Effect of vapor‐grown carbon nanofibers and in situ hydrolyzed silica on the mechanical and shape memory properties of water‐borne epoxy composites

Vapor‐grown carbon nanofiber (VGCNF)/water‐borne epoxy (WEP) and SiO₂/WEP composites were successfully synthesized via freeze drying and hot‐press molding. VGCNFs were mixed directly with a WEP emulsion, while SiO₂ was synthesized by in situ hydrolysis of TEOS solution (3‐triethoxysilylpropylamine (KH550): tetraethoxysilane (TEOS): absolute ethanol = 1:5:20, w/w/w) dispersed in the WEP emulsion. WEP composites were obtained from these mixtures by freeze drying and compressing under a pressure of 10 MPa at 120°C for 2 h. The morphology and mechanical properties of the WEP composites were investigated by transmission electron microscopy, scanning electron microscopy, dynamic mechanical analysis and tensile testing. The shape memory (SM) properties of the WEP composites were evaluated by fold‐deploy SM testing. The effects of filler content and recovery temperature on the SM properties were revealed through systematic variation. The results confirmed that VGCNF and in situ hydrolyzed SiO₂ were homogenously dispersed and incorporated into the WEP matrices. Thus, significant improvements in the mechanical and SM properties of the composites were achieved. POLYM. COMPOS., 36:1712–1720, 2015. © 2014 Society of Plastics Engineers     

Response surface predictions of the viscoelastic properties of vapor‐grown carbon nanofiber/vinyl ester nanocomposites

A full factorial design of experiments and response surface methodology were used to investigate the effects of formulation, processing, and operating temperature on the viscoelastic properties of vapor‐grown carbon nanofiber (VGCNF)/vinyl ester (VE) nanocomposites. Factors included VGCNF type (pristine, oxidized), use of a dispersing agent (DA) (no, yes), mixing method (ultrasonication, high‐shear mixing, and a combination of both), VGCNF weight fraction (0.00, 0.25, 0.50, 0.75, and 1.00 parts per hundred parts resin (phr)), and temperature (30, 60, 90, and 120°C). Response surface models (RSMs) for predicting storage and loss moduli were developed, which explicitly account for the effect of complex interactions between nanocomposite design factors and operating temperature on resultant composite properties; such influences would be impossible to assess using traditional single‐factor experiments. Nanocomposite storage moduli were maximized over the entire temperature range (～20% increase over neat VE) by using high‐shear mixing and oxidized VGCNFs with DA or equivalently by employing pristine VGCNFs without DA at ～0.40 phr of VGCNFs. Ultrasonication yielded the highest loss modulus at ～0.25 phr of VGCNFs. The RSMs developed in this investigation may be used to design VGCNF‐enhanced VE matrices with optimal storage and loss moduli for automotive structural applications. Moreover, a similar approach may be used to tailor the mechanical, thermal, and electrical properties of nanomaterials over a range of anticipated operating environments. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of vapor‐grown carbon nanofibers on the sliding friction of natural rubber composites

The friction properties of vapor‐grown carbon nanofibers (VGCFs) reinforced natural rubber (NR) composites were investigated with the ball‐on‐plate sliding test. A mechanism was proposed on the basis of the viscoelastic properties, morphology and hardness of the composites, determined using dynamic mechanical analysis, optical microscopy, field emission scanning electron microscopy, transmission electron microscopy and a hardness‐testing device. The friction behavior of NR/VGCF composites showed three different stages: an increment trend at first stage, a decrement trend at second stage and a stable state at third stage. The peak values of friction coefficient were similar, and the peak shifted to a smaller cycle with increased VGCF content. The eventual friction coefficient decreased with increased VGCF content due to accelerated formation of abrasion patterns in the NR/VGCF composites. Moreover, the arranged VGCFs contributed to the self‐lubrication of NR/VGCF composites and the NR/20 wt% VGCF composite had the smallest friction coefficient. POLYM. COMPOS., 2011.© 2011 Society of Plastics Engineers     

Creep characterization of vapor‐grown carbon nanofiber/vinyl ester nanocomposites using a response surface methodology

