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1.
A simple and efficient approach for the high-purity CaSO4·2H2O (DH) whiskers and α-CaSO4·0.5H2O (α-HH) whiskers derived from such phosphogypsum (PG) was proposed. The impact of different experimental parameters on supersaturated dissolution–recrystallization and preparation processes of α-CaSO4·0.5H2O was elaborated. At 3.5 mol/L HCl concentration, the dissolution temperature and time were 90 °C and 20 min, respectively. After eight cycles and 5–8 times cycles, total crystallization amount of CaSO4·2H2O was 21.75 and 9.97 g/100 mL, respectively, from supersaturated HCl solution. The number of cycles affected the shape and amount of the crystal. Higher HCl concentration facilitated CaSO4·2H2O dissolution and created a much higher supersaturation, which acted as a larger driving force for phase transformation of CaSO4·2H2O to α-CaSO4·0.5H2O. The HCl solution system’s optimum experimental conditions for HH whiskers preparation involved acid leaching of CaSO4·2H2O sample, with HCl concentration 6.0 mol/L, reaction temperature 80 °C, and reaction time 30 min–60 min. Under the third cycle conditions, α-CaSO4·0.5H2O whiskers were uniform in size, clear, and distinct in edges and angles. The length range of α-CaSO4·0.5H2O whiskers was from 106 μm to 231 μm and diameter range from 0.43 μm to 1.35 μm, while the longest diameter ratio was 231. Purity of α-CaSO4·0.5H2O whiskers was approximately 100%, where whiteness reached 98.6%. The reuse of the solution enables the process to discharge no waste liquid. It provides a new reference direction for green production technology of phosphogypsum.  相似文献   

2.
In this study, we investigated a coarse phosphogypsum containing 49.63% SO3, 41.41% CaO, 10.68%, 4.47% SiO2, 1.28% P2O5, 0.11% F, CaSO4·2H2O purity of 80.65%, and whiteness of 27.68. Phosphogypsum contains calcium sulfate dehydrate as the main mineral, with small amounts of brushite, quartz, muscovite, and zoisite. Harmful elements, such as silicon, phosphorus, and fluorine, are mainly concentrated in the +0.15 mm and −0.025 mm fraction, which can be pre-selected and removed by the grading method to further increase the CaSO4·2H2O content. Gypsum was recovered using a direct flotation method, which included one roughing, one scavenging, and two cleaning operations, from −0.15 mm to +0.025 mm. The test results show that a gypsum concentrate with a CaSO4·2H2O purity of 98.94%, CaSO4·2H2O recovery of 80.02%, and whiteness of 37.05 was achieved. The main mineral in the gypsum concentrate was gypsum, and limited amounts of muscovite and zoisite entered the gypsum concentrate because of the mechanical entrainment of the flotation process.  相似文献   

3.
Yanbing Tang  Li Liu  Lei Fan  Ying Li  Fuhui Wang 《Materials》2014,7(9):6144-6157
The corrosion behavior of pure Fe under a Na2SO4 deposit in an atmosphere of O2 + H2O was investigated at 500 °C by thermo gravimetric, and electrochemical measurements, viz. potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and surface characterization methods viz. X-ray diffraction (XRD), and scanning electron microscope (SEM)/energy dispersive spectroscopy(EDS). The results showed that a synergistic effect occurred between Na2SO4 and O2 + H2O, which significantly accelerated the corrosion rate of the pure Fe. Briefly, NaFeO2 was formed in addition to the customary Fe oxides; at the same time, H2SO4 gas was produced by introduction of water vapor. Subsequently, an electrochemical corrosion reaction occurred due to the existence of Na2SO4, NaFeO2, and H2O. When this coupled to the chemical corrosion reaction, the progress of the chemical corrosion reaction was promoted and eventually resulted in the acceleration of the corrosion of the pure Fe.  相似文献   

