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By P. H. Metzger, D. W. Fuerstenau

The activation of sphalerite was found to occur at a much lower rate with Pb++ then with Cut++ or Ag+. To prevent activation with Pb++, the ratio [m in solution must approximate 103. An example is given illustrating how this condition is met in practice through the addition of zinc sulfate and soda ash. In selective lead-zinc flotation, the mill operator, especially the one who is concentrating a partially oxidized ore, often must add zinc sulfate and/or soda ash for effective depression of the sphalerite. In the present paper the authors show how this practice prevents the activation of sphalerite in the presence of Pb++. A number of years ago Gaudin (1) postulated that Zn++ might control the activation of sphalerite with Pb++ through competitive adsorption. However, recent experimentation has shown the activation of sphalerite with Ag+ and Cut++ to be a chemical reaction in which silver or copper ions replace zinc in the sphalerite lattice through the formation of a more insoluble sul-fide (2,3,4) Thus, if activation with Pb++ is similar to that with Ag+ or Cu t+, zinc salts should control the activation of sphalerite not through competitive adsorption but because the ratio of [zn++/Pb++] in solution regulates the extent of the chemical exchange between Zn++ and Pb++ in the solid phase. The objective of this investigation has been to study the kinetics and equilibrium conditions for the uptake of Pb++ by sphalerite and to investigate the prevention of lead activation with zinc salts. BASIC PRINCIPLES Sphalerite activation has been shown to be a replacement reaction wherein a less soluble compound is formed at the expense of the more soluble zinc sul-fide (2,3,4) For example, if sphalerite is placed in an aqueous silver nitrate solution, ZnS gives to the solution more S= than can exist together with Ag+, and hence the following reaction takes place: ZnS + 2 Ag+? Ag2 S + Zn ++; k = [zn ++]/[Ag ++]2 = 10 26 (1) Therefore, ZnS will dissolve in the presence of Ag+ and activation of sphalerite with Ag+ will proceed after monolayer coverage by solid state diffusion until equilibrium conditions are reached in the system (2, 4) Because of the large difference in the solubility of ZnS and Ag2S, zinc salts cannot affect the reaction unless a complexing agent, such as cyanide ions, is present to complex Ag+ more tightly than Zn++ . By complexing Ag+ and Zn++ in solution, the uptake of Ag+ by sphalerite can be regulated by controlling the ratio m. . Experimentally (2) it was found that the activation of sphalerite by Ag+ could be prevented through the addition of NaCN if this ratio reached a value of approximately 10 26. The mechanism of sphalerite activation with copper salts is given by the following reactions: ZnS + Cu ++ ? CuS + Zn + + ; (2) k = [Zn++]/[Cu++] = 10 11 ZnS + Cu + ? Cu2S+ Zn++; (3) Experimentally Mao (3) found that the activation of sphalerite with Cu++ or Cu + was prevented if the ratios expressed in Equations 2 and 3 were approximately l09 and l022, respectively, with cyanide ions as the deactivator. Although zinc salts do not affect the activation of sphalerite with silver or copper ions in the absence of a complexing agent, activation with lead ions theoretically can be controlled by the addition of zinc salts because of the relatively small differences between the solubility of ZnS and PbS (5). Equilibrium

Jan 1, 1961

By R. D. Nelson, F. E. Bowman

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.' The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970

By B. B. Rath, Hsun Hu

Rates of migration of large-angle boundaries have been studied in zone-refined aluminum crystals, defonned 80 pct by rolling in the (110)[112] orientation at -78°C followed by a recovery anneal at 80°C. Artificially nucleated grains show a marked variation. by an order of magnitude, in their growth rates in different directions. The average activation energy for the migration of all boundaries was found to be about 16,000 cal per mole. The anisotropy of the boundary migration is rationalized on the basis of the boundary structure. It has been observed by Beck and HU,1 Kohara el al,2,3 and Czjzek and Haessner4 that recrystallized grains formed upon annealing Of deformed sing1e crystals of aluminum show anisotropic growth characteristics. Kohara et al. found that single crystals rolled in the (110)[112] orientation, when random nuclei were provided on one side of the crystal by rubbing with emery paper and annealing, developed a sharp recrys-tallization texture on the other side of the crystal upon further annealing. This sharp recrystallization texture consisted of four components, which were related to the deformation texture of the crystal, i.e. (110)[112], by rotations of ±40 deg around each of the two common [ 111] axes' They also noted that recrystallized grains were elongated in directions perpendicular to either of these two common [1111 axes. They attributed this anisotropic growth to the difference in the rate of self-diffusion or diffusion of impurity atoms along the tilt and the twist boundaries. A somewhat similar investigation was conducted by Czjzek and Haessner4 On strained single-crystal sheets Of alum- inum. These authors claimed that the matrix structure of the deformed crystal had a greater effect on the growth anisotropy of the recrystallized grains than did the boundary orientation itself. In the present investigation quantitative measurements of the rate of grain boundary migration in anisotropic growth have been made in zone-refined aluminum (99.9999+pct pure) crystals deformed 80 pct by rolling in the (110) 112] orientation. Crystals of this particular orientation were chosen because of the following desirable features: 1) the crystal does not change its orientation during rolling; 2) the rolling plane contains all the significant crystallographic directions; and 3) when annealed, following deformation, the crystal does not re-crystallize spontaneously but polygonizes to a stable and homogeneous structure. Hence, the initial orientation of the crystal and a constant strain energy in the matrix can be maintained during subsequent grain boundary migration studies. It is essential to keep the driving force constant for the study of boundary mobility.5 EXPERIMENTAL PROCEDURE A cylindrical single crystal of 1 in. diam was grown by the Bridgman method in a high-purity graphite mold. The resistance ratio, R(4.2°K) /R(298°K) , of the grown crystal was approximately 2.0 x 10-4. A number of slices, 1/4 in. thick, were cut from the crystal along the (110) plane and were mechanically and electrolyti-cally polished to remove the strained surface layer. The crystals were then rolled along the [112] direction to 80 pct reduction in thickness at -78°C. To minimize surface friction, the crystals were rolled between two layers of 0.005-in. teflon sheet. Rolling was interrupted, prior to completion, to remove the surface layers and the edges by electropolishing. These and similar precautions in handling the rolled crystals

