Surface modification of polypropylene non-woven fibers with TiO2 nanoparticles via layer-by-layer self assembly method: Preparation and photocatalytic activity

Polypropylene (PP) meltblown fibers were coated with titanium dioxide (TiO₂) nanoparticles using layer-by-layer (LbL) deposition technique. The fibers were first modified with 3 layers of poly(4-styrenesulfonic acid) (PSS) and poly(diallyl-dimethylammonium chloride) (PDADMAC) to improve the anchoring of the TiO₂ nanoparticle clusters. PDADMAC, which is positively charged, was then used as counter polyelectrolyte in tandem with anionic TiO₂ nanoparticles to construct TiO₂/PDADMAC bilayer in the LbL fashion. The number of deposited TiO₂/PDADMAC layers was varied from 1 to 7 bilayer, and could be used to adjust TiO₂ loading. The LbL technique showed higher TiO₂ loading efficiency than the impregnation approach. The modified fibers were tested for their photocatalytic activity against a model dye, Methylene Blue (MB). Results showed that the TiO₂ modified fibers exhibited excellent photocatalytic activity efficiency similar to that of TiO₂ powder dispersed in solution. The deposition of TiO₂ 3 bilayer on the PP substrate was sufficient to produce nanocomposite fibers that could bleach the MB solution in less than 4 hr. TiO₂-LbL constructions also preserved TiO₂ adhesion on substrate surface after 1 cycle of photocatalytic test. Successive photocatalytic test showed decline in MB reduction rate with loss of TiO₂ particles from the substrate outer surface. However, even in the third cycle, the TiO₂ modified fibers are still moderately effective as it could remove more than 95% of MB after 8 hr of treatment.     

Efficacy of Cinnamaldehyde Against Enteric Viruses and Its Activity After Incorporation Into Biodegradable Multilayer Systems of Interest in Food Packaging

Cinnamaldehyde (CNMA), an organic compound that gives cinnamon its flavor and odor, was investigated for its virucidal activity on norovirus surrogates, murine norovirus (MNV) and feline calicivirus (FCV), and hepatitis A virus (HAV). Initially, different concentrations of CNMA (0.1, 0.5 and 1 %) were individually mixed with each virus at titers of ca. 6–7 log₁₀ TCID₅₀/ml and incubated 2 h at 4 and 37 °C. CNMA was effective in reducing the titers of norovirus surrogates in a dose-dependent manner after 2 h at 37 °C, while HAV titers were reduced by 1 log₁₀ after treatment with 1 % of CNMA. When incubation time was extended, HAV titers were reduced by 3.4 and 2.7 log₁₀ after overnight incubation at 37 °C with 1 and 0.5 % of CNMA, respectively. Moreover, this paper analyzed, for the first time, the antiviral activity of adding an active electrospun interlayer based on zein and CNMA to a polyhydroxybutyrate packaging material (PHB) in a multilayer form. Biodegradable multilayer systems prepared with 2.60 mg/cm² (~9.7 %) of CNMA completely inactivated FCV according to ISO 22196:2011, while MNV titers were reduced by 2.75 log₁₀. When the developed multilayer films were evaluated after one month of preparation or at 25 °C, the antiviral activity was reduced as compared to freshly prepared multilayer films evaluated at 37 °C. The results show the excellent potential of this system for food contact applications as well as for active packaging technologies in order to maintain or extend food quality and safety.     

