Aminofunctionalization effect on the microtribological behavior of carbon nanotube/bismaleimide nanocomposites

Original multiwalled carbon nanotubes (O‐MWCNTs) and aminofunctionalized ethylenediamine‐treated multiwalled carbon nanotubes (MWCNTs‐EDA) were mixed with bismaleimide (BMI) resin to prepare O‐MWCNT/BMI and MWCNT‐EDA/BMI composites, respectively. Raman spectroscopy, thermogravimetric analysis, and infrared spectroscopy were used to investigate the influence of aminofunctionalization on the multiwalled carbon nanotube (MWCNT) framework. Dynamic mechanical analysis, scanning electron microscopy images of the fractured surface, and field emission scanning electron microscopy of the worn surface were used to determine the possible friction and wear mechanisms of the system. The MWCNT‐EDA/BMI composite exhibited a higher friction coefficient value and a lower wear loss rate value than the O‐MWCNT/BMI composite, which was attributed to the larger number of defects caused by the aminofunctionalization of the MWCNTs, the stronger interfacial adhesion formed between the MWCNTs‐EDA and the BMI resin, and the better dispersive state of the MWCNTs‐EDA in the BMI matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Natural rubber/multiwalled carbon nanotube composites developed with a combined self-assembly and latex compounding technique

Carbon nanotubes (CNTs), with their high aspect ratio and exceptionally high mechanical properties, are excellent fillers for composite reinforcement if they are uniformly dispersed without aggregation. Combining the latex compounding and self-assembly techniques, we prepared a novel natural rubber (NR)/multiwalled carbon nanotube (MWCNT) composite. Before self-assembly, the MWCNTs were treated with mixed acid to ensure that the MWCNTs were negatively charged under an alkaline environment. The structure of the MWCNTs was tested with Fourier transform infrared spectroscopy. The properties of composites with different MWCNT loadings were characterized with transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, and tensile testing. The results indicate that the MWCNTs were homogeneously distributed throughout the NR matrix as single tubes and had good interfacial adhesion with the NR phase when the MWCNT loading was less than 3 wt %. In particular, the addition of the MWCNT led to a remarkable reinforcement in the tensile strength, with a peak value of 31.4 MPa for an MWCNT content of 2 wt %, compared to the pure prevulcanized NR (tensile strength = 21.9 MPa). The nanocomposites reinforced with MWCNTs should have wide applications because of the notable improvement in these important properties. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effects of glucose‐functionalized multiwalled carbon nanotubes on the structural,mechanical, and thermal properties of chitosan nanocomposite films

A series of multiwalled carbon nanotubes (MWCNTs) grafted by chitosan nanocomposite (NC) films were prepared by a direct blending process and solution casting method. In this study, we modified multiwalled carbon nanotubes with glucose (MWCNT–Gl) for this purpose, and the effects of MWCNT–Gl on the structural, mechanical, and thermal properties of chitosan films with different contents of MWCNT–Gl were investigated. The structure, thermal stability, and mechanical properties of the composite were examined by X‐ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, and mechanical testing. The results indicate that the MWCNTs treated by glucose were dispersed well in the chitosan matrix, and the tensile properties of the NC films were improved greatly compared with neat chitosan. Also, with increasing MWCNT–Gl content, the crystalline nature of chitosan decreased. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42022.     

High performance polyurethane composites with isocyanate‐functionalized carbon nanotubes: Improvements in tear strength and scratch hardness

A microwave‐assisted functionalization of carbon nanotubes (CNTs) with isocyanate groups allowed a reduction of functionalization time from 24 h to 30 min with no change in the degree of functionalization or in the nanotube characteristics. Polymer nanocomposites with enhanced mechanical properties were obtained because of the tailored interface by the covalent linkage between the surface‐modified multiwalled‐carbon nanotubes (MWCNTs) and an elastomeric polyurethane (PUE) matrix. The mechanical data revealed that the composite containing 0.25 wt % of MWCNT‐NCO showed an increase of 31% in tear strength and 28% in static toughness. A good adhesion between the matrix and individually dispersed nanotubes was observed in the scanning electron microscopy and transmission electron microscopy images. Nanoindentation and nanoscratch experiments were conducted to investigate the properties on the sub‐surface. An increase by a factor of 3 in the scratch hardness was observed for the composite with 0.50 wt % of MWCNT‐NCO with respect to the neat PUE. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44394.     