Jan 1, 1967

By J. W. Wolfe

The Benedict-Webb-Rmbin equation of state was used in digital computer programs to make rapid determinations of natural gas equilibrium phase compositions. Mixture components were the nine hydrocarbons, methane through heptane. Comparative tests were made with data from field separators, plant exchangers and literature sources. For most tests made, the B-W-R equations predrcted component K-vallles, mixture enthalpies and phase aensities within tile accuracy of available correlations for rune-component mixtures: significant deviations were noted when mixtures contained components heavier than heptune. INTRODUCTION Rapid, accurate methods for calculating the properties of hydrocarbon mixtures are needed for predicting the behavior of natural gas processes. For example, because of the common use of two-phase separation methods in gas proccssing, calculations must be made for the density and composition of equilibrium vapor and liquid phases. In addition, predictions must often be made for the temperature and pressure changes associated with the flow of single- and two-phase natural gas fluids through heat exchangers, chokes and turbines. The complex nature of non-ideal mixtures makes rigorous calculations for these natural gas properties difficult and time-consuming. Natural gas properties have conventionally been determined with generalized data correlations. These correlations, such as the K-values presented in the NGAA Equilibrium Ratio Data Book, are usually based on some average property of the mixture and have proven to give satisfactory estimates for the properties of most oil and gas systems. Digital computers, however, have not only increased the utility of these correlations, but also have made practical the use of equations of state for calculating the properties of natural gases. Potentially, if basic pure component data are available, all the desired thermodynamic properties of mixtures can be derived from a single equation of state describing the mixture. Currently. the best equation of state for describing the behavior of pure, light hydrocarbons over single-and two-phase regions, both below and above critical pressure, is that of Benedict. Webb and Rubin.' The equation contains eight constants which are determined by empirically fitting the equation to pure-component PVT data. Benedict and his co-workers presented the clevelopment of their equation as early as 1940.2 The B-W-R equation is a modification of the Beattie-Bridgeman equation of state and gives better PVT predictions than the Beattie equation at densities above the critical density. Benedict et al. made the equation applicable to mixtures by relating the mixture constants to composition and the constants for pure compounds. These authors, in a serics of articles in 1951,' showed the accuracy of the B-W-R equation when applied to light hydrocarbons and their simple mixtures, and demonstrated the equation's utility for making vapor-liquid equilibria calculations. Since its inception, the B-W-R equation has been the subject of many papers. Numerous additions and modifications have been proposed,'-',"'-':' the purpose of most being to improve the equation's ability to predict PVT properties of specific mixture systems. In 1959, Opfell, Pings and Sage summarized much of the work on the B-W-R equation in their book on equations of state." Since natural gases are primarily mixtures of light hydrocarbons, the B-W-R equation is a natural choice for an equation of state to compute both phase equilibria and thermodynamic properties of natural gases. Consequent-

Jan 1, 1967

By A. Haghighat, B. Lattimer

"Mine face ignition due to a high levels of methane is one of the most common fire incidents in underground coal mines. This work exams ignition scenarios in continuous miner headings. Depending on the magnitude of the ignition or resulting fire, the ventilation curtain in the continuous miner (CM) heading may be damaged or dislodged, affecting the ventilation into the area. A computational study was conducted to investigate the effects of different levels of damage to the ventilation curtain on the ventilation flow into the CM area. The computational fluid dynamics software Fire Dynamics Simulator (FDS), Version 6.0 was used to predict the conditions that develop due to a 200 kW fire in the coal mine face following a methane ignition with different levels of curtain damage. Smoke layer depth, temperatures and mass flow into the CM area were used to evaluate the impact of no damage to the curtain, partially dislodged curtain, and fully removed of the curtain. Partial removal of the curtain allowed more smoke to accumulate in the CM area and a reduction in ventilation into the CM area. With full removal of the curtain, the smoke accumulated through the entire depth of the CM area and flowed out the entrance to the CM area and the ventilation completely bypassed the region. INTRODUCTION Active working faces in underground coal mines are one the most hazardous locations in terms of fire events. According to Mine Safety and Health Administration (MSHA) data analysis, the highest number of non-fatal fire incidents was reported at mining faces, intersections and crosscut areas in comparison with other locations from 2000 to 2012. About 464 fires happened at active working faces from 2000 to 2012, most consisting of a methane ignition, in some cases followed by localized fire. These are high risk incidents due to the potential to raise float dust and damage ventilation systems, particularly auxiliary systems such as curtain or tubing. Depending on the magnitude of the ignition or fire, the ventilation curtain in the continuous miner (CM) area may be damaged or dislodged, affecting the ventilation into the area. Five computational fluid dynamics (CFD) scenarios were considered to investigate the smoke layer depth, temperature, visibility, mass flow rate, and the behavior of airflow in an entry with a continuous miner (CM) located in it. The state of the auxiliary ventilation was varied based on the assumption that as an ignition increases it magnitude it will affect ventilation curtain proportionally. Visibility and temperature along the height of the entry at different sections were investigated and the interface height at each section was determined. Also, the fresh air height was studied for tenability analysis in future. FDS, Version 6.0 was used to predict the conditions that develop due to a 200 kW fire on the coal mine face following a methane ignition with different levels of curtain damage. Smoke view software was used as the post processor to visualize and analyze methane fire behavior at the face. Most entry fires are reported as fuel-controlled fires as they are rarely restricted to air access (Ingason et al, 2014). The working face fire in the following models was assumed to be a fuel-controlled fire."

