Nano-silica modified lightweight and high-toughness carbon fiber/phenolic ablator with excellent thermal insulation and ablation performance

Lightweight and high-toughness carbon fiber/phenolic ablator(CFPA)is required as the Thermal Protection System(TPS)material of aerospace vehicles for next-generation space missions.To improve the ablative properties,silica sol with good particle size distribution prepared using tetramethoxysilane(TMOS)was blended with natural rubber latex and deposited onto carbon fiber felt,which was then integrated with phenolic aerogel matrix,introducing nano-silica into the framework of CFPA.The modified CFPA with a low density of 0.28—0.31 g/cm3exhibits strain-in-fracture as high as 31.2%and thermal conductivity as low as 0.054 W/(m·K).Furthermore,a trace amount of nano-silica could effectively protect CFPA from erosion of oxidizing atmosphere in different high-temperature environments.The oxyacetylene ablation test of 3000°C for 20 s shows a mass ablation rate of 0.0225 g/s,a linear ablation rate of 0.209 mm/s for the modified CFPA,which are 9.64%and 24.82%lower than the unmodified one.Besides,the long-time butane ablation test of 1200°C for 200 s shows an insignificant recession with mass and linear ablation rate of 0.079 g/s and 0.039 mm/s,16.84%and 13.33%lower than the unmodified one.Meanwhile,the fixed thermocouple in the test also demonstrates a good thermal insulation performance with a low peak back-face temperature of 207.7°C,12.25%lower than the unmodified one.Therefore,the nano-silica modified CFPA with excellent overall performance presents promising prospects in high-temperature aerospace applications.

Synthesis of Single-stranded Polynorbornene with Pendant Group Bearing Benzenedicarboxaldehyde and Long Alkyl Chain

An unprecedented single-stranded polynorbornene with the pendant group containing benzenedicarboxaldehyde and a long alkyl chain（12） was synthesized by ring-open metathesis polymerization（ROMP） of the corresponding monomer（11）,which was obtained via the esterification of two crucial intermediates,namely,2-hexadecyloxy-5-hydroxymethyl-1,3-benzenedicarboxaldehyde（7,obtained via 6 steps） and 4-（4-aza-tricyclo[5.2.1.0 2.6 ]-dec-8en-4-yl）benzoic acid（10）.The target compound and all the intermediates were characterized by infrared（IR）,1 H NMR and high resolution mass spectroscopy（HRMS） analysis.

磺化聚醚醚酮复合膜的制备及其性能研究

采用共混溶液浇铸法制备了磺化聚醚醚酮(SPEEK)/季铵化聚降冰片烯聚合物(TAPNM)复合质子交换膜,并对其力学性能、尺寸稳定性、离子交换容量和质子传导率进行表征。结果表明,制备的复合膜具有良好的透明性和均匀性,且致密无明显缺陷,具有良好的相容性。复合膜的尺寸稳定性测试和力学性能测试结果表明,TAPNM的引入显著增强了复合膜的尺寸稳定性和力学性能。在TAPNM质量分数为5%左右时,可以有效提升复合膜的质子传导率,30℃条件下质子传导率达到53.19 mS/cm,是SPEEK膜的1.2倍。

Performance evaluation of nano-silica and silica fume on enhancing acid resistance of cement-based composites for underground structures

This study aims to evaluate the performance of silica fume(SF)and nano-silica(NS)on enhancing the sulfuric acid resistance of mortar mixtures.The NS and SF were added as substitutions for cement at various dosages.The cured samples were immersed in the sulfuric acid solution with a pH of 2 for 75 d.A compressive strength test and absorption and voids tests were conducted before sulfuric acid immersion.It was found that the addition of SF and NS reduced the volume of permeable voids and increased compressive strength.A thermo-gravimetric analysis was carried out to investigate the hydration of mixtures.The mixtures with SF showed a higher level of pozzolanic reaction compared with mixtures with NS.After the 75 d of immersion,the mixtures with 5%SF and 1%NS showed the best resistance against sulfuric acid because they showed the lowest mass change and length change.

