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1.
We report analysis of chemical durability of UK HLW MW+25% simulant glass under model hyperalkaline conditions of a colocated geological disposal facility. Glass powders and monoliths were dissolved for 168 days in saturated Ca(OH)2. Dissolution in the presence of high concentrations of Ca (>200 mg/L) was an order of magnitude lower than dissolution in water. Dissolution of Si did not occur until a Ca:Si ratio of <2 was achieved. The mechanism of dissolution involved the incorporation of Ca into the hydrated surface (initial, incubation regime), the precipitation of C-S-H phases, including a range of compositions in the C-(N)-(A)-S-H and M-S-H systems (intermediate regime), and the precipitation of C-S-H phases (the residual regime). Thermodynamic analysis and consideration of the CaO-SiO2-H2O phase diagram suggest that the rate-limiting step of glass dissolution in Ca-rich solutions is Ca-Si equilibrium, involving the precipitation of C-S-H phases, which change in chemical composition as a function of solution chemistry. In low SA/V ratio experiments, the dissolution progressed only to the initial incubation regime, resulting from fewer surface sites for Ca incorporation. Overall, these results suggest that Ca and Si in solution play an important role in the long-term durability of UK HLW in Ca-rich solutions.  相似文献   

2.
A thermodynamic incongruent dissolution/precipitation model of calcium silicate hydrate (C-S-H) is proposed, assuming a binary nonideal solid solution of Ca(OH)2 and SiO2. Using this model, both dissolution and precipitation of the C-S-H phase, with a continuous change in the Ca / Si ratio of the solid phase, can be predicted. The notable features of the model are its good continuity and simplicity so that calculation can be easily compiled in a calculation code. A series of experiments were carried out. C-S-H precipitates were prepared using two techniques: precipitation by contacting Ca(OH)2 solution with C-S-H gel and hydrolysis in a mixture of Ca and Si solutions. The equilibria in these experiments were predicted well by the proposed model. A calculation using the model also predicted well the dissolution of ordinary Portland cement hydrate with water exchange.  相似文献   

3.
In this study, oxidatively stable minimal neutralized sunflower seed oils were produced using three chemicals (Ca(OH)2, MgO, and Na2SiO3) under previously determined optimal process conditions. Lipid oxidation rates at these optimum conditions were compared to the oils neutralized with NaOH (0.20%, 40°C, 15 min). It was concluded that the oils neutralized by NaOH had the shortest hydroperoxide and hexanal lag phases, thus were the least stable oils. Oils neutralized by Ca(OH)2, MgO, and Na2SiO3 had lower FFA and higher oxidative stability than oil neutralized by NaOH. The study focused on which weak alkaline has higher oxidation stability and minimum FFA content and maximum acceptable tocopherol content. The oil neutralized by Ca(OH)2 had the lowest FFA value and highest total phenolics and α-tocopherol contents and it had better oxidative stability than oil neutralized by NaOH. It suggests that Ca(OH)2 could be more effective in producing a high quality oil.  相似文献   

4.
Calcined clays are attracting significant research attention because of their potential to partially replace CO2-intensive portland cement. This potential depends largely on their reactivity, especially dissolution under alkaline conditions. Identification and characterization of reactive sites in these amorphous calcined clays has so far not been reported. Here, we investigate kaolinite (1:1 clay) and montmorillonite (2:1 clay) calcined at different temperatures under alkaline conditions (0.1 mol/L NaOH). Solution compositions are determined in batch dissolution experiments, whereas 27Al and 29Si MAS and CP/MAS NMR are used to investigate the structure of the undissolved residues to identify sites that are reactive and undergo preferential dissolution. The highest Si and Al dissolution rates for kaolinite are observed for calcination at 700°C, corresponding to the temperature of optimum reactivity, whereas the rates decrease and become increasingly incongruent at higher temperatures. The Si and Al dissolution rates for optimally calcined kaolinite are 4 and 12 times larger than the corresponding rates for optimally calcined montmorillonite, in accord with the much higher reactivity of calcined kaolinite compared to calcined 2:1 clays. This superior performance of kaolinite is explained by novel 27Al NMR results, which show strong evidence for preferential dissolution of highly reactive pentahedral aluminum sites.  相似文献   

