Study on morphology control and how to affect mechanical properties of polyimide/silica hybrid films

A series of polyimide (PI)/silica hybrid films were prepared by sol–gel method, using hydrolyzed tetraethoxysilane and poly amic acid‐imides (PAA‐Is), which were different imidization degree controlled by chemical imidization method. The imidization degree was characterized by Fourier transform infrared spectra and their corresponding morphology was characterized by scanning electron microscopy. The results show that there are two kinds of silica particles and their formative morphology obeys the double phase separation mechanism. According to the increase of PAA‐I imidization degree, amount of nano silica particles decreased and the diameter of macro silica particles increased in the hybrid films. Tensile testing, dynamic mechanical analysis, and thermal mechanical analysis results show that, according to the amount of nano silica particles increasing, the hybrids have the higher the mechanical properties, glass transition temperature (T_g), and thermal expansion coefficient. Through controlling PI/silica hybrid films microstructure, its mechanical properties can be controlled. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of surface chemistry and morphology of silica on the thermal and mechanical properties of silicone elastomers

In this study, high‐temperature vulcanized silicone rubbers (HTV‐SRs) using fumed silica (FSi), precipitated silica (PSi), and modified precipitated silica (MPSi) as reinforcing fillers were prepared. The effect of morphology and surface chemistry of the silica on the thermal and mechanical properties of the resultant silicone rubbers was investigated using curing rheometer, scanning electron microscopy, mechanical test, and dynamic mechanical analysis. The thermo‐oxidative stability and solvent resistance of the vulcanized silicone rubbers were further evaluated via heat ageing test, extraction, and swelling experiments. It is shown that the mechanical properties (tensile modulus and tensile strength) of the as‐prepared HTV‐SRs are in the order of FSi > PSi > MPSi, which could be attributed to the molecular interaction between the filler and the matrix. FSi has the highest surface area, which enhances the hydrogen bonding interaction between the filler and the silicone matrix; while MPSi, in which part of Si? OH groups have been consumed during modification, shows the weakest interaction among the three. The filler–matrix interaction could also explain the lowest swelling and sol fraction in FSi‐filled HTV‐SR, and the low viscosity and good processibility of PSi‐ and MPSi‐filled HTV‐SR. Furthermore, it is also shown that the MPSi‐filled HTV‐SR exhibits the highest retention of mechanical properties after thermal aging at 250 °C for 24 h, which could be attributed to the lowest acidity of the fillers. The possible mechanism for acid catalyzed hydrolytic chain scission and intramolecular chain backbiting has been proposed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46646.     

Effects of water on the preparation,morphology, and properties of polyimide/silica nanocomposite films prepared by sol–gel process

Polyimide/silica (PI/SiO₂) nanocomposite films with 10 wt % of silica content were prepared by sol–gel process under the conditions with and without additional water. The presence of additional water has great effect on the silica particle size and thus on the properties of the prepared PI/SiO₂ films. The results indicated that with additional water, the silica particles formed before the imidization of poly(amic acid) (PAA) and aggregated with the increasing of temperature and degree of the proceeding imidization process. For the nonaqueous process, the hydrolysis condensation reaction of tetraethoxysilane (TEOS) did not occur until the imidization of PAA took place, and no silica particles were found in the unimidized PAA films. The hydrolysis–condensation reaction of TEOS was initiated simultaneously by the trace water released from the imidization reaction, the self‐catalysis mechanism of the approach provide a means of achieving uniformly dispersed silica particles formed in the PI matrix with particle size in the range of 30–70 nm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1579–1586, 2007     

Wear,thermal, and physical properties of fluorine-containing polyimide/silica hybrid nanocomposite coatings

This study prepared fluorine and SiO₂ particles containing organic–inorganic hybrid polyimide nanocomposite coatings (PISFs) with inorganic content in the range of 5–20% in pure polyimide solutions via the sol–gel process. Polyimide hybrid structures containing fluorine and SiO₂ particles were synthesized by using perfluorooctyltriethoxysilane and tetraethyl orthosilicate. These formulations were applied on aluminum sheets by using a 75 μm wire wound applicator, and the coatings were cured for 8 h at room temperature and then 24 h at 100 °C. Increased inorganic contents caused slight decreases in the initial decomposition temperatures, but the char yield values increased for PISF15 and PISF20. All samples exhibited hydrophobic properties. When all samples were compared, PISF5 and PISF10 exhibited hydrophobicity, high wear resistance and thermal properties. Additionally, PISF5 and PISF10 showed high adhesion, hardness, and methyl ethyl ketone solvent resistance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47399.     

