Structure and infrared emissivity of polyimide/mesoporous silica composite films

Polyimide/mesoporous silica composite films were prepared by direct mixing of polyamic acid solution and silylated mesoporous silica particles, or by condensation polymerization of dianhydride and diamine with silylated mesoporous silica particles in N,N-dimethylacetamide, followed with thermal imidization. Structure and glass transition temperatures of the composite films were measured with FTIR, SEM, EDX, XPS and DMTA. The results show that the silylated mesoporous silica particles in the composites tend to form the aggregation with a strip shape due to phase separation. The composite films exhibit higher glass transition temperature as comparing with that of pure polyimide. It is found that the composite films present lower infrared emissivity value than the pure polyimide and the magnitude of infrared emissivity value is related to the content of silylated mesoporous silica in the composite films. Inhibiting actions of silylated mesoporous silica on infrared emission of the composite films may be owing to presence of nanometer-scale pores in silylated mesoporous silica.     

Synthesis, characterization and hydrolytic stability of poly (amic acid) ammonium salt

A series of new poly (amic acid) ammonium salt (PAAS) precursors were prepared by incorporating different amounts of triethylamine (TEA) into terpolymer polyamic acid (PAA), which was synthesized by pyromellitic dianhydride (PMDA), 4,4’-oxydianiline (ODA) and p-phenylenediamine (PDA) in dimethylacetamide (DMAc). Then, the PAAS films were made by casting their solutions onto glass plates followed by the evaporation of the solvent. The chemical structure of PAAS films was confirmed by ¹H NMR and FTIR spectroscopy. Mechanical properties, intrinsic viscosities and solubility of PAAS precursors were examined, respectively. It was found that the intrinsic viscosity of PAA solution obviously decreased with storage time during 30 days, while no distinct changes were observed in the intrinsic viscosity of the PAAS (the mole ratio of TEA/repeating unit of PAA = 2/1) solution after 90 days. The results suggested that hydrolytic stability of the PAAS films was significantly improved as compared with that of PAA film due to the polyelectrolyte structure of PAAS. Moreover, the thermal and mechanical properties of polyimide (PI) films prepared from PAAS precursors were also investigated, respectively.     

Microstructure and properties of organosoluble polyimide/silica hybrid films

Organosoluble polyimide/silica hybrid materials were prepared via the sol-gel process and their pervaporation properties were studied. The organosoluble polyimide (PI) was based on 4,4′-oxydiphthlic dianhydride (ODPA) and 4,4′-diamino-3,3′-dimethyldiphenylmethane (DMMDA). The surface chemical structure of polyimide/silica films was analyzed by Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) and the results show that the completely hydrolysis of alkoxy groups of precursors and formation of the three-dimensional Si-O-Si network in the hybrid films. The morphology and the silica domain thus obtained were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. The silica particle size in the hybrid is in the range of 40-100 nm for the hybrid films when the amount of silica is less than 20 wt%. The strength and the modulus of the hybrid films are improved and the mechanical properties were found to be strongly dependent on the density of the crosslink. The glass transition temperature (T_g) of the hybrid films was determined by dynamic mechanical analysis (DMA) and the value increased 15-20 °C as the silica content increased. Furthermore, the pervaporation performances of the prepared hybrid films were also investigated for the ethanol/water mixtures at different temperature.     

Preparation and characterization of polyimide/pure silica zeolite hybrid films

In this study, amino derivative of pure silica zeolite nanocrystal (A‐PSZN) was dispersed into polyimide (PI) matrix to prepare PI/A‐PSZN hybrid films, and their thermal and mechanical properties, as well as hydrophobicity, were characterized scientifically. The test results show that PI/A‐PSZN hybrid films possess higher glass transition temperature, higher thermal stability and lower in‐plane coefficient of thermal expansion than pristine PI. The mechanical property data suggest that the incorporation of A‐PSZN results in an increase in Young's modulus and tensile strength of the hybrid films, but as its content exceeds the critical value (maybe 5 wt%), its enhancement effect on the hybrid's strength and toughness gets weaker. Furthermore, liquid dripping imaging analysis results indicate that the film's hydrophobicity is clearly improved by the introduction of A‐PSZN. As compared with PSZN, A‐PSZN exhibits better effect on enhancing the overall performance of pristine PI films. A comparison with other studies suggests that PI/A‐PSZN is a hybrid film with superior comprehensive properties. Copyright © 2013 John Wiley & Sons, Ltd.     

