Organo-Inorganic Hybrid Intumescent Fire Retardant Coatings for Thermoplastics Based on Poly(Vinylphosphonic Acid).

Thin coatings of crosslinked poly(vinylphosphonic acid), PVPA, display good adhesion and excellent intumescent, fire-retardant barrier properties when applied to the surfaces of a typical thermoplastic, such as poly(methyl methacrylate), but perform relatively poorly in water-soak tests. To strengthen and further improve the barrier properties of the intumescent char and to make the coating more hydrophobic, PVPA has been complexed with various inorganic and organic species. The chars formed from coatings of some of these hybrid materials are less friable than chars from coatings synthesized from crosslinked PVPA alone, and show higher levels of water tolerance with no significant reduction in dry adhesion to the substrate.

Application of Natural Antibacterial Plants in the Extraction of Uranium from Seawater.

Marine biofouling directly affects the performance and efficiency of uranium (U(VI)) extraction from seawater. Compared to traditional chemical methods, natural plant extracts are generally biodegradable and nontoxic, making them an environmentally friendly alternative to synthetic chemicals in solving the marine biofouling problem. The effectiveness of natural antibacterial plants (i.e., pine needle, peppermint, Acorus gramineus Soland, Cacumen platycladi, and wormwood) in solving the marine biofouling problem was evaluated in this work. Experimental results showed that natural antibacterial plants could kill Vibrio alginolyticus in solution and effectively solve the marine biofouling problem of U(VI) extraction. To improve the adsorption capacity of natural plants for U(VI) in seawater, poly(vinylphosphonic acid) (PVPA) was modified on natural antibacterial plant surfaces by irradiation grafting technology. PVPA and natural antibacterial plants work as active sites and base materials for the U(VI) extraction material, respectively. The recovery performance of PVPA/pine needle for U(VI) was preliminarily studied. Results show that the adsorption of U(VI) on PVPA/pine needle follows pseudo-second-order and Langmuir models, and the maximum adsorption capacity is 111 mg/g at 298 K and pH 8.2.

STMP and PVPA as Templating Analogs of Noncollagenous Proteins Induce Intrafibrillar Mineralization of Type I Collagen via PCCP Process.

The phosphorylated noncollagenous proteins (NCPs) play a vital role in manipulating biomineralization, while the mechanism of phosphorylation of NCPs in intrafibrillar mineralization of collagen fibril has not been completely deciphered. Poly(vinylphosphonic acid) (PVPA) and sodium trimetaphosphate (STMP) as templating analogs of NCPs induce hierarchical mineralization in cooperation with indispensable sequestration analogs such as polyacrylic acid (PAA) via polymer-induced liquid-like precursor (PILP) process. Herein, STMP-Ca and PVPA-Ca complexes are proposed to achieve rapid intrafibrillar mineralization through polyelectrolyte-Ca complexes pre-precursor (PCCP) process. This strategy is further verified effectively for remineralization of demineralized dentin matrix both in vitro and in vivo. Although STMP micromolecule fails to stabilize amorphous calcium phosphate (ACP) precursor, STMP-Ca complexes facilely permeate into intrafibrillar interstices and trigger phase transition of ACP to hydroxyapatite within collagen. In contrast, PVPA-stabilized ACP precursors lack liquid-like characteristic and crystallize outside collagen due to rigid conformation of PVPA macromolecule, while PVPA-Ca complexes infiltrate into partial intrafibrillar intervals under electrostatic attraction and osmotic pressure as evidenced by intuitionistic 3D stochastic optical reconstruction microscopy (3D-STORM). The study not only extends the variety and size range of polyelectrolyte for PCCP process but also sheds light on the role of phosphorylation for NCPs in biomineralization.

Developing a novel glass ionomer cement with enhanced mechanical and chemical properties.

