Mechanochemical fabrication of geopolymer composites based on the reinforcement effect of microfibrillated cellulose

In this study, microfibrillated cellulose-reinforced geopolymer organic/inorganic hybrid materials, were prepared via a simple green mechanochemical method. The interaction between microfibrillated nanocellulose and geopolymer was further investigated by molecular dynamics simulation. The study established that mechanical ball milling could effectively promote the microfibrillation of bamboo pulp fibers to form reinforced geopolymer composites with a uniformly distributed cellulose skeleton network. The compressive strength of geopolymer blended with 2% microfibrillated cellulose was shown to be 85.1% higher than that of the pristine geopolymer after 30 days. In addition, the hybrid system was found to maintain excellent thermal stability due to the effective protection of the biomass components by the inorganic matrix. This one-step mechanochemical process provided an efficient approach for preparing geopolymer composites, which offers significant application potential for use in road repairs, high-temperature-resistant materials, and additive manufacturing via 3D printing.     

Novel hybrid organic-geopolymer materials

Novel hybrid organic–inorganic materials were prepared through an innovative synthetic approach based on a co-reticulation in mild conditions of epoxy based organic resins and an MK-based geopolymer inorganic matrix. A high compatibility between the organic and inorganic phases, even at appreciable concentration of resin, was realized up to micrometric level. A good and homogeneous dispersion (without the formation of agglomerates) of the organic particles was obtained just by hand mixing. These new materials present significantly enhanced compressive strengths and toughness in respect to the neat geopolymer allowing a wider utilization of these materials for structural applications.     

Synthesis,characterization and thermal properties of novel epoxy/expandable graphite composites

Epoxy resins are widely used as coatings, adhesives and primers and in semiconductor encapsulation. A requirement that has recently gained importance is that of flame resistance, and imparting flame retardancy to epoxy resins has attracted much attention. Expandable graphite (EG) can improve flame‐retardant properties of polymers. Due to poor compatibility between polymer matrix and EG, flame‐retardant performance will be impaired. EG can be functionalized using a coupling agent. This gives rise to covalent bonding between organic and inorganic phases. This will improve the compatibility between filler and polymer to enhance the thermal stability of composites. X‐ray photoelectron spectroscopy was used to characterize the functionalizing reaction between coupling agent and EG. Thermogravimetric analysis (TGA) and integral procedural decomposition temperature (IPDT) were used to calculate the thermal stability of composites. The results show that functionalized EG can improve the thermal stability of the composites. TGA/mass spectroscopy (MS) shows that the amount of toxic gases liberated from the composites is less than that from pure epoxy. Novel epoxy/EG composites were prepared successfully via the sol–gel method. The results of TGA, IPDT and TGA/MS showed that functionalized EG can enhance the thermal stability of composites and can suppress the production of toxic gases. The composite materials could provide a safer choice. Copyright © 2009 Society of Chemical Industry     

Effect of various fibers on the ablation resistance of poly(diaryloxyphosphazene) elastomer

Poly(diaryloxyphosphazene) elastomer (PDPP) is an alternative and promising thermal insulation material to protect the combustion chamber of solid rocket motors. The hybrid inorganic–organic macromolecule with the backbone of alternating nitrogen and phosphorus atoms has good thermal stability and compatibility for inorganic and organic fillers. This article focused on the effect of inorganic and organic fibers on the ablation resistance of PDPP at slow and fast pyrolysis, which was performed by thermogravimetric analysis and oxyacetylene ablation. Two inorganic fibers (alumina and mullite) and two organic fibers (polyimide and phenolic) were introduced into PDPP elastomer. During the process of slow pyrolysis, two inorganic fibers provided higher char yields due to their higher thermal stability. However, SiC in situ formed on the surface of organic fibers effectively improved the ablation resistance of the composites under the process of fast pyrolysis according to the micromorphology and structure analyses of charred layers. In addition, terminal groups of organic fibers affected the in situ formation of SiC. The phenolic/PDPP composite have a better ablation resistance than the other three composites at fast pyrolysis, owing to more in situ formed SiC on its surface and its higher decomposition activation energy. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48534.     