黄绵土中碳酸钙含量和有机肥施用对土壤有机碳组分及CO2排放的影响

为探讨碳酸钙(CaCO_3)和有机肥对土壤有机碳矿化和CO_2排放的影响,本研究通过向一种黄绵土中分别添加0、30、50 g·kg~(-1)CaCO_3模拟陕西省境内具有不同CaCO_3含量(9%~15%)的黄绵土,随后再添加0、20 g·kg~(-1)有机肥(M),交互组合设L0、L0-M、L30、L30-M、L50和L50-M等6个处理进行室内培养试验(105 d),测定了土壤pH、微生物量碳(MBC)、水溶性有机碳(DOC)、颗粒碳(POC)、易氧化有机碳(ROC)和CO_2释放量.结果表明:未施用有机肥时,土壤pH和MBC含量随CaCO_3含量的增加而增加,但CaCO_3含量对DOC、POC、ROC和有机碳氧化稳定性(Kos)无显著影响,其差异亦不会对土壤CO_2排放产生显著影响.当施用有机肥后,随着土壤CaCO_3含量增加,土壤pH上升、活性有机碳(MBC、DOC、POC和ROC)含量增加、Kos降低,土壤CO_2排放也随之增加.CaCO_3不仅能促进有机肥的矿化分解,而且它和有机肥会对土壤CO_2排放产生显著的交互效应,其效果与CaCO_3含量密切相关.低量CaCO_3和有机肥对土壤CO_2的释放具有负的表观交互效应,但高量CaCO_3和有机肥对其产生正的表观交互效应.因此,CaCO_3对土壤有机碳转化的影响不能一概而论,它与土壤中CaCO_3含量密切相关.在农业管理中,根据土壤CaCO_3含量合理施用有机肥对土壤碳素循环和温室气体(CO_2)排放都具有重要意义.     

Effects of amine, amine salt and amide on the behaviour of carbon dioxide absorption into calcium hydroxide suspension to precipitate calcium carbonate

The amount of carbon dioxide （CO2） absorption and calcium ion （Ca^2＋） concentration besides the pH of aqueous solution were observed during the COz absorption to precipitate calcium carbonate （CaCO3） from calcium hydroxide （Ca（OH）2）. A reaction rate-limiting effect of an amount of CO2 absorption without any organic additives in the early stage of the precipitation was observed, which was attributed to an interruption effect of bicarbonate ion （HCO3） on the precipitation of CaCO3. The improvement for the reaction rate was achieved not only by amine additives but also by neutral additives such as ε-caprolactam or amine salt. When the hexamethylene diamine was dissolved in the solution, successive change of crystal forms of CaCO3 aragonite to calcite in aqueous suspensions, confirmed by Ca^2＋ concentration change and X-ray diffraction, was concluded that a local environment around the amine group in aqueous solution and an interaction of the diamine with precipitated CaCO3 particles were important factors for these reactions.     

碱土金属钙沉积对Mn-Ce/TiO2低温SCR催化剂脱硝性能的影响

本研究采用浸渍法分别制备CaCl2、CaCO3和CaSO4这3种钙盐前驱体沉积的Mn-Ce/TiO2催化剂,通过分析催化剂活性与催化剂理化特性之间的关系,考察碱土金属钙沉积对Mn-Ce/TiO2低温SCR催化剂脱硝性能的影响.结果表明,钙的加入会导致催化剂中毒,且不同钙前驱体掺杂对催化剂中毒效应不同.CaCO3的沉积对Mn-Ce/TiO2催化剂脱硝效率的影响最小,而CaCl2沉积对催化剂活性抑制作用最为强烈.通过比表面积测试(BET)、X射线光电子能谱(XPS)、X射线晶体衍射(XRD)、程序升温脱附(TPD)等方法对不同催化剂进行表征发现,催化剂的晶型变化、孔道结构破坏、表面活性元素及酸性点位的减少是催化剂中毒的主要原因.     

化学沉淀法去除稀土湿法冶炼废水中钙与高浓度氨氮研究

离子型稀土湿法冶炼过程中会产生大量氨氮废水,由于废水中含有大量Ca2+,而Ca2+是影响磷酸铵镁沉淀法脱氮效率的重要因素.向废水中投入Na2CO3固体生成CaCO3沉淀物,去除废水中的Ca2+,再利用磷酸铵镁(MAP)沉淀法去除废水中的氨氮.实验采用响应面实验设计方法中的中心复合设计法,利用响应面分析法对磷酸铵镁沉淀法反应参数进行优化,得到最优反应条件及最优反应条件下沉淀产物.利用扫描电子显微镜(SEM)及X射线衍射(XRD)对最优反应条件下两种沉淀物进行分析.结果表明,当n(Ca2+)∶n(CO23-)=1∶1.05,搅拌速率为1 500 r.min-1,反应时间为30 min时,Ca2+去除率接近100%;对除钙后废水进行磷酸铵镁法脱氮处理的最优反应条件为:pH=9.03,n(Mg)∶n(N)=1.20,n(P)∶n(N)=1.1,反应时间为30 min,搅拌速率为1 000 r.min-1,氨氮去除率达到95.40%,剩余总磷浓度为5.65 mg.L-1;沉淀物分别为纯净的CaCO3及MgNH4PO4.6H2O.     

