The Post-Curing of Waterborne Polyurethane-Acrylate Composite Latex with the Dynamic Disulfide-Bearing Crosslinking Agent.

The development of a dynamic network for commodity polymer systems via feasible methods has been explored in the context of a society-wide focus on the environment and sustainability. Herein, we demonstrate an adaptive post-curing method used to build a self-healable network of waterborne polyurethane-acrylate (WPUA) composite latex. The composite latex was synthesized via the miniemulsion polymerization of acrylates in the dispersion of waterborne polyurethane (PU), with commercial acetoacetoxyethyl methacrylate (AAEM) serving as the functional monomer. Then, a dynamic disulfide (S-S)-bearing diamine was applied as the crosslinking agent for the post-curing of the hybrid latex via keto-amine condensation, which occurred during the evaporation of water for film formation. It was revealed that the microphase separation in the hybrid films was suppressed by the post-curing network. The mechanical performance exhibited a high reliability as regards the contents of the crosslinking agents. The reversible exchange of S-S bonds meant that the film displayed associative covalent-adaptive networks in the range of medium temperature in stress relaxation tests, and ≥95% recovery in both the stress and the strain was achieved after the cut-off films were self-healed at 70 °C for 2 h. The rebuilding of the network was also illustrated by the >80% recovery in the elongation at break of the films after three crushing-hot pressing cycles. These findings offer valuable insights, not only endowing the traditional WPUA with self-healing and reprocessing properties, but broadening the field of study of dynamic networks to polymer hybrid latex.

The Multi-Step Chain Extension for Waterborne Polyurethane Binder of Para-Aramid Fabrics.

The comprehensive balance of the mechanical, interfacial, and environmental requirements of waterborne polyurethane (WPU) has proved challenging, but crucial in the specific application as the binder for high-performance polymer fiber composites. In this work, a multi-step chain extension (MCE) method was demonstrated using three kinds of small extenders and one kind of macro-chain extender (CE) for different chain extension steps. One dihydroxyl blocked small molecular urea (1,3-dimethylolurea, DMU) was applied as one of the CEs and, through the hybrid macrodiol/diamine systems of polyether, polyester, and polysiloxane, the WPU was developed by the step-by-step optimization on each chain extending reaction via the characterization on the H-bonding association, microphase separation, and mechanical properties. The best performance was achieved when the ratio of polyether/polyester was controlled at 6:4, while 2% of DMU and 1% of polysiloxane diamine was incorporated in the third and fourth chain extension steps, respectively. Under the condition, the WPU exhibited not only excellent tensile strength of 30 MPa, elongation of break of about 1300%, and hydrophobicity indicated by the water contact angle of 98°, but also effective interfacial adhesion to para-aramid fabrics. The peeling strength of the joint based on the polysiloxane incorporated WPU after four steps of chain extension was 430% higher than that prepared through only two steps of chain extension. Moreover, about 44% of the peeling strength was sustained after the joint had been boiling for 40 min in water, suggesting the potential application for high-performance fabric composites.

Recent Advances in Self-Assembly and Application of Para-Aramids.

Poly(p-phenylene terephthalamide) (PPTA) is one kind of lyotropic liquid crystal polymer. Kevlar fibers performed from PPTA are widely used in many fields due to their superior mechanical properties resulting from their highly oriented macromolecular structure. However, the "infusible and insoluble" characteristic of PPTA gives rise to its poor processability, which limits its scope of application. The strong interactions and orientation characteristic of aromatic amide segments make PPTA attractive in the field of self-assembly. Chemical derivation has proved an effective way to modify the molecular structure of PPTA to improve its solubility and amphiphilicity, which resulted in different liquid crystal behaviors or supramolecular aggregates, but the modification of PPTA is usually complex and difficult. Alternatively, higher-order all-PPTA structures have also been realized through the controllable hierarchical self-assembly of PPTA from the polymerization process to the formation of macroscopic products. This review briefly summarizes the self-assembly methods of PPTA-based materials in recent years, and focuses on the polymerization-induced PPTA nanofibers which can be further fabricated into different macroscopic architectures when other self-assembly methods are combined. This monomer-started hierarchical self-assembly strategy evokes the feasible processing of PPTA, and enriches the diversity of product, which is expected to be expanded to other liquid crystal polymers.

