Synthesis of soluble polyimide/silica–titania core–shell nanoparticle hybrid thin films for anti-reflective coatings

In this study, researchers prepared polyimide/silica–titania core–shell nanoparticle hybrid thin films (PI/SiO₂–TiO₂) from soluble fluorine-containing polyimide, colloidal silica, and titanium butoxide. The soluble polyimide with carboxylic acid end groups (6FDA–6FpDA–4ABA–COOH) could condense with titanium butoxide to provide organic–inorganic bonding, and thus prevent macrophase separation. TGA and DSC analysis showed that the decomposition temperature of hybrid materials increased with an increase in the content of silica–titania nanoparticles within the hybrid films. FTIR spectra indicated that the imidization was complete and the cross-linking Ti–O–Ti network formed. HRTEM and HRSEM images showed that the size of the core–shell nanoparticles were 18–20 nm. The thickness of titania shell on the silica is about 2.5 nm. The n&k and UV–Vis analysis showed that the prepared hybrid films had good optical properties and a high refractive index of 1.735. Researchers applied the prepared PI/SiO₂–TiO₂ hybrid thin films to develop a three layer antireflective (AR) coating on the glass and PMMA substrate. Results showed that the reflectance of the AR coating on the glass and PMMA substrate at 550 nm was 0.356 and 0.495%, respectively. The transparency was greater than 90% for both AR coatings on the glass and PMMA substrates.     

Highly transparent polyimide/nanocrystalline-titania hybrid optical materials for antireflective applications

This study prepared polyimide/titania hybrid thin films of, poly(3,3′,4,4′-Benzophenone tetra carboxylic dianhydride)–(4,4-Diaminodiphenyl Ether)/nanocrystalline titania (BTDA-ODA/TiO₂), with a high refractive index. FTIR analysis confirmed the formation of a polyimide and titania matrix. TGA and DSC analysis gauged the decomposition temperature in the range of 455–532 °C, indicating that the addition of titania could increase the glass transition temperature of hybrid films. XRD results indicate the formation of nanocrystalline titania domains of approximately 8–11 nm in the hybrid films. AFM, SEM, TEM, and XRD results show the formation of well-dispersed nanocrystalline titania. The refractive index was measured by ellipsometry, demonstrating an increase in the refractive index of the prepared hybrid thin films from 1.657 to 1.958, when the titania content was increased from 0 to 90 wt.%. UV–vis analysis gauged the cutoff wavelength in the range of 288–357 nm. The prepared polyimide/titania hybrid thin films were used to develop a three layer antireflective (AR) coating on a glass substrate. The average reflectance of the AR was 0.5% for the PT20/PT90/F-siloxane layer and 0.6% for the PT20/PT90/porous silica. Transparency at 550 nm exceeded 90% for both AR coatings.     

Reinforcement of ramie fibers on regenerated cellulose films

All-cellulose composite films reinforced with ramie fibers were prepared from aqueous NaOH–urea solvent system via a simple pathway. The structure and physical properties of the modified ramie fibers and composite films were characterized by scanning electron microscope (SEM), wide angle X-ray diffraction (WAXD), Fourier transform infrared spectrometer, ultraviolet–visible spectroscope, thermogravimetry, biodegradation tests and tensile tests. The results revealed that a good compatibility existed between the modified ramie fibers and cellulose matrix. The all-cellulose composite films exhibited high tensile strength, good optical transmittance, thermal stability, and biodegradability. The tensile strength and elastic modulus of the composite films increased with an increase of the ramie fibers. These high-strength biodegradable films prepared by a “green” pathway have potential applications as packaging materials and biomaterials.     

Fluorographene/polyimide composite films: Mechanical,electrical, hydrophobic,thermal and low dielectric properties

Nowadays, dielectric materials with excellent mechanical and hydrophobic properties are desired for use in the integrated circuits (ICs). For this reason, low dielectric constant fluorographene/polyimide (FG/PI) composite films were prepared by a facile solution blending method, suggesting that the mechanical, electrical, hydrophobic and thermal properties were significantly enhanced in the presence of FG. With addition of 1 wt% FG, the tensile strength, Young’s modulus and elongation at break were dramatically increased by 139%, 33% and 18% respectively when compared with pure PI film. Furthermore, composite films exhibit superior hydrophobic and thermal stability performance. Especially, the FG/PI film with 0.5 wt% of FG possessing a low dielectric constant of 2.48 and a good electrical insulativity that is lower than 10⁻¹⁴ S m⁻¹. Therefore, by their excellent performance, FG/PI hybrid films represent suitable candidate solutions with applications in the microelectronics and aerospace industries.     

