Reinforcing effects of aminosilane-functionalized graphene on the tribological and mechanical behaviors of epoxy nanocomposites

In this study, aminopropyl trimethoxysilane as an interfacial modifier was introduced on the surface of graphene (Gr) nanoplatelets. The effects of the silane-modified graphene (SGr) loading (0, 0.05, 0.1, 0.3, and 0.5 wt %) and silane modification on the tensile, compressive, interlaminar shear stress (ILSS), and tribological properties of the epoxy-based nanocomposites were investigated. Out of these specimens, the highest values of ILSS and compressive strength were related to the 0.3 wt % SGr–epoxy nanocomposite. The addition of SGr enhanced the tensile strength and strain to failure only at low contents (i.e., 0.05 wt %). Also, the tensile and compressive moduli were improved, and the highest values were observed at a 0.5 wt % SGr loading. In addition, decreases of approximately 40 and 68% in the coefficient of friction and wear rate, respectively, were observed at a 0.3 wt % SGr loading. Enhanced tensile, compressive, ILSS, and wear properties in the SGr–epoxy specimens were observed compared to those in the Gr–epoxy specimens. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47410.     

Synthesis of poly(arylene disulfide)–vermiculite nanocomposites via in situ ring‐opening polymerization of macrocyclic oligomers

Exfoliated poly(4, 4′‐oxybis(benzene)disulfide)/vermiculite (POBDS/VMT) nanocomposites were successfully synthesized via in situ melt intercalation of cyclo(4, 4′‐oxybis(benzene)disulfide) oligomers (COBDS) into octadecylammonium‐exchanged VMT (organo‐VMT). The POBDS/VMT nanocomposites were melt fabricated in a two‐step process. First, the COBDS/VMT nanocomposite precursor was fabricated by melt delaminating organo‐VMT with COBDS at a temperature slightly higher than its melting point. Subsequently, exfoliated POBDS‐VMT nanocomposites can be prepared in situ via instant melt ring‐opening polymerization of the COBDS‐VMT nanocomposite precursor. The nanoscale dispersion of VMT layers within POBDS polymer was confirmed by X‐ray diffraction, scanning electron microscopy and transmission electron microscopy. High molecular weight POBDS polymer was formed in a few minutes at the same time as the nanocomposite formation. The results of dynamic mechanical analysis showed that the storage modulus and glass transition temperature of the nanocomposites are much higher than those of the POBDS matrix, even with a very small amount of VMT addition. This methodology provides a potential approach to synthesize high‐performance polymer/clay nanocomposites. Copyright © 2004 Society of Chemical Industry     

Mechanical properties study of micro‐ and nano‐hydroxyapatite reinforced ultrahigh molecular weight polyethylene composites

This is a comparative study between ultrahigh molecular weight polyethylene (UHMWPE) reinforced with micro‐ and nano‐hydroxyapatite (HA) under different filler content. The micro‐ and nano‐HA/UHMWPE composites were prepared by hot‐pressing method, and then compression strength, ball indentation hardness, creep resistance, friction, and wear properties were investigated. To explore mechanisms of these properties, differential scanning calorimetry, infrared spectrum, wettability, and scanning electron microscopy with energy dispersive spectrometry analysis were carried out on the samples. The results demonstrated that UHMWPE reinforced with micro‐ and nano‐HA would improve the ball indentation hardness, compression strength, creep resistance, wettability, and wear behavior. The mechanical properties for both micro‐ and nano‐HA/UHMWPE composites were comparable with pure UHMWPE. The mechanical properties of nano‐HA/UHMWPE composites are better compared with micro‐HA/UHMWPE composites and pure UHMWPE. The optimum filler quantity of micro‐ and nano‐HA/UHMWPE composites is found to be at 15 wt % and 10 wt %, separately. The micro‐ and nano‐HA/UHMWPE composites exhibit a low friction coefficient and good wear resistance at this content. The worn surface of HA/UHMWPE composites shows the wear mechanisms changed from furrow and scratch to surface rupture and delamination when the weight percent of micro‐ and nano‐HA exceed 15 wt % and 10 wt %. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42869.     

