Zhanpeng Wu

Dynamic random access memory effect and memory device derived from a functional polyimide containing electron donor-acceptor pairs in the main chain.

A functional polyimide, hexafluoroisopropyl bis(phthalic dianhydride)/3,6-diaminocarbazole (6FDA/DAC), in which DAC serves as electron donor and 6FDA as electron acceptor, has been synthesized in our present work. Electrical characterization results on the sandwiched polyimide memory device (ITO/Thin polyimide Layer/Au) indicate that the polyimide possesses electrical bistability and the device exhibits two accessible conductivity states, which can be reversibly switched from the low-conductivity (OFF) state to the high-conductivity (ON) state with an ON/OFF current ratio of about 10(4). Different from the widely reported write-once-read-many-times (WORM) effects, the device with the 6FDA/DAC polyimide as the active layer shows dynamic random access memory (DRAM) behavior. The ON state of the device was lost immediately after removal of the applied voltage, while by applying a constant bias (e.g., 3 V) the ON state can be electrically sustained. The roles of donor and acceptor components in the polyimide main chain were elucidated through molecular simulation.

Preparation of highly reflective and conductive metallized polyimide films through surface modification: processing, morphology and properties

Silvered polyimide films have been prepared by potassium hydroxide hydroxylation of polyimide film surfaces and incorporation of silver ions through subsequent ion exchange. Thermal curing not only recycloimidized the poly(amic acid) into polyimide, but also reduced silver ions into silver atoms and near-atomic silver clusters, which diffused and aggregated to give reflective and conductive surfaces without need of the addition of reducing agents. Films were characterized by X-ray photoelectron spectrometer, transmission electron microscopy, scanning electron microscopy and tapping mode atomic force microscopy. The thickness of the silvered layers and the reflectivity and conductivity of the silvered films can be controlled. By this method, the double-sided silvered polyimide films with excellent reflective (reflectivity > 97%) and conductive surfaces (surface resistivity = 0.02 Ω cm−2) could be easily fabricated. Their essential mechanical properties could be maintained, and the silver–polymer adhesion was outstanding.

Preparation of polyimide/zinc oxide nanocomposite films via an ion-exchange technique and their photoluminescence properties

Polyimide (PI) composite films with ZnO nanoparticles embedded in the surface layer were prepared by alkali hydrolyzation following ion exchange in Zn(NO3)2 solution and thermal treatment of the zinc ion-doped PI films in air atmosphere. The effect of alkali treatment, ion exchange, and thermal treatment conditions was investigated in relation to the amount of zinc atomic loading, morphology, photoluminescence (PL), and thermal properties of the PI/ZnO composite films using ICP, XPS, FE-SEM, TEM, Raman microscope, TGA, and DSC. ZnO nanoparticles were formed slowly and dispersed uniformly in the surface-modified layers of PI films with an average diameter of 20 nm. The PL spectra of all the PI/ZnO nanocomposite films obtained at 350°C/7 h possessed a weak ultraviolet emission peak and a broad and strong visible emission band. The PI/ZnO nanocomposite films maintained the excellent thermal property of the host PI films.

Fabrication of nickel oxide nanocomposite layer on a flexible polyimide substrate via ion exchange technique.

Continuous nickel oxide (NiO) nanocomposite layer on flexible polyimide (PI) substrate was prepared via an ion exchange technique. First, nickel(Pi) poly(amate) layers were formed on both surfaces of PI film through chemical surface modification of PI films in aqueous NaOH solution and then ion exchange in aqueous NiSO4 solution. Subsequently, hydrothermal treatment of the Ni2+-loaded PI films in an aqueous urea solution led to Ni(OH)2 formation in the surface-modified layers. Final thermal annealing in ambient air made Ni(OH)2 decompose to NiO, which diffused and aggregated to give continuous layers on both surfaces of PI film. The composite films were characterized by XRD, XPS, SEM, TEM, TGA, and DSC, respectively. Results from SEM and TEM measuring revealed that the NiO layers consisted of NiO nanoparticles with diameter ranging from 10 to 15 nm. Thermal properties of PI/NiO nanocomposite films were similar to those of host PI. This paper provides an effective methodology for the preparation of polymer/metal oxide nanocomposite films, which hold great promise toward the potential application in the areas of flexible microsensors and devices.

Synthesis and characterization of stimuli-responsive poly(acrylic acid) grafted silica nanoparticles

Silica-poly(acrylic acid) (PAAc) core–shell nanoparticles (NPs) were successfully prepared via graft copolymerization of acrylic acid (AAc) onto vinyl-bond-modified silica NPs. Transmission electron microscopy (TEM) results indicated that the obtained micropheres have a core–shell morphology. Fourier transform infrared (FTIR) analysis and x-ray photoelectron spectroscopy (XPS) measurements confirmed that the surface of the nanoparticles was polymer-rich, consistent with the core–shell morphology. The influence of the synthetic conditions, such as reaction time and AAc concentration on the graft yield of PAAc grafted on the silica NPs was investigated. Dynamic light scattering (DLS) analysis showed that the silica-PAAc core–shell nanoparticles possessed excellent response to pH and ion strength. Because of their pH-responsive behavior and small feature size, nanostructure devices designed from the smart silica nanoparticles have potential applications including sensors and membranes.