Preparation and optical properties of organic/inorganic nanocomposite materials by UV curing process

In this study, photo-polymerized poly(acrylic)/silica hybrid thin films were prepared from various acrylic monomers and monodispersed colloidal silica with the coupling agent, 3-(trimethoxysilyl)propyl methacrylate (MSMA). The silica content in the hybrid thin films varied from 0 to 50 wt.%. The experimental results show that the particle size of silica in hybrid films could be effectively controlled at 15–20 nm as the weight ratio of MSMA to colloidal silica is higher than 0.68 and 0.60 for the poly(methyl methacrylate)/silica (US) and poly(ethylene glycol dimethacrylate-trimethylolpropane trimethacrylate)/silica (UDT) hybrid materials, respectively. The polymerization conversion for US and UDT hybrid materials could reach to 100% and 94.5%, respectively. The comparison of surface roughness with the film thickness is less than 0.10%, indicating the excellent surface planarity of the prepared hybrid thin films. Besides, the prepared hybrid films from the crosslinked acrylic polymer moiety show much better film uniformity, thermal stability and mechanical properties than those obtained from poly(methyl methacrylate). The refractive index decreases with increasing the silica content in the hybrid films. Excellent optical transparency is obtained in the prepared hybrid films. These results show that the prepared hybrid thin films have potential applications as passive films for optical devices.     

Polyimide/silica/titania nanohybrids via a novel non-hydrolytic sol–gel route

Polyimide/silica/titania hybrid films were prepared via a non-hydrolytic sol–gel route. Silicic acid and titanium tetrachloride were used as the precursors of silica and titania, respectively. The absorption band of Si–O–Ti bonds in FTIR spectra of the hybrid films revealed the formation of the hybrid inorganic network between SiO₂ and TiO₂. Scanning electron microscopy results indicated that the nanometer-scaled inorganic domains were homogeneously dispersed in polyimide matrix due to the introduction of silica-stabilized TiO₂ and the interactions between organic and inorganic phases. The studies on the optical properties of the hybrid films indicated the red-shift of the absorption band increased with increasing TiO₂ content, while all the hybrid films maintained their transparencies. The surface resistances of the hybrid samples decreased with increasing TiO₂ content. The thermal decomposition temperature of the ternary hybrid films decreased slightly with increasing TiO₂ content. This kind of hybrid materials may have potential application in the preparation of opto-electronic devices.     

PMMA–SiO2 hybrid films as gate dielectric for ZnO based thin-film transistors

In this paper we report a low temperature sol–gel deposition process of PMMA–SiO₂ hybrid films, with variable dielectric properties depending on the composition of the precursor solution, for applications to gate dielectric layers in field-effect thin film transistors (FE-TFT). The hybrid layers were processed by a modified sol–gel route using as precursors Tetraethyl orthosilicate (TEOS) and Methyl methacrylate (MMA), and 3-(Trimethoxysilyl)propyl methacrylate (TMSPM) as the coupling agent. Three types of hybrid films were processed with molar ratios of the precursors in the initial solution 1.0: 0.25, 0.50, 0.75: 1.0 for TEOS: TMSPM: MMA, respectively. The hybrid films were deposited by spin coating of the hybrid precursor solutions onto p-type Si (100) substrates and heat-treated at 90 °C for 24 h. The chemical bonding in the hybrid films was analyzed by Fourier Transform Infrared Spectroscopy to confirm their hybrid nature. The refractive index of the hybrid films as a function of the TMSPM coupling agent concentration, were determined from a simultaneous analysis of optical reflectance and spectroscopic ellipsometry experimental data. The PMMA–SiO₂ hybrid films were studied as dielectric films using metal-insulator-metal structures. Capacitance–Voltage (C–V) and current–voltage (I–V) electrical methods were used to extract the dielectric properties of the different hybrid layers. The three types of hybrid films were tested as gate dielectric layers in thin film transistors with structure ZnO/PMMA–SiO₂/p-Si with a common bottom gate and patterned Al source/drain contacts, with different channel lengths. We analyzed the output electrical responses of the ZnO-based TFTs to determine their performance parameters as a function of channel length and hybrid gate dielectric layer.     