Improving thermal conductivity and shear strength of carbon nanotubes/epoxy composites via thiol‐ene click reaction

This study investigates the effect of the thiol‐ene click reaction on thermal conductivity and shear strength of the epoxy composites reinforced by various silane‐functionalized hybrids of sulfhydryl‐grafted multi‐walled carbon nanotubes (SH‐MWCNTs) and vinyl‐grafted MWCNTs (CC‐MWCNTs). The results of Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, thermal gravimetric analysis (TGA), and transmission electron microscopy (TEM) show that the sulfhydryl groups and vinyl groups are successfully grafted onto the surface of MWCNTs, after treatment of MWCNT with triethoxyvinylsilane and 3‐mercaptopropyltrimethoxysilane, respectively. Scanning electron microscopy (SEM), HotDisk thermal constant analyzer (HotDisk), optical microscope, and differential scanning calorimetry (DSC) are used to characterize the resultant composites. It is demonstrated that the hybrid of 75 wt % SH‐MWCNTs and 25 wt % CC‐MWCNTs has better dispersion and stability in epoxy matrix, and shows a stronger synergistic effect in improving the thermal conductivity of epoxy composite via the thiol‐ene click reaction with 2,2′‐azobis(2‐methylpropionitrile) as thermal initiator. Furthermore, the tensile shear strength results of MWCNT/epoxy composites and the optical microscopy photographs of shear failure section indicate that the composite with the hybrid MWCNTs has higher shear strength than that with raw MWCNTs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44579.     

Toughening of cycloaliphatic epoxy resin by multiwalled carbon nanotubes

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

High dispersion ability of fluorene‐based polyester as a polymer matrix for carbon nanotubes

The high compatibility of fluorene‐based polyester (FBP‐HX) as a polymer matrix for multiwalled carbon nanotubes (MWCNTs) is discussed. A low surface resistivity due to the fine dispersion of MWCNTs in FBP‐HX and polycarbonate (PC) is reported. With a solution‐casting method, a percolation threshold with the addition of between 0.5 and 1.0 wt % MWCNTs was observed in the MWCNT/PC and MWCNT/FBP‐HX composites. Because of the coverage of FBP‐HX on the MWCNTs, a higher surface resistivity and a higher percolation ratio of the MWCNT/FBP‐HX composites were achieved compared with the values for the MWCNT/PC composites. In the MWCNT/FBP‐HX composites, MWCNTs covered with FBP‐HX were observed by scanning electronic microscopy. Because of the coverage of FBP‐HX on the MWCNTs, FBP‐HX interfered with the electrical pathway between the MWCNTs. The MWCNTs in FBP‐HX were covered with a 5‐nm layer of FBP‐HX, but the MWCNTs in the MWCNT/PC composites were in their naked state. MWCNT/PC sheets demonstrated the specific Raman absorption of the MWCNTs only with the addition of MWCNTs of 1 wt % or above because of the coverage of the surface of the composite sheet by naked MWCNTs. In contrast, MWCNT/FBP‐HX retained the behavior of the matrix resin until a 3 wt % addition of MWCNTs was reached because of the coverage of MWCNTs by the FBP‐HX resin, induced by its high wettability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dispersion of multiwalled carbon nanotubes in polyacrylonitrile‐co‐starch copolymer matrix for enhancement of electrical,thermal, and gas barrier properties

Nanomaterials gained great importance on account of their wide range of applications in many areas. Carbon nanotubes (CNTs) exhibit exceptional electrical, thermal, gas barrier, and tensile properties and can therefore be used for the development of a new generation of composite materials. Functionalized multiwalled carbon nanotubes (MWCNTs) reinforced Polyacrylonitrile‐co‐starch nanocomposites were prepared by in situ polymerization technique. The structural property of PAN‐co‐starch/MWCNT nanocomposites was studied by X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. The conductivity, tensile strength, and thermal properties of nanocomposites were measured as a function of MWCNT concentrations. The thermal stability, conductivity, and tensile strength of PAN‐co‐starch/MWCNT nanocomposites were improved with increasing concentration of MWCNTs. Oxygen barrier property of PAN‐co‐starch/MWCNT nanocomposites was calculated and it was found that, the property was reduced substantially with increase of MWCNTs proportion. The synthesized PAN‐co‐starch/MWCNT nanocomposites may used for electrostatically dissipative materials, aerospace or sporting goods, and electronic materials. © 2013 Society of Plastics Engineers     

Preparation and characterization of poly(trimethylene terephthalate)‐poly(ethylene oxide terephthalate) segmented copolymer/multiwalled carbon nanotubes composites by in situ polymerization

