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1.
高岭石表面的酸碱性质   总被引:5,自引:0,他引:5  
魏俊峰  吴大清 《矿物学报》2002,22(3):207-210
采用双位模式(即假定高岭石表面存在>AIOH和>SiOH基团)拟合高岭石表面的酸碱滴定数据并描述表面上发生的质子化反应,Al位和Si位的表观常数拟合值分别为pKal,Al=1.78、pKa2,Al=8.47和pKa2,Si=5.12,它们的酸性比对应的(氢)氧化物表面位的更强。高岭石的总表面位密度远大于氧化铝和二氧化硅,其原因很可能是溶液中的质子或羟离子能够渗入高岭石的层间,与层间的羟基发生反应。此外,Al位密度也比Si位大近一个数量级,这种与理论化学式偏离的现象可受多种因素的影响。高岭石表面总体在pH低于4.0时带正电荷,在pH高于4.0时带负电荷。正电荷仅由>AlOH基团通过质子化作用形成>AlOH2^ 表面化合态来提供,而负电荷则由>AlOH和>SiOH基团的去质子化作用产生,分别形成>AlO^-和>SiO^-表面化合态。  相似文献   

2.
Al hydroxide was prepared by hydrolysis of Al(NO3)3, and oc-B-Al hydroxide was prepared by hydrolysis of Al(NO3)3 in the presence of boric acid solution. Curve-fitted B1s XPS spectrum of oc-B-Al hydroxide demonstrated that the boron atom was probably incorporated with Al hydroxide to some extent. The IR band of Al–OH at 1,074 cm?1 of oc-B-Al hydroxide was weaker than that of Al hydroxide. This indicated some surface hydroxyl groups of Al–OH of oc-B-Al hydroxide had disappeared. These peaks at 1,320 and 1,458 cm?1 bands found in the oc-B-Al hydroxide were closer together than the salts containing boron, which are attributed to an interaction of aluminum hydroxide with boron. Analysis of XRD patterns indicated that Al hydroxide was very poorly crystalline boehmite, and oc-B-Al hydroxide appeared to have crystallite dimensions slightly smaller than those present in Al hydroxide. TEM showed that the presence of boron significantly decreased the size of Al hydroxide particles. The specific surface area of oc-B-Al hydroxide (556.0 m2 g?1) using BET method was larger than that of Al hydroxide (421.6 m2 g?1). This indicated the likelihood of Mn2+ adsorption ability of oc-B-Al hydroxide than the Al hydroxide. Boron-doped Al hydroxide always adsorbed more Mn2+, stabilized the sample solution pH to a higher value and slowed soil acidification than the Al hydroxide. It is suggested that boron in soils not only serves as a plant nutrient, but can also decrease the Mn2+ toxicity and slows soil acidification by formation of oc-B-Al hydroxide.  相似文献   

3.
固体酸是70年代末发展起来的一类新型的催化材料,对有机反应具有较强的催化活性,且副反应少,产物易分离,污染少[1]。粘土固体酸是以蒙脱石类粘土为基质材料,通过采用不同的物理或化学方法在不同的条件下调控层间域而制备的,其催化活性和选择性与其表面酸的类型、浓度及强度等有关[2],为此我们采用离子交换法,以不同类型的阳离子为取代剂,在不同条件下取代交换进入蒙脱石层间,研究制备方法及条件对表面酸性的影响,并考察了催化性能。1 实验部分1-1 原料与试剂钠基膨润土(浙江临安产,主要成分为蒙脱石,用沉降法提…  相似文献   