Hybrid organosiloxane coatings containing epoxide precursors for protecting mild steel against corrosion in a saline medium

Hybrid organic–inorganic materials made from sol–gel precursors can be used as anticorrosion barriers on metal substrates. The modification of epoxy resins with silicones is an interesting approach toward the synthesis of hybrid materials that combine the advantages offered by epoxy resins with those of silicones. In this study, novel hybrid epoxy‐silicon materials were synthesized using sol–gel chemistry and subsequently functionalized with 4,4′‐methylenebis(phenyl isocyanate), incorporating urethane functionality into the final polymer. The study screened five different epoxide precursors for use in the synthesis of the new hybrid materials and optimizing their anticorrosion properties. Spectral characterization confirms the proposed chemical structures of the newly synthesized polymers. The newly developed polymers were painted on mild steel panels, thermally cured, and their thermal, surface morphological, adhesion, and anticorrosion properties were fully characterized. The new coatings were found to have excellent thermal stability and adherence properties to steel surface. The results of corrosion testing on coated steel panels following long‐term immersion in a 3.5 wt % aqueous NaCl medium revealed that the polymer prepared using the epoxide precursor bisphenol A diglycidyl ether provided the best anticorrosion protection property among the synthesized polymers. This could be attributed to the excellent integrity and crosslink density properties in addition to the lack of microdefects in the surface of this coated sample as confirmed by scanning electron microscopy analyses. The newly prepared hybrid coatings reported in this study are very promising as an alternative to toxic chromate‐based coatings. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43947.     

聚合物/新型导热填料复合电介质的研究进展

综述了非常规新型导热粒子如纳米金刚石、碳化物、铁电陶瓷及其他无机功能粒子及其填充聚合物电介质的最新研究进展，重点探讨了新型导热粒子的含量、表面改性、加工方式等对聚合物复合材料的导热及介电性能的影响。介绍和分析了基于有机分子晶体为连续声子传递通路改性聚合物导热性能的研究及机理;在基体树脂内利用无机导热粒子及有机分子晶体可构筑连续的声子导热通路，从而达到降低界面热阻、提高体系热导率的目的。相比传统导热粒子，新型导热粒子在提高绝缘聚合物热导率的同时，还赋予体系其他物理性能如磁性、优良介电性能及储能等性能。     

Synthesis and mechanical properties of novel composites of inorganic polymers (geopolymers) with unidirectional natural flax fibres (phormium tenax)

This study reports the synthesis and mechanical properties of new inorganic polymer (geopolymer) composites unidirectionally reinforced with 4–10 vol.% natural cellulose-based fibres (NZ flax, phormium tenax). The geopolymer matrix was derived from dehydroxylated kaolinite-type clay. The mechanical properties of the fibre-reinforced composites improve with increasing fibre content, achieving ultimate flexural strengths of about 70 MPa at 10 vol.% fibre content. This represents a significant improvement on the flexural strength of the unreinforced geopolymer matrix (about 5.8 MPa), and all the composites show graceful failure, unlike the brittle failure of the matrix. Scanning electron microscopy was used to study the morphology of the fibre-matrix regions and a combination of thermogravimetric analysis (TGA) and thermal shrinkage measurements of these composites suggests that despite the formation of microcracks due to water loss from the geopolymer matrix, the fibres are thermally protected by the matrix up to 400 °C. The flax fibres do not appear to be compromised by the alkaline environment of the matrix, suggesting new possible applications for these low-cost simply prepared construction materials.     

Thermally and mechanically superior hybrid epoxy–silica polymer films via sol–gel method

Hybrid organic–inorganic polymer films composed of an epoxy resin crosslinked with a flexible diamine hardener, and a silica reinforcing phase were produced and their thermo-mechanical properties were determined. Two types of hybrid epoxy–silica polymer films, named EAS-1 and EAS-2, were obtained by hydrolysis and condensation of various amounts of tetraethoxysilane within epoxy network matrix. In EAS-2 hybrids, minor amounts of an amine silane coupling agent were added to enhance interfacial compatibility. FTIR spectroscopy confirmed the formation of organic and inorganic networks. The grafting of amine silane on to the epoxy resin influenced the size and distribution of hyper-branched clusters of silica as indicated by transmission electron microscopy (TEM). The dynamic mechanical and thermal analysis (DMTA) and thermo-gravimetric analysis (TGA) results showed an increase in the storage modulus, the glass-transition temperature, and the thermal stability of hybrid polymer films as compared to the neat matrix. The integration of amine silane coupling agent produced smaller, effectively dispersed silica nanoparticles and consequently improved the ultimate properties of polymer films.     

