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By Frederick V. Lawrence

Broadly speaking, fluxes are substances which promote wetting and spreading or enhance the fluidity and manipulative properties of materials in joining, fusion, and smelting operations. The term most strictly applies to substances used to facilitate soldering and brazing; but in the discussion which follows, the definition will be broadened to include materials used to promote fusion in arc welding and which aid in the smelting of metals. In each of the mentioned applications, the role of flux and its composition differs considerably; consequently in the discussion which follows, fluxes for soldering, brazing, arc welding, and smelting applications will be considered separately. Soldering and Brazing Fluxes Soldering and brazing are metallurgical joining processes in which a joint is formed using a filler metal of composition dissimilar to that of the joined pieces (base metal). The filler metal, solder or braze, is always of lower melting point than the base metal. Consequently with these processes there is no melting of the base metal. The successful creation of the joint depends upon the wetting and spreading of the solder or braze around or throughout the joint. The obstacles to successful soldering and brazing are contaminants and tenacious oxide films on the metal surfaces. In soldering and brazing applications, fluxes act to remove and exclude oxides and other impurities from the joint. There is no fundamental difference between soldering and brazing. The distinction between them is made on the basis of temperature. Join¬ing operations carried out at temperatures above 500° C are termed brazing. The higher temperatures used in brazing enable higher melting point filler metals to be used which generally provide stronger joints. The higher temperatures of brazing processes also require fluxes which are substantially different from those used in soldering and which will remain effective at high temperatures. Consequently the distinction between soldering and brazing can also be made on the basis of the fluxes used. Soldering Fluxes Even thoroughly cleaned and degreased, metal surfaces still possess tenacious oxide films which inhibit the soldering of the joint. The reactions which form these films increase with increasing temperature. The rate of oxide formation and the tenacity of the film varies with each base metal. Aluminum, magnesium, stainless and high alloy steels, aluminum and silicon bronzes when exposed to air form hard, adherent oxide films. These metals require highly active and corrosive fluxes to remove and prevent the reformation of oxide films during soldering. Metals such as copper and silver, on the contrary, form less tenacious films at a lower rate, so that mild fluxes are sufficient. Soldering fluxes must dissolve or remove oxides and promote rapid wetting and spreading of the solder. The flux removes the oxide film by loosening and floating it off into the main body of the flux. The oxide removal is often aided by the alloying of the solder with the base metal, undermining small areas of the oxide and detaching them (Anon., 1959). The flux coagulates and suspends the oxide particles which have been loosened. The flux forms a protective cover preventing the reformation of the oxides, permitting the spreading of the solder and the formation of a metallic bond between the solder and the base metal. Constituents of Soldering Fluxes: Soldering fluxes are commonly grouped into three categories: highly corrosive, intermediate, and noncorrosive. One normally would choose to use the least corrosive flux which will give satisfactory performance.

Jan 1, 1983

By Charles R. Cavanaugh, John F. Elliott

The activity of nickel in liquid Pb-iVi alloys which are rich in lead was measured in the temperature region of 700° to 1100°C by means of the galvanic cell: The electrolyte used was stabilized zirconia. Tlze data were correlated using the a function, and a plot of the temperature coefficient aE/aT All subsequent calculations of the thermodynamic properties are based on these two functions. The activity, activity coefficient, and molar properties of mixing of nickel are reported. Nicke1 shows extreme positive deviations frorn ideality while lead shows a very slight positive deviation in the composition range studied The study of the activity of nickel in liquid Pb-Ni alloys reported herein was undertaken to explore the use of stabilized zirconia, an oxygen-ion electrolyte, with liquid-metal electrodes, and to obtain further information on the thermodynamic properties of the liquid binary Pb-Ni system. The cell The reversible electromotive force of the cell results from the difference in the chemical potential of the oxygen at the two electrodes: po, (left) - p~ (right) = -4E5 [I] The chemical potential of oxygen on the right is fixed by the activity of nickel in the solution and pure solid nickel oxide. That on the left is set by pure solid nickel in equilibrium with pure solid NiO. By definition: Since the chemical potential of nickel is related to the chemical potential of oxygen through the equilibrium constant for the formation of NiO from nickel and oxygen gas, the electromotive force of the cell is also expressed In this case, n is 2, E is the reversible potential of the cell, and 5 is Faraday's constant. The work of Kuikkola and wagnerl and Schmalz-reid2 has shown that the stabilized zirconia electrolyte is essentially an ionic conductor at the oxygen levels encountered in the experimental arrangement of the work, i .e., PG > 10-l7 atm. THE EXPERIMENTS The advantage of this type of reversible cell over those using a liquid electrolyte is the simplicity arising because the electrolyte also functions as one of the containing crucibles. A further simplification was the choice of the Ni (sat.)-NiO electrode as the standard. This permitted a ready check on the behavior of the electrolyte, as the potential of the cell must become zero when the right electrode becomes saturated with nickel, either because of a change of temperature or because of the addition of nickel to the electrode. It also permitted the potentials being measured to lie in the most satisfactory experimental range of 0 to 100 mv. Although it was not theoretically necessary, lead was included in the standard electrode as it assured good contact between the electrode and electrolyte. Cell Design. The general arrangement of the experimental cell assembly is shown in Fig. l(a) and the details of the cell itself are contained in Fig. l(b). The anode lead wire on the interior of the cell was connected to a coil of perforated sheet nickel. Within this coil were nickel oxide pellets which were held beneath the surface of the liquid Pb-Ni alloy. A disc of nickel oxide was held at the bottom of the external crucible (alumina) by means of the thermocouple protection tube. The nickel oxide disc and pellets were compressed dry at 10,000 psi and sintered at approximately 1000°C for an hour in air. A major experimental difficulty of reversible electromotive force cells with liquid electrodes is the selection of suitable materials for connecting

