The potential of polymerization in a dispersed system as an attractive technique for polymer/graphene composite synthesis is discussed. This overview is focused on the preparation of graphene/polymer composite materials by two methods: (i) emulsion mixing or blending of polymer and graphene aqueous dispersions, and (ii) in situ polymerization in a dispersed system (emulsion, miniemulsion, microemulsion, and Pickering‐stabilized emulsion). Various methods for the stabilization of graphene nanoplatelets (GNPs) prior to composite preparation are presented, and the established specific interactions between the filler and the matrix are discussed. The determination of the electrical conductivity and the opportunity offered by polymerization in a dispersed system for the formation of a segregated network of graphene filler in the frame of a polymer matrix are presented. The mechanical and thermal properties of the composites are also discussed. A short summary of the open questions regarding the synthesis of water‐borne polymer/graphene composites is presented.
A facile method to fabricate ionic polymer‐metal composite (IPMC) actuators is proposed. A blend of mesoporous graphene (MG) and Nafion is used as the ionic matrix, which is sandwiched by two layers of blend of reduced graphene oxide (rGO) and Nafion as the electrodes. When subjected to an electrical field of 3 V, the IPMC actuator exhibits a blocking force of 10 gf g?1 for 20 s, and the same behavior can be repeatedly played for hundreds of cycles. MG improves the mechanical properties of Nafion‐based IPMC, more importantly, the mesopores in graphene provide additional pathway for the diffusion of cationic clusters and thus enhance the actuation speed. In addition, the surface electrodes of rGO protect the interlamellar liquid from evaporation thus ensure the durability.
Although graphene‐based materials have been used as fillers in polymer nanocomposites, a deleterious trade‐off in mechanical strength and ductility is typically observed with increasing graphene loading, resulting in strong but brittle polymer nanocomposite materials. To provide outstanding compatibility with a standard high strength polymer, thermoplastic polyurethane (TPU), the use of a simple and mild sol‐gel reaction to chemically attached silica nanoparticles to graphene oxide (GO) basal plane is reported. The silica modification imparts a highly porous GO surface structure, providing noncovalent attachment sites that improve physical entanglement between the GO and TPU. Furthermore, the silica modification enhances surface polarity, which imparts chemical affinity between the silica/GO nanocomposite and TPU. As a result, the prepared polymer nanocomposites exhibit significantly improved Young's modulus and tensile strength with only a small reduction of elongation at break over the neat polymer.
Composites of ethylene‐vinyl acetate (EVA) reinforced with graphene platelets are fabricated. Morphological, thermal, mechanical, electrical properties as well as moisture absorption of the composites are characterized. Transmission electron microscopy shows a good dispersion of graphene platelets in the matrix. The unidirectional orientation of graphene platelets parallel to the surface of the composites is revealed by field emission scanning electron microscopy and is validated using the Halpin–Tsai model. Tensile strength and elongation of the composites are respectively improved by 109 and 83%, after the addition of 3 wt% graphene platelets. The incorporation of 5 wt% graphene platelets enhances the char residue of the composites from 0.544% for pure EVA to 6.63% for the composites. The electrical conductivity of the composite with 3 wt% graphene platelets is two orders of magnitude higher than that of pure EVA with 10−13 S cm–1 electrical conductivity.
This study deals with the investigation of photocurable thiol‐yne resins covering several important aspects for the production of medical devices by UV‐based manufacturing processes. In this context, the performance of different low‐toxic photoinitiators (PIs) and stabilizers are evaluated in thiol‐yne formulations based on di(but‐1‐yn‐4‐yl) carbonate and various multifunctional thiol monomers. Photodifferential scanning calorimetry measurements reveal that the conversion of all resin formulations is mostly independent on the type and concentration of the applied photoinitiator; however, significant differences in their curing speed are observed. It turns out that the migration of an alkyne derivatized photoinitiator is significantly reduced while providing almost similar photoactivity as its nonfunctionalized reference. Moreover, it is found that lauryl gallate and butylated hydroxytoluene lead to significant stabilization without affecting the overall photoreactivity. Notably, the thermomechanical properties of the investigated photopolymers are only slightly affected by water absorption. Using ester free thiols, water absorption can be reduced and hydrolytically stable polymers are realized. These results highlight the versatility of the present thiol‐yne system for the production of medical materials by photopolymerization.