Nanoaramid Dressed Latex Particles: The Direct Synthesis via Pickering Emulsion Polymerization.

The direct synthesis of polymer microspheres modified by aramid nanofibers (ANFs) is an interesting challenge. This work describes a simple aqueous process to prepare polystyrene (PS)/ANF composite microspheres, where the specific ANF network was "dressed" on PS. ANF was derived from the copolymerization of terephthaloyl chloride, p-phenylene diamine, and methoxypolyethylene glycol and could be dispersed in water stably. We applied the as-synthesized ANF as a Pickering emulsifier in the o/w emulsion of styrene monomer. Radical polymerization was subsequently initiated in the Pickering emulsion system. The combination of ANF with polymer spheres was revealed by scanning electron microscopy (SEM) and thermal gravity analysis. The role of ANF in the monomer emulsion as well as in the polymerization was studied through SEM, optical microscopy, optical stability analyzer, and pulse nuclear magnetic resonance combined with the polymerization kinetic analysis. Moreover, we investigated the effects of other synthesis parameters, such as monomer type, monomer content, pH value, and salt concentration.

Solution Blow Spinning of the Benzimidazole-Containing Aramid Nanofibers for Separators of Lithium-Ion Batteries.

Nanofibers based on high-performance polymers are much highlighted in recent studies toward advanced lithium-ion batteries. Herein, we demonstrate one scalable poly(ethylene oxide) (PEO)-assisted solution blow spinning strategy for the preparation of heterocyclic aramid (HA) nanofibers of poly(p-phenylene-benzimidazole-terephthalamide). The incorporation of PEO is essential to improve the spinnability of the HA solution achieved directly through the low-temperature-solution copolymerization process. Additionally, the flexible PEO with a strong H-bonding affinity is also utilized as the molecular zipper to adjust the pore size of the nanofiber membrane during the post-treatment process. The obtained membrane combines the good wettability of PEO to the liquid electrolytes, with outstanding mechanical strength, modulus, toughness, and environmental resistance of HA. The nonwoven separator membranes with a porosity of 83.6% exhibited excellent comprehensive performance, which could be seen not only on the high tensile strength (68.2 MPa), modulus (3.0 GPa), and toughness but also on the high thermal stability (Td > 405 °C) and flame retardancy, as well as the high electrolyte uptake (302.4%). The ion conductivity of the porous separators reached 0.83 mS/cm, with the bulk resistance dropping to 1/4 of the reference polypropylene separator. In the assembly of the Li/LiFePO4 half battery, the HA separators displayed improved discharge specific capacity and high retention in both rate capability and cycling tests, providing the potential industrial preparation for advanced lithium-ion batteries.

Highly Efficient Thermo-Acoustic Insulating Aerogels Enabled by Resonant Cavity Engineering.

Lightweight, flexible, and noncombustible thermo-acoustic insulating (TAI) materials have great potential in vehicles, cold-chain transportation, and aerospace engineering, where weight and space savings are critical. However, the TAI capabilities of many commodities are hindered by the lack of diverse and reasonable resonant cavities with broadband and highly efficient acoustic responsiveness. This study demonstrates a layer-by-layer freeze-casting method for superelastic cellular aerogel construction from varied nanofibers and ice particulates with widely distributed resonant cavities from 0.5 to 300 µm. The method enabled the cumulative freezing of the nanofiber solution from one side to the other side, resulting in vertical pore channels with random holes across the entire freezing distance. The formed cellular networks of stable hinged ternary nanofiber membranes, functionalized as ultrathin nanofiber drums, exhibit strong resonances and efficiently dissipate sound waves in a broad frequency range. A high noise reduction coefficient of 0.65 at a frequency range of 63-6300 Hz and a low thermal conductivity of 0.026 W m-1 K-1 at room temperature was obtained. This work presents the bottom-up fabrication of high-performance TAI aerogels that are beneficial for practical energy-saving devices and buildings and broadband acoustic absorption applications.

Self-Stacked 3D Anisotropic BNNS Network Guided by Para-Aramid Nanofibers for Highly Thermal Conductive Dielectric Nanocomposites.

