Polyimide/silica hybrids via the sol-gel route: High performance materials for the new technological challenges

The present review article describes in detail the state-of-the-art of organic-inorganic hybrid materials based on polyimide/silica components. The article is divided in three parts. In the first the basic processing route for the preparation of these systems is described, i.e. the sol-gel technique, along with the strategies developed to control the final morphology. In the second part the curing characteristics, the dynamic-mechanical and the mechanical and fracture properties of hybrids with different morphologies are reviewed. Finally, the more technologically relevant applications devised for these high performance materials are discussed

Ultra-long-term reliable encapsulation using an atomic layer deposited Hfo2/Al2o3/Hfo2 triple-interlayer for biomedical implants

Long-term packaging of miniaturized, flexible implantable medical devices is essential for the next generation of medical devices. Polymer materials that are biocompatible and flexible have attracted extensive interest for the packaging of implantable medical devices, however realizing these devices with long-term hermeticity up to several years remains a great challenge. Here, polyimide (PI) based hermetic encapsulation was greatly improved by atomic layer deposition (ALD) of a nanoscale-thin, biocompatible sandwich stack of HfO2/Al2O3/HfO2 (ALD-3) between two polyimide layers. A thin copper film covered with a PI/ALD-3/PI barrier maintained excellent electrochemical performance over 1028 days (2.8 years) during acceleration tests at 60 °C in phosphate buffered saline solution (PBS). This stability is equivalent to approximately 14 years at 37 °C. The coatings were monitored in situ through electrochemical impedance spectroscopy (EIS), were inspected by microscope, and were further analyzed using equivalent circuit modeling. The failure mode of ALD Al2O3, ALD-3, and PI soaking in PBS is discussed. Encapsulation using ultrathin ALD-3 combined with PI for the packaging of implantable medical devices is robust at the acceleration temperature condition for more than 2.8 years, showing that it has great potential as reliable packaging for long-term implantable devices

Synthesis of PDMS-metal oxide hybrid nanocomposites using an in situ sol-gel route

Organic-inorganic hybrid nanocomposites are widely studied and applied in broad areas because of their ability to combine the flexibility, low density of the organic materials with the hardness, strength, thermal stability, good optical and electronic properties of the inorganic materials. Polydimethylsiloxane (PDMS) due to its excellent elasticity, transparency, and biocompatibility has been extensively employed as the organic host matrix for nanocomposites. For the inorganic component, titanium dioxide and barium titanate are broadly explored as they possess outstanding physical, optical and electronic properties. In our experiment, PDMS-TiO2 and PDMS-BaTiO3 hybrid nanocomposites were fabricated based on in-situ sol-gel technique. By changing the amount of metal precursors, transparent and homogeneous PDMS-TiO2 and PDMS-BaTiO3 hybrid films with various compositions were obtained. Two structural models of these two types of hybrids were stated and verified by the results of characterization. The structures of the hybrid films were examined by a conjunction of FTIR and FTRaman. The morphologies of the cross-sectional areas of the films were characterized by FESEM. An Ellipsometer and an automatic capacitance meter were utilized to evaluate the refractive index and dielectric constant of these composites respectively. A simultaneous DSC/TGA instrument was applied to measure the thermal properties. For PDMS-TiO2 hybrids, the higher the ratio of titanium precursor added, the higher the refractive index and the dielectric constant of the composites are. The highest values achieved of refractive index and dielectric constant were 1.74 and 15.5 respectively for sample PDMS-TiO2 (1-6). However, when the ratio of titanium precursor to PDMS was as high as 20 to 1, phase separation occurred as evidenced by SEM images, refractive index and dielectric constant decreased. For PDMS-BaTiO3 hybrids, with the increase of barium and titanium precursors in the system, the refractive index and dielectric constant of the composites increased. The highest value was attained in sample PDMS-BaTiO3 (1-6) with a refractive index of 1.6 and a dielectric constant of 12.2. However, phase separation appeared in SEM images for sample PDMS-BaTiO3 (1-8), the refractive index and dielectric constant reduced to lower values. Different compositions of PDMS-TiO2 and PDMS-BaTiO3 hybrid films were annealed at 60 °C and 100 °C, the influences on the refractive index, dielectric constant, and thermal properties were investigated