The effects of selected factors such as vapor‐grown carbon nanofiber (VGCNF) weight fraction, applied stress, and temperature on the viscoelastic responses (creep strain and creep compliance) of VGCNF/vinyl ester (VE) nanocomposites were studied using a central composite design (CCD). Nanocomposite test articles were fabricated by high‐shear mixing, casting, curing, and post curing in an open‐face mold under a nitrogen environment. Short‐term creep/creep recovery experiments were conducted at prescribed combinations of temperature (23.8–69.2°C), applied stress (30.2–49.8 MPa), and VGCNF weight fraction (0.00–1.00 parts of VGCNF per hundred parts of resin) determined from the CCD. Response surface models (RSMs) for predicting these viscoelastic responses were developed using the least squares method and an analysis of variance procedure. The response surface estimates indicate that increasing the VGCNF weight fraction marginally increases the creep resistance of the VGCNF/VE nanocomposite at low temperatures (i.e., 23.8–46.5°C). However, increasing the VGCNF weight fraction decreased the creep resistance of these nanocomposites for temperatures greater than 50°C. The latter response may be due to a decrease in the nanofiber‐to‐matrix adhesion as the temperature is increased. The RSMs for creep strain and creep compliance revealed the interactions between the VGCNF weight fraction, stress, and temperature on the creep behavior of thermoset polymer nanocomposites. The design of experiments approach is useful in revealing interactions between selected factors, and thus can facilitate the development of more physics‐based models. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42162.     

Tensile properties and reinforcement mechanisms of natural rubber/vapor‐grown carbon nanofiber composite

Natural rubber (NR) composites with different contents of 1, 3, 10, and 20 wt% vapor‐grown carbon nanofibers (VGCFs) were synthesized using a solvent casting method. The initial modulus of composites was improved by 26.5 %/wt% as the VGCFs were added, and the NR/3 wt%VGCF composite had the largest tensile strength. The experiment values of initial moduli agreed well with the values predicted by the Halpin‐Tsai theory. The reinforcement mechanisms of the composites were investigated by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy and wide‐angle X‐ray diffraction (WAXD). It was found that an efficient stress transfer occurred from NR to VGCFs under the uniaxial stretching. The addition of 10 wt% VGCFs could promote the nucleation process of NR, which resulted in the characteristic of the strain‐induced crystallization (SIC) in NR/10 wt%VGCF composite even for low strain. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Electrical and mechanical properties of carbon nanotube‐epoxy nanocomposites

In this work, electrical conductivity and thermo‐mechanical properties have been measured for carbon nanotube reinforced epoxy matrix composites. These nanocomposites consisted of two types of nanofillers, single walled carbon nanotubes (SW‐CNT) and electrical grade carbon nanotubes (XD‐CNT). The influence of the type of nanotubes and their corresponding loading weight fraction on the microstructure and the resulting electrical and mechanical properties of the nanocomposites have been investigated. The electrical conductivity of the nanocomposites showed a significantly high, about seven orders of magnitude, improvement at very low loading weight fractions of nanotubes in both types of nanocomposites. The percolation threshold in nanocomposites with SW‐CNT fillers was found to be around 0.015 wt % and that with XD‐CNT fillers around 0.0225 wt %. Transmission optical microscopy of the nanocomposites revealed some differences in the microstructure of the two types of nanocomposites which can be related to the variation in the percolation thresholds of these nanocomposites. The mechanical properties (storage modulus and loss modulus) and the glass transition temperature have not been compromised with the addition of fillers compared with significant enhancement of electrical properties. The main significance of these results is that XD‐CNTs can be used as a cost effective nanofiller for electrical applications of epoxy based nanocomposites at a fraction of SW‐CNT cost. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

含氟形状记忆环氧树脂体系的制备与性能

将氢化环氧树脂(AL-3040)和自制的含氟环氧树脂按不同的物质的量比共混,以聚丙二醇二缩水甘油醚(XY-207)为环氧稀释剂、1,8-薄荷烷二胺(MDA)为固化剂,完全固化之后制备出一种新型的含氟形状记忆环氧树脂体系,并表征了其分子结构、含氟环氧树脂含量对固化体系储能模量和形状记忆性能的影响,测试了体系表面和冲击断面含氟量以及冲击力学性能。研究结果表明:增大体系含氟环氧树脂含量时,固化体系的交联度增大;固化体系的储能模量随含氟环氧树脂含量的增加而增大;该形状记忆含氟环氧树脂体系具有良好的形状记忆性能,形变完全的时间随体系含氟环氧树脂含量的增加而缩短。     

