It is a great challenge for traditional hydrogel-based sensors to be effective underwater due to unsatisfactory water resistance and insufficient wet adhesion. Herein, a tough supramolecular hydrogel aiming at underwater sensing is prepared by the modification of hydrophilic poly(acrylic acid) (PAA) with a small amount of hydrophobic lauryl methacrylate (LMA) in the presence of high concentrations of the cationic surfactant cetyltrimethylammonium bromide (CTAB). Owing to the synergistic effects of the electrostatic interactions and hydrophobic associations of CTAB with the P(AA-co-LMA) copolymer, the hydrogel with a water content of approximately 58.5 wt % demonstrates outstanding anti-swelling feature, superior tensile strength (≈1.6 MPa), large stretchability (>900%), rapid room-temperature self-recovery (≈3 min at 100% strain), and robust wet adhesion to diverse substrates. Moreover, the strain sensor based on the hydrogel displays keen sensitivity in a sensing range of 0–900% (gauge factor is 0.42, 3.44, 5.44, and 7.39 in the strain range of 0–100, 100–300, 300–500, and 500–900%, respectively) and pronounced stability both in air and underwater. Additionally, the hydrogel can be easily recycled by dissolving in anhydrous ethanol. This work provides a facile strategy to fabricate eco-friendly, tough supramolecular hydrogels for underwater sensing.
The orientation and crystallization during melt stretching were characterized, and their influence on the lamellar morphology and stretched polypropylene pore structure was clarified. During melt stretching, the MDR range from 40–200 could be divided into two regions. In region I, MDR below 120, the crystalline morphology transformed from ellipsoid spherulites to lamellae structure, and the orientation, elastic recovery, and lamellar lateral dimension were enhanced. The porosity of corresponding stretched microporous membrane was increased from 37.8–45.5%. In region II, with the MDR increasing to 200, the orientation and lamellae lateral dimension were increased, but the elastic recovery did not change much. The porosity of corresponding microporous membrane was improved further to 60.3%. The long period, crystalline phase thickness, crystallinity, and lamellae cluster size were kept constant within the whole MDR range, but the orientation was improved from 0.23 ± 0.02 to 0.41 ± 0.03. Apparently, the orientation induced the increase of lamellar lateral dimension, and it was the main factor deciding the properties of stretched microporous membrane.
The room-temperature stretching process of polypropylene annealed film with rownucleated crystalline structure was studied by in-situ small-angle X-ray scattering (SAXS) setup and off-line wide-angle X-ray scattering (WAXS), temperature-modulated differential scanning calorimetry (TMDSC) and stress-strain curves testing. The formation process of initial connecting bridges and pores was clarified. For the annealed film, except for the initial lamellae structure, the recrystallized part formed by the melting and crystallization of imperfect crystals during annealing, tie chains connecting the lamellae structure among the amorphous region, secondary crystals from the crystallization of tie chains during annealing and daughter crystals from the special cross-hatched crystalline structure of PP coexist. It was found that 10 % stretching lead to the pronounced increase of long period and the appearance of a few initial connecting bridges. The stretching of daughter crystal and recrystallized part contributed to the formation of initial bridges. At stretching ratio of 30 %, uniform distributed connecting bridges were observed and the stretched film showed maximum structure periodicity. At this stretching ratio, except for the stretching of daughter crystal, the stretching of tie chains and secondary crystals within the amorphous region lead to the formation of more connecting bridges. At higher stretching ratios into the strain-hardening region and beyond the second yield point, except for the stretching of the above mentioned crystalline
Herein, polylactic acid cast films were prepared with different melt-draw ratios via an extrusion casting process. The oriented structure appeared at first and then a chi structure crystal was formed at higher MDR.