Road Performances of Mesoporous Nano-silica Modified Asphalt Binders

The objective of this paper was to find new modifier to improve the aging resistance and low temperature cracking resistance of asphalt. To investigate the aging resistance of modified asphalt binders, mesoporous nano-silica（doping Ti^（4＋）） was used as a asphalt modifier. Some physical properties including penetration, ductility, and softening point of asphalt were analyzed with RTFO（Rotating thin film oven） aging and ultraviolet aging. Moreover, the performances of high and low temperature of modified asphalt binders with pressure aging were tested by dynamic shear rheometer（DSR） test and bending beam rheometer（BBR） test. These results showed that the penetration decreased, low temperature ductility, and softening point increased when adding mesoporous nano-silica to base asphalt. After ultraviolet radiation aging, the penetration loss and ductility loss of modified asphalt decreased than that of original asphalt, the increase of softening point was also significantly reduced than that of base asphalt. Furthermore, The test results of DSR and BBR showed that the G＊sinδ and creep modulus‘s＇ of pressure aged asphalt decreased, but the creep rate ‘m＇ increased. It can be concluded that the aging resistance and cracking resistance of modified asphalt are improved by adding mesoporous nano-silica, especially the doping of Ti^（4＋） could improve the aging resistance obviously.

Synthesis of a Green Nano-Silica Material Using Beneficiated Waste Dunites and Its Application in Concrete

Nano-silica, one of the substances boosting the field of nanomaterials, can be produced by dissolving olivine in acid. The dissolution of olivine is a convenient alternative route to the existing methods of nano-silica production (neutralization of sodium silicate and flame hydrolysis) because the olivine dissolution is a low temperature process making this method cheaper and greener. Furthermore, this process can use waste olivine materials for the production of nano-silica. The produced nano-silica has a specific surface area between 100 and 400 m2/g;a primary particle size between 10 and 25 nm, which is agglomerated in clusters;and an impurity content below 5 wt.%. In addition, olivine nano-silica can be classified as a pozzolanic material with an activity index of 101%. The optimum replacement level of olivine nano-silica in conventional vibrated concrete is around 5% by volume resulting in: 1) a compressive strength increase of 20%;2) a CO2 emission reduction of 3%. Therefore, the use of the olivine nano-silica in CVC does not only improve the compressive strength but also reduce the CO2 emissions.

Colored Nano-Silica and Its Adsorption on Cellulosic Materials

Deep understanding has been achieved for nanotechnology,which has greatly advanced the development of technology.The adsorption property,as one of conventional properties of nanomaterials,is well known but has not been fully applied.In this paper,nanomaterials were used as adsorbents,and further their adsorption properties on substrates were studied.Spherical nano-silica was selected as a representative,which was labeled with a dye.The chemical bonding between the dye and nano-silica was confirmed by Fourier transform infrared(FTIR)spectroscopy.It was proved that the adsorption was a spontaneous,endothermic and entropy increase process.The adsorption model conformed to the Langmuir-type adsorption model.Reaction kinetic studies showed that the number of reaction stages in the adsorption process was about 1.45.The adsorption state was studied to verify the existence of nanomaterials as an adsorbent on the surface of the polymer,and then provided a demonstration for feasibility of the general polymer surface modification method.

Development and Evaluation of Nano-Silica Dispersed Polyurethane Based Coatings for Improved Anti-Graffiti and Scratch Resistance

Polyurethane based anti-graffiti coatings have been developed by incorporating varying amounts of OH-functional Silicone modified polyacrylate. Optimization of Silicone polyacrylate concentration in neat PU was done by testing its performance for graffiti resistance. Tests which include static contact angle measurements with water and spray paint, visual inspection of stain removal and color change measurements were performed. It was observed that 5 wt % of Silicone polyacrylate in the neat PU showed 95% stain removability. These coatings showed excellent graffiti resistance but poor mechanical properties. Hence modification of these coatings was done by nano-particle incorporation. Nano-silica particle concentration was optimized for surface mechanical properties such as surface hardness, elastic modulus and scratch resistance. FEG-TEM revealed that nano-silica particles were uniformly distributed over the surface. 5 wt % nano-silica particle additions in PU-5 wt % silicone polyacrylate base showed superior mechanical properties than other concentrations. Color change measurements showed that nano-silica particle addition had no effect on its graffiti resistance. Hence PU-5 wt % silicone polyacrylate, 5 wt % nano-silica showed excellent graffiti resistance and mechanical properties.