Characterization,prediction, and optimization of flexural properties of vapor‐grown carbon nanofiber/vinyl ester nanocomposites by response surface modeling

A design of experiments and response surface modeling were performed to investigate the effects of formulation and processing factors on the flexural moduli and strengths of vapor‐grown carbon nanofiber (VGCNF)/vinyl ester (VE) nanocomposites. VGCNF type (pristine, surface‐oxidized), use of a dispersing agent (no, yes), mixing method (ultrasonication, high‐shear mixing, and a combination of both), and VGCNF weight fraction (0.00, 0.25, 0.50, 0.75, and 1.00 parts per hundred parts resin (phr)) were selected as independent factors. Response surface models were developed to predict flexural moduli and strengths as a continuous function of VGCNF weight fraction. The use of surface‐oxidized nanofibers, a dispersing agent, and high‐shear mixing at 0.48 phr of VGCNF led to an average increase of 19% in the predicted flexural modulus over that of the neat VE. High‐shear mixing with 0.60 phr of VGCNF resulted in a remarkable 49% increase in nanocomposite flexural strength relative to that of the neat VE. This article underscores the advantages of statistical design of experiments and response surface modeling in characterizing and optimizing polymer nanocomposites for automotive structural applications. Moreover, response surface models may be used to tailor the mechanical properties of nanocomposites over a range of anticipated operating environments. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2087–2099, 2013     

Preparation and properties of LDHs/epoxy nanocomposites

Layered double hydroxides (LDHs)/epoxy nanocomposites were prepared by mixing the amino laurate intercalated LDHs, EPON 828 resin, and Jeffamine D400 as a curing agent. The organo-modified LDHs with hydrophobic property easily disperse in epoxy resin, and the amino laurate intercalated LDHs with large gallery space allow the epoxy molecules and the curing agents to easily diffuse into the LDHs galleries at elevated temperature. After the thermal curing process, the exfoliated LDHs/epoxy nanocomposites were formed. X-ray diffraction was used to detect the formation process of the exfoliated LDHs/epoxy nanocomposites. TEM was used to observe the dispersed behavior of the LDHs nanolayers, and the LDHs nanolayers were exfoliated and well dispersed in these nanocomposites. Owing to the reaction between the amine groups of the intercalated amino laurate and epoxy groups, the adhesion between the LDHs nanolayers and epoxy molecules makes these LDHs/epoxy nanocomposites more compatible. Consequently, the tensile properties from tensile test and the mechanical properties from DMA were enhanced, and the T_g of these nanocomposites from DMA and TMA were increased. Coefficients of thermal expansion (CTEs, below and above T_g) of these nanocomposites from TMA decreased with the LDHs content. The thermal stability of these nanocomposites was enhanced by the well dispersed LDHs nanolayers.     

Electrical conductivity of vapor‐grown carbon nanofiber/polyester textile‐based composites

Polyamide 6/ethylene–propylene–diene metallocene terpolymer/(ethylene–propylene–diene copolymer)‐graft‐(maleic anhydride) blends with clay (3 and 5 wt % depending on the formulation), different clays (montmorillonite and sepiolite) and different surface functionalization (ammonium salts and silanes) were studied to analyze the effect of the shape of clay and type of modifier on their properties. The results have shown that sepiolite has higher influence on the morphology and on the mechanical properties than montmorillonite. In that sense, blends with 3 wt % of sepiolite have reached the best balanced properties, i.e., tensile modulus and impact strength, than their homologous with montmorillonite. Furthermore, the blends with 3 wt % of sepiolite have reached the highest mechanical properties compared with blends with higher montmorillonite content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and mechanical properties of polybenzimidazole nanocomposites reinforced by vapor grown carbon nanofibers