The enhancement of the heat-dissipation property of polymer-based composites is of great practical interest in modern electronics. Recently, the construction of a three-dimensional (3D) thermal pathway network structure for composites has become an attractive way. However, for most reported high thermal conductive composites, excellent properties are achieved at a high filler loading and the building of a 3D network structure usually requires complex steps, which greatly restrict the large-scale preparation and application of high thermal conductive polymer-based materials. Herein, utilizing the framework-forming characteristic of polymerization-induced para-aramid nanofibers (PANF) and the high thermal conductivity of hexagonal boron nitride nanosheets (BNNS), a 3D-laminated PANF-supported BNNS aerogel was successfully prepared via a simple vacuum-assisted self-stacking method, which could be used as a thermal conductive skeleton for epoxy resin (EP). The obtained PANF-BNNS/EP nanocomposite exhibits a high thermal conductivity of 3.66 W m-1 K-1 at only 13.2 vol % BNNS loading. The effectiveness of the heat conduction path was proved by finite element analysis. The PANF-BNNS/EP nanocomposite shows outstanding practical thermal management capability, excellent thermal stability, low dielectric constant, and dielectric loss, making it a reliable material for electronic packaging applications. This work also offers a potential and promotable strategy for the easy manufacture of 3D anisotropic high-efficiency thermal conductive network structures.

Synthesis and properties novel polyurethane-hexafluorobutyl methacrylate copolymers.

Novel physically crosslinked polyurethane-hexafluorobutyl methacrylate (PU-M) copolymers were prepared by the macroiniferter-controlled radical polymerization method. The chemical structures of the PU-M copolymers were characterized by FT-IR, (1)H-NMR, GPC, DSC, and XPS. The self-assembly and surface properties of the PU-M copolymers have been investigated. The results revealed that PU-M copolymers have good hydrophobility, so the hydrophobility of polyurethane could be easily adjusted by controlling the content of the hydrophobic vinyl monomers. The mechanical evaluation shows that PU-M copolymers exhibit good mechanical properties. The effects of the fluorine content on the surface properties and self-assembly of the PU-M copolymers were investigated. The morphology of the PU-M copolymers' self-assembly was observed by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), and the mechanism of self-assembly was investigated. Antimicrobial property of the chlorinated PU-M copolymers against both Escherichia coli and Bacillus subtilis bacteria was examined and showed increase compared to that of pure polyurethane.

The Aramid-Coating-on-Aramid Strategy toward Strong, Tough, and Foldable Polymer Aerogel Films.

Aerogel has been much highlighted as an emerging lightweight thermal insulation material, but problems such as fragility, low strength, liquid permeability, and lack of flexibility greatly limit further applications. In this work, a facile aramid-coating-on-aramid (ACoA) method is demonstrated to fabricate all-aramid aerogel composite films for thermal insulation. The method started from the bottom-up synthesis of polymerization-induced para-aramid nanofibers (PANF), which were easily transformed into aerogel films through the vacuum-assisted filtration followed by the freeze-drying techniques. Then, the heterocyclic aramid (HA) solution prepared through the low-temperature-solution polycondensation was used as the coating to be applied onto the PANF aerogel films, and composite films of HA/PANF aerogel were simply achieved with HA contributed to the dense and continuous surface layer. The bulk HA film is of superior mechanical and thermal properties to those of the PANF film. Moreover, reliable interfacial interlocking structures were developed beneath the outermost surface via the interpenetration of the infiltrated HA with PANF network. The comprehensive result was the 15 times enhanced tensile strength, 33 times enhanced fracture toughness, the high thermal decomposition temperature, and the additional flexibility for the foldable films of HA/PANF aerogel. The sealing of the surface macropores greatly suppressed the surface chalking and high water absorption. However, the survival of the tiny pores inside the composite maintained the low enough level of the thermal conductivity to provide effective protections against high temperature not only in air but also under wet or even liquid conditions, suggesting the broader applications for thermal insulation.

Construction of Aramid Engineering Materials via Polymerization-Induced para-Aramid Nanofiber Hydrogel.