Non-conjugated Polynorbornene Hosts with High Triplet Energy Levels for Solution-processed Narrowband Blue OLEDs

Three polymer hosts(namely PNB-tBuCz,PNB-Ac,PNB-TAc)containing non-conjugated polynorbornene(PNB)backbone and hole-transporting arylamine segments(carbazole,acridan and dendritic teracridan)in side chains are developed for solution-processed narrowband blue organic light-emitting diodes(OLEDs).It is found that the non-conjugated polynorbornenes can keep high triplet energy(ET)levels in range of 3.12-3.20 eV by interrupting the conjugation of repeating units,making them capable as host materials for blue emitters.Meanwhile,by increasing the electron-donating capability of side chain arylamine from carbazole to acridan and dendritic teracridan,the highest occupied molecular orbital(HOMO)levels for the polymer hosts are elevated from-5.50 eV to-5.11 eV,beneficial for reducing the hole injection barrier from anode to emissive layer.As a result,solution-processed OLEDs employing polynorbornenes with dendritic teracridan side chain(PNB-TAc)as host and boron,selenium,nitrogen-containing multiple resonance thermally activated delayed fluorescence emitter as dopant reveal efficient narrowband blue electroluminescence with emission peak at 474 nm,full-width at half maximum of 30 nm,together with maximum external quantum efficiency of 20.2%,representing the state-of-the-art device efficiency for solution-processed OLEDs with narrowband blue emission.

Ni(acac)_(2)Mediated Vinyl Polymerization of Norbornene in the Presence of Bulky Salicylaldiminate Ligands:An Effective Strategy to Access Soluble Polynorbornenes

Late transition metals have long served as workhorses for vinyl polymerization of norbornene derivatives.Nevertheless,for such catalytic systems,insoluble polynorbornene(PNB)products are often produced which hampers their further detailed characterizations,such as molecular weights,polydispersities,stereoregularities,etc.In this work,we surprisingly found that for a traditional Ni(acac)_(2)/MAO system that was previously reported to give insoluble PNBs,incorporation of highly bulk salicylaldiminate ligands could significantly improve the solubility of the PNBs in common organic solvents,which allowed for subsequent thorough detailed analysis of the polymer products.Moreover,it was also observed that high-temperature polymerization was beneficial for further improving the PNB’s solubilities due to the decreased molecular weights and stereoregularities.Different ligand skeletons and ligand equivalents were also investigated to give a comprehensive view of their influences on the polymers’solubilities,and based on these results,a plausible mechanism that caused such a big difference was tentatively proposed.

Toughness Effect of Graphene Oxide-Nano Silica on Thermal-Mechanical Performance of Epoxy Resin

A graphene oxide/nano-silica(GOS)hybrid was rapidly and easily synthesized using graphene oxide(GO)and nano-silica(nano-SiO_(2))as raw materials,and the synthesized GOS was used to improve the mechanical properties of epoxy resin(EP).The modified EP with different mass fractions of GOS(0,0.1%,0.2%,0.3%and 0.4%)were prepared and studied.The structure,thermal stability,mechanical properties,fracture toughness and failure morphology of the modified EP were analyzed.The results showed that the tensile strength of GOS modified EP increased from 40.6 MPa to 80.2 MPa compared with EP,the critical stress intensity factor of GOS modified EP increased by 65.9%from 0.82 MPa·m^(1/2)to 1.36 MPa·m^(1/2),indicating a significant enhancement in fracture toughness.In addition,failure morphology was observed by scanning electron microscopy(SEM)observation.The toughness mechanism of the modified EP was also discussed.Finally,the thermal stability of the modified EP was improved by the addition of GOS.Compared with neat EP,the initial thermal degradation temperature and glass transition temperature of GOS modified EP increased by 4.5℃and 10.3℃,respectively.