Effect of hydrocarbon resin on the morphology and mechanical properties of isotactic polypropylene/clay composites

The article reports an investigation of the effect of a hydrocarbon resin, Necirés TR100, on the structure, morphology, and properties of two isotactic polypropylene/clay composites. The clays are Dellite HPS, a purified montmorillonite, and Dellite 67G, a purified and modified montmorillonite with a high content of quaternary ammonium salt. Necirés TR100 contains hydroxyl and acid groups, which were expected to interact during the melt mixing with the polar surface of the clays to have intercalation with Dellite HPS and/or exfoliation of Dellite 67G, which is already intercalated by the quaternary ammonium salt. The morphological results indicate that the composite isotactic polypropylene/Dellite HPS presents large and coarse clay domains, whereas the composite isotactic polypropylene/Dellite 67G presents a better distribution of the clay clusters, although the presence of some clay domains of a few μm are also detected. Although results from Wide Angle X‐ray Diffraction have indicated that Necirés TR100 has no effect on the layers distance of Dellite HPS and Dellite 67G its addition produces composites with clay particles homogenously distributed in the polyolefin matrix, better tensile properties (higher values of Young's modululs and elongation to break) and decrease of permeability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Compatibilizing polyimide/silica hybrids by alkoxisilane‐terminated oligoimides: Morphology–Properties relationships

A fluorinated polyimide (PI), synthesized from 4,4′‐(hexafluoroisopropylidene) diphthalic anhydride and 4,4′‐diaminodiphenyl ether, was used as matrix for the preparation of PI/silica hybrids. The inorganic phase was obtained in situ by a sol–gel route with tetraethoxysilane as precursor. Both micron‐ and nano‐scale hybrids were obtained depending on the interfacial interaction between the organic and inorganic phases. To promote such interaction a compatibilizing agent was synthesized, in the form of an alkoxisilane‐terminated oligoimide. Both the PI and the coupling agent were characterized by FTIR and Raman spectroscopies and by GPC measurements. The effect of the coupling agent on the morphology of the hybrids and on the size of the silica particles was investigated by scanning electron microscopy. The viscoelastic, mechanical, and thermal properties of hybrid composites were studied. It was shown that by adding appropriate amounts of the compatibilizer it was possible to control the morphology and to obtain homogeneous nanostructured systems. A general improvement of the mechanical performances and of the thermal stability was demonstrated, together with an increase of T_g, which was found more pronounced for the nanocomposites than for the microcomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation,morphology, and mechanical properties of elastomers based on polydimethylsiloxane/ polystyrene blends

Polydimethylsiloxane/polystyrene (PDMS/PS) blends were prepared by radical copolymerization of styrene (St) and divinylbenzene (DVB) in the presence of α,ω‐dihydroxy‐polydimethylsiloxane (PDMS), using benzoyl peroxide as initiator. The PDMS/PS blends obtained by this method are a series of stable, white gums, when the feed ratio of PDMS to St is 60/40 and DVB to St is not more than 2.0 wt %. Elastomers based on PDMS/PS blends were formed by crosslinking PDMS with methyl‐triethoxysilicane (MTES). The MTES dosage was much larger than the amount necessary for end‐linking hydroxy‐terminated chains of PDMS, with the excess being hydrolyzed to crosslinked networks, which were similar to SiO₂ and acted as filler. Mechanical property measurements show that the elastomers thus formed exhibit superior mechanical properties with respect to pure PDMS elastomer and the elastomers based on PDMS/PS system we prepared before. Moreover, investigations were carried out on the elastomers by extraction measurement and scanning electron microscopy (SEM). The extraction data show that the sol‐fraction decreases with increasing the feed ratio of DVB to St. SEM observation demonstrates that the elastomer has a microphase‐separated structure consisting of dispersed PS domains within a continuous PDMS matrix, and the extracted material exhibits a porous structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of TiO2 on morphology and mechanical properties of PVDF/PMMA blend films prepared by melt casting process