Jan 1, 2016

By Paul A. Flinn, Jean-Marie Robert Genin

The MCssbauer effect was used to study the distribution of carbon in Fe-C alloys of high carbon content during room-temperature aging. In freshly formed rnartensite the carbon distribution is approximately random; carbon clustering occurs dun'ng aging. In the retained austete the carbon atoms are isolated, suggesting an efiective repulsion; and no rearrangement during room-temperature aging is evident. The kinetics of the carbon clustering in martensite has been studied in detail at 0" . 10". and 20°C. The time and temperature dependence observed is sinzilar to that reported for a variety of other aging effects, such as resistance change, hardness increase, and recovery of internal friction. The stabilization of the martensite kransformation also appears to be related to the clustering effect. DESPITE extensive efforts since the early days of Reaumur, the mechanism which provides the strengthening of steel remains controversial in many cases for several reasons: 1) The structure of as-quenched martensite is not well-determined. 2) Experimental methods capable of distinguishing between various hardening mechanisms are not well-developed. 3) The temperature of formation of many low-alloy martensites is so high that the martensite formed during quenching may be already tempered to some extent before any observation. Among all the hardening phenomena, the most puzzling one occurs at room temperature, where no structural changes have been detected by the usual methods of X-ray diffraction or electron microscopy. However, a new and more sensitive technique became available with the discovery of the MBssbauer effect. This effect makes possible the detection of changes in the local environment of iron atoms in solid solution. It has been extensively used in the study of substitutional alloy systems, for example, Fe-Al,1 Fe-Si,2,3 Fe-Rh,4 and Fe-Ni.5 Making use of the possibility of obtaining new structural information, we undertook an investigation of the aging of high-carbon Fe-C martensite to follow the structural changes involved in the aging at room temperature. Preliminary results6 showed that a clustering of the carbon atoms occurs with time. A systematic study of the kinetics of the process showed a striking similarity to the kinetics of stabilization of the marten-sitic transformation, thus suggesting further investigation of the relationship. EXPERIMENTAL TECHNIQUE To eliminate difficulties with the aging of martensite prior to the first experimental measurements, we needed an alloy with an M, temperature not above room temperature. Other investigators7 were misled by results obtained on alloys which transformed above room temperature and underwent structural changes prior to the first Mossbauer measurements. Winchell and cohen8 dealt with this difficulty by using a third element, nickel, to depress the MS below room temperature. The presence of nickel did not seriously interfere with hardness or resistivity measurements, but it would complicate the interpretation of the Mossbauer data by increasing the variety of iron environments. We chose, therefore, to obtain the necessary lowering of the M, simply by increasing the carbon content. After the first quench to room temperature, our specimens are retained austenite, which we later quench into liquid nitrogen. The martensitic transformation takes place suddenly, so that the as-quenched condition of the samples is retained, since the temperature is low enough to prevent any carbon diffusion. A Massbauer spectrum at 77°K can be taken and analyzed; after an appropriate up-quenching to the aging temperature, a new Mossbauer measurement at 77°K can be made. Fig. 1 shows a typical cycle of experiments. The samples were foils 25 p thick of high-purity

Jan 1, 1969

By M. Bevis, A. G. Crocker

A. G. Crocker and M. Bevis (Battersea College of Technology)— Richman and Richman and conard17 have recently published the very interesting results of their studies on the plastic deformation of Fe-Ni-C martensites and of an Fe-5 wt pct Be alloy. Other work on the range of Fe-Be alloys containing between 16 and 27 at. pct Be has also been reported by Richman." One of the fascinating features of this work is that the materials investigated deform primarily by means of twinning and that several twinning modes are operative in addition to the well-established (112 ) mode of bcc materials The composition planes of these unusual twins were determined using a single-surface analysis and reported as (0131, "{045)" or "{089)", and It is now thought1' that the "{0,1,13)" habit reported for the Fe-Ni-C alloys'' is more likely to be near "{127)". Although the full twinning elements of these unusual twinning modes could not be determined directly from the experimental results, the authors attempt to deduce the elements by considering twin intersectionslQ and by using the projection technique of Jaswon and Dove. The basic assumption of their approach is that the (013) habits are truly rational planes but that the other habits are irrational and merely approximated to by the indices quoted above. They thus deduce that the twinning mode describing the (013) habit is either Type I or compound and that the modes describing the other habits are Type 11. This deduction must however be false as all twinning modes in cubic structures obeying the classical orientation relationships of deformation twinning must be compound. Type-I and Type-I1 modes can occur in all of the other crystal systems (indeed in the triclinic system compound modes are not allowed), but in the cubic system only compound modes can arise. This fact, which does not appear to be well-known, fol- lows immediately from the relations between the four twinning elements defining a twinning mode. Thus for a Type-I mode which is uniquely defined by the rational twinning elements K1 = hi and given by: where the summation convention of the tensor calculus has been adopted. For cubic materials the metrics and reduce to the unit tensors and j so that we have It is clear from these equations that both ki and ui must take on integral values; i.e., Kz, and ql must be rational, if hi and vi are integers, i.e., if K1 and are rational. Thus for cubic materials a Type-I mode must degenerate into a compound mode and the same result also arises for Type-II modes. The apparently irrational habits observed by the authors can thus not be explained in terms of Type-I1 twinning if the classical laws of deformation twinning are to be obeyed. An alternative explanation of the irrational habits is that they may arise from twinning modes with four irrational twinning elements. These modes, which do not obey the classical orientation relationships associated with deformation twinning, have been shown to arise as the result of double twinning processes in magnesium,22 but may also describe a simple shear on an irrational plane in an irrational direction. Indeed double twinning processes in bcc