5.
Kinetics of hydrothermal reactions have been studied for mixtures of CaO and quartz (<10 μm 10–20 μm) with Ca/Si = 0.8 and 1.0 in stirred suspensions at 120 – 180°C. Reaction proceeds through the sequence: Ca(OH)2 + SiO2 → Ca-rich C-S-H + SiO2 (at 120°C) → poorly crystalline tobermorite (at 140°C)→ highly crystalline tobermorite (at 180°C) → xonotlite at 180°C and Ca/Si = 1.0 and 180°C and Ca/Si = 0.8 if 10–20 μm quartz is used. Reaction is controlled by dissolution of the quartz. For both Ca/Si ratios the radius of the 10–20 μm quartz decreases at a constant rate, viz 0.85 μm/h at 180°C, 0.13 μm/h at 140°C, 0.04 μm/h at 120°C.  相似文献   

6.
In this study, C/SiOC and C/SiO2 composites were prepared by using carbonaceous microspheres with different surface functional groups. Carbonaceous microspheres based on hydrothermal reaction of glucose contains hydroxyl group, while the surface carboxyl group increases after NaOH etching. The hydroxyl group increases the oxygen-enriched structural units of SiOC ceramics, and the C spheres are closely enwrapped in SiOC matrix after pyrolysis at 900 °C. However, the interfacial reaction of surface carboxyl with Si–OH results in the formation of cristobalite SiO2, and C spheres are not only encased inside the SiOC matrix, but also dispersed outside of SiOC ceramics. After removal of C via calcination at 500 °C for 5 h, C/SiOC and C/SiO2 composites are transformed into amorphous SiO2 and cristobalite SiO2, respectively. The thermogravimetric analysis indicates the oxidation resistance of SiOC is superior to that of C and SiO2.  相似文献   

7.
Silicate bioglass is of great importance in bone engineering because of its excellent bioactivity and osteogenic effects. In this study, hydroxyapatite-like bioactive glass based on the xSiO2-CaO-P2O5 (x = 30, 45, 60 and 90 mol.%, Ca/P = 1.67) system was synthesized by the sol-gel method, and the corresponding structural evolution, apatite-forming ability and cytotoxicity were systematically investigated. The results suggest that both a higher heat treatment temperature and a lower SiO2 content increase the crystallinity tendency of the bioglass, and the samples become obviously compact as the SiO2 amount increases from 30 to 90 mol.%. Compared with the samples with higher SiO2 content, the 30Si sample shows more remarkable internal connected mesoporous structures, with a higher specific surface area up to 129.12 m2/g, exhibiting excellent hydroxyapatite formation in simulated body fluid. Moreover, no obvious inhibitory effect was presented on human periodontal ligament cells (hPDLCs) for any of the silicate glass samples.  相似文献   

8.
Hierarchical TS-1 with grooves and intracrystalline voids was prepared by TPAOH/NaOH treatment. With increasing NaOH concentration, the dissolution–recrystallization process was intensified, the relative crystallinity and microporous properties decreased, the secondary pore volume increased. Although the dissolved species could be recrystallized, Na+ prevented the titanium incorporation, which increased the extra-framework titanium content. In phenol hydroxylation, improved activity and H2O2 efficiency were achieved when NaOH was no more than 0.1 mol/L, which may be a result of the positive influences of the secondary pores. At higher NaOH concentration (> 0.1 mol/L), the activity and H2O2 efficiency decreased due to the negative influences of the non-framework titanium.  相似文献   