The processing of poly(p-phenylene terephthalamide) (PPTA) has long been a great challenge. This work reports a simple "monomers-nanofibers-macroscopic product" (MNM) hierarchical self-assembly approach to build 3D all-PPTA engineering materials. This approach mainly includes the preparation of polymerization-induced aramid nanofibers (PANFs) from monomers and the fabrication of all-PPTA materials from PANF hydrogel. Various 3D architectures, including simple solid bulks and sophisticated honeycombs (HCs), are obtained after the dehydration and shrinking of the PANF hydrogel. The tensile strength and compressive yield strength of PANF bulk are more than 62 and 90 MPa, respectively, which are comparable to typical engineering plastics. The compressive strength of PANF HC with a density of 360 kg m-3 is more than 24 MPa. The thermal stability of PANF bulk and PANF HC are as good as that of Kevlar fiber and almost no decomposition occurred before 500 °C in a nitrogen atmosphere. Furthermore, the MNM process is performed under mild conditions, without high temperature, high pressure, or corrosive solvent. The MNM process is a novel strategy for the processing of all aromatic polyamide materials with complex structures and high performances and would be another development since the breakthrough of liquid crystal spinning technology of PPTA.

Comparison of Three Interfacial Conductive Networks Formed in Carbon Black-Filled PA6/PBT Blends.

Interfacial localization of carbon fillers in cocontinuous-structured polymer blends is well-known as a high-efficiency strategy for conductive network formation. However, a comparison with interfacial localization of carbon fillers in sea-island-structured polymer blends is lacking. Here, three types of highly efficient conductive networks formed on the basis of interfacial localization of carbon black (CB) in polyamide 6 (PA6)/poly(butylene terephthalate) (PBT) blends with different blend compositions (80/20, 50/50 and 20/80 vol/vol) were investigated and compared in terms of electrical resistivity, morphology as well as rheological and mechanical properties. The order of the electrical percolation threshold of CB in the three blends is 50/50 < 20/80 < 80/20, which can be attributed to different network structures. The rheological percolation thresholds are close to the electrical ones, confirming the formation of CB networks. The formation mechanisms for the three types of CB network structures are analyzed. All the three types of PA6/PBT-6 vol% CB composites showed improved tensile strength compared with PA6/PBT blends, being in favor for practical applications.

Macroscopic-Scale Preparation of Aramid Nanofiber Aerogel by Modified Freezing-Drying Method.

Aerogel has been widely known as a low-density and highly porous material and is closely connected with the complex processing methods, such as freeze-drying or supercritical drying. In this work, using the polymerization-induced aramid nanofiber (PANF) as a building block, we put forward a modified freezing-drying method for the high-efficiency preparation of all-para-aromatic-amide aerogels. In the preparation process, PANF hydrogel is first frozen at -18 °C and then dried at 20-150 °C for the formation of PANF aerogel. The PANF framework formed during the freezing process is crucial for the formation of the PANF aerogel. Moreover, the space-occupying effect of ice crystals is also helpful for the formation of the macroscopic pore structure in the aerogel. Aerogels with large size or well-controlled shape could be successfully obtained by this method. Through the variation of PANF concentration in the hydrogel and drying temperature, aerogels with different densities (20-185 mg/cm3) could be achieved, and the lowest density is reached at 150 °C, with the PANF concentration of 0.7%. The low-density PANF aerogels show high specific compressive strengths and low thermal conductivities, which are comparable to those resulting from the freeze-drying or supercritical drying method. Furthermore, the shrinkage phenomenon in the drying process could be skillfully utilized for the preparation of PANF aerogel-coated objects. The PANF aerogels could be applied as a thermal insulating material or shock absorption material in practical applications.

Selective fusion, solvent dissolution, and local symmetry effects in inversion of colloidal crystals to ordered porous films.

Polystyrene-methacrylic core-shell nanospheres, self-assembled into face-centered-cube-like colloidal crystals with their (001) planes parallel to the substrate, have been transformed into ordered pore structures by a toluene treatment. Detailed analysis by transmission electron microscopy reveals that the morphological transformation is preceded by an internal neck formation due to selective fusion of the polystyrene-rich core material, at the contacts between the nanoparticles, followed by the selective dissolution of the polystyrene-rich cores. We have demonstrated the importance of local symmetry and compactness of the nanospheres assembly in determining the nature of the neck formation and the existence of multiscale ordered pore structures in the square facing colloidal crystals. The pseudo layer-by-layer nature of the selective dissolution of square arranged nanosphere multilayers is responsible for the observed three-dimensional pore structures.

