Influence of frothers on floatability. I. Flotation of single minerals (quartz and synthetic chalcocite)

The flotation and sorption properties of chalcocite and quartz in potassium ethyl xanthate (EtXK), frothers (α-terpineol and n-amyl alcohol), and (xanthate + frother) mixed solutions were investigated. Surface tension and frothing properties of the solutions were also measured.Floatability and sorption properties of the minerals investigated strongly depended on any controlled or uncontrolled change occurring at the mineral surface. Surface oxidation of chalcocite was shown to be an especially important parameter.The frothers studied showed some collecting properties in respect to chalcocite and quartz and influenced the xanthate sorption on chalcocite.Comparison of the flotation recoveries in frother solutions respectively with and without xanthate indicated an occurrence of noticeable collector-frother interactions during formation of the bubble/chalcocite grain aggregate. No such interactions were found for quartz.Influence of the frothers on floatability of the minerals was observed at different frother concentrations but at close values of surface pressure (π) and of retention time (rt).     

The influence of surface oxidation of chalcocite on its floatability and ethyl xanthate sorption

The results obtained from measurements of potassium ethyl xanthate (EtXK) sorption by synthetic chalcocite (Cu₂S) and the results of chalcocite floatability measurements are presented.Five chalcocite samples, denoted as Cu₂S A, B, C, D and E, were used for the measurements. Chalcocite samples of 60–75 μm were prepared in the same manner but were kept under conditions which differed in their degree to prevent surface oxidation by atmospheric oxygen.Chalcocite surface oxidation has a strong effect both on xanthate sorption and on chalcocite floatability. The maximal amount of xanthate abstracted (Q_max) by chalcocite samples from deoxygenated solutions after a long sorption period increases with increasing oxidation of the samples. The Q_max values give information concerning the total amount of surface oxidation products.Chalcocite decreases its floatability with increasing surface oxidation. Most oxidized chalcocite samples required an about 100 times greater collector consumption to obtain the same flotation results than the least-oxidized samples studied.     

Effect of frothers on bubble size

The size of bubbles in flotation cells was measured using the UCT bubble size meter and the HUT bubble size analyser. While both methods provided similar critical coalescence concentration (CCC) values for the three tested frothers, they also revealed important differences. Using the HUT bubble size analyser, which does not impose any lower bubble size limit, it was possible to find differences in bubble size measured for three frothers at concentrations exceeding the corresponding CCC values.Frothers affect both the break-up phenomena in the impeller/stator zone in flotation cell, and bubble coalescence. While longer chain polyglycols (e.g. DF-1012) are able to produce larger stable bubbles than the short chain DF-250 and DF-200 polyglycols, the CCC values for DF-1012 are lower than those for DF-250 and DF-200.     

Surface complexation modeling of Co(II) adsorption on mixtures of hydrous ferric oxide, quartz and kaolinite

Co sorption was measured as a function of pH, ionic strength (0.001-0.1 M NaNO₃) and sorbate/sorbent ratio on pure quartz, HFO and kaolinite and on binary and ternary mixtures of the three solids. Sorption data measured for the pure solids were used to derive internally-consistent diffuse layer surface complexation model (DLM) stability constants for Co sorption. Co sorption on HFO could be adequately modeled over a broad range of ionic strengths and sorbate/sorbent ratios with a two variable-charge site model. Fits based on a single variable-charge site model were reasonable, but were improved by using ionic-strength dependent stability constants. A single variable-charge site model with an additional permanent ion exchange site produced the best fit to Co edges measured on kaolinite over a range of ionic strength and sorbate/sorbent ratios. These DLM fits were also improved by using ionic-strength dependent stability constants. The DLM approach could not adequately describe the slope of Co sorption edges on quartz. This study demonstrates that for accurate prediction of Co sorption over wide ranges of ionic strength and sorbate/sorbent ratio, the DLM may require ionic-strength dependent stability constants. DLM stability constants for Co sorption derived for the pure solids were used to predict sorption as a function of pH and solid concentration on binary and ternary mixtures of the three solids. Discrepancies between predictions and measurements were quantitatively similar to those observed for the pure mineral systems. Thus, a simple component additivity approach provides useful predictions of metal sorption in the mixed solid systems.     