Polybenzimidazole (PBI) nanocomposites containing 0.5–5 wt% vapor grown carbon nanofibers (VGNFs) were successfully synthesized by solvent evaporation method. Fracture morphology examination confirmed the uniform dispersion of VGNFs in the matrix. The mechanical properties of neat PBI and the nanocomposites were systematically measured by tensile test, dynamic mechanical analysis (DMA), hardness measurement, and friction test. Tensile tests revealed that Young's modulus increased by about 43.7% at 2 wt% VGNFs loading, and further modulus growth was observed at higher filler loadings. DMA studies showed that the nanocomposites have higher storage modulus than neat PBI in the temperature range of 30–350°C, holding storage modulus larger than 1.54 GPa below 300°C. Outstanding improvement of hardness was achieved for PBI upon incorporating 2 wt% of VGNFs. The results of friction test showed that coefficient of friction of PBI nanocomposites decreased with VGNFs content compared with neat PBI. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Mechanical and physical properties of epoxy composites reinforced by vapor grown carbon nanofibers

Epoxy/vapor grown carbon nanofiber composites (VGCF) with different proportions of VGCF were fabricated by the in situ process.The VGCFs were well dispersed in both of the low and high viscosity epoxy matrices, although occasional small aggregates were observed in a high viscosity epoxy of 20 wt.%. The dynamic mechanical behavior of the nanocomposite sheets was studied. The storage modulus and the glass transition temperature (T_g) of the polymer were increased by the incorporation of VGCFs.The electrical and mechanical properties of the epoxy-VGCFs nanocomposite sheets with different weight percentages of VGCFs were discussed. The results were that both had maximum tensile strength and Young’s modulus at 5 wt.% for both materials and reduced the fracture strain with increasing filler content. The electrical resistivity was decreased with the addition of filler content. Mechanical, electrical and thermal properties of low viscosity epoxy composites were resulted better than that of the high viscosity composites.     

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     

Bio‐based hyperbranched polyurethane/multi‐walled carbon nanotube nanocomposites as shape memory materials

Mesua ferrea L. seed oil based hyperbranched polyurethane/multi‐walled carbon nanotube nanocomposites were prepared by solution polymerization technique. The multi‐walled carbon nanotubes were modified with the polyoxyethylene octyl phenyl ether (Triton X‐100). The transmission electron microscopy and Fourier transform infrared spectroscopic study revealed the homogeneous distribution of the multi‐walled carbon nanotubes in the polymer matrix and the presence of strong interfacial interaction between them, respectively. The tensile strength (5.5–21.5 MPa) and scratch resistance (3–6.1 kg) increase with the increase of the content of carbon nanotubes (0 to 2 wt%). The thermo‐gravimetric analysis result showed the increment of thermal stability (240–275°C) of the nanocomposites. All the prepared nanocomposites exhibited the excellent shape fixity and shape recovery. The shape recovery time decreases (127–73 s) with the increase of the concentration of carbon nanotubes in the nanocomposites. Thus the prepared nanocomposites might be utilized as advanced shape memory applications. POLYM. COMPOS., 35:636–643, 2014. © 2013 Society of Plastics Engineers     

Preparation and mechanical properties of epoxy/diamond nanocomposites

Nanodiamond (ND) has recently attracted much attention for its outstanding mechanical and other interesting properties. Surface functionalization of ND is necessary for applications in polymers. In this study, ND particles were functionalized with amine by covalent linking of triethylene tetramine, and further grafted with epoxy which was cured with amine curing agent. The particle dispersion and mechanical properties of epoxy/ND nanocomposites were evaluated. Both fracture toughness and storage modulus of epoxy resin were significantly improved with a low loading of ND‐NH₂ particles. The morphological structure of the epoxy/ND nanocomposites was examined, and toughening mechanism was explored. POLYM. COMPOS., 35:2144–2149, 2014. © 2014 Society of Plastics Engineers     

Rheological analysis of vapor‐grown carbon nanofiber‐reinforced polyethylene composites