From Monomers to a Lasagna-like Aerogel Monolith: An Assembling Strategy for Aramid Nanofibers.

The manipulation of nanobuilding blocks into a 3D macroscopic monolith with ordered hierarchical structures has been much desired for broad and large-scale practical applications of nanoarchitectures. In this paper, we demonstrate a fully bottom-up strategy for the preparation of aramid aerogel monoliths. The process starts from the synthesis of poly(p-phenylene terephthalamide) (PPTA) through the polycondensation of p-phenylenediamine and terephthaloyl chloride, with the assistance of a nonreactive dispersing agent (polyethylene glycol dimethyl ether), which helps the dispersal of the as-synthesized PPTA in an aqueous medium for the formation of p-aramid nanofibers (ANF). Then the vacuum-assisted self-assembly (Vas) technique is skillfully connected with the ice-templated directional solidification (I) technique, and the combined VasI method successfully tailors the self-assembly of ANF to transform the 1D nanofibers into a 3D aerogel monolith with a specific long-range aligned, lasagna-like, multilaminated internal structure. The study of the aerogel microstructure revealed the dependence of the lamina orientation on the direction of the freezing front of ice crystals. This direction should be parallel to the deposition plane of the Vas process if a long-range aligned lamellar structure is desired. The anisotropy of the multilaminated aerogel was proven by the different results in the radial and axial directions in the compression and thermal conductivity tests. As a kind of organic aerogel, the ANF monolith has typical low density, high porosity, and low thermal conductivity. Additionally, the ANF monolith exhibits high compressive stress and excellent thermal stability. Considering its high performance and facile preparation process, potential applications of the ANF aerogel monolith can be expected.

Large-scale self-organized growth of (001) surface-oriented colloidal crystals by edge meniscus effect.

Millimeter-sized films of (100) facing face-centered crystals (fcc) of colloidal nanoparticles have been fabricated by self-assembly on silicon substrates and studied by both optical and scanning electron microscopy. The top surface layer sometimes also reconstructs to form a 1 x n (n varies from 2-7) superstructure. Such (100) oriented regions of the colloidal film are apt to concentrate near the edge of the substrate, and changing the width of the substrate could control the areas of the (100)-oriented domains. The formation of the square packing surface pattern is related to the shape of the meniscus at the edges of the substrate, where the particles suffer additional shear force and higher evaporation, which can be used to control the location and size of the square arrangement of nanoparticles.

Theoretical study on the trans-cis isomerization and initial decomposition of energetic azofurazan and azoxyfurazan.

In this work, we carried out the hybrid density functional theory (DFT) calculations in order to understand the thermal trans-cis isomerization and initial thermal decomposition of 3,3'-diamino-4,4'-azofurazan (DAAzF), 3,3'-diamino-4,4'-azoxyfurazan (DAAF), 3,3'-dinitro-4,4'-azofurazan (DAAF) and 3,3'-dinitro-4,4'-azoxyfurazan (DAAzF). The relative energy between the trans- and cis-isomer was also calculated at the B3LYP/6-311++G(d,p)//B3LYP/6-31G(d) level of theory. We found that a negative correlation existed between the relative energy and the sensitivity for these energetic azofurazan and azoxyfurazan compounds, where the higher relative energy means the lower the sensitivity. It was also found that the oxidation of azo-group could cause the decreasing in the relative energy between the trans- and cis-isomer, as well as the alteration of the isomerization mechanism. An inversion mechanism operates for azofurazan compounds (DAAzF and DNAF) while a rotation mechanism works for azoxyfurazan compounds (DAAF and DNOAF). Compared with the thermal trans-cis isomerization, the homolytic cleavage of C-N bond needs to overcome a much higher energy barrier, which indicates that the energy of the external stimulus should firstly trigger the trans-cis isomerization, rather than the breakage of C-N bond. A self-desensitization effect caused by the reversible thermal trans-cis isomerization process was firstly proposed to explain that the azofurazan and azoxyfurazan compounds are class of energetic materials with lower sensitivity. This new concept (self-desensitization effect) is expected to be useful to design the novel high density, insensitive energetic material.