海藻酸锆/聚N-异丙基丙烯酰胺半互穿网络凝胶球的除磷性能

利用离子交联和自由基聚合反应制备了一种海藻酸锆/聚(N-异丙基丙烯酰胺)半互穿网络凝胶球(ZA/PNIPAM),用于吸附水中的磷酸盐.考察了溶液初始pH、吸附剂投加量、初始磷酸盐浓度和共存阴离子等因素对凝胶球吸附性能的影响.结果表明:ZA/PNIPAM在pH=2时可获得较大的吸附能力;随着投加量的减少、初始磷酸盐浓度的升高,凝胶球的吸附性能逐渐增大;SO_4~(2-)对吸附性能影响较Cl~-和NO_3~-明显.准二级动力学模型和颗粒内部扩散模型可以较好地拟合动力学吸附数据,表明表面吸附和颗粒内部扩散是吸附速率的主要控制步骤.吸附等温线数据可以较好地被Freundlich模型描述,表明吸附过程为非均匀多分子层吸附.FTIR、XPS、零电荷点(pH_(pzc))的结果以及相关吸附数据揭示凝胶球吸附磷酸盐的机制为静电吸附(物理吸附)以及配位交换(化学吸附)的共同作用.经过4次循环再生后,ZA/PNIPAM吸附性能保持稳定,具有良好的重复使用性.     

Photocatalytic activity of Fe-doped CaTiO3 under UV-visible light

The photocatalytic degradation of methylene blue（MB） over Fe-doped CaTiO3 under UV-visible light was investigated. The as-prepared samples were characterized using X-ray diffraction（XRD）, scanning electron microscope（SEM） equipped with an energy dispersive spectrometer（EDS） system, Fourier transform infrared spectra（FT-IR）, and UV-visible diffuse reflectance spectroscopy（DRS）. The results show that the doping with Fe significantly promoted the light absorption ability of CaTiO3 in the visible light region. The Fe-doped CaTiO3 exhibited higher photocatalytic activity than CaTiO3 for the degradation of MB.However, the photocatalytic activity of the Fe-doped CaTiO3 was greatly influenced by the calcination temperature during the preparation process. The Fe-doped CaTiO3 prepared at500°C exhibited the best photocatalytic activity, with degradation of almost 100% MB（10 ppm）under UV-visible light for 180 min.     

氮肥、磷肥、粉煤灰和CaCO3对As(Ⅲ)胁迫下小麦幼苗生物效应及成熟期籽粒As含量的影响

采用盆栽的方法,研究了在As污染土壤中施加氮肥、磷肥、粉煤灰和CaCO₃对小麦籽粒萌发、幼苗生理及成熟期籽粒w(As)的影响,并探讨了4种改良剂对在As污染土壤上种植小麦的有效改良方法. 结果表明:适量的氮肥、磷肥、粉煤灰和CaCO₃对As污染土壤的小麦萌发和幼苗生长具有明显的促进作用,能有效缓解As对小麦的毒害,并降低成熟期籽粒的w(As). 表现为出苗率、幼苗株高、植株鲜重增大,w(叶绿素a)升高,丙二醛(MDA)含量和w(游离脯氨酸)下降,成熟期籽粒的w(As)降低.      

茶园土壤水溶性氟含量的模拟调控

以湖北英山、大悟、竹山、赤壁和浙江杭州茶园土壤为研究对象,通过施加一定量的CaCO3、CaO、Ca3(PO4)2、CaCl2和CaSO4来调控土壤中水溶性氟含量,结果表明：英山、大悟和竹山茶园土壤中施加一定量的CaCl2或CaSO4均可降低土壤中水溶性氟含量,英山和大悟茶园土壤中可施加1～2 g·kg-1的CaCl2或...     