Application of the thermal energy storage concept to novel epoxy–short carbon fiber composites

For the first time, multifunctional epoxy–short carbon fiber reinforced composites suitable for thermal energy storage technology were developed. Paraffin microcapsules (MC) and short carbon fibers (CFs) were added at different relative amounts to an epoxy matrix, and the microstructural and thermomechanical properties of the resulting materials were investigated. Scanning electron microscopy images of the composites showed a uniform distribution of the capsules within the matrix, with a rather good interfacial adhesion, while the increase in the polymer viscosity at elevated CF and MC amounts caused an increase in the void content. Differential scanning calorimetry tests revealed that melting enthalpy values (up to 60 J/g) can be obtained at high MC concentrations. The mixing and thermal curing of the composites did not lead to breakage of the capsules and to the consequent leakage of the paraffin out of the epoxy matrix. The thermal stability of the prepared composites is not negatively affected by the MC addition, and the temperatures at which the thermal degradation process begins were far above the curing or service temperature of the composites. Flexural and impact tests highlighted that the presence of MC reduces the mechanical properties of the samples, while CF positively contributes to retaining the original stiffness and mechanical resistance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47434.     

氰酸酯树脂/纳米氧化铜复合材料制备及性能

将无机纳米氧化铜(CuO)粒子加入氰酸酯树脂(CE),以有机锡(DBTDL)实现自由基引发,定量加入环氧树脂(E–54)制得CE/CuO系列复合材料。测试了复合材料的力学性能、导热性能和耐酸碱腐蚀性能,讨论了复合材料性能得以改变的原因。结果表明,无机纳米CuO粒子的引入,有利于CE基体树脂的聚合,无机纳米CuO粒子含量为10.0%时,复合材料差示扫描量热峰顶温度由286.3℃降至223.6℃,下降21.9%;无机纳米CuO粒子质量分数为6.0%时,复合材料弯曲强度达到165.36 MPa,较纯CE基体树脂提高了95.34%,复合材料冲击强度达14.18 kJ/m²,较纯CE基体树脂提高了62.24%;随无机纳米CuO粒子含量的增加,复合材料导热性能得以改善,当无机纳米CuO粒子含量为10.0%时,复合材料热导率增大10.24倍;无机纳米CuO粒子引入量为7.0%时,复合材料强碱腐蚀率为0.155%,比纯CE基体树脂下降38.0%;复合材料强酸腐蚀率为0.072%,比纯CE基体树脂下降60.4%。     

Nanoclay and long-fiber-reinforced composites based on epoxy and phenolic resins

In this study, high-performance thermoset polymer composites are synthesized by using both long fibers and nanoclays. Epoxy and phenolic resins, the two most important thermoset polymers, are used as the polymer matrix. The hydrophobic epoxy resin is mixed with surface modified nanoclay, while the hydrophilic phenolic resin is mixed with unmodified raw nanoclay to form nanocomposites. Long carbon fibers are also added into the nanocomposites to produce hybrid composites. Mechanical and thermal properties of synthesized composites are compared with both long-fiber-reinforced composites and polymer- layered silicate composites. The optimal conditions of sample preparation and processing are also investigated to achieve the best properties of the hybrid composites. It is found that mechanical and thermal properties of epoxy and phenolic nanocomposites can be substantially improved. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of epoxy resin modified with alkoxysilane‐ functionalized poly(urethane‐imide) by the sol–gel process

The sol–gel process has been frequently employed for preparation of high performance silica/polymer composites. In this paper, novel sol–gel precursor triethoxysilane‐terminated poly(urethane‐imide) (PUI‐Si), combining the advantages of polyurethane (PU) and polyimide, was synthesized and characterized. Then PUI‐Si was incorporated into the epoxy resin matrix to prepare a series of EP/PUI‐Si organic‐inorganic hybrids through an in situ sol–gel process and crosslinking reactions. The thermal stability of EP/PUI‐Si hybrids was evaluated by thermogravimetric analysis and the results show that the PUI‐Si could significantly improve the thermal properties of epoxy resin. The initial decomposition temperature of composites with 50 wt% PUI‐Si reached 347.1 °C, 157.3 °C higher than that of neat epoxy resin. Furthermore, the tensile strength and breaking elongation can also be clearly improved by adding a suitable amount of PUI‐Si. Similarly, the water contact angle increased to 97.4° with 70 wt% PUI‐Si, showing a hydrophobic surface. The morphology was investigated by transmission electron microscopy and the results reveal that the silica particles are smaller than 20 nm and have a strong interaction with the epoxy resin matrix, resulting in the above‐mentioned high performance properties. Copyright © 2011 Society of Chemical Industry     