4.
Lead sorption efficiencies of natural and synthetic Mn and Fe-oxides   总被引:1,自引:0,他引:1  
Lead sorption efficiencies (sorption per specific surface area) were measured for a number of natural and synthetic Mn and Fe-oxides using a flow-through reactor. The Mn-oxide phases examined included synthetic birnessite, natural and synthetic cryptomelane, and natural and synthetic pyrolusite; the Fe-oxides studied were synthetic akaganéite, synthetic ferrihydrite, natural and synthetic goethite, and natural and synthetic hematite. The sorption flow study experiments were conducted with 10 ppm Pb with an ionic strength of either 0.01 M NaNO3 or 0.01 M KNO3, both at pH 5.5. The experimental effluent solution was analyzed using aqueous spectroscopic methods and the reacted solids were analyzed using microscopy (field emission scanning electron microscopy, FE-SEM), structure analysis (powder X-ray diffraction, XRD), bulk chemical spectroscopy (energy dispersive spectroscopy, EDS), and surface sensitive spectroscopy (X-ray photoelectron spectroscopy, XPS). Overall and under these conditions, the synthetic Mn-oxides have higher sorption efficiencies than the natural Mn-oxides, which in turn are higher than the natural and synthetic Fe-oxides. Only natural pyrolusite had a sorption efficiency as low as the Fe-oxides. Most of the natural and synthetic Fe-oxides examined in this study removed about the same amount of Pb from solution once normalized to BET N2 surface area, although synthetic akaganéite and hematite were significantly less reactive than the rest.It is suggested that the observed efficiency of Mn-oxides for Pb sorption is directly related to internal reactive sites in the structures that contain them (birnessite and cryptomelane, in the case of this study). Comparisons of solution data to XPS data indicated that Pb went into the interlayer of the birnessite, which was supported by XRD; similarly some Pb may go into the tunnels of the cryptomelane structure. Layer structures such as birnessite have the highest Pb sorption efficiency, while the 2 × 2 tunnel structure of cryptomelane has lower efficiencies than birnessite, but higher efficiencies than other Mn- or Fe-oxide structures without internal reactive sites.  相似文献   

5.
Batch and flow-through experiments were performed on quartz–feldspar granular aggregates at hydrothermal conditions (up to ≈150 °C, up to 5 MPa effective pressure, and near-neutral pH) for up to 141 days. The effect of dissolution–precipitation reactions on the surface morphology of the mineral grains was investigated. The starting materials as well as the solids and fluids resulting from the experiments were characterized using BET, energy dispersive X-ray spectroscopy, electron microprobe analysis, inductively coupled plasma-optical emission spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, and X-ray fluorescence spectroscopy. The electrical conductivity of fluid samples was used as a proxy for the evolution of the fluid composition in the experiments. The chemical analyses of the fluids in combination with hydrogeochemical simulations with PHREEQC suggested the precipitation of Al–Si-bearing solid phases. Electron microscopy confirmed the formation of secondary amorphous Al–Si-bearing solid phases. The microscopic observations are consistent with a process of stoichiometric dissolution of the mineral grains, transport of dissolved ions in the fluid phase, and spatially coupled precipitation of sub-μm sized amorphous particles on mineral surfaces. These findings shed light onto early stages of diagenesis of quartz–feldspar sands and indicate that amorphous phases may be precursors for the formation of crystalline phases, for example, clay minerals.  相似文献   

6.
Iron and aluminium oxides are available in many climatic regions and play a vital role in many environmental processes, including the interactions of microorganisms in contaminated soils and groundwater with their ambient environment. Indigenous microorganisms in contaminated environments often have the ability to degrade or transform those contaminants, a concept that supports an in situ remediation approach and uses natural microbial populations in order to bio-remediate polluted sites. These metal oxides have a relatively high pH-dependent surface charge, which makes them good candidates for studying mineral–bacterial adhesion. Given the importance of understanding the reactions that occur at metal oxide and bacterial cell interfaces and to investigate this phenomenon further under well-characterized conditions, some of the most common iron and aluminium oxides; hematite, goethite and aluminium hydroxide, were synthesized and characterized and a coating method was developed to coat polystyrene well-plates as a surface exposable to bacterial adhesion with these minerals (non-treated polystyrene-12 well-plates which are used for cell cultures). The coating process was designed in a way that resembles naturally coated surfaces in aquifers. Hematite, Fe2O3, was synthesized from acidic FeCl3 solution, while goethite, FeOOH, and aluminium hydroxide, Al(OH)3, were prepared from an alkaline solution of Fe(NO3)3 and Al(NO3)3. They were further characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR), potentiometric titration and contact angle measurements. Characterization results show that the pure phases of hematite, goethite and aluminium hydroxides are formed with a point of zero charge (PZC) of 7.5, 8.5 and 8.9, respectively. The coating process was based on the direct deposition of mineral particles from an aqueous suspension by evaporation. Then, altered polystyrene surface properties were analyzed using X-ray photoelectron spectroscopy (XPS), attenuated total reflection-Fourier transform infrared (ATR-IR), water drop contact angle measurements and vertical scanning interferometry (VSI). The surface analysis tests prove that the coated polystyrene surface has physicochemical properties that are similar to the reference synthetic hematite, goethite and aluminium hydroxide minerals. These prepared and well-characterized mineral well-plates are similar to naturally occurring surfaces in aquifers and enable us to study the different steps of bacterial adhesion and biofilm formation on these metal oxides under laboratory-controlled conditions.  相似文献   