Jan 1, 1964

By M. R. Yalamanchili, C. A. Young, J. J. Kellar, W. M. Cross, J. D. Miller

Introduction Researchers have long speculated regarding the adsorption state of collectors on mineral surfaces. Only recently have analytical techniques become available that allow direct in situ analysis of adsorbed layers. With reactive internal reflection elements (IREs), Fourier transform infrared spectroscopy coupled with internal reflection spectroscopy (FT-IR/IRS) allows for unobtrusive investigation of the adsorbed layer (Harrick, 1979). This technique has been used both for the in situ identification of adsorbed species and for the direct calculation of collector adsorption density in real time from infrared spectral data (Miller and Kellar. 1988). The reactive mineral IRE serves both to internally reflect the infrared light and to act as a substrate at which collector adsorption can be monitored. Shown in Fig. I is a schematic of light being internally reflected in an IRE. As the light is totally reflected at the interface, an evanescent wave propagates a short distance (typically a few microns) away from the IRE, and sampling of the interfacial region occurs. Because of multiple internal reflections, great sensitivity can be obtained. Flotation systems for which this method has been demonstrated include CaF2/oleate, Al2O3/dodecylsulfate, CaCO3/oleate, ZnS/xanthate and KCI/octylamine (Miller and Kellar, 1988; Kellar et al., 1989, 1990; Miller et al., 1990). Of particular interest to flotation chemists is the conformational behavior of the alkyl chain of adsorbed collector molecules. In the simplest sense, conformation can bethought of as the relative flexibility of the hydrocarbon chain caused by rotations about carbon-carbon single bonds. The flexibility is described by the amount of gauche/trans conformations in the alkyl chain. Figure 2 shows examples of gauche and trans conformations (rotational isomers or rotamers) in a hydrocarbon chain. These two conformations are observed when the terminal methylene groups in any four-carbon subchain are on the same side (gauche) or opposites sides (trans) of the plane of the middle carbon-carbon bond. A gauche conformer (rotamer) is thus a state of maximum potential energy, whereas a trans conformer is a state with minimum potential energy. The difference between these states has been found to be approximately 0.5 to 0.8 kcal/mole (Mead et al., 1986). The relative number of butane molecules present as gauche conformers with respect to trans conformers can be calculated from the Boltzmann equation (Mead et al., 1986). At 25° C approximately 66% of the butane molecules are trans rotamers. [ ] However at 100° C, only 33% of butane molecules are trans rotamers. Exposing the hydrocarbon chain to a polar, rather than an a polar, medium should also cause an increase in the number of gauche butylene groups in a hydrocarbon chain, although this effect has been difficult to observe experimentally (Mead et al., 1986). Forming a crystalline hydrocarbon is equivalent to decreasing the temperature, which greatly increases the amount of trans butylene groups present in the chain. From the preceding discussion, a picture of the solution species of concern can be developed. The collector monomer should exhibit the greatest number of gauche rotamers and most likely will look crumpled or balled-up to reduce the surface area in contact with water. The micellar form is expected to be aggregated, with the hydrocarbon chain existing in a less polar environment. These characteristic conformational features have been examined by FT-IR spectroscopy for various liquid phases of alkanoic acids (Umemura et al., 1981; Cameron et al., 1982a; Yang et al., 1986; Wong, 1987; Wong and Mantsch, 1983; Cross et al., 1992), phospholipid membranes (Fringe Ii, 1980; Casal and Mantsch, 1985: Wong et al.. 1988;

Jan 1, 1994

By D. Mills, G. B. Craig

The defortnaliotz of zirconicltt single crystals conlaining osygen in the range 740 to 6800 atom parts per nilllion was esanined oc7er the range 77" to 950°K. An anctlsis of the dqfarmaliotz parameters leads to the cotcllsiotr that the rale -cotzfrolling thermally activated dqivr,irrtion process oe-r /he range 77" to 560°K is oc.crco,ling osvgen alotns. A thermally actitaled defor,ilntion process is not found between 600" and 800", but does occur aboz%e 800°K. THE present investigation was undertaken to measure the effects of controlled amounts of oxygen on the deformation parameters of a zirconium single crystals over the temperature range 77" to 950°K and to determine the rate-controlling mechanisms. Although there is no doubt that the mechanical properties of the group IV metals, titanium, zirconium, and hafnium, are strongly influenced by the interstitial impurities oxygen, nitrogen, carbon, and hydrogen, there are many conflicting theories as to the role played by the interstitials during the deformation proess.'- There is general agreement that the mechanisms which control plastic flow in a metal impose characteristic values on such parameters as the flow stress and its temperature dependence, the activation volume, and the activation energies. These parameters will be used to analyze the deformation mechanisms. eltham,' Sargent,16 and ibbs' have shown that the stress relaxation technique allows the activation volume characteristic of the deformation process to be found during the course of a simple tension test. In many cases it is found that the relaxation of stress is logarithmic with time and obeys a relationship of the following form: T-T = AT =S logl0(qt + C) [I] where t, is the shear stress at the start of the relaxation test, t is the shear stress at time t, and S. q, and C are experimental constants, and S is the strain rate sensitivity of the stress t as shown in the appendix. The slope found from a semilogarithmic plot of At vs time is approximately equal to S. The activation volume u, association with the deformation process, is found from the following relationship: The theoretical treatment of thermally activated plastic flow due to schoeck18 shows that the activation volume when combined with the temperature dependence of the flow stress gives the activation energy for the process according to equations: seegerZ3 considers that the flow stress at lower temperatures ld is composed of two parts such that Tapplied = tinternal + Teffective , where Teffective 3 ff , is the stress necessary to overcome the local obstacles to deformation and Tinternal, ri, is the stress necessary to overcome the long-range elastic stress field of dislocations on other planes. ri is considered to be largely elastic in origin and can be estimated from the stress value at the temperature independent portion of the flow stress-temperature curve. EXPERIMENTAL The crystal bar zirconium used in this investigation was supplied by Wah Chang Corp. whose certified analysis gave the following impurity contents in parts per million by weight: oxygen, 150; nitrogen, 10; iron, 180. All others were less than 100 ppm. The oxygen and iron contents were confirmed by neutron activation and chemical analyses, respectively. Single crystals were grown in an electron beam furnace according to the method of Wilson and Pickle-simer'' and ills.'' The orientation of the crystals was such that the specimen axes were located in the lower third of the standard section of the basal plane stereographic projection for zirconium. This orienta-

Jan 1, 1969

By M. J. Spendlove, H. W. St. Clair

An automatic surface-follower mechanism was used to measure the surface temperature and the rate of evaporation of molten zinc while undergoing distillation at low pressure. At pressures of 50 to 100 microns Hg, the rate of evaporation may be 60 to 80 pct of the theoretical maximum corresponding to the measured temperature. The rate decreases rapidly at pressures above 100 microns Hg, to only 7 pct of the theoretical maximum at 2000 microns Hg. Measured temperature gradients at the surface are in agreement with theoretical gradients calculated from the heat of vaporization, rate of evaporation, and thermal conductivity of molten zinc. THIS paper covers a series of careful measurements of the rate of evaporation of molten zinc at low pressures, undertaken as a part of a general investigation on the separation of metals by distillation.' Preliminary results on the rate of evaporation of zinc were described in a previous publication.' The results of the preliminary study are as follows: 1—The observed rates of evaporation of zinc were as high as 0.60 g per sq cm per min, corresponding to 75 pct of the maximum rate as determined by the temperature of the metal. 2—The evaporation rate was decreased from 0.30 g per sq cm per min at a pressure of 25 microns to only 0.09 g per sq cm per min when the pressure was increased to 5 mm. 3—The temperature of the surface during rapid evaporation may be 35" to 100°C less than the main mass of metal. Observed temperature gradients at the surface are consistent with those calculated from the heat of vaporization and the thermal conductivity of liquid zinc. In the preliminary experiments, the rate of evaporation was determined from the loss in weight of the metal in the crucible during the test. This was compared with the weight of the condensate. Obviously, this method was subject to error because of some uncertainty as to the period of evaporation that should correspond to the loss in weight. Furthermore, this method did not permit taking into account probable variations in the rate of evaporation during the test. A more serious shortcoming was that the temperature at the evaporating surface was not known, so the maximum theoretical rate of evaporation could not be calculated accurately. To improve the precision of rate measurements and to allow accurate measurements of the surface temperature, a refined experimental technique was developed whereby the temperature and position of the surface could be measured accurately. This was done by an automatic surface-follower mechanism that gave a continuous record of the surface temperature and the amount of zinc evaporated. These data permitted an instantaneous determination of the actual rate of evaporation and the surface temperature throughout the test. Pure zinc (99.99 pct Zn) was used in all experiments. Description of Distillation Furnace The details of construction of the distillation furnace are shown in Fig. l. The furnace is enclosed in a large quartz tube open at one end. The open end of the quartz tube is sealed by means of a water-cooled head. The entire enclosure is vacuum tight. The connection between the water-cooled head and the quartz tube is sealed by means of a rubber gasket which fits tightly against the smooth end of the tube. The metal is heated by induced current set up in the molten zinc and the walls of the graphite crucible by means of a water-cooled induction coil outside the quartz tube. High frequency current is passed through the induction coil from a 6 kw mer-