9.
Waste resources containing CaO and SiO2 were leached by an acetic acid solution. Most CaO exist as calcium aluminosilicate and calcium silicate in steel slag and wollastonite, respectively. Silicate leaching was enhanced steeply by heating to 50 °C or increasing acid concentrations to 4 wt%. The Si and/or Al in the leachate then precipitated independently, depending on the solubility. This enabled to improve the selectivities of Ca and Si in the leachate and precipitate, respectively. However, CaO and SiO2 are separate constituents of waste cement. The dissolution of Ca thus took place relatively fast while the ‘free’ silica leached little.  相似文献   

10.
Silicon-oxide incorporated amorphous hydrogenated diamond-like carbon films (SiOx–DLC, 1  x  1.5) containing up to 24 at.% of Si (H is excluded from the atomic percentage calculations reported here) were prepared using pulsed direct current plasma-enhanced chemical vapour deposition (DC-PECVD). Molecular structure, optical properties and mechanical properties of these films were assessed as a function of Si concentration. The spectroscopic results indicated two structural regimes. First, for Si contents up to ~ 13 at.%, SiOx–DLC is formed as a single phase with siloxane, O–Si–C2, bonding networks. Second, for films with Si concentrations greater than 13 at.%, SiOx–DLC with siloxane bonding and SiOx deposit simultaneously as segregated phases. The variations in mechanical properties and optical properties as a function of Si content are consistent with the above changes in the film composition.  相似文献   

11.
A glassy material similar to fulgurites (fusion of the soil which has been struck by lightning) was prepared by continuous wave (CW) CO2 laser (λ = 10.6 μm) ablation of lime–pozzolan mortar at medium‐vacuum conditions and atmospheric pressure. In all the irradiated samples, the determined surface temperature is higher than the melting temperature of mortar (1556 K), so the surface is melted and converted into an amorphous glassy when cooled. The samples were studied combining laser‐induced breakdown spectroscopy (LIBS) and Raman spectroscopy. The emission induced by the CW CO2 laser is mainly due to electronic relaxation of Na, K, Si, Si+, Ca, O, N, and CaOH species along with an intense continuum due to blackbody emission. The emission induced on both natural and produced fulgurite is mostly due to electronic relaxation of Ca, Ca+, Si, Si+, Si2+, Si3+, H, Na, K, Mg, N, O, CaOH, and OH species with different relative intensities in some of them. Raman spectra show that the glassy formed material is similar to natural fulgurites, with the main difference arising from portlandite formed over the surface of the lime–pozzolan mortar. As the laser power increases, less density SiO2 glass is formed with more Q4 and Q1 units present.  相似文献   

12.
Phase equilibria of the ZnO–SiO2, Al2O3–SiO2 and ZnO–Al2O3–SiO2 systems at liquidus were characterized at 1340–1740 °C in air. The ZnO–Al2O3 subsolidus phase equilibria were derived from the experiments with the SiO2- and CaO + SiO2-containing slags. High-temperature equilibration on silica or platinum substrates, followed by quenching and direct measurement of Zn, Al, Si and Ca concentrations in the phases with the electron probe X-ray microanalysis (EPMA) was used to accurately characterize the system. Special attention was given to zincite phase that was shown to consist of two separate ranges of compositions: round-shaped low-Al zincite (<2 mol.% AlO1.5) and platy high-Al zincite (4–11 mol.% AlO1.5). A technique was developed for more accurate measurement of the ZnO solubility in the low-ZnO phases (corundum, mullite, tridymite and cristobalite) surrounded by the ZnO-containing slag, using l-line for Zn instead of K-line, avoiding the interference of secondary X-ray fluorescence. Solubility of ZnO was found to be below 0.03 mol.% in corundum and cristobalite, and below 0.3 mol.% in mullite. Present experimental data were used to obtain a self-consistent set of parameters of the thermodynamic models for all phases in this system using FactSage computer package. The modified quasichemical model with two sublattices (Zn2+, Al3+, Si4+) (O2?) was used for the liquid slag phase; the compound energy formalism was used for the spinel (Zn2+,Al3+)[Zn2+,Al3+,Va]2O2-4 and mullite Al3+2(Al3+,Si4+) (O2?,Va)5 phases; the Bragg-Williams formalism was used for the zincite (ZnO, Al2O3); other solid phases (tridymite and cristobalite SiO2, corundum Al2O3, and willemite Zn2SiO4) were described as stoichiometric. Present study is a part of the research program on the characterization of the multicomponent Pb–Zn–Cu–Fe–Ca–Si–O–S–Al–Mg–Cr–As–Sn–Sb–Bi–Ag–Au–Ni system.  相似文献   

