Processing and properties of syntactic foams reinforced with carbon nanotubes

This article presents synthesis and mechanical characterization of carbon nanotube (CNT)‐reinforced syntactic foams. Following a dispersion approach (comprising ultrasonic, calendering, and vacuum centrifugal mixing), single‐ and multi‐walled functionalized CNTs (FCNTs) were incorporated into two foam composites containing various commercially available microballoon grades (S38HS, S60HS, and H50 from 3M). The FCNT‐reinforced composites were tested for compressive strength and apparent shear strength before and after hot/wet conditioning. The results showed that the FCNT‐reinforced composites' mechanical properties depended on the vacuum pressure used during processing. Compared with pristine and commercially available syntactic foam (EC‐3500 from 3M), the FCNT‐reinforced composites processed at high vacuum (0.2 kPa) showed significant increase in compressive strength and apparent shear strength before and after hot/wet conditioning. Dynamic mechanical analysis showed an increase of about 22°C in glass transition temperature for composites processed at high vacuum with 0.5 wt % FCNT and 45 wt % S38HS–5 wt % S60HS microballoons. Thermogravimetric analysis indicated water absorption and lower decomposition temperature for the FCNT‐reinforced composite mixed at atmospheric pressure, whereas no significant change was observed for the compound processed at high vacuum. Fracture analysis showed matrix failure for the composite processed at high vacuum and microballoon crushing for the composite mixed at atmospheric pressure. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel high‐performance wave‐transparent aluminum phosphate/cyanate ester composites

Advanced wave‐transparent composites are the key materials for many cutting‐edge industries including aviation and aerospace, which should have outstanding heat resistance, low dielectric constant and loss as well as good mechanical properties. A novel kind of high‐performance wave‐transparent composites based on surface‐modified aluminum phosphate AlPO₄(KH‐550) and cyanate ester (CE) was first developed. The dielectric and dynamic mechanical properties of AlPO₄(KH‐550)/CE composites were investigated intensively. Results show that AlPO₄(KH‐550)/CE composites have decreased dielectric loss and higher storage moduli than pure CE resin; in addition, the composites with suitable AlPO₄(KH‐550) concentration remain the outstanding thermal property and low dielectric constant of pure CE resin. The reasons attributing to these results are discussed from the effects of AlPO₄(KH‐550) on the key aspects such as morphology, curing mechanism, and interfacial adhesion of composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and properties of maleimide‐functionalized hyperbranched polysiloxane and its hybrids based on cyanate ester resin

A new hyperbranched polysiloxane containing maleimide (HPMA) was synthesized through the reaction between N‐(4‐hydroxyphenyl) maleimide and 3‐glycidoxypropyltrimethoxysilane, which was then used to prepare cyanate ester (CE) resin‐based hybrids (coded as HPMAx/CE, where x is the weight fraction of HPMA in the hybrid). The curing behavior of uncured hybrids and the typical properties (impact strength and dielectric properties) of cured hybrids were systemically investigated. Results show that the performance of hybrids is greatly related with the content of HPMA. Hybrids have obviously lower curing temperature than CE, overcoming the poor curing characteristics (higher curing temperature and longer curing time) of neat CE, for example, the curing peak temperature of HPMA20/CE is about 65°C lower than that of CE. In the case of cured resin and hybrids, the hybrids exhibit decreased dielectric constant and loss than CE resin; moreover, the former also exhibits lower water absorption than the latter. Specifically, the dielectric loss of HPMA15/CE hybrid is only about 27% of that of neat CE resin. In addition, the hybrids with suitable contents of HPMA have significantly improved impact strengths. The overall improved properties suggest that HPMAx/CE hybrids have great potential in applications needing harsh requirements of curing feature, dielectric properties, and toughness. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel hyperbranched polyphenylsilsesquioxane‐modified cyanate ester resins with improved toughness and stiffness

High‐performance thermosetting resins should have good toughness and stiffness, so simultaneously toughening and stiffening is the main target in developing high‐performance resins. A novel modified cyanate ester resin with improved toughness and stiffness was developed by copolymerizing 2,2′‐bis(4‐cyanatophenyl)isopropylidene (CE) with hyperbranched polyphenylsilsesquioxane (HBPPSi). The mechanical properties and their nature were systematically investigated from the viewpoint of structure‐property relations using positron annihilation lifetime spectroscopy and spectral analyses. It is found that a suitable content of HBPPSi in CE resin can effectively improve toughness and stiffness. In the case of the CE resin modified with 10 wt% HBPPSi, its impact and flexural strengths are 21 kJ m^?2 and 148 MPa, respectively, about 2.6 and 1.4 times of those of neat CE resin. The flexural modulus increases from 3.0 (for neat CE resin) to 3.4 GPa. The results of dynamic mechanical analyses also corroborate the static mechanical properties. The improved toughness and stiffness of CE resin can be attributed to the synergistic effect resulting from changes of both polymer chain structure and aggregation state structure. These attractive features of HBPPSi/CE resins suggest that the method proposed herein may be a new approach for the development of high‐performance resins for cutting‐edge industries. Copyright © 2011 Society of Chemical Industry     