Synthesis of poly(cyclooctene) by ring‐opening metathesis polymerization: Characterization and shape memory properties

Cis‐cyclooctene was polymerized via ring‐opening metathesis polymerization using a well‐defined ruthenium catalyst (Grubbs' type) under varying reaction conditions. Control over molecular weight was achieved by the inclusion of a chain transfer agent and its influence on the behavior of the obtained polymers was evaluated. The resulting polymers were characterized by means of differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical thermal analysis. Taking into account their thermal behavior, samples of appropriate molecular weight were subjected to a suitable treatment by chemical crosslinking to obtain a material showing thermally induced shape memory effect. The material recovers its original shape after several cycles of deformation into different shapes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Zinc‐based catalyst for the ring‐opening polymerization of cyclic esters

A zinc‐based catalyst zinc bis[bis(trimethylsilyl)amide] was used for the polymerization of cyclic esters including L ‐lactide (L ‐LA) and 2‐methyl‐2‐carboxyl‐propylene carbonate (MBC). The polymerization of L ‐lactide in THF could be carried out successfully under mild conditions in very short time by using the zinc catalyst and alcohols as the initiators. Kinetic study in solution polymerization prooved the polymerization has high monomer conversion degree close to 100% and the molecular weight of the resulting polyester has linear increase with the increase of [M]₀ /[I] (molar ratio of monomer to initiator). Sequential polymerization of L ‐LA and MBC in THF also showed high MBC conversion of 94% with a narrow molecualr weight maintained, indicating a living nature of this polymerization. The zinc catalyst system has also been used for the L ‐LA bulk polymerization with a high monomer conversion. ¹³C NMR indicated the polymer possesses high regioregularity and the minor regioirregular component was owing to the D ‐LA in the monomer inserted into the polymer mainchain during the transesterifcation. Interaction between monomer and zinc catalyst has been found to be a key factor to sustain a homogenous solution during the initiating procedure. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and ring‐opening polymerization of macrocyclic aromatic sulfide oligomers

A series of macrocyclic(arylene sulfide) oligomers were synthesized by reaction of 4,4′‐oxybis(benzenethiol) with a number of difluoro compounds in dimethylformamide (DMF) in the presence of anhydrous K₂CO₃ under high dilution conditions. The difluoro compound can be 4,4′‐difluorobenzophenone, bis(4‐fluorophenyl)sulfone or 1,3‐bis(4‐fluorobenzoyl)benzene. Detailed structural characterization of these oligomers by matrix‐assisted laser desorption and ionization‐time of flight‐mass spectroscopy (MALDI‐TOF‐MS) demonstrated their cyclic nature. The MALDI‐TOF‐MS technique has proved to be a powerful tool to analyze these cyclics. These cyclic oligomers are amorphous and highly soluble in DMF and N,N′‐dimethyl acetamide. Moreover, these cyclic(arylene sulfide) oligomers readily underwent ring‐opening polymerization in the melt at 285 °C in the presence of 2,2′‐dibenzothiazole disulfide, affording linear, high molecular weigh poly(aromatic sulfide)s. These polymers are insoluble in most common solvents. Copyright © 2004 Society of Chemical Industry     

UV‐ and thermally triggered ring‐opening metathesis polymerization for the spatially resolved functionalization of polymeric monolithic devices