Jan 1, 1963

By M. Bevis, A. G. Crocker

A. G. Crocker and M. Bevis (Battersea College of Technology)— Richman and Richman and conard17 have recently published the very interesting results of their studies on the plastic deformation of Fe-Ni-C martensites and of an Fe-5 wt pct Be alloy. Other work on the range of Fe-Be alloys containing between 16 and 27 at. pct Be has also been reported by Richman." One of the fascinating features of this work is that the materials investigated deform primarily by means of twinning and that several twinning modes are operative in addition to the well-established (112 ) mode of bcc materials The composition planes of these unusual twins were determined using a single-surface analysis and reported as (0131, "{045)" or "{089)", and "{2,3,10)" or "(127)". (It is now thought1' that the "{0,1,13)" habit reported for the Fe-Ni-C alloys'' is more likely to be near "{127)". Although the full twinning elements of these unusual twinning modes could not be determined directly from the experimental results, the authors attempt to deduce the elements by considering twin intersectionslQ and by using the projection technique of Jaswon and Dove.' The basic assumption of their approach is that the (013) habits are truly rational planes but that the other habits are irrational and merely approximated to by the indices quoted above. They thus deduce that the twinning mode describing the (013) habit is either Type I or compound and that the modes describing the other habits are Type 11. This deduction must however be false as all twinning modes in cubic structures obeying the classical orientation relationships of deformation twinning must be compound. Type-I and Type-I1 modes can occur in all of the other crystal systems (indeed in the triclinic system compound modes are not allowed), but in the cubic system only compound modes can arise. This fact, which does not appear to be well-known, fol- lows immediately from the relations between the four twinning elements defining a twinning mode. Thus for a Type-I mode which is uniquely defined by the rational twinning elements K1 = hi and tj2 = vi (i = 1, 2, 3), the Kz qd 771 elements are given by: where the summation convention of the tensor calculus has been adopted. For cubic materials the metrics cij Iand cij reduce to the unit tensors 6ij and 6ij so that we have It is clear from these equations that both ki and ui must take on integral values; i.e., Kz, and ql must be rational, if hi and vi are integers, i.e., if K1 and 77~ are rational. Thus for cubic materials a Type-I mode must degenerate into a compound mode and the same result also arises for Type-II modes. The apparently irrational habits observed by the authors can thus not be explained in terms of Type-I1 twinning if the classical laws of deformation twinning are to be obeyed. An alternative explanation of the irrational habits is that they may arise from twinning modes with four irrational twinning elements. These modes, which do not obey the classical orientation relationships associated with deformation twinning, have been shown to arise as the result of double twinning processes in magnesium,22 but may also describe a simple shear on an irrational plane in an irrational direction. Indeed double twinning processes in bcc

Jan 1, 1963

By J. M. Eriksen, T. Rosenqvist, H. Elstad, S. Seim, A. Hildal

The titanium industry demands high titanium feedstock for their processes. As rutile resources are limited, ilmenite has become the most important titanium source. Ilmenite smelting is an important part of upgrading ilmenite to high titanium feedstock. In the year 2005, upgrading of ilmenite by smelting, producing a slag with 80-90% Ti02, accounted for approximately 40% of the feedstock to the Ti02 pigment industry. In ilmenite smelting molten iron is produced together with a slag, which in addition to titanium oxide contains iron oxide as well as various impurity oxides of manganese, magnesium, silicon, aluminium, etc. Titanium is present mainly as Ti02 but partly also as Ti203. It is known that the concentration of Ti203 increases with decreasing concentration of FeO, but this dependency is affected by the nature of the impurity oxides. Sigurdson and Moore1 showed that slags high in CaO and MgO had a lower concentration of Ti203 than slags high in Si02 for the same amount of FeO. Pistorius2 showed in 2002 that if the impurity oxides MnO and MgO are counted, on a molar basis, as FeO, and Cr203, V203 and part of the A1203*), as Ti203, industrial slags will have a composition close to that of the M305 phase, where M denotes the elements Ti, Fe, Mn, etc, and which has the pseudobrookite structure. However, for equilibrium with liquid metallic iron he computed, by means of a computer program FACT, that the slag equilibrium composition is represented by a curved line in the ternary phase diagram FeTi03-TiO2-Ti2O3, but with a significantly higher concentration of trivalent titanium than actually observed in the industrial slags, and he discussed various mechanisms by which the slag during solidification could change its composition to a lower Ti203 content, but the possibility that the computed compositions might be wrong was not mentioned. Trane113 found in her research on titaniferous silicate slags a lower Ti3+/ Ti4+ ratio than that which is computed by the FACT program. The purpose of the present investigation was to study the equilibrium composition of Fe-Ti-O slag in equilibrium with liquid metallic iron, as well as the effects of impurities such as Si02, CaO and MgO on the slag composition. Industrial slags from TINFOS Titan and Iron KS (TTI) will also be discussed and their compositions will be plotted in the ternary phase diagram. These are slags produced from Tellnes ilmenite, quite high in magnesium and iron. Experimental In the past, equilibrium studies of the Fe-Ti-O slag system were difficult when it came to producing the slag. It was difficult to find a suitable crucible for the meltings. The highly corrosive slag would attack all known refractories, and the metal would attack metallic crucibles such as those made of platinum and molybdenum. In the present investigations the slag-metal combination was prepared in a high-frequency induction furnace with a vertically segmented water-cooled copper crucible. The crucible is shown in Figures 1 a and 1b. It was designed by the Australian Nuclear Science and Technology Organisation (ANSTO) with power from a 75 kVA high-frequency generator (750 kHz) supplied by Farfield Electronics Pty, Ltd, Australia. This enabled the slag-metal combination to be melted with turbulent stirring and is expected to be isothermal. The entire temperature gradient