7.
玄武岩—水相互作用的溶解机理研究   总被引:11,自引:0,他引:11  
党志  侯瑛 《岩石学报》1995,11(1):9-15
在常温常压排除大气干扰的封闭体系条件下,将一定粒度的玄武岩样品浸泡在不同酸度的水溶液里,研究玄武岩-水相互作用过程中元素释放和溶液酸度的变化情况。结果发现:(1)经过一段时间后,溶液中主要元素的浓度趋向平衡;(2)溶液酸度发生明显变化,即不论反应初始溶液是碱性的还是酸性的,最终都将趋于中性,我们把此现象称为溶液的中性化效应。根据溶液中溶解组分的浓度和样品表面组成的XPS测定结果,提出玄武岩在碱性和酸性溶液中不同的溶解机理。  相似文献   

8.
We studied uptake mechanisms for dissolved Al on amorphous silica by combining bulk-solution chemistry experiments with solid-state Nuclear Magnetic Resonance techniques (27Al magic-angle spinning (MAS) NMR, 27Al{1H} cross-polarization (CP) MAS NMR and 29Si{1H} CP-MAS NMR). We find that reaction of Al (1 mM) with amorphous silica consists of at least three reaction pathways; (1) adsorption of Al to surface silanol sites, (2) surface-enhanced precipitation of an aluminum hydroxide, and (3) bulk precipitation of an aluminosilicate phase. From the NMR speciation and water chemistry data, we calculate that 0.20 (±0.04) tetrahedral Al atoms nm−2 sorb to the silica surface. Once the surface has sorbed roughly half of the total dissolved Al (∼8% site coverage), aluminum hydroxides and aluminosilicates precipitate from solution. These precipitation reactions are dependent upon solution pH and total dissolved silica concentration. We find that the Si:Al stoichiometry of the aluminosilicate precipitate is roughly 1:1 and suggest a chemical formula of NaAlSiO4 in which Na+ acts as the charge compensating cation. For the adsorption of Al, we propose a surface-controlled reaction mechanism where Al sorbs as an inner-sphere coordination complex at the silica surface. Analogous to the hydrolysis of , we suggest that rapid deprotonation by surface hydroxyls followed by dehydration of ligated waters results in four-coordinate (>SiOH)2Al(OH)2 sites at the surface of amorphous silica.  相似文献   

9.
The identification of the mineral species controlling the solubility of Al in acidic waters rich in sulfate has presented researchers with several challenges. One of the particular challenges is that the mineral species may be amorphous by X-ray diffraction. The difficulty in discerning between adsorbed or structural sulfate is a further complication. Numerous studies have employed theoretical calculations to determine the Al mineral species forming in acid sulfate soil environments. The vast majority of these studies indicate the formation of a mineral species matching the stoichiometry of jurbanite, Al(OH)SO4·5H2O. Much debate, however, exists as to the reality of jurbanite forming in natural environments, particularly in view of its apparent rare occurrence. In this work the use of Al, S and O K-edge XANES spectroscopy, in combination with elemental composition analyses of groundwater precipitates and a theoretical analysis of soluble Al concentrations ranging from pH 3.5 to 7, were employed to determine the mineral species controlling the solubility of Al draining from acid sulfate soils into Blacks Drain in north-eastern New South Wales, Australia. The results indicate that a mixture of amorphous Al hydroxide (Al(OH)3) and basaluminite (Al4(SO4)(OH)10·5H2O) was forming. The use of XANES spectroscopy is particularly useful as it provides insight into the nature of the bond between sulfate and Al, and confirms the presence of basaluminite. This counters the possibility that an Al hydroxide species, with appreciable amounts of adsorbed sulfate, is forming within these groundwaters.Below approximately pH 4.5, prior to precipitation of this amorphous Al(OH)3/basaluminite mixture, our studies indicate that the Al3+ activity of these acidic sulfate-rich waters is limited by the availability of dissolved Al from exchangeable and amorphous/poorly crystalline mineral species within adjacent soils. Further evidence suggests the Al3+ activity below pH 4.5 is then further controlled by dilution with either rainwater or pH 6-8 buffered estuarine water, and not a notional Al(OH)SO4 mineral species.  相似文献   

