Toughening of cycloaliphatic epoxy resin by multiwalled carbon nanotubes

The toughness of cycloaliphatic epoxy resin 3,4‐epoxycyclohexylmethyl‐3′,4′‐epoxycyclohexane carboxylate (ERL‐4221) has been improved by using multiwalled carbon nanotubes (MWCNTs) treated by mixed acids. The MWCNT/ERL‐4221 composites were characterized by Raman spectroscopy and their mechanical properties were investigated. A significant increase in the tensile strength of the composite from 31.9 to 55.9 MPa was obtained by adding only 0.05 wt % of MWCNTs. And a loading of 0.5 wt % MWCNTs resulted in an optimum tensile strength and cracking energy, 62.0 MPa and 490 N cm, respectively. Investigation on the morphology of fracture surface of the composites by field emission scanning electron microscopy demonstrated the crack pinning‐front bowing and bridging mechanisms of toughening. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of MWCNTs/poly(acrylonitrile‐ styrene‐butadiene)/epoxy hybrid composites

Poly(acrylonitrile‐styrene‐butadiene) (ABS) was used to modify diglycidyl ether of bisphenol‐A (DGEBA) type epoxy resin, and the modified epoxy resin was used as the matrix for making multiwaled carbon tubes (MWCNTs) reinforced composites and were cured with diamino diphenyl sulfone (DDS) for better mechanical and thermal properties. The samples were characterized by using infrared spectroscopy, pressure volume temperature analyzer (PVT), thermogravimetric analyzer (TGA), dynamic mechanical analyzer (DMA), thermo mechanical analyzer (TMA), universal testing machine (UTM), and scanning electron microscopy (SEM). Infrared spectroscopy was employed to follow the curing progress in epoxy blend and hybrid composites by determining the decrease of the band intensity due to the epoxide groups. Thermal and dimensional stability was not much affected by the addition of MWCNTs. The hybrid composite induces a significant increase in both impact strength (45%) and fracture toughness (56%) of the epoxy matrix. Field emission scanning electron micrographs (FESEM) of fractured surfaces were examined to understand the toughening mechanism. FESEM micrographs reveal a synergetic effect of both ABS and MWCNTs on the toughness of brittle epoxy matrix. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

增强增韧PET工程塑料用玻璃纤维的表面处理

研制出两种适用于增强增韧ＰＥＴ工程塑料用玻璃纤维的表面处理剂。研究了表面处理对玻璃纤维增强ＰＥＴ体系界面张力、界面粘结、力学性能及结晶行为的影响。结果表明，虽然双官能团环氧树脂水乳液和水溶性环氧树脂两种表面处理剂均适合于玻璃纤维增强ＰＥＴ体系，但前者对ＰＥＴ／玻璃纤维复合体系的浸润性、界面粘结和增强增韧效果优于后者。     

Synergetic effects of graphene platelets and carbon nanotubes on the mechanical and thermal properties of epoxy composites

A remarkable synergetic effect between the multi-graphene platelets (MGPs) and multi-walled carbon nanotubes (MWCNTs) in improving the mechanical properties and thermal conductivity of epoxy composites is demonstrated. Stacking of individual two-dimensional MGPs is effectively inhibited by introducing one-dimensional MWCNTs. Long and tortuous MWCNTs can bridge adjacent MGPs and inhibit their aggregation, resulting in a high contact area between the MGP/MWCNT structures and the polymer matrix. Scanning electron microscope images of the fracture surfaces of the epoxy matrix showed that MWCNT/MGP hybrid nanofillers exhibited higher solubility and better compatibility than individual MWCNTs and MGPs did. The tensile strength of GD400-MWCNT/MGP/epoxy composites was 35.4% higher than that of the epoxy alone, compared to only a 0.9% increase in tensile strength for MGP/epoxy composites over the epoxy compound. Thermal conductivity increased by 146.9% using GD400-MWCNT/MGP hybrid fillers and 23.9% for MGP fillers, compared to non-derivatised epoxy.     

