Preparation of Silica/Poly(divinylbenzene) Composite Particles by Dispersion Polymerization in Supercritical Carbon Dioxide

Silica/poly(divinylbenzene) (PDVB) composite particles were synthesized by the dispersion polymerization of divinylbenzene (DVB) with ultrafine silica particles in supercritical carbon dioxide (scCO₂). Silica particles of average diameter 130 nm were pretreated with 3-(trimethoxysilyl) propyl methacrylate in order to be well dispersed in CO₂ and participated in the polymerization. Random copolymeric dispersant, poly(diisopropylaminoethyl methacrylate-co-heptafluorobutyl methacrylate) was used as a stabilizer to provide sufficient stabilization to latexes in scCO₂ and the silica/PDVB composite powder was obtained in high yield from the polymerization. SEM analysis revealed that the composite particles prepared at 5% silica loading ratio and 6% stabilizer concentration with respect to monomer have the average diameter of 1.60 μm with uniform and spherical morphology. The composites were also characterized by FTIR spectroscopy and TGA.     

The preparation of clay nanosheets-poly(ethylene terephthalate) hybrid materials

The preparation of hybrid materials of poly(ethylene terephthalate) (PET) with montmorillonite (Mont) clay was investigated using anchor monomers, i.e. hydroxyethyl isonicotinamide (HENA) or hydroxypentyltrimethylammonium iodide (HPTA), which both have cationic substituents to adsorb onto clay surfaces and a hydroxyethyl moiety (–CH₂CH₂OH) to react with the polymer chain terminal of PET. The condensation of the mixtures of the intercalation compounds, bis (2-hydroxyethyl) terephthalate (BHET) and HENA/Mont or HPTA/Mont, led to a homogenous and transparent PET hybrid in which the Mont clay particles were scattered homogenously. The HPTA/Mont hybrid films copolymerized with BHET exhibited a dramatic improvement in such characteristics as tensile strength and optical transparency.     

Covalent attachment of poly(ethylene glycol) on multi-walled carbon nanotubes

A new 'graft-onto' method to attach poly(ethylene glycol) (PEG) onto multi-walled carbon nanotubes (MWNTs) has been developed. The method is based on the coupling reaction of radicals formed at the chain end of PEG onto the surface of MWNTs. The polymeric radicals are generated by atom (halogen) transfer reaction between chloroacetyl-terminated PEG and transition metal catalysts. The method allows direct covalent attachment of PEG to pristine MWNTs without pretreatment that could alter their original structure. The resulting PEG-grafted MWNTs showed improved dispersion stability in isopropanol and methanol.     

Annealing effect on adhesion properties of poly(butylene terephthalate)

Injection-molded poly(butylene terephthalate) (PBT) is generally annealed at a temperature above the operating temperature to remove residual internal stress and obtain high-dimensional stability. However, this annealing treatment causes poor adhesion property and affected quality and lifetime for the products. In this study, a plausible mechanism for why such problems are caused by the annealing treatment is proposed using additive free PBT. After PBT was annealed under given conditions, surface structure and adhesion strength with an epoxy adhesive were examined. Surface roughness of the PBT film monotonically increased with increasing annealing time, and the tensile adhesive strength concurrently decreased. In addition, the height difference between hill and valley of the surface after adhesive failure became larger, meaning that the failure took place in the PBT phase beneath the interface with the epoxy region. Based on these findings, it was claimed that the poor adhesion of PBT after the annealing treatment originated from a weak boundary layer, which was formed at the outermost surface of PBT. Finally, the presence of the weak boundary layer was directly confirmed by transmission electron microscopy.     

PATP在Ag/TiO_2纳米管基底上的表面增强拉曼散射和光催化过程研究

表面增强拉曼散射(SERS)是一种超灵敏、高选择性的分析方法,越来越受到人们的关注。对巯基苯胺(PATP)由于其易吸附在大多数SERS基底表面,并可以产生极强的SERS信号,因此常被用作SERS的探针分子。二氧化钛(TiO_2)是一种目前常用的光催化剂,但是其催化效率仍有待提高。将贵金属与TiO_2复合是提高其催化效率的有效手段。本文采用电化学阳极氧化法制备了二氧化钛纳米管(TiO_2NTs),并采用光化学还原方法在表面沉积了贵金属银,制备了一种同时具有SERS和催化性能的双功能基底,即银纳米粒子修饰的二氧化钛纳米管(Ag/TiO_2NTs),研究了PATP分子在该基底上的光催化过程,并与在银镜基底上的光催化过程进行了比较。我们发现,Ag/TiO_2NTs基底上的PATP在催化过程中峰强度逐渐减弱,但没有新峰的出现;而在银镜基底上PATP的峰强度随光照时间却几乎没有变化,证明了PATP分子在Ag/TiO_2 NTs上的光催化降解过程。本文还对Ag/TiO_2NTs上PATP的催化过程进行了动力学分析,结果表明PATP在该基底表面的催化反应为一级反应。     