Jan 1, 2007

By Frank E. Williams

This Bureau of Mines report describes 147 known fluorspar deposits in New Mexico and briefly mentions 54 miscellaneous occurrences for which little or no information was obtained. Most miscellaneous occurrences are minor and too poorly exposed to be considered more than prospects. History and production of fluorspar in New Mexico, type of deposition, mineralogy, uses, and grade specifications are discussed. Total mine production of fluorspar in New Mexico is nearly 641,000 tons of various grades of crude ore and hand-sorted material. Fluorspar deposits occur in 13 of the State's 32 counties. Grant, Valencia, and Luna Counties account for 86.4 percent of the total production. During the investigation, 141 deposits were visited. A total of 72 character samples was collected for assay, and 3 larger samples were collected for bench-scale metallurgical tests. Results of these metallurgical tests indicate that an acid-grade product can be obtained with 95 percent recovery of the CaF2 content of the crude ore.

Jan 1, 1966

By Frank E. Williams

This Bureau of Mines report describes 147 known fluorspar deposits in New Mexico and briefly mentions 54 miscellaneous occurrences for which little or no information was obtained. Most miscellaneous occurrences are minor and too poorly exposed to be considered more than prospects. History and production of fluorspar in New Mexico, type of deposition, mineralogy, uses, and grade specifications are discussed. Total mine production of fluorspar in New Mexico is nearly 641,000 tons of various grades of crude ore and hand-sorted material. Fluorspar deposits occur in 13 of the state's 32 counties. Grant, Valencia, and Luna Counties account for 86.4 percent of the total production. During the investigation, 141 deposits were visited. A total of 72 character samples was collected for assay, and 3 larger samples were collected for bench-scale metallurgical tests. Results of these metallurgical tests indicate that an acid-grade product can be obtained with 95 percent recovery of the CaF2 content of the crude ore.

Jan 1, 1966

By M. S. Seehra, R. S. Pandurangi

"Investigations of the infrared spectra of crystalline and amorphous silica particles of different sizes (0.05, 5, 10, 15, 30, 45, and 260 um) in the range of 400-4000 cm-1 using Fourier transform infrared/photoacoustic spectroscopy we reported. The change in the intensity I of the signal with porosity e of powders follows the e/(1 - e) dependence for strong bands and e dependence for weaker bands as pre¬dicted by the theory of McGovern of al. For strong bands, I also follows the empirical relation I ~ D-n, where D Is the particle diameter in cm and n = 0.34-0.42. The anomalous positive frequency dependence of I on the modulation fre¬quency f observed for the stronger bands in the 45-pm and 260-pm particles Is believed to result from saturation. Some observations on the effect of changing the background from (carbon black) powder to pellet are also made.INTRODUCTIONSince the publication of the Rosencwaig—Gersho (RG) theory on the photoacoustic effect in solids (1, 2), Fourier transform infrared/photoacoustic spectroscopy (FTIR/PAS) has become an important technique for obtaining the IR spectra of surfaces and materials in their natural state (1-12). In the one-dimensional RG theory, the incident radiation, modulated at frequency f, is absorbed by the material to a depth pp = 1/B (B = absorption coefficient), thus setting up temperature variations in the material. These variations heat the adjacent gas/solid interface leading to the pressure fluctuations of the gas above the sample, which in turn is detected by microphone as a PA signal. The thermal wave originating from no deeper than the thermal diffusion length(2k/npcf) 1/2 in the material contributes to the PA signal (here k, p, and c are respectively the thermal conductivity, density, and specific heat of the material). Since u2, can be varied by varying the experimental parameter f, depth pro¬filing by PAS is possible and a number of papers on this subject have appeared in recent years (2-10). Another im¬portant phenomenon is saturation which occurs when the material thickness 1> u> us (1-12).The original promise of PAS for use with powder samples, without the need to ""prepare"" samples as in FTIR spectros-copy, has not yet been fully realized because of several com¬plications. Theoretical works by Monchalin et al. (13) and McGovern et al (14) showed that the interstial gas in the voids of the powders can act as amplifier and that, for the same mass, a finer powder is expected to yield higher PA signal than a coarser powder. Although in a number of earlier studies (15-21) an increase of PA signal with decreasing particle size has been observed, a quantitative check on the equations developed by McGovern et al. (14) has not yet been made. It is necessary to understand the particle size effects in PAS if the promise of PAS for IR spectroscopy of powders is to be realized. In this paper, we report results of a detailed study on the PAS of silica powders for the particle size range of 0.05-260 um and compare the results with theory (14). We have also investigated the frequency dependence of the variousIR modes in these powders and show that the saturation phenomenon affects at least some of the observations. Some observations on the effects of pellet vs powder background are also reported (22-24). Details of these findings are presented and discussed in this paper."

