Enhanced mechanical and thermal properties of polyurethane/functionalised graphene oxide composites by in situ polymerisation

ABSTRACT

Isocyanate-functionalised graphene (iGO) was prepared and incorporated into a thermoplastic polyurethane via an in situ polymerisation. Firstly, graphene oxide was successfully modified using a mixture of isocyanate- and diisocyanate-containing compounds, leading to the formation of good dispersions of resulting functional graphene oxide in organic solvents, such as N,N-dimethylacetamide and N,N-dimethylformamide. The addition of iGO into polyurethane matrix improved both mechanical and thermal properties in the polyurethane/iGO composites relative to neat polyurethane. An addition of only 0.03?wt-% of functionalised graphene into the polyurethane increased Young’s modulus by 1.4 times and tensile strength by two times. Meanwhile, the elongation at break was similar to that of the neat polymer. In addition, dynamic mechanical analysis also confirmed the improvement in storage modulus of the polymer composites especially at high-temperature range. We believe that the developed modification approach for graphene oxide and polyurethane/graphene composites presented herein could be useful in polymer/graphene composite development.     

Electrical and mechanical properties of polyimide-carbon nanotubes composites fabricated by in situ polymerization

Polyimide (PI)-carbon nanotubes composites were fabricated by in situ polymerization using multi wall carbon nanotubes (MWNT) as fillers. It suggested that in situ polymerization is an ideal technique to make a perfect dispersion of carbon nanotubes into matrixes. Besides it, the pre-treatment of carbon nanotubes in solvent to make the networks untied enough and to let solvent percolated into the networks is very important for forming uniform entanglements between carbon nanotubes and polymer molecular chains. The results imply that the percolation threshold for the electric conductivity of the resultant PI-MWNT composites was ca. 0.15 vol%. The electrical conductivity has been increased by more than 11 orders of magnitude to 10⁻⁴ S/cm at the percolation threshold. The mechanical properties of the polyimide composite were not improved significantly by addition of carbon nanotubes.     

Multifunctional polyimide/graphene oxide composites via in situ polymerization

In this article, we detail an effective way to improve electrical, thermal, and gas barrier properties using a simple processing method for polymer composites. Graphene oxide (GO) prepared with graphite using a modified Hummers method was used as a nanofiller for r‐GO/PI composites by in situ polymerization. PI composites with different loadings of GO were prepared by the thermal imidization of polyamic acid (PAA)/GO. This method greatly improved the electrical properties of the r‐GO/PI composites compared with pure PI due to the electrical percolation networks of reduced graphene oxide within the films. The conductivity of r‐GO/PI composites (30:70 w/w) equaled 1.1 × 10¹ S m^?1, roughly 10¹⁴ times that of pure PI and the oxygen transmission rate (OTR, 30:70 w/w) was reduced by about 93%. The Young's modulus of the r‐GO/PI composite film containing 30 wt % GO increased to 4.2 GPa, which was an approximate improvement of 282% compared with pure PI film. The corresponding strength and the elongation at break decreased to 70.0 MPa and 2.2%, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40177.     

Improvement of mechanical,thermal and tribological properties of (3-aminopropyl) triethoxysilane-modified graphene/polyimide nanocomposites by in situ polymerisation

To elucidate the improvement and the principle of graphene modification on the polyimide (PI), (3-aminopropyl) triethoxysilane-modified graphene (PMG), was designed and prepared by anchoring the (3-aminopropyl) triethoxysilane (APTS) chain on the graphene sheet surface, and used to synthesise PI composites by in situ polymerisation. The unique surface modification significantly improved the compatibility and dispersion of graphene in the PI matrix. Tensile strength and Young’s modulus of 1.0PMG/PI was 109.45?MPa and 1.73?GPa, which increased by 54.26 and 86.02% from neat PI, respectively. The tribological properties and mechanism were also discussed. The friction coefficient and wear rate of 1.0PMG/PI (0.287, 2.291×10^?5mm³?Nm^?1) decreased by 47.53% and 35.06%, respectively. This improvement of the tribological properties was mainly caused by the cooperative interaction of the improved mechanical and thermal properties of the composites and the high self-lubricity of modified graphene.     