A comparison of the effects of multi-wall and single-wall carbon nanotube additions on the properties of zirconia toughened alumina composites

The use of multi-wall carbon nanotubes (MWCNTs) or single-wall carbon nanotubes (SWCNTs) as filler in ceramic matrices could create composites with exceptional mechanical properties. We have prepared dense monolithic alumina (Al₂O₃) and zirconia-toughened alumina (ZTA) composites with additions of 0.01 wt% of MWCNTs or 0.01 wt% of SWCNTs by conventional sintering and have demonstrated that the mechanical properties depend on (a) the distribution of CNTs in the matrix and (b) the interaction between the ceramic phases and CNTs. The fracture toughness of Al₂O₃ ceramics reinforced with SWCNTs was significantly better than those reinforced with MWCNTs. However, fracture toughness in MWCNT-reinforced ZTA increased 41% over ZTA free of the toughening agent and 44% over ZTA reinforced with SWCNTs. A well dispersed and small amount of MWCNTs was enough to produce an increase of fracture toughness in ZTA composites.     

Fabrication and mechanical properties of Al2O3–TiC ceramic composites synergistically reinforced with multi-walled carbon nanotubes and graphene nanoplates

In this study, Al₂O₃–TiC composites synergistically reinforced with multi-walled carbon nanotubes (MWCNTs) and graphene nanoplates (GNPs) were prepared via spark plasma sintering (SPS). The effects of the MWCNT and GNP contents on the phase composition, mechanical properties, fracture mode, and toughening mechanism of the composites were systematically investigated. The experimental results indicated that the composite grains became more refined with the addition of MWCNTs and GNPs. The nanocomposites presented high compactness and excellent mechanical properties. The composite with 0.8 wt% MWCNTs and 0.2 wt% GNPs presented the best properties of all analysed specimens, and its relative density, hardness, and fracture toughness were 97.3%, 18.38 ± 0.6 GPa, and 9.40 ± 1.6 MPa m^1/2, respectively. The crack deflection, bridging, branching, and drawing effects of MWCNTs and GNPs were the main toughening mechanisms of Al₂O₃–TiC composites synergistically reinforced with MWCNTs and GNPs.     

Hard and tough carbon nanotube-reinforced zirconia-toughened alumina composites prepared by spark plasma sintering

It is demonstrated that 0.1 wt% of multi-walled carbon nanotubes (MWCNTs) or single-walled carbon nanotubes (SWCNTs) added to zirconia toughened alumina (ZTA) composites is enough to obtain high hardness and fracture toughness at indentation loads of 1, 5, and 10 kg. ZTA composites with 0.01 and 0.1 wt% of MWCNTs or SWCNTs were densified by spark plasma sintering (SPS) at 1520 °C resulting in a higher hardness and comparable fracture toughness to the ZTA matrix material. The observed toughening mechanisms include crack deflection, pullout of CNTs as well as bridged cracks leading to improved fracture toughness without evidence of transformation toughening of the ZrO₂ phase. Scanning electron microscopy showed that MWCNTs rupture by a sword-in-sheath mechanism in the tensile direction contributing to an additional increase in fracture toughness.     

环氧树脂/ABS复合材料的制备及性能表征

以环氧树脂为基体,苯乙烯-丙烯腈-丁二烯（ABS）树脂为增韧剂,制备了环氧树脂/ABS复合材料,讨论了增韧剂对复合材料的热性能和机械性能的影响。结果表明,ABS的添加可提高复合材料的断裂韧性。扫描电镜结果显示,基体的剪切屈服和橡胶颗粒的微孔洞是ABS增韧环氧树脂的主要增韧机理。     

Mechanical,thermal, and viscoelastic response of novel in situ CTBN/POSS/epoxy hybrid composite system