Nanocomposites Derived from Polymers and Inorganic Nanoparticles

Polymers are considered to be good hosting matrices for composite materials because they can easily be tailored to yield a variety of bulk physical properties. Moreover, organic polymers generally have long-term stability and good processability. Inorganic nanoparticles possess outstanding optical, catalytic, electronic and magnetic properties, which are significantly different their bulk states. By combining the attractive functionalities of both components, nanocomposites derived from organic polymers and inorganic nanoparticles are expected to display synergistically improved properties. The potential applications of the resultant nanocomposites are various, e.g. automotive, aerospace, opto-electronics, etc. Here, we review recent progress in polymer-based inorganic nanoparticle composites.open565

An Investigation of the Use of Cerium and Polyhedral Oligomeric Silsesquioxanes for the Protection of Polymeric Epoxy Compounds in the Low Earth Orbit Environment

Low Earth orbit presents many hazards for composites including atomic oxygen, UV radiation, thermal cycling, micrometeoroids, and high energy protons. Atomic oxygen and vacuum ultraviolet radiation are of concern for space-bound polymeric materials as they degrade the polymers used as matrices for carbon fiber composites, which are used in satellites and space vehicles due to their high strength to weight ratios. Epoxy-amine thermosets comprise a common class of matrix due to processability and good thermal attributes. Polyhedral oligomeric silsesquioxanes (POSS) have shown the ability to reduce erosion in polyimides, polyurethanes, and other polymers when exposed to atomic oxygen. The POSS particle is composed of a SiO1.5 cage from which up to eight organic pendant groups are attached at the silicon corners of the cage. POSS reduced atomic oxygen impact on polymers by a process known as glassification wherein the organic pendants are removed from the cage upon atomic oxygen exposure and then the cage rearranges to a passive silica network. In addition, POSS shows good UV absorbance in the UVb and UVc ranges and POSS can aid dispersion of titanium dioxide in a nanocomposite. In this work, Chapter 1 focuses on hazards in low Earth orbit, strategies for protecting organic material in orbit, and the capabilities of POSS. Chapter 2 details the experimental practices used in this work. Chapter 3 focuses on work to induce POSS phase separation and layering at the surface of an epoxy-amine thermoset. Generally, POSS is dispersed throughout a nanocomposite, and in the process of erosion by atomic oxygen some polymer mass loss is lost before enough POSS is exposed to begin glassification. Locating POSS at a surface of composite could possibly reduce this mass loss and the objective of this research was to investigate the formation of POSS-rich surfaces. Three POSS derivatives with different pendant groups were chosen. The POSS derivatives had a range of miscibilities with the epoxy-amine matrix. A sedimented layer of the most incompatible POSS moiety was observed at the bottom of bars at the highest loading level of 5 wt% POSS. It was concluded that POSS could form a sedimented layer in this epoxy during cure. Epoxy amine materials containing POSS derivatives were tested by exposure to atomic oxygen at NASA Glenn Research Center with each POSS derivative present in separate samples at 2.5 wt% loading levels. Mass loss did not decrease against an unfilled control and glassification was not observed, leading to the conclusion that POSS could not be effectively concentrated at a surface to reduce degradation given the methods used. Taking this into account, the study transitioned into seeking ways to integrate highly UV absorbent cerium compounds with POSS. This part of the study is reported in Chapter 4. It was anticipated that POSS with a polar pendant group would interact through intermolecular forces with cerium (IV) oxide and produce a suspension that could be cured at the surface of polymers. However, in every experiment the cerium (IV) oxide was not dispersed. However, a homogeneous dispersion of a cerium-containing compound was achieved by combining trisilanol phenyl POSS with cerium (III) nitrate hexahydrate. NMR and mass spectrometry showed that the mixture of Cerium nitrate and trisilanol phenyl POSS did not result in the formation of a chemical compound but FTIR studies indicated the presence of hydrogen bonding between the POSS silanols and cerium-associated water. The resulting material was termed “CePOSS”. CePOSS was more UV absorbent in the UVc region than POSS or other cerium compounds as measured by solution UV-vis spectroscopy. In addition, CePOSS could be mixed into a POSS-epoxy coating, after pre-blending with poly(ethylene glycol) POSS, to produce films that were essentially opaque in the UV region below a wavelength of about 300 nm, and transparent in the visible region above 300 nm. The discovery of a ‘window of transparency’ in the visible region is significant in view of the fact that the epoxy-amine polymers, sans the POSS and cerium additives, were opaque across the entire UV/ visible range. The investigation of the UV transmittance and glassification response of these CePOSS-POSS-epoxy films is described in Chapter 5. UV transmittance of the POSS-epoxy coating was predicted to decrease below 275 nm with the presence of CePOSS given the solution UV-vis spectroscopy results. However, there was no difference seen in transmittance between coatings with and without CePOSS below 275 nm. The transparent region above 300 nm was seen in all samples with any type of POSS. In addition, UV/ozone exposure was completed on epoxy, POSS-epoxy, and CePOSS-POSS-epoxy coatings to examine the effect of cerium on POSS glassification. Oxidation was achieved even in the presence of CePOSS as verified by x-ray photoelectron spectroscopy, scanning electron microscopy, and contact angle. Finally, UV transmittance was done on pre and post exposed materials

