半纤维素/TiO2复合凝胶的光催化降解性能

以半纤维素和TiO₂纳米粒子为原料制得半纤维素/TiO₂复合凝胶。分别用红外光谱分析和扫描电镜对复合水凝胶进行了表征,分析表明半纤维素上成功接枝聚丙烯酸,凝胶呈现多孔结构,且随着TiO₂含量的增加凝胶孔径减小。考察了半纤维素/TiO₂复合凝胶的溶胀性能以及对亚甲基蓝的光催化降解性能,研究表明半纤维素/TiO₂复合凝胶的溶胀率随着TiO₂粒子含量的增加而减小,随着pH的增大先增大后减小;对亚甲基蓝染料的降解率随着TiO₂含量的增加先增大后减小,随着pH的增大先增大后减小,随着亚甲基蓝初始浓度的增大而增大。     

水热合成二氧化钛纳米颗粒及光致发光性能研究

以价格较为低廉的钛酸丁酯为钛源,不同添加量的十六烷基三甲基溴化铵（CTAB）为模板剂,采用水热合成法制备二氧化钛纳米颗粒。利用氮吸附仪、扫描电子显微镜（SEM）、X射线衍射仪（XRD）、荧光光谱仪（PL）对材料进行结构分析及光致发光性能测试。结果表明,所制备的二氧化钛纳米材料均为锐钛矿结构,粒径较小的纳米颗粒堆积形成介孔结构。样品具有特殊的光致发光特性,由于纳米颗粒粒径大小不同,孔径大小不等使得光致发光特性的强度产生较大差异,发射峰位置产生明显红移。     

TiO_2-过渡金属光催化降解有机废水

纳米TiO2掺杂过渡金属离子,能有效提高其光催化活性和反应效率,在处理有机废水等方面具有广阔的应用前景。综述了纳米TiO2的光催化氧化降解机理,纳米TiO2掺杂过渡金属离子的制备方法,掺杂不同金属离子对TiO2光催化性能的影响以及在多种有机废水降解方面的应用等。     

Synthesis of bismuth oxide nanoparticles by the polyacrylamide gel route

A polyacrylamide gel route has been adopted for the preparation of bismuth oxide nanoparticles. Thermal behaviour of the polyacrylamide gel has been studied by means of thermogravimetry (TGA). The formation of monoclinic Bi₂O₃ nanocrystallites is confirmed by X-ray diffraction (XRD). Transmission electron microscopy (TEM) investigation revealed the average particle size of Bi₂O₃ nanoparticles to range from 30 nm to 50 nm.     

Friction and wear behavior of the hybrid PTFE/cotton fabric composites filled with TiO2 nanoparticles and modified TiO2 nanoparticles

A chemical grafting method was applied to modify TiO₂ nanoparticles through covalently introducing glycidoxypropyltrimethoxy silicane (KH560) followed by polyoxymethylene onto the particles to overcome the disadvantages generated by the agglomeration of nanoparticles. TiO₂ nanoparticles unmodified and modified were introduced into hybrid polytetrafluoroethylene (PTFE)/cotton fabric composites. Friction and wear test demonstrated that TiO₂ nanoparticles unmodified and modified can significantly increase the wear resistance of hybrid PTFE/cotton fabric composites but cannot reduce the friction coefficient. Fabric composites filled with grafted TiO₂ nanoparticles exhibited a lower wear rate due to the disintegration of agglomeration and the improvement of interfacial adhesion between filler/matrix. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

PC/纳米SiO2复合材料的热降解行为

采用熔融共混法制备了聚碳酸酯(PC)/纳米二氧化硅(SiO2)复合材料。采用X射线衍射和扫描电子显微镜研究了PC和PC/纳米SiO2复合材料的结构,采用热重分析了PC和PC/纳米SiO2复合材料的热降解行为,用Kissinger-Akahira-Sunose法研究了PC和PC/纳米SiO2复合材料的热降解动力学。结果表明:PC的内部结构没有发生变化,且纳米SiO2在基体中分散均匀;加入纳米SiO2能显著改善PC的热稳定性,且PC和PC/纳米SiO2复合材料的热降解温度均随升温速率提高呈线性增加;PC和PC/纳米SiO2复合材料的热降解活化能均随转化率升高而增加,且PC/纳米SiO2复合材料的活化能明显高于PC。     

