Sulfonic Acid-Functionalized Fe3O4 Reinforced Soluble Polyimide: Synthesis and Properties

In this study, a series of nanocomposite films based on an aromatic polyimide and sulfonic acid-functionalized magnetic nanoparticles was successfully prepared via an in situ technique. For this purpose, new soluble aromatic polyimide containing sulfone group as a polymeric matrix of the nanocomposites was synthesized. The surfaces of MNP were grafted with 3-mercaptopropyl trimethoxysilane. Then sulfonic acid-functionalized magnetic nanoparticle was obtained by oxidation of the thiol group. Effects of sulfonic acid-functionalized magnetic nanoparticles on thermal, tensile, and magnetic properties of the prepared nanocomposite films were studied. The magnetic nanoparticles containing the sulfonic acid groups could have strong intermolecular bond interactions between the hydroxyl groups of SO₃H and the sulfone and carbonyl groups of the polyimide matrix which caused the better dispersion of nanoparticle and exhibited superior mechanical properties, good magnetic properties, and high thermal stability.     

Synthesis and Optical Properties of Soluble Polyimide/Titania Hybrid Thin Films

Summary: In this study high‐refractive‐index polyimide/titania hybrid optical thin films were successfully prepared using a sol‐gel process combined with spin coating and multistep baking. The hybrid thin films were prepared from a soluble polyimide, a coupling agent, and a titania precursor. Transparent hybrid thin films can be obtained at TiO₂ content as high as 40 wt.‐%. The FE‐SEM results suggest that the TiO₂ particles in the hybrid thin films have diameters in the nanometer range. The thermal decomposition temperatures of the prepared hybrid materials are above those of the respective polyimide except for the highest TiO₂ content hybrids. The refractive indices at 633 nm of the prepared hybrid thin films increase linearly from 1.66 to 1.82 with increasing TiO₂ content. The excellent optical transparency, thermal stability, and tunable refractive index provide the potentials of the polyimide/titania hybrid thin films in optical applications.

     

TEM,XPS and thermo-mechanical properties of novel sustainable hybrid coatings

This work contributes to the development of a new generation of protective coatings composed of organic–inorganic materials. A silica based hybrid film was used in this work as high performance materials. The silica sol–gel film reveals enhanced thermo-mechanical properties in comparison with the pure polymer film. Herein, we demonstrate the possibility of employing cheap SiO₂ as prospective nano-fillers for hybrid coatings with active thermo-mechanical properties. Organic–inorganic hybrid coatings based on polyimide and silica were synthesized through a simple physical mixing technique. 3,3′,4,4′-Biphenyltetracarboxylic dianhydride (BPDA), benzene-1,3-diamine (BDA), 3,3′-oxydianiline (ODA) and SiO₂, were used as precursors for the hybrid coatings. These hybrid coatings were deposited via spin coating onto a galvanized iron, aluminum and copper in order to study the adhesive strength. The effects induced by the silica content on the mechanical properties of the coated samples were investigated. The mechanical properties of hybrid composite were found to be enhanced compared to polyimide coating. The main objective was to observe potential improvements in the mechanical and thermal properties of PI–silica hybrid films. Morphology, and structural changes in the composite films were studied as well as adhesion and impact strength and these characteristics were compared with those of unreinforced polyimide films.     

Effect of alumina on the structure and properties of polyimide matrix films

To improve the properties of polyimide (PI), different mass fractions of alumina (Al₂O₃) nanoparticles, unmodified or modified by KH550, were incorporated into PI matrix to form PI/Al₂O₃ hybrid films by in situ polymerisation. The effects of Al₂O₃ additives on the structure, dielectric and mechanical properties of the films were studied. Fourier transform infrared spectroscopy confirmed the successful preparation of PI/Al₂O₃ hybrid films, and the microstructures of the samples showed a more uniform dispersion of the modified Al₂O₃ nanoparticles than the unmodified ones in the matrix. The dielectric constant of the films increased with increasing filler content, and the maximum electrical breakdown strength of 311 MV m^?1 was obtained with a filler content of 8.0 wt-% modified Al₂O₃ in the matrix. Both unmodified and modified Al₂O₃-reinforced PI hybrids demonstrated improved mechanical properties compared with the PI matrix. Moreover, the properties of films with Al₂O₃ modified by KH550 were better.     