10.
Crushed rock from two caprock samples, a carbonate-rich shale and a clay-rich shale, were reacted with a mixture of brine and supercritical CO2 (CO2–brine) in a laboratory batch reactor, at different temperature and pressure conditions. The samples were cored from a proposed underground CO2 storage site near the town of Longyearbyen in Svalbard. The reacting fluid was a mixture of 1 M NaCl solution and CO2 (110 bar) and the water/rock ratio was 20:1. Carbon dioxide was injected into the reactors after the solution had been bubbled with N2, in order to mimic O2-depleted natural storage conditions. A control reaction was also run on the clay-rich shale sample, where the crushed rock was reacted with brine (CO2-free brine) at the same experimental conditions. A total of 8 batch reaction experiments were run at temperatures ranging from 80 to 250 °C and total pressures of 110 bar (∼40 bar for the control experiment). The experiments lasted 1–5 weeks.Fluid analysis showed that the aqueous concentration of major elements (i.e. Ca, Mg, Fe, K, Al) and SiO2 increased in all experiments. Release rates of Fe and SiO2 were more pronounced in solutions reacted with CO2–brine as compared to those reacted with CO2-free brine. For samples reacted with the CO2–brine, lower temperature reactions (80 °C) released much more Fe and SiO2 than higher temperature reactions (150–250 °C). Analysis by SEM and XRD of reacted solids also revealed changes in mineralogical compositions. The carbonate-rich shale was more reactive at 250 °C, as revealed by the dissolution of plagioclase and clay minerals (illite and chlorite), dissolution and re-precipitation of carbonates, and the formation of smectite. Carbon dioxide was also permanently sequestered as calcite in the same sample. The clay-rich shale reacted with CO2–brine did not show major mineralogical alteration. However, a significant amount of analcime was formed in the clay-rich shale reacted with CO2-free brine; while no trace of analcime was observed in either of the samples reacted with CO2–brine.  相似文献   

11.
增强型地热系统(EGS)用于通过人工形成地热储层的方法从深部低渗透性岩体中开采地热能;国际上常采用水力压裂辅以化学刺激的方法改造EGS 储层以提高其渗透率。本文以采自青海共和盆地的花岗闪长岩样品为对象,选用3种不同化学刺激剂(氢氧化钠、盐酸和土酸),在3组不同注入流速条件下开展了系统化学刺激实验。结果表明:注入盐酸和土酸后样品渗透率均有提高,且采用土酸时渗透率提高幅度明显大于盐酸;但注入氢氧化钠后,样品渗透率反而降低。在3类化学刺激剂中,土酸对长石类矿物的溶蚀能力最强,而氢氧化钠溶液对石英的溶蚀能力最强,但氢氧化钠溶液在溶解岩石样品裂隙表面矿物后极易形成非定形态二氧化硅或非定形态铝硅酸盐蚀变矿物并阻塞裂隙,反而对化学刺激效果造成负面影响。总体来看,土酸是青海共和盆地干热岩体的最佳化学刺激剂。在中等注入速度(3 mL·min-1)条件下,土酸对岩石样品的溶蚀程度就可达到最高;在此基础上进一步降低流速,则可能使溶解组分更易从液相中沉淀而充填于样品裂隙,导致样品渗透率有所下降。  相似文献   