In situ Synthesis and mechanical,thermal properties of polyimide nanocomposite film by addition of functionalized graphene oxide

Polyimide (PI) and chemical modified graphene oxide nanocomposite films are prepared by in situ polymerization from solutions of pyromellitic dianhydride and 4,4′‐oxydianiline with various amount (0.5–2 wt%) of 3‐aminopropyltriethoxysilane (APTS) functionalized graphene oxide (GO) sheets in dimethylacetamide. The APTS functionalized GO (GO‐APTS) is a versatile platform for polymer grafting, improving excellent dispersion of GO in the PI matrix, and forming strong interaction with the PI matrix. The GO‐APTS/PI nanocomposites exhibited improvement in mechanical and thermal properties by addition of a small amount of GO‐APTS. With the addition of a small amount of GO‐APTS (1.5 wt%) to PI matrix, mechanical properties with the tensile strength and Young's modulus improved by 45% and 15%, respectively. The thermal analysis showed that the thermal stability of PI was slightly enhanced by the incorporation of GO‐APTS (1.5 wt%). This approach provides a strategy for developing high performance functionalized GO‐polymer composite materials. POLYM. COMPOS., 37:907–914, 2016. © 2014 Society of Plastics Engineers     

Polymer-clay nanocomposites prepared via in situ emulsion polymerization

A series of novel polystyrene and poly(butyl methacrylate) montmorillonites (MMT-Na) nanocomposite latexes have been successfully prepared by emulsion polymerization. First of all, chemical modification of MMT-Na with a reactive coupling agent (MMT-QS) has been employed for the synthesis of hybrids. Subsequently, in situ seeded emulsion polymerization of hydrophobic vinyl monomers, such as butyl methacrylate and styrene, using sodium dodecyl sulfate (SDS) and ammonium persulfate (APS) as surfactant and initiator, respectively, were used for nanocomposite preparation. This technique allowed preparing of stable nanocomposite latexes with high (30–45 wt.%) solids contents and with loading of inorganic particles up to 5 wt.%. The prepared wet dispersions were subsequently characterized by light scattering method. In order to characterize the microstructure of the clay layers, and that of the organoclay in polystyrene and poly(butyl methacrylate) nanocomposites, wide and small angle X-ray analyses (WAXS, SAXS) and transmission electron microscopy (TEM) techniques were used.     

The role of functional groups on graphene oxide in epoxy nanocomposites

The role of functional groups on the surface of graphene oxide (GO) upon its ability to reinforce an epoxy resin has been investigated. It is known that a base-washing process removes oxidative debris from as-prepared GO and reduces the number of functional groups in the material. Both as-prepared (aGO) and base-washed graphene oxide (bwGO) fillers were incorporated into an epoxy resin matrix and the mechanical properties of the different nanocomposites were investigated. The best levels of reinforcement were found with the addition of low loadings of aGO while the bwGO gave inferior levels of reinforcement at the same loading level. Raman spectroscopy was used to both assess the dispersion of the fillers and efficiency of stress transfer to the GO in the nanocomposites during deformation. It was found that for a given filler loading the aGO materials had the most uniform dispersion of filler and the largest Raman band shifts per unit strain, indicating the importance of the presence of functional groups in both dispersing the GO and giving good interfacial stress transfer in the nanocomposites.     

Thermal,electrical, and mechanical properties of polyethylene–graphene nanocomposites obtained by in situ polymerization

In this study, we investigated the thermal, dynamic mechanical, mechanical, and electrical properties of polyethylene (PE)–graphene nanosheet (GNS) nanocomposites, with GNS amounts from 0 to 20 wt %, prepared by in situ polymerization. The thermal stability was evaluated by thermogravimetric analysis (TGA) and showed that the addition of GNSs to the polyolefin matrix increased the onset degradation temperature by 30°C. The electrical conductivity, measured by the impedance technique, presented a critical percolation threshold of 3.8 vol % (8.4 wt %) of GNS. A slight decrease in the tensile strength was found. On the other hand, dynamic mechanical analysis showed an increase in the storage modulus of the nanocomposites compared with that of neat PE. The glass‐transition temperature value increased from ?111°C (neat PE) to ?106°C (PE/6.6 wt % GNS). All of these results show that PE became stiffer and thermally more stable and could be transformed from an insulator to a semiconductor material in the presence of GNSs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Performance improvement of polybenzoxazine by alloying with polyimide: effect of preparation method on the properties

