Polymer/organosilica nanocomposites based on polyimide with benzimidazole linkages and reactive organoclay containing isoleucine amino acid: Synthesis,characterization and morphology properties

Polyimide–silica nanocomposites are attractive hybrid architectures that possess excellent mechanical, thermal and chemical properties. But, the dispersion of inorganic domains in the polymer matrix and the compatibility between the organic and inorganic phases are critical factors in these hybrid systems. In this investigation, a reactive organoclay was prepared via ion exchange reaction between protonated form of difunctional l-isoleucine amino acid as a swelling agent and Cloisite Na⁺ montmorillonite. Amine functional groups of this swelling agent formed an ionic bond with the negatively charged silicates, whereas the remaining acid functional groups were available for further interaction with polymer chains. Then organo-soluble polyimide (PI) have been successfully synthesized from the reaction of 2-(3,5-diaminophenyl)-benzimidazole and pyromellitic dianhydride in N,N-dimethylacetamide. Finally, PI/organoclay nanocomposite films enclosing 1%, 3%, 5%, 7% and 10% of synthesized organoclay were successfully prepared by an in situ polymerization reaction through thermal imidization. The synthesized hybrid materials were subsequently characterized by Fourier transform infrared spectroscopy, X-ray diffraction, electron microscopy, and thermogravimetric analysis techniques. The PI/organoclay nanocomposite films have good optical transparencies and the mechanical properties were substantially improved by the incorporation of the reactive organoclay.     

Preparation and characterization of polyimide/ladder like polysiloxane hybrid films

Novel polyimide (PI)/ladder like polyphenylsilsesquioxane (PPSQ) hybrid films was prepared. PI was made from poly(amide acid) of 4, 4′’-diaminodiphenylether and pyromellitic dianhydride. PPSQ was prepared from phenyltrimethoxysilane through sol-gel process. The chemical structure of PPSQ was characterized by Fourier transform infrared and nuclear magnetic resonance. The coefficients of thermal expansion for the hybrid films decrease with the increasing content of PPSQ. The thermal and mechanical properties of the hybrid films were essentially similar to the neat PI.     

Influence of fibre surface oxidation–reduction followed by silsesquioxane coating treatment on interfacial mechanical properties of carbon fibre/polyarylacetylene composites

Carbon fibre was treated with oxidation–reduction followed by silsesquioxane coating method to improve the interfacial properties of carbon fibre/polyarylacetylene (CF/PAA) composites. The treatment method was divided into three phases, i.e., oxidation with oxygen plasma, reduction with LiAlH₄, and coating treatment with vinyl silsesquioxane (VMS–SSO). The fibre surface composition and functional group were analyzed using X-ray photoelectron spectroscopy (XPS). The polar functional groups, especially C–OH which could react with Si–OH on silsesquioxanes, were increased after redox reaction. VMS–SSO coating treatment imported vinyl groups which could react with PAA resin during PAA cure process. The surface morphology of carbon fibre was observed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The mechanical interfacial properties of the CF/PAA composites were characterized by short-beam bending testing method. Interlaminar shear strength (ILSS) of the CF/PAA composites in different treatment phases were increased by 31.7%, 28.8%, and 59.3%, respectively. The conclusion that oxidation–reduction followed by silsesquioxane coating treatment is an effective method to improve the interfacial properties of the CF/PAA composites can be drawn. This method can be used in other resin systems if the functional groups on silsesquioxane are changed according to those in resins.     

原位氨基化氧化石墨烯/聚酰亚胺复合材料的制备及性能

以1,4-双（4-氨基-2-三氟甲基苯氧基）苯（6FAPB）和3,3',4,4'-二苯醚四酸二酐（ODPA）为合成聚酰亚胺（PI）的单体,首先采用原位氨基化方法使氧化石墨烯（GO）与6FAPB反应转变为原位氨基化GO,再与ODPA和剩余的6FAPB发生聚合反应得到原位氨基化GO/聚酰胺酸（PAA）溶液。涂膜后,经热酰亚胺化制备出GO质量分数分别为0.05wt%、0.1wt%、0.3wt%、0.5wt%和1.0wt%的原位氨基化GO/PI复合材料膜。利用FTIR、XPS、XRD、UV-vis、TGA、TMA、SEM、拉伸性能测试及接触角测试对原位氨基化GO/PI复合材料的结构和性能进行表征。结果表明,原位氨基化使GO以化学键与PI大分子链连接,有利于GO在复合材料基体中的稳定和均匀分散。XRD结果表明,所得到的原位氨基化GO/PI复合材料膜均为无定型结构。随GO质量分数增加,原位氨基化GO/PI复合材料薄膜的光学透明性急剧降低,但力学性能和热稳定性有一定提高。当GO的质量分数为1.0wt%时,原位氨基化GO/PI复合材料的拉伸强度由64 MPa增加到83 MPa,杨氏模量由1.67 GPa提高到2.10 GPa,10%热失重温度由593℃增加到597℃,玻璃化转变温度变化不大。由于热酰亚胺化后GO表面的大部分含氧官能团消失,原位氨基化GO/PI复合材料膜的吸水率由0.86%降低至0.58%,水接触角由72.5°增加到77.8°。     