Controlled direction of electrical and mechanical properties in nickel tethered graphene polyimide nanocomposites using magnetic field

Oriented hybrid nickel tethered graphene polyimide resin nanocomposites with different degrees of orientation were prepared by in-situ magnetic field solvent casting method. Magnetization of the hybrid Ni-graphene polyimide nanocomposites exhibited a maximum in the magnetic field direction and a minimum perpendicular to the magnetic field direction indicating the orientation of the superparamagnetic nickel nanoparticles. In-plane dc electrical conductivity of the 1.3 vol.% Ni-graphene was 2.5 times higher when cast in a high magnetic field compared to films cast without an applied magnetic field. The through-plane dc conductivity of the 1.3 vol.% oriented Ni-graphene polyimide nanocomposites decreased with increasing magnetic field strength and reached insulation (10⁻¹² S/cm) for the films cast in high magnetic field. The in-plane tensile modulus of the polyimide exhibited a 35% increase when 0.16 vol.% Ni-graphene was added to the polyimide and cast in a low-strength magnetic field. Further addition of Ni-graphene, up to 1.3 vol.%, to the polyimide resulted in nearly constant tensile moduli. Tensile strength of nickel graphene nanocomposites showed up to 2-fold increase compared to the neat polyimide. Scanning electron microscopy (SEM) revealed that the Ni-graphene nanosheets were oriented in the magnetic field direction.     

Insights into the physico-chemical behavior of CoCl<Subscript>2</Subscript>/polyimide hybrid materials

Hybrid fluorinated polyimide materials have been obtained by incorporation of various quantities of cobalt(II) chloride (CoCl₂) into polyimide matrix. Polycondensation reaction of equimolar amounts of 4,4′-diamino-3′3′-dimethyldiphenylmethane and 2,2′-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride has been carried out to produce in the first stage a polyamidic acid solution in which CoCl₂?×?6H₂O has been placed. Further thermal treatment of this system led to the corresponding imide structure filled with the halide salt. An exhaustive study was directed to the influence of Co²⁺ ions on the modified polyimide behavior as a function of its surroundings. To survey the functional properties of as-obtained Co²⁺-containing polyimide systems, several techniques such as FTIR, UV-vis and broadband dielectric spectroscopy, differential scanning calorimetry, and thermogravimetric and scanning electron microscopy were employed. A special concern was directed to the study of the optical properties induced by the addition of CoCl₂ into polymer solutions and films. The magnetic response of the polyimide was investigated in correlation with the salt quantity embedded in the PI film. The variation of the real and imaginary parts of the hybrid films’ dielectric permittivity was registered in a broad frequency and temperature range, from 10 to 10⁶ Hz and from ?130 to 230 °C, respectively.     

Low-dielectric, nanoporous polyimide films prepared from PEO-POSS nanoparticles

Dielectric insulator materials that have low dielectric constants (k<2.5) are required as inter-level dielectrics to replace silicon dioxide (SiO₂) in future semiconductor devices. In this paper, we describe a novel method for preparing nanoporous polyimide films through the use of a hybrid PEO-POSS template. We generated these nanoporous foams are generated by blending polyimide as the major phase with a minor phase consisting of the thermally labile PEO-POSS nanoparticles. The labile PEO-POSS nanoparticles would undergoes oxidative thermolysis to releases small molecules as byproducts that diffuse out of the matrix to leave voids into the polymer matrix. We achieved significant reductions in dielectric constant (from k=3.25 to 2.25) for the porous PI hybrid films, which had pore sizes in the range of 10-40 nm.     

Effect of organosilica isomers on the interfacial interaction in polyimide/aromatic organosilica hybrids

We report the effect of organosilica precursor isomers on the interfacial interaction between polyimide and organosilica in polyimide/organosilica hybrid composite films. Poly(4,4′‐oxydianiline biphenyltetracarboxamic acid) (BPDA‐ODA PAA) was used as the polyimide precursor, while the organosilica was made using o‐substituted, m‐substituted, and p‐substituted phenyl organosilica precursor isomers. For the preparation of precursor hybrid films, BPDA‐ODA PAA and organosilica precursors were mixed and then the organosilica precursors were converted to corresponding organosilica via sol–gel process. Finally, these precursor films were converted to corresponding polyimide/organosilica hybrid films by the thermal imidization of BPDA‐ODA PAA, which results in poly(4,4′‐oxydianiline biphenyltetracarboximide) (BPDA‐ODA PI). The polyimide/organosilica hybrid films were characterized using three distinctive nuclear magnetic resonance spectroscopies (¹H NMR, ¹³C‐CPMAS‐NMR, and ²⁹Si‐MAS‐NMR), wide‐angle X‐ray diffraction (WAXD), small‐angle X‐ray scattering (SAXS), and peel strength measurement. We found that the m‐substituted phenyl organosilica shows poorer interfacial interaction with BPDA‐ODA PI than do the o‐ or p‐substituted phenyl organosilicas. It was observed, however, that the peel strength of the hybrid films against an aluminum substrate increased with increasing contents of organosilicas, regardless of the nature of the organosilica isomers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2507–2513, 2007     