Although the microporous membrane prepared based on the melt stretching mechanism has been commercialized for more than 20 years, the formation process from the initial lamellae structure to final fiber connecting bridges and pores is still unclear. In this work, to clarify the transformation mechanism, in situ SAXS and WAXS were carried out during hot stretching at 130 °C to 100%. The scattering patterns from the annealed film, cold stretched film to 20% (stretched at room temperature), and heating to 130 °C were also collected. The preparation technology was similar to that during the commercial fabrication. It was found that during cold stretching to 20% many long and narrow crazes are formed between separated lamellae clusters, and a part of destroyed crystals appeared. After heating to 130 °C, oriented structure and needlelike voids appeared, which was related to the shrinkage of oriented amorphous chains along the transverse direction, due to the tension stress effect. Also some oriented crystal structure was formed. During hot stretching to 20%, the lamellae which are close to the craze wall are rotated as the fibril crystal as the axle and the connecting bridges were formed among the separated lamellae cluster. Further stretching to 100%, these connecting bridges transformed to fiber bridges, contributed by strain-induced crystallization. During the whole hot stretching, the amorphous chains oriented along the machine direction and also crystallized into fiber bridges. This is the first time to clearly describe the lamellae to fiber bridges transformation during the preparation of microporous membrane.
A planar-like inorganic α-zirconium phosphate (α-ZrP) particles were modified by a kind of cyclophosphazene derivative via three-step hybridization method, first modified by melamine (MA), then combined with hexachlorocyclotriphosphazene (HCCP) through nucleophilic substitution and further integrated with excessive MA. Thus, a hybrid flame retardant (HAC) was successfully synthesized. The composites based on poly(vinyl alcohol) (PVA) and HAC were prepared by solution blending. The thermal, mechanical properties and flame retardancy of the composites were studied. It was found that HAC showed a catalytic effect in the initial decomposition stage and promoted the formation of char at high temperatures. When the content of HAC was 15 wt%, the limiting oxygen index (LOI) reached 28.4% and classified V-0 rating, whereas with the same content of fire retardant, for PVA/α-ZrP and PVA/product of MA with HCCP composites (one kind of intumescent flame retardant IFR), the LOI values were only 24.7% and 27.1%, respectively. The combination of IFR and α-ZrP could remarkably improve the yield and graphitization of char residues, make the char more stable, compact and continuous, inhibiting underlying PVA from contacting heat and oxygen. Moreover, the mechanical properties could be reinforced and toughened with certain content of HAC.
Nanofibrous scaffolds were obtained by co‐electrospinning poly (3‐hydroxybuty‐rate‐co‐3‐hydroxyvalerate) (PHBV) and fibroin regenerated from silk in different proportions using 1,1,1,3,3,3‐hexafluoro‐2‐isopropanol (HFIP) as solvent. Field emission scanning electron microscope (FESEM) investigation showed that the fiber diameters of the nanofibrous scaffolds ranged from 190 to 460 nm. X‐ray diffraction (XRD) and Fourier transform infrared spectroscopy analysis (FT‐IR) showed that the main structure of silk fibroin (SF) in the nanofibrous scaffold was β‐sheet. Compared to the PHBV nanofibrous scaffold, the surface hydrophilicity and water‐uptake capability of the PHBV/SF nanofibrous scaffold with 50/50 were improved. The results of cell adhesion experiment showed that the fibroblasts adhered more to the PHBV/SF nanofibrous scaffold with 50/50 than the pure PHBV nanofibrous scaffold. The proliferation of fibroblast on the PHBV/SF nanofibrous scaffold with 50/50 was higher than that on the pure PHBV nanofibrous scaffold. Our results indicated that the PHBV/SF nanofibrous scaffold with 50/50 may be a better candidate for biomedical applications such as skin tissue engineering and wound dressing. POLYM. ENG. SCI., 55:907–916, 2015. © 2014 Society of Plastics Engineers
The polyvinylidene fluoride cast film was prepared with different melt-draw ratios by a cast extrusion process. The structure and properties of the prepared films were characterized by differential scanning calorimetry, X-ray diffraction, Fourier transform infrared and scanning electrical microscopy. The results showed that with increasing melt-draw ratio, the crystalline orientation increased and the crystalline morphology transformed from spherulites to parallel lamellae perpendicular to the extrusion direction. At the same time, necking behavior in the stress-strain curves disappeared and strain-hardening behavior became apparent. The lamellae thickness distribution became uniform. The polarized Fourier transform infrared results also indicated the existence of some b-phase for the samples with different melt-draw ratios.
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