Preparation SnO₂ nanolayer on flexible polyimide substrates via direct ion-exchange and in situ oxidation process

Tin oxide (SnO(2)) nanolayers were formed on flexible polyimide (PI) substrate via direct ion-exchange and in situ oxidation process utilizing pyromellitic dianhydride/4,4'-oxidianiline-based poly(amic acid) films as polyimide precursor. During an ion-exchange process, stannous ions were doped into the precursor by immersion in ethanolic solution of stannous chloride. Subsequent thermal treatment of the tin(II)-containing precursor at a constant heating rate not only imidized poly(amic acid) to PI but also converted stannous ions into SnO(2) clusters, which diffused and aggregated onto the surface of polymer matrix, forming continuous tin oxide layers. Inductively coupled plasma (ICP) was used to investigate the ion-exchange process. Changes in chemical structure of the poly(amic acid) film and the crystal structure of tin oxides were analyzed by attenuated total reflection-Fourier transform infrared (ATR-FTIR) and X-ray diffraction (XRD). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to study the microstructure of the PI/SnO(2) nanocomposite films. The nanocomposite film maintained essential mechanical property and thermal stability of pristine PI films.     

Interactions at fiber/matrix interface in short fiber reinforced amorphous thermoplastic composites modified with micro- and nano-fillers

This study aims at systematically extracting fiber/matrix interfacial strength in short-glass fiber-reinforced polymer composites using an experimental micromechanics approach which employs mechanical properties and residual fiber length distributions to derive the apparent interfacial shear strength. We started from neat high-impact polystyrene matrix short-glass fiber-reinforced composites (HIPS/GF) with varying fiber loading and proceeded toward HIPS/GF hybrid composites containing micro- and nano-fillers where complex fiber/matrix interfacial interactions exist. It was found that apparent interfacial shear strength does not vary with fiber content, while the presence of fillers with different length-scales alters fiber/matrix interactions depending on their influence on physical properties of the polymer matrix, particularly in the vicinity of reinforcing fiber surfaces.     

Effect of interfacial interaction between graphene oxide derivatives and poly(vinyl chloride) upon the mechanical properties of their nanocomposites

In this work, graphene oxide (GO) and poly(methyl methacrylate) (PMMA) grafted GO reduced by dopamine (rGO@PDA-g-PMMA) were employed to determine the key factor responsible for the improved mechanical properties of poly(vinyl chloride) (PVC). Dopamine was utilized to reduce GO and simultaneous coating of polydopamine (PDA) on the GO surface. rGO@PDA-g-PMMA was prepared by a combination of mussel-inspired chemistry and surface-initiated atom transfer radical polymerization techniques. The resulting derivatives were characterized by thermogravimetric analysis, Fourier transforms infrared spectroscopy, X-ray diffraction, and Raman spectroscopy. PVC nanocomposites containing GO derivatives were prepared by solution blend and the nanocomposite films were obtained using a casting method. The mechanical properties of the nanocomposites were studied using both dynamic mechanical thermal analysis and tensile testing. The results revealed that the vital components responsible for the improved mechanical properties and thermal stability of rGO@PDA-g-PMMA/PVC nanocomposites compared to pure PVC are the interfacial interactions between the GO derivatives and the PVC matrix.     

B_4C_P/PI聚酰亚胺复合薄膜耐高温及热中子辐照屏蔽性能研究

以耐高温型聚酰亚胺为基体,微米碳化硼(B_4C)为热中子吸收剂,采用粉体表面改性及超声湿混-热亚胺化成膜工艺成功制备了一系列B_4CP/PI聚酰亚胺复合薄膜,重点探讨了不同B_4C含量条件下复合薄膜的耐热性能和力学性能以及不同B_4C含量、不同复合薄膜厚度条件下复合材料的热中子屏蔽性能。研究表明:采用上述工艺,B_4C功能粒子在聚酰亚胺基体中可均匀分散;B_4CP/PI复合薄膜的耐热性随B_4C含量的增加显著提高,力学性能则呈相反趋势;所制备的B_4CP/PI复合薄膜表现出优异的热中子屏蔽性能,中子透射率I/I0随复合薄膜厚度增加及B_4C含量增加呈指数变化规律。据此,可通过材料结构设计,满足不同领域对该类耐高温中子防护材料的应用需求。     