Porous polymeric monolithic supports were prepared via electron beam‐triggered free radical polymerization using a mixture of ethyl methacrylate and trimethylolpropane triacrylate in 2‐propanol, 1‐dodecanol and toluene. Bicyclo[2.2.1]hept‐5‐en‐2‐ylmethyl acrylate (1) was grafted onto these monolithic supports in a spatially resolved way with the aid of masks using both electron beam‐ (EB) and UV‐triggered free radical polymerization. The thus immobilized norborn‐2‐ene‐containing graft polymers were further treated with the 2^nd‐generation Grubbs initiator, i.e., RuCl₂(PCy₃)(IMesH₂)(CHPh) (4) (IMesH₂ = 1,3‐dimesitylimidazolin‐2‐ylidene), and then reacted with bicyclo[2.2.1]hept‐5‐en‐2‐ylmethyl pyrene‐1‐carboxylate (2). Alternatively, monoliths completely grafted with poly‐ 1 were surface grafted with 2 in a spatially resolved way in the presence of a latent, UV‐triggerable precatalyst, i.e., [Ru(IMesH₂)(CF₃COO)(t‐BuCN)₄⁺ CF₃COO^?] (5). Finally, to demonstrate the utility of this chemistry, a 2^nd‐generation Grubbs initiator‐based approach was used to prepare a trypsin‐functionalized monolith‐containing chip device that allowed for the online digestion of N‐α‐benzoyl‐L ‐argininethylester hydrochloride. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Cure characterization of the ring‐opening metathesis polymerization of linseed oil‐based thermosetting resins

BACKGROUND: Bio‐based polymers from vegetable oils are excellent alternatives to petroleum‐based resins for both environmental and economic reasons. A detailed understanding of the cure behavior of bio‐based polymers is essential to optimize cure schedules and the final properties of the polymers. In this work, the cure of newly developed linseed oil‐based thermosetting resins, synthesized using Grubbs' first‐generation catalyst and a bis‐norbornadiene cross‐linking agent by ring‐opening metathesis polymerization, is characterized using differential scanning calorimetry (DSC) and parallel plate oscillatory rheometry. RESULTS: Experimental results reveal that the rate of cure increases and the gel time decreases with increasing cross‐linker loading; however, the activation energy of the cure does not vary systematically with cross‐linker loading. Phenomenological reaction models are used to describe the dynamic DSC measurements and to determine the kinetic parameters which facilitate cure predictions under isothermal conditions. CONCLUSION: This work demonstrates that the cure kinetics of a linseed oil‐based thermosetting resin can be controlled by varying the cross‐linker loading. Furthermore, the kinetic parameters and cure rates at any cross‐linker loading for this system can be described by a simple autocatalytic reaction model which facilitates development of cure schedules. Copyright © 2009 Society of Chemical Industry     

The mechanical and tribological properties of nitric acid‐treated carbon fiber‐reinforced polyoxymethylene composites

The carbon fibers have been exposed to nitric acid oxidation treatments and introduced into polyoxymethylene composites (POM/CF). The nitric acid treatment increases the number of the flaws, roughness of the surface, and disorder of carbon atoms on fiber, as well as introduces reactive functional groups, which could lead to a better mechanical bonding between fiber and the matrix. It is shown that the impact strength and fiber‐matrix adhesion in composites (POM/mCF) are superior to those for POM/CF composites. Simultaneously, the addition of mCF improves flexural strength and modulus relative to virgin POM significantly. Average friction coefficient values of POM/CF composites are lower than that of POM/mCF composites. As the percentage of fiber increases, the trend of wear ratio of the composites goes down initially and bumps up afterwards. The results indicate that the proper contents of CF and mCF in composites range from 5 wt % to 20 wt %. Scanning electron microscopy of worn surface morphology has revealed that the main wear mechanism of the composites were adhesive wear and ploughing wear. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41812.     