Jan 1, 1952

By E. L. Dougherty, J. W. Sheldon

Using the numerical techniques shown in this paper it is possible to compute the simultaneous dynamical behavior of multiple fluid-fluid interfaces in two dimensions. Hence, fluid-fluid inter face models of several oil recovery processes can be constructed which allow prediction of the effect of fluid flow in two dimensions on the behavior of these processes while taking into account various physical effects, such as saturation gradients, phase changes and thermal stimulation. Techniques for constructing fluid-fluid interface approximations for several oil recovery processes are reuiewed. The validity of these techniques is established by comparison to experimental results. The availability of a computer program for computing the behavior of multiple fluid-fluid interface problems makes the use of potentiometric models uneconomic. The results indicate the areal sweep efficiencies obtained from potentiometric model studies at high mobility ratios may be somewhat optimistic. The results also indicate that the areal sweep efficiency curves obtained at high viscosity ratios 2—4 using miscible fluids in porous media are misleading and that considerable care must be taken in defining the mobility ratio for a displacement process, especially for miscible fluids. INTRODUCTION Many of the methods used to estimate areal sweep efficiency assume that the oil recovery process can be represented by one or more fluid-fluid interfaces. When the mobilities of the displaced and displacing phases are assumed equal, this quantity can be computed using analytical mathematical methods.l.2 For non-unit mobility ratio, experimental methods based upon the fluid-fluid interface concept include potentiometric and electrolytic blotter models. Scaled models of porous media have also been used to study this problem. Fay and Prats3 and Aronofsky4 used numerical techniques to compute breakthrough sweep efficiency, but neither of these studies were extended beyond breakthrough. Numerical techniques which have been developed for solving a general fluid-fluid interface problem are presented in a companion paper.5 These techniques have been incorporated into a program for a large-scale digital computer which can treat simultaneously the dynamical behavior of as many as six fluid-fluid interfaces. Thus it is possible to simulate the behavior of several oil recovery processes taking into account such effects as saturation gradients. Techniques for representing several oil recovery processes by fluid-fluid interfaces are presented. Processes considered are conventional water flooding with and without a mobile gas phase, hot water flooding, miscible flooding and enriched gas drive. Other processes, whose effects could be studied by this technique, but are not considered in detail here, are underground combustion and steam injection processes and various slug processes such as gas-water injection and alcohol-solvent processes. Theoretical results obtained with single interfaces for mobility ratios of 0.25, 1, 2, 4, 8, 16, 32 and 64 in a repeated five-spot are compared to experimental results for this geometrical configuration obtained using miscible fluids and conductive analogs. Predicted recovery curves for water flooding in a repeated five-spot are compared to experimental results reported in the literature. Example calculations are shown for a conventional water flood in the presence of a free gas phase and for a hot-water flood. MATHEMATICAL PRELIMINARIES We assume that the rock matrix is homogeneous with constant thickness, absolute permeability and porosity. The fluids are incompressible. We also neglect the effects of gravity.

Jan 1, 1965

By Eamonn F. Maher

Superconductivity is one of the most remarkable scientific phenomena ever investigated. It is the phenomenon whereby some materials exhibit zero resistance to the passage of an electric current when cooled to low temperatures, and requires a quantum mechanical explanation. Four Nobel prizes in physics have been awarded specifically on the subject of superconductivity, with many more enabled by superconducting technology. For example, particle beams are generated in accelerators and manipulated in ?particle beam lines? in the ?Big Physics? projects around the world eg. at CERN, Geneva, leading to major discoveries in fundamental particle physics. Similarly, at the JET Propulsion laboratory near Oxford, U.K, controlled nuclear fusion has been demonstrated, and magnetic containment of plasmas is key. In the chemical and biological sciences high field NMR spectroscopy has become indispensable for examining organic matter, revealing the mysteries of the workings of cells, genetics, and in the development of new polymers and pharmaceuticals. With all these very advanced uses for superconducting magnets, it is easy to forget that superconductivity is big business, not just a scientific curiosity. MRI (Magnetic Resonance Imaging) superconducting magnets, the key component of high resolution body scanners, use approximately half of the world?s superconducting wire ? the other half being mostly used in accelerator magnets. The MRI market is about 3 billion dollars per annum, and one MRI magnet uses 200km of wire. New applications for superconducting magnets are now appearing including ?Catheter steering?, enabling much shorter timescales for life-saving brain tumour removals and ?Functional MRI?, a whole new area in patient diagnostics. Whilst the use of low temperature superconductors (LTS) is now well established commercially in superconducting magnets and niche electronic applications, the application of LTS in electric power distribution and transport has been very limited to date. It is now more than fifteen years since the so-called High Temperature Superconductor (HTS) materials were discovered: these can be operated at liquid nitrogen temperatures rather than liquid helium temperatures. However, materials processing and scale-up issues have prevented their widespread use, and in particular the required price/performance criteria are only beginning to be reached except in certain niche markets. BSCCO (Bismuth Strontium Calcium Copper Oxide) tapes up to one km long are now readily available, and have been demonstrated in high current cables for power distribution networks, but the general consensus is that 1) it is difficult to reduce the price much further because of the silver matrix required and 2) in applications where coils are required eg. motors, generators, transformers etc the properties of BSCCO are rather poor because of the critical current dependence on magnetic field. Magnetic fields are always associated with coils and windings, and such fields are of course fundamental to the operation of all electrical machines. YBCO (Yttrium Barium Copper Oxide) however, has good characteristics in field and for the last few years there has been intensive research and development costing several tens of millions of dollars worldwide into the scale-up of production of so-called ?coated conductor?. This ?second generation? tape can be produced by any of many different film deposition techniques, with more or less success for short lengths, but as yet it is unavailable in lengths more than a few tens of metres.

