A Novel Organophosphorus Hybrid with Excellent Thermal Stability: Core-Shell Structure, Hybridization Mechanism, and Application in Flame Retarding Semi-Aromatic Polyamide.
An organophosphorous hybrid (BM@Al-PPi) with unique core-shell structure was prepared through hybridization reaction between boehmite (BM) as the inorganic substrate and phenylphosphinic acid (PPiA) as the organic modifier. Fourier transform infrared spectra (FTIR), solid state (31)P and (27)Al magic angle spinning nuclear magnetic resonance, X-ray diffraction, and element analysis were used to investigate the chemical structure of the hybrids, where the microrod-like core was confirmed as Al-PPi aggregates generated from the reaction between BM and PPiA, and those irregular nanoparticles in the shell belonged to residual BM. Compared with the traditional dissolution-precipitation process, a novel analogous suspension reaction mode was proposed to explain the hybridization process and the resulting product. Scanning electronic microscopy further proved the core-shell structure of the hybrids. BM exhibited much higher initial decomposition temperature than that of Al-PPi; therefore, the hybrid showed better thermal stability than Al-PPi, and it met the processing temperature of semi-aromatic polyamide (HTN, for instance) as an additive-type flame retardant. Limiting oxygen index and cone calorimetric analysis suggested the excellent flame-retardant performance and smoke suppressing activity by adding the resulting hybrid into HTN.
Fire-Resistant, Strong, and Green Polymer Nanocomposites Based on Poly(lactic acid) and Core–Shell Nanofibrous Flame Retardants
Despite extraordinary mechanical properties and excellent biodegradability, poly(lactic acid) (PLA) still suffers from a highly inherent flammability, restricting its wide applications in the electric and automobile fields. Although a wide range of flame retardants have been developed to reduce the flammability, so far, they normally compromise the mechanical strength of PLA. Herein, we have demonstrated the fabrication of a novel core–shell nanofibrous flame-retardant system, PN-FR@CNF, through in situ chemically grafting the phosphorus–nitrogen-based polymer onto the cellulose nanofiber (CNF) surface. The results show that adding 10 wt % PN-FR@CNF enables PLA to achieve a V-0 flame resistance rating during vertical burning tests and to exhibit a dramatically reduced peak heat release rate in cone calorimetry measurements, indicating a significantly reduced flammability. In addition, the tensile strength of PLA also increases by around 24% (about 72 MPa). This work offers an innovative methodology for th...
Submicron polymer structures with X-ray lithography and hot embossing
This article describes the process chain for replication of submicron structures with varying aspect ratios (AR) up to 6 in polymethylmethacrylate (PMMA) by hot embossing to show the capability of the entire LIGA process to fabricate structures with these dimensions. Therefore a 4.7 μm thick layer of MicroChem 950k PMMA A11 resist was spin-coated on a 2.3 μm Ti/TiOx membrane. It was patterned with X-ray lithography at the electron storage ring ANKA (2.5 GeV and λc ≈ 0.4 nm) at a dose of 4 kJ/cm3 using a Si3N4 membrane mask with 2 μm thick gold-absorbers. The samples were developed in GG/BDG and resulted in AR of 6–14. Subsequent nickel plating at 52°C resulted in a 200 μm thick nickel tool of 100 mm diameter, which was used to replicate slit-nozzles and columns in PMMA. Closely packed submicron cavities with AR 6 in the nickel shim were filled to 60% during hot embossing.