Polymer alloys of polyimide and polybenzoxazine were prepared from the combination of a bifunctional benzoxazine monomer, 6,6′-(1-methylethylidene)bis(3,4-dihydro-3-2H-1,3-benzoxazine) (B-a) and a soluble polyimide (PI) or its precursor, poly(amide acid) (PAA), that was synthesized from oxydianiline (ODA) and bisphenol A di(phthalic anhydride) ether (BPADA). It was observed from DSC that the onset temperature for the curing exotherm of B-a in the blend with PAA was remarkably lowered compared with that of pristine B-a, while the curing temperature of B-a in the blend with PI was almost the same as that of pristine B-a. The cast films of PI/B-a or PAA/B-a were thermally treated at 150, 200 and 240 °C for 2 h each, affording deep wine, transparent films. The PI component in the polymer alloy films from PI/B-a dissolved thoroughly. On the other hand, the polymer alloy films from PAA/B-a were not soluble at all in NMP. The polymer alloy films from both PI/B-a and PAA/B-a showed only one glass transition temperature (T_g) from their viscoelastic analyses. The T_g values remarkably increased as the content of PI increased. The thermal stabilities of both films from PI/B-a and PAA/B-a increased as the PI component increased in the similar manner.     

Surface modification of polyimide films via plasma polymerization and deposition of allylpentafluorobenzene

Plasma polymerization of allylpentafluorobenzene (APFB) on the plasma-pretreated polyimide (PI) films was carried out. The fluorinated aromatic groups of the plasma-polymerized APFB (pp-APFB) could be preserved, to a large extent, by controlling the glow discharge parameters. The effect of the glow discharge parameters, including the type of the carrier gas and the input RF power, on the surface composition and chemical structure of the pp-APFB films were studied by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and time-of-flight secondary ion mass spectrometry. The surface topography of the APFB plasma-polymerized PI (pp-APFB-PI) films was studied by atomic force microscopy. For plasma polymerization carried out at a high RF power and using argon as the carrier gas, an ultra-hydrophobic pp-APFB-PI surface was also obtained. The ultra-hydrophobic surface exhibited advancing/receding water contact angles (θ_A/θ_R) of 174°/135°. The effectiveness of the carrier gas in defluorinating the pp-APFB films followed the order of O₂>N₂>H₂>Ar. Thus, the role of the carrier gas in improving the surface hydrophobicity of the resulting pp-APFB-PI films followed the order of O₂22® tape adhesion test.     

Preparation of polyimide/siloxane‐functionalized graphene oxide composite films with high mechanical properties and thermal stability via in situ polymerization

An effective approach to prepare polyimide/siloxane‐functionalized graphene oxide composite films is reported. The siloxane‐functionalized graphene oxide was obtained by treating graphene oxide (GO) with 1,3‐bis(3‐aminopropyl)‐1,1,3,3‐tetra‐methyldisiloxane (DSX) to obtain DSX‐GO nanosheets, which provided a starting platform for in situ fabrication of the composites by grafting polyimide (PI) chains at the reactive sites of functional DSX‐GO nanosheets. DSX‐GO bonded with the PI matrix through amide linkage to form PI‐DSX‐GO films, in which DSX‐GO exhibited excellent dispersibility and compatibility. It is demonstrated that the obvious reinforcing effect of GO to PI in mechanical properties and thermal stability for PI‐DSX‐GO is obtained. The tensile strength of a composite film containing 1.0 wt% DSX‐GO was 2.8 times greater than that of neat PI films, and Young's modulus was 6.3 times than that of neat PI films. Furthermore, the decomposition temperature of the composite for 5% weight loss was approximately 30 °C higher than that of neat PI films. © 2015 Society of Chemical Industry     

Enhanced thermal and mechanical properties of epoxy composites by mixing noncovalently functionalized graphene sheets

Polymer Bulletin - In this study, a novel thermotropic liquid crystal perylene bisimides polyurethane (LCPU) was synthesized using 3,4,9,10-perylenetetracarboxylic acid anhydride (PTCDA),...     