4.
Flue-gas desulphurization (FGD) gypsum is a highly prevalent industrial by-product worldwide, which can be an excellent alternative to natural gypsum due to its high content of CaSO4·2H2O. The preparation of α-calcium sulfate hemihydrate is a high-value pathway for the efficient use of FGD gypsum. Here, a dynamic method, or an improved autoclaved process, was used to produce α-calcium sulfate hemihydrate from FGD gypsum. In this process, the attachment water of the mixture of FGD gypsum and crystal modifiers was approximately 18%, and the pH value was approximately 6.0. The mixture did not need to be pressed into bricks or made into slurry, and it was directly sent into the autoclave reactor for reaction. It was successfully applied to the practical production and application of FGD gypsum, citric acid gypsum and phosphogypsum. In this work, the compositions and morphology of the product at different stages of the reaction were examined and compared. In particular, single-crystal diffraction was used to produce the crystal structure of CaSO4·0.5H2O, and the results were as follows: a = 13.550(3); b = 13.855(3); c = 12.658(3); β = 117.79(3)°; space group C2. The preferential growth along the c-axis and the interaction mechanism between the carboxylate groups and the crystal were discussed throughout the analysis of the crystal structure.  相似文献   

5.
The article presents the effect of the thermo-chemical treatment of Al2O3 layers on their nanostructure, surface morphology, chemical composition as well as their micromechanical and sclerometric properties. Oxide layers were produced on EN AW-5251 aluminium alloy (AlMg2) by the method of direct current anodizing in a three-component electrolyte. The thermo-chemical treatment was carried out in distilled water and aqueous solutions of Na2SO4·10H2O and Na2Cr2O7·2H2O. It was shown that the thermo-chemical treatment process changes the morphology of the surface of the layers (the formation of a sub-layer from the Na2SO4·10H2O and Na2Cr2O7·2H2O solutions), which directly increases the thickness of the layers by 0.37 and 1.77 µm, respectively. The thermo-chemical treatment in water also resulted in the formation of a 0.63 µm thick sub-layer. The micromechanical tests indicated a rise in the surface microhardness of the layers in the case of their thermo-chemical treatment in water and the Na2SO4·10H2O solution and a decrease in the case of the layers modified in the Na2Cr2O7·2H2O solution. The highest microhardness (7.1 GPa) was exhibited by the layer modified in the Na2SO4·10H2O solution. Scratch tests demonstrated that the thermo-chemically treated layers had better adhesive properties than the reference layer. The best scratch resistance was exhibited by the layer after thermo-chemical treatment in the Na2SO4·10H2O solution (the highest values, practically for all the critical loads) which, together with its low roughness and high load capacity, predispose it to sliding contacts.  相似文献   

6.
Crystalline walled SBA-15 with large pore size were prepared using alkali and alkali earth metal ions (Na+, Li+, K+ and Ca2+). For this work, the ratios of alkali metal ions (Si/metal ion) ranged from 2.1 to 80, while the temperatures tested ranged from 500 to 700 °C. The SBA-15 prepared with Si/Na+ ratios ranging from 2.1 to 40 at 700 °C exhibited both cristobalite and quartz SiO2 structures in pore walls. When the Na+ amount increased (i.e., Si/Na increased from 80 to 40), the pore size was increased remarkably but the surface area and pore volume of the metal ion-based SBA-15 were decreased. When the SBA-15 prepared with Li+, K+ and Ca2+ ions (Si/metal ion = 40) was thermally treated at 700 °C, the crystalline SiO2 of quartz structure with large pore diameter (i.e., 802.5 Å) was observed for Ca+2 ion-based SBA-15, while no crystalline SiO2 structures were observed in pore walls for both the K+ and Li+ ions treated SBA-15. The crystalline SiO2 structures may be formed by the rearrangement of silica matrix when alkali or alkali earth metal ions are inserted into silica matrix at elevated temperature.  相似文献   