Effect of SiO2 nanoparticles-decorated SCF on mechanical and tribological properties of cenosphere/SCF/PEEK composites

A silicon oxide (SiO₂) nanoparticles-decorated short carbon fiber (SCF) hybrid (SCF-SiO₂) was designed to improve the weak interfacial bonding between fibers and matrix. Nano-SiO₂ was grafted onto carbon fibers by introducing amino group and epoxy group on the surface of carbon fibers and SiO₂, respectively. The chemical composition of SCF-SiO₂ was analyzed by Fourier transform infrared spectrometer and energy-dispersive spectrometry, the microstructure of SCF-SiO₂ were investigated by scanning electron microscope, and then the hybrid filler was introduced into Poly(ether ether ketone) (PEEK). Due to the strong interfacial interaction between filler and matrix, the mechanical and tribological properties of SCF-SiO₂/PEEK composites were significantly better than SCF/PEEK composites. In order to further improve the tribological properties of the composites, micrometer-sized cenosphere (CS) particles were introduced into the aforementioned system to prepare multicomponent composites. The test results of friction and wear indicate that the CS/SCF-SiO₂/PEEK composites have the optimal tribological properties. Compared with pure PEEK, the friction coefficient of CS/SCF-SiO₂/PEEK composites under 200 N load decreases by 56.4% and the specific wear rate decreases by 87.4%. Meanwhile, the thermal decomposition temperature of CS/SCF-SiO₂/PEEK composites is increased by 40 °C compared to pure PEEK. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48749.     

Investigation of the surface properties of polymeric soaps obtained by ring‐opening polymerization of epoxidized soybean oil

Epoxidized soybean oil (ESO) was converted to a polysoap (PESO) via a two‐step synthetic procedure of catalytic ring‐opening polymerization, followed by hydrolysis (HPESO) with a base. Various molecular weights of PESO and HPESO were prepared by varying the reaction temperature and/or catalyst concentration. In addition, the counter ion chemistry was varied by changing the base used for saponification. The PESO and HPESO products were carefully characterized and identified using a combination of FTIR, ¹H‐NMR, solid state ¹³C‐NMR, and GPC. The effect of HPESO polysoaps on the surface tension of water and the interfacial tension of water‐hexadecane was investigated as a function of HPESO concentration, molecular weight, and counter ion chemistry. HPESO polysoaps were effective at lowering the surface tension of water and the interfacial tension of water‐hexadecane and displayed minimum values in the range of 20–24 and 12–17 dyn/cm, respectively, at concentration of 200–250 μM. Water‐hexadecane interfacial tension was also calculated from measured surface tension data using the Antonoff, harmonic mean (HM), and geometric mean (GM) methods. Measured values agreed well with those calculated using the HM and GM methods, but not the Antonoff method. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Anionic ring‐opening polymerization of adipic anhydride initiated by potassium poly(ethylene glycol)ate

Poly(adipic anhydride) (PAA) was prepared by the ring‐opening polymerization of adipic anhydride (AA) initiated by potassium poly(ethylene glycol)ate. The effects of various factors, such as the amount of initiator, concentration of the monomer, reaction time and temperature, and polarity of the solvent on the polymerization were investigated. The crude polymerized product was a mixture of PAA homopolymer and poly(ethylene glycol)–poly(adipic anhydride) block copolymer, as confirmed by ¹H‐NMR and gel permeation chromatography. Chain‐transfer reactions occurred intensively for the AA polymerization in both the nonpolar solvent toluene and the polar solvents CHCl₃ and tetrahydrofuran, which predominantly determined the molecular weight and the monomer conversion for the polymerized product. The lower monomer conversion in toluene was ascribed to a lower livingness for the initiator in the nonpolar solvent when compared with other two, polar solvents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2194–2201, 2003     

One step synthesis and rapid ring‐opening polymerization of macrocyclic (arylene thioether ketone) oligomers