OBJECTIVE: To develop a novel glass ionomer cement (NGIC) with enhanced mechanical and chemical properties and assess its biocompatibility, mechanical strength, and ion release. METHODS: Nanosilver doped bioactive glass (NanoAg BAG) was synthesized by sol-gel method and characterized by scanning electron microscopy with energy-dispersive X-ray spectroscopy and transmission electron microscopy. The NanoAg BAG, together with poly(vinylphosphonic acid) (PVPA), alumino-fluorosilicate glass and poly-acrylic acid were used to synthesize NGIC. The optimal PVPA concentration for NGIC was determined by PVPA modified GIC's biocompatibility and mechanical properties and used to prepare NGIC specimens. NGIC specimens with NanoAg BAG at 0%, 1%, 2%, and 5% were allocated into Groups NGIC0, NGIC1, NGIC2, and NGIC5, respectively. The biocompatibility, surface morphology, elemental composition, surface topography, chemical properties, compressive strength, diametral tensile strength, and ion release of the NGIC were assessed. A conventional glass ionomer cement (GIC) was used as a control. RESULTS: A granular BAG with nano silver particles attached on its surface were found, indicating the successful synthesis of NanoAg BAG. PVPA at 10% presented the best effect in enhancing the biocompatibility and mechanical properties of PVPA modified GIC and was used to prepare NGIC specimens. NGIC1 showed similar biocompatibility, surface morphology and topography to GIC. Chemical properties results showed that NGICs showed the same adsorption peaks to GIC. The compressive strength (mean±SD in MPa) was 168.1 ± 29.7, 205.5 ± 29.5, 221.8 ± 46.8, 216.6 ± 59.3 and 167.7 ± 36.4, and the diametral tensile strength (mean±SD in MPa) was 14.1 ± 1.7, 18.3 ± 4.9, 21.2 ± 2.2, 17.2 ± 3.8 and 13.3 ± 3.3 for GIC, NGIC0, NGIC1, NGIC2 and NGIC5 respectively. NIGC0, NGIC1 and NGIC2 showed higher compressive and diametral tensile strength than GIC (p < 0.01). NGIC2 and NGIC5 showed higher release of fluoride, calcium, phosphate and silver ion than GIC and NGIC0 (p < 0.05). CONCLUSION: A biocompatible NGIC with enhanced mechanical properties were developed. It presented enhanced fluoride, calcium, phosphate and silver ion release compared to conventional GIC.

Diblock versus block-random copolymer architecture effect on physical properties of Gd3+-based hybrid polyionic complexes.

HYPOTHESIS: Random insertion of vinylphosphonic acid (VPA) units into a of PEG-PAA block copolymer improves the chemical stability and properties of hybrid nanoobjects obtained from the complexation of the copolymer with metal ions. EXPERIMENTS: Block polymers based on poly(acrylic acid) (PAA) and poly(ethylene glycol) (PEG) are modified by random insertion of 0 to 100 % of phosphonic acid functions in PAA block by a RAFT polymerization process. These polymers are then used to form hybrid polyionic complexes (HPICs) by complexation with gadolinium or europium ions. The properties of the obtained assemblies are evaluated by magnetic relaxivity, fluorescence and light scattering measurements. FINDINGS: The insertion of VPA units within the PAA block increases the chemical stability of the hybrid micelles by maintaining their integrity even at low pH. This insertion also minimizes the exchange of ions between HPICs and the surrounding medium thanks to a strengthening of interactions toward lanthanide ions. When such systems are used as MRI contrast agents or luminescent probe, 50/50 AA/VPA composition appears to be a good compromise to achieve optimal relaxivity or luminescent properties while ensuring a good chemical stability.

Flame Retardancy, Thermal and Mechanical Properties of Novel Intumescent Flame Retardant/MXene/Poly(Vinyl Alcohol) Nanocomposites.

Poly(vinylphosphonic acid) (PVPA) and polyethylenepolyamine (PEPA) are used as novel intumescent flame retardants to improve the properties of MXene (2D Ti3C2Tx)/poly(vinyl alcohol) (PVA) nanocomposites. We investigated the flame-retardant properties, thermal stability, and mechanical properties of MXene/PVA nanocomposites. The results show that MXene was homogeneously dispersed in the PVA matrix containing PVPA and PEPA. PVPA and PEPA effectively improved the flame-retardant properties of MXene/PVA nanocomposites and they did not obviously change the thermal degradation of the MXene/PVA nanocomposites. Moreover, MXene improved the thermal stability of the PVA matrix. The elongation at break of MXene/PVA nanocomposites reached its maximum when the MXene mass fraction was 1.0 wt.%, regardless of whether PVPA and PEPA were present in the PVA matrix, whereas the tensile strength and Young's modulus of MXene/PVA nanocomposites increased with the increase in MXene content in the PVA matrix.

Regulation Mechanism for Friction Coefficient of Poly(vinylphosphoric acid) (PVPA) Superlubricity System Based on Ionic Properties.