纳米Ag粒子原位杂化PVDF超滤膜的抗污染性能

以AgNO3为前驱体,聚偏氟乙烯(PVDF)为聚合物基体,聚乙烯吡咯烷酮(PVP)为分散剂和成孔剂,N,N-二甲基甲酰胺(DMF)为还原剂和溶剂,利用相转化法制备了纳米Ag粒子原位杂化PVDF超滤膜.采用扫描电镜、透射电镜、原子力显微镜及接触角测定仪对杂化膜的结构和性能进行了表征.结果表明:原位形成的纳米Ag粒子均匀地分散在聚合物基体中,纳米Ag粒子的添加改善了PVDF膜的亲水性能.以腐殖酸和牛血清蛋白作为污染物的代表,考察了Ag/PVDF膜的抗有机污染性能.以大肠杆菌、耐甲氧西林金黄色葡萄球菌及活性污泥作为微生物的代表,考察了杂化膜的抗生物污染性能.结果证实了与纯PVDF膜相比,Ag/PVDF膜通量衰减较慢,可有效抑制微生物的生长,表面受活性污泥污染程度小,具有显著的抗有机污染和抗生物污染性能.     

Study on polyepoxysuccinic acid reverse osmosis scale inhibitor

The effectiveness and applicability of polyepoxysuccinic acid (PESA) as a reverse osmosis (RO) scale inhibitor were studied using static and dynamic methods. In the static study, PESA performed very well in the treatment of water samples with various types of scale that commonly exist in RO water (i.e., CaCO₃, CaSO₄, BaSO₄, SrSO₄), showing an average scale inhibition ratio of above 90% at a dosage of 10 mg/L. SEM analysis showed a disordered CaCO₃ crystal in the presence of PESA, suggesting the scale-inhibiting mechanism. In the dynamic experiment, PESA also showed great performance in the treatment of 10 samples of synthetic tap water or sea water with different ion composition (i.e., Ca²⁺, HCO₃^?, Fe³⁺, Al³⁺). After one cycle (7 d) of RO treatment of each sample at full recycle operation mode under a constant pressure of 1×10⁶ Pa, the differences in water permeability and desalination ratio among samples are within 5%, suggesting that PESA is capable of treating waters of different quality, and has a strong resistance to ions that are harmful to scale inhibiting (i.e., Fe³⁺ and Al³⁺). All these results suggest that PESA should be an effective scale inhibitor that is applicable to RO treatment of waters with a wide range of ion compositions.     

碳纳米管基复合吸附剂的制备及其吸附性能

为了解决碳纳米管(CNTs)在吸附水中污染物时易聚集、难分离的问题,本文采用静电自组装技术将碳纳米管固定化在具有微米级粒径的碳酸钙颗粒表面,设计制备了壳-核结构的CNTs基复合吸附剂.实验考查了不同碳纳米管分散体系对复合吸附剂制备的影响,并采用Zeta电位、拉曼光谱、扫描电镜等手段对复合吸附剂的制备过程和结构进行表征,探讨了制备的碳纳米管基复合吸附剂对菲的吸附性能.结果发现,复合吸附剂对菲的吸附能力随CNTs载量的增加而增大,CNTs标化的吸附系数则随CNTs载量的增加而下降,碳纳米管是复合吸附剂的主要吸附位点.     