β-二酮钛非茂催化剂催化降冰片烯聚合

用 (dibenzoylmethanato) 2 Ti(OPh) 2 [(dbm) 2 Ti(OPh) 2 ]/甲基铝氧烷 (MAO)为代表的新型 β 二酮钛非茂催化剂实现了降冰片烯的聚合 ,得到加成聚合和开环易位聚合的混合物 ,研究了实现高聚合活性所需的特殊条件及所得的聚合物结构 ,主要应用傅立叶转变红外技术 (FTIR)

5-丁氧基亚甲基-2-降冰片烯的合成及其加成聚合反应

采用降冰片烯-5-甲醇和溴丁烷在氢化钠作用下合成了5-丁氧基亚甲基-2-降冰片烯,双-(β-酮萘胺)镍(Ⅱ)/B(C6F5)3催化体系使之聚合。考察了聚合时间对其均聚合的影响以及5-丁氧基亚甲基-2-降冰片烯和降冰片烯不同摩尔投料比对其共聚行为的影响。采用1HNMR、FTIR和TGA测试技术对所得的聚合物进行了结构表征和性能测试。结果表明,双-(β-酮萘胺)镍(Ⅱ)/B(C6F5)3催化体系对5-丁氧基亚甲基-2-降冰片烯均聚和共聚具有较高的催化活性。得到的均聚物和共聚物为加成型聚合物,料液中5-丁氧基亚甲基-2-降冰片烯的摩尔分数为10%～90%时,其在共聚物中的插入率为22.1%～76.9%,所得聚合物具有较好的热稳定性(Td>360℃),在THF和CHCl3等许多普通溶剂中有很好的溶解性能。

纳米SiO_2负载镍催化剂催化环烯烃聚合

利用硅烷偶联剂将乙酰丙酮二氯化镍连结在纳米SiO_2表面,制备了纳米SiO_2负载的镍催化剂,并以三五氟苯基硼为助催化剂,催化降冰片烯的加成聚合,原位制备了纳米SiO_2杂化的聚降冰片烯,观察了杂化材料的形貌及纳米SiO_2的分布情况,并研究了其力学性能。结果表明:通过改变聚合温度、n(B)∶n(Ni)、催化剂与降冰片烯投料比等,可以实现对聚合活性以及所得聚合物性能的调控;当聚合温度为60℃,n(B)∶n(Ni)为20时,聚合活性最高可达0.36 kg/(mmol·h);当降冰片烯与催化剂的摩尔比为2 000∶1时,所制纳米SiO_2杂化的聚降冰片烯力学性能最佳。

萘酰亚胺负载聚降冰片烯荧光传感器的合成及应用

聚合物荧光化学传感器广泛用于环境及生命体内一些重要物质检测,受到人们广泛关注。通过开环易位聚合反应得到了一种新型的基于萘酰亚胺修饰聚降冰片烯共聚物P-NB-NA-PEG,通过红外光谱和核磁氢谱确定了其结构,并研究了该材料的热稳定性。该聚合物在530 nm具有明显的特征荧光发射峰。同时由于酰胺键和咪唑钅翁识别位点的引入,聚合物传感器P-NB-NA-PEG可以对H_(2)PO^(-)_(4)达到特异性的荧光识别,这可归因于其ICT激发态的“推-拉”效应进而导致荧光发射明显增强。P-NB-NA-PEG对H_(2)PO^(-)_(4)的络合常数为6.04×10^(4)mol·L^(-1),检测限低至0.148μmol·L^(-1),表明该聚合物传感器材料具有很高的灵敏度。