The melt rheological analysis of high‐density polyethylene reinforced with vapor‐grown carbon nanofibers (VGCNFs) was performed on an oscillatory rheometer. The influence of frequency, temperature, and nanofiber concentration (up to 30 wt %) on the rheological properties of composites was investigated. Specifically, the viscosity increase is accompanied by an increase in the elastic melt properties, represented by the storage modulus G′, which is much higher than the increase in the loss modulus G″. The composites and pure PE exhibit a typical shear thinning behavior as complex viscosity decreases rapidly with the increase of shearing frequency. The shear thinning behavior is much more pronounced for the composites with high fiber concentration. The rheological threshold value for this system was found to be around 10 wt % of VGCNF. The damping factor was reduced significantly by the inclusion of nanofibers into the matrix. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 155–162, 2004     

Fabrication and characterization of vapor grown carbon nanofiber/epoxy magnetic nanocomposites

Co₃O₄ nanoparticle‐decorated vapor‐grown carbon nanofiber (VGCNF) hybrid materials were successfully synthesized and served as nanofillers for preparing magnetic epoxy (EP) nanocomposites. The Co₃O₄‐decorated VGCNF (Co₃O₄‐VGCNF) and Co₃O₄‐VGCNF/EP nanocomposites were systematically and explicitly investigated by combined analytical techniques. The composition and phase structure of Co₃O₄‐VGCNF hybrid materials were characterized by Fourier transform infrared spectroscopy and X‐ray diffraction analyses. The morphology of Co₃O₄ was investigated using field‐emission scanning electronic microscopy (FE‐SEM). Results revealed the presence of Co₃O₄ nanoparticles firmly immobilized on VGCNF sidewalls. The tensile mechanical, thermomechanical, and magnetic properties of Co₃O₄‐VGCNF/EP nanocomposites were also investigated in detail. Results indicated that the tensile strength of Co₃O₄‐VGCNF/EP nanocomposites (filler = 0.5 wt%) improved by 44.6% compared with that of raw VGCNF/EP nanocomposites (filler = 0.5 wt%). Magnetization measurements revealed that Co₃O₄‐VGCNF/EP nanocomposites exhibited ferromagnetic behavior, and the saturation magnetization and coercivity of the nanocomposites with 2 wt% of Co₃O₄‐VGCNF were 0.055 emu g⁻¹ and 0.75 kOe, respectively. POLYM. COMPOS., 37:1728–1734, 2016. © 2014 Society of Plastics Engineers     

Piezoresistivities of vapor‐grown carbon fiber/silicone foams for tactile sensor applications

Due to the growing demand for tactile sensors, the possibility of detecting an external uniaxial pressure by the piezoresistive measuring of a conductive filler/elastomer composite was investigated. A series of piezoresistive models are discussed. Novel highly sensitive piezoresistive foams with excellent elasticity were fabricated using vapor‐grown carbon fiber (VGCF), two‐component silicone elastomer and a new type of thermally expandable micro beads foaming agent to overcome the disadvantages of the silicone elastomer in the utilization of a tactile sensor. Deformations of the foams caused by uniaxial pressure were observed using scanning electron microscopy from cross‐sections. Effects of the VGCF and the foaming agent on the piezoresistivitiy were investigated. The piezoresistive mechanisms of the foams are discussed according to the measurements, and good fit was found between the theoretical calculations and the experimental piezoresistivity measurements. It is found that the addition of the micro beads foaming agent can improve the piezoresistivity of the VGCF/silicone foam and increase the sensitivity and repeatability for its application in a tactile sensor. © 2016 Society of Chemical Industry     

In‐situ grown silica/water‐borne epoxy shape memory composite foams prepared without blowing agent addition

Shape memory (SM) silica/epoxy composite foams were successfully synthesized via latex technology and prepared without blowing agent addition. Silica was synthesized via tetraethoxysilane (TEOS) hydrolysis. Silica/epoxy foams were obtained from the TEOS solution and water‐borne epoxy mixtures after freeze‐drying and foaming in the presence of residual moisture as the blowing agent under a vacuum at 110°C. The morphologies of the resulting foams were evaluated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Compression and thermo‐mechanical cycle tests were performed to measure the mechanical and SM properties of the foams. Experimental results indicated that the micrographs and mechanical properties of the foams were closely related to freeze‐drying time. The final composite foams exhibited high shape recovery and fixity ratios and could maintain both properties at more than 90% even after five thermo‐mechanical cycles. The properties obtained in the epoxy foams may offer new opportunities for their use in future structural applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42599.