Synthesis and Dielectric Properties of Polyimide-Titania Hybrid Composites

A new class of polyimide-titania (TiO₂) composites with chemical bonds between the polyimide and titania system has been synthesized by the sol–gel reaction and characterized. The hybrid composite films were obtained by the reaction of lysine-organotitane monomer, which is formulated as [(EtO)₃Ti (lysinate)]_2, followed by polycondensation with dianhyride in N-methyl-2-pyrrolidone (NMP) solution, followed by heating at 100, 200, and 300 °C. The presence of chemical bonds between polyimide (PI) and titania has great effect on the properties of polyimide films, especially on their thermal and dielectric properties. The dielectric constants of the resultant nanocomposites are lower than the usual polyimide films due to the increased free volume and less polar Ti–O–Ti groups, and can be tuned by varying the molar ratio of tetraethoxysilane (TEOT) in the feed. The polyimide units offer additional advantages of imparting thermal and mechanical strength.     

Dielectric and conduction properties of polyimide/silica nano‐hybrid films

Dielectric and conduction properties of polyimide/silica nano‐hybrid films were investigated with the silica content and the testing frequency, using a small electrode system. The hybrid films were prepared through sol‐gel process and thermal imidization, by using pyromellitic dianhydride and 4,4′‐oxydianiline as polyimide precursors, and tetraethoxysilane and methyltriethoxysilane as silica precursors. The dielectric coefficient of PI/SiO₂ films was monotonically increased with increasing silica content, and decreased with increasing testing frequency. The dielectric loss of PI/SiO₂ films had no obvious changes with increasing silica content, but monotonically increased with increasing testing frequency. These can be contributed to the different quantity and migration chunnels of current carriers, which were mainly influenced by a few of complicated factors. There were remarkable differences between conduction property of PI/TEOS‐SiO₂ films and PI/MTEOS‐SiO₂ films because of the different size and dispersion status of silica particles in the polyimide matrix. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Microstructure and properties of polyimide/poly(vinylsilsesquioxane) hybrid composite films

Polyimide (PI)/poly(vinylsilsesquioxane) (PVSSQ) (PI/PVSSQ) hybrid composite films were prepared from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA)-4,4′-oxydianiline (ODA) polyamic acid and triethoxyvinylsilane (TEVS or VSSQ) via sol-gel process and thermal imidization. The presence of the PVSSQ showed a remarkable effect on the microstructure and properties of the polyimide based hybrid films. The transparency of the hybrid films decreased with increasing the content of the PVSSQ. The compatibility and interfacial interaction of the hybrid composites were evaluated by scanning electron microscope (SEM) and atomic force microscope (AFM), respectively. The PI/PVSSQ hybrids showed nanocomposite formation when the contents of PVSSQ was less than 20 wt%. It was found that the surface topography was influenced by the composition of the PVSSQ. Incorporating of the PVSSQ increased the thermal stability and T_g of hybrid composites. The dielectric constant of the hybrid composites was reduced by adding PVSSQ up to a certain content, showed a minimum and then found to be increased. The dielectric constant values of the hybrid composites ranged from 2.59 to 3.78. The presence of the PVSSQ also showed significant effects on the mechanical properties of the polyimide films.     

Preparation and characteristics of polyimide–TiO2 nanocomposite film

A sol–gel approach has been developed to prepare polyimide–TiO₂ hybrid films from soluble polyimides and a modified titanium precursor. The rate of the hydrolysis reaction of titanium alkoxide can be controlled by using acetic acid as a modifier. FTIR and XPS indicated that TiO₂ particles were well distributed in polyimide matrixes with particle size small per than 60 nm. Polyimide hybrid films having the TiO₂ component ≤10% exhibited high thermal stability, high optical transparency and good mechanical properties and possessed higher dielectric constants than correspondingly polyimides. © 2000 Society of Chemical Industry     

Enhanced red photoluminescence in a nanocomposite thin film composed of Bi3.6Eu0.4Ti3O12 and Au-decorated ZnO nanorods

This paper firstly reports on a series of nanocomposite thin films composed of a ferroelectric Bi_3.6Eu_0.4Ti₃O₁₂ (BET) and Au-decorated ZnO nanorods (Au-ZnO), which are prepared by a ultraviolet-induced hybrid chemical solution method. The effects of Au nanoparticles (NPs) and ZnO nanorods on the significantly red photoluminescence enhancement of Eu³⁺ ions are investigated. The results indicate that the larger near band edge (NBE) emission of ZnO by the SPR effect of Au NPs can make an energy transfer from ZnO to Eu³⁺ ions. Simultaneously, the depression of the deep-level emission of ZnO can improve the monochromaticity in the visible range. Furthermore, the dielectric and ferroelectric properties of the thin films are also enhanced. The findings suggest that the nanocomposite thin films of a ferroelectric BET and Au-ZnO could be used as a multifunctional material in the ferroelectric optoelectronic devices with bright light emitting.     