有机小分子杂化聚降冰片烯形状记忆性能的研究

以聚降冰片烯(PNB)为研究对象,研究增塑剂(塑分T和环保芳烃油)和有机小分子(微晶蜡、淀粉和碱木质素)对PNB形状记忆性能的影响。结果表明:添加环保芳烃油的PNB玻璃化温度在室温(20℃)附近,塑分T对PNB的玻璃化温度影响不大,有利于PNB在室温下的形变固定;在玻璃化温度起始温度下拉伸时,几种填充PNB均出现屈服现象,且呈现硬而韧的应力-应变特征;几种填充PNB均具有优良的传统形状记忆性能,形状固定率在98%以上,形状恢复率在70%以上,其可逆塑性形状记忆性能低于传统形状记忆性能,可逆塑性形状固定率为49%~77%;微晶蜡杂化PNB具有优异的形状记忆性能。

原子转移自由基聚合制备聚降冰片烯电解质

采用双(β-酮萘胺)镍(II)、B(C6F5)3及AlEt3三元催化体系催化降冰片烯(NB)及5-降冰片烯-2-甲醇(NB-CH2OH)的加成聚合,合成聚(降冰片烯-co-降冰片烯基甲醇)(PNB-OH)。通过PNB-OH与2-溴-异丁酰溴反应合成Br-PNB,以引发与对苯乙烯磺酸钠(SSA)或甲基丙烯酰氧丙基磺酸钾(SPMA)的原子转移自由基聚合(ATRP),得到以聚降冰片烯为主链的侧链含磺酸基团的接枝共聚物。所有的聚合物有良好的热稳定性,且PNB-g-PSPMA的离子交换容量(IEC)值达到0.787meq/g,PNB-g-PSSA的IEC为1.05meq/g。

卟啉降冰片烯聚合物的合成、表征及性质研究

本文设计合成了卟啉的降冰片烯单体,采用Grubbs催化剂与长链烷基的降冰片烯单体开环易位聚合,直接得到了卟啉降冰片烯聚合物,通过紫外-可见吸收光谱、荧光光谱、电化学等手段研究了卟啉降冰片烯聚合物的性质,与小分子单体相比,所得卟啉高分子共聚物相当好地保持了卟啉应有的光物理、电化学等特性.

MORPHOLOGY EVOLUTION OF POLY(St-co-BuA)/SILICA NANOCOMPOSITE PARTICLES SYNTHESIZED BY EMULSION POLYMERIZATION

Poly（St-co-BuA）/silica nanocomposite latexes were synthesized via conventional emulsion polymerization in the presence of 3-（trimethoxysilyl）propyl methacrylate modified colloidal nano-silica. The effects of surface property, particle size and content of colloidal nano-silica as well as the concentrations of monomer and surfactant on the morphology of nanocomposite latex particles were investigated by transmission electron microscope （TEM） and scanning electron microscope （SEM） in detail. Various interesting morphologies such as grape-like, Chinese gooseberry-like, pomegranate-like and normal core-shell structures were observed. Droplet nucleation mechanism competing with micelle nucleation mechanism was proposed to explain the morphological evolution of the nanocomposite particles.

含聚降冰片烯主链结构甲壳型液晶弹性体的制备及其性能

为了研究甲壳效应对液晶弹性体热致形变和力学性能的影响。通过多步反应设计并合成了具有降冰片烯主链结构的甲壳型液晶弹性体。利用1H NMR表征化合物结构,采用热台偏光显微镜和动态力学热分析仪研究弹性体的液晶行为、热致形变性质和力学性能。将甲壳型液晶聚合物与双官能度的二苯甲酮交联剂混合,熔融拉丝,得到取向单一的纤维,在液晶相温度下紫外光照引发交联反应,制备出甲壳型液晶弹性体。实验结果表明甲壳型液晶弹性体纤维样品在常温下具有双折射性质,表现为沿纤维长轴方向的单畴取向。在外力作用下,纤维样品具有可逆的热致形变性质,最大形变率达到62%。力学性能测试显示,该纤维样品在玻璃相态下具有较高的杨氏模量,而在液晶相态下则表现为较大的应变量。