超疏水有机-无机杂化凝胶的制备和表征

采用1,2-双-(三甲氧基硅基)-乙烷(BTME)和聚甲基含氢硅氧烷(PMHS)作为反应组分,在无需模板剂的溶胶-凝胶体系中制备了孔壁镶嵌乙基和孔道表面挂载甲基的有机-无机杂化多孔凝胶材料.用固体硅核磁共振、傅里叶红外光谱、低温氮气吸附/脱附、高分辨透射电镜、接触角测定和热重分析等手段研究了材料的结构和性能.结果表明,...     

Mesoporous titania films with adjustable pore size coated on stainless steel substrates

Mesoporous layers of titania were prepared on stainless steel substrates of defined roughness by dip coating. Ordered arrays of micelles formed from amphiphilic block copolymers served as pore templates during film drying. Coating of the precursors solution on freshly grinded steel resulted in extensively fractured films with severely distorted templated porosity. In contrast, films produced on precalcined steel showed good integrity, high substrate coverage and narrow pore size distribution with pores interconnected and ordered in a short range. This difference in film quality and morphology was ascribed to the reaction between template polymers and metal ions leached from the steel of grinded substrate surfaces. Films were ca. 700 nm thick and composed of nanocrystalline titania. The pore size of titania coatings was varied between 5 and 16 nm employing polymer templates of different structure and molecular weight.     

Effects of modified Clay on the morphology and thermal stability of PMMA/clay nanocomposites

The potential to improve the mechanical, thermal, and optical properties of poly(methyl methacrylate) (PMMA)/clay nanocomposites prepared with clay containing an organic modifier was investigated. Pristine sodium montmorillonite clay was modified using cocoamphodipropionate, which absorbs UVB in the 280–320 nm range, via ion exchange to enhance the compatibility between the clay platelets and the methyl methacrylate polymer matrix. PMMA/clay nanocomposites were synthesized via in situ free-radical polymerization. Three types of clay with various cation-exchange capacities (CEC) were used as inorganic layered materials in these organic–inorganic hybrid nanocomposites: CL42, CL120, and CL88 with CEC values of 116, 168, and 200 meq/100 g of clay, respectively. We characterized the effects of the organoclay dispersion on UV resistance, effectiveness as an O₂ gas barrier, thermal stability, and mechanical properties of PMMA/clay nanocomposites. Gas permeability analysis demonstrated the excellent gas barrier properties of the nanocomposites, consistent with the intercalated or exfoliated morphologies observed. The optical properties were assessed using UV–Visible spectroscopy, which revealed that these materials have good optical clarity, UV resistance, and scratch resistance. The effect of the dispersion capability of organoclay on the thermal properties of PMMA/clay nanocomposites was investigated by thermogravimetric analysis and differential scanning calorimetry; these analyses revealed excellent thermal stability of some of the modified clay nanocomposites.     

Structures and properties of titania thin films annealed under different atmosphere

The effects of crystallinity, phase and oxygen vacancies on optical and photocatalytic properties of titania (TiO₂) thin films were systematically studied. The as-deposited amorphous titania films were prepared by reactive sputtering titanium metal targets in argon–oxygen plasma at 100 °C and subsequently annealed at various temperatures of 400–800 °C in air, vacuum and H₂ atmosphere. The results indicate that in general the crystallinity of the annealed films is enhanced with the increasing annealing temperature. At the same temperature, the H₂ annealed films achieve better crystallinity but containing more oxygen vacancies than the films annealed in air and in vacuum. In H₂ or in vacuum, the concentration of oxygen vacancies in the annealed films increases with increasing temperature, while in air it remains constant. Oxygen vacancies in titania film not only facilitate phase transformation but also lower the band gap of titania, and make the film visible-light responsive. Photocatalytic properties of the TiO₂ films were characterized in UV and visible light irradiation by following the Ag reduction and degradation of methylene blue. The films annealed at 600–700 °C in H₂ possess the best film crystallinity and the proper concentration of oxygen vacancies and exhibit the best photocatalytic performance under both UV and visible light.     

Facile preparation and characterization of free-standing stiff carbon-based composite films with excellent performance

Novel free-standing stiff all carbon films based on multi-walled carbon nanotube (MWNT)/glassy carbon (GC) with excellent performance were fabricated. MWNTs, as excellent reinforcing materials, were successfully dispersed in polyimide (PI) matrix by in situ polymerization. The resultant MWNT/PI nanocomoposite films were used as precursors and underwent carbonization process. As a result, all carbon constituted MWNT/GC composite films were obtained. Mechanical results showed the maximum 3-point bending strength and modulus reached 575.5 MPa and 7.7 GPa respectively, improved by 54% and 78% compared to those of neat GC films. This method is simple, and the free-standing composite films can be prepared in large scales, which hold great potential in many applications.     