Formation of anatase TiO2 nanoparticles by simple polymer gel technique and their properties

Pure anatase nano-TiO₂ powders were successfully prepared by a simple polymer gel technique using poly-(vinylpyrrolidone) (PVP) as the polymer. The products were systematically characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HR-TEM), UV–visible spectroscopy and photoluminescence studies. The XRD and XPS results indicate that the prepared powder had a pure anatase nano-TiO₂ structure with lattice parameters a and c of 0.378 and 0.951 nm, respectively. The particle size analysed by TEM ranged between 7 and 12 nm. The maximum UV absorption for the TiO₂ nanoparticles was below 400 nm with an estimated direct band gap (Eg) of 3.55 eV. The photoluminescence peaks of the nanopowder were observed at 391 and 468 nm. The nanosized materials were produced using a simple and cost effective polymer gel technique.     

Thermal and swelling studies of hydrophobically modified polyacrylamide hydrogels

Hydrophobically modified polyacrylamide hydrogels were prepared by polymerizing acrylamide, using n‐butyl acrylate and 2‐ethyl hexyl acrylate as comonomers and dimethyl formamide as a solvent. We report here for the first time that the Alfred Q‐e reactivity ratios are matching with the experimental value (elemental analysis result) for the terpolymer hydrogel systems. Differential scanning calorimetry (DSC) thermograms of the hydrogel samples revealed two endothermic transitions, one near 0°C, corresponding to the melting transition of ice and another above ambient temperature. This high temperature transition is due to the rearrangement of water molecules engaged in hydrophobic hydration surrounding the hydrophobic groups (alkyl side chains). This depends on the type of hydrophobic groups and the gel compositions. Swelling and deswelling studies of the gels were performed using various solvents such as water and isopropyl alcohol. An abnormally high swelling and deswelling behavior was observed in the homopolymer gels and the gels with low amount of hydrophobic comonomers. This could be attributed to the more intramolecular cross‐linked structure formed during synthesis in organic solvent. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Enhancement of MTBE photocatalytic degradation by modification of TiO2 with gold nanoparticles

The photocatalytic degradation of methyl tert-butyl ether by gold-modified TiO₂ has been studied by a combination of high resolution electron microscopy, X-ray photoelectron spectroscopy and reactor measurements. The optimum gold loading corresponded to a mean Au particle size of ⩽ 3 nm at which point the gold may no longer be metallic. Such catalysts exhibited a threefold rate enhancement compared to unmodified TiO₂, possibly due to injection of photo-excited electrons from semiconducting Au into the TiO₂ conduction band. Since the presence of dissolved oxygen was crucially important to good performance, it is possible that an additional factor was lowering of the local work function, thus promoting electron transfer to dioxygen molecules adsorbed at the Au/TiO₂ interface.     

聚丙烯的热降解和燃烧行为

采用热重分析法对聚丙烯(PP)的热降解行为进行了表征,测定了不同升温速率下PP的热降解过程,得出其热降解活化能为239.58 kJ/mol;用锥形量热仪研究了PP的燃烧行为,随着辐射强度增加,PP的热释放速率增加,质量损失速率加快且分解起始时间提前,热释放总量保持恒定;试样厚度对表征材料的燃烧行为有一定影响。     

掺杂过渡金属离子的纳米TiO_2光催化降解制革废水

以石英砂为载体,液相沉积水解法制备的纳米TiO2膜为光催化剂,通过掺杂过渡金属离子对膜进行改性。在高压紫外灯光、低压紫外灯光和自然光照射条件下,分别对制革废水进行处理。以CODCr为评价指标,分析了不同光照条件对TiO2膜光催化性能的影响。结果表明,在高压紫外灯光照15 min后,Hg/TiO2膜光降解率最高,CODCr去除率为50.23%。通过探讨各种掺杂离子对膜的改性规律发现,改性效果与过渡金属离子电荷和半径的比值有关。对于同周期的元素,第二过渡周期的掺杂效果好于第一、第三过渡周期,但掺杂规律不像第一、第三过渡周期那样明显,随原子半径的减小而增大。对于同一族的元素,离子的掺杂作用基本上随着原子半径的增大而增大。     

