Co-reporter:Dechao Hu, Bangchao Zhong, Zhixin Jia, Jing Lin, Maolin Liu, Yuanfang Luo, Demin Jia
Materials Letters 2017 Volume 188() pp:327-330
Publication Date(Web):1 February 2017
DOI:10.1016/j.matlet.2016.08.144
•A novel hybrid filler (HNTs-silica) was fabricated by electrostatic assembly.•HNTs was uniformly adsorbed by the silica.•The silica nano-protrusions on nanotubes surface enlarge the specific area of HNTs.A novel halloysite nanotubes (HNTs)/silica hybrid filler (HNTs-silica) was successfully fabricated by coassembly between negatively charged HNTs and positively charged silica particles modified with 3-triethoxysilylpropylamine in deionized water. In this unique hybrid architecture, it was found that HNTs was uniformly adsorbed by the silica (about 20 wt%) particles, which can suppress the aggregation of HNTs and silica and effectively enlarge the specific surface area of HNTs through the silica nano-protrusions on the surface of the nanotubes, making HNTs-silica ideally suited as a novel hybrid filler and opening up new opportunities for the preparation of high performance polymer nanocomposites.
Co-reporter:Lijuan Chen, Zhixin Jia, Yuhan Tang, Lianghui Wu, Yuanfang Luo, Demin Jia
Composites Science and Technology 2017 Volume 144(Volume 144) pp:
Publication Date(Web):26 May 2017
DOI:10.1016/j.compscitech.2016.11.005
A high reactive sulfocompound, sulfur monochloride, was chemically supported onto the surface of silica (silica-s-S2Cl2) by the reaction between chloric atom and silanol hydroxyl to obtain a novel vulcanizing agent, silica supported sulfur monochloride (silica-s-S2Cl2). Silica-s-S2Cl2 can be homogeneously dispersed in SBR matrix as a modifier and cure the styrene-butadiene rubber (SBR) without sulfur as a novel high-efficiency vulcanizing agent. The sulfur and Bis[3-(triethoxysilyl)propyl] Tetrasulfide (TESPT) silane coupling agent vulcanized SBR composites were mainly polysulfide crosslinks, on the contrary, the vulcanization by silica-s-S2Cl2 give priority to the mono- and disulfides crosslinks. The highlight of this work lies in the fact that apparent improvement has been achieved by novel and high efficient functional particles due to the silica surface supported with sulfur monochloride, which may open up new opportunities for the preparation of functional nano-fillers in rubber industry.
Co-reporter:
Journal of Applied Polymer Science 2017 Volume 134(Issue 14) pp:
Publication Date(Web):2017/04/10
DOI:10.1002/app.44605
ABSTRACTEpoxidized natural rubber (ENR)–silica hybrids without any other additives were prepared by an open-mill mixing method at room temperature. The curing characteristics, crosslinking density, mechanical properties, and dynamical mechanical properties were investigated. The results indicate that the ENR–silica hybrid materials could be cured with silica as a crosslinking and reinforcing agent. Attenuated total reflection–Fourier transform infrared spectroscopy and solid-state 13C-NMR spectroscopy exposed the characteristics of the interfacial interaction in the hybrids and confirmed the existence of chemical bonds and hydrogen bonds between the epoxy group and SiOH. Scanning electron microscopy illustrated a good dispersion of silica in the ENR matrix. Meanwhile, the modulus at 100% elongation of the hybrid reached 9.64 MPa when 100-phr silica was loaded; a similar trend was observed for the hardness. Finally, our findings might extend the concept of rubber curing and open a new space for making an environmentally friendly rubber composite. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44605.
Co-reporter:Bangchao Zhong, Jing Lin, Maolin Liu, Zhixin Jia, Yuanfang Luo, Demin Jia, Fang Liu
Polymer Degradation and Stability 2017 Volume 141(Volume 141) pp:
Publication Date(Web):1 July 2017
DOI:10.1016/j.polymdegradstab.2017.05.009
Halloysite nanotubes (HNTs) loaded poly(1,2-dihydro-2,2,4-trimethyl-quinoline) (RD), HNTs-RD, was successfully prepared and added as filler and antioxidant to form natural rubber (NR) composites. The thermo-oxidative aging behaviour of NR composites and the migration of the loaded RD were investigated by mechanical testing, X-ray photoelectron spectroscopy, differential scanning calorimetry and energy dispersive spectroscopy. For the composites with only HNTs-RD as antioxidant, due to the changed conformation and mobility of the immobilized rubber chains approaching HNTs-RD surface, it took a long time for the released RD from the HNTs lumen to migrate into the free rubber phase, during which the free rubber chains were highly oxidized, leading to the poor thermo-oxidative stability of the rubber composites. For the NR composites with HNTs-RD and free RD, it was found that the free rubber chains were protected against oxygen and heat by the free RD. Besides, the released RD steadily migrated and dispersed into the free rubber phase, ensuring the relatively stable and high concentration of total antioxidant in the free rubber phase for a long time, leading to the much better thermo-oxidative stability compared to the rubber composites with only HNTs-RD. In general, this work is believed to provide better guidance for the preparation of rubber composites with long-term aging resistance.