Crystal Phases of TiO2 Ultrafine Particles Prepared by Laser Ablation of Solid Rods

Titanium dioxide ultrafine particles (UFPs) are produced by pulsed laser ablation of titanium or titanium dioxide (anatase and rutile) rods in an atmosphere of He or O₂/He mixture. The collected UFPs on cellulose membrane filters at the exit of the ablation chamber are analyzed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The TiO₂ particles produced are composed of very small particles (diameter: 10–50nm) that are completely anatase, irrespective of the rod material, and relatively large particles (diameter: 100nm–1m) that are a mixture of anatase and rutile. The large particles consist of the direct strip-off fragments coming from the rod surface. The particles obtained from the laser ablation on TiO₂ rods in an atmosphere of He contains gray particles that are supposed to be amorphous TiO₂ (x < 2). In the presence of O₂ in the ablation chamber, these oxygen defects in amorphous TiO₂ are stabilized and anatase UFPs are formed. These results suggest that the crystal phase of the products can be controlled by adjusting the rod material and the gases used in the ablation process.     

First principles study of oxygen adsorption on the anatase TiO2 (101) surface

The main objective of this study is to understand the sensing origin of anatase TiO₂ and provide an insight into why gas sensitivity of anatase TiO₂ is not so excellent.

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Preparation of nanocomposite superabsorbents based on hydrotalcite and poly(acrylic-co-acrylamide) by inverse suspension polymerization

Firstly, hydrotalcite (HT) was synthesized by the urea method. Then, sodium methyl allyl sulfonate (SMAS) was used as intercalation agent to prepare intercalated HT (SMAS–HT). Finally, a novel poly(acrylic-co-acrylamide)/HT nanocomposite superabsorbent was prepared by inverse suspension polymerization, using N,N′-methylenebisacrylamide (NMBA) as a cross-linking agent and potassium persulfate (KPS) as an initiator. The morphology of the superabsorbents was characterized by FT-IR, XRD, SEM and TEM. The influences of the amount of SMAS–HT on the water (salt) absorbency were investigated. Results showed that the intercalation was successful and the intercalated SMAS–HT incorporated into the superabsorbent was completely exfoliated. The superabsorbent particles approach a spherical shape and the average size is 200–300 nm. The particle sizes of the superabsorbents decrease with increasing the content of SMAS–HT. In addition, the superabsorbent acquired its highest water (salt) absorbency when the content of SMAS–HT is 3 wt%. The highest absorbencies of the superabsorbent for deionized water and 0.9% NaCl_(aq) were 900 g/g and 140 g/g, respectively.     

掺杂Er^3＋的TiO2的发射光谱研究

用无水乙醇、冰醋酸、钛酸丁酯凝胶法制备了掺杂Er^3＋的TiO2粉末，测量了其在488m激发下的Stokes发射光谱和980nm激发下的上转换发光光谱。在可见光范围内，观察到了绿光和红光，绿光从500-570nm，对应Er^3＋的^2H11/2,^4S3／2→^4I15/2，红光从650～690m，对应Er^3＋的^4F9／2→^4I15／2的跃迁。由ln Ivis-In Iin曲线可知，绿光和红光均为双光子过程，光强正比于泵浦功率的二次方，即Iout ∝Iin。初步研究了此材料的上转换过程。     

Effect of a Novel Polymeric Coupling Agent on the Water Uptake Property and Warp Stability of Poly(vinyl chloride)/Bamboo Flour Composite

Water uptake property and warp stability of poly(vinyl chloride) (PVC)/bamboo flour composite were investigated employing a novel polymeric coupling agent, poly(styrene-co-maleic anhydride)-block-poly(styrene-co-acrylonitrile) {P[(SMA)-b-(SAN)]}. P[(SMA)-b-(SAN)] was synthesized through controlled/'living' radical polymerization (CRP) technique in an one-pot reaction and incorporated into the composite to improve the interfacial adhesion between PVC and bamboo flour. The structure of P[(SMA)-b-(SAN)] was confirmed by ¹H-NMR, FT-IR and GPC. PVC/bamboo flour composite sheets were then prepared from a single screw extruder and two-roll mill in the presence of P[(SMA)-b-(SAN)] coupling agent. As the content of the coupling agent increased, improved interfacial bonding between PVC and bamboo flour filler was observed. Water uptake property and warp stability were also improved in the presence of the coupling agent. These results suggest that the block copolymer successfully acted as a coupling agent in PVC/bamboo flour composites.     