7.
The main hydration product and source of strength of magnesium oxysulfate cement is 5Mg(OH)2·MgSO4·7H2O (known as the 517 phase). Hardened pastes containing 92.38% of the 517 phase were synthesized in this study, and the influence of different types of chloride solutions on the stability and compressive strength of the 517 phase was investigated. X-ray diffraction and the Rietveld method were used to investigate the 517 phase transition in chloride solutions. Ion chromatography and inductively coupled plasma spectrometry were used to analyze the ion concentrations of the chloride solutions. Scanning electron microscopy and mercury injection porosimetry were used to investigate the effect of ion erosion on the microstructure and pore size distribution. The results showed that the crystal structure of 517 phase remained stable upon immersion in chloride solutions (except for the CaCl2 solution) up to 28 days, and there was no discernible attenuation in the compressive strength of the hardened pastes. Immersion of the 517 phase in CaCl2 solution for 28 days caused Ca2+ ions to combine with SO42− groups to generate CaSO4·2H2O, thereby decomposing the 517 phase. An increase in the concentration of magnesium and sulfate ions in the immersion solutions confirmed the decomposition of the 517 phase. Gel-like Mg(OH)2 was observed in the microstructure of the decomposed 517 phase, and the decomposition of the 517 phase increased the porosity of the hardened pastes.  相似文献   

8.
This paper presents a new modification of the nanostructure of CaSO4·2H2O crystals containing nanopores. This nanoporous structure was achieved in phosphogypsum samples that were modified by sodium carbonate and alum. The effects of sodium carbonate and alum on the properties of phosphogypsum were studied. X-ray diffraction (XRD) and scanning electron microscopy (SEM) methods were used to explore the micro-mechanism of the composite system. Subsequently, molecular dynamics simulations were used to study the nanopore structures of the modified CaSO4·2H2O. The results show that the addition of sodium carbonate and alum reduced the absolute dry density by 23.1% compared with the original phosphogypsum sample, with a bending strength of 2.1 MPa and compressive strength of 7.5 MPa. In addition, new hydration products, sodium sulfate and sodium aluminum sulfate, were formed in the sample doped with sodium carbonate and alum. A new nanostructure of CaSO4·2H2O crystal containing nanopores was formed. Molecular simulations show that the hydration products were responsible for the surface nanopore formation, which was the main factor leading to an increase in mechanical strength. The presented nanopore structure yields lightweight and high strength properties in the modified phosphogypsum.  相似文献   

9.
As a hazardous waste, water pickling liquors must be properly treated. An alternative consists of promoting the formation of ferrous salts from this residue due to their higher ferrous content. Since FeCl2·4H2O is widely used in several applications, obtaining pure crystals of this material appears to be an interesting prospect. However, this compound has scarcely been investigated. In the present work, FeCl2·4H2O crystals were obtained from water pickling liquors. Their structural and morphological characteristics were investigated by X-ray diffraction, scanning electron microscopy as well as Mössbauer spectroscopy. In addition, the photoluminescence study of the obtained samples was also assessed. It was observed that after some aging time, the obtained crystals changed in colour from green to more yellowish. As such, the aged sample was also evaluated, and their structural characteristics were compared with the original crystals. Despite this, the obtained crystals exhibit a FeCl2·4H2O structure, which is not modified with the aging of the sample.  相似文献   

10.
Polyvinyl alcohol (PVA) and calcium sulphoaluminate (CSA) cement were used to prepare repair mortar for the restoration of the walls of a building built with bricks. The preparation, hydration, and properties of the PVA-modified CSA cement repair mortar were studied. Besides this, the mechanism by which PVA improves the bonding strength is also discussed. The results demonstrate that PVA prolongs the setting time of CSA cement, which is ascribed to PVA inhibiting the dissolution of C4A3$ (4CaO·3Al2O3·SO3) and the precipitation of AFt (3CaO·Al2O3·3CaSO4·26H2O) within the hydration age of 0~60 min. PVA lowers the mechanical strength of CSA cement repair mortar at the hydration age of 6 h. After 6 h, the mechanical strength is improved. PVA could also improve the bonding strength between CSA repair mortar and bricks. This is mainly ascribed to the Al ions in both the hydration products of CSA cement and the clay bricks reacting with the hydroxyl group of PVA and forming the chemical bond C-O-Al. Therefore, a tighter combination between CSA cement repair mortar and the clay bricks forms, thereby improving the bonding strength.  相似文献   