Morphology and size control of inorganic particles in polyimide hybrids by using SiO2-TiO2 mixed oxide

Polyimide/inorganic hybrids were prepared by sol-gel reaction starting from tetraethoxysilane (TEOS), and tetrabutyl titanate (TBT) in the solution of polyamic acid in N,N-dimethylformamide. The hybrid films were obtained by the hydrolysis-polycondensation of TEOS and TBT in polyamic acid solution, followed by the elimination of solvents and imidization process. Binary polyimide/SiO₂ and polyimide/TiO₂ hybrids, as well as ternary polyimide/SiO₂-TiO₂ hybrids (with varied ratio of SiO₂ to TiO₂) were prepared to study the effects of the recipes and inorganic components on the morphologies of the polyimide hybrids. Transparent films with much higher inorganic content can be obtained in ternary polyimide hybrids, while lower inorganic content in binary hybrids. The results also indicate that the inorganic particles are much smaller in the ternary systems than in the binary systems, the shape of the inorganic particles and the compatibility for polyimide and inorganic moieties are varied with the ratio of the inorganic moieties in the hybrids. The completely imidization temperature of the polyamic acid was delayed, and furthermore, the thermal stability of polyimide was enhanced through the incorporation of the inorganic moieties in the hybrid materials.     

Synthesis and characterization of polyimide/oligomeric methylsilsesquioxane hybrid films

In this study, polyimide/silsesquioxane hybrid materials were synthesized from aminoalkoxysilane‐capped poly(pyromellitic dianhydride‐co‐4,4′‐oxydianiline) (PMDA‐ODA) and oligomeric methylsilsesquioxane (O‐MSSQ) precursors. The O‐MSSQ moiety was used to obtain well characterized nano‐inorganic cage and network structures in the hybrid materials. The effects of molecular structures and composition on the morphologies and properties of the prepared hybrid materials were studied. The phase separation of the prepared hybrid materials could be controlled by varying the molecular weight of the polyimide moiety, the Si? OH end group content of the O‐MSSQ or the coupling agent. Homogeneous and transparent hybrid thin films were obtained from the low molecular weight polyimide moiety with a coupling agent, 3‐aminopropyltrimethoxysilane (APrTMS). However, microphase separation occurred if the molecular weight of the polyimide moiety was enhanced or was prepared without a coupling agent, as evidenced by atomic force microscopy (AFM), field emission scanning electron microscopy (FE‐SEM), and electron spectroscopy for chemical analysis (ESCA). The high Si? OH content of the O‐MSSQ could enhance the bonding density between the organic and inorganic moiety and thus retard phase separation. The thermal and mechanical properties of the prepared hybrid materials were largely improved compared with the parent polyimide, PMDA‐ODA, and were demonstrated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and thermal‐stress analysis. The hybrid materials showed adjustable refractive index and dielectric constant by varying the O‐MSSQ content. The birefringence of the PMDA‐ODA was reduced by incorporating the O‐MSSQ moiety. This work revealed that the polyimide/O‐MSSQ hybrid materials could have potential applications as optical films or low dielectric constant materials. Copyright © 2004 Society of Chemical Industry     

Synthesis and physicochemical investigation of imide-functionalized silica nanocomposites

The incorporation of inorganic nanoparticles into polymers have gained significant attention to improving functional properties. The ultimate nanocomposite behaviors are influenced by many parameters, such as microstructural distribution that are produced during the treatment process. Herein, a hybrid material integrating a modified network into a polyimide PI matrix was produced via the sol–gel method by the reaction of pyromellitic dianhydride, 4, 4-oxydianaline, and 1, 5-diaminonaphthalene to synthesize copolyimides nanocomposite. The modified polyimide and unmodified polyimide silica (SiO₂) nanoparticles were incorporated in the polyimide matrix to have polyimide silica nanocomposite. In modified silica nanoparticles, 3-aminopropyltriethosilane was introduced to have better compatibility among inorganic–organic hybrid with similar chemical contact due to their flexible alkyl group. The surface morphology or structure of silica and polyimide was affirmed by scanning electron microscopy, Fourier transforms infrared spectroscopy confirmed the synthesis of pure polyimide, unmodified polyimide, and modified polyimide silica via presence and absence of certain peaks. Thermogravimetric analysis (TGA) results showed high thermal stability of nanocomposites as silica content increases. In contrast to unmodified silica, the modified silica provides more thermal stability to the nanocomposites. Dynamic mechanical analysis was used to investigate the tensile stress of pure polyimide, unmodified, and modified silica nanocomposites. Thermal stability, storage modulus, and moisture absorption of these hybrid materials were improved with silica nanoparticles. The TG mass spectrum confirms the successful synthesis of modified silica networks. The substituted silica nanoparticles show higher mechanical toughness and storage in modified compared to unmodified silica nanocomposite, which exhibits stronger binding attraction between silica nanoparticles and polyimide matrix.     