Radiation-induced defects in quartz. II. Single-crystal W-band EPR study of a natural citrine quartz

Single-crystal electron paramagnetic resonance (EPR) spectra of a natural citrine quartz without any artificial irradiation, measured at W-band frequencies (∼94 GHz) and temperatures of 77, 110 and 298 K, allow better characterization of three previously-reported Centers (#6, #7 and B) and discovery of three new defects (B′, C′ and G′). The W-band EPR spectra reveal that Centers #6 and #7 do not reside on twofold symmetry axes, contrary to results from a previous X-band EPR study. The W-band spectra also show that the previously reported Center B is a mixture of two defects (B and B′) with similar g matrices but different-sized ²⁷Al hyperfine structures. Center C′ has similar principal g values to the previously reported Center C but is distinct from the latter by a larger ²⁷Al hyperfine structure with splittings from 0.10 to 0.22 mT. Also, Center G′ has a similar g matrix to the previously reported Center G but a different ²⁷Al hyperfine structure with splittings from 0.41 to 0.53 mT. These spin-Hamiltonian parameters, together with observed thermal properties and microwave-power dependence, suggest that Centers #6 and #7 probably represent O₂³⁻ type defects. Centers B and B′ are probably superoxide radicals (O₂⁻) with the unpaired spin localized on the same pair of oxygen atoms around a missing Si atom but linked to a substitutional Al³⁺ ion each at different neighboring tetrahedral sites. Similarly, Centers G and G′ are most likely superoxide radicals with the unpaired spin localized on another pair of oxygen atoms around a missing Si atom and linked to a substitutional Al³⁺ ion each at different neighboring tetrahedral sites. Center C′ is probably an ozonide radical associated with a missing Si atom and linked to a substitutional Al³⁺ ion at the neighboring tetrahedral site. This study exemplifies the value of  high-frequency EPR for discrimination of  similar defect centers and determination of  small local structural distortions that are often difficult to resolve in conventional  X- and Q-band EPR studies.     

Synthetic fluid inclusions in natural quartz. II. Application to PVT studies

Synthetic fluid inclusions have been used to determine volumetric properties of H₂O and a 20 wt.% KCl solution from 300–700°C and 1–3 kb. Comparison of results obtained for H₂O with previously published data indicates that the synthetic fluid inclusion technique provides PVT data that are within a few percent of those obtained from conventional PVT studies. This technique thus provides a fast, relatively simple means of determining PVT properties of many fluids of geologic interest.     

The surface chemistry and flotation of scheelite,II. Flotation “collectors”

The mechanism of flotation of calcium tungstate with non-complexing ionic surfactants has been examined. With fatty-acids, precipitation of the calcium soap sets in at very low concentrations. None of the conventional reagents alone provides sufficient selectivity to permit separation of scheelite from calcite.As an example of a possible chelating collector for tungstate minerals, 4-tertiary butyl catechol (4 TBC) was examined. Although such reagents are, indeed, adsorbed and induce floatability, they are useless as collectors, for several reasons. For example, 4TBC was found (unexpectedly) to be more strongly adsorbed by calcite than by scheelite; furthermore, soluble tungsten complexes were also formed.     

Oxidation-Reduction effects in the flotation of chalcocite and cuprite

A laboratory study of the batch flotation of chalcocite from chalcocite-quartz mixtures and of cuprite from cuprite-quartz mixtures with potassium ethyl xanthate as collector has shown that the oxidation-reduction state of the flotation pulp can have a pronounced influence on mineral floatabilities. At pH 11 chalcocite floated over a relatively narrow Eh range of about 300 mV; pH had no influence on the potential of the lower flotation boundary in reducing conditions but had a significant effect on the potential of the upper boundary in oxidizing conditions. Below this upper limit, the floatability was reversible with respect to Eh. Provided the Eh was in correct region chalcocite could be floated in the absence of measurable concentrations of dissolved oxygen.Cuprite displayed a high level of floatability with ethyl xanthate for which, by contrast with chalcocite, no flotation limit in reducing conditions was found; over a small range of potentials close to zero, its behaviour was strongly pH dependent.An attempt to account for the floatabilities of chalcocite and cuprite in terms of the formation of cuprous ethyl xanthate on their surfaces did not lead to correlations with the observed behaviour in reducing conditions but provided a rough correlation with the upper flotation potential limit. It is believed that more detailed and properly controlled comparative flotation studies of the chalcocite-xanthate and cuprite-xanthate systems could help to resolve some of the uncertainties associated with the effects of Eh, pH and oxygen concentration in sulphide mineral flotation.     

Selective flocculation of cassiterite in mixtures with quartz using a modified polyacrylamide flocculant

Polyacrylamide was modified to give a linear polymer containing 69% amide, 23% carboxylic and 8% hydroxamic acid groups. The modified polymer selectively flocculates cassiterite from mixtures with quartz in aqueous suspensions at a pH between 3.5 and 7.     