12.
The surface binding site characteristics and Ni sorptive capacities of synthesized hydrous Mn oxyhydroxides experimentally conditioned to represent three hydrological conditions—MnOXW, freshly precipitated; MnOXD, dried at 37°C for 8 d; and MnOXC, cyclically hydrated and dehydrated (at 37°C) over a 24-h cycle for 7 d—were examined through particle size analysis, surface acid-base titrations and subsequent modelling of the pKa spectrum, and batch Ni sorption experiments at two pH values (2 and 5). Mineralogical bulk analyses by XRD indicate that all three treatments resulted in amorphous Mn oxyhydroxides; i.e., no substantial bulk crystalline phases were produced through drying. However, drying and repeated wetting and drying resulted in a non-reversible decrease in particle size. In contrast, total proton binding capacities determined by acid-base titrations were reversibly altered with drying and cyclically re-wetting and drying from 82 ± 5 μmol/m2 for the MnOXW to 21 ± 1 μmol/m2 for the MnOXD and 37 ± 5 μmol/m2 for the MnOXC. Total proton binding sites measured decreased by ≈75% with drying from the MnOXW and then increased to ≈50% of the MnOXW value in the MnOXC. Thus, despite a trend of higher surface area for the MnOXD, a lower total number of sites was observed, suggesting a coordinational change in the hydroxyl sites. Surface site characterization identified that changes also occurred in the types and densities of surface sites for each hydrologically conditioned Mn oxyhydroxide treatment (pH titration range of 2-10). Drying decreased the total number of sites as well as shifted the remaining sites to more acidic pKa values. Experimentally determined apparent pHzpc values decreased with drying, from 6.82 ± 0.06 for the MnOXW to 3.2 ± 0.3 for the MnOXD and increased again with rewetting to 5.05 ± 0.05 for the MnOXC. Higher Ni sorption was observed at pH 5 for all three Mn oxyhydroxide treatments compared to pH 2. However, changes in relative sorptive capacities among the three treatments were observed for pH 2 that are not explainable simply as a function of total binding site density or apparent pHzpc values. These results are the first to our knowledge, to quantitatively link the changes induced by hydrologic variability for surface acid base characteristics and metal sorption patterns. Further, these results likely extend to other amorphous minerals, such as Fe oxyhydroxides, which are commonly important geochemical solids for metal scavenging in natural environments.  相似文献   

13.
This study investigated possible geochemical reactions during titration of a contaminated groundwater with a low pH but high concentrations of aluminum, calcium, magnesium, manganese, and trace contaminant metals/radionuclides such as uranium, technetium, nickel, and cobalt. Both Na-carbonate and hydroxide were used as titrants, and a geochemical equilibrium reaction path model was employed to predict aqueous species and mineral precipitation during titration. Although the model appeared to be adequate to describe the concentration profiles of some metal cations, solution pH, and mineral precipitates, it failed to describe the concentrations of U during titration and its precipitation. Most U (as uranyl, UO22+) as well as Tc (as pertechnetate, TcO4) were found to be sorbed and coprecipitated with amorphous Al and Fe oxyhydroxides at pH below ∼5.5, but slow desorption or dissolution of U and Tc occurred at higher pH values when Na2CO3 was used as the titrant. In general, the precipitation of major cationic species followed the order of Fe(OH)3 and/or FeCo0.1(OH)3.2, Al4(OH)10SO4, MnCO3, CaCO3, conversion of Al4(OH)10SO4 to Al(OH)3,am, Mn(OH)2, Mg(OH)2, MgCO3, and Ca(OH)2. The formation of mixed or double hydroxide phases of Ni and Co with Al and Fe oxyhydroxides was thought to be responsible for the removal of Ni and Co in solution. Results of this study indicate that, although the hydrolysis and precipitation of a single cation are known, complex reactions such as sorption/desorption, coprecipitation of mixed mineral phases, and their dissolution could occur simultaneously. These processes as well as the kinetic constraints must be considered in the design of the remediation strategies and modeling to better predict the activities of various metal species and solid precipitates during pre- and post-groundwater treatment practices.  相似文献   

14.
After reaction with a pH < 4, the surface of labradorite is extensively enriched in Si and H, and depleted in Al, Ca and Na relative to an unreacted crystal. However, the amount of hydrogen measured in the reacted surface is less than that predicted on the basis of exchange of hydrogen (or hydronium) ions for cations in the feldspar. By analogy with studies of silicate glass, this low concentration of hydrogen suggests that some silanol groups in the reacted surface repolymerize subsequent to ion-exchange and depolymerization reactions. The net result is a relatively porous, Si-rich leached layer which is amorphous to electron diffraction, and which allows rapid diffusion of unreactive solutes.