Homo and copolymers of metallocenic poly(propylene) with 1‐hexene and 1‐octadecene are used to prepare nanocomposites via melt mixing by using graphite nanosheets (GNSs) as filler. Different amounts of GNSs are used in order to study the influence of the filler on the thermal, mechanical, and electrical properties of nanocomposites. Significant changes have been observed in the crystallization temperature (Tc) of the nanocomposites. Thermogravimetric analysis shows improvement in thermal stability. Young's modulus and elongation at break of the nanocomposites are depended on the type of the matrix and the amount of GNSs. Materials with high flexibility are obtained in the cases of matrices based on copolymers even at high filler loading. Nanocomposites have become a semiconductor material reaching conductivity of 10?4 S cm?1. Two different thermal treatments have been applied in the preparation of the films by compression molding. X‐ray diffraction analysis shows the existence of polymorphism according to the thermal treatment applied.
Graphene has resulted in significant research effort to generate polymer nanocomposites with improved mechanical, thermal as electrical properties as compared to pure polymers. A large number of studies have been undertaken using different graphene derivatives, filler loadings, synthesis methods, and so on to obtain optimum filler dispersion as well as filler–matrix interactions, which are crucial for achieving significant enhancement in the properties, especially at low filler fraction. This review summarizes the mechanical and thermal properties of numerous studies carried out for the property enhancements of commercially relevant thermosetting materials such as epoxy, polyurethane, natural rubber, melamine formaldehyde, phenol formaldehyde, silicones, vinyl ester, cyanate ester, and unsaturated polyester resin.
Subwavelength nanostructure arrays on surfaces improve their optical transmittance by reducing the reflection of light over a wide range of wavelengths and angles of incidence. A method to imprint a sub‐100 nm nanostructure array on a large surface (Ø 20 mm) made from thermoplastic materials is reported. Transmittance through the flat polymer is improved by ≈6.5%, reaching values of up to 97.5%, after imprinting. The optical properties of the nanostructured samples are highly reproducible. After eight repeated imprinting operations with the same stamp, the transmittance of the nanostructured surface is decreased by less than 0.2%. Moreover, the nanostructures can also be imprinted on curved polymethylmethacrylate surfaces, achieving a maximum transmittance of 97%. This method to prepare large‐scale antireflective nanostructures on flat and flexible curved polymer surfaces is of interest for the production of antireflective screens, optical devices, and biomedical devices such as contact lenses and intraocular lenses.
Intelligence of living and nonliving systems is often characterized by the ability to communicate through signal and response. In the polymer science community, this intelligence is realized through the reaction of a material construct to environmental triggers. These smart materials are modeled after natural materials, which utilize matrix–fiber architectures to detect stimuli, release small molecules, or alter their macroscopic morphology in response to stimuli. As such, researchers have designed matrix–fiber composites, which function as release vehicles, sensors or switches, and actuators. Through the examination of the architecture and environmental triggering of these natural muses, the fundamental design parameters necessary for functional response in matrix–fiber composites and the ability to utilize these composites in targeted applications are highlighted. Opportunities for innovation in composite design are also discussed.
Polymer‐based electrospun fibers have been intensively studied as antimicrobial membranes, drug carriers, and energetic materials. Inorganic fillers or small molecules have been routinely added into polymer matrices in order to enhance product functions. However, the electrospinning process is kinetically controlled and solvent rapidly evaporates due to the large surface‐to‐volume ratio of spinning liquid jet. When electrospinning a multicomponent system, complex phase behavior may occur and give rise to interesting internal structures of resulting products. Such kinetically driven phenomena deserve more attention for optimizing product performance. Here, electrospun poly(ε‐caprolactone)(PCL)/aminopropyl‐heptaisobutyl‐polyhedral oligomeric silsesquioxane (AMPOSS) fibers with AMPOSS content up to 30 wt% are studied as a model system to understand the impact of kinetically controlled phase separation on the fibers' internal structure, properties, and thermal stability. With sufficient AMPOSS loading, the hybrid fibers are found to have an AMPOSS‐shell/PCL‐core structure. The thermal stability of the as‐spun PCL/AMPOSS fibers is therefore greatly enhanced.