Poly(trimethylene terephthalate)‐poly(ethylene oxide terephthalate) block copolymer (PTG)/multiwalled carbon nanotubes (MWCNTs) composites were prepared via in situ polymerization. To improve the dispersion of MWCNTs in the PTG matrix, the poly(ethylene glycol)‐grafted multiwalled carbon nanotubes (MWCNT‐PEG) were produced by the “graft to” method. The transmission electron microscopy observation demonstrated that a homogeneous dispersion of MWCNT‐PEG was obtained. As a consequence, the percolation threshold for the rheology was around 0.5 wt% and the conductivity was ～1 wt%, respectively. Differential scanning calorimetry and polarized optical microscopy results confirmed that MWCNT‐PEG can act as an effective heterogeneous nucleating agent. Interestingly, the effects of MWCNT‐PEG on crystallization and melting of the poly(ethylene oxide terephthalate) blocks were more pronounced than on those of the PTT blocks. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Nanocomposites of poly(ethylene oxide) and multiwall carbon nanotube prepared using an organic salt‐assisted dispersion technique

Poly (ethylene oxide) (PEO)/multiwall carbon nanotubes (MWCNT) nanocomposites were prepared by dispersion of MWCNTs in aqueous solution using half neutralized sodium salt of sebacic acid as a modifier. The physical interaction of half neutralized sodium salt of sebacic acid with MWCNT (cation‐π interaction) has been established by using Fourier transform infrared and Raman spectroscopic analyses. Such interaction helps in debundling the MWCNTs and resulted in a better dispersion in PEO matrix as confirmed by scanning electron microscopy and transmission electron microscopy. Addition of MWCNT significantly improves the storage modulus in rheological measurements as well as in dynamic mechanical thermal analysis. The crystallization behaviors of the composites made with the unmodified and modified MWCNTs were investigated. The modified MWCNT‐based composites shows large number of spherulite with smaller size compared to those observed in unmodified MWCNT‐based composite. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers     

Fabrication of polystyrene/multiwalled carbon nanotube composite films synthesized by in situ microemulsion polymerization

A microemulsion polymerization method was used to achieve better compatibility between polystyrene (PS)/multiwalled carbon nanotubes (MWCNTs) nanocomposites and the host PS matrix to form films with excellent electrical and thermal properties. The films were prepared by embedding the PS/MWCNTs nanocomposite into the PS matrix. The MWCNTs were functionalized with PS nanoparticles to avoid the phase separation problem between the filler and host matrix and to enhance the good dispersibility of MWCNTs in the PS host matrix. The confirmation of the synthesis was analyzed by Fourier transform infrared spectroscopy, nuclear magnetic resonance, and Raman spectroscopy. The variation effect of the PS‐linking density on the MWCNT was revealed by scanning electron microscopy and transmission electron microscopy. An enhancement of the thermal and mechanical properties was revealed by thermal gravimetric analysis, differential scanning colorimetric analysis, and dynamic mechanical analysis. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Microwave assisted functionalization of carboxylated‐multiwalled carbon nanotubes with 5‐aminoisophthalic acid and its application for the preparation of chiral poly(ester‐imide)/CNT nanocomposites

This article presents the results of investigation into surface modification of carboxylated‐multiwalled carbon nanotubes (MWCNT)s by 5‐aminoisophthalic acid under microwave irradiation as a fast, safe, and simple method. The different contents of functionalized MWCNTs (5, 10, 15 wt%) were effectively dispersed in an aromatic polymer through ultrasonic irradiation to prepare MWCNT reinforced polymer nanocomposites (NC)s. The chiral poly(ester‐imide) (PEI) was prepared by a direct polycondensation of chiral diacid with 4,4′‐thiobis(2‐tert‐butyl‐5‐methylphenol). The effect of the presence of MWCNTs on morphological and thermal properties of the NCs was investigated by X‐ray diffraction, FT‐IR spectroscopy, thermogravimetric analysis (TGA), transmission electron microscopy, and field emission scanning electron microscopy. According to TGA data, the PEI/MWCNT NCs showed a much better thermal stability than pristine polymer. The microstructure study of the NCs indicated the compatibility of functionalized MWCNTs with PEI and uniform distribution of them in the polymer matrices. POLYM. COMPOS., 37:835–843, 2016. © 2014 Society of Plastics Engineers     

Multiwalled carbon nanotubes functionalized with maleated poly(propylene) by a dry mechano-chemical process