Oct 1, 2003

By F. E. Jaumot, A. Sawatzky

IT as long been recognized that there is a need for accurate systematic data on diffusion in solids. Originally, such data were needed to check existing theories but, more recently, it would appear that it could be used most advantageously as a guide to, or a check for, much needed extensions of the theory of diffusion. The awareness of the conditions which are important to experimental accuracy, the availability of the materials for accurate experiments, and the techniques have improved to the extent that it would now seem to an experimentalist that, unless extensions of the theory are made which take into account the fundamental parameters of the atoms, the electrons, and the lattice in some detail, the field of diffusion will rapidly become an empirical or semi-empirical field. The present series of experiments was designed to provide accurate data on the diffusion of the elements of the IB and IIB subgroups in silver; that is, to provide data on the diffusion in silver of three face-centered-cubic elements with roughly similar chemical properties, but with different atomic or ionic sizes and, similarly, for three noncubic elements. The elements of these two subgroups have different valences, so that the data will not give any significant information on differences due to the crystal structure of the solute. The present paper reports data on the diffusion of copper and mercury in single crystals of silver; the data for the other elements of the IB and IIB subgroups were reported previously by the authors1'2 and by Tomizuka and Slifkin.8 Experiment The general technique used was identical to that previously described1,2 and will not be repeated here. In all cases, the sectioning technique and high specific activity isotopes" were used. The short half-life of Cu64 made decay corrections more important than for the other isotopes, and necessitated around the clock shifts while data were being taken. Each section was counted at least twice (as was true for all longer half-life isotopes) and a monitor was counted along with each sample. Data for the diffusion of mercury in silver are presented at a greater number of temperatures than for the other solutes. This is a result of two circumstances. First, six (of 30) samples had to be discarded because of pitting or recrystallization which occurred during the diffusion runs, even though the samples had sustained high temperature prediffusion anneals. Either of these was a very rare phenomenon in the other experiments, and their occurrence in this case is considered in more detail below. Second, the curves of the logarithm of the activity of the sections vs the square of the penetration deptht were, in general, quite good, but frequently seemed to show one point to have high activity and the next point to have slightly low activity in terms of the best straight line. When this occurred, there was remarkable regularity of the high-low sequence. In any event, the results, as far as diffusion coefficients are concerned, were not affected by this amalgam effect. In fact, the mercury data had the highest internal consistency of any of the data. Results Diffusion of Copper in Silver—-Diffusion runs were made at eight temperatures In the temperature range from 700° to 950°C, for times ranging from 5 to 45 hr. A linear curve of the logarithm or the activity vs the square of the penetration depth was obtained for all samples. Table I summarizes the results for individual samples and Fig. 1 gives a plot 02 the logarithm of the diffusion coefficients as

Jan 1, 1958

By W. B. Gogarty, H. R. Bailey

Methods are presented for determining molecular diffusion coefficients by using data from, capillary flow experiments. These methods are based on a numerical solution (presented in a previous paper) of the partial differential equation describing the combined mechanisms of flow and diffusion. Results from this numerical solution are given and compared with the approximate analytical solution of G. I. Taylor. The numerical solution is valid over a much larger time range. These methods are applied to experimental results for the fluid pairs water-potassium permanganate solution and amyl acetate-orthoxylene. Both of these fluid pairs have approximately equal densities and viscosities. Graphical and numerical techniques are presented for deter mining diffusion coefficients from the flow data. Values obtained by these techniques are compared with values obtained by other methods. INTRODUCTION The molecular diffusion coefficient is known to be a variable in determining the amount of mixing in a miscible displacement process. The effect of molecular diffusion on dispersion in longitudinal flow through porous media -has been examined by different investigators. These investigators concluded that at low velocities of flow, the amount of dispersion is approximate1y proportional to the molecular diffusion coefficient. The influence of diffusion on fingering, channeling, and overriding has been mentioned by other investigators.4 Recent studies5,6 have been made on the effects of molecular diffusion in connection with the problem of gravity segregation. Many different methods have been developed for the experimental determination of molecular diffusion coefficients? These methods differ mainly according to boundary conditions selected and analytical procedures used. Nevertheless, all of these methods have the condition in common that the bulk fluids in which diffusion is occurring are stationary with respect to each other. In connection with a series of papers on mixing in capillary flow,8-10 Taylor suggested the use of a flow method for determining molecular diffusion coefficients. Additional studies 11-13 have been conducted on miscible displacements in capillary tubes, but the data from these studies were not used for the specific purpose of determining diffusion coefficients. The flow method proposed by Taylor results in a single value of the diffusion coefficient for the fluid pair used in the displacement experiments. This single value represents the true value for the fluid pair when the diffusion coefficient is independent of concentration. If the diffusion coefficient is a function of concentration, the single value obtained by the flow method gives an average value for the coefficient of the fluid pair. These average values are based on diffusion taking place over the entire range of concentration, i.e., from 0 per cent of one fluid to 100 per cent of that same fluid. In field applications of the miscible displacement process, gradients occur over the same range of concentration as are found in the displacements in capillary tubes. Molecular diffusion coefficients obtained from the capillary flow method should, therefore, be especially relevant to field operations. This investigation was undertaken to evaluate the feasibility of obtaining molecular diffusion coefficients from capillary -flow experiments. In making this evaluation, diffusion coefficients were first determined for two systems from data obtained in capillary flow experiments. These values of the diffusion coefficient were then compared to values obtained by other methods. MIXING IN CAPILLARY FLOW—THEORETICAL The theoretical basis for determining molecular diffusion coefficients from capillary flow experiments is the partial differential equation relating the mechanisms of flow and diffusion. For the case of laminar flow and with a fluid pair having equal densities and viscosities, the equation is given by