Photo‐reversible polyurethane (PU) coatings based on coumarin diol (CD) are obtained. Initially, pre‐polymers based on different amounts of coumarin (5, 15, and 25 mol%) and 1,6‐hexamethylene diisocyanate are prepared to obtain PUs with a large incorporation of CD and high molecular weight. The pre‐polymer is posterior reacted with poly(ε‐caprolactone) diol (PCL‐diol), either with molecular weight = 530 or 2000 g mol–1. The thermal stabilities of the PUs are studied using thermogravimetric analysis. Polymers with a higher content of CD present higher stability. The thermal transitions and the mechanical response are analyzed using differential scanning calorimetry and strain‐stress tests, respectively. Moreover, the photo‐reversibility of CD‐based PUs is followed by UV absorption. In general, photo‐dimerization induces better mechanical properties of the final PUs. Materials obtained with short PCL‐diol ( = 530 g mol–1) and the highest amount of CD present higher reversibility processes. Therefore, these polymers are promising for application as coating systems.
This study introduces the concept of ion selective actuation in polymer metal composite actuators, employing crown ether bearing aromatic polyether materials. For this purpose, sulfonated poly(arylene ether ketone) (SPAEK) and crown ether containing SPAEK with molar masses suitable for membrane preparation are synthesized. The synthesized polymers are characterized using Nuclear magnetic resonance (NMR) and fourier transform infrared spectroscopy (FTIR) spectroscopy, thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). Ionic polymer metal composite (IPMC) actuators are fabricated by electroless chemical deposition of a platinum (Pt) layer on both sides of SPAEK and crown‐ether containing SPAEK membranes, resulting in electrode layers of around 120 nm thickness. Actuation experiments demonstrate cation specific responses and bending degrees of the IPMC actuators. Incorporation of crown ether units in the polymer backbone results in an improved and ion‐selective bending displacement compared with SPAEK actuators. S(25)C(50)PAEK actuators show an increased bending displacement of 28% for Na+ and 20% for K+ ions.
In this study, a facile method about generating porous poly (l ‐lactide) (PLLA) materials with uniform morphology by gradual precipitation is reported. By adjusting the solvents, concentrations of polymer solution, and drying process, petal‐like PLLA nanosheets can be conveniently obtained, which can further form porous materials with tunable porosities (85–92%). X‐ray diffraction affirms that α‐form crystals of PLLA with high crystallinity (51.66% according to differential scanning calorimetry) can be obtained. Mechanical test shows that the compression modulus is tunable with values ranging from 1.76 to 19.98 MPa. Notably, because of its high porosity, interconnected pore structure, and tunable mechanical properties, these versatile porous materials are especially fit for being utilized in polymer scaffold field.
Conductive textiles with exceptional electrical properties have been prepared by coating the conjugated polymer, poly(3,4‐ethylenedioxyphiophene)‐polystyrenesulfonate(PEDOT‐PSS), on polyethylene terephthalate (PET) nonwoven fabrics. Phase segregation from covalent bond formation to surface silica particles generates PEDOT‐PSS coated textiles that hold potential for wearable electronics due to the breathability of the fabric, low toxicity, easy processing and lightweight with high current carrying capacity. The conductive textiles were demonstrated for applications such as electrical connections and resistive heating.