Ball milling was used to graft maleated polypropylene (MAPP) on the surface of multiwalled carbon nanotubes (MWCNTs), with a view to preparing MWCNT/polypropylene composites with improved matrix/nanotube compatibility. The occurrence of the grafting reaction was evaluated by FTIR spectroscopy and the yield was quantified by thermogravimetric analysis, as a function of the milling time. Dispersion experiments confirmed the nanotube surface modification of the nanotubes since functionalized MWCNTs remained stably dispersed in an ethanol/xylene solution for more than 48 h after sonication. No evidences of significant structural damage after the mechano-chemical treatment were shown by Raman spectroscopy. Moreover, a layer attributable to the presence of grafted MAPP chains on MWCNT walls was clearly detected by transmission electron microscopy. The average thickness of this amorphous layer was evaluated and compared with quantitative TGA data.     

in situ synthesis of biopolyurethane nanocomposites reinforced with modified multiwalled carbon nanotubes

Biopolyurethane nanocomposites reinforced with silane‐modified multiwalled carbon nanotubes (s‐MWCNT) were successfully prepared. The carbon nanotube surfaces were modified by means of functional amine groups via ozone oxidation followed by silanization. The surface structure of the s‐MWCNTs was characterized by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and thermogravimetric analysis. The s‐MWCNTs were incorporated into a vegetable oil‐based polyurethane (PU) network via covalent bonding to prepare PU nanocomposites. The effect of s‐MWCNT loading on the morphology, thermomechanical, and tensile properties of the PU nanocomposites was studied. It was determined that the s‐MWCNTs were dispersed effectively in the polymer matrix and that they improved the interfacial strength between the reinforcing nanotubes and the polymer matrix. Storage modulus, glass transition temperature, Young's modulus, and tensile strength of the nanocomposites increased with increasing s‐MWCNT loading up to 0.8%. However, increasing the s‐MWCNT content to 1.2 wt % resulted in a decrease in thermomechanical properties of the PU nanocomposites. This effect was attributed to the fact that at high s‐MWCNT contents, the increased number of amine groups competed with the polyol's hydroxyl groups for isocyanate groups, causing a decrease in the integrity of the PU matrix. High s‐MWCNT contents also facilitated aggregation of the nanotubes, causing a decrease in thermomechanical properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42515.     

Controlled dispersion of multiwalled carbon nanotubes modified by hyperbranched polylysine

Hyperbranched polymers have been found effective in controlling the dispersibility of carbon nanotubes in aqueous solutions. In this study, hyperbranched polylysine (HBPL) was synthesized using lysine and N,N′‐methylenebisacrylamide as precursors via Michael addition. The HBPL then was used to noncovalently modify multiwalled carbon nanotubes (MWCNTs) to prepare MWCNTs‐HBPL. The obtained MWCNTs‐HBPL composites were characterized using FTIR spectroscopy, Raman spectroscopy, thermogravimetric analysis, and scanning electron microscopy. The results showed that the HBPL was successfully attached to the surface of MWCNTs via noncovalent interactions. The dispersibility of the MWCNTs‐HBPL composites in aqueous solutions was investigated using digital photographs, ultraviolet–visible absorption spectroscopy, and zeta potential measurements. The results demonstrated that both the mass ratio of MWCNT to HBPL and the pH of the solution had a significant impact on the dispersibility of the MWCNTs/HBPL solution, suggesting that HBPL treatment is an effective method of controlling the dispersibility of MWCNTs in aqueous solutions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46249.     

Polystyrene composites containing crosslinked polystyrene‐multiwalled carbon nanotube balls

Crosslinked polystyrene‐multiwalled carbon nanotube (PS‐MWCNT) balls, which act as conductive microfillers, were prepared by the in situ suspension polymerization of styrene with MWCNTs and divinyl benzene (DVB) as a crosslinking agent. The diameters of the synthesized crosslinked PS‐MWCNT balls ranged from 10 to 100 μm and their electrical conductivity was about 7.7 × 10^?3 S/cm. The morphology of the crosslinked PS‐MWCNT balls was observed by scanning electron microscopy and transmission electron microscopy. The change in the chemical structure of the MWCNTs was confirmed by Raman spectroscopy and Fourier transform infrared spectroscopy. The mechanical and electrical properties of the PS/crosslinked PS‐MWCNT ball composites were investigated. It was found that the tensile strength, ultimate strain, Young's modulus, and impact strength of the PS matrix were enhanced by the incorporation of the crosslinked PS‐MWCNT balls. In addition, the mechanical properties of the PS/crosslinked PS‐MWCNT ball composites were better than those of the PS/pristine MWCNT composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Properties of surface‐modified multiwalled carbon nanotube filled poly(ethylene terephthalate) composite films