TiO_2/白云母纳米复合材料的色度学研究

利用化学液相沉积法制备了系列TiO2白云母纳米复合材料.在利用扫描电子显微镜、X射线衍射对其进行表面形貌、TiO2纳米镀层物相组成研究的基础上,仔细研究了TiO2白云母纳米复合材料在可见光下的反射光谱特征,并利用Munsell新坐标(HVC)色度学系统对其可见光下的干涉色颜色进行了定量表征. 关键词： TiO_2/白云母纳米复合材料 反射光谱 色度学 Munsell新坐标     

TiO2薄膜光学性质的研究

以磁控溅射制备的TiO2薄膜为样品,通过对薄膜折射率、吸收系数、膜厚度与入射光波长相互关系的分析。获得了TiO2薄膜的折射率、吸收系数与入射光波长的关系式。以及TiO2薄膜厚度的计算公式．     

偏振模色散影响色散控制孤子传输的理论研究

采用变分法分析高速色散控制孤子在双折射光纤中的传输规律。首先建立了色散控制孤子在双折射光纤中的扰动传输模型 ,然后解析了偏振模色散影响下色散控制孤子各参量的传输演化规律 ,最后对解析结果进行了计算。研究结果表明 ,偏振模色散参量对色散控制孤子能量、脉宽的演化影响很大 ,当偏振模色散很大时 ,如Dp>0 .3ps/km1/ 2 时 ,必须考虑采用某些在线控制手段来有效抑制偏振模色散对传输系统的影响 ,然而 ,当Dp≤ 0 .1ps/km1/ 2 时 ,系统几乎不受影响 ,同时本文还证明了色散控制孤子抗偏振模色散扰动的能力强的这一特点。为研究偏振模色散对高速非线性传输系统、特别是色散控制孤子传输系统的影响提供了理论依据和研究方法。     

C(膜)/Si(SiO2)(纳米微粒)/C(膜)热处理的形态及结构分析

用直流辉光溅射＋真空镀膜法制备了一种新型结构的硅基纳米发光材料－C（膜）／Si（SiO2)(纳米微粒）／C（膜）夹层膜,并对其进行了退火处理,用TEM,SEM,XRD和XPS对其进行了形态结构分析,TEM观察表明：Si(SiO2)纳米微粒基本呈球形,粒径在30nm左右,SEM观察表明：夹层膜样品总厚度约为50um ,膜表面比较平整,致密,400度退火后,样品表面变得凹凸不平,出现孔状结构;650度退火后,样品表面最平整,致密且颗粒均匀,XRD分析表明：制备出的夹层膜主要由SiO2和Si 组成,在C原子的还原作用和氧气的化作用的共同作用下,SiO2和Si含量随加热温度的升高而呈现交替变化;400度时,C的还原作用占主导地位,SiO2几乎全部被还原成了Si,此时Si含量最高;400－650度时,氧化作用占主导地位,Si又被氧化成SiO2,Si 含量降低,SiO含量逐渐上升,在650度达到最高,XS分析表明：在加热过程中,C原子逐渐扩散进入Si(SiO2)_微粒层,在650度与Si反应生成了新的SiC。     

Titanium atoms dimerization phenomenon and magnetic properties of titanium-antisite (TiO) and chromium doped rutile TiO2, ab-initio calculation

The ab-initio calculations based on the Korringa Kohn Rostoker approximation approach combined with coherent potential approximation (KKR-CPA), were used to study the magnetic properties of the titanium anti-site (Ti_O) and chromium (Cr) doped TiO₂. In the considered systems, we used different concentrations for Ti_O defect and Cr doping. In TiO_2(0.98)(Ti_O)_0.02, the obtained results indicate that Ti_O is a donor having half-metal behavior. Ti_O[3d] band is located at the Fermi level, although isn’t 100% polarized, the ferromagnetic (FM) state is verified as being more stable than disordered local moment (DLM) state. For Ti_0.98Cr_0.02O₂ the Cr doping introduced new states which give the material half-metallic feature. The majority spin of Cr impurities are located at the Fermi level and the conduction electrons around the Fermi level are 100% spin polarized. This indicates the stability of (FM) state. Moreover, in Ti_0.98Cr_0.02O_2(0.98)(Ti_O)_0.02, the top of the valence band is shifted to lower energy compared to pure TiO₂, and the n-type of TiO₂ is verified. The majority spin of Cr[3d] are located at 0.025 Ry close to the Fermi level. The predicted Curie temperatures (Tc) were calculated using the mean field approximation (MFA) and we predicted that Ti_O defect in Cr doped TiO₂ makes Tc higher. This kind of defect makes the material useful for spinotronics's applications and devices.     