Preparation, characterization and dielectric properties of 4,4-diphenylmethane diisocyanate (MDI) based cross-linked polyimide films

Four different types of cross-linked polyimides based on 4,4-diphenylmethane diisocyanate (MDI) were prepared by the reaction of different types of conventional poly(amic acid) intermediates with MDI as a cross-linking agent. Subsequently, they were thermally imidized in order to obtain corresponding cross-linked polyimide structure. The results of FTIR-ATR showed that MDI can effectively react with carboxylic acid groups of PAA to form cross-linked polyimide films. TGA, FTIR-ATR and SEM analyses were carried out for characterization of cross-linked polyimide (CPI) films. Moreover, the electrical properties such as dielectric breakdown strength, dielectric constant, I-V characteristics and loss factor of MDI based cross-linked polyimides have been checked. In addition, some physical properties such as water uptake, adhesion, hardness and solubility properties of the films were investigated.The results showed that all CPI films have good insulating properties such as high dielectric breakdown voltage, low loss factor (tan δ), leakage density and excellent physical properties.     

Preparation and characterization of polypropylene/mesoporous silica nanocomposites with confined polypropylene

Polypropylene (PP)/Ti-MCM-41 nanocomposites were prepared by isospecific propylene polymerization with Ti-MCM-41/Al(i-C₄H₉)₃ catalyst. The cross polarization/magic angle spinning (CP/MAS) ¹³C NMR spectrum of the composite was similar to that of the conventional isotactic PP, and the decrease in the pore volume of Ti-MCM-41 in the nanocomposites, as measured by N₂ adsorption, was consistent with the value calculated from the weight loss in the thermogravimetric analysis (TGA) curve; both these facts attest to propylene polymerization within the mesopores of Ti-MCM-41. Alkali treatment followed by extraction with o-dichlorobenzene allows us to extract the confined PP out of the Ti-MCM-41 mesopores. Although the PP/Ti-MCM-41 nanocomposites do not exhibit a crystalline melting point, the same PP when extracted from the mesopores showed a clear melting point at 154.7 °C; this indicates that the crystallization of PP confined in mesopores is strongly hindered. For the PP polymerized within the confinement, the molecular weight (M_w) and molecular weight distribution (M_w/M_n) were 84,000 and 4.3, respectively; these values were considerably smaller than those of the PP polymerized concurrently outside the Ti-MCM-41 mesopores (M_w = 200,000–450,000, M_w/M_n = 40–75). Therefore, the confinement also has a marked effect on the molecular weight of the PP. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3324–3332, 2003     

Preparation of hemispherical polyimide particles by inverse emulsion technique from poly(amic acid) ammonium salts

Nonspherical polymer particles have attracted increasing attention recently. In this paper, micron-scale hemispherical polyimide (PI) particles were fabricated using water-soluble poly(amic acid) ammonium salts (PAAS) by a novel inverse emulsion technique. In the process, liquid paraffin was used as a continuous phase, the mixed solution of PAAS and water as a dispersed phase and sorbitan monooleate (Span80) as a surfactant. The research suggested that water as a stabilizing agent played an important role in forming stable emulsion. As the amount of water increased, stability of the emulsion increased gradually and morphology of PI particles transformed from sphere to ellipsoid, and finally to hemisphere. The concentration of PAAS solution and Span80 both affected the shape of particles, which changed from spherical to hemispherical by increasing the PAAS/Span80 concentration. The mechanism of forming hemispherical PI particles was discussed based on interfacial tension and interfacial free energy changes. Via adjusting the composition of the system to change the corresponding interfacial tension, we could get the particles with different morphologies. Furthermore, the change in structure characterized by FT-IR spectroscopy demonstrated that PAAS had been converted to PI after adding the dehydrating agent to the emulsion. And TGA results showed that the obtained PI particles had excellent thermal stability.     