Novel aluminum phosphate/cyanate ester composites: Thermodegradation behaviors and kinetic analyses

Thermodegradation behaviors of novel aluminum phosphate/cyanate ester (AlPO₄(KH550)/CE) composites were studied in detail. Results show that thermodegradation behaviors and kinetic parameters of AlPO₄(KH550)/CE composites are greatly dependent on the AlPO₄(KH550) loading. The addition of AlPO₄(KH550) into CE resin changes the thermodegradation mechanism (mainly at the temperature lower than 450°C) and degradation process from two steps to three steps. Comparing with CE resin, AlPO₄(KH550)/CE composites have lower initial degradation temperature and greatly higher char yield. Besides, for each thermodegradation step, the more the AlPO₄ content, the smaller the activation energy value is. All reasons leading to these outcomes are investigated intensively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of novel 4,4′‐biphenylene‐bridged flame‐retardant cyanate ester resin

The bisphenol‐containing 4,4′‐biphenylene moiety was prepared by the reaction of 4,4′‐bis(methoxymethyl) biphenyl with phenol in the presence of p‐toluenesulfonic acid. The bisphenol was end‐capped with the cyanate moiety by reacting with cyanogen chloride and triethylamine in dichloromethane. Their structures were confirmed by Fourier transform infrared spectroscopy, ¹H‐NMR, and elemental analysis. Thermal behaviors of cured resin were studied by differential scanning calorimetry, dynamic mechanical analysis, and TGA. The flame retardancy of cured resin was evaluated by limiting oxygen index (LOI) and vertical burning test (UL‐94 test). Because of the incorporation of rigid 4,4′‐biphenylene moiety, the cyanate ester (CE) resin shows good thermal stability (T_g is 256°C, the 5% degradation temperature is 442°C, and char yield at 800°C is 64.4%). The LOI value of the CE resin is 42.5, and the UL‐94 rating reaches V‐0. Moreover, the CE resin shows excellent dielectric property (dielectric constant, 2.94 at 1 GHz and loss dissipation factor, 0.0037 at 1 GHz) and water resistance (1.08% immersed at boiling water for 100 h). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Silica fiber–polybenzoxazine–syntactic foams; Processing and properties

Polybenzoxazine filled with chopped silica fibers and their syntactic foams of varying composition and densities were processed. The composition and density variations were achieved by regulating the relative concentrations of silica fiber and glass microballoons (MB). The variation of tensile, compressive, and flexural properties with change in composition was investigated. For the silica‐fiber filled materials, the property attained a maximum at about 40% volume content of fiber, and thereafter, the properties showed a diminishing trend. The incorporation of microspheres significantly lowered the strength of silica filled materials. However, the decrease in the specific flexural strength was less pronounced and the strength was unaffected beyond a certain microsphere content. During processing and mechanical testing, a large quantity of fibers was fractured, which reduced the strength of silica filled systems. The diminution in material strength on embedding microspheres is attributed to the presence of stress concentrating loci as evidenced from SEM analysis. The various factors leading to the property variation with composition are discussed with microscopic analyses, like clustering of fibers, crack propagation, fiber pull out, and debonding of fibers from resin phase. Dynamic mechanical analysis revealed an improved damping property for the filled materials in contrast to the unfilled polymer. The T_g (deduced from tan δ maximum from DMTA) decreased in silica fiber containing materials and on incorporating the MB, the values reverted back to that of the neat polymer. Both silica and MB conferred better thermal and thermooxidative stabilities to the polybenzoxazine. However, the degradation mechanism is nonoxidative in nature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

VARI成型泡沫夹层复合材料界面质量控制方法研究

采用本体树脂涂覆、胶膜和辅助织物粘贴在泡沫加工表面的方法分别改善胶接界面,解决了真空树脂浸渗工艺(VARI)制备的非屈曲碳纤维织物(NCF)/聚甲基丙烯胺(PMI)泡沫夹芯复合材料中泡沫与蒙皮的脱粘问题。结果表明,在相同VARI工艺参数条件下,采用890树脂涂覆的方法可以达到大约80%区域面积的良好粘接界面,对应的抗平拉强度提高了30%;同时胶膜和辅助织物粘贴方法则可达到接近100%改善胶接界面质量的效果,其对应的抗平拉强度则分别提高了76%和56%。     