High transparent polyimide/titania multi-layer anti-reflective hybrid films

In this study, polyimide-titania hybrid thin films (6FDA-6FpDA-4ABA/TiO₂, PIT) were prepared from soluble fluorine-containing polyimide and titanium butoxide. The soluble polyimide with carboxylic acid terminal groups (6FDA-6FpDA-4ABA-COOH) was synthesized from the precursor s 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 4,4′-(hexafluoroisopropylidene) dianiline (6FpDA), and 4-aminobenzoic acid (4ABA). Such end groups undergo a condensation reaction with titanium butoxide to provide organic-inorganic bonding and thus prevent macrophase separation. The titania content in the hybrid films was varied from 0 to 90 wt.% (PIT0-PIT90). The effects of TiO₂ content on the hybrid film properties and the optimum operating conditions were also investigated. TGA and DSC analysis showed that the decomposition temperature of polyimide was about 468 °C. T_d increased as the titania content in hybrid thin films increased. HRTEMM and XRD results indicated the formation of nanocrystalline-titania domains of around 4-11 nm in the hybrid films. AFM, SEM, TEM, and XRD results indicated the formation of well-dispersed nanocrystalline-titania. FTIR spectra indicated that the amidization was complete and that a cross-linked Ti-O-Ti network had formed. UV-vis and n&k analysis showed that the prepared hybrid films had high refractive index (1.931) and good optical properties. Moreover, the prepared polyimide/titania hybrid thin films were further applied to develop a three layer antireflective (AR) coating on glass and PMMA substrates. The results showed that the average reflectance of the AR coating on the glass and PMMA substrates was 0.5% and 0.8%, respectively. The transparency at 550 nm was greater than 90% for both AR coatings.     

Preparation and hydrophilicity of TiO2 sol-gel derived nanocomposite films modified with copper loaded TiO2 nanoparticles

In this study, TiO₂ nanocomposite films with 10 g/L of TiO₂ and copper loaded TiO₂ nanoparticles as nanofillers were deposited on the glass substrates using the sol gel dip-coating method. FE-SEM and UV-vis spectrophotometer were used to evaluate morphological and optical properties of copper loaded titania nanoparticles. In addition, XPS and water contact angle techniques were used to study the surface properties and superhydrophilicity of titania nanocomposite films, respectively. The results indicated that copper loaded TiO₂ nanoparticles had a significant effect on the hydrophilicity of nanocomposite film and maintaining it in a dark place for a long time (6.2 degree for titania nanocomposite films with copper loaded nanoparticle and 23.7 degree for nanocomposite film with titania nanoparticles).     

Synthesis and optical properties of photosensitive polyimide/silica hybrid thin films

In this study, the photopatternable fluorinated polyimide/silica hybrid materials were synthesized by 4,4′-hexafluoroisopropylidenediphthalic anhydride (6FDA), oxydianiline (ODA), aminopropyltriethoxysilane (APrTEOS), and 12 nm colloidal silica with a coupling agent. The monodispersed colloidal silica was used to form a silica domain instead of alkoxysilanes in the conventional process. The coupling agents used were 3-methacryloxypropyl trimethoxysilane (MPTMS) or (4-vinylphenethyl)trimethoxysilane (VPTMS). The coupling agent and the silica domain were designed to reduce the volume shrinkage and enhance the thermal properties, respectively. The retention of 2-methyl acrylic acid 2-dimethylamino-ethyl ester (MDAE) in the prepared hybrid films was supported by X-ray photoelectron spectroscopy (XPS) and thickness variation during the curing process. The particle size of silica in the hybrid materials based on SEM analysis was in the range of 10–25 nm. The prepared hybrid materials also exhibited a reduced refractive index after increasing the silica content. The SEM diagram suggested the prepared photosensitive hybrid materials could obtain lithographical patterns with a good resolution. These results indicate that the newly prepared photosensitive polyimide/silica hybrid materials may have potential applications for optical devices.     