Preparation of nonwoven polyimide/silica hybrid nanofiberous fabrics by combining electrospinning and controlled in situ sol-gel techniques

A controlled in situ sol-gel synthesis combined with the electrospinning technique and postspun imidization was applied in the fabrication of polyimide/silica hybrid nonwoven nanofiberous fabrics with excellent thermal and mechanical performance. The nanofiberous fabrics were prepared by electrospinning of the solution of tetraethoxysilane (TEOS) and polyamic acid (PAA). The different silica contents in the fabrics were achieved by varying the amount of TEOS while fitting the solid content of PAA. The final polyimide/silica fabrics was obtained after imidization of PAA and gelation of silica phase simultaneously accomplished through a step-wise heating process. Some specific IR techniques and other characterizations indicated the successful incorporation of the silicon dioxide (SiO₂) into the PI matrix and the relatively even distribution of the SiO₂ in the fabrics. An increase of 133 °C in the decomposition temperature and 4-fold enhancement of the ultimate tensile strength were achieved for the hybrids with a 6.58 wt.% of SiO₂ content, compared to the pure PI fabric. The excellent performance could be attributed to the good compatibility between the polyimide and silica, and good adhesion among the fibers, which resulted from the controlled TEOS hydrolysis and the simultaneous imidization and gelation process.     

Preparation and applications of novel fluoroalkyl end‐capped oligomers/polyimide/silica nanocomposites

Fluoroalkyl end‐capped acrylic acid, N,N‐dimethylacrylamide, N‐(1,1‐dimethyl‐3‐oxobutyl)acrylamide and vinyltrimethoxysilane oligomers reacted with polyamic acid possessing trimethoxysilyl groups under alkaline conditions to yield the corresponding fluoroalkyl end‐capped oligomers/polyamic acid/silica nanocomposites. These isolated fluorinated composite powders were found to afford nanometer size‐controlled fine particles with a good dispersibility and stability in water and traditional organic solvents. We succeeded in preparing new fluoroalkyl end‐capped oligomers/polyimide/silica nanocomposites by the imidization of fluorinated polyamic acid silica nanocomposites through the stepwise heating at 110 and 270°C under air atmosphere conditions. These fluorinated polyimide/silica nanocomposites thus obtained were applied to the surface modification of glass and poly(methyl methacrylate) (PMMA) to exhibit good hydro‐ and oleo‐phobic characteristics imparted by fluoroalkyl groups in the composites on their surface. In addition, the surface morphology of the modified glass treated with these fluorinated nanocomposites were analyzed by using FE‐SEM and DFM. Copyright © 2011 John Wiley & Sons, Ltd.     

Dispersion of nano-carbon filled polyimide composites using self-degradated low molecular poly(amic acid) as impurity-free dispersant

Polyimide (PI)-based composite films incorporated with carbon black (CB), carbon nanotube (CNT) and carbon nanofiber (CNF), respectively, were prepared using low-molecular-weight poly(amic acid) (PAA), a precursor of PI, as an impurity-free dispersant. High-energy ball mill was employed not only to downsize the nano-carbon agglomerates, but also to cut off the PAA chains for in-situ stabilizing the dispersion. Effect of the ball milling time, procedure, and filler species on the filler dispersion was investigated by means of electrical resistivity reproducibility, morphology observation, and mechanical testing. Comparing with direct dispersion of the nano-carbon in PAA, the composite films fabricated by a two-step approach, that is dispersion from the in-situ degradated low-molecular-weight PAA stabilized nano-carbon slurry, presented a uniform electrical conductivity with a lower percolation concentration and excellent reproducibility in the percolation region. A significant improvement in the Young’s modulus for the CNT loaded PI film was achieved, which was much more effective than those filled with CB or CNF.     

Preparation, microstructure, and properties of novel low-κ brominated epoxy/mesoporous silica composites

Brominated epoxy resin (BER) composites containing various amounts of SBA-15 and SBA-16 types mesoporous silicas were prepared through the thermal curing with 3-methyl-tetrahydrophthalic anhydride, and their morphologies, dielectric constants (κ), thermal properties and mechanical properties were studied. The investigation suggested that the dielectric constant could be reduced from 4.09 of the pure thermosetting BER to 3.74 and 3.7 by incorporating 3 wt.% SBA-15 and SBA-16, respectively. The reduction of the dielectric constant is attributed to the incorporation of the air voids (κ = 1) stored within the mesoporous silica materials, the air volume existing in the gaps on the interfaces between the mesoporous silica and the BER matrix, and the free volume created by introducing large-sized domains. The BER/mesoporous silica composites also present stable dielectric constants across the wide frequency range. An improvement of thermal stability of the BER is achieved by incorporation of the mesoporous silica materials. The enhanced interfacial interaction between the surface-modified mesoporous silica and the BER matrix has also led to an improvement of the toughness.     