13.
Chloride penetration and calcium dissolution have been investigated for a saturated concrete after exposure to a 0.5 mol/L NaCl solution for a period of up to 3150 days. Simultaneous ion transport model (SiTraM) that allows the transport of chloride and calcium ions to be simultaneously simulated in a hydrated cement system has been used to verify the experimental results.Self-compacting concrete (SCC) with a water to cement ratio of 0.3 resulted in a limited chloride penetration depth while the calcium dissolution was also reduced within the near surface zone. Increased unit water content for normal concrete resulted in higher chloride penetration depth and larger dissolution front of Ca(OH)2 regardless of having the same water to cement ratio.It was revealed that the SiTraM can predict the profiles of chloride and calcium for self-compacting concrete. It was also found that the primary factor to control chloride penetration front and the dissolution front of Ca(OH)2 was the pore structure characteristic of concrete.  相似文献   

14.
Spin-coating was performed to fabricate amorphous high-entropy oxide (HEO) (AlTiVZrHf)Ox films on Si substrates. The films were evaluated through X-ray photoelectron spectroscopy and through transmission electron microscopy (TEM)-based energy-dispersive spectroscopy (EDS) mapping, which respectively revealed all constituent elements and the homogenous distributions and no aggregation of those elements. TEM analysis revealed four distinct layers—a crystalline Al metal gate, an amorphous Al2O3 interfacial layer, amorphous (AlTiVZrHf)Ox, and native amorphous SiO2—in a patterned metal–oxide–semiconductor (MOS) gate stack on the Si substrate. The resulting stack exhibited a low leakage current density (JL) and no frequency dispersion in its capacitance–voltage characteristics after undergoing forming gas annealing. The obtained dielectric constant (k ≈ 32) for the HEO film is promising for advanced gate stacks and transistor applications. Although the film exhibited minor nanocrystallinity and the stack exhibited no interfacial Al2O3 layer after rapid thermal annealing at 900 °C, a low JL, distinct layers, and a clearly defined interface between the (AlTiVZrHf)Ox and SiO2 were observed, indicating no substantial diffusion among these layers. EDS mapping revealed the homogenous distribution of each constituent element without aggregation. Medium-entropy-oxide films and their MOS devices were fabricated for comparison; however, they exhibited inferior performance.  相似文献   

15.
Calcined clays can be potential supplementary cementitious materials if effects of heat-treatment on their structure and reactivity are understood. This work reports structural characterization of an interstratified illite/smectite clay, including a quartz impurity, upon heating using 27Al and 29Si MAS NMR spectroscopy and ICP-OES analysis. During dehydroxylation (600–900 °C) the Q3-type SiO4 sites become disordered and octahedral AlO6 sites transform into tetrahedral sites, resulting in an amorphous material with substantial pozzolanic properties, as demonstrated by reactivity tests and hydration studies of a Portland cement–calcined clay blend. At higher temperatures (above 950 °C), inert Q4-type phases crystallize which radically reduce the reactivity. At optimum calcination temperature (900 °C), the amorphous material contains highly dissolvable elemental species as seen from complementary ICP-OES analysis. The quartz impurity exhibits a unique variation in 29Si spin–lattice relaxation times upon heat-treatment which is ascribed to changes in the concentration of impurity ions in quartz.  相似文献   