By Randolph C. Specht

A two year study was made of the waste disposal of the pebble rock phosphate industry. Solid slimes are impounded in large settling areas and the process water is re-used. Clear effluent was not found to be toxic to fish or animal life in field tests or in controlled experiments. Survey: The pebble rock phosphate mining and washing operations in Florida (fig. 1) are along the river basins of the Alafia to the west and the Peace to the east. The elevation of the area varies between 40 and 170 ft above sea level. Effluents from the operations find their way into one of the two river systems (fig. 2), the Peace River which flows into Charlotte Harbor and the Alafia into Tampa Bay, both along the Gulf of Mexico. There are no major industries along these rivers below the phosphate operations. On the Peace River, the town of Arcadia, approximately 50 miles below the phosphate operations, obtains its water from the river. No other communities along the rivers use them as a source of water supply. Small communities, farms, and ranches are located along the rivers and both rivers drain vast swamp areas. Complaints had been received at the office of the Chief Sanitary Engineer, of the Florida State Board of Health,' that both rivers were turbid at various times and that fishing in the Alafia River was "not as good as it used to be." Tests made by another agency on the dissolved oxygen content of the Alafia River revealed that the oxygen content, at times, was comparatively low.= However, it was not shown that the phosphate wastes had any effect upon the oxygen content of the stream. The river waters are normally brown in color due to drainage from vast swamp areas and are very shallow, from 2 to 6 ft in depth. Turbid waters have been noted in streams coming from the present phosphate operations and also from streams along which there are no operations at the present time. It was learned from "old timers" that, when many more companies than at present were operating along both the Alafia and Peace Rivers forty or fifty years ago, no attention was paid to prohibiting the disposal of slimes along the river basins. During dry periods now in some of the river swamps where drainage ditches have been dug, it is indicated clearly that phosphate slimes were disposed of directly into the river swamps for many years past. Places have been observed where there were alternating strata of phosphate mud, leaf mold, and quartz sand. The former practice of indiscriminate disposal of wastes accounts for some turbidity, particularly after heavy rains and washouts and during clearing of land and digging of drainage ditches. During a six months' period in which a large tract of land was being cleared and drainage ditches dug, a small stream (Six Mile Creek), which previously had been clear, showed a turbidity of 600 ppm and remained turbid until the clearing was completed; after which the stream again flowed clear. An interview with the operator of the municipal water plant, which is about 50 miles below the phosphate operations on the Peace River and which used this river as a source of supply, revealed that there had been no taste in the water for the past ten years, other than that occasionally encountered from increased growth of algae. The operations of each of the cooperating com-

Jan 1, 1951

By R. J. Sandrea, S. M. Farouq Ali

The results of an experimental and theoretical study of the effects of rectilinear impermeable barriers and highly permeable channels on the sweep efficiency and conductivity of a five-spot network are presented. The study was carried out using Hele-Shaw, and conductive sheet analogs for both. normal and inverted flood patterns. A functional relationship was developed which provides quantitative prediction of the above parameters; i.e., sweep efficiency and conductivity, for the nonhomogeneous system. To evaluate this, it is necessary only to measure the interference modulus of the obstacle using a simple expression. The results indicate that impermeable barriers, with an interference modulus greater than zero, always cause a decrease in the conductivity and the sweep efficiency of the pattern. On the other hand, permeability channels do not have a significant effect on these parameters, unless they are located along the streamlines. The study also discusses a method of formulating the difference equations pertaining to the two-dimensional Laplacian in a system containing rectilinear barriers. In addition, a technique is described for tracing the progress of a free surface, using marked particles, in a stream containing discontinuities SuCh as those occurring at the extremities of barriers. The above computational scheme was used in a digital computer program to simulate results of the Hele-Shaw analog. The computed values of sweep efficiency mere in good agreement with the experimental values. INTRODUCTION At the present time waterflooding remains the most widely used technique for the secondary recovery of oil. Among the numerous factors that affect the performance of a waterflood, the areal sweep efficiency constitutes one of the most critical parameters. It is a function only of the geometric distribution of the wells for a homogeneous medium and unit mobility ratio. Geological considerations, however, such as the presence of sealing faults or solution channels in the rock matrix, would generally exert an adverse effect on the areal sweep efficiency of a waterflood network. Surprisingly little information is presently available on the quantitative implications of such permeability interferences. It was the object of this investigation to consider the presence of rectilinear, impermeable and highly permeable interferences in an otherwise homogeneous five-spot pattern, and to analyze their effects on the resulting sweep efficiency and pattern conductivity. The experimental phase of the study was conducted using two different models: the Hele-Shaw flow cell and the field plotter. For experimental convenience, the geometric boundaries of the five-spot were assumed to constitute streamlines even in the case where the interference was asymmetrically placed with respect to a repeated five-spot pattern. A second object of the study was to develop a computational scheme for numerically calculating the pressure distribution in a five-spot flow pattern containing rectilinear, impermeable barriers, and to use this distribution to compute the sweep efficiency. EXPERIMENTAL PROCEDURE HELE-SHAW ANALOG The Hele-Shaw analog was used both as a visual model and for determining the sweep efficiency for systems involving impermeable barriers. The physical limitations of this model as a means of experimentally studying the motion of a fluid in porous medium have been adequately discussed elsewhere.2,7 Likewise, it can be easily verified that the analogy remains valid when a portion of the region between the plates contains an obstacle of the same thickness as the distance between the plates. The model used in this study was composed of

By C. Perez-Rosales

A statistical method for determining simultaneously some of the basic geometrical characteristics of porous media such as porsity, specific surface* mean pore width, mean grain thickness and absolute permeability is presented. The proposed method is characterized by its simplicity and the minimum amount of laboratory equipment that it requires. The experimental procedure used to evaluate the various geometrical characteristics is based 'pan the 'surface analysis Of a a In view of this fact the app1icability Of the method is limited to homogeneous and isotropic materials. INTRODUCTION The behavior of a fluid flowing through a porous medium depends, among other things, upon the internal geometry of the medium; hence the importance of developing efficient methods to determine the geometrical properties of porous materials. This paper describes a statistical method to determine simultaneously some of the basic geometrical properties of porous materials such as porosity, specific surface, mean pore width, mean grain thickness and absolute permeability. The mathematical formulation has been developed that the data required to calculate the various geometrical characteristics of a sample can be easily measured by analyzing a section of the sample with an evenly spaced grid. THEORY A simple way of obtaining information about the internal geometry of a porous material is to throw a point at random over a cross-section of a sample. l-Through this procedure the porosity can be detemined.l,2 By considering that the material is homogeneous and isotropic, and that the point is dropped many times, the porosity 4 is given by where N is the total number of times the point is thrown and n is he number of times the point falls within pore areas. Another simple manner of analyzing the structural characteristics of a porous material is to superimpose an arbitrarily long line on a cross-section so that its length is evenly distributed over the surface area. Through this procedure the porosity can also be determined. If L is the total length of the line, and 1 is the sum of the lengths of the line segments within void spaces, the porosity is given by 4 = —.1.............. (2) The advantage of this type of analysis is that geometrical characteristics other than porosity can be obtained. Thus, if c represents the number of intersections between the line and the perimeter of pores, it can be shown3 that the specific surface, defined as he surface area of pores per unit bulk volume, is given by To give a proper description of the internal geometry of a porous medium, it is necessary to define quantities that characterize the notions of pore size and grain size. Unfortunately, because of the complexity of porous materials, it is difficult to give exact geometrical definitions of what is meant by the ConCePtS of "poresl' and "grains", especially when dealing with consolidated materials. Never theless, one often talks about the "size of pores" and the "size of grains" without defining accurately the terms. A possible solution to this problem follows. Assume that an arbitrarily long line is placed on a section of a sample so that the line is evenly distributed over the surface area (see Fig. 1). 1n a system like this, each line segment within a void space will be, by definition, the pore width in a given location and direction. Consequently, if the