11.
Inconel 625 samples, obtained by Selective Laser Melting (SLM) and conventional technology, were tested for hot corrosion resistance against a molten mixture of Na2SO4 and V2O5. The assessments were performed in air, at 900 °C with exposure time of up to 96 h, and at 1000 °C for 8 h. Weight gain was higher for samples obtained by SLM, with 37.4% after 8 h, 3.98% after 24 h, 4.46% after 48 h, and 5.8% after 96 h at 900 °C (22.6% at 1000 °C, 8 h). Three stages of corrosion were observed, the first and last with a high corrosion rate, while the second one showed a slower corrosion rate. Corrosion behaviour depends on the morphology of the grain boundary, which can influence the infiltration of corrosive salts, and on the formation of Cr2NiO4 compound, which acts as a temporary barrier.  相似文献   

12.
The use of seawater to prepare geopolymers has attracted significant research attention; however, the ions in seawater considerably influence the properties of the resulting geopolymers. This study investigated the effects of magnesium salts and alkaline solutions on the microstructure and properties of ground-granulated-blast-furnace-slag-based geopolymers. The magnesium salt–free Na2SiO4-activatied geopolymer exhibited a much higher 28 d compressive strength (63.5 MPa) than the salt-free NaOH-activatied geopolymer (31.4 MPa), with the former mainly containing an amorphous phase (C-(A)-S-H gel) and the latter containing numerous crystals. MgCl2·6H2O addition prolonged the setting times and induced halite and Cl-hydrotalcite formation. Moreover, mercury intrusion porosimetry and scanning electron microscopy revealed that the Na2SiO4-activated geopolymer containing 8.5 wt% MgCl2·6H2O exhibited a higher critical pore size (1624 nm) and consequently, a lower 28 d compressive strength (30.1 MPa) and a more loosely bound geopolymer matrix than the salt-free geopolymer. In contrast, MgSO4 addition had less pronounced effects on the setting time, mineral phase, and morphology. The Na2SiO4-activated geopolymer with 9.0 wt% MgSO4 exhibited a compressive strength of 42.8 MPa, also lower than that of the salt-free geopolymer. The results indicate that Cl is more harmful to the GGBFS-based geopolymer properties and microstructure than SO42− is.  相似文献   

13.
With the view of developing new materials for sodium and sodium-ion power sources, NaFeO2-SnO2 (0–50 mol.% SnO2) powders were synthesized using a solid state method, and their phase composition and crystal structure were studied. A phase of the Na0.8Fe0.8Sn0.2O2 composition with a layered rhombohedral structure of the α-NaFeO2 type was found when the tin dioxide content was 20 mol.%. The phase produced was of an O3 structural type. O3-type phases have sufficiently good performance when used as cathode materials in sodium-ion batteries and, moreover, often have a rather high sodium-cation conductivity. A two-dimensional migration map was built using Voronoi–Dirichlet partition and TOPOS software package. The sodium-ion conductivity of Na0.8Fe0.8Sn0.2O2 at room temperature was rated low (10−8 S × cm−1 at 20 °C), which may be the result of channels too narrow for Na+ migration. The results obtained show that the application of the compound studied in this work as a solid electrolyte in sodium power sources is unlikely. It is the potential use of Na0.8Fe0.8Sn0.2O2 as the active material of cathodes in Na and Na-ion power sources that presents practical interest.  相似文献   

