and zinc salts were prepared by dissolving especially pure lead and zinc in C.P. nitric and sulphuric acid solution and the crystals drained. The standard solutions were checked by titration. It was felt desirable to use the sulphate radical wherever possible, but since lead sulphate was insufficiently soluble for the purpose of the experiments, it was necessary to use some other lead salt. A.R. copper sulphate was used without further purification. Results The results are presented in the accompanying figures; the areas of noncontact (nonflotation) are shaded in Figs. 8, 9, 10 and 11; in the remainder they lie to the right of the curve. Zinc Sulphate The curves in Fig. I are to be compared with those for Fig. 2, for which zinc sulphate is absent. This comparison shows that the influence of the zinc ion is usually small. Its influence is more marked, however, for chalcopyrite in the absence of cyanide. The influence of zinc sulphate is also marked for copper-activated sphalerite, for which tests were made only in the "absence of cyanide. The results are of importance in the separation of pyrite from copper-activated sphalerite when zinc sulphate is added in the lead flotation section (p. 204 of ref. I). Sphalerite does not adsorb the collector (i.e., become floatable) under the conditions chosen.

Jan 1, 1943