Jan 1, 1970

By C. E. Shoenfelt

There was a notable decrease in drilling operations in 1940 in all of the Rocky Mountain states except Montana, where the two large fields on the Canadian border, Cut Bank and Kevin-Sunburst, were espe-cially active. The expanding markets for Montana natural gas made necessary the more intensive development of such fields as Rowdoin, Cedar Creek and Devon. While there were no important oil and gas discoveries in 1940 in any of the Rocky Mountain states, a few small pools were opened, which may constitute separate areas but may prove with later development to be extensions of old fields. Some of the old fields were extended and deeper pay zones were discovered in others. These have given the areas greatly increased oil reserves and therefore are just as important as the discovery of new fields. The more important of the developments in 1940 are given, by states, in the following paragraphs. Colorado Hiawatha Field, Moffat County.—The Mountain Fuel Supply Co. began the development at Hiawatha of its oil reserves, which were discovered in about 1929, and late in the summer oil began moving from the field by truck to the shipping point at Rock Springs, Wyoming. The Hiawatha field of northwestern Moffat County was discovered in 1927 by the Sormir Petroleum Co., with the completion of No. r Florence Wilson for 4,5,000,000 cu. ft. of gas a day from a Wasatch sand lens at 2200 it. In later development of the field, oil showings were reported in several wells but no development of this resource was undertaken until 1940, when a test of the oil possibilities was started with the release in April of a location for No. 5-A Wilson on the S\W. SW. NW. of sec. 23-1zN-1ooW., on the east side of the field. The Well had an initial production of 327 bbl. of oil a day pumping from three Wasatch (Tertiary) sands between 2005 and 2540 ft. It was drilled to 2562 ft., where the 65/8-in. casing was cemented and gun-perforated at 2005 to 2125 ft., 2260 to 2335 ft. and 2513 to 2540 ft. At the end of the year, this well was averaging zoo bbl. of oil per day, pumping. Two other wells were drilled for oil on Hiawatha during the summer—one a small well of 60 bbl. per day and the other a small gas well. Powder Wash Field, Moffat County.—The development of the Powder Wash field in northwestern Colorado was resumed in 1940 by the Mountain Fuel Supply Co., with the release of a location for No. 2-A Musser in the CWL.NW.SE. of sec. 4-1rN-97W. The Powder Wash field was discovered in 1931 by the Mountain Fuel Supply Co. and the discovery well, No. I Musser, on C.NW. of sec. 5-IIN-97W., was completed at 2152 ft. in the Hiawatha member of the nonmarine Wasatch for-mation for an open flow of 34,000,000 cu. ft. of gas per day under a natural pressure of 685 lb. per sq. inch. Oil was discovered in the Powder Wash field on Nov. 26, 1936, in the company's No. I Carl Allen on the NE.SW.SE. of sec. 32-12N-97W. The oil production was

Jan 1, 1941

By J. G. Richardson, F. M. Perkins

Results and procedures are pre-cented covering a laboratory investigation of the effect of rate of water advance on the displacement of oil from clean water-wet sands. The experiments included water floods at atmospheric pressure with and without gas present over a range of flow rates from reservoir rates to rates ten thousand-fold higher. Water floods were also conducted at various rates at elevated pressure with no gas present. Other tests were made at elevated pressures by forming a free gas saturation by evolution of gas from solution in the oil before water flooding. Recovery of oil was found to be independent of the rate of water advance with or without gas present and independent of the pressure level of the water flood. A dimensionally-scaled model of a reservoir composed of a thick uniform sand was used to study the effect of rate on the tendency of water to underrun the oil because of the greater density of the water. Another model was used to study the effect of rate on the tendency of water to channel down the more permeable sand in a stratified reservoir composed of sands of diffierent per-meability in intimate contact. The effect of the presence of gas on the flooding conformance was studied with both models. The results obtained using these simple models provide a basis for predicting behavior in more complicated systems. INTRODUCTION In spite of the great amount of research on the flow of fluids in porous rocks, there still exists some disagreement as to the influence of the rate of water advance on the displacement of oil by water flooding. Various investigators have found that increasing the rate of water injection would decrease, increase, or have no effect on recovery of oil. One reason for this disagreement has been a lack of understanding of the effects of the capillary forces which influence the results obtained in the laboratory at low rates with short columns. Other causes of the disagreement have undoubtedly been inconstancy and uncertainty of the wetting properties of the porous media studied, inaccurate saturation determinations, and in some instances conclusions based on insufficient data. Capillary forces are involved in the displacement of oil by water in two ways. On the microscopic scale, the capillary forces control the dis- tribution of oil and water in the pore spaces of the sand. The magnitude of these forces is governed by the preference of the sand to be wet by water, the pore sizes and geometrical shapes, and the interfacial tension between the water and oil. On the macroscopic scale, differences in saturation at the flooding "front" when water displaces oil result in capillary pressure gradients. These gradients cause water to flow preferentially ahead of the front. In short laboratory columns at low rates, the front can span the entire column length. Also, at the outflow boundary the preference of sand to be wetted by water results in retention of water and a high water saturation in the region of the outflow face. This effect is commonly called the boundary effect.' The capillary pressure gradients which complicate the interpretation of flooding performance of short laboratory columns at low rates of water advance become negligibly small under certain conditions. The conditions where capillary pressure gradients are negligible are in long, homogeneous reservoir sands,' at high rates of water advance in short laboratory columns,3 and at any rate in laboratory columns as the residual oil saturation is approached. Thus, laboratory water floods, conducted