Effect of titanium dioxide (TiO₂) on morphology and mechanical properties of poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) blend films prepared at different TiO₂ contents by a melt casting process was studied. The results showed that tensile moduli in both the machine direction (MD) and the transverse direction (TD) increased with increasing TiO₂ content, and calculated tensile moduli based on the Halpin–Tsai and the Kerner model were consistent with experimental ones in both the MD and TD of films containing 10 wt % TiO₂. However, experimental tensile moduli exhibited smaller values compared with calculated ones, as the TiO₂ content increased to 30 wt %_, and it was assumed that this is due to the decrease of crystallinity of PVDF. Morphological observations indicated that TiO₂ particles did not affect crystal structures of PVDF and the morphology of PVDF/PMMA amorphous phase, but hindered the crystallization of PVDF. The MD and TD elongation at break exhibited >200 and <20%, respectively. The SEM micrographs revealed that spherulites could deform along the MD when the tensile force was applied along the direction. By contrast, spherulites could not deform along the TD and fractured at very small elongation, owing to the anisotropic morphology of spherulites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40454.     

Preparation and properties of rigid‐rod polyimide/silica hybrid materials by sol–gel process

Polyimide (PI) materials with a low coefficient of thermal expansion (CTE) while still retaining high strength and toughness are desirable in various applications. In this study a sol–gel process was used to incorporate silica into homopolyimides and copolyimides with highly rigid structures in an attempt to pursue this aim. A number of highly rigid monomers were used, including pyromellitic dianhydride (PMDA), p‐phenylene diamine (PPA), m‐phenylene diamine (MPA), benzidine, 2,4‐diaminotoluene, and o‐toluidine. No homopolyimide flexible films were obtained. However, it was possible to obtain flexible films from the copolyimides. Therefore, a copolyimide based on PPA, MPA, and PMDA (PPA/MPA = 2/1 mol) was then chosen as the matrix to prepare the PI/silica hybrids. Flexible films were obtained when the silica content was below 40 wt %. The hybrid films possessed low in‐plane CTEs ranging from 14.9 to 31.1 ppm with the decrease of the silica content. The copolyimide film was strengthened and toughened with the introduction of an appropriate amount of silica. The thermal stability and the Young's modulus of the hybrid films increased with the increase of the silica content. The silica particle size was assessed by scanning electron microscopy and was about 100 nm for the hybrids containing 10 and 20 wt % silica and 200–500 nm for the hybrids containing 30 and 40 wt % silica. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 794–800, 2001     

Effect of chemical interaction on morphology and mechanical properties of CPI‐OH/SiO2 hybrid films with coupling agent

A novel hybrid film composed of copolyimide with hydroxyl group, silica and γ‐glycidyloxypropyltrimethoxysilane (CPI‐OH/SiO₂/GOTMS) was prepared by the sol–gel process based on hydrolyzed tetraethoxysilane (TEOS) under acidic condition. GOTMS, as the coupling agent, and hydroxyl group in PI chain were used to improve the compatibility between the PI and SiO₂. The components, morphologies, and mechanical properties of the hybrids were investigated by FTIR, UV–vis, SEM, stress–strain tests, and DMA. The results showed that SiO₂ particle size significantly decreased, fractured cross sections of hybrid were rougher, and the surfaces of spherical SiO₂ particles were more widely covered by PI component. The tensile mechanical properties of hybrids increased when adding GOTMS. The critical points of maximum tensile strength and elongation at break move from 11 to 16 wt % SiO₂ content. DMA results showed that the storage moduli of hybrids with GOTMS, when above 260°C, were obviously higher than those without GOTMS; the tan δ transition temperature of hybrid films went up from 317 to 337°C. It suggests that chemical interaction between CPI‐OH and SiO₂ is formed and the PI molecular mobility is restricted by the chemical interaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3530–3538, 2007     