Area-Selective Molecular Layer Deposition of Polyimide on Cu through Cu-Catalyzed Formation of a Crystalline Interchain Polyimide

Novel area-selective molecular layer deposition (AS-MLD) of polyimide (PI) on Cu versus native SiO2 was studied. By use of 1,6-diaminohexane (DAH) and pyromellitic dianhydride (PMDA) as precursors, PI films can be selectively deposited on the Cu surface at 200-210 degrees C with a rate around 7.8 A/cycle while negligible growth takes place on SiO2. The selectivity was successfully demonstrated also on Cu/SiO2 patterns at 200 degrees C; after 180 MLD cycles, around 140 nm thick PI was deposited on Cu regions whilePeer reviewe

Preparation and enhanced properties of Fe3O4 nanoparticles reinforced polyimide nanocomposites

Polyimide (PI) nanocomposite reinforced with Fe3O4 nanoparticles (NPs) at various NPs loadings levels of 5.0, 10.0, 15.0, and 20.0 wt% were prepared. The chemical interactions of the Fe3O4 NPs/PI nanocomposites were characterized using Fourier Transform Infrared (FT-IR) spectroscopy. X-ray Diffraction (XRD) results revealed that the addition of NPs had a significant effect on the crystallization of PI. Scanning electron microscope (SEM) and the atomic force microscope (AFM) were used to characterize the dispersion and surface morphology of the Fe3O4 NPs and the PI nanocomposites. The obtained optical band gap of the nanocomposites characterized using Ultraviolet-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS) was decreased with increasing the Fe3O4 loading. Differential scanning calorimetry (DSC) results showed a continuous increase of Tg with increasing the Fe3O4 NPs loading. Some differences were observed in the onset decomposition temperature between the pure PI and nanocomposites since the NPs and the PI matrix were physically entangled together to form the nanocomposites. The contact angle of pure PI was larger than that of Fe3O4/PI nanocomposites films, and increased with increasing the loading of Fe3O4. The degree of swelling was increased with increasing the Fe3O4 loading and the swelling time. The dielectric properties of the nanocomposite were strongly related to the Fe3O4 loading levels. The Fe3O4/PI magnetic property also had been improved with increasing the loading of the magnetic nanoparticles