A novel cross-linked polyimide film: synthesis and dielectric properties

A novel cross-linked polyimide (CPI) has been prepared by imidization of cross-linked poly(amic acid) (CPAA). In this work, the Ac conductivity and dielectric properties of this polyimide are presented comparitively with those of conventional polyimide (PI), in the 0.2-100 kHz frequency range and 300-463 K temperature interval. Although the frequency and temperature dependencies of dielectric constant of both conventional and cross-linked polyimides show the same behaviour, the dielectric constant of CPI takes lower values. The Ac conduction studies suggest that electron hopping is responsible for conduction of the PI and CPI films. The activation energy calculated in 296-353 K temperature interval and the ß-relaxation was also observed for CPI.     

Enhanced mechanical properties of glass fibre epoxy composites by 2D exfoliated graphene oxide filler

Graphene oxide (GO) received a significant attention in the scientific community due to their excellent mechanical properties identifying themselves as an alternative and combinatory to various other metals and composites. Though GO possess excellent strength, it was observed from the literature that graphene oxide consisting of hydroxyl group elements ensue in poor bonding. Thus reduced functional group density (rFGD) graphene is preferred which has an advantage of good bonding, alongside very small quantity as a filler is required to achieve the enhancement equivalent to graphene oxide which forms the novelty of the current work. In current case, 3, 6 and 9 wt% of rFGD is dispersed into E-glass fibre reinforced composite by traditional hand layup technique. The obtained results revealed that, the tensile, flexural and impact strength have shown superior enhancement with 3 and 6 wt% of rGO than neat E-glass epoxy (0 wt% rGO), whereas an asymptotic decrement is noticed at 9 wt% when tested with ASTM standards except for impact strength. The microstructural studies also indicated the proper adhesion and alignment of fibres without any agglomerations corroborate the enhancement of properties. These overall finding supports the suitability of the developed laminates for potential use in structural applications in aerospace industry.     

Nano-sized graphene oxide as sole surfactant in miniemulsion polymerization for nanocomposite synthesis: Effect of pH and ionic strength

Miniemulsion polymerization of styrene using AIBN as initiator at 70 °C has been performed with nano-dimensional graphene oxide (GO) sheets as surfactant (no conventional surfactants employed) with a view to exploring the effects of pH and ionic strength (NaCl concentration). The pH value of the emulsion exerted a relatively minor influence on the polymerization, with a somewhat narrower particle size distribution being obtained at pH = 3.2 relative to pH = 2.4 and 5.2. The ionic strength had a more significant effect – the presence of a suitable concentration of NaCl resulted in increased colloidal stability and narrower particle size distribution. The results are explained in terms of the effects of pH on degree of ionization of COOH groups of GO and the influence of ionic strength on the electric double layer, and have implications with regards to synthesis of polymer/graphene nanocomposite materials for a variety of applications.     

Relationship between microstructure of lamellar graphene sheets and properties of polyimide/graphene nanocomposites film under different imidization stages

Herein, polyimide/graphene sheets (PI/GS) nanocomposite films with different GS distribution structures have been successfully obtained by controlling the imidization degrees, and the effect of the lamellar structure on the properties of PI film has been investigated. The results show that GS are gradually parallel to the surface of PI nanocomposite film with the increase of the imidization temperature, and 150 °C is the critical temperature, where the imidization rate is the fastest and the lamellar structure begins to form. Furthermore, with the drying temperature increasing, the corresponding thermal, electrical and mechanical properties of PI/GS nanocomposite films are significantly improved compared with that of pure PI films, which are ascribed to both the higher imidization degree and the lamellar GS structure. It is noteworthy that the formation process of the lamellar structure at different imidization stages can be directly observed by scanning electron microscope. Based on these results, a model has been proposed to explain the relationship between the lamellar structure and properties of PI composite film under different imidization stages, and the confinement of the thickness may be the most important factor for the formation of lamellar GS structure. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43575.     