芳纶沉析纤维-多巴胺/聚酰亚胺-酚醛树脂复合膜的力学及摩擦磨损性能

以聚酰亚胺（PI）纤维和酚醛树脂（PF）为基体,通过对PI纤维表面进行多巴胺（PDA）修饰,并引入芳纶沉析纤维（AF）作为增强体,采用湿法成型和热压固化技术制备了15wt% AF和7.5wt% PDA的AF-PDA/PI-PF复合膜,重点研究了AF的添加和PDA改性修饰对PI-PF复合膜力学性能和摩擦磨损性能的影响,并探讨了其磨损机制。研究结果表明:当添加AF并对PI纤维进行PDA改性时,AF-PDA/PI-PF复合膜的应力为47.54 MPa,抗张指数为56.91 Nmg-1,层间结合强度为1 265.6 Jm-2,相比PI-PF复合膜分别提高了33.65%、41.67%和64.11%;磨损率为1.01×10-4 mm3J-1,约降低了34.84%,其磨损机制主要为黏着磨损。这是由于PI纤维与AF可形成"互穿网络"结构,此外,PDA对PI纤维的化学改性处理可增加PI纤维表面活性,AF和PDA对提高PI纤维与树脂间的界面结合力及AF-PDA/PI-PF复合膜的力学性能和摩擦磨损性能起到协同作用。      

新型耐电晕聚酰亚胺杂化薄膜的制备与性能研究

通过超声分散和原位聚合法制备了以s-BPDA/1,3,4-APB为树脂基体,以具有不同SiO2添加量的新型球型SiO2/聚酰亚胺杂化薄膜,所制备的杂化薄膜具有优异的力学、热学和耐电晕性能.通过SEM、TEM、FT-IR、UV-vis、DSC、TGA等实验手段对产物进行了分析和表征,并系统研究了SiO2的添加量对杂化薄膜...     

Effect of side-chain structure of rigid polyimide dispersant on mechanical properties of single-walled carbon nanotube/cyanate ester composite

Three kinds of polymer, polyimide without side-chain (PI), polyimide-graft-glyceryl 4-nonylphenyl ether (PI-GNE), and polyimide-graft-bisphenol A diglyceryl acrylate (PI-BDA), have been synthesized and used to disperse single-walled carbon nanotubes (SWNTs) and to improve the interfacial bonding between SWNTs and cyanate ester (CE) matrix. Visual observation, UV-vis-near-IR (UV-vis-NIR) spectra, and atomic force microscopy (AFM) images show that both PI-GNE and PI-BDA are highly effective at dispersing and debundling SWNTs in DMF, whereas PI is less effective. Interaction between SWNTs and PI, PI-GNE or PI-BDA was confirmed by computer simulation and Raman spectra. A series of CE-based composite films reinforced with different loadings of SWNTs, SWNTs/PI, SWNTs/PI-GNE and SWNTs/PI-BDA were prepared by solution casting. It was found that, because of the unique side-chain structure of PI-BDA, SWNTs/PI-BDA disperse better in CE matrix than do SWNTs/PI-GNE, SWNTs/PI, and SWNTs. As a result, SWNTs/PI-BDA/CE composites have the greatest improvement in mechanical properties of the materials tested. These results imply that the choice of side-chain on a dispersant is very important to the dispersion of SWNTs in matrix and the filler/matrix interfacial adhesion, which are two key requirements for achieving effective reinforcement.     

Layer-by-layer assembled PVA/Laponite multilayer free-standing films and their mechanical and thermal properties

Structural arrangements of nanoplatelets in a polymer matrix play an important role in determining their properties. In the present study, multilayered composite films of poly(vinyl alcohol) (PVA) with Laponite clay are assembled by layer-by-layer (LBL) deposition. The LBL films are found to be hydrated, flexible and transparent. A facile and solvent-free method-by depositing self-assembled monolayers (SMA) of a functional silane on substrates-is demonstrated for preparing free-standing LBL films. Evolution of nanostructures in LBL films is correlated with thermal and mechanical properties. A well-dispersed solvent-cast PVA/Laponite composite film is also studied for comparison. We found that structurally ordered LBL films with an intercalated nanoclay system exhibits tensile strength, modulus and toughness, which are significantly higher than that of the conventional nanocomposites with well-dispersed clay particles and that of pure PVA. This indicates that clay platelets are oriented in the applied stress direction, leading to efficient interfacial stress transfer. In addition, various grades of composite LBL films are prepared by chemical crosslinking and their mechanical properties are assessed. On account of these excellent properties, the LBL films may find potential use as optical and structural elements, and as humidity sensors.     