CdSe纳米颗粒敏化TiO_2纳米管阵列的光催化降解及光电催化制氢

采用胶体化学法制备不同尺寸的硒化镉纳米颗粒(CdSe-NP)胶体,并利用原位吸附法将CdSe-NP与由阳极氧化法得到的TiO2纳米管阵列(TN)复合,在可见光下降解甲基橙溶液和外加偏压制氢,分别考察CdSe-NP敏化的TiO2纳米管阵列(CdSe-NP/TN)的光催化性能和光电催化性能。对比TN,CdSe-NP/TN表现出明显增强的光催化活性及更优异的光电催化性能,而过大的CdSe-NP尺寸则不利于复合材料的催化活性。表征结果表明,CdSe-NP/TN优异的性能是由于敏化CdSe-NP后吸收边红移以及光生电子和空穴复合率降低。     

Thermal degradation behavior and kinetic properties of 1, 8-naphthalic anhydride loaded hybrid bimodal mesoporous silicas

The novel luminescent hybrid bimodal mesoporous silicas (LHMS) with 1, 8-naphthalic anhydride (NA) as the fluorescence materials were synthesized through post-synthesis route and grafting method. The resulting materials were characterized by XRD, TEM, N₂ adsorption?Cdesorption isotherms and FT-IR. Particularly, thermal degradation behavior and kinetic properties of LHMS were investigated in detail by using thermogravimetric analyzer (TGA) at different heating rates in flowing N₂ . TG experiments were performed to elucidate their thermal properties and the degradation behaviors. Meanwhile, using Kissinger and Flynn?CWall?COzawa principles, the apparent activation energies were calculated and the thermal decomposition mechanism of the grafting process was put forward on the basis of the Coats-Redfern method.     

One-step hydrothermal synthesis of a TiO2-Ti3C2Tx nanocomposite with small sized TiO2 nanoparticles

A TiO₂-Ti₃C₂T_x nanocomposite was prepared using a simple and facile one-step hydrothermal method. The small sized TiO₂ nanoparticles were synthesized and assembled on the surface of Ti₃C₂T_x nanosheets using Ti₃C₂T_x itself as titanium source by in-situ technique. The microstructure of TiO₂-Ti₃C₂T_x nanocomposite was characterized by means of XRD、FESEM、TEM、XPS and Raman, respectively. The effects of ethanol and hydrothermal holding time on the size of TiO₂ nanoparticles were investigated. The results show that adding proper amount of ethanol into pure water results in decrease of the size of TiO₂ nanoparticles. Under ethanol-water mixed solution, increasing the time of hydrothermal treatment results in growth and even aggregation of TiO₂ nanoparticles. The TiO₂ nanoparticles with average particle size of 30 nm were obtained when the hydrothermal treatment was conducted in ethanol-water mixed solution at 200 ℃ for 12 h.     

两种合成方式对制备纳米二氧化钛粉体的影响

以钛酸四丁酯为原料,分别通过溶胶-凝胶法和硬脂酸凝胶法制得TiO2前驱体,在450℃煅烧后分别得到粒径在42.4,9.4 nm的混晶纳米TiO2。运用XRD和TEM等方法对TiO2进行表征,探讨了两种合成方式对纳米TiO2粒径大小及TiO2晶型转变温度的影响。结果表明,以硬脂酸凝胶法合成的纳米TiO2纯度高、粒径小,且晶型转变温度低,这是由于晶粒细化后晶型转变温度降低的缘故。     

Preparation,characterization, and photocatalytic degradation properties of polyacrylamide/calcium alginate/TiO2 composite film

Titanium dioxide (TiO₂) nanoparticles were dispersed in the sodium alginate and acrylamide aqueous solution to prepare the casting solution. The casting solution was spread on a glass plate by a glass rod enlaced with brass wires to control the thickness of the film. Then polyacrylamide/calcium alginate/TiO₂ (PAM/CA/T) composite film was obtained after UV irradiation and crosslinking by CaCl₂. The PAM/CA/T film was characterized by scanning electron microscopy and transmission electron microscope. The mechanical properties of the films were tested in wet form and the results showed that PAM/CA/T film had good strength and toughness. PAM/CA/T films did not rupture after swelling in 5.0 wt% NaCl solution and still had good mechanical properties. The PAM/CA/T hydrogel film provided a suitable carrier for TiO₂ in the photocatalytic degradation of dyes and the degradation rate of PAM/CA/T‐30 for methyl orange reached 80.8%. The PAM/CA/T film had good reusability and could degrade dyes in a high concentration of NaCl solution. POLYM. COMPOS. 37:1292–1301, 2016. © 2014 Society of Plastics Engineers     