Poly(ethylene terephthalate) (PET)/multiwalled carbon nanotube (MWCNT) composites were prepared by in situ polymerization. To improve the dispersion of MWCNTs in the PET matrix, functionalized MWCNTs having acid groups (acid‐MWCNTs) and acetic groups (acetic‐MWCNTs) on their surfaces were used. The functional groups were confirmed by infrared spectrometry. Scanning electron microscopy showed that acetic‐MWCNTs had a better dispersion in the PET matrix than pristine MWCNTs and acid‐MWCNTs. A reaction between PET and acetic‐MWCNTs was confirmed by a shift of the Raman G band to a higher frequency and an increase of the complex viscosity in the rheological properties. The composites containing functionalized MWCNTs showed a large increase in their tensile strengths and moduli. The values of the strengths and moduli of the PET/acetic‐MWCNT composites were higher than those of the PET/acid‐MWCNT composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Functionalization of carbon nanotubes with (3‐glycidyloxypropyl)‐trimethoxysilane: Effect of wrapping on epoxy matrix nanocomposites

In this work, multiwalled carbon nanotubes (MWCNT), after previous oxidation, are functionalized with excess (3‐glycidyloxypropyl)trimethoxysilane (GLYMO) and used as reinforcement in epoxy matrix nanocomposites. Infrared, Raman, and energy‐dispersive X‐ray spectroscopies confirm the silanization of the MWCNT, while transmission electron microscopy images show that oxidized nanotubes presented less entanglement than pristine and silanized MWCNT. Thickening of the nanotubes is also observed after silanization, suggesting that the MWCNT are wrapped by siloxane chains. Field‐emission scanning electron microscopy reveals that oxidized nanotubes are better dispersed in the matrix, providing nanocomposites with better mechanical properties than those reinforced with pristine and silanized MWCNT. On the other hand, the glass transition temperature of the nanocomposite with 0.05 wt % MWCNT‐GLYMO increased by 14 °C compared to the neat epoxy resin, suggesting a strong matrix–nanotube adhesion. The functionalization of nanotubes using an excess amount of silane can thus favor the formation of an organosiloxane coating on the MWCNT, preventing its dispersion and contributing to poor mechanical properties of epoxy nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44245.     

Improvement in properties of multiwalled carbon nanotube/polypropylene nanocomposites through homogeneous dispersion with the aid of surfactants

The effects of different surfactants on the properties of multiwalled carbon nanotubes/polypropylene (MWCNT/PP) nanocomposites prepared by a melt mixing method have been investigated. Sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate (NaDDBS) were used as a means of noncovalent functionalization of MWCNTs to help them to be dispersed uniformly into the PP matrix. The effects of these surfactant‐treated MWCNTs on morphological, rheological, thermal, crystalline, mechanical, and electrical properties of MWCNT/PP composites were studied using field emission scanning electron microscopy, optical microscopy, rheometry, tensile, and electrical conductivity tests. It was found that the surfactant‐treatment and micromixing resulted in a great improvement in the state of dispersion of MWCNTs in the polymer matrix, leading to a significant enhancement of Young's modulus and tensile strength of the composites. For example, with the addition of only 2 wt % of SDS‐treated and NaDDBS‐treated MWCNTs, the Young's modulus of PP increased by 61.1 and 86.1%, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of aminosilane‐functionalized carbon nanotubes on the rheometric,mechanical, electrical and thermal degradation properties of epoxidized natural rubber nanocomposites

We describe the preparation, characterization and physical properties of multiwalled carbon nanotube (MWCNT)‐filled epoxidized natural rubber (ENR) composites. To ensure better dispersion in the elastomer matrix, the MWCNTs were initially subjected to aminopropyltriethoxysilane (APS) treatment to bind amine functional groups (?NH₂) on the nanotube surface. Successful grafting of APS on the MWCNT surface through Si–O–C linkages was confirmed using Fourier transform infrared spectroscopy. Grafting of APS on the MWCNT surface was further corroborated using elemental analysis. ENR nanocomposites with various filler loadings were prepared by melt compounding to generate pristine and APS‐modified MWCNT‐filled elastomeric systems. Furthermore, we determined the effects of various filler loadings on the rheometric, mechanical, electrical and thermal degradation properties of the resultant composite materials. Rheometric cure characterization revealed that the torque difference increased with pristine MWCNT loading compared to the gum system, and this effect was more pronounced when silane‐functionalized MWCNTs were loaded, indicating that this effect was due to an increase in polymer–carbon nanotube interactions in the MWCNT‐loaded materials. Loading of silane‐functionalized MWCNTs in the ENR matrix resulted in a significant improvement in the mechanical, electrical and thermal degradation properties of the composite materials, when compared to gum or pristine MWCNT‐loaded materials.© 2013 Society of Chemical Industry