Effect of nanosized carbon black on the morphology,transport, and mechanical properties of rubbery epoxy and silicone composites

Three different types of nanosized carbon black (CB), Printex XE2 (CBP), Vulcan XC72, and Printex 140 U (CBU), were dispersed by mechanical mixing in rubbery epoxy (RE) and silicone to produce composites. It was found that the maximum possible loading of CB in the polymers depended on the surface area of CB. For a given loading, all three CBs produced similar improvements in the thermal conductivity of the resulting composites, but their effects on the electrical conductivity varied and ranged from insulating composites with CBU to conducting composites with CBP. CBP produced a greater improvement in the electrical conductivity than the thermal conductivity of the polymers compared to the other CBs. This was attributed to the high structure of CBP, which led to the formation of a concatenated structure within the matrix. The CB/silicone composites had a similar thermal conductivity to that of the CB/RE composites, but only the CBP/silicone composite produced at 8 wt % loading was electrically conducting. The compression and hardness properties of RE were also significantly improved with the addition of CB. However, in the case of silicone, only CBP had a considerable effect on the compression properties. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Improvement of mechanical,thermal and tribological properties of (3-aminopropyl) triethoxysilane-modified graphene/polyimide nanocomposites by in situ polymerisation

To elucidate the improvement and the principle of graphene modification on the polyimide (PI), (3-aminopropyl) triethoxysilane-modified graphene (PMG), was designed and prepared by anchoring the (3-aminopropyl) triethoxysilane (APTS) chain on the graphene sheet surface, and used to synthesise PI composites by in situ polymerisation. The unique surface modification significantly improved the compatibility and dispersion of graphene in the PI matrix. Tensile strength and Young’s modulus of 1.0PMG/PI was 109.45?MPa and 1.73?GPa, which increased by 54.26 and 86.02% from neat PI, respectively. The tribological properties and mechanism were also discussed. The friction coefficient and wear rate of 1.0PMG/PI (0.287, 2.291×10^?5mm³?Nm^?1) decreased by 47.53% and 35.06%, respectively. This improvement of the tribological properties was mainly caused by the cooperative interaction of the improved mechanical and thermal properties of the composites and the high self-lubricity of modified graphene.     

Melt flow properties,mechanical properties,thermal properties and morphology of polycarbonate/highly branched polystyrene blends

A highly branched polystyrene (HBPS) was synthesized via the copolymerization of 4‐(chloromethyl) styrene with styrene using the self‐condensing atom transfer radical polymerization method. The addition of HBPS as a melt modifier for polycarbonate (PC) was attempted. Melt flow properties, mechanical properties, thermal properties and morphology of the blends were studied. The results showed that a significant drop in the blend viscosity occurs immediately on addition of HBPS. Impact strength, tensile strength and glass transition temperature (T_g) of all the blends have not been significantly reduced compared with those of pure PC. The TGA analyses showed that an initial weight loss temperature of all the blends is above 458 °C and slightly low compared with that of pure PC, but all the blends still have excellent thermal stability. Morphological studies using SEM showed that a two‐phase morphology is characteristic of all the blends, with more or less spherical droplets of the minor HBPS phase dispersed in the continuous PC phase. Copyright © 2006 Society of Chemical Industry     

Effect of C5 petroleum resin content on damping behavior,morphology, and mechanical properties of BIIR/BR vulcanizates

In this work, the white‐silica‐filled vulcanizates of brombutyl rubber (BIIR)/cis 1,4 polybutadiene rubbers (BR) with hydrogenated aromatic hydrocarbon (C5) petroleum resins were prepared by compression molding, and the effects of C5 petroleum resin content on the damping behaviors and mechanical properties of BIIR/BR vulcanizates were investigated by foam force rheometer, dynamic mechanical analysis (DMA), scanning electron microscopy, and mechanical measurements. The results of this study showed that, the C5 resins could retard the vulcanization, and reduce the crosslink density and Mooney viscosity of vulcanizates. The DMA curves exhibited two independent peaks of loss factor (tanδ) corresponding to the glass transition of BR and BIIR vulcanizates, respectively. The addition of C5 resin had a positive impact on the damping of BIIR/BR vulcanizates, with the increment content of C5 resin, the main tanδ peaks shifted significantly to higher temperature and the effective damping temperature range was broadened remarkably, especially in the range of the BIIR glass transition. The mechanical properties such as tensile strength and abrasion performance were influenced by the C5 resin and the changes in mechanical properties were mainly due to the decline of crosslink density and the improvement of filler dispersion. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of clay modification on the morphology and the mechanical/physical properties of ABS/PMMA blends