Construction of a pH-responsive drug delivery platform based on the hybrid of mesoporous silica and chitosan

Mesoporous silica nanoparticles (MSN) have been widely used for drug delivery due to their large specific surface area and excellent biocompatibility. However, the mesoporous structure of MSN would lead to the inevitable “premature release” of the drugs, and therefore the modification of MSN for controlled delivery seems to be a necessary step. Herein, chitosan (CS) was used for the surface functionalization of MSN via amidation reaction, and the introduced CS could function as a “gatekeeper” and the drug of methotrexate (MTX) might be encapsulated in the mesopores of MSN. As a result, the “premature release” of the encapsulated MTX could be effectively circumvented with the aid of the CS cap. More importantly, the drug delivery from the hybrid of MSN and CS (MSN/CS) can be endowed with pH-sensitivity by the introduction of CS because the amide bonding between CS and MSN is highly pH-sensitive. The cumulative release of MTX from the MSN/CS is more pronounced at pH 5.0 (80.86%) than those at pH 6.8 (40.46%) and pH 7.4 (18.25%).     

高介电常数石墨烯/聚酰亚胺复合材料的制备与性能

在原位聚合制备氧化石墨烯/聚酰亚胺复合材料的过程中,加入季铵盐表面活性剂,抑制氧化石墨烯在高温亚胺化时的聚集,同时将氧化石墨烯原位还原,获得高介电常数的石墨烯/聚酰亚胺复合材料.结果表明,采用四丁基溴化铵和四丁基碘化铵作为还原剂,利用原位化学还原方法所制备的石墨烯/聚酰亚胺复合材料的介电常数超过聚酰亚胺薄膜40倍以上,复合材料的热稳定性和机械性能也优于聚酰亚胺薄膜.热重分析结果表明,在复合材料高温亚胺化过程中,季铵盐发生热分解,未残留在复合材料中.     

Preparation of polyimide/silica hybrid material by sol–gel process under basic catalysis: Comparison with acid conditions

Hybrid polyimide/silica materials were prepared from polyimides bearing reactive functions along the polymer backbone, which can react with. The silica phase was formed by sol–gel process using ammonium hydroxide catalyst. Silica fillers prepared under basic conditions were compared with materials prepared using chlorhydric acid. The synthesized hybrid materials were characterized by TGA, IRTF, and NMR. The density of the different systems was also measured. The morphology of these hybrid systems were investigated by both scanning and transmission electron microscope. Thermal properties of the composites were also evaluated by DSC and DMA. The morphology of silica fillers highly depends on the catalyst, on the reaction conditions of the sol–gel process, and the linking formation with the polyimide. It results that optimized conditions lead to homogeneous hybrid films containing 12 wt % of silica particles of about 20 nm. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1891–1902, 2008     

Lipid,protein and poly(NIPAM) coated mesoporous silica nanoparticles for biomedical applications

In the past decade, mesoporous silica nanoparticles (MSNs) as nanocarriers have showed much potential in advanced nanomaterials due to their large surface area and pore volume. Especially, more and more MSNs based nanodevices have been designed as efficient drug delivery systems (DDSs) or biosensors. In this paper, lipid, protein and poly(NIPAM) coated MSNs are reviewed from the preparation, properties and their potential application. We also introduce the preparative methods including physical adsorption, covalent binding and self-assembly on the MSNs' surfaces. Furthermore, the interaction between the aimed cells and these molecular modified MSNs is discussed. We also demonstrate their typical applications, such as photodynamic therapy, bioimaging, controlled release and selective recognition in biomedical field.     

Synthesis and characterization of poly1-hexene/silica nanocomposites

SiO₂ nano particles, with particle size of 12 nm, were first modified by substituting surface OH groups with O-hexyl moiety. Then, poly1-hexene/modified-SiO₂ composites with various nano-SiO₂ weight fractions were prepared by three different methods: in situ, solution, and melt methods and designated as PH-SiO₂/Insitu, PH-SiO₂/Sol and PH-SiO₂/Melt, respectively. PH-SiO₂/Insitu samples showed highly uniform particle dispersion up to 30 wt. % of silica while in PH-SiO₂/Sol and PH-SiO₂/Melt samples agglomeration of the silica nanoparticles occurred for filler contents ≥5 wt. % (i.e. 5, 10, 20 and 30 wt%). In the synthesized composites, the storage modulus significantly increased as high as 20.7 times when compared with neat poly1-hexene. Maximum decomposition temperature (T_max) and char yield at 600 °C increased with increasing silica level. Rheological results showed that G^ʹ> G^ʺ over the frequency range, illustrating the elastic behavior of the composite samples. In fact, samples showed the characteristic of a non-Newtonian fluid with a strong shear thinning effect in which η* increased with increasing filler weight fraction. From the results, it can be expected that modified silica could replace silica nanoparticles in polyolefin nanocomposite reinforcement.     