环氧树脂基介电复合材料的制备和性能研究

以环氧树脂(EP)为基体树脂、经硅烷偶联剂改性后的压电陶瓷钛酸钡(BaTiO3)为增强填料,采用浇铸法制备了有机/无机介电复合材料。研究了填料用量对复合材料介电性能、力学性能和热性能的影响。实验结果表明,BaTiO3能显著提高材料的介电常数,当w(BaTiO3)=60%时,复合材料的介电常数为23.6,比纯EP的介电常数(4.0)提高了近6倍,而且复合材料的介电常数受频率影响较小,具有较好的频率稳定性;随着BaTiO3含量的增加,材料的弯曲强度和冲击强度都呈先增后减的趋势,最大弯曲强度和冲击强度分别为123.8 MPa和26.3 kJ/m2;材料的热稳定性研究表明,材料的起始热分解温度随着BaTiO3含量的增加而提高,材料的耐热性能得到改善。     

Properties of Geopolymer Composites Reinforced with Basalt Chopped Strand Mat or Woven Fabric

Geopolymers or polysialates are inorganic polymeric, ceramic‐like materials composed of alumina, silica, and alkali metal oxides that can be made without any thermal treatment. Additions of reinforcing phases vastly improve the mechanical properties and high‐temperature stability of the geopolymer. The processing and mechanical properties of both chopped strand mat as well as 2‐D woven fabric‐reinforced potassium geopolymer composites have been evaluated. Hand lay‐up and hydraulic press processing methods were used to produce composite panels. The room‐temperature tensile and flexural strength of chopped strand mat composites was 21.0 ± 3.1 and 31.7 ± 4.4 MPa, respectively, while those of basalt weave‐reinforced geopolymer composites reached 40.0 ± 5.9 and 45.2 ± 9.3 MPa, respectively. Composite microstructures were examined using optical microscopy as well as scanning electron microscopy (SEM). Mass, volume, and porosity fractions were also determined. The effect of high‐temperature treatments at 25°C, 300°C, 600°C, and 800°C were analyzed. Finally, Weibull statistical analysis was performed, which showed an increase in reliability when a reinforcement phase was added to K‐geopolymer.     

Thermal and ablative properties of binary carbon nanotube and nanodiamond reinforced carbon fibre epoxy matrix composites

The thermal and ablative properties of carbon nanotube (CNT) and nanodiamond (ND) reinforced carbon fibre epoxy matrix composites were investigated by simulating shear forces and high temperatures using oxyacetylene torch apparatus. Three types of composite specimens—(i) carbon fibre epoxy matrix composite (CF/Epoxy), (ii) carbon fibre epoxy matrix composite containing 0.1 wt-% CNTs and 0.1 wt-% NDs, and (iii) carbon fibre epoxy matrix composite containing 0.2 wt-% CNTs and 0.2 wt-% NDs—were explored. The ablative response of composites was studied through pre- and post-burnt SEM analysis and further related with thermogravimetric analysis, weight loss profile and thermal conductivity measurements. The novel nanofiller composites showed marked improvement in their thermal and ablative properties. A 22% and 30% increase in thermal conductivity was observed for composites containing 0.1 wt-% CNTs/0.1 wt-% NDs and 0.2 wt-% CNTs/0.2 wt-% NDs respectively. These nanofillers also improved the thermal stability of thermosetting epoxy matrix, and an increase of 13% and 20% was recorded in the erosion rate of composites containing 0.1 wt-% CNTs/0.1 wt-% NDs and 0.2 wt-% CNTs/0.2 wt-% NDs respectively. This improvement is due to the increased char yield produced by the increase in the loading of nanofillers, i.e. CNTs and NDs. Insulation index and insulation to density performance have also been improved due to increased thermal conductivity and char yield.     