Jan 1, 1958

By A. L. Jr. Pozzi, A. O. Garder, D. W. Peaceman

A new numerical method is proposed for the solution of multidimensional miscible displacement problems. Besides the usual stationary grid associated with numerical procedures, the method uses moving points for which positions and concentrations are computed each time step. Based on the method of characteristics for treating combined transport and dispersion, the method applies equally well to any number of dimensions and, in contrast with other numerical procedures, properly takes into account the physical dispersion, no matter how small. Extensive tests show that accurate solutions of one-dimensional problems can be obtained over a wide range of values of the dispersion coefficient, including zero. They also show that the moving points do not need to be uniformly spaced, and that increasing the number of moving points beyond 2/grid interval does not significantly improve the accuracy of the solution. Two-dimmsional calculations using the new method were carried out to simulate laboratory model displacements in which gravity caused overriding of solvent. Good agreement between observed and computed profiles and measured and computed concentrations of produced fluid was obtained for a viscosity ratio of 1.89; at higher viscosity ratios, fair agreement was obtained Computed results were found to be significantly affected by vertical dispersion, and negligibly affected by dispersion in the direction of flow, in agreement with conclusions based on experimental observations. INTRODUCTION Although miscible displacement processes are potentially of great economic significance, limited progress has been made in developing mathematical methods for predicting the outcome of a solvent flood. Because of the complexity of the partial differential equations which describe multidimensional miscible displacement, numerical methods are a natural approach to their solution. The task of finding suitable numerical approximations to one of the partial differential equations, which involves both dispersion and convective transport, has been particularly difficult. Dispersion in the absence of transport is described by the heat flow equation, a second-order equation of parabolic type. This equation has been very successfully treated by numerical methods. Transport in the absence of dispersion is described by a first-order equation of hyperbolic type. This equation has been treated numerically with some success in one dimension, both by Lagrangian and Eulerian techniques, 1.2 but extension to two or more dimensions has not been satisfactorily accomplished. Usually one of two things happens: either the numerical solution develops oscillations or it becomes smeared by artificial dispersion resulting from the numerical process. When transport and dispersion are considered simultaneously, this numerical dispersion may dominate the low physical dispersivicy that generally characterizes miscible displacement. Stone and Brian2 have developed a new difference equation for treating combined transport and dispersion in one dimension. By suitable choice of certain parameters, they succeeded in markedly reducing both oscillation and numerical dispersion. However, a satisfactory extension to higher dimensions has not yet been found. Peaceman and Rachford3 presented a centered-in-time and centered-in-distance difference equation combined with a 1,transfer of overshoot" procedure which was demonstrated to work well in one dimension. The technique was applied to the two-dimensional miscible displacement problem, but subsequent calculations with zero dispersivity showed little change in results compared with the calculations they presented. This indicates that their method involved a numerical dispersion of the same order as the physical dispersion. The present paper describes an alternate method for solving the combined transport-dispersion

Jan 1, 1965

By K. Torssell, U. Lindborg

The kinetics of precipitation deoxidation is considered from a theoretical point of view. The size distribution and the total content of deoxidation products are estimated statistically as a function of time, taking into account Stokes and gradient collisions between the particles and separation at the top surface of the bath. The assumption is made that two particles coalesce into one larger particle as a result of a collision. General expressions are derived and calculations are carried out numerically for the case of silica particles in liquid iron. The analysis predicts a three-stage behavior for the removal of oxygen, an incubation stage, a stage of rapid separation, and a slow final stage where the content approaches the equilibrium value. The agreement with experimentally determined size distributions and deoxidation times is considered to be good. A quantitative estimation of such growth mechanisms as diffusion from the melt and redistribution of oxygen from small particles to large ones shows that these latter mechanisms cannot explain the experimentally observed gvowth of inclusions. This also indicates that collisions provide the important growth mechanism. OXIDE inclusions precipitate when a deoxidizer like silicon or aluminum is added to a steel bath. The inclusions grow and the large particles tend to separate from the bath. For each type of oxide the growth determines the sizes of the final inclusions as well as the total inclusion content of the steel. The mechanism of growth is controversial, however. It has been suggested that an inclusion grows principally by diffusion of atoms through the melt to the inclusion particle or principally by collisions and coalescence with other inclusions. Diffusion growth is always present to some extent but recent experiments and calculations by Torssell,' Kniippel et 'a1.,2 Sano et al. and Miya-shita4 indicate that collisions may be more important than previously realized. A detailed analysis has so far been lacking. The present paper is a quantitative, statistical analysis of the growth and separation of inclusions and is based on a collision theory. Nuclea-tion is not considered. The numerical estimates are based on the experimental conditions of Torssell's' investigation and comparisons are made with his observations. Torssell' studied the growth and separation of silica particles in liquid iron. Samples were taken from a 0.6 kg iron bath at various times after the addition of silicon. By a particle-counting technique developed by Bergh and Lindber~the size distribution of the inclu- sions was determined. The number of particles at the first sampling, 10 sec after silicon addition, was of the order of 3 x lo7 to 10' per cu cm, the largest particles having a radius of 2 to 4 pm. The volume fraction was 0.001 to 0.004; i.e., the dispersion was very dilute. During subsequent holding the largest particles increased their radius by a factor of 10 after about a minute, and the whole size distribution was displaced toward larger values. These results were obtained with allowance for precipitation of the equilibrium concentration of oxygen during solidification. The bath contained less than 0.01 pct of C. Figs. 1 and 2 show the typical appearance of the inclusions. Most particles are very closely spherical and appear to have been liquid or semiliquid in the melt. The observed number of inclusions, about 5x 10' per cu cm, is of the same order of magnitude as found by ~er~h.' This is a large value. It follows that the diffusion distances are very short and that the precipitation

Jan 1, 1969

By Irwin Politziner F. M. Townsend, L. S. Reid

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,' (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.'"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard' dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951

By Norman F. Schulz, Emert W. Lindroos, Strathmore R. B. Cooke

DURING the course of an investigation of the effects of various starch products on hematite and quartz in regard to their separation by flotation, it was found that whereas most starches flocculated suspensions of hematite in water, they did not flocculate similar suspensions of quartz. However, a derivative of whole corn starch containing approximately one tenth aminoethyl group (-—CH,CH2NH2) per glucose unit proved to be an exception. This aminoethyl starch was a very good flocculant for both hematite and quartz, and also possessed the property of depressing both minerals in cationic flotation tests. In view of the widespread use of starch as a flocculating agent of solids in tailing water, pulps, and for coal slimes, ore and various other purposes in sulphide and nonsulphide flotation, attention is called to the effective surface activity of aminoethyl starch in flocculating suspensions of the two minerals investigated. Test Materials The starch products employed included Globe Pearl starch No. 144 and fresh aminoethyl starch, both supplied by the Corn Products Refining Co. Dr. A. L. Elder" has kindly furnished a description The minerals used in the various tests are listed in Table I. Their specific surfaces were determined by the air permeability method, which gave results reproducible to within plus or minus 3 pct. Surface areas obtained by krypton adsorption were greater than the air permeability values by a factor of 2.0 for quartz and 62.4 for hematite. Starch Adsorption on Mineral Surfaces Starch adsorption data were obtained by agitating for 1 hr measured volumes of neutral starch solutions of known concentrations with weighed quantities of finely divided mineral of measured specific surface. The mineral then was separated from the pulp liquor by centrifugation and the residual starch content determined by chemical analysis. The analytical procedure consisted of oxidizing the starch with an excess of dichromate in acid medium at elevated temperature and titrating the excess dichromate by the ferrous ammonium sulphate—potassium permanganate method. Analytical results were reproducible to within less than 1 pct. Adsorption data obtained in unbuffered solutions near the neutral point are plotted in Fig. 1. The adsorption on either mineral was far greater for the aminoethyl starch than for the Pearl starch. Flocculation The degree of flocculation was determined for a given pulp by measuring the time required for the supernatant liquid to reach a certain degree of clarity. This was accomplished by passing a standard light beam through the pulp, contained in a glass settling tube, and measuring the time required after agitation ceased for the intensity of the transmitted beam to reach a predetermined value. Starch reagent was added to each pulp in small uniform increments, and the settling time was determined after each such addition. Increase in pulp liquor volume due to the added starch reagent was ignored in these tests. Pulps were maintained at or near neutrality. of the preparation of the aminoethyl starch: "Three hundred and sixty grams of powdered unmodified corn starch was slurried in 3 liters of water and stirred during gelatinization. Eighty-six grams of ethylenimine was added slowly during reflux which was continued for 4 hr. The yellow solution set to a gel upon cooling. This was broken up and neutralized with HC1. The thick paste was dried on hot rolls. Adsorbed polyethylenimine and salts were removed from the yellowish products by washing first with acidified aqueous '60 per cent' alcohol. The white product contained nitrogen corresponding to about one aminoethoxy group per ten glucose residues." Only laboratory samples of this starch derivative have been prepared. The starch reagents for use in flocculation, flotation, and adsorption tests were made up by dispersing the appropriate quantities of air-dry starch in cold water, adding boiling water, and heating for 30 min at 120°C under pressure. When used ip adsorption tests, the starch solutions first were cleared of insoluble matter by centrifugation.