16.
《Ceramics International》2023,49(5):7424-7437
The current work presents and discusses the findings of a comprehensive study on the structural, chemical and thermal properties of SrO and CuO incorporated SiO2–CaO–Na2O–P2O5 amorphous silicate glass with a novel composition. Here, fundamental features (experimental density, oxygen density, and hardness) of all glasses were determined and chemical as well as phase composition of the glasses was verified with XRF and XRD, respectively. Moreover, the thermal behavior (viscos flow and crystallization kinetics) of amorphous silicate glass was investigated by non-isothermal methods using DTA analysis. The activation energies of glass transition (Eg) were calculated in the range of 546–1115 kJ/mol by Kissinger method, whereas the activation energies of crystallization (Ec) were calculated in the range of 164–270 kJ/mol by three different methods (Kissinger, Ozawa, Yinnon and Uhlmann). Avrami exponent (n) values ranged from 1.17 to 3.28 demonstrated that amorphous silicate glasses have different crystallization mechanism. Working temperature, which is one of the parameters indicating glass stability, increased with the incorporation of Sr and Cu from 187 °C to 245 °C. The initial dissolution measurement has been applied to study the degradability behavior of Sr and Cu incorporated amorphous glasses in vitro. Quantitative evaluation of Si4+ (0.156–0.373 kV), Ca2+ (0.043–0.332 kV), Na+ (0.044–0.329 kV), P5+ (0.057–0.289 kV), Sr2+ (0.134–0.385 kV), and Cu2+ (0.090–0.203 kV) depending on the ion activation energy (Ea-ion) and ion concentration at different temperature values (24, 37 and 55 °C) was performed in contact with Tris-HCl solution by ICP-OES analysis. The results revealed that investigated glasses were degradable and incorporation of Sr and Cu affected the glass initial dissolution. Overall, investigated glasses are suitable for various application such as hot-working production, glass-ceramic manufacturing, and glass or glass-ceramic scaffolds fabrication, due to wide working temperature ranges and high crystallization tendencies of the developed glasses.  相似文献   

17.
A porous silicate material derived from silica fume was successfully prepared and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FT-IR) spectroscopy, Thermogravimetry and Differential thermal gravity (TG-DTG), N2 adsorption and desorption isotherms, and scanning electron microscopy (SEM). Raw silica fume was analyzed by XRD, FT-IR and SEM. The analysis results of silica fume indicated that SiO2 in silica fume is mainly determined as amorphous state, and that the particles of raw silica fume exhibited characteristic spherical structure with a diameter of from 50 nm to 200 nm. The preparation of the porous silicate material involved two steps. The first step was the extraction of the SiO 3 2? leachate from raw silica fume. The maximum value of SiO 3 2? extraction yield was obtained under the following conditions: reaction temperature of 120 °C, reaction time of 120 min, NaOH concentration of 15%, and alkali to SiO2 molar ratio of 2. The second step was the preparation of the porous silicate material though the reaction of SiO 3 2? leachate and Ca(OH)2 suspension liquid. The optimum preparation conditions were as follows: preparation temperature of 90 °C, preparation time of 1.5 h, Si/Ca molar ratio of 1 : 1, and stirring rate of 100 r/min. The BET surface area and pore size of the porous silicate material were 220.7 m2·g?1 and 8.55 cm3/g, respectively. The porous silicate material presented an amorphous and unordered structure. The spectroscopic results indicated that the porous silicate material was mainly composed of Si, Ca, O, C, and Na, in the form of Ca2+, SiO 3 2? , CO 3 2? and Na+ ions, respectively, which agreed with the XRD, TG-DSC, and FT-IR data. The N2 adsorption-desorption isotherm mode indicates that the porous silicate material belonged to a typical mesoporous material. The porous silicate material presented efficiency for the removal of formaldehyde: it showed a formaldehyde adsorption capacity of 8.01 mg/g for 140 min at 25 °C.  相似文献   