The present study focuses on the preparation of a novel hybrid epoxy nanocomposite with glycidyl polyhedral oligomeric silsesquioxane (POSS) as nanofiller, carboxyl terminated poly(acrylonitrile‐co‐butadiene) (CTBN) as modifying agent and diglycidyl ether of bisphenol A (DGEBA) as matrix polymer. The reaction between DGEBA, CTBN, and glycidyl POSS was carefully monitored and interpreted by using Fourier transform infrared (FTIR) and differential scanning calorimetry (DSC). An exclusive mechanism of the reaction between the modifier, nanofiller, and the matrix is proposed herein, which attempts to explains the chemistry behind the formation of an intricate network between POSS, CTBN, and DGEBA. The mechanical properties, such as tensile strength, and fracture toughness, were also carefully examined. The fracture toughness increases for epoxy/CTBN, epoxy/POSS, and epoxy/CTBN/POSS hybrid systems with respect to neat epoxy, but for hybrid composites toughening capability of soft rubber particles is lost by the presence of POSS. Field emission scanning electron micrographs (FESEM) of fractured surfaces were examined to understand the toughening mechanism. The viscoelastic properties of epoxy/CTBN, epoxy/POSS, and epoxy/CTBN/POSS hybrid systems were analyzed using dynamic mechanical thermal analysis (DMTA). The storage modulus shows a complex behavior for the epoxy/POSS composites due to the existence of lower and higher crosslink density sites. However, the storage modulus of the epoxy phase decreases with the addition of soft CTBN phase. The T_g corresponding to epoxy‐rich phase was evident from the dynamic mechanical spectrum. For hybrid systems, the T_g is intermediate between the epoxy/rubber and epoxy/POSS systems. Finally, TGA (thermo gravimetric analysis) studies were employed to evaluate the thermal stability of prepared blends and composites. POLYM. COMPOS., 37:2109–2120, 2016. © 2015 Society of Plastics Engineers     

Enhancement of Interlaminar Fracture Toughness of Carbon Fiber/Epoxy Composites Using Silk Fibroin Electrospun Nanofibers

In this article, the effect of silk fibroin nanofibers as a toughening agent of carbon fiber/fabric-reinforced epoxy composites is experimentally investigated. The composites showed up to 30% improvement in Mode II fracture toughness at 0.1 wt% of silk fibroin nanofibers content. The scanning electron microscopy observation revealed that the fracture surface of silk fibroin nanofibers modified carbon fiber/fabric-reinforced epoxy composites appearance of the broken fiber and the ductile-like matrix cracks showed a good adhesion between matrix resin and carbon fibers, which are reasons for the enhanced mode II interlaminar fracture toughness.     

Preparation and properties of multi‐walled carbon nanotubes/carbon fiber/epoxy composites

Multi‐walled carbon nanotubes/carbon fiber (MWCNTs/CF) hybrid fillers are employed to prepare MWCNTs/CF/epoxy composites. Results reveal that a great improvement of the thermal conductivities of the epoxy composites with the addition of MWCNTs/CF hybrid fillers, and the thermal conductivity of the MWCNTs/CF/epoxy composites is 1.426 W/mK with 8 vol% treated MWCNTs/CF hybrid fillers (5 vol% MWCNTs + 3 vol% CF). Both the flexural and impact strength of the MWCNTs/CF/epoxy composites are increased firstly, but decreased with the excessive addition of MWCNTs. The flexural and impact strength of the MWCNTs/epoxy composites are optimal with 2 vol% MWCNTs. For a given MWCNTs/CF hybrid fillers loading, the surface treatment of MWCNTs/CF hybrid fillers can further increase the thermal conductivities and mechanical properties of the MWCNTs/CF/epoxy composites. POLYM. COMPOS., 35:2150–2153, 2014. © 2014 Society of Plastics Engineers     

Mode II interlaminar fracture behavior of carbon bead‐filled epoxy/glass fiber hybrid composite

To investigate the effect of including carbon beads on the mechanical properties of epoxy resin, the fracture toughness of carbon bead‐filled epoxy was earlier evaluated using a CT (compact tension) specimens and Mode I fracture toughness was observed. Based on those results, in this study, the Mode II interlaminar fracture toughness of carbon bead filled epoxy/glass fiber hybrid composites was evaluated using end notch flexure (ENF) specimens. The hybrid composites showed increased Mode II interlaminar fracture toughness. The optimal bead volume fraction was around 15%.     

环氧树脂/蒙脱土纳米复合材料的性能及增韧机理

将有机蒙脱土添加到环氧树脂中,制备环氧树脂/纳米复合材料,考察复合材料的力学和热学性能,研究发现,5%的添加量可以使环氧树脂的冲击、断裂强度得到大幅度的提高,添加3%的有机蒙脱土,热变形温度提高了6.1℃.通过SEM和AFM,对环氧树脂/蒙脱土纳米复合材料冲击断口进行微观研究,发现断口呈现出明显的韧性断裂.结合微观形貌,对有机蒙脱土增韧环氧树脂的各种机理进行探讨,认为符合基体剪切屈服增韧机理.     