Well‐crystal macrocyclic (arylene thioether ketone) oligomers were synthesized under high dilution condition by the reaction of Na₂S with bis(4‐fluoro‐phenyl)‐methanone in 1‐methyl‐pyrrolidone (NMP). The oligomers were fully characterized by Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectra (MALDI‐TOF‐MS), high‐pressure liquid chromatography (HPLC), gel permeation chromatography (GPC), ¹H NMR, ¹³C‐NMR, and differential scanning calorimetry (DSC). According to DSC studies, uncatalyzed and rapid ring‐opening polymerization (ROP) of the oligomers took place instantly when they were heated to melting point. Extracted by dichloro‐methane, the obtained polymer neither loses any weight nor dissolves in boiling 1‐chloro‐ naphthalene. These facts indicated that there are no residual oligomers within the resultant polymer. The as‐prepared oligomers could be potentially used as high‐temperature hot‐melt adhesive at a high temperature > 350°C, and matrices for high‐performance composites and nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 161–166, 2006     

Zinc lactate‐catalyzed ring‐opening polymerization of trimethylene carbonate under microwave irradiation

Microwave‐assisted ring‐opening polymerization (MROP) of trimethylene carbonate (TMC) was carried out with four different types of zinc lactate, as the catalyst. Poly(trimethylene carbonate)s (PTMC) with a number–average molar mass ranging from 2990 to 75,410 g/mol and a TMC conversion ranging from 85.2% to 98.2% were synthesized effectively in 30 min at 120°C under microwave irradiation. The effects of the catalyst type, catalyst concentration, and microwave irradiation time on the MROP of TMC were studied. The MROP of TMC was much faster than that under conventional heating conditions. Thermal analysis suggested that PTMC with higher molar mass exhibited higher glass transition temperature (T_g) and thermal stability. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetics of the anionic ring‐opening polymerization of octamethylcyclotetrasiloxane initiated by potassium isopropoxide

Kinetics of the anionic ring‐opening polymerization of octamethylcyclotetrasiloxane (D₄) in bulk initiated by potassium isopropoxide was studied. Several promoters including N‐methyl‐2‐pyrrolidinone (NMP), N,N‐dimethylformamide (DMF), and diglyme were used. It is indicated that the reactions are first‐order in D₄ during the initial stage of polymerization. The polymerization rate of D₄ is influenced by a number of factors, such as the nature of promoters, the molar ratio of promoter to initiator (C_p/C_i ratio), and the reaction temperatures. With the use of NMP as promoter, the polymerization rate constant at 30°C is 10.482 h^?1 with the C_p/C_i ratio equal to 3.0. As the C_p/C_i ratio increases, the polymerization rate constant increases sharply and the cyclic oligomers content in polymer decreases evidently. The back‐biting reaction that leads to the formation of decamethylcyclopentasiloxane (D₅) occurred in the polymerization of D₄. The rate of the D₅ formation relatively to the rate of D₄ conversion increases with the conversion of D₄. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3510–3516, 2006     

The tribological properties of benzoxazine‐bismaleimides composites with functionalized nano‐SiO2

To improve the tribological properties of benzoxazine (BOZ) resin, bismaleimides (BMI) resin is chosen as organic phase, hyperbranched polysilane functionalized SiO₂ nanoparticles (HBPSi‐SiO₂) are chosen as inorganic modifiers to prepare HBPSi‐SiO₂/BOZ‐BMI composites using high shear and ultrasonic processes. The effect of content of HBPSi‐SiO₂ on the mechanical properties and tribological properties of the composites are investigated. The results show that suitable addition of HBPSi‐SiO₂ can largely enhance the impact strength, reduce the friction coefficient, and wear rate of BOZ‐BMI resin. Scanning electron microscopy is employed to research the wearing mechanism of materials. The severe wear of the BOZ pure resin is owing to fatigue wear, and the moderate wear of BOZ‐BMI resin is attributed to adhesive wear. While, the mild wear of the composites with HBPSi‐SiO₂ is due to abrasive wear. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Tribological properties of polyimide coatings filled with PTFE and surface‐modified nano‐Si3N4