18.
A new type of double-tail trisiloxane surfactants of the general formula R1NR2CH2CH(OH)CH2O(CH2CH2O)xCH3 (x = 8.4, 12.9, 17.5, 22; R 1 = Me3SiOSiMe(CH2)3OSiMe3, R 2 = CH2CH(OH)CH2OR3, R 3 = CH2CH(C2H5)CH2(CH2)2CH3) has been synthesized by reacting single-tail trisiloxane surfactants with 2-ethylhexyl glycidyl ether. Their structures were characterized with 1H-NMR and 13C-NMR spectroscopy. These double-tail trisiloxane surfactants reduce the surface tension of water to less than 24 mN/m at a level of 10−5 mol/L. The spreading ability (SA) of the double-tail trisiloxane surfactant solution on Parafilm (or Ficus microcarpa leaf) surfaces is better than that on polyethylene terephthalate surface. The SA of the solution of the double-tail trisiloxane surfactants 1J with average ethoxy units of 8.4 is far better than the others, and its solution (5.0 × 10−3 mol/L) possesses an SA value of over 15 within 10 min on Parafilm and Ficus microcarpa leaf surfaces. The surface tension values of aqueous solutions (1.0 × 10−3 mol/L) of the double-tail trisiloxane surfactants 1J are still less than 25 mN/m over 21 days in an acidic environment (pH 4.0) and 139 days in an alkaline environment (pH 10.0), respectively. It is suggested that the SA and hydrolysis resistance of double-tail trisiloxane surfactants are able to be improved by changing the structure of the hydrophobic group, such as increasing the molar ratio of methyl to methylene.  相似文献   

19.
《Fuel》2006,85(10-11):1329-1334
Using the amorphous aluminosilicate in coal fly ash (FA), a single phase Na–A zeolite was synthesized from FA by dialysis. The FA and NaOH solution added into the tube made by semipermeable membrane were pretreated in the same NaOH solution at 85 °C for 24 h. After the pretreatment, the tube was removed and NaOH–NaAlO2 solution was added into the residual solution to control SiO2/Al2O3 molar ratio of the solutions from 0.9 to 4.3. The precipitates thus formed were aged for 24 h at 85 °C. The amorphous aluminosilicate in FA was dissolved during the pretreatment. When the NaOH–NaAlO2 solution was added into the solution after the pretreatment and then aged, white precipitates were yielded over the whole SiO2/Al2O3 range. At SiO2/Al2O3=0.9, the material formed was identified as a single phase Na–A zeolite. The Na–X zeolite was slightly produced at SiO2/Al2O3≥1.7.  相似文献   

20.
《Ceramics International》2020,46(17):26598-26607
A highly stable Si/SiOx/C composite was synthesized in this study through NaOH etching and carbon-coating approaches for use as an anode material in Li-ion batteries (LIBs). The two-step process not only enhanced the electronic conductivity of the as-synthesized Si/SiOx/C composite by using the two-step etching/coating processes to enhance the columbic efficiency of Si during cycling processes but also architecturally provided an amorphous Si/SiOx composite to buffer volume expansion. The Raman spectroscopy and X-ray diffraction results demonstrate that the etching process involves a transition from crystalline Si to amorphous SiOx. The Fourier transform infrared spectroscopy results further confirm that the vibration mode of Si–O bonding changes from symmetric to asymmetric. The Brunauer–Emmett–Teller analysis reveals that we can control specific surface area and pore-size distribution of NaOH-modified Si by tuning the parameters pertaining to the solid content of Si in NaOH solution. After optimizing the etching and carbon-coating processes, the modified Si/C composite delivered ~780 mAh g−1 for more than 200 cycles at 0.5C, which was better than un-modified one of 315 mAh g−1 after 200 cycles. The results clearly indicate that we could improve cycle stability of Si anode drastically through the NaOH etching process and carbon coating modification. The proposed methodology may provide a potential approach to promoting the synthesis of Si-based anodes for use in the commercial applications of LIBs.  相似文献   

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