SBA-15／PMMA杂化材料力学性能及热性能研究

采用溶胶一凝胶法制备了二维六方介孔结构的SBA-15,利用原位分散聚合法制备（SBA-15／0wt％DBP／PMMA,SBA-15／15wt％DBP／PMMA和SBA—15,25wt％DBP／PMMA）三种三维纳米网络结构的杂化材料。通过FT—IR、XRD、TEM、DSC和SEM等方法对SBA-15／DBP／PMMA杂化材料进行了表征。结果表明：DBP和SBA-15的加入对PMMA分子链的化学结构未造成任何影响,且SBA-15在PMMA基体中仍能保持介观有序结构;SBA-15对脆性PMMA具有较好的增强增刚作用,且DBP的含量越高,杂化材料拉伸强度和模量提高程度相对减小;三种杂化材料的rrg均随SBA-15含量的增加而提高,且DBP的含量越高,杂化材料的Tg提高幅度越小。     

多壁碳纳米管表面羧基化及其阻燃ABS的性能

采用硝酸氧化/低温等离子处理两步法,将多壁碳纳米管(MWCNTs)羧基化(MWCNTs-COOH),以改善其在ABS基体中的分散性。通过熔融共混的方法制备不同组分ABS/MWCNTs-COOH复合材料。利用红外、拉曼分析、扫描电镜对改性修饰后MWCNTs结构进行研究;利用扫描电镜、热重分析、极限氧指数、残炭分析、力学性能测试对ABS/MWCNTs-COOH复合材料分散性、热性能、阻燃性能、力学性能进行研究。实验结果表明,MWCNTs羧基化改性后提高了在ABS基体材料中的分散性;当MWCNTs-COOH含量为1%时,复合材料初始分解温度和最大分解温度分别提高了22.69℃和27.90℃,热稳定性提高,同时复合材料力学性能也得到改善,拉伸强度提高了18.3%;极限氧指数和残炭测试表明,MWCNTs-COOH加入提高了复合材料的极限氧指数,MWCNTs-COOH在复合材料燃烧过程中,会在材料表面形成网络状炭层,提高复合材料的阻燃性能。     

POSS/PMMA杂化材料的制备及性能研究

采用八乙烯基倍半硅氧烷（OV-POSS）通过原位聚合法制备了POSS/PMMA杂化材料。通过FTIR、SEM,EDS以及力学性能和透光性雾度的测定等方法对杂化材料的结构和性能进行了表征。结果表明,POSS的加入对PMMA可见光的透过性无影响。POSS含量较低时,POSS的引入能明显改善材料力学性能,但当POSS含量较高时,力学性能下降。当POSS的含量为0.6%时,与纯的PMMA相比,断裂伸长率略有降低,降低了5.8%,然而,其他力学性能均有提高,其中,拉伸模量和强度分别提高了22.7%和32.0%,弯曲强度和模量分别提高了9.8%和27.0%。     

G-POSS/CE杂化材料的制备及性能研究

采用共混法制备八环氧基POSS(G-POSS)/氰酸酯树脂(CE)有机-无机杂化材料。研究了环氧基POSS含量对杂化材料的固化反应、介电性能、力学性能等的影响,并对杂化材料的微观相态结构进行了表征和分析。结果表明,G-POSS的引入使氰酸酯树脂基体的介电性能显著改善,同时反应活性、韧性等都有所提高。且当G-POSS的质量分数为2.5%时,杂化材料的介电性能、力学强度和刚性提高较为明显,且其断面形貌呈韧性断裂。     

聚酰亚胺/二氧化钛杂化材料的制备及性能研究

采用超声分散-原位聚合工艺制备了聚酰亚胺(PI)/二氧化钛(TiO2)杂化膜。通过傅里叶转换红外光谱、紫外-可见光谱、扫描电子显微镜等对杂化膜进行了表征,探讨了杂化膜中TiO2含量对杂化膜的热性能、吸湿性能和力学性能的影响。结果表明,纳米TiO2粒子均匀分散在PI基体中,TiO2的掺入及与有机基体的杂化提高了材料的热分解温度与玻璃化转变温度,降低了材料的吸湿性能,改善了材料的力学性能。当TiO2含量为6%时,杂化膜的拉伸弹性模量和断裂强度达到最大值,分别为纯PI膜的2.17倍和1.63倍。     

有机刚性粒子增韧聚苯硫醚的研究

采用有机刚性粒子聚甲基丙烯酸甲酯(PMMA)增韧改性聚苯硫醚(PPS)。考察了加工温度及PMMA用量对聚苯硫醚复合材料微观形态结构和力学性能的影响。结果表明,复合材料的力学性能随着加工温度的升高而下降。PMMA与PPS基体以“海岛”状的形式存在;少量PMMA加入时,PMMA同PPS结合较好,冲击强度显著提高;当增加PMMA的用量时,PMMA在PPS基体中的相区尺寸增大,界面变得明显,各项力学性能有小幅下降。     

