稀土石膏常压酸化法制备硫酸钙晶须的研究

以含稀土的石膏为原料运用常压酸化法合成硫酸钙晶须,探讨了不同工艺条件对生成的硫酸钙晶须形貌的影响,同时还考察了晶型助长剂的种类和晶型助长剂的含量对硫酸钙晶须生长的影响,利用SEM和XRD分别对硫酸钙晶须的表面形貌、物相特征做了表征分析。实验得到制备硫酸钙晶须的最佳的反应条件：稀土石膏质量浓度为0.22 g/mL、反应时间为25 min、盐酸浓度为2.8 mol/L、反应温度为70 ℃、陈化时间为4 h,在此条件下合成的硫酸钙晶须平均长度为61 μm,平均长径比为30.5;通过对比实验选出了CuCl₂作为促进硫酸钙晶须生长的助长剂,在添加5%（质量分数）的CuCl₂的情况下可使硫酸钙晶须长径比从30.5增至41,长度从61 μm增至81 μm。     

Microstructural and electrical changes in Ca0.9R0.1CeNbMoO8 (R = Y,Sm, Nd,La) ceramics induced by rare-earth ion doping

Rare-earth ions doped Ca_0.9R_0.1CeNbMoO₈ (R = Y, Sm, Nd, La) ceramics have been successfully prepared by solid-state method, and their modifications to the microstructure and electrical properties are also investigated. The rare-earth ions doped ceramics exhibit the scheelite structure. With the increase in the radius of rare-earth ions, the lattice distortion and bond interaction will be enhanced, and the consistency of grain size will be reduced. The ceramics exhibit negative temperature coefficient (NTC) thermistor characteristics in the temperature range of 473 K-1273 K, and the activation energy decreases with the increase of the radius of rare-earth ions. Rare-earth ions doping can increase the content of Ce³⁺ ions and promote the conductivity of ceramics. Except for Sm³⁺-doped ceramics, the high-temperature aging rate of other ceramics is less than 2%. The existence of some metastable Sm²⁺ ions in Sm³⁺-doped ceramics not only increases the activation energy, but also reduces the high-temperature stability of the ceramics.     

Rare-earth free sensitizer in NaLuCrF4:Er upconversion material

Upconversion phosphors are known as a material system that can convert near-infrared light into visible/ultraviolet emissions by sequentially absorbing multiple photons. The studies on upconversion materials often use two rare earth (RE) ions as a sensitizer-activator pair. We investigated the influences on luminescence intensity depending on Cr-doping content (x) of hexagonal NaLu_0.98–xCr_xF₄Er_0.02 (x = 0–0.9) upconversion material by substituting Lu³⁺ ions with Cr³⁺in the absence of Gd³⁺. The change in upconversion luminescence intensity appears with saddle-like shape. We suggest that Cr³⁺ ions play the dual role as a constituent in host lattice and a sensitizer in the upconversion process. Optimal conditions for gaining the strongest upconversion emission correspond to x = 0.3–0.5, where there are effective energy transfers between Cr³⁺ and Er³⁺ ions and CrEr dimers. Apart from these values, the emission intensity decreases rapidly which can be ascribed to the absence of multiple-photon absorption for the case of low Cr³⁺ contents, and to the coupling between Cr³⁺ and/or Er³⁺ ions for the case of high Cr³⁺ contents. Magnetization and electron-spin-resonant measurements were performed to understand the correlation between the optical and magnetic properties.     

不同粒径改性粉煤灰对磷酸根吸附性能的影响

废水排放过量的磷导致水体污染日益严重，将粉煤灰通过化学改性制备成了水化硅酸钙吸附剂，研究了改性吸附剂对磷酸根的吸附效果。利用XRD, SEM及BET比表面积等手段对粒度分级前后的吸附剂进行表征，研究不同粒级吸附剂对磷酸根的吸附性能，并考察其吸附机理。结果表明，不同粒级的吸附剂其化学成分出现了明显的偏析现象，孔隙结构也差异显著。相比其他粒径下的吸附剂颗粒，颗粒粒径在50?75 μm时，吸附剂中钙和硅含量较多，铝、铁和镁含量较低，水化硅酸钙组分含量最高，且伴有含铝的托贝莫来石晶体出现，钙离子的增加使其可以与更多的磷酸根结合形成沉淀。同时此粒径下具有较高的比表面积及孔隙度，疏松多孔的结构为钙离子提供更多活性位点。当使用粒径在50?75 μm的吸附剂吸附磷酸根时，磷的饱和吸附量可达到17.1 mg/g，比未分级的吸附剂高19.58%。     

Synthesis and characterization of a novel Ca-alginate-biochar composite as efficient zinc (Zn2+) adsorbent: Thermodynamics,process design,mass transfer and isotherm modeling

In this present work, Ca-alginate-biochar adsorbent has been synthesized, characterized and tested its effectiveness in the removal of aqueous phase Zn²⁺ metal. The removal efficiency was studied under various physicochemical process parameters. External mass transfer model, intraparticle diffusion model and pseudo-first-order and pseudo-second-order models were used to fit the experimental Zn²⁺ adoption kinetic results and to identify the mechanism of adsorption. The desorption studies indicate the possibilities of ion-exchange and physical–chemical adsorption of Zn^2+. The adsorption was best described by Langmuir isotherm model. Thermodynamic parameters suggested that the adsorption process becomes spontaneous, endothermic and irreversible in nature.     