Both the surface area of the reacted feldspar and the porosity increase with acid hydrolysis. Modeling of nitrogen sorption onto the surface suggests that the pores have a nominal radius of 20–80 Å or less. This distribution of pore sizes resembles other acid-reacted silicate materials, such as glass, chrysotile and kaolinite. Although the mineral surface clearly becomes more porous during acid hydrolysis, the increase in powder area also does not coincide with an increase in the flux of dissolved Si from the powder. We thus attribute most of this increase in area to spallation of the silica-rich surface from the feldspar upon drying.  相似文献   


15.
Models of geochemical controls on elements of concern (EOCs; e.g., As, Se, Mo, Ni) in U tailings are dominated by ferrihydrite. However, the evolution of aqueous concentrations of Al and Mg through the Key Lake (KL) U mill bulk neutralization process indicates that secondary Al and Mg minerals comprise a large portion of the tailings solids. X-ray diffraction, Al K-edge XAS, and TEM elemental mapping of solid samples collected from a pilot-scale continuous-flow synthetic raffinate neutralization system of the KL mill indicate the secondary Al–Mg minerals present include Mg–Al hydrotalcite, amorphous Al(OH)3, and an amorphous hydrobasaluminite-type phase. The ferrihydrite present contains Al and may be more accurately described as Al–Fe(OH)3. In the final combined tailings sample (pH 10.5) collected from the model experiments using raffinate with Al, Mg, and Fe, solid phase EOCs were associated with Al–Fe(OH)3 and Mg–Al hydrotalcite. In model experiments using raffinate devoid of Fe, aqueous EOC concentrations decreased greatly at pH 4.0 (i.e., where ferrihydrite would precipitate) and largely remained in the solid phase when increased to the terminal pH of 10.5; this suggests Al–Mg minerals can control aqueous concentrations of EOCs in the raffinate in the absence of Fe. Maximum adsorption capacities for individual and mixtures of adsorbates by Mg–Al hydrotalcite were determined. A revised model of the geochemical controls in U mill tailings is presented in which Al and Mg minerals co-exist with Fe minerals to control EOC concentrations.  相似文献   

16.
水库渗漏水中氢氧化铁的矿化特征   总被引:5,自引:2,他引:5       下载免费PDF全文
对富水水库大坝渗漏水和析出物进行了分析和研究。析出物的主要成分为Fe2O3,并含少量Al2O3和SiO2,铁质析出物的XRD、IR、SEM和TEM分析表明,氢氧化铁的结晶程度较低,主要结晶相为针铁矿,其次为少量伊利石、蒙脱石和石英。电子显微分析观察到在非晶质氢氧化铁凝胶团和亚微米级微粒聚集体中存在特殊的显微管状和螺旋状针铁矿,显示出明显的生物矿化特征。  相似文献   

17.
The oxidation of the iron sulfide, pyrite, in acid sulfate soil floodplains generate substantial acidity and this acid has caused further weathering of the soil profile. The movement of groundwater from these soils is an important geochemical control on surface water quality. The flux of acidified and metal-rich water during a wet season rainfall event has been examined at two study catchments on the Tweed River in eastern Australia. At the sites, 81 kg/ha and 60 kg/ha of oxidisable acidity are exported, along with Al, Fe and Zn during the flood event. The main contributors to the acid flux are H+, Fe and Al at the first site and whilst Fe and Al are present in the drainage waters at the second site, the main contributor is likely to be H+. The different flux characteristics at the sites may be caused by different surface soil hydraulic conductivities and oxidation history.  相似文献   