Synthesis and characterization of polyimide‐γ‐Fe2O3 nanocomposites

Novel polyimide‐γ‐Fe₂O₃ hybrid nanocomposite films (PI/γ‐Fe₂O₃) has been developed from the poly(amic acid) salt of oxydianiline with different weight percentages (5, 10, 15 wt %) of γ‐Fe₂O₃ using tetrahydrofuran (THF) and N,N‐dimethylacetamide (DMAc) as aprotic solvents. The prepared polyimide‐γ‐Fe₂O₃ nanocomposite films were characterized for their structure, morphology, and thermal behavior employing Fourier transform infrared spectroscopy (FTIR), scanning electron micrograph (SEM), transmission electron micrograph (TEM), X‐ray diffraction (XRD), ¹³C‐NMR, and thermal analysis (TGA/DSC) techniques. These studies showed the homogenous dispersion of γ‐Fe₂O₃ in the polyimide matrix with an increase in the thermal stability of the composite films on γ‐Fe₂O₃ loadings. Magnetization measurements (magnetic hysteresis traces) have shown very high values of coercive force indicating their possible use in memory devices and in other related applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 834–840, 2007     

Preparation and structural properties of Fe3O4–polyimide hybrid nanocomposites

Polyimide films in which magnetic Fe₃O₄ nanoparticles are uniformly distributed are prepared. Before the preparation of the Fe₃O₄–polyimide composites, pure magnetite nanoparticles (Fe₃O₄) have been synthesized in water by co-precipitation (from ferric chlorides). Its surface was firstly modified with the 3-aminopropyl triethoxysilane. The prepared polyimide–Fe₃O₄ nanocomposite films were characterized for their structure, morphology, and thermal behavior employing Fourier transform infrared spectroscopy, scanning electron micrograph, X-ray diffraction, and thermal analysis (DTA/TGA/DSC) techniques.     

Preparation and properties of polyimide/silica hybrid composites based on polymer‐modified colloidal silica

A new type of polyimide/silica (PI/SiO₂) hybrid composite films was prepared by blending polymer‐modified colloidal silica with the semiflexible polyimide. Polyimide was solution‐imidized at higher temperature than the glass transition temperature (T_g) using 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 4,4′‐diaminodiphenyl ether (ODA). The morphological observation on the prepared hybrid films by scanning electron microscopy (SEM) pointed to the existence of miscible organic–inorganic phase, which resulted in improved mechanical properties compared with pure PI. The incorporation of the silica structures in the PI matrix also increased both T_g and thermal stability of the resulting films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2053–2061, 2006     

Residual stress and mechanical properties of polyimide thin films

Four different structure polyimide thin films based on 1,4‐phenylene diamine (PDA) and 4,4′‐oxydianiline (ODA) were synthesized by using two different dianhydrides, pyromellitic dianhydride (PMDA) and 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), and their residual stress behavior and mechanical properties were investigated by using a thin film stress analyzer and nanoindentation method. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. The morphological structure of polyimide thin films was characterized by X‐ray diffraction patterns and refractive indices. The residual stress was in the range of ?5 to 38 MPa and increased in the following order: PMDA‐PDA < BPDA‐PDA < PMDA‐ODA < BPDA‐ODA. The hardness of the polyimide films increased in the following order: PMDA‐ODA < BPDA‐ODA < PMDA‐PDA < BPDA‐PDA. The PDA‐based polyimide films showed relatively lower residual stress and higher hardness than the corresponding ODA‐based polyimide films. The in‐plane orientation and molecularly ordered phase were enhanced with the increasing order as follows: PMDA‐ODA < BPDA‐ODA < BPDA‐PDA ～ PMDA‐PDA. The PDA‐based polyimides, having a rigid structure, showed relatively better‐developed morphological structure than the corresponding ODA‐based polyimides. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009