Synergistic antimicrobial effect of lactocin AL705 and nisin combined with organic acid salts against Listeria innocua 7 in broth and a hard cheese

The effectiveness of antimicrobial mixtures against Listeria innocua 7, used as a L. monocytogenes surrogate, was investigated in broth and a food system. Synergistic effects were found for nisin (Nis), potassium sorbate (PS), calcium propionate (CP) and sodium lactate (SL), Nis + PS being the most effective binary mixture that exhibited listericidal activity in broth. To assess the effect of adding lactocin AL705 (AL705) to Nis + organic acid salt combinations, tridimensional isobolograms were generated. Sub-MIC combinations of the antimicrobials exerted bactericidal activity against L. innocua 7 after AL705 addition to the binary mixtures. However, when applied on Sardo cheese contaminated with L. innocua 7 (initial inoculum 4.45 ± 0.06 CFU g⁻¹), only Nis + PS + AL705 produced count reductions respect to the control, reaching 3.04 ± 0.35 CFU g⁻¹ counts after 15 days at 15 °C. Ternary combinations containing AL705 showed potential to reduce antimicrobial usages for L. innocua 7 inhibition.     

3D pore-interconnected calcium phosphate bone blocks for bone tissue engineering

Pore size and connectivity of artificial bone scaffolds play key role in regulating cell ingrowth and vascularization during healing. The objective of this study was to develop a novel process for preparing 3D pore-interconnected open-cell bone substitutes with varying pore sizes. This was achieved by thermal-induced expansion, drying, then sintering the mixture of biphasic calcium phosphate (BCP) and a thermal responsive porogen comprising chitosan (CS) and hydroxypropyl methyl cellulose (HPMC). The interpolymer complexes (IPCs) of CS/HPMC were prepared and investigated by FT-IR. The mixtures of IPCs/BCP were heated up to 100 °C for analyzing their thermal expansion properties. This resulted in ~13% and ~42% volume increment for IPC-1/BCP and IPC-2/BCP, respectively, while ~230% volume increased in the case of IPC-3/BCP (therefore chosen for sintering bone blocks). Heating rate-dependent (0.20–0.25 °C/min range) sintering profiles for IPC-3/BCP were utilized to produce BCP bone blocks. Gasification of IPC during sintering resulted in the formation of interconnected porous structures, and the morphology was investigated by SEM, revealing varying sizes ranging from 106 ± 13 μm to 1123 ± 75 μm. The pore size range of bone blocks from 235 ± 46 μm to 459 ± 76 μm portrayed significantly high MC3T3-E1 cell viability with prominent filopodial extensions, and elongated cells, depicting efficient biocompatibility. Therefore, the process for preparing porous interconnected 3D bone blocks were feasible, thereby serving as an alternative for potential bone tissue engineering applications.     

A comparative study on in vitro behavior of calcium silicate ceramics synthesized from biowaste resources

Calcium silicate ceramics have received significant attention for biomedical applications for their excellent bioactivity and osteoconduction properties. Sol-gel process is extensively used for the fabrication of calcium silicates. In sol-gel process, calcium nitrate tetra hydrate (Ca(NO₃)₂·4H₂O) and tetraethylorthosilicate (TEOS) are used as precursors. However, these precursors are expensive. The objective of this work was to compare in vitro behavior of calcium silicate (CaSiO₃) produced using biowaste such as rice husk ash (RHA) and eggshells (coded; NCS) with CaSiO₃ prepared using TEOS and Ca(NO₃)₂·4H₂O (coded; CCS). Thermal investigation results revealed that the crystallization temperature for NCS is relatively lower (772°C) than for CCS (870°C). Bioactivity was studied in vitro using simulated body fluid (SBF) with respect to mineralization rate of hydroxyapatite. Mineralization of a greater hydroxyapatite was observed on NCS ceramics than CCS ceramics after incubation for 3, 7, 14 days in SBF solution, which was confirmed using X-ray diffractometer, Fourier transform infrared spectroscopy, scanning electron microscopy-energy dispersive spectroscopy. Degradation studies were conducted in Tris-HCl solution and the test results revealed that NCS ceramics has lower dissolution rate than CCS ceramics. The antimicrobial assay has shown that NCS samples exhibit significant zone of inhibition against Escherichia coli and Staphylococcus aureus which confirmed that the CaSiO₃ prepared from RHA and eggshell can prevent bacteria from adhering to the surface. In addition cell culture studies revealed that NCS ceramics possess good cytocompatibility with MG-63 cells and significantly promoted cell proliferation.     

基于萤石溶解/表面转化的含钙矿物表面定向调控浮选技术及机理研究

研究了萤石在白钨矿和方解石表面溶解和转化的可能性, 发现萤石可以在特定的捕收剂体系下作为抑制剂实现含钙矿物的浮选分离。浮选实验结果表明, 萤石作为抑制剂, 在白钨矿和方解石的浮选中, 用量小、作用效果明显; 动电位检测结果证实了萤石能明显降低方解石的动电位, 但对白钨矿基本没有影响; XPS检测结果证明了萤石对方解石的作用主要在于对Ca-O键能的减弱和Ca-F基团的生成, 即在方解石表面生成CaF2膜; AFM检测则可直观观察到方解石表面经过萤石处理之后出现明显的起伏, 印证了离子的侵蚀与CaF₂膜的生成。