Effect of alcohol and polyglycol ether frothers on foam stability,bubble size and coal flotation

The frothers of alcohol family (MIBC and Alpha-terpineol) were compared with polyglycol ethers (DF-1012) in terms of two phase characterization parameters like foamability, foam stability, surface activity and bubble size distribution. In this research, fundamental two phase frother characterization parameters were linked with three phase coal flotation behavior.     

Modification of fluid inclusions in quartz by deviatoric stress. III: Influence of principal stresses on inclusion density and orientation

Extraction of useful geochemical, petrologic and structural information from deformed fluid inclusions is still a challenge in rocks displaying moderate plastic strain. In order to better understand the inclusion modifications induced by deviatoric stresses, six deformation experiments were performed with a Griggs piston-cylinder apparatus. Natural NaCl–H₂O inclusions in an oriented quartz crystal were subjected to differential stresses of 250–470 MPa at 700–900 °C and at 700–1,000 MPa confining pressure. Independently of the strain rate and of the crystallographic orientation of the quartz, the inclusions became dismembered and flattened within a crystallographic cleavage plane subperpendicular to σ ₁. The neonate (newly formed) inclusions that result from dismemberment have densities that tend towards equilibrium with P _fluid = σ ₁ at T _shearing. These results permit ambiguities in earlier deformation experiments on CO₂–H₂O–NaCl to be resolved. The results of the two studies converge, indicating that density changes in neonate inclusions are promoted by high differential stresses, long periods at high P and high T, and fluid compositions that maximize quartz solubility. Neonates spawned from large precursor inclusions show greater changes in density that those spawned from small precursors. These findings support the proposal that deformed fluid inclusions can serve as monitors of both the orientation and magnitude of deviatoric stresses during low-strain, ductile deformation of quartz-bearing rocks.     

掺砂率对膨润土与砂混合物膨胀特性的影响

膨润土与砂混合物的膨胀特性是评估核废料深层地质处置工程长期性能的重要指标。对比不同膨润土及其与砂混合物的膨胀试验结果可知,对纯膨润土及其低掺砂率混合物,浸水膨胀完成后蒙脱石孔隙比em与竖向应力?v在双对数坐标内呈惟一的线性关系,利用该线性关系可预测浸水完成后不同竖向应力下的体积变化量及不同初始状态对应的膨胀力;对高掺砂率混合物,在砂骨架形成之前,em-?v线性关系成立,随着竖向应力的增大,砂骨架形成,对应的em值脱离em-?v线性关系,混合物中掺砂率越大,脱离该线性关系时的竖向应力就越小。砂骨架形成前,砂颗粒被蒙脱石包围,外力由蒙脱石承担,最终变形量由试样中单位体积蒙脱石的含量决定;砂骨架形成后,竖向应力最终由砂骨架和蒙脱石共同承担。利用砂骨架孔隙比的概念可确定各种不同掺砂率混合物形成砂骨架时的应力起偏点。同时,还可确定混合物能够形成砂骨架的掺砂率范围。     

不同成因类型石英与石英玻璃气泡缺陷间关系探讨

对不同成因类型石英的气液包体含量与石英玻璃气泡缺陷间的关系进行了对比研究，总结了一些规律，对石英玻璃工业原料的地质找矿具有一定的指导意义。     

Flotation of galena. Influence of grain size,of pulp deoxygenation,and of cleaning with ammonium acetate

The flotation of < 10, 10–20, and 20–40 μm galena fractions was studied. For uncleaned galena a given collector coverage produced better floatability with increasing grain size. Nitrogen had a detrimental effect only for the < 10 μm fraction, producing at a given collector coverage a recovery smaller than that obtained with air.Galena cleaned with 400 g/l ammonium acetate had very poor floatability, although xanthate abstraction was fairly high; this confirms that strong xanthate adsorption is necessary for flotation. Formation of monothiocarbonate was small in all cases, which points to a very minor influence, if any, of this compound in the flotation process.In blank flotation tests, or for very low residual xanthate concentrations, a peak at 208 nm and a shoulder at 255 nm were observed. The former was assigned to the uncomplexed Pb²⁺ ion, and the latter was tentatively attributed to the PbOH⁺ ion.Lead in solution results from dissolution of the oxidation products of galena, as galena itself has an exceedingly low solubility. The curve for total lead in solution vs. initial xanthate concentration, had a minimum for an initial xanthate concentration of 10^?5M, the further increase in dissolved lead is attributed to formation of complexes such as PbX⁺ (X = xanthate). Dissolved lead concentrations were nearly as high for cleaned as for uncleaned galena, which indicates a high oxidation rate of the mineral.     