氧化石墨烯/聚酰亚胺复合薄膜的制备及阻水性能

以石墨粉为原料,采用改进的Hummers法制备氧化石墨烯（GO）,采用原位聚合法制备GO/聚酰亚胺酸（PAA）前驱体,GO/PAA前驱体经高温固化处理后得到GO/聚酰亚胺（PI）复合薄膜;采用XRD、Raman、FTIR、AFM等表征手段对GO的结构进行表征;此外,研究了不同固化温度下PI薄膜的结构;最后测试了GO/PI复合薄膜的透湿率和力学性能。结果表明:GO为单层结构,厚度为1.26 nm。GO/PI复合薄膜表现出良好的阻水性能,当GO/PI复合薄膜中GO的添加量为0.025wt%、薄膜厚度为50 μm时,GO/PI复合薄膜的透湿率低至56.7 g（m2·d）-1。此外,0.025wt% GO/PI复合薄膜拉伸强度和断裂伸长率分别为150.8 MPa和13.5%,与PI薄膜（分别为126.9 MPa和8.1%）相比,分别增加了18.8%和66.7%。      

废印刷电路板非金属粉负载二氧化硅杂化填料的制备及其在不饱和聚酯中的应用

为增强废印刷电路板非金属粉(WPCBP)与聚合物基体之间的界面结合作用,采用溶胶-凝胶法在WPCBP表面原位负载了一层纳米二氧化硅粒子(SiO_2),制备了一种新型的WPCBP-SiO_2杂化填料。SEM、TGA和FTIR证明SiO_2通过化学键成功负载到了杂化填料的表面。采用含双键的界面改性剂对杂化填料进行改性后,应用于不饱和聚酯树脂基体,探讨了未改性杂化填料及表面改性杂化填料对不饱和聚酯复合材料的力学性能、界面结合作用和热稳定性能的影响。结果表明,新型的杂化填料WPCBP-SiO_2能够与不饱和聚酯基体形成强的界面结合作用,显著提高不饱和聚酯复合材料的力学性能和热稳定性能,且表面改性后复合材料的各项性能得到进一步提高。     

废印刷电路板非金属粉负载二氧化硅杂化填料的制备及其在不饱和聚酯中的应用

为增强废印刷电路板非金属粉(WPCBP)与聚合物基体之间的界面结合作用,采用溶胶-凝胶法在WPCBP表面原位负载了一层纳米二氧化硅粒子(SiO2),制备了一种新型的WPCBP-SiO2杂化填料.SEM、TGA和FTIR证明SiO2通过化学键成功负载到了杂化填料的表面.采用含双键的界面改性剂对杂化填料进行改性后,应用于不饱和聚酯树脂基体,探讨了未改性杂化填料及表面改性杂化填料对不饱和聚酯复合材料的力学性能、界面结合作用和热稳定性能的影响.结果表明,新型的杂化填料WPCBP-SiO2能够与不饱和聚酯基体形成强的界面结合作用,显著提高不饱和聚酯复合材料的力学性能和热稳定性能,且表面改性后复合材料的各项性能得到进一步提高.     

Enhancement of thermal and mechanical properties of flexible graphene oxide/carbon nanotube hybrid films though direct covalent bonding

The thermal conductivity and mechanical properties of graphene oxide/multiwalled carbon nanotube (GO/MWCNT) hybrid films with and without covalent bonding were examined. Chlorinated GO and amino-functionalized MWCNT were bonded covalently to fabricate chemically bonded GO/MWCNT hybrid films. Mixtures of surface-modified GO and MWCNT were filtered and then subjected to hot-pressing to fabricate stacked films. Examination of these chemically bonded hybrid films revealed higher thermal conductivity than in physically bonded hybrid films, because of the synergetic interaction of functional groups in GO and MWCNT in the films. However, the addition of excess MWCNT to the films led to an increased phonon scattering density and a decreased thermal conductivity. The hybrid films fabricated by the optimized process endured about 20000 bending cycles without rupturing or losing their thermal conductivity. The mechanical properties showed enhanced performance after increased MWCNT loading at elevated temperature due to the reinforcement effect of the MWCNT between GO layers.     