Epoxy‐functionalized polyhedral oligomeric silsesquioxane/cyanate ester resin organic–inorganic hybrids with enhanced mechanical and thermal properties

A series of cyanate ester resin (CE) based organic–inorganic hybrids containing different contents (0, 5, 10, 15 and 20 wt%) of epoxy‐functionalized polyhedral oligomeric silsesquioxane (POSS‐Ep) were prepared by casting and curing. The hybrid resin systems were studied by the gel time test to evaluate the effect of POSS‐Ep on the curing reactivity of CE. The impact and flexural strengths of the hybrids were investigated. The micromorphological, dynamic mechanical and thermal properties of the hybrids were studied by SEM, dynamic mechanical analysis (DMA) and TGA, respectively. Results showed that POSS‐Ep prolonged the gel time of CE. CE10 containing 10 wt% POSS‐Ep displayed not only the optimum impact strength but the optimum flexural strength. SEM results revealed that the improvement of mechanical properties was attributed to the large amount of tough whirls and fiber‐like pull‐outs observed on the fracture surfaces of CE10. DMA results indicated that POSS‐CE tended to decrease E′ of the hybrids in the glassy state but to increase E′ of the hybrids in the rubbery state. TGA results showed that CE10 also possesses the best thermal stability. The initial temperature of decomposition (T_i) of CE10 is 426 °C, 44 °C higher than that of pristine CE. © 2013 Society of Chemical Industry     

Processing and mechanical properties of bio‐derived vinyl ester resin‐based composites

A “green” vinyl ester resin (GVER) is investigated for use in structural applications. The GVER was formulated using a monodisperse vinyl ester created via a novel synthetic route capable of using bio‐waste material from paper and biodiesel industries. The GVER was used either as a neat resin or as blended with a commercial vinyl ester resin. The processing viscosity and gel times are investigated. The GVER reaches a similar viscosity as the commercial resin with only half the styrene monomer content, thereby reducing the volatile organic compounds associated with manufacturing. Composites of the GVER matrix reinforced by carbon fabric were tested for their tensile and flexural properties. The mechanical performance of the GVER compares favorably with commercial resin and provide a route for composites manufacturing from sustainably sourced vinyl ester matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44642.     

偶联剂表面处理纳米SiO_2改性氰酸酯的摩擦性能

采用浇铸成型法制备了纳米SiO2/CE复合材料,考察了偶联剂SCA-3表面处理nm-SiO2对其摩擦性能的影响。在MM-200型磨损机上测试了材料的磨损率和稳定摩擦系数,利用SEM观察了脆断面和对磨钢环表面的微观形貌。结果表明,nm-SiO2能够有效地改善CE的摩擦磨损性能,特别是SCA-3表面处理的nm-SiO2效果更好,相对纯CE,摩擦系数、磨损率分别降低了22.50%和76.21%。     

Surface preparation for adhesive bonding of polycyanurate‐based fiber‐reinforced composites using atmospheric plasma treatment

In this article, the effects of atmospheric plasma treatment on the microstructural, chemical, and mechanical behavior of epoxy‐bonded polycyanurate composites are investigated. Adhesive bond strength of plasma‐treated specimens exhibited strength increases of over 35% to that of peel‐ply and solvent‐wiped surface preparation techniques. The improvements were as much as 50% greater than those obtained using abrasive surface preparation techniques. X‐ray photoelectron spectroscopy analysis showed an increase in the surface concentration of oxygen as a function of plasma treatment passes. However, the levels were substantially lower than that of epoxy composites treated under identical conditions. In addition, the concentration of carboxyl groups (O CO), which have been associated with improved adhesive strength in epoxy‐based composites, was shown to saturate in cyanate ester composites after a much lower exposure period than what was observed when treating epoxies. The effect of plasma surface treatment on the surface morphology of the cyanate ester composite was also studied using scanning electron microscopy and atomic force microscopy. Atomic force microscopy analysis showed a progressive increase in surface roughness with treatment; however, this increase only translated into a marginal increase in surface area and is not believed to contribute significantly to adhesive strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Ethylene–propylene‐diene terpolymer/halloysite nanocomposites: Thermal,mechanical properties,and foam processing