LNAPL污染物及水含量对石英砂介电常数的影响

为研究LNAPL污染物及水含量对石英砂介电常数的影响,首先以石英砂模拟单一土壤环境,利用柴油和水的混合物来模拟轻非水相液体(LNAPL)污染物污染土壤,然后通过矢量网络分析仪和开口同轴探头,分析高频超宽带电磁波在土壤中的反射并计算介电常数。实验结果显示,石英砂介电常数随着体积含水量和含油量的增加而增加,直到达到饱和状态,此时石英砂介电常数趋于稳定;石英砂介电常数实测值处于极化模型和De Loor模型之间,结果与De Loor模型接近。     

Thermoluminescence spectra of igneous quartz and hydrothermal vein quartz

Variations in thermoluminescence spectra are reported for four types of geological quartz examined with a new spectrometer featuring dual imaging photon detectors that separately and simultaneously detect (1) uv-blue (200–450 nm) and (2) blue to near infrared (400–800 nm) emission. Samples show striking differences which appear to be characteristic of their geological origin. Volcanic quartz phenocrysts from acid volcanics show red thermoluminescence (TL) emission bands centered at 620–630 nm that are 100 times more intense than similar bands in other quartz, while a violet emission at 420–435 nm was observed exclusively in igneous quartz (volcanic and granitic). A broad emission band centered at 560–580 nm was observed only in quartz formed hydrothermally. Massive quartz from Li-rich pegmatite bodies shows narrow, intense 470 nm emission bands at 230° C apparently related to Al and to Ge defects detected with electron paramagnetic resonance (EPR), and emission bands at 330 and 280 nm, possibly related to recombination at oxygen vacancies. The common 380 nm emission band of quartz was observed in both volcanic and granitic quartz, but was not detected in either the pegmatitic or the hydrothermal vein quartz. Observed spectral variation is identified as a potential source of error in luminescence dating.     

Electrochemical reaction control of contact angles on copper and synthetic chalcocite in aqueous potassium diethyldithiophosphate solutions

The contact angles on synthetic chalcocite in potassium diethyldithiophosphate (KDTP) solutions have been compared with those on copper to delineate physico-chemical factors which might contribute to the flotation response of copper sulfides. The influence of a number of variables such as KDTP concentration, solution pH, gaseous environment and electrochemical pretreatment has been investigated. The results are discussed in terms of the thermodynamic and kinetic aspects of the system.     

Perturbation theory based equation of state for polar molecular fluids: II. Fluid mixtures

The equation of state (EOS) for 98 pure organic and inorganic fluids formulated by Churakov and Gottschalk (2003) is extended to complex fluid mixtures. For the calculation of the thermodynamic properties of mixtures, theoretical combining rules from statistical mechanics are used. These mixing rules do not involve any empirical parameters. The properties of the fluid mixtures are directly derived from those of the pure constituents. As an example we show that the EOS describes accurately the thermodynamic relations in the H₂O-CO₂ binary at high pressures and temperatures. At subcritical conditions the EOS is able to reproduce accurately the phase relations within mixtures of non-polar fluids. In particular the EOS predicts phase separations within various fluid mixtures of polar and non-polar molecules.     

Modification of fluid inclusions in quartz by deviatoric stress. II: experimentally induced changes in inclusion volume and composition

Fluid inclusions in quartz are known to modify their densities during shear deformation. Modifications of chemical composition are also suspected. However, such changes have not been experimentally demonstrated, their mechanisms remain unexplained, and no criteria are available to assess whether deformed inclusions preserve information on paleofluid properties. To address these issues, quartz crystals containing natural CO₂–H₂O–NaCl fluid inclusions have been experimentally subjected to compressive deviatoric stresses of 90–250 MPa at 700°C and ~600 MPa confining pressure. The resulting microcracking of the inclusions leads to expansion by up to 20%, producing low fluid densities that bear no relation to physical conditions outside the sample. Nevertheless, the chemical composition of the precursor inclusions is preserved. With time the microcracks heal and form swarms of tiny satellite inclusions with a wide range of densities, the highest reflecting the value of the maximum principle stress, σ ₁. These new inclusions lose H₂O via diffusion, thereby passively increasing their salt and gas contents, and triggering plastic deformation of the surrounding quartz via H₂O-weakening. Using microstructural criteria to identify the characteristic types of modified inclusions, both the pre-deformation fluid composition and syn-deformation maximum stress on the host mineral can be derived from microthermometric analysis and thermodynamic modelling.