聚丙烯基杂化材料的动态力学性能与流变行为

研究了烷基铵离子对有机蒙脱土片层在聚丙烯基杂化材料中的分散状态和聚丙烯基杂化材料的动态力学性能、熔体流变行为的影响。结果表明:烷基铵离子N 上取代基空间效应增大,有机蒙脱土片层间距随之增大;适当的空间效应将有助于有机蒙脱土片层在聚丙烯基体中的剥离分散;与基体聚丙烯相比,聚丙烯基杂化材料表现出较高的动态储能模量和损耗模量,在低频区,3种杂化材料熔体的动态剪切黏度和模量的提高幅度在1个数量级以上。     

裂解炭黑/纤维素纳米晶杂化体粉末的制备及其在天然橡胶中的应用

采用氨基化纤维素纳米晶（CCP）与裂解炭黑（CBp）球磨杂化,CBp/CCP（CBC）杂化体浆料经喷雾干燥后得到CBC杂化体粉末,将其用于天然橡胶（NR）补强。结果表明：CCP与CBp均匀杂化,有效阻止了CCP的团聚,提高了CBp在NR中的分散性;得益于NR/CBC复合材料的交联密度提高和CCP与CBp的协同补强作用以及CBC杂化体粉末在NR基体中的均匀分散,NR/CBC复合材料的物理性能显著提高,CBp/CCP质量比为85/15的CBC杂化体粉末的NR/CBC复合材料的300%定伸应力、拉伸强度和撕裂强度比NR/CBp复合材料分别提高了30.4%,14.9%和75.7%,DIN磨耗量减小了13.7%,压缩温升降低。选用生物基填料CCP作为共杂化材料,以球磨杂化、喷雾干燥方式对CBp进行提质改性,为便捷制备高性能NR/CBp复合材料提供了可能,有利于推动CBp的高附加值利用及解决废旧轮胎的污染问题。     

环氧树脂/POSS杂化材料力学性能和耐热性研究

以自行合成的环氧基倍半硅氧烷（POSS）为改性剂,分别对环氧树脂139S/六氢苯酐和环氧树脂BE 188EL/六氢苯酐进行改性,制备环氧树脂/POSS杂化材料。力学性能分析结果表明,两种杂化材料的冲击强度和弯曲强度都有明显的提高,冲击强度分别提高了57.45 %和32.26 %,弯曲强度分别提高了9.23 %和5.07 %。热性能分析结果表明,两种杂化材料在高温时的热残留量都有所提高,分别提高了50.19 %和20.16 %。两种杂化材料的热膨胀系数也得到了降低,即热稳定性得到了提高。     

改性TiO2在PVC基体中的分散行为研究

通过熔融共混法制备了聚氯乙烯/二氧化钛(PVC/TiO2)复合材料,通过扫描电镜观察TiO2粒子在PVC中的分散状态,并测定了材料的力学性能。结果表明,在粒径一定的条件下,TiO2粒子在PVC中的分散状态及复合材料的力学性能与表面改性方法密切相关;经过钛酸四丁酯偶联剂[Ti(OBu)4]、γ-氨丙基三乙氧基硅烷偶联剂（KH-550）、聚甲基丙烯酸甲酯（PMMA）改性的TiO2粒子能有效提高粒子在塑料中的分散性及冲击强度,当PMMA改性的TiO2粒子添加量为2.5份时,冲击强度提高超过100 %;而经十二烷基磺酸钠（SLS）改性的粒子团聚严重,复合材料力学性能明显下降。     

Effects of SBA-15 and its content on MMA solution polymerization and PMMA composites

An ordered mesoporous material, such as SBA-15 was considered as a promising reinforcement agent for polymeric materials due to its large surface area and uniform pore structure. In this paper, poly(methyl methacrylate) (PMMA)/SBA-15 composites were prepared by in situ free-radical solution polymerization of MMA in the presence of SBA-15. The effects of SBA-15 content on solution polymerization and the properties of the final polymer composite were investigated. The PMMA molecular weight and its distribution in PMMA/SBA-15 composites were determined by gel permeation chromatography. Fourier-transform infrared spectra, X-ray diffraction, thermal gravimetric analysis (TGA), differential scanning calorimeter and dynamic mechanical analysis were used to characterize the structure and properties of the composites. The morphology of the composites was observed by scanning electric microscopy (SEM) and transmission electron microscopy (TEM). The results showed that the monomer conversion dropped off, but the polymer average molecular weight increased upon the introduction of SBA-15 into solution polymerization process. When compared with pure PMMA, the storage modulus of the composites was improved and the highest improvement was acquired at 1 wt% of SBA-15, based on the monomer feed content. The glass transition temperatures of the composites were increased slightly. TGA results confirmed that the thermal stability of the composite was not influenced much and a higher degree of terminal vinyl groups was formed in the product of polymerization. SEM and TEM images indicated that SBA-15 particles were incorporated into the polymer matrix.     