Controllable embedding of silver nanoparticles on silica nanospheres using poly(acrylic acid) as a soft template

Silver nanoparticles embedded on silica nanospheres were prepared by using ion-exchangeable poly(acrylic acid) (PAAc) grafted on the silica surface as a soft template followed by chemical reduction. The prepared hybrid nanospheres were characterized using x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet–visible (UV–vis) absorption spectroscopy, and bactericidal activity measurements. The results suggest that mono-dispersed Ag nanoparticles with controllable diameters can be obtained on the surface of silica nanospheres by varying the concentration of the silver nitrate and the pH value of the suspension, and the hybrid nanospheres have excellent bactericidal activity and potential applications as bactericidal agents in biomedical fields.

Nonvolatile electrical switching behavior observed in a functional polyimide thin film embedded with silver nanoparticles

In this paper, we report our works on the synthesis of a silver-nanoparticle-embedded polyimide (PI) thin film and its electrical bistability. A soluble PI, (4,4′-(hexafluoroisopropylidene) diphthalic anhydride/4,4′-oxydianiline (6FDA/ODA), where the 6FDA part serves as an effective electron-accepting moiety, was synthesized in our current work as the polymer matrix. Silver nanoparticles (Ag NPs) with diameters less than 7 nm were subsequently generated in situ in the parent PI film via ultraviolet (UV) reduction of the (1,1,1-trifluoro-2,4-pentadionato) silver(I) complex (AgTFA) previously incorporated in the matrix. Electrical characterization results on the sandwiched device (ITO|PI (6FDA/ODA)/silver nanohybrid film|Au) indicate that the nanohybrid material possesses electrical bistability and the device exhibits two accessible conductivity states, which can be reversibly switched from the low-conductivity state to the high-conductivity state with an ON/OFF current ratio of about 102. The device with the PI (6FDA/ODA)/silver nanohybrid film as the active layer shows nonvolatile memory behavior. The high-conductivity state and the low-conductivity state of the device can be sustained after the removal of the applied voltage. Mechanisms regarding the charge transfer in the nanohybrid material were discussed.

Interfacial growth of controllable morphology of silver patterns on plastic substrates.

Controllable growth of newly born silver nanoparticles to fractal, cauliflower-like, microscale disks and continuous silver layers with high conductivity and reflectivity on plastic substrates has been developed via solid-liquid interfacial reduction and growing of ion-doped polymeric films. Such approaches involve polyimide (PI) films as substrates, its corresponding silver-ion-doped precursors as solid oxidants, and facile immersion of ion-doped polymeric films in aqueous reducing solution. The solution reducing process belongs to liquid-solid interfacial reduction processes, during which silver ions doped in polymeric matrix transformed to newly born silver nanoparticles which further aggregated and migrated along the liquid-solid interface to form dendrite, cauliflower-like and lamella disk-like architecture and/or severely compact continuous silver nanolayers with highly reflective and conductive properties. Time-dependent morphology evolutions of silver particles were traced by scanning electron microscopy (SEM), atomic force microscopy (AFM), and transmission electron microscopy (TEM). This strategy can also extend to synthesis of many other metals on polymeric films while maintaining outstanding metal-polymer adhesion based on incorporation of various metal ions, and may offer an opportunity to fabricate large scale, high-output, cost-effective processes for metal patterns on flexible polymeric substrates.

Nitrile butadiene rubber-based heat-shielding insulations for solid rocket motors Effect of polyimide fibrous reinforcement on the morphology and properties

Chopped polyimide (PI) fiber-filled nitrile butadiene rubber (NBR) insulations for solid rocket motors were fabricated by surface modification of chopped PI fibers treated under oxygen plasma and subsequently by mixing formulation of NBR insulations on a two-roll mill. The effects of chopped PI fibers’ surface modification on the mechanical and ablative properties were investigated. Results showed that excellent mechanical and ablative properties of the NBR insulations were attributable to the high thermal stability and unique interfacial interactions between fiber and the matrix because of the rougher surface character of modified chopped PI fibers. The microstructures of insulation and ablated charred layers were also characterized by scanning electron microscopy and atomic force microscopy.

Preparation of Polyimide/BaTiO 3 /Ag Nanocomposite Films via in situ Technique and Study of Their Dielectric Behavior

Triphase polyimide nanocomposite films were fabricated using barium titanate (BaTiO3) with high dielectric constant and silver (Ag) with high conductivity as fillers. In situ method was utilized to obtain the homogeneous dispersion of nanoparticles. The in situ polymerization of polyimide precursor-poly(amic acid) was performed in the presence of BaTiO3 particles. Silver compound 1,1,1-trifluoro-2,4-pentadionato silver(I) was added into the BaTiO3 containing poly(amic acid) solution to achieve silver nanoparticles via in situ self metallization technique. The thermally induced reduction converted silver (I) to metallic silver with concomitant imidization of poly(amic acid) to polyimide. Both BaTiO3 and silver nanoparticles were uniformly dispersed in the polyimide substrate. The dependence of dielectric behavior on the BaTiO3 and Ag contents was studied. The incorporation of small amount of silver nanoparticles greatly increased dielectric constant of composite films.