Preparation and characterization of poly(imide siloxane) (PIS)/titania(TiO2) hybrid nanocomposites by sol-gel processes

Poly(imide siloxane)(PIS)/titania(TiO₂) hybrid nanocomposites with organic-inorganic covalent bonding have been successfully synthesized by sol-gel processes. The PIS copolymer synthesized in this study was characterized by the observed coexisting two segments: the polyimide (PI) segment and polydimethyldiphenylsiloxane segment, and the latter were specially featured with the introduction of a diphenyl group for improved homogeneity.The obtained TiO₂ networks in PIS matrix were well dispersed and their average diameter was less than 50 nm. Meanwhile, the PIS/TiO₂ hybrid nanocomposite films exhibited good optical transparency at 20 wt% of TiO₂ content. The thermal stability, tensile strength and elongation of the nanocomposites decreased with increasing TiO₂ content. The glass transition temperature (T_g) and Young’s modulus increased with increasing TiO₂ content. The chemical structure and morphologies of PIS/TiO₂ hybrid nanocomposites was characterized by Fourier transform infrared spectroscope (FT-IR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscope (TEM). The T_g and thermal stability were measured by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA), respectively. The mechanical properties were examined by dynamic mechanical analysis (DMA) under controlled force mode.     

Preparation, characterization and biodegradation of biopolymer nanocomposites based on fumed silica

PLA and PCL based nanocomposites prepared by adding three different types of fumed silica were obtained by melt blending. Materials were characterized by means of Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA) and Dynamic–Mechanical Thermal Analysis (DMTA).A good distribution of the fumed silica into both polymer matrices was observed. The highest thermo-mechanical improvements were reached by addition of the fumed silica with higher surface area. PLA and its nanocomposites were degraded in compost at 58 °C; at this temperature all samples presented a significant level of polymer degradation, but a certain protection action of silica towards PLA degradation was observed, whereas the addition of fumed silica did not show considerable influence on the degradation trend of PCL. These dissimilarities were attributed to the different degradation mechanism of the two polymers.     

Preparation, morphology and properties of nano-sized Al2O3/polyimide hybrid films

Nano-sized Al₂O₃/polyimide (PI) hybrid films based on 4,4′-oxydianiline (ODA) and pyromellitic dianhydride (PMDA) were prepared by incorporation with different content of nano-sized Al₂O₃ via in situ polymerization. The TEM and SEM micrographs indicated that the Al₂O₃ particles were homogenously dispersed in the polyimide matrix by means of the ultrasonic treatment and the addition of coupling agent. The mechanical properties and thermal stability of the pure PI film can be improved by adequate addition of Al₂O₃. The PI hybrid film was strengthened and toughened simultaneously by the introduction of the well-dispersed Al₂O₃ particles. The PI hybrid films showed improved electrical aging performance as compared with pure PI film. Especially, the PI hybrid films with 10 wt.% of Al₂O₃ content exhibited obviously enhanced electrical aging performance with the time to failure of 3.4 times longer than that of pure PI film. The improved electrical aging performance of the hybrid film was attributed to the nano-sized Al₂O₃ particles highly dispersed in the hybrid film, which confirmed by the investigation of the morphology and the surface composition of PI hybrid film before and after electrical aging.     

Highly permeable mesoporous silica membranes synthesized by vapor infiltration of tetraethoxysilane into non-ionic alkyl poly(oxyethylene) surfactant films

Mesoporous silica membranes were prepared on porous alumina substrates by a vapor infiltration of tetraethoxysilane (TEOS) into a non-ionic poly(oxyethylene) (Brij56) surfactant film. Periodic mesostructured silica membranes were formed on both α- and γ-alumina substrates pre-treated with polystyrene. The polystyrene polymer plugged the pores of the alumina substrates and inhibited the deposition of silica in the alumina pores, resulting in the formation of a very thin silica membrane without a silica/alumina composite layer at the interface between mesoporous silica and the alumina substrates. The calcined mesoporous silica membrane showed very high nitrogen permeance (>10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹). The single gas permeation was governed by the Knudsen diffusion mechanism. The durability of the mesoporous silica membrane against moisture in air was improved by a silylation with trimethylethoxysiliane.