The role of fly-ash particulate material and oxide catalysts in stone degradation

Studies of fly-ash composition identified the presence of calcium and sulphur, indicating their potential role as sources of calcium sulphate. Residual acidity (particularly for oil fly ash) suggested the possibility of enhanced chemical reaction, and the presence of transition metals, probably as oxides, might accelerate the oxidation of SO₂ to SO₄²⁻. Exposure tests in a laboratory-based rig simulating dry deposition on Portland and Monks Park limestone, either seeded or unseeded with fly-ash particulate material or transition metal oxide catalysts, were carried out using an SO₂-containing environment at 95% r.h. Enhanced sulphation of these seeded limestones due to the above factors was minimal; at high loadings of fly ash, there was even evidence of masking the limestone surface, reducing sulphation. However, pure CaCO₃ powder in the exposure rig showed increases in sulphation when seeded with metal oxide catalysts. Thus the limestones examined contained sufficient inherent catalysts for the oxidation of SO₂ to SO₄²⁻ to proceed at such a rate that external catalysts were superfluous. This implies that dissolution rate of SO₂ in moisture films controls the availability of species for reaction with these carbonate-based stones and that fly ash deposited from the atmosphere does not enhance the reaction.     

Crater Wear Evolution in Multilayer Coated Carbides During Machining Using Confocal Microscopy

Steady-state turning experiments were carried out with multilayer coated inserts consisting of TiN/Al₂O₃/TiCN deposited on a carbide substrate. Confocal microscopy was used for the first time to observe the topography of crater wear evolution in multilayer coated inserts. A hump made of TiN coating next to a growing crater of Al₂O₃, traces of attached steel, and the maximum depth regions have been identified. Scoring marks were also detected in the TiN layer, indicating the presence of abrasion wear. Interestingly, the crater depth was stagnant once it reached the Al₂O₃ layer, and the wear progresses by broadening the area of exposed Al₂O₃. It was concluded that the effectiveness of multilayer coated tools comes from the dissolution resistance of the Al₂O₃ layer, which delays depth growth and develops the wear front into a wider area. Confocal microsocopy was found to be a valuable tool to obtain wear topography for multilayer coated tools.     

餐厨垃圾的黑水虻处理中含钙矿物及微生物对油脂转化效率的影响

黑水虻处理是近年来发展起来的一种餐厨垃圾的有效资源化方法,但由于黑水虻的生理特性,油脂类物质经常不能被彻底降解和去除,残渣仍有酸败气味,需堆肥化二次处理.为了提高油脂类成分的降解效率,提升黑水虻富集油脂的资源化能力,本研究拟以含钙矿物和微生物为主要辅助手段,通过向餐厨垃圾中添加湿重比例为0~10%的CaCO₃、0~10%的Ca(OH)₂、5%CaCO₃和菌液的混合物及6种不同菌液,研究含钙矿物和微生物对于油脂减量化和虫油转化效率的影响.结果发现,向餐厨垃圾中添加含钙矿物,能够显著调节和缓冲黑水虻处理过程中的环境pH值,但对增加油脂的去除效率和黑水虻油脂的转化能力没有显著作用.而且添加7%~10% 的CaCO₃对于餐厨垃圾的减量化率和黑水虻的虫产率有负作用,添加5%~10%的Ca(OH)₂会导致显著的幼虫死亡率.同时添加CaCO₃和菌液对于油脂的去除不利.仅添加微生物菌液是提高垃圾油脂减量化率和黑水虻油脂富集率的最有效方法.枯草芽孢杆菌NJZ菌株、地衣芽孢杆菌NY菌株、植物乳酸杆菌RS72菌株和粪肠球菌L102菌株,是提高黑水虻油脂转化效率的有效菌株.添加微生物后,黑水虻的虫油产率由对照组的10.4%提升至12.8%~14.4%,虫油富集率由对照组的93.9%提升至116%~130%.虫油富集率超过100%,说明餐厨垃圾中碳水化合物、蛋白质等非油脂成分的一部分转化为黑水虻的体脂,而微生物的辅助降解可能是强化这一过程的主要因素.但即使在接种微生物以后,虫沙中仍然有29%~44%的油脂在处理结束时剩余,说明餐厨垃圾中的油脂较难被彻底降解和利用.未来研究中,可以继续筛选高效降解油脂的微生物,与黑水虻共同处理餐厨垃圾,实现油脂成分的资源化全利用.     