Jan 1, 1990

By M. A. Cook

Sutherland used an ion-pair adsorption model to derive the author's hy-drolytic pee-acid) adsorption equation for the contact bubble curves of Wark and Cox. To do so it was necessary to postulate that the sum of coverages of surface anion sites by the collector and depressant anions is practically unity. It is here shown that the free energy of Sutherland's postulated collector ion (x-)-depressant ion (OH-) exchange reaction (for no other than the OH- to compete with X-), namely EX + (OH-) Z SOH- + X-, is in some cases positive and X- should not even adsorb. Also, in many cases the (OH-) adsorption must be quite negligible even though the collector covers only about a sixth of the mineral surface at the threshold of air bubble contact. This, however, contradicts the postulate that permits one to derive the correct bubble contact eqwztion for the ion-pair model. Furthermore, the requirement for charge neutrality leads in the ion-pair model to the (impossible) constancy of the ratio @+)/(OH-) along a contact bubble curve in which pH may change by more than seven units. HYDROLYTIC ADSORPTION EQUATION Hydrolytic (free-acid or free-base) and ion-pair (H', X-, or R', OH-) adsorption models of the collector in metal sulfide and similar flotation systems are superficially alike and somewhat difficult to differentiate. This is because they yield, under seemingly valid assumptions, equivalent forms of the equations describing the distribution of the collector between the aqueous solution and the mineral surface. This has been discussed by the author and associates1-4 and more recently by Sutherland,' both for simple collector-mineral and for more complicated collector-depressant-mineral systems. In the hydrolytic adsorption model the equations describing the contact bubble curves of Wark and coxeJ7 are as follows :2 Here X is the collector anion, D- the depressant anion, 9, and On are the fractions of the free-acid sites S on the surface of the mineral covered by collector and depressant free acids, respectively, and @ is the fraction of uncovered sites. Kx is the free-acid collector dissociation equilibrium con- stant, K1 that for the free-acid collector adsorption, KD that for the free-acid depressant dissociation, and K2 the equilibrium constant for the free-acid depressant adsorption. Eqs. 1 to 5 yield upon simultaneous solution the result is the critical free-acid concentration for bubble contact in the absence of depressant-free acid. Eq. 8 expresses the conditions along a simple collector-mineral contact bubble curve for the case HD = 0, or V = 0. Last and Cook showed that Eq. 6 applies generally and with good accuracy in the collector-depressant-metal sulfide mineral systems. Inci-dentally, it has been shown by infrared absorption studies that in some cases the free-acid adsorption process splits out water.' In this case, Eq. 2 might be written SHOH + HX Z SHX + H20, with a similar equation replacing Eq. 4 for depressant-free acid-water exchange. This possibility does not change, however, the basic equations or considerations of the hydrolytic adsorption model. Indeed, this type of free acid-water exchange reaction was predicted for fluorite and iron ore flotation by oleic acid in the dry grinding and boiling processes.410

Jan 1, 1961

By J. E. Hanlon, S. R. Butler, R. J. Wasilewski

It is known that stoichiometric NiTi transforms to a structure of lower symmetry near room temperature. The present investigation deals primarily with the changes in the electrical and magnetic properties which occur at the transformation. The effects of composition and various heat treatments on electrical properties are also discussed. In recent investigations by Purdy and Parr,' Wang et a1.,2 Dautovich and Purdy,~ Dautovich et a1.,4 and the authors, ~,' NiTi has been observed to undergo a martensitic phase transformation from the ordered CsCl (B2) structure to one of lower symmetry. The crystal structure of the low-temperature modification is still not completely worked out. This transformation occurs near room temperature for the stoichiometric composition. The thermodynamic, elastic, crystallographic, and microstructural characteristics of this transformation for some compositions have been previously reported.'-= In the present investigation, the changes in the electrical transport properties and magnetic susceptibility of NiTi when it undergoes the martensitic phase transformation have been measured. The approximate composition range covered is 48 to 52 pct Ti.* *All compositions are given in atomic percent._____________________ EXPERIMENTAL PROCEDURES AND RESULTS 1) Sample Preparation. The NiTi alloys were prepared from iodide titanium (>99.92 pct Ti) and vacuum-premelted carbonyl nickel (>99.95 pct Ni) by repeated arc melting under gettered argon and casting in a water-cooled copper mold. After the cast buttons were hot-forged at 800" to 950°C, the oxidized surface was removed by grinding and etching. Samples were cut from the worked polycrystalline buttons. After fabrication, the samples were annealed 1 hr at 900°C and water-quenched. The composition of the alloys was assumed to be the same as in the initial feed. This assumption was supported by material balance checks on 100-g arc-melted buttons which demonstrated quantitative recovery to within k0.02 pct. The oxygen content of the alloys was '150 ppma (weight) and the carbon content was 30 to 50 ppm. 2) Electrical Resistivity and Hall Effect. The electrical resistivity was measured over the composition range 48 to 52 pct Ti for temperatures varying from 4.2"K to 900°C. The high-temperature and many of the low-temperature experiments were carried out using conventional 4-probe dc techniques.7 The Hall coefficient and ac resistivity were measured at 20 cps using the apparatus shown schematically in Fig. 1. The equipment is basically an ac potentiometer: The resistive or Hall voltage of the sample is balanced by a comparison voltage provided by a dividing network across a standard series resistance. The off-balance signal is amplified by a Tektronix 122 amplifier and detected by a Princeton Applied Research (PAR) phase-sensitive detector. The precision of the resistivity and Hall coefficient measurements is i0.1 and i3 pct, respectively. The uncertainty in the data is increased by i2 pct from the precision limits because of uncertainty in dimensions and possible end effects. The temperature dependence of the electrical resistivity and Hall effect for a stoichiometric (50.0 pct Ti) NiTi sample are illustrated in Fig. 2. Above 75"C, this sample has essentially the B2 structure, while below about 0°C it is completely in the low-tempera-

Jan 1, 1968

By Paul Worsey, Dave McCool, Ryan Freeman, Chris Wolters, Rick Hines, John Bowles

Carroll Cave, located in Camden County, in south central Missouri, is one of the most significant caves in Missouri with over 12 miles of mapped passages and over 100 known but unmapped side passages. In the early 1990’s there was a breakdown of the originally excellent landowner/caver relations as the ownership of the only known entrance moved to a new generation and grottos squabbled for control. Subsequently the current owner of the natural cave entrance refused to grant anyone permission to enter.