Adjustable lubrication aims to achieve active control of the relative motion of the friction interface, providing a new idea for intelligent operation. A new phenomenon of sudden changes of friction coefficient (COF) in the poly(vinylphosphoric acid) (PVPA) superlubricity system by mixing different lubricants, was found in this study. It was found that anions were the critical factor for the COF change. The change degrees of the COF were investigated by a universal micro tribometer (UMT). A quartz crystal microbalance (QCM)-D was used to analyze the adsorption quantity of anions on the PVPA surface. The hydratability of the PVPA interface was controlled by changing the anionic properties (the amount of charge and structure), thus regulating the COF. The adsorption difference of anions is an important reasoning of how anionic properties can regulate the hydratability. It was analyzed by molecular dynamics simulation. For anions carrying different numbers of charges or double bonds, the adsorption quantity of anions was mainly affected by the adsorption degree on the PVPA surface, while the adsorption quantity of anions with different molecular configuration was synergistically regulated by the adsorption degree and adsorption area of anions on the PVPA surface. This work can be used to develop smart surfaces for applications.

Interpolymer Complexes of Poly(methacryloyloxyethyl phosphorylcholine) and Polyacids.

It has been shown that macromolecules of poly(methacryloyloxyethyl phosphorylcholine) can form hydrogen bonded interpolymer complexes with homo- and copolymers of carboxylic acids and with poly(vinylphosphonic) acid in aqueous solutions. Polarized luminescence and IR spectroscopy were applied in the investigation. Nanosecond relaxation times characterizing the mobility of the chain fragments for the initial luminescent labeled polymers were determined and their changes by a factor of 2-50 were established during the formation of an interpolymer complex. Hydrogen bonds play a dominant role in the formation of these complexes. Hydrophobic interactions serve as an additional stabilizing factor. It is established that poly(methacryloyloxyethyl phosphorylcholine)/poly(vinylphosphonic acid) complex forms a looser structure in comparison with those for polycarboxylic acids as result of electrostatic repulsion between charged groups.

Design of Crosslinked Hydrogels Comprising Poly(Vinylphosphonic Acid) and Bis[2-(Methacryloyloxy)Ethyl] Phosphate as an Efficient Adsorbent for Wastewater Dye Removal.

The development of adsorbents with high adsorption capacity and fast separation is of utmost importance for the environmental management of dye-bearing wastewaters. Within this scope, crosslinked hydrogels including poly(vinylphosphonic acid) (PVPA) and bis[2-(methacryloyloxy)ethyl] phosphate (BMEP) were designed with varying mole ratios of BMEP (5-40%). The Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Brunauer-Emmett-Teller (BET) results revealed that the fabrication of crosslinked PVPA-BMEP hydrogels enhanced: (i) functionalities of PA groups in the structure of hydrogels, (ii) thermal stabilities up to 250 °C, and (iii) interaction between methylene blue (MB) molecules and hydrogels. The pseudo second-order kinetic model best described the experimental adsorption data. The behaviors of the isotherms were more appropriate for Langmuir than Freundlich isotherm for the experimental data. PVPA-BMEP (40%) hydrogel indicated a fast and an outstanding MB adsorption capacity of 2841 mg g-1, which has not been reported yet for polymer hydrogels, to the best of our knowledge. The thermodynamic studies concluded that MB adsorption process was spontaneous and exothermic in nature. The overall results suggest that the designed and fabricated PVPA-BMEP hydrogels have great potential for the efficient removal of coloring materials from wastewaters.

A Highly-Durable CO-Tolerant Poly(vinylphosphonic acid)-Coated Electrocatalyst Supported on a Nanoporous Carbon.

For direct methanol fuel cells (DMFCs) to be commercialized, the durability of the anodic electrocatalyst needs to be highly considered, especially under high temperature and methanol concentration conditions. Low durability caused by carbon corrosion as well as carbon monoxide (CO) poisoning of the platinum nanoparticles (Pt-NP) leads to a decrease in active Pt-NPs and increases inactive Pt-NPs covered by CO species. In this study, we deposited Pt-NPs on poly[2,2'-(2,6-pyridine)-5,5'-bibenzimidazole] (PyPBI)-wrapped nanoporous carbon (NanoPC) and coated the as-synthesized electrocatalyst with poly(vinylphosphonic acid) (PVPA). The durability of the as-synthesized NanoPC/PyPBI/Pt/PVPA was tested in 0.1 M HClO4 electrolyte at 60 °C by cycling the potential from 1.0 to 1.5 V relative to RHE, and the results indicated that NanoPC/PyPBI/Pt/PVPA showed ∼5 times better durability relative to that of the commercial CB/Pt. The methanol oxidation reaction (MOR) of the electrocatalyst was tested before and after the potential cycling in the presence of 4 or 8 M methanol at 60 °C and found that the CO tolerance of the electrocatalyst was ∼3 times higher than that of the commercial CB/Pt. Such a higher CO tolerance is due to the coating of the PVPA, which was proven by an EDX mapping measurement. The NanoPC/PyPBI/Pt/PVPA showed a high durability and CO tolerance under high temperature and high methanol concentration conditions, indicating that the electrocatalyst could be used in real fuel applications.