Ethylene–propylene‐diene terpolymer (EPDM)/halloysite nanotube (HNT) nanocomposites were prepared by melt mixing in an internal mixer using a commercially available maleated semicrystalline EPDM and HNT. Transmission electron microscopy analysis of the EPDM/HNT composites revealed that the HNTs are uniformly dispersed at a nanometer scale in the matrix. Differential scanning calorimeter studies indicated that the HNT caused an increase in the nonisothermal crystallization temperature of the EPDM. Tensile and dynamic mechanical analysis exhibited that a small amount of the HNTs effectively enhanced the stiffness of the EPDM without adversely affecting its elongation‐at‐break. The EPDM/HNT nanocomposites were used to produce foams by using a batch process in an autoclave, with supercritical carbon dioxide as a foaming agent. The nanocomposite foams showed a smaller cell size and higher cell density as compared to the neat EPDM foam, and the nanocomposite with 10 phr HNT produced a microcellular foam with average cell size as small as 7.8 μm and cell density as high as 1.5 × 10¹⁰ cell/cm³. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40307.     

Eco‐friendly cardanol‐based phenalkamine cured epoxy‐cenosphere syntactic foams: Fabrication and characterisation

The performance of epoxy/cenosphere syntactic foams cured using phenalkamine (PA) were analyzed and characterized. The PA system was found to cure faster at room temperature, had lower density, and lower water absorption values. The thermogravimetric analysis result implied higher thermal stability. The cure studies using DSC inferred faster cure reaction in the ambient temperature conditions. The compression studies confirmed that unlike the epoxy system based on conventional triethylenetetramine curative, PA‐based system did not undergo brittle failure. This was also confirmed with the scanning electron microscope images. Dynamic mechanical analysis inferred the glass transition temperatures (T_g) as 81.4°C. The specific modulus and specific strength were higher for 40% cenosphere loading in PA‐based syntactic foams. As the need for light weight core materials is continually increasing, there is a great possibility for the utilization of this novel bio‐based curing agent to produce sustainable products. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44189.     

Tribological and mechanical properties of carbon‐nanofiber‐filled polytetrafluoroethylene composites

The effects of various filler concentrations (0.1, 0.5, 1, 1.5, 2, 2.5, and 3 wt %) on the tribological and mechanical properties of carbon‐nanofiber (CNF)‐filled polytetrafluoroethylene (PTFE) composites were studied. Moreover, the influence of various loads (50, 100, 150, and 200 N) and sliding velocities (0.692 and 1.39 m/s) on the friction and wear behaviors of the PTFE composites was investigated. The results showed that the friction coefficients of the PTFE composites decreased initially up to a 0.5 wt % filler concentration and then increased, whereas the antiwear properties of the PTFE composites increased by 1–2 orders of magnitude in comparison with those of pure PTFE. The composite with a 2 wt % filler concentration had the best antiwear properties under all friction conditions. The friction coefficients of the CNF/PTFE composites decreased with increases in the load and sliding velocity, whereas the wear volume loss of the PTFE composites increased. At the same time, the results also indicated that the mechanical properties of the PTFE composites increased first up to a 1 wt % filler concentration and then decreased as the filler concentration was increased above 1 wt %. In comparison with pure PTFE, the impact strength, tensile strength, and elongation to break of the PTFE composites increased by 40, 20, and 70%, respectively, at a 1 wt % filler concentration. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2430–2437, 2007     

Synthesis and characterization of siloxane‐based cyanate ester elastomers from readily available materials: a top‐down approach

A number of siloxane‐based cyanate ester (SiCE) elastomers were prepared from commercially available starting reagents employing a hydrosilylation reaction. Each elastomer was designed to utilize 2,4,6‐tris(allyloxy)‐1,3,5‐triazine as a crosslinker and multifunctional vinyl component in the hydrosilylation reaction, ensuring that the triazine rings were completely formed, and thus the elastomers resemble fully cured cyanate ester networks. The hydride‐terminated siloxane components used were varied from small‐molecule siloxanes to pre‐polymers of different molecular weights. Attenuated total reflectance Fourier transform infrared analysis confirmed the successful hydrosilylation reaction and complete curing of the SiCE elastomers via functional group analysis. Thermal characterization by thermogravimetric analysis and differential scanning calorimetry demonstrated that thermal properties of the elastomers could be tailored depending on the type of siloxane component that was utilized. The gel content of the elastomers was also determined. Investigations into the effects of a platinum catalyst on the elastomers determined that the presence of the catalyst affected the thermochemical stability of the SiCE elastomers. Published 2016. This article is a U.S. Government work and is in the public domain in the USA.     

