Natural Polymers-Based Materials: A Contribution to a Greener Future

Natural polymers have emerged as promising candidates for the sustainable development of materials in areas ranging from food packaging and biomedicine to energy storage and electronics. In tandem, there is a growing interest in the design of advanced materials devised from naturally abundant and renewable feedstocks, in alignment with the principles of Green Chemistry and the 2030 Agenda for Sustainable Development. This review aims to highlight some examples of the research efforts conducted at the Research Team BioPol4fun, Innovation in BioPolymer-based Functional Materials and Bioactive Compounds, from the Portuguese Associate Laboratory CICECO–Aveiro Institute of Materials at the University of Aveiro, regarding the exploitation of natural polymers (and derivatives thereof) for the development of distinct sustainable biobased materials. In particular, focus will be given to the use of polysaccharides (cellulose, chitosan, pullulan, hyaluronic acid, fucoidan, alginate, and agar) and proteins (lysozyme and gelatin) for the assembly of composites, coatings, films, membranes, patches, nanosystems, and microneedles using environmentally friendly strategies, and to address their main domains of application.     

Damage monitor and life prediction of carbon fiber-reinforced ceramic-matrix composites at room and elevated temperatures using hysteresis dissipated energy-based damage parameter

In this paper, the damage monitor and life prediction of carbon fiber-reinforced ceramic-matrix composites (C/SiC CMCs) have been investigated using the hysteresis dissipated energy-based damage parameter. The evolution of the interface shear stress, hysteresis dissipated energy, hysteresis dissipated energy-based damage parameter and the broken fibers fraction vs. cycle number, the fatigue life S?N curves of unidirectional, cross-ply and 2.5D C/SiC composites at room temperature and 800 °C in air atmosphere have been analyzed. For unidirectional C/SiC, the hysteresis dissipated energy and hysteresis dissipated energy-based damage parameter first increase and then decrease with cycle number, and the fatigue limit stress decreases from 88% tensile strength at room temperature to 20% of the tensile strength at 800 °C in air atmosphere; for cross-ply C/SiC, the hysteresis dissipated energy and hysteresis dissipated energy-based damage parameter decrease with increasing applied cycles, and the fatigue limit stress decreases from 85% tensile strength at room temperature to 22% tensile strength at 800 °C in air; and for 2.5D C/SiC, the hysteresis dissipated energy and hysteresis dissipated energy-based damage parameter increases with cycle number, and the fatigue limit stress decreases from 70% tensile strength at room temperature to 25% tensile strength at 800 °C in air.     

Surface modification of Mg2B2O5 whisker and its effect on the mechanical properties and thermostability of polycarbonate/Mg2B2O5w composites

The Mg₂B₂O₅ whiskers (Mg₂B₂O₅w) were modified by boric acid ester (BE) coupling agent and used to prepare polycarbonate (PC) composites. Surface wettability test and evaluation of dispersibility of BE-modified Mg₂B₂O₅w (BE-Mg₂B₂O₅w) in n-heptane were carried out by water contact angle measurement and polarizing microscopy, respectively. The surface chemical characteristics of BE-Mg₂B₂O₅w and estimation of the amount of tightly bonded organic modifier were examined by Fourier transform infrared spectrometry (FT-IR) and thermogravimetric analysis (TGA), respectively. The influence of BE-Mg₂B₂O₅w on the mechanical property, morphology and thermostability of PC composites was investigated by using universal testing machine, scanning electron microscopy (SEM), dynamic mechanical analysis (DMA) and TGA, respectively. It was found that BE was successfully grafted to the surface of Mg₂B₂O₅w, and the hydrophobic BE-Mg₂B₂O₅w leads to high ratio of adhesion work to interfacial tension between PC and BE-Mg₂B₂O₅w, and its better dispersibility in n-heptane. Furthermore, the incorporation of BE-Mg₂B₂O₅w into PC matrix resulted in higher tensile properties of PC/BE-Mg₂B₂O₅w than that of PC/Mg₂B₂O₅w composites and lower maximum weight loss rate than that of PC. The storage modulus of the PC/Mg₂B₂O₅w composites increased obviously as a function of whisker content, especially for the composites with BE-Mg₂B₂O₅w, but the T_g value changed little.     

Design and tensile properties of aluminum borate whiskers reinforced aluminum composite with low whisker volume fraction

ZnO was firstly coated on the surface of aluminum borate whiskers (ABOw) by sol–gel. Then, ZnO-coated ABOw was added into soybean slurry to make a preform with low volume fraction and the preform was sintered at high temperatures to obtain a sufficient strength. ABOw reinforced aluminum composite (ABOw/Al) was fabricated by squeeze casting. Interfacial microstructures, tensile properties, and fracture mechanisms of the ABOw/Al composite were investigated. The results show that the coating of ABOw and the addition of soybean sacrificial filler can effectively decrease the volume fraction of whiskers in the composite. The ultimate tensile strength of composite has not changed much with the decrease of whiskers volume fraction in the composite. However, the elongation to fracture of the composite evidently increases and it can reach 11.1% at room temperature.     