Polyimide (PI) coatings filled with PTFE and nano‐Si₃N₄ were prepared by a spraying technique and successive curing. Nano‐Si₃N₄ particles were modified by grafting 3‐aminopropyltriethoxysilane to improve their dispersion in the as‐prepared coatings. Friction and wear performances and wear mechanisms of the coatings were evaluated. The results show that the incorporations of PTFE and modified nano‐Si₃N₄ particles greatly improve the friction reduction and wear resistance of PI coating. The friction and wear performance of the composite coating is significantly affected by the filler mass fraction and sliding conditions. PI coating incorporated with 20 wt % PTFE and 5 wt % modified nano‐Si₃N₄ displays the best tribological properties. Its wear rate is more than one order of magnitude lower and its friction coefficient is over two times smaller than that of the unfilled PI coating. Differences in the friction and wear behaviors of the hybrid coatings as a function of filler or sliding condition are attributed to the filler dispersion, the characteristic of transfer film formed on the counterpart ball and the wear mechanism of the coating under different sliding conditions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40410.     

Enhancement in pyroelectric properties of PZT‐PVA polymer nanocomposites with addition of PAA

Composites comprising of pyroelectric ceramics and electro‐active polymers have gained importance currently as materials for thermal sensing applications, as their unique features and relevant properties can be tailored easily. In this work nanoparticles of PZT have been embedded into PVA/PAA copolymer matrix to form 0 to 3 nanocomposites. Films of the composites are prepared following solvent cast method after dispersing ceramic nanopowder homogeneously in the copolymer matrix with different wt % of the PZT powder. Relevant properties such as dielectric constant and loss factor, pyroelectric coefficients, thermal conductivity, and specific heat capacity as well as Shore hardness have been measured. The material figures of merit for pyroelectric detection have also been determined and reported. It is found that pyroelectric sensing properties of a film of the composite with 20 wt % PZT are comparable to those of commercially used β‐PVDF film for the same application, but with a lower figure of merit. However, it provides greater mouldability and simpler processibility for the fabrication of bulk sensors and actuators. So this composite can be considered as a potential material for the design and fabrication of mouldable pyroelectric detectors and actuators. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41142.     

Thermo‐mechanical behavior of poly(butylene terephthalate)/silica nanocomposites

In this work, experimental results about poly(butylene terephthalate) (PBT) based nanocomposites filled with various amounts of silica nanoparticles (NPs) are reported. Two different types of filler are used: silica gel NPs, produced through the Stöber method, and a commercial fumed silica, both coated by a PBT shell. Melt‐mixed samples have been thoroughly investigated by scanning and transmission electron microscopy, infrared Fourier transform spectroscopy (FTIR), thermal gravimetric analysis, differential scanning calorimetry, wide and small angle X‐ray diffraction, and dynamic mechanical analysis. A fine and very good dispersion of NPs into the polymeric matrix is revealed through the morphological analysis when Stöber NPs were used as filler with respect to systems including commercial fumed silica particles. This evidence, combined with matrix–filler interactions revealed by FTIR spectroscopy, justifies the enhancement of both storage modulus and glass transition temperature of the former samples in comparison with reference pristine PBT. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46006.     

Surface modification of starch nanocrystals through ring‐opening polymerization of ε‐caprolactone and investigation of their microstructures

Bionanoparticles of starch obtained by submitting native potato starch granules to acid hydrolysis conditions. The resulted starch nanoparticles were used as core or macro initiator for polymerization of ε‐caprolactone (CL). Starch nanoparticle‐g‐polycaprolactone was synthesized through ring‐opening polymerization (ROP) of CL in the presence of Sn(Oct)₂ as initiator. The detailed microstructure of the resulted copolymer was characterized with NMR spectroscopy. Thermal characteristic of the copolymer was investigated using DSC and TGA. By introducing PCL, the range of melting temperature for starch was increased and degradation of copolymer occurred in a broader region. X‐ray diffraction and TEM micrographs confirmed that there was no alteration of starch crystalline structure and morphology of nanoparticles, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008