Enhancement of physical properties of electroactive polyimide nanocomposites by addition of graphene nanosheets

Electroactive polyimide (EPI) nanocomposites with amino‐capped aniline trimer and 4′‐(4,4′‐isopropylidene‐diphenoxy)bis(phthalic anhydride) as monomers, and functionalized with carboxyl‐graphene nanosheets, were prepared by thermal imidization. The as‐prepared electroactive polyimide/graphene nanocomposite (EPGN) materials were then characterized by Fourier transform infrared spectroscopy and transmission electron microscopy. In situ monitoring of the redox behavior of the as‐prepared EPGN materials was performed by cyclic voltammetry studies. The effects of material composition on the mechanical, thermal, thermal transport, dielectric and molecular barrier properties of EPGN membranes were investigated by dynamic mechanical analysis, TGA, DSC, the transient plane source technique, LCR meter and gas permeability analyzer, respectively. It should be noted that all the properties of the EPGN membranes were found to improve substantially over those of non‐electroactive polyimide and EPI. For example, upon loading of 1 wt% graphene, EPGN membranes were found to have an increase of over 20%, 5%, 65% and 20% in mechanical strength, thermal stability, thermal conductivity and dielectric constant, respectively, and a reduction of over 20% in gas permeability. © 2013 Society of Chemical Industry     

A review on synthesis and properties of polymer functionalized graphene

This review highlights the functionalization chemistry of graphene with polymers by both covalent and non-covalent approaches. Due to the strong cohesive interactions graphene platelets agglomerate, causing difficulty to attain its optimum properties. The covalent functionalization is illuminated both from ‘grafting to’ and ‘grafting from’ techniques discussing the merits and demerits of the processes. The controlled free radical polymerization techniques used for this purpose e.g. ATRP, SET–LRP and RAFT etc. are discussed along with the conventional free radical polymerization. We have also noted the various approaches used in non-covalent functionalization e.g. π–π, H-bonding and hydrophobic interactions. These functionalized graphenes show good and stable dispersion facilitating composite formation with commodity plastics enhancing it's mechanical, thermal and conductivity properties. The optoelectronic properties of these functionalized graphene are interesting to fabricate sensors, photovoltaics, supercapacitors etc. A short account of the properties of these modified graphenes is also embodied with an emphasis on different area where future developments are expected.     

Poly(trimethylene terephthalate) nanocomposite fibers by in situ intercalation polymerization: thermo-mechanical properties and morphology (I)

A series of poly(trimethylene terephthalate) (PTT) nanocomposites, containing an organically modified montmorillonite (C₁₂PPh-MMT), were prepared by in situ intercalation polymerization of dimethyl terephthalate (DMT) and 1,3-propanediol (PDO). The PTT nanocomposites were melt-spun at different organoclay contents and different draw ratios (DRs) to produce monofilaments. The nanocomposites were characterized by X-ray diffraction, electron microscopy, universal tensile testing, differential scanning calorimetry and thermogravimetric analysis. Some of the clay particles appeared well dispersed within the PTT matrix, while others were found to agglomerate with a size greater than 10 nm. The addition of a small amount of C₁₂PPh-MMT was sufficient to improve the thermo-mechanical properties of the PTT hybrid fibers. Both the thermal stability and the tensile strength increased with increasing clay content at DR=1. As the DR was increased from 1 to 9, the ultimate tensile strength of the hybrid fibers decreased, while the initial modulus remained constant.     

Enhanced mechanical and thermal properties of biodegradable poly(butylene succinate‐co‐adipate)/graphene oxide nanocomposites via in situ polymerization

Poly(butylene succinate‐co‐butylene adipate) (PBSA)/graphene oxide (GO) nanocomposites were synthesized via in situ polymerization for the first time. Atomic force microscopy demonstrated the achievement of a single layer of GO, and transmission electron microscopy proved the homogeneous distribution of GO in the PBSA matrix. Fourier transform infrared spectroscopy results showed the successful grafting of PBSA chains onto GO. With the incorporation of 1 wt % GO, the tensile strength and flexural modulus of the PBSA were enhanced by 50 and 27%, respectively. The thermal properties characterized by differential scanning calorimetry and thermogravimetric analysis showed increases in the melting temperatures, crystallization temperatures, and thermal stability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4075–4080, 2013