14.
A 28-electron reduced C2h-Mo-blue 34Ǻ outer ring diameter circular ring, [Mo142O429H10(H2O)49(CH3CO2)5(C2H5CO2)]30- (≡{Mo142(CH3CO2)5(C2H5CO2)}) comprising eight carboxylate-coordinated (with disorder) {Mo2} linkers and six defect pockets in two inner rings (four and three for each, respectively), reacts with La3+ in aqueous solutions at pH 3.5 to yield a 28-electron reduced elliptical Ci-Mo-blue ring of formula [Mo134O416H20(H2O)46{La(H2O)5}4{La(H2O)7}4{LaCl2(H2O)5}2]10- (≡{Mo134La10}), isolated as the Na10[Mo134O416H20(H2O)46{La(H2O)5}4{La(H2O)7}4{LaCl2(H2O)5}2]·144 H2O Na+ salt. The elliptical structure of {Mo134La10} showing 36 and 31 Å long and short axes for the outer ring diameters is attributed to four (A-D) modes of LaO9/LaO7Cl2 tricapped-trigonal-prismatic coordination (TTP) geometries. Two different LaO2(H2O)7 and one LaO2(H2O)2Cl2 TTP geometries (as A-C modes) for each of two inner rings result from the coordination of all three defect pockets of the inner ring for {Mo142(CH3CO2)5(C2H5CO2)}, and two LaO4(H2O)5 TTP geometries (as D mode) result from the displacement of two (acetate/propionate-coordinated) binuclear {Mo2} linkers with La3+ in each inner ring. The isothermal titration calorimetry (ITC) of the ring modification from circle to ellipsoid, showing the endothermic reaction of [La3+]/[{Mo142(CH3CO2)5(C2H5CO2)}] = 6/1 with ΔH = 22 kJ⋅mol-1, ΔS = 172 J⋅K-1⋅mol-1, ΔG = −28 kJ⋅mol-1, and K = 9.9 × 104 M-1 at 293 K, leads to the conclusion that the coordination of the defect pockets to La3+ precedes the replacement of the {Mo2} linkers with La3+. 139La- NMR spectrometry of the coordination of {Mo142(CH3CO2)5(C2H5CO2)} ring to La3+ is also discussed.  相似文献   

15.
This study analyzed the performance evaluation of alkali-activated composites (AAC) with an alkali-sulfate activator and determined the expected effects of applying AACs to actual sites. Results revealed that when the binder weight was increased by 100 kg/m3 at 7 days of age, the homogel strength of ordinary Portland cement (OPC) and AAC increased by 0.9 and 5.0 MPa, respectively. According to the analysis of the matrix microstructures at 7 days of age, calcium silicate hydrates (C–S–H, Ca1.5SiO3.5·H2O) and ettringite (Ca6Al2(SO4)3(OH)12·26H2O) were formed in AAC, which are similar hydration products as found in OPC. Furthermore, the acid resistance analysis showed that the mass change of AAC in HCl and H2SO4 solutions ranged from 36.1% to 88.0%, lower than that of OPC, indicating AAC’s superior acid resistance. Moreover, the OPC and AAC binder weight ranges satisfying the target geltime (20–50 s) were estimated as 180.1–471.1 kg/m3 and 261.2–469.9 kg/m3, respectively, and the global warming potential (GWP) according to binder weight range was 102.3–257.3 kg CO2 eq/m3 and 72.9–126.0 kg CO2 eq/m3. Therefore, by applying AAC to actual sites, GWP is expected to be 29.5 (28.8%)–131.3 (51.0%) kg CO2 eq/m3 less than that of OPC.  相似文献   

16.
An Al2O3/5 vol%·ZrO2/5 vol%·Y3Al5O12 (YAG) tri-phase composite was manufactured by surface modification of an alumina powder with inorganic precursors of the second phases. The bulk materials were produced by die-pressing and pressureless sintering at 1500 °C, obtaining fully dense, homogenous samples, with ultra-fine ZrO2 and YAG grains dispersed in a sub-micronic alumina matrix. The high temperature mechanical properties were investigated by four-point bending tests up to 1500 °C, and the grain size stability was assessed by observing the microstructural evolution of the samples heat treated up to 1700 °C. Dynamic indentation measures were performed on as-sintered and heat-treated Al2O3/ZrO2/YAG samples in order to evaluate the micro-hardness and elastic modulus as a function of re-heating temperature. The high temperature bending tests highlighted a transition from brittle to plastic behavior comprised between 1350 and 1400 °C and a considerable flexural strength reduction at temperatures higher than 1400 °C; moreover, the microstructural investigations carried out on the re-heated samples showed a very limited grain growth up to 1650 °C.  相似文献   