Effects of preparation methods on the property of PMMA/SBA-15 mesoporous silica composites

In the paper, poly(methyl methacrylate)(PMMA)/SBA-15 composite materials were prepared by four different methods, that is, in-situ batch emulsion polymerization in the presence of mesoporous SBA-15, PMMA emulsion mixed with SBA-15 powder or dispersion in water, PMMA powder mixed with SBA-15 powder, and the properties of the composite materials were determined and compared. The composites were characterized by infrared spectroscopy (IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanics analysis (DMA) and scanning electron microscope (SEM). The results showed that the glass transition temperatures (Tg), the storage modulus and tensile strength of the PMMA/SBA-15 composites were all improved obviously, while the thermal decomposition temperature did not influenced apparently. The composite made by in-situ batch polymerization exhibited the most improvement in the mechanical properties and Tg while the composite prepared by mixing PMMA emulsion and SBA-15 dispersion gave rise to the least improvement in the mechanical properties and Tg. These results were contributed to introducing different amount of voids into polymer matrix which were demonstrated by dielectric constant measurement and SEM morphology observation.     

SrTiO3 as a new solar reflective pigment on the cooling property of PMMA-ceramic composites

Polymer-ceramic hybridization is an important method for preparing functional materials. Strontium titanate (SrTiO₃, ST), a typical perovskite ceramic, has been widely applied in the electronics industry and photocatalytic fields. However, ST was barely reported to be utilized in cool materials. Herein, ST ceramic, as a solar reflective pigment, was introduced into a polymer matrix to prepare cool material. Specifically, the influences of both weight contents and surface grafting modification about ST on the properties of poly(methyl methacrylate) (PMMA)/ST composites were investigated, which include cooling performance, surface roughness, thermal emissivity, dispersion of particles and mechanical strength. The obtained composites containing 20 wt% unmodified ST possess excellent cooling property due to high thermal emissivity (86.8%, in 8–13 μm) and high solar reflectance (70.7%, in the whole solar band) which increased by 142% than that of pure PMMA resin. Temperature test highlighted that the composites containing 20 wt% unmodified ST was only 26.6 °C, 11.4 °C lower than that of PMMA resin and only 2 °C higher than initial temperature. Moreover, the surface grafting modification of ST by the silane coupling agent was proved to improve the dispersibility of ST in PMMA resin. Both the cooling and mechanical properties of composites containing modified ST particles were further improved. Though the solar reflectance of PMMA/ST composites was lower than that of PMMA/TiO₂ composites, temperature tests showed that the PMMA/ST composites had a similar cooling performance with the PMMA/TiO₂ composites when the content of the ceramic particles were 5.8 v%. This work not only prepared the polymer-ceramic hybrid materials with excellent cooling performance but also expanded the application of ST ceramic in the field of composites.     

Surface‐modified silica nanoparticles for reinforcement of PMMA

Polymethyl methacrylate (PMMA) was introduced onto the surface of silica nanoparticles by particle pretreatment using silane coupling agent (γ‐methacryloxypropyl trimethoxy silane, KH570) followed by solution polymerization. The modified silica nanoparticles were characterized by Fourier‐transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). Sedimentation tests and lipophilic degree (LD) measurements were also performed to observe the compatibility between the modified silica nanoparticles and organic solvents. Thereafter, the PMMA slices reinforced by silica‐nanoparticle were prepared by in situ bulk polymerization using modified silica nanoparticles accompanied with an initiator. The resultant polymers were characterized by UV–vis, Sclerometer, differential scanning calorimetry (DSC). The mechanical properties of the hybrid materials were measured. The results showed that the glass transition temperature, surface hardness, flexural strength as well as impact strength of the silica‐nanoparticle reinforced PMMA slices were improved. Moreover, the tensile properties of PMMA films doped with silica nanoparticles via solution blending were enhanced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of surface modifiers and surface modification methods on properties of acrylonitrile–butadiene–styrene/poly(methyl methacrylate)/nano‐calcium carbonate composites