Rigid polyisocyanurate–waterglass foam composite: Preparation,mechanism, and thermal and flame‐retardant properties

A rigid polyisocyanurate–waterglass foam (PIWGRF) composite was prepared with polyaryl poly(methylene isocyanate) and waterglass (WG) as the main materials; water as a blowing agent, and no polyols. We speculated the formation mechanism of the PIWGRFs on the basis of the analysis of experiment data, scanning electron microscopy characterization, and transmission electron microscopy. The results show that three‐dimensional nanoflakes derived from the cured WG was observed; this was connected with polyisocyanurate by secondary bonding (Si? O? H?N). Thermogravimetric testing indicated that the thermal stability and residual mass (34%) of the PIWGRFs were significantly higher than those of rigid traditional polyurethane foams (T‐PUFs). When the core density of the PIWGRFs was 32.6 kg/m³, the strength was up to 162.9 KPa by excessive filling. The flame retardancy of the PIWGRFs, including the time to ignition, heat‐release rate, total smoke of release, and limiting oxygen index, was obviously better than that of the T‐PUFs. The structure of the residual char was more dense and orderly; this was also an effective barrier layer. The reason was attributed to the fact that the WG did not contain combustible elements. So, the PIWGRFs had excellent thermal stability, flame retardancy, and environmental friendliness. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46182.     

Preparation and properties of nano diamond/6F‐bisphenol A‐based cyanate ester composites

The aim of this study was to improve thermal conductivity, thermal stability, and mechanical properties of bisphenol A dicyanate ester (BADCy) by adding bisphenol A dicyanate ester containing fluorine (F‐BADCy) and nano diamond. The cyanate esters containing fluorine/nano diamond composites having various ratios of BADCy, F‐BADCy, and nano diamond were prepared. Thermal stability and thermal conductivity of the samples were evaluated by thermogravimetric analysis, differential scanning calorimetry and laser flash method, respectively. The samples were characterized with the following analysis; gel content, water absorption capacity, and stress‐strain test. Hydrophobicity of the samples was determined by the contact angle measurements. Moreover, the surface morphology of the samples was investigated by a scanning electron microscopy (SEM). The obtained results prove that the cyanate ester containing fluorine/nano diamond composites have good thermal and mechanical properties and they can be used in many applications such as electronic devices, materials engineering, and other emergent. POLYM. COMPOS., 34:1977–1985, 2013. © 2013 Society of Plastics Engineers     

Preparation and properties of composites based on melamine‐formaldehyde foam and nano‐Fe3O4

In this work, a novel melamine‐formaldehyde‐Fe₃O₄ foam was prepared from a mixture containing melamine‐ethanolamine‐formaldehyde resin, melamine‐glycol‐formaldehyde resin and carboxylated Fe₃O₄ nanoparticles by microwave foaming method. The two resins were characterized by ¹³C‐NMR, respectively. The structures of foams, mechanical and fire‐retardant properties were experimentally characterized separately by scanning electron microscopy, universal testing machine, limit oxygen index, thermogravimetry‐differential thermal analysis, and Fourier transform infrared spectra. The effects of the resin viscosity, emulsifier, nucleating agent, curing agent, silicone oil, microwave heating time and blowing agent on the structure of foam were investigated. Results showed that the properties of foam were decided by not only the molecular structure but also structure of foam, and the carboxylated Fe₃O₄ nanoparticles can improve the toughness and flame retardant properties of magnetic foam obviously from both aspects. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2688–2697, 2013     

Synergistic effect of expandable graphite and aluminum hypophosphite on flame‐retardant properties of rigid polyurethane foam

A series of flame retarding rigid polyurethane foam (RPUF) composites based on expandable graphite (EG) and aluminum hypophosphite (AHP) were prepared by the one‐pot method. The properties were characterized by limiting oxygen index (LOI) test, cone calorimeter test, thermogravimetric analysis (TGA), real‐time Fourier transform‐infrared spectra (RT‐FT‐IR), X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), etc. The results indicate that both EG and AHP could enhance the flame retardency of RPUF composites. Besides, the flame retardant effect of EG was better than that of AHP. The results also show that partial substitution of EG with AHP could improve the flame retardency of RPUF, and EG and AHP presented an excellent synergistic effect on flame retardancy. What is more, compared with RPUF/20EG and RPUF/20AHP, the heat release rate (HRR) and total heat release (THR) of RPUF/15EG/5AHP were lower.TGA results indicate that partial substitution of EG with AHP could improve the char residue which provided better flame retardancy for RPUF composites. The thermal degradation process of RPUF composites and the chemical component of the char residue were investigated by RT‐FT‐IR and XPS. And the results prove that RPUF/15EG/5AHP had higher heat resistance in the later stage. Compared with the RPUF composites filled with EG, a better cell structure and mechanical properties were observed with the substitution of AHP for part of EG. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42842.