Mechanical characterization of sol-gel alumina-based ceramics with intragranular reinforcement of multiwalled carbon nanotubes

Multiwalled carbon nanotubes (MWCNTs) have been widely considered for mechanical reinforcement of ceramic matrix composites. Nevertheless, the efficiency of this reinforcement strategy is under debate due to fabrication issues, such as a good homogenization or the location of the MWCNTs inside the matrix composite. Regarding this, the intragranular location of the MWCNTs has been deemed a crucial feature for optimizing the reinforcement compared to the typical intergranular placement achieved by conventional procedures. Recently, the sol-gel method has been reconsidered, as it promotes the intragranular placement of the MWCNTs. This work presents the mechanical characterization of these composites synthesized by the sol-gel method, where crack-bridging has been revealed as toughening mechanism. Finally, the conventional use of the bibliographical Young's modulus of pure alumina for the estimation of the fracture toughness is discussed, obtaining significant improvements of the fracture toughness when indentation measurements are treated by considering elastic moduli obtained by nanoindentation.     

Microstructural,mechanical, and thermal characteristics of recycled cellulose fiber‐halloysite‐epoxy hybrid nanocomposites

Epoxy hybrid‐nanocomposites reinforced with recycled cellulose fibers (RCF) and halloysite nanotubes (HNTs) have been fabricated and investigated. The dispersion of HNTs was studied by synchrotron radiation diffraction (SRD) and transmission electron microscopy (TEM). The influences of RCF/HNTs dispersion on the mechanical properties and thermal properties of these composites have been characterized in terms of flexural strength, flexural modulus, fracture toughness, impact toughness, impact strength, and thermogravimetric analysis. The fracture surface morphology and toughness mechanisms were investigated by SEM. Results indicated that mechanical properties increased because of the addition of HNTs into the epoxy matrix. Flexural strength, flexural modulus, fracture toughness, and impact toughness increased by 20.8, 72.8, 56.5, and 25.0%, respectively, at 1 wt% HNTs load. The presence of RCF dramatically enhanced flexural strength, fracture toughness, impact strength, and impact toughness of the composites by 160%, 350%, 444%, and 263%, respectively. However, adding HNTs to RCF/epoxy showed only slight enhancements in flexural strength and fracture toughness. The inclusion of 5 wt% HNTs into RCF/epoxy ecocomposites increased the impact toughness by 27.6%. The presence of either HNTs or RCF accelerated the thermal degradation of neat epoxy. However, at high temperature, samples reinforced with RCF and HNTs displayed better thermal stability with increased char residue than neat resin. POLYM. COMPOS. 2012. © 2012 Society of Plastics Engineers     

Desirable electrical and mechanical properties of continuous hybrid nano-scale carbon fibers containing highly aligned multi-walled carbon nanotubes

The continuous highly aligned hybrid carbon nanofibers (CNFs) with different content of acid-oxidized multi-walled carbon nanotubes (MWCNTs) were fabricated through electrospinning of polyacrylonitrile (PAN) followed by a series of heat treatments under tensile force. The effects of MWCNTs on the micro-morphology, the degree of orientation and ordered crystalline structure of the resulting nanofibers were analyzed quantitatively by diversified structural characterization techniques. The orientation of PAN molecule chains and the graphitization degree in carbonized nanofibers were distinctly improved through the addition of MWCNTs. The electrical conductivity of the hybrid CNFs with 3 wt% MWCNTs reached 26 S/cm along the fiber direction due to the ordered alignment of MWCNTs and nanofibers. The reinforcing effect of hybrid CNFs in epoxy composites was also revealed. An enhancement of 46.3% in Young’s modulus of epoxy composites was manifested by adding 5 wt% hybrid CNFs mentioned above. At the same time, the storage modulus of hybrid CNF/epoxy composites was significantly higher than that of pristine epoxy and CNF/epoxy composites not containing MWCNTs, and the performance gap became greater under the high temperature regions. It is believed that such a continuous hybrid CNF can be used as effective multifunctional reinforcement in polymer matrix composites.     