Nano‐calcium carbonate (nano‐CaCO₃) was used in this article to fill acrylonitrile–butadiene–styrene (ABS)/poly(methyl methacrylate) (PMMA), which is often used in rapid heat cycle molding process (RHCM). To achieve better adhesion between nano‐CaCO₃ and ABS/PMMA, nano‐CaCO₃ particles were modified by using titanate coupling agent, aluminum–titanium compound coupling agent, and stearic acid. Dry and solution methods were both utilized in the surface modification process. ABS/PMMA/nano‐CaCO₃ composites were prepared in a corotating twin screw extruder. Influence of surface modifiers and surface modification methods on mechanical and flow properties of composites was analyzed. The results showed that collaborative use of aluminum–titanium compound coupling agent and stearic acid for nano‐CaCO₃ surface modification is optimal in ABS/PMMA/nano‐CaCO₃ composites. Coupling agent can increase the melt flow index (MFI) and tensile yield strength of ABS/PMMA/nano‐CaCO₃ composites. The Izod impact strength of composites increases with the addition of titanate coupling agent up to 1 wt %, thereafter the Izod impact strength shows a decrease. The interfacial adhesion between nano‐CaCO₃ and ABS/PMMA is stronger by using solution method. But the dispersion uniformity of nano‐CaCO₃ modified by solution method is worse. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of SBA-15 extrudates: Evaluation of textural and mechanical properties

SBA-15 powder (P) was shaped into cylindrical extrudates (Ex) by compounding with additives such as bentonite (binder), methylcellulose and tetraethylorthosilicate (TEOS). The extrudates of SBA-15 were characterized by XRD, N₂ adsorption and thermogravimetric analysis. The orderly growth of SBA-15 is evident from the XRD patterns. The surface area and pore volume of SBA-15 (P) were around 884 m²/g and 1.1 cm³/g, respectively. The decrease in surface area and pore volume were observed for SBA-15 (Ex) in comparison to SBA-15 (P). This may be due to partial blocking of pore entry and surface coverage of additives during shaping of extrudates. The mechanical strength of SBA-15 (Ex) was examined by vertical crushing method. The effect of additives on the mechanical strength of SBA-15 (Ex) was examined by varying the composition. The results indicate linear increase of mechanical strength with increase in the content of bentonite and methylcellulose, but non-linear response with increase of TEOS and water. Compounding additives have been established to improve the mechanical strength of the extrudates.     

Grafting of lignin onto nanostructured silica SBA-15: preparation and characterization

The slow decline in oil reserves with mounting oil prices is pushing industry to find more sustainable sources for industrial manufacturing. Lignin is the second most abundant natural renewable biopolymer that is underutilized and has many functional groups (–OH, phenolics) that make the biopolymer a convenient substrate for materials manufacturing by the industry. The present study thus describes grafting of lignin onto nanostructured silica SBA-15 (Santa Barbara amorphous 15) by first silylating lignin with triethoxychlorosilane followed by treatment of silylated lignin with SBA-15. The resulting nanocomposite denoted as LIG–SBA-15-G was then characterized by powder X-ray diffraction, infra-red (FTIR), ³¹P nuclear magnetic resonance (³¹P NMR), N₂ adsorption (BET), scanning and transmission electron micrographs (SEM and TEM) and thermogravimetric analysis (TGA). X-ray data showed that LIG–SBA-15-G exhibited hexagonal structure closely similar to that observed for the SBA-15 host. FTIR of LIG–SBA-15-G showed characteristic absorption bands from lignin and attenuated Si–OH band due to its conversion to Si–O–Si ether bonds. Whereas, ³¹P NMR revealed that the majority of hydroxyl groups in lignin were replaced by Si–O–LIG ether bonds in LIG–SBA-15-G. SEM images of LIG–SBA-15-G displayed little changes in the macroscopic structure as compared to SBA-15. TEM images showed some disordered area in LIG–SBA-15-G and the grafted lignin appeared as black film on the silica surface. Using BET analysis the surface area of LIG–SBA-15-G was found to be 560 m² g^?1. Finally, TGA showed that LIG–SBA-15-G was more thermally stable than lignin and contained 13 % w/w lignin. Understanding the physicochemical and structural properties of the resulting lignin-nanosilica hybrid material should help engineer a robust and sustainable biomaterial suitable for various application, e.g. removal of contaminants from contaminated water.     

载锌抗菌剂在发泡EVA中的应用研究

以铝酸酯、硅烷、硼酸酯偶联剂为改性剂，分别对栽锌抗菌剂粉体进行表面改性，并用吸水性测定法、粘度法、红外光谱法评价抗菌粉体表面改性效果。用扫描电镜观察了抗菌粉体在EVA（乙烯／醋酸乙烯共聚物）基材中的分散性，以及对EVA发泡材料泡孔的影响；同时检测了EVA／抗菌粉体复合发泡材料的力学性能和抗菌性能。结果表明：3种偶联剂中，硼酸酯的改性效果最好，抗菌粉体表面与硼酸酯产生了明显的化学键合；加2％抗菌粉体（硼酸酯处理）的EVA发泡材料，撕裂强度提高28．6％，断裂伸长率提高45．8％，密度降低13．5％，对大肠杆菌和金黄色葡萄球菌具有良好的抗菌抑菌效果。