[Experimental study of novel injectable nucleus pulposus prostheses implant].

OBJECTIVE: To explore the histological and the hematological change of rabbits after implanting novel injectable artificial nucleus prostheses, and to evaluate the biological safety. METHODS: In accordance with Biological Evaluation of Medical Devices, materials of polyurethane, silicone rubber and macromolecular polyethylene for medical use were made into short column 1 cm in length and 0.3 cm in diameter. Forty-eight SPF New Zealand white rabbits weighing 2.5-3.0 kg were used, and cavity 1 cm in depth was made in the area 2 cm away from the spinal midline by separating muscle. Then according to different material being implanted, the rabbits were divided into 3 groups (n = 16): Group A, polyurethane; group B, silicone rubber; group C, macromolecular polyethylene for medical use as negative control. General condition of the rabbits was observed after operation. Gross and histology observation were conducted 1, 4, 12 and 26 weeks after operation. Blood routine, biochemical function and electrolyte assays were performed 26 weeks after operation to observe pathological changes of organs. Meanwhile, physicochemical properties of the materials were detected, and the material in the same batch was used as negative control. RESULTS: All rabbits survived until the end of experiment, and all wounds healed by first intention. In each group, red swollen muscles were observed 1 week after operation and disappeared 4 weeks after operation, connective tissue around the implanted materials occurred 12 and 26 weeks after operation. At 26 weeks after operation, there were no significant differences among three groups in blood routine, biochemical function and electrolyte assays (P > 0.05). Organs had smooth surface without ulceration, ecchymosis, obvious swelling, hyperemia or bleeding, and nodules. There were no significant differences among three groups in percentage weight of each organ (P > 0.05). Histology observation: granulation tissue proliferation and inflammatory cell infiltration were observed in each group 1 week after operation, fibrous capsule formation around the materials and the disappearance of inflammatory cell infiltration were evident 4 weeks after operation, cyst wall grew over time and achieved stability 12 weeks after operation. The inflammatory response and the fiber cyst cavity of groups A and B met the standard of GB/T 16175 and were in line with group C. No specific pathological changes were discovered in the organs 26 weeks after operation. For group A, no significant difference was evident between before and after material implantation in terms of weight average molecular weight, number average molecular weight, tensile strength at break and elongation at break (P > 0.05). For group B, no significant difference was evident between before and after material implantation in shore hardness (P > 0.05). CONCLUSION: Novel injectable nucleus pulposus prostheses do not damage local tissue and function of organs, but provide good biocompatibility and biological safety.

Ab initio calculations of the effects of H+ and NH4+ on the initial decomposition of HMX.

In this work, the effects of H(+) and NH(4)(+) on the initial decomposition of HMX were investigated on the basis of the B3P86/6-31G** and B3LYP/6-31G* calculations. Three initial decomposition pathways including the N-NO(2) bond fission, HONO elimination and C-N bond dissociation were considered for the complexes formed by HMX with H(+) (PHMX1 and PHMX2) or with NH(4)(+) (AHMX). We found that H(+) and NH(4)(+) did not evidently induce the HMX to trigger the N-NO(2) heterolysis because the energy barrier of N-NO(2) heterolysis was found to be higher than the bond dissociation energy of N-NO(2) homolytic cleavage. Meanwhile, the transition state barriers of the HONO elimination from the complexes were found to be similar to that from the isolated HMX, which means that the HONO elimination reaction of HMX was not affected by the H(+) and NH(4)(+). As for the ring-opening reaction of HMX due to the C-N bond dissociation, the calculated potential energy profile showed that the energy of the complex (AHMX) went uphill along the C-N bond length and no transition state existed on the curve. However, the transition state energy barriers of C-N bond dissociation were calculated to be only 5.0 kcal/mol and 5.5 kcal/mol for the PHMX1 and PHMX2 complexes, respectively, which were much lower than the C-N bond dissociation energy of isolated HMX. Moreover, among the three initial decomposition reactions, the C-N bond dissociation was also the most energetically favorable pathway for the PHMX1 and PHMX2. Our calculation results showed that the H(+) can significantly promote the initial thermal decomposition of C-N bond of HMX, which, however, is influenced by NH(4)(+) slightly.