Preparation and characterization of Pd/Fe bimetallic nanoparticles immobilized on Al2O3/PVDF membrane: Parameter optimization and dechlorination of dichloroacetic acid

Using a liquid–solid phase inversion method, a hybrid matrix poly(vinylidene fluoride)(PVDF) membrane was prepared with alumina(Al2O3) nanoparticle addition. Pd/Fe nanoparticles(NPs) were successfully immobilized on the Al2O3/PVDF membrane, which was characterized by Scanning Electron Microscopy(SEM) and Transmission Electron Microscopy(TEM). The micrographs showed that the Pd/Fe NPs were dispersed homogeneously. Several important experimental parameters were optimized, including the mechanical properties, contact angle and surface area of Al2O3/PVDF composite membranes with different Al2O3 contents. At the same time, the ferrous ion concentration and the effect of hydrophilization were studied. The results showed that the modified Al2O3/PVDF membrane functioned well as a support. The Al2O3/PVDF membrane with immobilized Pd/Fe NPs exhibited high efficiency in terms of dichloroacetic acid(DCAA) dechlorination. Additionally, a reaction pathway for DCAA dechlorination by Pd/Fe NPs immobilized on the Al2O3/PVDF membrane system was proposed.     

CaCO3 production using liquid waste from Solvay method

Process of obtaining CaCO₃ from the waste post-distillation liquid DS and post-filtration liquid from Solvay method of the soda production at 303 K was investigated. Reagents were dosed in a stoichiometric ratio without dilution, for different concentrations of the DS and post-filtration liquids. The dosage time was varied in the range 2–30 min, the reagent stirring rate was 500 rpm. For the obtained samples of CaCO₃, the bulk and packing densities, water, paraffin oil and dibutyl phthalate absorption capacities, distribution of the particle size as well as the crystalline form were determined.     

Use of coatings to minimise acid emissions during ceramic tile firing

The manufacture of traditional ceramic products (ceramic tiles, roof tiles, and bricks) is often associated with the emission of F, Cl, and S compounds during the firing stage. According to the literature, fluorine emissions can be reduced by adding CaCO₃ to the raw materials mixture used in fabricating these products. However, data available to the authors indicate that this procedure, which has been successfully applied in manufacturing structural ceramics (roof tiles and bricks), is ineffective in ceramic tile manufacture and modifies tile end properties.This paper examines the possibility of reducing such emissions by applying coatings of alkaline-earth carbonates on to the ceramic tile bottom surface to retain the acid compounds emitted during tile firing. The effectiveness of MgCO₃, CaCO₃, SrCO₃, and BaCO₃ coatings for retaining these acid emissions was studied, using the evolved gas analysis (EGA) technique with a TG-DSC-FTIR-QM instrument.The SrCO₃ coating was found to provide the greatest retention, showing that SO₂ and HCl were retained more efficiently than HF. The presence of fluorides, chlorides, and sulphates of Ca, Sr, and Ba was verified in the respective fired coatings, confirming the existence of chemical reactions between the emitted acid compounds and the coating materials at high temperature.     

加速碳酸化技术对城市垃圾焚烧飞灰重金属稳定性影响研究

对南方某城市生活垃圾焚烧厂新鲜焚烧飞灰对CO₂的吸收及其碳酸化的过程进行了研究,实验从水分添加量、CO₂的分压等因素,考察了飞灰中重金属Pb的稳定化效果,并利用X射线衍射实验(XRD)、扫描电镜实验(SEM)对反应机理进行了分析.结果表明,不添加水分时,焚烧飞灰对CO₂的吸收效果较差;当水分添加量大于10％时,焚烧飞灰对CO₂的吸收效果较好.焚烧飞灰对纯CO₂的吸收效果较好,空气中的CO₂含量较低,在反应1 d后吸收效果不是十分明显.XRD实验结果表明,CO₂的吸收会使焚烧飞灰中大量的Ca(OH)₂与CO₂反应转化为CaCO₃,从而降低焚烧飞灰的碱性;部分重金属的氧化物会被碳酸化成生相应的碳酸盐.SEM实验结果表明,经过碳酸化处理后的飞灰颗粒表面生成了片状和圆柱状的晶体物质.