Co-reporter:Bangchao Zhong, Huanhuan Dong, Yuanfang Luo, Dongqiao Zhang, Zhixin Jia, Demin Jia, Fang Liu
Composites Science and Technology 2017 Volume 151(Volume 151) pp:
Publication Date(Web):20 October 2017
DOI:10.1016/j.compscitech.2017.08.019
Preparation of elastomer/graphene composites with high aging resistance and thermal conductivity is of great significance for constructing many advanced materials, such as solar cells and light emitting diodes. Herein, an efficient one-step approach was developed to simultaneously reduce and functionalize GO via N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine (antioxidant 4020). It was found that oxygen-containing groups in GO were effectively removed and sp2 carbon network was restored after reduction. In addition, antioxidant molecules (∼10 wt%) were chemically immobilized on the surface of reduced GO (G-4020). The immobilized antioxidant not only showed much better antimigratory efficiency than free antioxidant in styrene-butadiene rubber (SBR), but also prevented the restacking of G-4020. Consequently, apart from the enhanced mechanical strength, SBR/G-4020 composites exhibited exceptionally high long-term thermo-oxidative aging resistance compared with SBR/r-GO/4020 composites (SBR with hydrazine hydrate reduced GO and 4020). Moreover, the thermal conductivity of SBR/G-4020 composites was superior to that of SBR/r-GO/4020 composites due to the reduced interfacial thermal resistance. Potentially, one-step reaction and high-efficiency make the approach of using antioxidants a promising strategy for the eco-friendly reduction and functionalization of GO, which may offer a new path to construct high-performance elastomer/graphene composites.
Co-reporter:Bangchao Zhong, Zhixin Jia, Dechao Hu, Yuanfang Luo, Baochun Guo, Demin Jia
Applied Surface Science 2016 Volume 366() pp:193-201
Publication Date(Web):15 March 2016
DOI:10.1016/j.apsusc.2016.01.084
Highlights
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Vulcanization accelerant was used to modify halloysite nanotubes (HNTs).
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The modified HNTs reduced the activation energy of vulcanization.
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Strong filler–rubber interaction was achieved in rubber/modified HNTs composites.
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The modified HNTs exhibited excellent reinforcement effect on rubber.
Co-reporter:Zhixin Jia;Qiwen Luo;Song Wang;Yongjun Chen;Xiangyang Zhou;Mingxian Liu;Yuanfang Luo;Demin Jia
Journal of Applied Polymer Science 2016 Volume 133( Issue 7) pp:
Publication Date(Web):
DOI:10.1002/app.43014
ABSTRACT
A solid-phase preparation method is applied to the synthesis of a novel supported rubber antioxidant, silica–supported 2,2′-methylenebis(6-tert-butyl-4-methyl-phenol) (SiO2-2246), by directly reacting 2,2′-methylenebis (6-tert-butyl-4-methyl-phenol)(antioxidant 2246) with silica. FTIR, Raman spectroscopy and TGA confirm that the antioxidant 2246 is chemically bonded on the surface of the silica particles. The SEM observation shows that the SiO2-2246 is homogeneously dispersed in the styrene-butadiene rubber (SBR) matrix. The results of the apparent activation energy and the attenuated total reflectance infrared spectrometry indicate that the antioxidative efficiency of the SiO2-2246 in SBR is superior to the corresponding low-molecular-weight 2246. The thermal oxidative stability of the SBR/SiO2-2246 composites is much higher than that of the SBR/SiO2/2246 composites by comparing their mechanical properties retentions and crosslinking densities. Additionally, the advantages of SiO2-2246 also include low migration, low volatility, and low pollution. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43014.