Jan 1, 1953

By Adam L. Wesner, A. C. Richardson

This paper describes the development of a continuous float-and-sink process to produce coal low enough in ash content to be suitable for production of electrodes. The cleaned coal had a combined iron and silicon content of 0.239 pct. The efficiency of recovery was 84 pct. DURING World War I1 the demand for electrode carbon was greater than could be met by the supply of petroleum coke available for this use. It was believed that coke made from an extremely low-ash coal might be a suitable substitute for petroleum coke. Requirements for electrode carbon to be used for the production of aluminum are that the silicon plus iron content shall be not more than 0.14 pct of the coke. However, during the period when petroleum coke was in short supply, it appeared that relaxations of the specifications might be allowed to permit 0.4 pct iron plus silicon in the coke. For this work, the specifications were that the coal should contain less than 1 pct of ash, and the combined iron and silicon content of the coal should not exceed 0.28 pct. Heavy-liquid separations made on a number of coals showed that if certain size fractions of some coals Were separated at low specific gravities the resulting float products would meet the required specifications. The objective of this work was to develop a continuous, commercially feasible process for producing low-ash coal. After consideration of various processes, the method chosen was a float-and-sink separation using a solution of calcium chloride as the separating medium. Eagle Seam coal was used for the experiments. The —10 +35 mesh fraction was found to be the most promising feed for producing the low-ash content coal. A batch of 30 tons of — --in. coal was screened at 10 and 35 mesh; the yield of —10 +35 mesh was 20 pct of the feed. This fraction comprised the feed for the separation tests. In spite of the fact that this portion was screened a second time at 35 mesh, the coal still contained 16 pct that was finer than 35 mesh. Three-fourths of the undersize was in the —35 +48 mesh range. A representative portion of the —10 +35 mesh fraction was subjected to batch float-and-sink separations to determine the best gravity to be used in the continuous tests to obtain a high recovery of low-ash content coal. The heavy liquid used was a mixture of carbon tetrachloride and benzene which assured complete wetting of all of the particles. As usual in batch separations, adequate time was allowed for each separation so that even the near gravity particles had ample time to separate. The separations were made at increments of 0.01 sp gr from 1.25 to 1.28 and also at 1.32 and 1.59. Each specific-gravity increment was assayed for ash content. From these data it was concluded that 1.27 sp gr was best for the continuous separation of the coal. The products from the batch separation were composited into float 1.27 and sink 1.27 sp-gr fractions; these were assayed for ash, iron, and silicon. Table I shows the results of the batch separations. The composite float 1.27 fraction contained 66.04 pct of the total weight, and had an analysis of 0.79 pct ash, 0.073 pct iron, and 0.112 pct silicon, or 0.185 pct iron and silicon combined. These data are indicative of the results possible if a perfect separation is made at 1.27 sp gr under static conditions. Inasmuch as the method under investigation is a dynamic system these results could not be obtained. It remained to be determined, however, just how close to the theoretical results the actual continuous separation would be.

Jan 1, 1953

By H. F. Yancey, M. R. Geer, C. L. Allyn, R. H. Eckhouse

Four coals were treated in the Humphreys spiral concentrator, and the products were examined by float-and-sink and screen-sizing tests to determine fundamental performance characteristics. The efficiency of the separation between coal and impurity was shown to be influenced greatly by particle size. FOUR coals exhibiting different washability characteristics were washed in the Humphreys spiral concentrator and the products examined by float-and-sink and screen-sizing tests to determine the mechanics of the separation between coal and impurity. With one coal, each 1/2-in. increment of the full width of the stream in the spiral was examined separately to determine where each size and specific-gravity fraction of the feed was stratified. The basic performance characteristics of the spiral were found to be the same for all of these coals. The coarsest fraction of heavy impurity stratified so far out in the stream that it could not be removed through the refuse ports and thus either entered a middling product or contaminated the washed coal in the case of a two-product separation. Impurity particles finer than about 100-mesh also were carried out in the main body of the stream and therefore were not removed in the refuse product. Little loss of clean coal in the refuse occurred in sizes coarser than 28-mesh or finer than 100-mesh, but considerable coal of intermediate size stratified in the stream that was drawn off through the refuse ports. Because of this modifying influence of particle size, the spiral is unable to make an efficient two-product separation between coal and impurity without some retreatment. Recirculation of a middling product through the same spiral as a means of obtaining more efficient operation was not attempted in this investigation. The size and specific-gravity composition of the middling product are, however, such as to render it amenable to simple hydraulic classification for recovery of coal. Retreatment of a middling product would improve the efficiency of the spiral, but even when making a substantial amount of middling, considerable clean coal enters the refuse product. Consequently, retreatment of a combined refuse-middling product would appear to offer greater promise for providing maximum efficiency. Because of the sizing characteristics of the spiral, a classified feed can be treated with higher efficiency than is possible on a natural raw coal. For this reason, semiclassified feeds, such as silt-bank or classifier-underflow materials, can doubtless be treated with higher efficiencies than those shown for raw coals in this report. Performance is, of course, only one of many factors that enter into the choice of cleaning equipment. The fact that the one company now using the spiral for cleaning coal has built a second spiral plant is ample evidence that the inherently low efficiency of this unit may be overshadowed by the low operating costs afforded by its extreme simplicity. Introduction A number of factors enter into the selection of coal-cleaning equipment, and most of them bear directly on the final cost of prepared coal. One of these factors is performance of the cleaning unit in terms of the efficiency of the separation it effects between clean coal and refuse. The importance of performance in the selection of a coal-cleaning unit varies with the difficulty of the cleaning problem. Obviously, if the character of the coal is such that only certain types of cleaning units are capable of yielding a clean product meeting market requirements, performance is of prime importance. If, on the other hand, the cleaning problem is so simple that any type of cleaner will provide coal of suitable quality, performance is important only insofar as it affects costs by determining the amount of salable coal lost in the washery refuse. With the objective of providing the coal industry with information that is helpful in the selection of

Jan 1, 1951