Toughening of aromatic diamine-cured epoxy resins by modification with hybrid modifiers composed of N-phenylmaleimide–styrene copolymers and N-phenylmaleimide–styrene–p-hydroxystyrene terpolymers

Hybrid modifiers composed of N-phenylmaleimide–styrene copolymers (PMS), and N-phenylmaleimide–styrene–p-hydroxystyrene terpolymers (PMSH) containing pendent p-hydroxyphenyl groups as functionalities, were used to improve the toughness of bisphenol-A diglycidyl ether epoxy resin cured with p,p′-diaminodiphenyl sulphone. The hybrid modifiers were effective in toughening the epoxy resin. When using the modifier composed of 10 wt% PMS (M?_w 313000) and 2.5 wt% PMSH (2.5 mol% p-hydroxystyrene units, M?_w 316000), the fracture toughness (K_IC) for the modified resins increased 100% with no deterioration in the flexural properties and the glass transition temperature. The improvement in toughness of the epoxy resins was attained because of the co-continuous phase structure and the improvement in interfacial adhesion. The toughening mechanism is discussed in terms of the morphological characteristics of the modified epoxy resin systems.     

Fracture and toughening behavior of aramid fiber/epoxy composites

The effect of short Aramid fibers on the fracture and toughening behavior of epoxy with high glass transition temperature has been studied. Fine dispersion of the fibers throughout the matrix is evidenced by optical microscopy. Compared with neat epoxy resin, the fracture toughness (K_IC) of the composites steadily increases with increasing fiber loading, indicating that addition of Aramid fibers has an effective toughening effect to the intrinsically brittle epoxy matrix. Scanning electron microscopy (SEM) indicates that formation of numerous step structures for fiber‐filled epoxy systems is responsible for the significant toughness improvement. SEM and transmitted optical microscopy show that fiber pullout and fiber breakage are the main toughening mechanisms for the Aramid fiber/epoxy composites. POLYM. COMPOS. 26:333–342, 2005. © 2005 Society of Plastics Engineers.     

Morphology and properties of an epoxy alloy system containing thermoplastics and a reactive rubber

A novel approach for toughening thermosetting epoxy matrices using both thermoplastics and liquid reactive rubbers as modifiers has been investigated. The network structure of the modified epoxy systems was characterized using dynamic mechanical analysis, and the morphology of the multiphase structure was examined using scanning electron microscopy (SEM). To investigate the continuity of the phase domains, the constituents in the phase domains were positively identified using solving etching and RuO₄ staining techniques for transmission electron microscopy (TEM). The fracture toughness of the modified and basic epoxy samples was measured using compact tension (CT) specimens. Quite limited toughness improvement was achieved for the epoxy modified with only the PSu thermoplastic, or the liquid rubber by itself. However, the fracture toughness was found to increase dramatically when a proper combination of both the liquid reactive rubber and thermoplastic was simultaneously incorporated into the epoxy. Toughening by using dual modifiers resulted in maximum improvement of fracture toughness with minimal compromises in processability and T_g depression by rubbers.     

Effect of resin modifiers on the structural properties of epoxy resins

Thermomechanical, mechanical and fracture mechanical properties of modified epoxy resins with two different modifiers are investigated. Carboxyl‐terminated butadiene‐acrylonitrile (CTBN) is used as toughening agent and hexanediole diglycidyl ether (HDDGE) as reactive diluent. Both modifiers are admixed in contents from 0 up to 100 phr (parts per hundred resin) and exhibit flexibilizing and toughening qualities. The glass transition temperature is strongly depressed by the admixed reactive diluent, whereas the tensile modulus exhibits greater dependency on the toughening agent contents. The tensile strength and strain at break values are higher for the formulations with diluent compared to resins with toughening agent. Up to a content of 45 phr both modified systems exhibit comparable fracture toughness values. Only the toughened systems comprise increasing values for modifier amounts higher than 45 phr. For the formulation with both modifiers (toughening agent and diluent) a significantly higher toughness but a reduced glass transition temperature was obtained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45348.