Co-reporter:Zhixin Jia, Tiwen Xu, Shuyan Yang, Yuanfang Luo, Demin Jia
Polymer Testing 2016 Volume 54() pp:29-39
Publication Date(Web):September 2016
DOI:10.1016/j.polymertesting.2016.06.022
SBR/unmodified HNT composites were prepared by open-mill mixing and vulcanization. The results showed that HNT could decrease the scorch and optimum cure time, and play a significant role in reinforcing SBR vulcanizates. Mechano-chemical grafting at the interface between HNT and SBR was investigated by using infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), solid-state 13C NMR spectra and bonded rubber content, etc. The results showed the shearing force during the mixing process can impel the grafting reaction of SBR onto the surfaces of HNT, which leads to interfacial chemical bonding between phenyl’s α-H of SBR and the surface groups of HNT with Si-OH or Al-OH. Thus, the mechanical properties of the composites were significantly enhanced.
Co-reporter:Tiwen Xu, Zhixin Jia, Yuanfang Luo, Demin Jia, Zheng Peng
Applied Surface Science 2015 Volume 328() pp:306-313
Publication Date(Web):15 February 2015
DOI:10.1016/j.apsusc.2014.12.029
Highlights
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Substantiate the ring open reaction between Si-OH of silica and epoxy groups of ENR.
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ENR can act as a bridge between NR and silica to enhance the interfacial interaction.
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As a modifier, ENR gets the potential to be used in the tread of green tire for improving the wet skid resistance apparently.
Co-reporter:Bangchao Zhong, Zhixin Jia, Yuanfang Luo, Demin Jia
Materials Letters 2015 Volume 145() pp:41-43
Publication Date(Web):15 April 2015
DOI:10.1016/j.matlet.2015.01.069
•Silica was chemically modified with N-cyclohexyl-2-benzothiazole sulfenamide (CZ).•Enhanced filler–rubber interaction was achieved in SBR/CZ modified silica composites.•CZ modified silica exhibits excellent reinforcement effect on SBR.Accelerator N-cyclohexyl-2-benzothiazole sulfenamide (CZ) was chemically bonded onto the surface of (3-glycidoxypropyl)trimethoxysilane modified silica (m-silica) to obtain CZ modified silica (silica-s-CZ). There was a much thicker immobilized polymer layer approaching the surface of silica-s-CZ than that approaching the surface of m-silica, indicating an enhanced filler–styrene–butadiene rubber (SBR) interaction in the SBR/silica-s-CZ composites. Owing to the improved modification effect, the tensile strength and tear strength of SBR/silica-s-CZ composites are much higher than those of SBR/m-silica composites containing equivalent accelerator component. The highlight of this work lies in the fact that apparent improvement has been achieved by a novel surface modification method of silica with rubber accelerator, which is relatively easy to realize and manipulate compared to other sophisticated methods.
Co-reporter:Cong Liu;Yuanfang Luo;Shuangquan Li;Dong Huang;Demin Jia
Polymer Composites 2014 Volume 35( Issue 5) pp:856-863
Publication Date(Web):
DOI:10.1002/pc.22729
Poly(vinyl chloride) (PVC)/halloysite nanotubes (HNTs) nanocomposites were synthesized by in situ suspension polymerization of vinyl chloride (VC) in the presence of HNTs. The microstructure, mean particle size, and cold plasticizer absorption (CPA) of these resins and the rheological property, mechanical properties and thermal properties of PVC/HNTs nanocomposites were investigated. The results show that the mean particle size, the degree of porosity, and the CPA of PVC resins decrease with the addition of HNTs. The plasticization time and the equilibrium torque of PVC/HNTs nanocomposites are found to be longer and higher than that for the neat PVC. HNTs are uniformly distributed in the PVC matrix and effective in toughening and stiffening PVC nanocomposites when the addition of HNTs is 4.0 wt% or less. The glass transition temperatures of the PVC/HNTs nanocomposites were nearly identical to that of pure PVC. POLYM. COMPOS., 35:856–863, 2014. © 2013 Society of Plastics Engineers
Co-reporter:Bangchao Zhong, Qifeng Shi, Zhixin Jia, Yuanfang Luo, Yongjun Chen, Demin Jia
Polymer Degradation and Stability 2014 110() pp: 260-267
Publication Date(Web):
DOI:10.1016/j.polymdegradstab.2014.09.008
Co-reporter:Shu-yan Yang;Zhi-xin Jia 贾志欣;Lan Liu;Wei-wen Fu
Chinese Journal of Polymer Science 2014 Volume 32( Issue 8) pp:1077-1085
Publication Date(Web):2014 August
DOI:10.1007/s10118-014-1486-x
A novel TU derivative, N-phenyl-N′-(γ-triethoxysilane)-propyl thiourea (STU), is prepared and its binary accelerator system is investigated in detail. Compared to the control references, the optimum curing time of NR compounds with STU is the shortest, indicating a more nucleophilic reaction occurs. The Py-GC/MS results present that the phenyl isothiocyanate fragment still remains in the NR/STU compounds with or without extracting treatment, but no silane segment can be found in the vulcanizate with extracting treatment. Vibrations of C=S, NH and aromatic ring in FTIR experiments and a new methyne carbon peak, as well as the peaks of phenyl group of STU, in the solid state 13C-NMR experiments are found in the NR/STU vulcanizate with extracting treatment. Moreover, the crosslinking density of vulcanizates with STU evolves to lower level, indicating the sulfur atom of STU does not contribute to the sulfur crosslinking. Therefore, a new vulcanization kinetic mechanism of STU is propounded that the thiourea groups can graft to the rubber main chains as pendant groups by chemical bonds during the vulcanization process, which is in accordance with the experimental observations quite well.