This study presents the development and successful 3D printing of siloxane composite. Complex structures are 3D printed using vector‐scanning stereolithography apparatus. Siloxane oligomer and a commercial resin in the presence of an appropriate photoinitiator combine to form a hybrid material that photopolymerizes when exposed to UV laser at 405 nm wavelength. Measurements with differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, universal testing machine (UTM), and material testing system (MTS) reveal various properties of methacrylate resin filled with different concentrations of siloxane. Fourier transform infrared and Raman spectroscopy results reveal molecular structural change due to chemical reaction with the siloxane introduction. Atomic force microscopy imaging displays the surface morphology characteristics of the hybrid polymer while the contact angle confirms the surface energy existing on the samples. The 3D‐printed structures show unique physicochemical and thermomechanical properties that can lead to great potential for new applications in the field. This work is the first comprehensive study on 3D printing using siloxane through stereolithography.
An efficient strategy for engineering nanostructured surfaces by coupling soft polymeric nanoarchitectures to functionalized surfaces is presented. Self‐assembly of polymeric nanoarchitectures from amphiphilic triblock copolymers can yield both filled and hollow spherical nanoarchitectures, depending on the properties of the polymer chosen. These nanoarchitectures are immobilized on solid substrates via a biocompatible thiol–ene reaction, and conditions are optimized to maintain structural integrity of polymeric assemblies. Two routes of surface modification are also implemented to allow inclusion of a polymeric spacer that can mediate between soft polymeric assemblies and solid substrates. Nanostructured surfaces with both filled and hollow nanoarchitectures attached to the surface directly or with a spacer are successfully generated with this protocol. This concept of generating nanostructured surfaces using preassembled polymeric architectures is an important step toward active surfaces, because entrapment of active molecules in the nanoarchitectures prior to their immobilization opens the door to easy generation of surfaces with predetermined activities.
A novel method of preparing skinned asymmetric membranes with two distinctive layers is described: a top layer composed of chemically cross‐linked polymer chains (dense layer) and a bottom layer of non‐cross‐linked polymer chains (porous substructure). The method consists of two simple steps that are compatible with industrial membrane fabrication facilities. Unlike conventional processes to prepare asymmetric membranes, with this approach it is possible to finely control the structure and functionalities of the final membrane. The thickness of the dense layer can be easily controlled over several orders of magnitude and targeted functional groups can be readily incorporated in it.
A chemical strategy is attempted to modify graphene for its facilitated dispersion in poly(ε‐caprolactone) (PCL) matrix. Herein, graphite oxide is subjected to sequential treatment with phenyl isocyanate and vitamin C (VC) to yield graphene nanosheets (iG‐VC). It is noteworthy that following the reduction treatment, iG‐VC graphene sheets exfoliate within the PCL matrix and show appreciable interfacial compatibility with PCL matrix in organic solvent by virtue of improved polarity from isocyanate treatment. The tensile yield strength and Young's modulus of the PCL/iG‐VC composite exhibit pronounced enhancement as compared to neat PCL, despite of mere composition of graphene sheets. The tensile yield stress of composite is increased notably to reach 18.6 MPa at 3 wt% graphene sheets as compared to neat PCL. Likewise, Young's modulus of composite is observed to increase from 370 to 470 MPa at 5 wt% graphene sheets. Moreover, the crystallization temperature (T c) and crystallinity of PCL increase significantly upon incorporation of small amount of iG‐VC. Ultimately, functional role of iG‐VC graphene sheets is demonstrated in enhancing electrical conductivity of PCL‐based nanocomposites. The plausible mechanisms are also proposed to explain the increased T c, improved mechanical property, and improved electrical conductivity of PCL/iG‐VC composite.
The direct injection of a drug into a joint can relieve osteoarthritic pain for a short period of time. The problem is that the drug will not stay at the allocated location. Therefore, a proof‐of‐concept in situ is designed forming hydrogel containing liposomes that are covalently linked to the hydrogel network. When the liposomes are filled with a cargo, the formed hydrogel is thus loaded with this cargo, too. Due to the link between the hydrogel and the liposomes, a compression or other mechanical force applied to the hydrogel will rupture the liposomes and release a small percentage of the cargo. Overall, a long‐term intra‐articular drug release is feasible.
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