17.
Silicon carbide (SiC) is a promising material used in the advanced semiconductor industry. Fabricating SiC-on-insulator via H implantation is a good method. He and H co-implantation into Si can efficiently enhance exfoliation efficiency compared to only H implantation. In this study, 6H-SiC single crystals were implanted with He+ and H2+ dual beams at room temperature, followed by annealing at 1100 °C for 15 min, and irradiations with 60 keV He ions with a fluence of 1.5 × 1016 ions/cm−2 or 5.0 × 1016 ions/cm−2 and 100 keV H2+ ions with a fluence of 5 × 1016 ions/cm−2 were carried out. The lattice disorder was characterized by both Raman spectroscopy and transmission electron microscopy. The intensity of Raman peaks decreased with increasing fluence. No Raman shift or new phases were found. A very high numerical density of bubbles was observed as compared to single H or He implantation. Moreover, stacking faults, Frank loops and tangled dislocations were formed in the damaged layer. Surface exfoliation was inhibited by co-implantation. A possible reason for this is an increase in fracture toughness and a decrease in elastic out-of-plane strain due to dense bubbles and stacking faults.  相似文献   

18.
The kinetics and mechanism of ternesite formation (calcium sulfosilicate, Ca5(SiO4)2SO4, C5S2$) were investigated by studying the reaction between beta-dicalcium silicate (β-C2S) and calcium sulfate dihydrate (CaSO4∙2H2O). Mineralogical composition development was monitored using X-ray diffraction (XRD) and backscattered scanning electron microscopy (BSEM) coupled to energy-dispersive X-ray spectroscopy (EDS). Ternesite can form in the 1100 to 1200 °C range by the solid-phase reaction of β-C2S and CaSO4. The formation of ternesite is favored by increasing the sintering temperature or extending the sintering time. The solid-phase reaction is carried out by diffusion of CaSO4 to β-C2S. The kinetics equation of ternesite is consistent with three-dimensional diffusion models (3-D model, D3 model or Jander model). The equation of the D3 model is 1 − 2α/3 − (1 − α)2/3 = kt. On the basis of the Arrhenius equation, the activation energy of ternesite is 239.8 kJ/mol.  相似文献   

19.
A mononuclear complex [MoOCl4(H2O)] readily forms a metal−metal bonded {Mo2O4}2+ core. A high content of pyridine in the reaction mixture prevents further aggregation of dinuclear cores into larger clusters and a neutral, dinuclear complex with the [Mo2O4Cl2(Py)4] composition is isolated as a product. Solid state structures of two compounds containing this complex, [Mo2O4Cl2(Py)4]·2.25Py (1) and [Mo2O4Cl2(Py)4]·1.5PyHCl (2), were investigated by X-ray crystallography.  相似文献   

20.
The paper presents studies on the early stages of biological corrosion of ordinary Portland cements (OPC) subjected to the reactive media from the agricultural industry. For ten months, cement pastes of CEM I type with various chemical compositions were exposed to pig slurry, and water was used as a reference. The phase composition and structure of hydrating cement pastes were characterized by X-ray diffraction (XRD), thermal analysis (DTA/TG/DTG/EGA), and infrared spectroscopy (FT-IR). The mechanical strength of the cement pastes was examined. A 10 to 16% decrease in the mechanical strength of the samples subjected to pig slurry was observed. The results indicated the presence of thaumasite (C3S·CO2·SO3·15H2O) as a biological corrosion product, likely formed by the reaction of cement components with living matter resulting from the presence of bacteria in pig slurry. Apart from thaumasite, portlandite (Ca(OH)2)—the product of hydration—as well as ettringite (C3A·3CaSO4·32H2O) were also observed. The study showed the increase in the calcium carbonate (CaCO3) phase. The occurrence of unreacted phases of cement clinker, i.e., dicalcium silicate (C2S) and tricalcium aluminate (C3A), in the samples was confirmed. The presence of thaumasite phase and the exposure condition-dependent disappearance of CSH phase (calcium silicate hydrate), resulting from the hydration of the cements, were demonstrated.  相似文献   

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