Sol–gel derived photonic bandgap coatings for solar control

Sol–gel derived photonic bandgap films have been investigated as possible multilayer coatings for solar control glass applications. Multilayer Bragg mirrors, in particular, have been modelled by the Transfer Matrix method, designed to have either near-UV or near-IR reflectivity, but visible transparency, based on alternating aluminosilicate glass/titania quarter-wave stacks. Such composite multilayer structures have been deposited by sol–gel processing on selected glasses and other types of substrates and their optical characteristics have been measured by optical absorption and reflection spectroscopies, as well as spectroscopic ellipsometry to determine the single layer refractive index and thickness. The UV–visible-IR absorption and reflection characteristics of these multilayer coatings revealed solar control properties, due to the presence of peaks near ∼350–400 nm and ∼900–1000 nm, with reflectivities of the order of 70%, which appear promising for solar control application.     

Preparation,optical and thermal properties of CdSe–ZnS/poly(lactic acid) (PLA) nanocomposites

In this study, CdSe–ZnS/poly(lactic acid) (PLA) nanocomposite films, containing different concentrations of surface-modified CdSe–ZnS quantum dots (QDs), were prepared via a solution casting method. The optical microstructural and thermal properties of the as-prepared QDs/PLA films were investigated. The QDs/PLA films exhibited strong and stable photoluminescence (PL) intensity with concentration dependent amplitudes. The transmission electron microscopy (TEM) pictures revealed that QDs of ∼5 nm diameter were uniformly dispersed in the PLA matrix. According to the results of thermogravimetric analysis, the weight-loss onset temperature of PLA clearly decreased with the QD content. A combination of Fourier transform infrared (FT-IR) spectroscopy, X-ray diffractometry (XRD) and differential scanning calorimetry (DSC) results suggested that the QDs exhibit obvious nucleation activity on the crystallization behavior of the PLA matrix. This research provides useful information to the foundations of practical applications of QDs/PLA nanocomposites as fluorescent and biodegradable functionalized materials.     

Temperature sensing with fluorescence intensity ratio technique in epoxy-based nanocomposite filled with Er-doped 7YSZ

Luminescent nanocomposite of epoxy filled with Er³⁺-doped yttria-stabilized zirconia (7YSZ) is prepared with their luminescence spectra measured in the temperature range 123–423 K. Fluorescence intensity ratio (FIR) of the two Er³⁺ emissions is also obtained in the same temperature range. Er–7YSZ/epoxy nanocomposites exhibited higher sensitivity of 0.18%/K as compared with the bare Er–7YSZ particles. Luminescence thermometry is demonstrated by using the nanocomposites as temperature sensitive paint (TSP) with a resolution of 1 K. The advantage of FIR technique combined with the excellent thermal stability of epoxy matrix makes the Er–7YSZ/epoxy nanocomposites viable as temperature sensitive paint for aerodynamic applications.     

Novel lanthanide hybrid functional materials for high performance luminescence application: The relationship between structures and photophysical behaviors

Functional luminescent hybrid materials have emerged as fascinating and promising materials for their versatile applications. In this report, novel efficient luminescent lanthanide (Tb³⁺, Eu³⁺) hybrid materials with a new kind of amide-type β-diketone ligands covalently bonded to the silica gels have been assembled through the sol–gel progresses. The hybrid materials have been characterized by the Fourier transform infrared (FTIR) spectra, UV–vis absorption spectra, powder X-ray diffraction (PXRD), scanning electron microscope (SEM), and thermal analyses. The relationship between structures and photophysical behaviors of these materials was discussed in detail. The materials assembled by the precursors containing aromatic end group (Si–L¹–Ln) exhibited longer luminescence lifetimes and higher quantum efficiencies, suggesting that the existence of a suitable conjugated system should allow a more efficient energy transfer. Under UV irradiation, the materials emitted either bright green light or red light with different intensity which may lead to potential functional applications in optical devices and electronic devices.     

Plasticized polylactic acid nanocomposite films with cellulose and chitin nanocrystals prepared using extrusion and compression molding with two cooling rates: Effects on mechanical,thermal and optical properties

Triacetate citrate plasticized poly lactic acid and its nanocomposites based on cellulose nanocrystals (CNC) and chitin nanocrystals (ChNC) were prepared using a twin-screw extruder. The materials were compression molded to films using two different cooling rates. The cooling rates and the addition of nanocrystals (1 wt%) had an impact on the crystallinity as well as the optical, thermal and mechanical properties of the films. The fast cooling resulted in more amorphous materials, increased transparency and elongation to break, (approx. 300%) when compared with slow cooling. Chitin nanocomposites were more transparent than cellulose nanocomposites; however, microscopy study showed presence of agglomerations in both materials. The mechanical properties of the plasticized PLA were improved with the addition of a small amount of nanocrystals resulting in PLA nanocomposites, which will be further evaluated for film blowing and thus packaging applications.