Co-reporter:Bangchao Zhong, Zhixin Jia, Dechao Hu, Yuanfang Luo, Demin Jia, Fang Liu
Composites Part A: Applied Science and Manufacturing (May 2017) Volume 96() pp:
Publication Date(Web):May 2017
DOI:10.1016/j.compositesa.2017.02.016
To modify the filler surface and simultaneously elude issues related to the physical loss by migration of rubber additives, the concept of “supported rubber additives” was proposed and vulcanization accelerator 2-benzothiazolethiol (M) was chemically grafted onto the surface of silane modified silica (m-silica) to prepare silica-supported vulcanization accelerator (silica-s-M). Silica-s-M could be homogeneously dispersed into styrene-butadiene rubber (SBR). Besides, the interfacial interaction between silica-s-M and SBR was significantly enhanced, which was confirmed by the constrained rubber chains approaching the filler surface. Consequently, silica-s-M effectively reduced the activation energy of vulcanization and SBR/silica-s-M composites showed much better mechanical properties than SBR/m-silica and SBR/silica composites containing equivalent accelerator component. From this work, it is envisioned that this methodology for the surface treatment of silica to prepare supported accelerator may be extended for other nanofillers and functional rubber additives, which may be promising for the preparation of high-performance and functional rubber/nanofiller composites.
Co-reporter:Bangchao Zhong, Zhixin Jia, Yuanfang Luo, Demin Jia, Fang Liu
Polymer Testing (April 2017) Volume 58() pp:31-39
Publication Date(Web):April 2017
DOI:10.1016/j.polymertesting.2016.12.010
Co-reporter:Jing Lin, Bangchao Zhong, Zhixin Jia, Dechao Hu, Yong Ding, Yuanfang Luo, Demin Jia
Applied Surface Science (15 June 2017) Volume 407() pp:
Publication Date(Web):15 June 2017
DOI:10.1016/j.apsusc.2017.02.149
•Nano hybrid was prepared by in-situ growth of silica onto HNTs surface.•Nanosilica was chemically bonded onto the surface of HNTs.•Strong interface strength between nano hybrid and polyester was achieved.•The nano hybrid exhibited excellent toughening effect on polyester.Silica nanoparticles was in-situ grown on the surface of halloysite nanotubes (HNTs) by a facile one-step approach to prepare a unique nano-structured hybrid (HNTs-g-Silica). The structure, morphology and composition of HNTs-g-Silica were investigated. It was confirmed that silica nanoparticles with the diameter of 10–20 nm were chemically grafted through SiO bonds and uniformly dispersed onto the surface of HNTs, leading to the formation of nano-protrusions on the nanotube surface. Due to the significantly improved interface strength between HNTs-g-Silica and polymer matrix, HNTs-g-Silica effectively toughened unsaturated polyester resin (UPE) and endowed UPE with superior thermal stability compared to HNTs. Based on the unique hybrid architecture and the improved properties of UPE nanocomposites, it is envisioned that HNTs-g-Silica may be a promising filler for more high performance and functional polymers composites and the fabrication method may have implications in the synthesis of nano hybrid materials.