Facile Enhancement in CO-Tolerance of a Polymer-Coated Pt Electrocatalyst Supported on Carbon Black: Comparison between Vulcan and Ketjenblack.

The CO poisoning and low durability of the anode platinum electrocatalyst in the direct methanol fuel cell (DMFC) are the two crucial obstacles of the wide commercialization of the DMFC. In this study, we synthesized two different electrocatalysts using VulcanXC-72R (VC) and Ketjenblack (KB) as the carbon supporting material for the methanol oxidation reaction (MOR) and long-term durability test, in which the carbon supporting materials were wrapped by poly[2,2'-(2,6-pyridine)-5,5'-bibenzimidazole] (PyPBI) before the platinum deposition and the fabricated electrocatalysts were coated by the poly(vinylphosphonic acid) (PVPA) via the base-acid reaction. We have found that the as-prepared KB/PyPBI/Pt/PVPA shows a higher durability (7% loss in ECSA) under the potential cycling from 1.0 to 1.5 V vs. RHE compared to that of the VC/PyPBI/Pt/PVPA, which showed a 20% loss in ECSA after 10 000 cycle-durability test. Meanwhile, the KB/PyPBI/Pt/PVPA shows a higher CO tolerance before and after the durability test compared to that of the VC/PyPBI/Pt/PVPA, especially under very high methanol concentration (4 M and 8 M), which is close to the practical application of the DMFC. The observed higher CO tolerance is due to the higher amount of the PVPA (14.6 wt %) in the KB/PyPBI/Pt/PVPA caused by the higher specific surface area of the KB (1232 m(2)/g) compared to the VC (235 m(2)/g).

Flame-Retardant Paper from Wood Fibers Functionalized via Layer-by-Layer Assembly.

The highly flammable character of cellulose-rich fibers from wood limits their use in some advanced materials. To suppress the flammability and introduce flame-retardant properties to individual pulp fibers, we deposited nanometer thin films consisting of cationic chitosan (CH) and anionic poly(vinylphosphonic acid) (PVPA) on fibers using the layer-by-layer (LbL) technique. The buildup of the multilayer film was investigated in the presence and absence of salt (NaCl) using model cellulose surfaces and a quartz crystal microbalance technique. Fibers were then treated with the same strategy, and the treated fibers were used to prepare paper sheets. A horizontal flame test (HFT) and cone calorimetry were conducted to evaluate the combustion behavior of paper sheets as a function of the number of bilayers deposited on fibers. In HFT, paper made of fibers coated with 20 CH/PVPA bilayers (BL), self-extinguished the flame, while uncoated fibers were completely consumed. Scanning electron microscopy of charred paper after HFT revealed that a thin shell of the charred polymeric multilayer remained after the cellulose fibers had been completely oxidized. Cone calorimetry demonstrated that the phosphorus-containing thin films (20 BL is ∼25 nm) reduced the peak heat release rate by 49%. This study identifies a unique and highly effective way to impart flame-retardant characteristic to pulp fibers and the papers made from these fibers.

Poly(vinylphosphonic acid) (PVPA) on titanium alloy acting as effective cartilage-like superlubricity coatings.

Poly(vinylphosphonic acid) (PVPA) is a type of hydrophilic polymer that can be used in surface modifications. In our study, PVPA coatings were formed on the surfaces of titanium alloy (Ti6Al4V) using a simple and novel method to achieve efficient lubrication at friction interfaces. The composition and 3D skeletal structure of the PVPA coatings were confirmed by X-ray photoelectron spectroscopy (XPS), focused ion beam/scanning electron microscopy (FIB/SEM), and solid-state nuclear magnetic resonance (NMR). The PVPA-modified Ti6Al4V/polytetrafluoroethylene (PTFE) interface shows a superlow friction coefficient (approximately 0.006) for at least 8 h under a contact pressure of 44.2 MPa (initial pressure), which means it falls into the superlubricity regime. Moreover, wear on the surfaces of both the Ti6Al4V and PTFE after the tribological experiment is superlow. It is proposed that the 3D skeletal structure of the PVPA coating and fluid-like manner at friction interfaces owing to the fast exchange of water molecules are the main factors accounting for the superlow friction and wear. The PVPA-modified Ti6Al4V has the potential uses in artificial cervical discs.