Preparation and characterization of organic–inorganic hybrid composites based on multiepoxy silsesquioxane and cyanate resin

A multiepoxy cubic silsesquioxane was prepared by the hydrolysis and polycondensation of trifunctional monomer (γ‐glycidoxypropyl)trimethoxysilane in a solvent mixture of methyl isobutyl ketone and anhydrous ethanol with a tetraethyl ammonium hydroxide aqueous solution acting as the catalyst, and it was successfully introduced into a cyanate resin and formed highly crosslinked organic–inorganic hybrid composites on a molecular level via a mutual cure reaction. The properties of the multiepoxy cubic silsesquioxane/bisphenol A dicyanate ester resin composites were investigated, and the results showed that introducing the cubic silsesquioxane unit into the cyanate resin successfully modified the local structure of the molecule, made the chain more rigid, restricted the chain mobility, and eventually improved the thermal stability and flame retardancy of the resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3652–3658, 2006     

In situ inorganic foams prepared from various clays at low temperature

Geopolymers are amorphous three-dimensional aluminosilicate binder materials that may be synthesized at room or slightly higher temperature by alkaline activation of aluminosilicates obtained from industrial wastes, calcined clays, natural minerals or mixtures of two or more of these materials. Among the different families of geopolymers, those based on potassium show modified thermal and mechanical properties due to the larger size of the potassium ion compared to sodium. This work deals with the preparation of geopolymer foams based on potassium silicate, industrial waste and various types of clays (kaolin, metakaolin, illite or montmorillonite). The influence of the clays used is assessed in terms of clay reactivity using structural data determined by FTIR spectroscopy, thermal analysis, XRD, and SEM characterizations.In situ geopolymer foam was obtained from all of the clays but its characteristics depended on the nature of the clays, including their structural alteration and chemistry. The extent of destruction of the clay structure was partial for kaolinite but was greater for illite, followed by montmorillonite. These inorganic foams have a potential use in housing construction, since they display thermal insulating properties.     

Structure–property relationship in epoxy‐silica hybrid nanocomposites: The role of organic solvent in achieving silica domains

The thermo‐mechanical properties of a series of epoxy‐silica hybrid composites prepared through sol–gel process are evaluated in a manner that the effect of organic solvent on the formation of silica domains is highlighted. By means of infrared spectroscopy, small‐angle X‐ray scattering, scanning electron microscope, dynamic mechanical thermal analysis, and thermo‐gravimetric analyzer, the specimens were morphologically studied varying the type of organic solvent. Among polar and nonpolar solvents incorporated by the organic–inorganic hybrid system, a mixture of xylene and ethanol (3:1) was properly comparable with tetrahydrofuran (THF) solvent regarding appearance and thermo‐mechanical characteristics. Enhanced thermal stability and modulus was observed upon increasing solvent content. Also, a proper dispersion of silica domains throughout the epoxy was seen in the case that the xylene/ethanol mixture or THF served as solvent. It is to be emphasized that the assigned mixture is environmentally better than that of THF. J. VINYL ADDIT. TECHNOL., 21:305–313, 2015. © 2014 Society of Plastics Engineers     

Synthesis of fluorinated/methacrylated epoxy based oligomers and investigation of its performance in the UV curable hybrid coatings

Organic–inorganic hybrid coatings based on fluorinated/methacrylated soybean oil and bisphenol A/F epoxy methacrylate were obtained by combining photopolymerization and sol–gel process. Hard and transparent hybrid coatings were prepared on polycarbonate panels and their physical and mechanical properties such as gel content, hardness, adhesion, gloss, contact angle as well as tensile strength were measured. Results from the mechanical measurements showed that the properties of hybrid coatings improved with the increase in fluorine and sol–gel precursor contents. Thermo gravimetric analysis results demonstrated that fluorine and silica incorporations significantly enhanced the thermal oxidative stability of the hybrid coating materials. The surface morphology was also characterized by scanning electron microscopy (SEM). SEM studies indicated that inorganic particles were dispersed homogenously throughout the organic matrix.     

Preparation and anticorrosive properties of hybrid coatings based on epoxy‐silica hybrid materials

A series of sol‐gel derived organic–inorganic hybrid coatings consisting of organic epoxy resin and inorganic silica were successfully synthesized through sol‐gel approach by using 3‐glycidoxypropyl‐trimethoxysilane as coupling agent. Transparent organic–inorganic hybrid sol‐gel coatings with different contents of silica were always achieved. The hybrid sol‐gel coatings with low silica loading on cold‐rolled steel coupons were found much superior improvement in anticorrosion efficiently. The as‐synthesized hybrid sol‐gel materials were characterized by Fourier‐transformation infrared spectroscopy, ²⁹Si‐nuclear magnetic resonance spectroscopy and transmission electron microscopy. Effects of the material composition of epoxy resins along with hybrid materials on the thermal stability, Viscoelasticity properties and surface morphology were also studied, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009