激光烧结(Ta_2O_5)_(1-x)(TiO_2)_x陶瓷的拉曼光谱研究

简介了激光快速烧结陶瓷技术;测量了采用激光快速烧结技术和传统电炉烧结技术制备的(Ta2O5)1-x(TiO2)x陶瓷的相对介电常数和介电损耗;分析了这两类试样的激光拉曼光谱和粉末XRD谱;发现:(Ta2O5)1-x(TiO2)x陶瓷经激光快速烧结后产生了新相,从而导致相对介电常数大幅度提高。     

液相纳米硒微粒的性质及其共振瑞利散射光谱研究

常温常压下,在0.24 mol·L-1的盐酸介质中,二氧化硒与过量的抗坏血酸(Vc)作用,生成单质硒Se(0),获得含有纳米硒微粒的均匀溶液;采用透射电镜和激光散射技术,测出Se(0)以26～243 nm的球形聚集状态存在,并在470 nm处有最强的共振瑞利散射(RRS),在入射波长2倍和1/2处分别有二级散射(SOS)和倍频散射(MFS),其共振瑞利散射强度ΔI₄₇₀与Se(Ⅳ)的浓度在2.82×10-9～5.64×10-6 g·mL-1范围内呈线性关系,相关系数为0.997。     

PVDF-Based Nanocomposite Solid Polymer Electrolytes; the Effect of Affinity Between PVDF and Filler on Ionic Conductivity

Nanocomposite solid polymer electrolytes (NSPEs) based on poly(vinylidene fluoride) (PVDF) were prepared by dispersing two kinds of organoclay (Cloisite^® 30B, Cloisite^® 15A) consisting of silicate layers in the polymer matrix. The effect of affinity between PVDF and organoclay as the filler on ionic conductivity was investigated in relation to its content, dispersed condition of organoclay, and structural changes of nanocomposites. The characterizations of PVDF-based nanocomposites with various organoclay contents were carried out by XRD, TEM, DSC, and DMA. In order to confirm the ion conduction properties of NSPEs with LiCF₃SO₃ at room temperature, ac impedance analyzer and FT-IR spectrometer were used. As a result, a higher ionic conductivity appeared in the case of NSPE with C15A than that with C30B and the maximum conductivity was 1.04 × 10^–3 S/cm for the NSPE containing 5 wt% of C15A and 40 wt% of LiCF₃SO₃.     

聚(2-甲氧基-5-辛氧基)对苯乙炔/TiO2纳米复合材料的光物理性能研究

通过原位强碱诱导下的脱氯化氢缩合聚合法制备了一系列不同纳米TiO2含量的聚(2-甲氧基-5-辛氧基)对苯乙炔/纳米二氧化钛(PMOCOPV/TiO2)光电复合材料。红外光谱和拉曼光谱证实了在纳米TiO2表面的包覆层为PMOCOPV。紫外-可见吸收光谱表明随着TiO2含量的增加PMOCOPV/TiO2纳米复合材料的吸收强度提高。高分辨透射电镜观察发现PMOCOPV/TiO2是具有核-壳结构的纳米复合粒子,直径约30 nm,其中PMOCOPV包覆层的厚度约为8~10 nm。荧光光谱研究表明,PMOCOPV/TiO2纳米复合材料的最大发射波长随着TiO2含量的增加发生红移,荧光寿命约为1 ns,且随着TiO2含量的增加荧光强度和荧光寿命得到显著提高,并通过PMOCOPV/TiO2纳米复合材料中的激子离化和电荷传输过程以及复合材料中的电势能级探讨了PMOCOPV/TiO2的荧光量子效率和荧光强度增加的机理。     

Thermal Cycloimidization Study of Polyimides and Poly(amide imide)s Synthesized from Low-Temperature Solution Polymerization

Polyimides (PI)s and Poly(amide imide)s (PAI)s containing di/tri-structural arrangements of monomer constituents were synthesized from 1,2,4,5 benzenetetracarboxylic anhydride/3,3′,4,4′ benzophenonetetracarboxylic dianhydride, diamines and trimellitic dianhydride chloride, i.e., a mixture of dianhydrides and diamines, using low-temperature solution polymerization. The majority of the resulting polymers were readily soluble in polar aprotic solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, etc. Thermal cycloimidization studies by thermogravimetic analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR) revealed that the rate of cycloimidization was much faster during the initial 15 min, and then occurred at much slower rates till the completion. The activation energies (Ea) for thermal cycloimidization of poly(amic acid)s was calculated from the rate of mass loss of the polymer heated at different temperatures according to the Coats and Redfern method. PI and PAIs derived from diamines containing single cyclic/benzene ring structures, such as m-phenylenediamine and 1,3-cyclohexanebis(methylamine), showed less amount of char yield than those having two benzene rings and separated by methylene, sulfone, or ether linkages. The structure of both diamine and trimellitic chloride had a profound effect on the polymer chain mobility, as indicated by the big variation in the glass transition temperatures. Thermally stable polymers were developed into membranes and tested for their mechanical strength by dynamic mechanical analysis(DMA).