Jan 1, 2003

By Charles W. Chesterman

Perlite is a glassy volcanic rock which will, upon rapid controlled heating, expand or "pop" into a frothy material of low bulk density, valued as a lightweight aggregate. The term perlite also is applied to the expanded product. The chemical composition of perlite ranges from that of rhyolite to that of andesite; the water content ranges from 2 to 5%. Most perlite is pale gray, but some is black, brown, or even green. Inclusions in perlite are common and include phenocrysts of quartz, feldspar, biotite, and hornblende, and miscellaneous rock fragments. Occurrences of perlite are restricted to areas of Tertiary and Quaternary volcanic rocks. Perlite occurs as flows associated with thick accumulations of pyroclastic debris and other flow rocks, as dikes, sills, domes, and as selvages of intrusive bodies of volcanic rock. Individual flows of perlite range in thickness from a few feet to as much as 100 ft and commonly cover several square miles. Dikes and sills of perlite generally are small, but domes generally are substantial in size and may be as much as several miles in diameter. Most perlite deposits are large enough and topographically situated so as to lend themselves to low-cost open pit mining methods. Conventional equipment is employed in the mining of perlite. Although milling procedures may appear to be simple, care is exercised in order to produce a carefully sized product and to minimize the production of excessive quantities of fine materials, which have limited use and are considered as waste. Perlite is processed, or "popped," in one of two basic types of furnaces: horizontal rotary or vertical stationary. Both types of furnaces include product collection and dust control systems. Many commercial deposits of perlite are known to occur throughout the world, and although no exact estimate of reserves is available, there appears to be an adequate supply to meet current and future worldwide requirements. End Uses The uses of expanded perlite are many and varied and are based primarily upon its physical and chemical properties. Because of its (1) low bulk density, which generally ranges between 2 and 20 lb per cu ft; (2) low thermal conductivity "K" factor (Btu per hr per sq ft per OF per in, of thickness), which ranges between 0.267 for loosely packed perlite (bulk density of 4.48 lb per cu ft) to 1.25 for perlite gypsum plaster; (3) high resistance to fire; and (4) low sound transmission, expanded perlite is used to a great advantage as aggregate and insulating material in the construction industry. Early uses of perlite were related exclusively to the construction industry, which now consumes about 60% of the domestic production. The primary use of perlite now is as aggregate in insulation boards. Other uses of perlite in 1971 were as aggregate for plaster, horticultural aggregate, low-temperature insulation (cryogenics), and concrete. Because of its low thermal conductivity ("K" factor), high adsorption of sound, low bulk density, and fire resistance, perlite aggregate plasters hold many advantages over conventional plaster. Perlite aggregate plaster lends itself to machine applications, dries quickly, and has relatively high elasticity which reduces cracking after drying. These same features make perlite useful as aggregate in portland cement concrete and asphalt concrete for construction wherever weight reduction, insulation, and acoustics are of prime importance. Perlite-portland cement concrete offers up to 20 times more thermal insulation than conventional concrete, and because of this it finds wide application in roof decks and floor fill in multistory buildings, in

Jan 1, 1975

Bacteria can play a key role in the processing of 'difficult' ores. Bioleaching opens the way to potentially extract copper from vast amounts of otherwise hard to process refractory low-grade chalcopyrite. In my talk I will outline our research philosophy to develop bioleaching as a Precision Processing unit process step. In our view, Precision Processing is a sophisticated approach to mineral processing where the ultimate goal is to measure and characterise the ore body in-ground and in real time during mining, allowing the down-stream unit processes (bioleaching, in this case) to be continuously tailored and tuned via feedback and feed-forward controls to obtain the highest possible recoveries at the lowest possible cost and environmental impact. I will describe some of the work that we are undertaking to better understand the interfacial phenomena underlying the fundamental bioleaching process with the aim of coming to a Precision Processing approach. We use techniques such as interfacial electrochemistry (scanning electrochemical microscopy, SECM), AFM, zeta potential measurement, and synchrotron science to elucidate the parameters that drive bacterial selectivity and adhesion, bacterial metabolism, and dissolution and precipitation processes for model systems and real chalcopyrite ores. As examples of our research, I will discuss in some detail our method to produce and characterise micro-patterned CuxS - silica thin films as model substrates for electrochemical and bacterial adhesion work and our approach to the interfacial chemical characterisation of extracellular polymeric substances of bio-active bacterial cells. I will also cover some of our recent findings relating to measurement and interpretation of bacterial adhesion on sulfidic substrates and its implications for bacterial adhesion and substrate selectivity. After having identified and discussed crucial leaching parameters, such as pH, Eh, T, [Cu2+], and [O2], the talk will go on addressing some of the early achievements and challenges encountered in our work to design and prepare low-cost, rugged sensing devices that allow the in-situ (in this case, in-dump or in-heap) localised measurement of these parameters. I will conclude my talk by painting the picture of how the work of our group might contribute to realising the dream of transforming bioleaching into genuine high-tech Precision Processing of minerals. This is an ABSTRACT ONLY. A full-length paper was not prepared for this presentation.