The effect of three types of organoclays on the morphology and mechanical properties of lower critical solution temperature‐type poly(acrylonitrile‐butadiene‐styrene)/poly(methyl methacrylate) (ABS/PMMA) blends was investigated. Polymers were melt‐compounded with 2 and 4 wt % of clays using a twin‐screw extruder. X‐ray scattering and transmission electron microscopy revealed that the intercalation of the nanoclay in the hybrid nanocomposite was more affected by the polarity of the organoclay. Although the morphology of the blends varied by PMMA content, scanning electron microscopy showed smaller PMMA domains for the hybrid systems containing clay particles. Although good dispersion of the nanoclay through the ABS matrix and at the blend interface led to enhancement of tensile strength, the increment of the stiffness was more noticeable for nanocomposites including less polar organoclay. Well‐dispersed clay platelets increased the glass transition temperature. In addition, nanoscratching analysis illustrated an improvement in scratch resistance of ABS because of the presence of PMMA and organoclay. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of morphology on the dynamic mechanical properties of hydrogenated acrylonitrile butadiene elastomer/coagent nanodispersions

Coagents are vinyl monomers that react with free radicals formed by peroxide dissociation and are either grafted to elastomer chains or homopolymerized within a segregated phase to form a crosslinked network. The initial phase distribution within the elastomer matrix is of great importance for the final user properties of a composite material. In this study, the morphology of blends of each of three different coagents, that is, zinc dimethacrylate (ZDMA), N,N′‐m‐phenylene dimaleimide (HVA‐2), and trimethylolpropane trimethacrylate (TMPTMA) on a reinforcing substrate with dicumyl peroxide and hydrogenated acrylonitrile butadiene elastomer after processing was investigated with scanning electron microscopy. The morphology that evolved during processing was then compared to the results obtained from dynamic mechanical analysis (DMA) of the blends. Dynamic mechanical properties were modeled with a continuous relaxation distribution function, the Williams–Landel–Ferry equation, and the modified Guth–Gold equation. In the case of ZDMA and TMPTMA, a microphase and a nanophase evolved during processing, whereas the HVA‐2 phase in the blends remained well segregated. The volume fraction of the particles under 100 nm in ZDMA and TMPTMA blends ranged from 79 to 89%. The DMA results revealed the reinforcing effect of ZDMA and TMPTMA during the glass‐transition and in the plateau region, whereas HVA‐2 exhibited plasticizer‐like behavior. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and properties of low‐color polyimide/silica hybrid films

A series of polyimide precursors, poly(amic acid)s, containing propyltrimethoxysliane at two chain ends were prepared from 4,4′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl ( I ) with six commercially available dianhydrides, followed by end‐capping with 3‐aminopropyltrimethoxysilane (APrTMOS). A new class of fluorine‐containing polyimide/silica composite films ( III ) with chemical bonds between the fluorinated polyimide backbone and the silica network has been synthesized from the APrTMOS‐terminated precursors with tetramethoxysilane via the sol‐gel process and thermal cyclodehydration. The resultant hybrid films were light‐colored, flexible, and tough. They had high levels of thermal stability associated with high glass‐transition temperatures (>251°C), 10% weight‐loss temperatures in excess of 527°C, and char yields at 800°C in nitrogen higher than 60%. For a comparative study, the analogous nonfluorinated polyimide/silica hybrid films ( III′ ), based on 4,4′‐bis(4‐aminophenoxy)biphenyl ( I′ ), and the neat fluorinated polyimide films ( IV ), based on diamine I , were also synthesized and characterized. The hybrid films of the fluorinated series III showed a higher transparency and less color intensity when compared with the nonfluorinated III′ analogs. They also revealed a lower refraction index and birefringence than pure polyimides ( IV ). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4046–4052, 2007     