PVA/LDH-aCNTs杂化薄膜的制备及其性能研究

采用恒定p H共沉淀法合成了层状双羟基氢氧化物(LDHs)和酸化碳纳米管(aCNTs)杂化材料,并将其作为填料应用到聚乙烯醇(PVA)薄膜中制备了PVA杂化薄膜。采用X射线衍射仪、拉曼光谱仪、扫描电子显微镜等对合成的LDH-aCNTs杂化材料进行了表征,并对PVA杂化薄膜进行了微观结构和力学性能测试。力学性能测试结果表明:当LDH-aCNTs的添加质量分数为3%时,PVA杂化薄膜的拉伸强度达到最大值,相比于纯PVA,拉伸强度约提高了41%。LDHs的存在有效地改善了aCNTs和PVA之间的相容性,使得PVA/LDH-aCNTs杂化薄膜具有较优异的力学性能。吸水性能测试结果表明:相比于纯PVA(吸水率为649%),添加质量分数为5%的PVA/LDH-aCNTs杂化薄膜的吸水率约下降了58%。LDH-aCNTs杂化纳米粒子中的含氧官能团能与PVA链中的羟基形成氢键,使裸露的亲水基团减少,吸水率下降。PVA/LDH-aCNTs杂化薄膜的力学性能和耐水性能的提高,有望拓宽PVA基复合薄膜的应用范围。     

Controlled Microstructure and Photochromism of Inorganic-organic Thin Films by Ultrasound

A series of inorganic-organic thin films based on uniformly dispersed nanoparticles of polyoxometalates （POM）entrapped in polyacrylamide （PAM） matrix were prepared by ultrasonic method with different irradiation time.The microstructure, photochromic behavior and mechanism of the films were studied by transmission electron microscopy （TEM）, ultraviolet-visible spectra （UV-VIS） and Fourier transform-infrared spectroscopy （FT-IR）.The microstructure and photochromic properties of the hybrid thin films could be controlled by ultrasound.TEM image revealed that the average size of phosphotungstic acid （PWA） nanoparticles decreased from 20 to 10 nm with the ultrasound irradiation time from 30 to 60 min. After irradiated with ultraviolet light,the transparent films changed from colorless to blue and showed reversible photochromism. The hybrid film, with ultrasound irradiation for 60 min had higher photochromic efficiency and faster bleaching reaction than the one with ultrasound irradiation for 30 min. FT-IR spectra showed that the Keggin geometry of heteropolyoxometalate was still preserved inside the composites, and the interactions between polyanions and polymer matrix increased as the ultrasound time prolonged. It is suggested that the mechanism of the different photochromic properties for the inorganic-organic thin films is the variation of the microstructure and interfacial interactions induced by ultrasound.     

氧化石墨烯/聚乙烯醇复合材料的纳米压痕实验及力学性能

为了研究氧化石墨烯(GO)对聚合物基复合材料力学性能的影响,通过溶液混合法制备了GO/聚乙烯醇(PVA)复合材料。然后,采用XRD、TEM、FTIR、DSC和纳米压痕实验等研究了GO/PVA复合材料的结构、界面结合性能、力学性能、蠕变行为和吸水膨胀率。结果表明:GO可以均匀分散在PVA基体中,二者之间主要通过氢键作用结合,具有较高的界面结合力;与纯PVA相比,1wt% GO/PVA复合材料的硬度和有效弹性模量分别提高了28.9%和23.3%,压入蠕变深度下降了19.8%;GO/PVA复合材料具有较低的无限剪切模量与瞬时剪切模量比,表明GO提高了PVA的蠕变抗力;GO的添加同时增加了GO/PVA复合材料的阻水性并降低了膨胀系数。吸湿纳米压痕实验结果表明:纯PVA的力学性能会随吸湿时间延长而下降,而GO/PVA复合材料吸湿72h后的力学性能基本保持不变。所得结论为石墨烯增强聚合物基复合材料的研究提供了理论指导。      

溶胶-凝胶法制备氧化硅-氧化铝共掺杂聚酰亚胺薄膜及其性能

采用溶胶-凝胶法制备纳米二氧化硅及氧化铝溶胶,将溶胶混合后掺入正在反应的聚酰胺酸中,制得聚酰亚胺/二氧化硅-氧化铝杂化薄膜。利用扫描电子显微镜对杂化薄膜的微观形貌进行了表征,并测试了无机组分含量不同的杂化薄膜的力学性能、热稳定性及介电性能。试验结果表明,杂化薄膜材料中无机相呈现纤维结构和颗粒结构,有效地提高了薄膜的力学性能。杂化薄膜与纯膜相比,热分解温度有较大提高,且随着无机组分含量增大,热分解温度呈现先上升后下降的趋势。介电性能分析表明,杂化薄膜的介电常数和介电损耗与频率的关系符合德拜松弛极化机理。