Sep 13, 2010

Man’s search beneath the earth for minerals has always required light, and the devices used to provide illumination have been both innovative and unusual —from stone vessels holding fat and a wick of grass or fiber to a shower of sparks produced by a thin steel disc. While the date when lamps were first used in mines is unknown, Greek and Roman records from 3000 BC definitely mention their use in underground mines. Early Remans most likely used a lamp similar to the one depicted at right. Over the ages, various types of devicives and methods of illumination have been tried and used. One interesting scheme for underground light was to reflect sunlight down the shaft and along drifts using mirrors or other reflective materials. Bunches of resinous wood were also used for underground lighting in many parts of England. In the mid-18th century, the speding mill was developed in England. It worked by rapidly turning a thin steel disc against a flint, causing a shower of sparks to appear. The light produced was uncertain, highly variable, and unsafe in gaseous environments. In Europe, an open pan-type hanging oil lamp was developed and used in some operations in the 1700s. This type of lamp had one opening for a wick and a second opening for refilling the oil reservoir. The lamps were embellished with goad luck charms – a good luck rooster was used in many parts of Europe while a frog and “gluck-auf” were used in Germany. These lamps were introduced in Mexican mines, and a few have found their way into the southwest US. By 1850, a small wick lamp known as the lard-oil lamp, which resembled a tea pot, was invented in Scotland. These lamps were fueled with grease from a packing house –lard, bacon grease, or tallow. Whale oil was also used. Many improvements were made on these lamps, such as the use of windshields and the attachment of miners’ candle-holdm to support the lamp. While these lamps were handy and inexpensive to operate, they were dangerous because their large flame could ignite support timbers or other flammable materials. Miners from the United Kingdom brought this type of lamp into the US. Domestic producers of oil wick lamps were primarily located in Hazleton, PA; What Cheer, IA; Pittsburgh, PA; and Frostburg, IN. The first patent for an oil wick lamp was granted to W. Seybold of McKeesport, PA. Incidentally, these lamps were advertised in a 1903 Sears-Roebuck catalog for 10 cents apiece. Oil wick

Jan 7, 1980

For years traditional optical microscopic techniques have been used successfully to carry out mineralogical studies on processing products. Essential information could be obtained by supplementing microscopic data with X-ray powder diffraction data, chemical analyses, etc. However, most of the time the mineralogists working on plant related issues, would supply qualitative information to the metallurgists, due to quantification not being possible in the available time. Since the late-80s, the use of semi-automated to automated techniques for mineral quantification has impacted positively on the use of mineralogy for optimising processing plants. Rustenburg Platinum Mines (now Anglo Platinum) were the first mining company to purchase a Qem*Sem in 1987. With the success achieved in quantifying the minerals in the concentrator streams of the Rustenburg Platinum operations, a second instrument was purchased soon after. These instruments have proven invaluable tools in understanding the flotation behaviour of the sulfide and gangue minerals in the various reefs of the Bushveld. Restrictions in the resolution of these earlier instruments, as well as the time involved in searching for and correctly identifying the fine-grained platinum-group minerals (PGM), meant that these investigations focused on the deportment of the more abundant base metal sulfides, rather than on the actual PGM. The Mineral Liberation Analyser (MLA), which became available in the late 1990s, was well suited to detect and analyse minerals occurring in trace amounts such as the PGM. Anglo Platinum was the first mining company to purchase such an instrument and now has fourteen systems operating at the AR Crown Mines site. One of the applications of these systems involves the study of feeds, concentrates and tailings from the various concentrators on a monthly basis. These routine investigations provide information on a variety of mineralogical parameters, including liberation, association, and grain size. Results are used to emphasise areas for improvement, and specifically underline those areas where improvements will have the most impact on recovery. After new or different technologies have been implemented, mineralogical characterisation of the different process streams is an essential component in the assessment of the impact of these changes on flotation performance. In addition, the knowledge is databased for future reference to draw trends across the various concentrators around the Bushveld complex, and is also used for comparative studies when plants experience high losses to tailings. Due to the success of these investigations the question was posed whether it was possible to obtain data on a daily basis, as compositing samples could hide the impact of daily events. Although the instruments currently used are suitable for a research environment, these are not ideal for mine-site implementation. For that reason Anglo Platinum, together with FEI embarked on a development program to develop a system that can be implemented on-site to measure the important mineralogical characteristics on a daily basis. Important requirements for such a system include time-to-data, ease of use and regular quality control. Highlighting some results from concentrator studies, the presentation will review the progress on the development of automated mineralogical techniques for fast, automated mineral measurements. This is an abstract only. No full paper was prepared for this abstract.

Sep 13, 2010

By Clarence A. Wright

The Missouri-Kansas-Oklahoma lead and zinc district, better known as the Joplin district, includes the mines in southwest Missouri and in those parts of Kansas and Oklahoma that are directly adjacent. (See PI. I.) This report of investigations carried on by the Bureau of Mines gives the methods used in mining and milling and indicates in some detail the conditions that affect the efficiency of those methods; it does not attempt to discuss the geology of the district, except incidentally, as this has been described in numerous reports by several geologists. Some of the more important recent publications are those of the United States Geological Survey by Smith and Siebenthal, a Bain, b and also those of the Missouri State geological survey by Buckley and Buehler." Other reports are those by Schmidt and Leonard," and Winslow,e of the Missouri geological survey, by Haworth and Crane,! of the Kansas geological survey, and by Jenney.g Although the lead and zinc ores are closely associated, the proportion of zinc ore mined at present is far greater than in former years. For this reason and because the losses in milling zinc ores are proportionately greater than in milling those of lead, the zinc ores are here given most consideration. Only the mines and mills actually examined and tested are discussed in detail, statements of results being restricted to the mines in general, with no special reference to anyone mine. Several mill tests were made to determine in a general way the efficiency of the milling practice in this district and to discover at what stage of the process the losses were greatest. Making these mill tests proved difficult,for, because of the arrangement of the mills and the necessity of estimating the tonnage treated, systematic mill testing and sampling can be done at only a few plants. Many tables giving results of mill tests and screen tests have been omitted because they would serve only to emphasize the important points shown by other data given. The writer has tried to bring out the possibilities of making certain improvements that would effect a greater saving, and has endeavored to avoid the use of technical terms and phrases in order that all statements may be clear and easily understood.

Jan 1, 1918