18.
The damage caused to structures and other human endeavours, on or in the ground, by swelling clay soils is considered as a natural hazard. In order to mitigate this hazard an attempt was made to stabilize the swelling clay mineral structure by the addition of Mg(OH)2. This will turn the swelling minerals, like montmorillonite, into non-swelling ones, e.g., chloride. Accordingly, the various factors affecting the precipitation-adsorption of the Mg-hydroxide by clays, was investigated, and the conditions giving the best results were established. The factors examined were: the base used as precipitant (NH4OH and NaOH); the preparation of the precipitate, inside or outside the clay suspension; the sequence and the duration of the reagents addition; the OH/Mg ratio; the time of clay-chemical contact; and the drying time and temperature. The method, was applied to different clay minerals (swelling and non-swelling). The material produced after the Mg-hydroxide precipitation was examined by the methylene blue dye adsorption test, XRD, DTA and DTGA methods; the results were treated statistically by factorial analysis. From the results obtained, it is concluded that the factors affecting the Mg-hydroxide adsorption by clays are: the base used as a precipitant, the preparation of the hydroxide directly inside or outside the clay suspension, the drying temperature, and the rate of titration of the reagents. Therefore, the best conditions for the laboratory preparation of hydroxy-Mg-interlayers are a dilute (1–2%) and well-dispersed clay suspension, pH between 10–12; some 12 meq Mg2+, as Mg-salt (e.g., MgCl2) per gram of clay, added before the base and followed by the dropwise titration of 1–2 N NaOH solution into the clay suspension, to give a molar ratio OH/Mg of about 1.5; vigorous agitation of the suspension during titration of the reagents; centrifugation and decantation of the supernatant liquid, and drying the product at about 250°C. Satisfactory results are also obtained with the fast titration of the base and drying at 105°C to complete dryness.  相似文献   

19.
The synthesis of illite mixed-layer minerals at surface conditions is possible through precipitation of Al hydroxides from Si-, Mg- and K-containing solutions. It has been shown that amorphous hydroxides of Al, Fe, etc. are capable of coprecipitating silica even from very dilute solutions. By aging of these X-ray amorphous hydroxide—silica precipitates under certain conditions, clay minerals can be synthesized at low temperatures. The presence of Mg particularly favors the formation of three-layer clay minerals. Mg-rich Al hydroxide—silica precipitates permit formation of tri- and di-octahedral smectite, illite and chlorite. The formation of three-layer clay minerals is only possible when the precipitates contain at least 6% MgO. The precipitates stay amorphous if the Mg content is lower. The adsorption of Mg and K on the hydroxide—silica precipitate controls the illite or montmorillonite portion in the mixture of the three-layer silicates. There is a competition for K and Mg adsorption on the hydroxide—silica precipitates. Higher K concentration inhibits the three-layer mineral formation through the lowering of the Mg content in the precipitates. Illite mineral formation is favored under certain K/Mg ratios. Higher NaCl contents do not favor the three-layer mineral formation.The enrichment of Mg and K in the precipitates is not as large as the enrichment of Si in the hydroxides. This means that the illite mineral formation is only possible from solutions with a high-salt content like seawater.  相似文献   

20.
针对目前市场上出现的一些因优化处理而产生轻微玻璃残余物的天然红宝石,经适当浓度的氢氟酸(浓度23%)浸泡后,位于红宝石内裂隙和表面凹坑中的轻微玻璃态残余物被溶解,达到清理玻璃态残余物的目的,并利用电感耦合等离子体-原子发射光谱仪(ICP-AES)分析含玻璃材料的溶液中Si和Al的浓度分别为28.60μg/mL和2.795μg/mL,进而估算玻璃态残留物的损失量以判定热处理过程中非人为加入的玻璃态物质在红宝石中的充填程度。利用红外光谱仪对玻璃残留物清理前后的红宝石红外光谱进行对比研究得出:清理前,红外光谱显示在1 100~1 000 cm-1内有1个单峰宽谱带,谱峰为1 050 cm-1,是由νas(Si—O—Si)非对称伸缩振动引起的,表明残留物为非晶质体,750~600 cm-1之间位于744 cm-1的吸收峰为νs(Si—O—Si)对称伸缩振动引起;清理后,未检测到玻璃残余物特征的Si—O振动峰,仅具950~600 cm-1范围内的宽谱带,为刚玉Al—O基频振动谱带736、622 cm-1,体现晶质金属氧化物的特征,表明样品中玻璃态物质已被清除,实验后红宝石可被划归为经人工优化范畴。宝石显微镜下观察到清理实验后红宝石中原先被玻璃残余物所掩盖的显著内裂隙及表面凹坑。  相似文献   

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