Adsorption behavior and shear degradation of ultrahigh-molecular-weight hydrolyzed polyacrylamide in a capillary flow

Ultrahigh-molecular-weight partially hydrolyzed polyacrylamides (HPAMs) are commonly used in polymer flooding to enhance oil recovery. However, the viscosity of the HPAM solution is susceptible to shear action. Viscosity change affects sweep range and displacement efficiency of the displacement fluid. Here, a macromolecular adsorption model in microcapillary is proposed to reveal the shear variation mechanism at low flow rates. The rheological behaviors of HPAMs with three different molecular weights are investigated using a stainless steel capillary. The shear rate distributions near contraction and within capillary are compared by numerical calculation using the laminar flow model. Experimental and numerical results show that the polymer solution was mechanically degraded at low flow rates, which is in agreement with the results predicted by the adsorption theory model. A new calculation method for the thickness of polymer adsorption layer at lower flow rates is proposed based on the adsorption model proposed in this study. It is found that the viscosity and adsorption of HPAM were changed with flow rate, and their changes are closely related to the displacement efficiency in the micropores of reservoirs. This study provides new perspectives for the selection of polymer injection flow rates and the water shutoff in reservoirs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48270.     

利用Sol-Gel法与水热合成法制备纳米TiO2及其光催化活性研究

以Sol-Gel法及水热合成方法制备了纳米TiO2,利用XRD进行了表征,以太阳光为光源,通过对亚甲基蓝溶液的降解反应,考察了两种方法所得样品的光催化活性。结果表明,利用水热合成法制备的锐钛矿型TiO2具有更小的粒径,而通过溶胶-凝胶制得的样品为混晶型TiO2,对亚甲基蓝降解具有较高的光催化活性。     

Photocatalytic activity of surface modified TiO2/RuO2/SiO2 nanoparticles for azo-dye degradation

SiO₂/RuO₂ modified high surface area titania dioxide nanoparticles prepared by hydrogen reduction were examined for their catalytic properties towards the photodegradation of methyl orange (MO), a common water pollutant in the textile industry. The modified materials present enhanced photocatalytic activity and can decompose the MO faster than the unmodified TiO₂. Results showed that doping with RuO₂ only offered a marginal benefit over TiO₂ alone. On the other hand, modification of TiO₂with RuO₂ and SiO₂ resulted in a marked increase in the rate constant and the photodegradation efficiency. These results are consistent with the unique structural, morphologoical and surface characteristics of the composite titania dioxide/ruthenium dioxide/silicon dioxide materials. The lower the average particle size and roughness of the materials, the higher the percentage of photodecomposition and the rate constant. The surface doping and modification effects thus appears synergetic to the charge separation process and the photocatalytic results are explained on the basis of the mechanism that involves efficient separation of electron–hole pairs induced by the silicon dioxide particles. This enhances the ability of the modified TiO₂ particles to effectively capture protons. Results also show that the modified nanoparticles can be used repeatedly over a long time without loss of efficiency.     

New method for evaluation of kinetic parameters and mechanism of degradation from pyrolysis–GC studies: Thermal degradation of polydimethylsiloxanes

Thermal degradation of polydimethylsiloxane (PDMS) polymers having hydroxyl (PS) and vinyl (PS‐V) terminals was studied by pyrolysis‐gas chromatography (PGC) in the temperature range from 550 to 950°C. The degradation products were primarily cyclic oligomers ranging from trimer (D₃) to cyclomer D₁₁ and minor amounts of linear products and methane. The product composition varied significantly with pyrolysis temperature and extent of degradation. A new method was developed to derive a mass loss‐temperature curve (pyrothermogram, PTG) and to determine the kinetic parameters of decomposition (k, n, and E_a) from sequential pyrolysis studies. It was shown that isothermal rate constants can be derived from repeated pyrolysis data. Good agreement between the rate constants derived from the two methods validates the methodology adopted. This was further confirmed from thermogravimetric studies. The E_a values for the decomposition of PS and PS‐V derived from sequential pyrolysis were 40 ± 2 and 46 ± 2 kcal mol⁻¹, respectively. Various mechanisms for the degradation of PDMS were reviewed and discussed in relation to the PGC results. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 441–450, 1999