Real-time visualisation of deformation fields using speckle interferometry and temporal phase unwrapping

A real-time system for analysing data from speckle interferometers, and speckle shearing interferometers, has been developed. Interferograms are continuously recorded by a digital camera at a rate of 60 frames s⁻¹ with temporal phase shifting carried out at the same rate. The images are analysed using a pipeline image processor. With a standard 4-frame phase-shifting algorithm (phase steps of π/2), wrapped phase maps are calculated and displayed at 15 frames s⁻¹. These are unwrapped using a temporal phase unwrapping algorithm to provide a real-time colour-coded display of the relevant displacement component. Each camera pixel (or cluster of pixels) behaves in effect as an independent displacement sensor. The reference speckle interferogram is updated automatically at regular user-defined intervals, allowing arbitrarily large deformations to be measured and errors due to speckle decorrelation to be minimised. The system has been applied to the problem of detecting sub-surface delamination cracks in carbon fibre composite panels.     

Nickel Oxide/Graphene Composites: Synthesis and Applications

Nickel oxide (NiO) has emerged as one of the most promising transition-metal oxides (TMOs) for electrochemical capacitors, batteries, catalysis, and electrochromic films, owing to its cost-effectiveness, abundance, and well-defined electrochemical properties. Recent studies have identified that mixing NiO with graphene or graphene derivatives results in novel composites with synergistic effects and superior electrochemical performance. This review summarizes the latest advances in composites of NiO with graphene or graphene derivatives. The synthetic strategies, morphologies, and electrochemical performance of these composites are introduced, as well as their electrochemical applications in supercapacitors, batteries, sensors, catalysis, and so forth. Finally, tentative conclusions and assessments regarding the opportunities and challenges for the future development of these composites and other TMOs/graphene or graphene-derived composites are presented.     

CYCU-3孔内合成聚吡咯及其电导性能表征

以具有一维介孔孔道的金属有机框架材料CYCU-3作为主体材料,采用碘氧化法在其孔道内进行了吡咯的聚合反应,从而得到了复合材料PPy@CYCU-3。利用粉末X射线衍射、扫描电镜、热重、红外、荧光光谱等对CYCU-3、吸附吡咯后的Py@CYCU-3以及孔内聚合后的复合材料PPy@CYCU-3进行了表征,证明了孔内聚合的成功进行,而且在聚合过程中,CYCU-3基本保持了结构的稳定,形貌也未发生改变。而且,PPy@CYCU-3复合材料是具有多孔性和电导性的多功能材料。氮气吸附表明该材料为典型的微孔材料,其BET比表面积为420 m2·g~(-1)。电导测试表明该材料的电导率为10-7 S·cm~(-1),高于CYCU-3的电导率(σ≈10-13S·cm-1)6个数量级,是一种半导体材料。     

Monitoring photopolymerization reactions through thermal imaging: A unique tool for the real‐time follow‐up of thick samples, 3D printing,and composites

The ever increasing applications of photopolymers from historical thin (<50 µm) coatings to very deep samples (>1 cm) require the development of robust 4D monitoring strategies able to assess photopolymerization efficiencies (first dimension) as a function of time (second dimension) and position (third and fourth dimensions). Therefore, here, we demonstrated that thermal imaging is a valuable photopolymerization monitoring device showing: (a) very high response times (<1 s); (b) high repeatability of the measurement; (c) strong adaptability of the setup to various conditions (e.g., onto irregular surfaces or inside a real time Fourier transformed infrared spectrometer (RT‐FTIR)); (d) extremely deep photopolymerization follow‐ups (and subsequent rationalization) with good resolution in time and in space (real‐time thermal imaging microscopy experiments); (e) adaptability to applied materials. This monitoring strategy was found particularly robust when taking into account all the heat generating phenomena (i.e., direct heating from the lamp vs. temperature raised due to monomer conversion). As a result, we propose thermal imaging as the next reference monitoring system for the new ranges of thick and/or filled samples (e.g., 3D objects, composites) and/or applied photopolymerizations (e.g., 3D printing) more and more present in the literature. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 889–899     

Optical responses of dilute anisotropic composites：numerical calculations via Green‘s function formalism

We investigate the linear and nonlinear optical responses of dilute anisotropic networks using Green's function formalism [Gu Y et al 1999 Phys. Rev. B 59 12847]. For different applied fields, numerical calculations indicate that a large third-order nonlinear enhancement and a broad infrared absorption arise from the geometric anisotropy. We also show the overlap and separation between the absorption peak and nonlinear enhancement peak when the applied field is parallel and perpendicular to the anisotropy, respectively. The results can be understood in terms of the inverse participation ratios with q=2 and the spectral distribution of optical responses.     

Non‐Isothermal Crystallization Kinetics of PA6/Attapulgite Composites Prepared by Melt Compounding

The non‐isothermal crystallization behaviors of neat polyamide 6 (PA6) and PA6/attapulgite (ATB) composites were examined using differential scanning calorimetry. The results show that ATB acts as a nucleator for PA6 matrix, accelerating the crystallization, and simultaneously obstructs the crystallization especially for the composites with higher ATB content. The analysis results using the Jeziorny and Liu equations verify the dual actions of the nucleation and the obstruction of crystallization of the ATB in the PA6 matrix. Kissinger's method is employed to obtain the activation energy of the crystallization processes; the results further indicate that the addition of ATB may also cause the above actions. It is speculated that there is a very complicated crystallization mechanism in the PA6/ATB composites based on the analysis of Avrami exponents obtained by the Jeziorny model.