Ternary nylon-6/rubber/modified rubber blends: Effect of the mixing procedure on morphology, mechanical and impact properties

Ternary polyamide-based blends have been prepared by adding to nylon-6 (PA6) an ethylene-propylene random copolymer (EPM) and the same EPM functionalized by inserting onto its backbone maleic anhydride groups (EPM-g-SA). Two kinds of processing have been used: (a) one-step mixing in which the three components were simultaneously introduced in the mixer; (b) two-step mixing in which the two rubbers EPM and EPM-g-SA were separately premixed before the final mixing with PA6. Also binary PA6/EPM-g-SA blends have been prepared to compare their properties with those of the ternary one.

Mechanical tensile characterization at room temperature and impact Izod tests at different temperatures as well as a morphological analysis of smoothed samples have been performed on all the blends. It has been shown by a model reaction that both in binary and ternary blends an EPM-g-PA6 graft copolymer is formed, which acts as an interfacial agent between the rubbery dispersed phase and the polyamide matrix. The blends obtained by the one-step mixing showed a gross morphology and a very poor impact resistance, whereas the ones prepared by the two-step mixing exhibited very fine morphologies and excellent impact performances. In addition, as shown at least in the case of one ternary blend, there seems to be good morphological stability of these materials after a second processing. This has been attributed to the influence of the interfacial agent formed during the melt mixing of the two premixed rubbers with PA6.     

Construction of fluorenyl-modified low dielectric constant polyimide films with excellent mechanical properties and optical transparency

In order to meet the requirements of highly integrated and miniaturized electronic components, there is an urgent need for low dielectric materials with high mechanical properties and optical transparency in the field of microelectronics. In this study, a series of novel polyimide films (FPI) containing fluorenyl were prepared, and the effects of the fluorenyl content on the thermal, mechanical, and dielectric properties of the copolymerized films were investigated and discussed. The results demonstrate a significant decrease in the dielectric constant of the FPI films following the introduction of fluorenyl into polyimide (PI) chain segment. The FPI films also exhibited high mechanical properties, including tensile strengths between 92 and 106 MPa and elongation at break in the range of 8.4%–13.0%. Additionally, the introduction of the noncoplanar fluorenyl considerably improved the optical transparency and solubility of the FPI film. It is noteworthy that the FPI-3 has the best dielectric properties, with a low dielectric constant of 2.61 at 10 MHz and shows low water absorption (0.49%). The results show that we have prepared a novel low dielectric PI material film with excellent mechanical properties and optical transparency by introducing fluorenyl into the PI chain segment. These FPI films with satisfactory properties may be good candidates for dielectric materials for electronic components.     

Synthesis and characterization of polyimide/silica hybrid nanocomposites

Polyimide/silica (PI/SiO₂) hybrid nanocomposites were prepared by the sol‐gel process directly from a soluble polyimide. This soluble PI was synthesized from a diamine with a pendant phenyl hydroxyl group, 4,4′‐diamino‐4″‐hydroxy triphenyl methane (DHTM) and a dianhydride, pyromellitic dianhydride (PMDA), followed by cyclodehydration. Three ways of preparing PI/SiO₂ hybrid nanocomposites were investigated in this study. Two of them used the coupling agent 3‐glycidyloxy propyl trimethoxysilane (GPTMOS) to enhance the compatibility between PI and silica. The coupling agent can react with the PI to form covalent bonds. The structures of the modified hybrid nanocomposites were identified with a FTIR, whereas the size of the silica in polyimides was characterized with a scanning electron microscope. The size of silica particles in the modified system was <100 nm. The covalently bonded PI/SiO₂ hybrid nanocomposites prepared by the novel third approach exhibited good transparency when the silica content was <15%. Moreover, their thermal and mechanical properties exhibited a significant improvement. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 382–393, 2004