Cross-linked Layer Research Articles

Oxygen plasma induced solvent resistance of polystyrene particles enables the fabrication of ultra-thin free-standing crosslinked polymer films

Plasma-treated polystyrene particles (PSP) are key building blocks in the fabrication of two- dimensional nanostructure arrays. Oxygen plasma etching can shrink PS particles and is a widespread tool in fundamental research and applications, but its effect has not been well understood. Here, we show that oxygen plasma induces an ultra-thin cross-linking layer on the surface of the PSPs, which increases their solvent resistance. We found in X-ray photoelectron spectroscopy (XPS) fine structure and valence band probing that the polymer CC bonds are breaking and recombining to form oxygenated functional groups. Our results explain, why oxygen plasma etched PS particles are more difficult to dissolve in nanofabrication procedures. Further, we used the ultra-thin cross-linked polymer layer to construct novel substrate-base microcavity arrays.

Enhancing surface adhesion of polytetrafluoroethylene induced by two-step in-situ treatment with radiofrequency capacitively coupled Ar/Ar+CH4+NH3 plasma

Although some progress in plasma modification of the polytetrafluoroethylene (PTFE) surface has been made recently, its adhesion strength still needs to be further improved. In this work, the surface of a PTFE sample was treated with a two-step in-situ method. Firstly, the PTFE surface was treated with capacitively coupled Ar plasma to improve its mechanical interlocking performance; then, Ar+NH3+CH4 plasma was used to deposit an a-CN x :H cross-linking layer on the PTFE surface to improve the molecular bonding ability. After treatment, a high specific surface area of 2.20 and a low F/C ratio of 0.32 were achieved on the PTFE surface. Its surface free energy was increased significantly and its maximum adhesion strength reached 77.1 N·10 mm−1, which is 56% higher than that of the single-step Ar plasma-treated sample and 32% higher than that of the single-step Ar+CH4+NH3 plasma-treated sample.

Crown ether modulated high-performance nanofiltration membrane for water purification

Nanofiltration (NF) membranes with high selectivity and high permeability are essential for efficient water purification. However, improving the performance of NF membranes by simple and effective methods remains challenging, as many of the reported improvements are difficult to scale up practically. In this work, we successfully prepared high-performance NF membranes using the hydrogen bonding interactions and host–guest interactions of crown ether (CE) and piperazine (PIP). Molecular dynamics (MD) simulation shows that the introduction of CE slows down the diffusion rate of PIP, thus effectively modulating the interfacial polymerization (IP) process, resulting in an ultra-thin (∼28 nm) and highly cross-linked polyamide selective layer. The TFC-CE0.5 membrane prepared under optimized conditions combines surprising permeability (water permeance: 23.6 L m−2 h−1 bar−1) and selectivity (Na2SO4 rejection: 99.2%). Our work demonstrates an elegant and efficient approach to prepare high-performance NF membranes without major modifications to existing manufacturing processes.

Molecular-scale polysiloxane-crosslinking hydrophobic coating boosting high-performance Ni-rich cathode in damp-heat environment

Ni-rich layered oxide, one of the most promising cathode materials for lithium-ion batteries (LIBs) with high energy density, is suffering from the intrinsic hypersensitivity to moisture and acid gas (CO2, SO2, etc.) in the environment, leading to the generation and growth of residual lithium compounds (e.g. Li2CO3), accompanied by surficial phase transition, high alkalinity and electrochemical deterioration. Eliminating these negative effects would require considerable energy and manpower, which hinders the promotion of Ni-rich cathode materials. Herein, we introduced crosslinked poly-methylhydrosiloxane (PMHS) and hydroxy‑terminated poly-dimethylsiloxane (denoted as PDMS-OH) hydrophobic film to in situ coat single-crystal LiNi0.8Co0.1Mn0.1O2 (NCM811), isolating its Ni-rich electrode surface from moisture and acid gas to prevent side reactions. Specifically, the desired crosslinking layer, which is optimized by increasing the relative content of PMHS and decreasing the absolute content of PDMS-OH, endows the coated NCM811 with an appreciable improvement in hydrophobicity and storage performances and effectively suppresses the formation and growth of residual lithium compounds on the surface of NCM811 particles in a simulated damp-heat storage environment. Simultaneously, the crosslinked coating diminished the extraction of Li and Ni during exposure and maintained the high electrochemical performance of NCM811. This proposed strategy to crosslink polysiloxane film on the surface of Ni-rich cathode materials greatly alleviates the problem of storage failure, which will promote the practical popularization of Ni-rich cathode materials in LIBs.

Interface Manipulations Using Cross-Linked Underlayers and Surface-Active Diblock Copolymers to Extend Morphological Diversity in High-χ Diblock Copolymer Thin Films

Top and bottom interfaces of high-χ cylinder-forming polystyrene-block-maltoheptaose (PS-b-MH) diblock copolymer (BCP) thin films are manipulated using cross-linked copolymer underlayers and a fluorinated phase-preferential surface-active polymer (SAP) additive to direct the self-assembly (both morphology and orientation) of BCP microdomains into sub-10 nm patterns. A series of four photo-cross-linkable statistical copolymers with various contents of styrene, a 4-vinylbenzyl azide cross-linker, and a carbohydrate-based acrylamide are processed into 15 nm-thick cross-linked passivation layers on silicon substrates. A partially fluorinated analogue of the PS-b-MH phase-preferential SAP additive is designed to tune the surface energy of the top interface. The self-assembly of PS-b-MH thin films on top of different cross-linked underlayers and including 0-20 wt % of SAP additive is investigated by atomic force microscopy and synchrotron grazing incidence small-angle X-ray scattering analysis. The precise manipulation of the interfaces of ca. 30 nm thick PS-b-MH films not only allows the control of the in-plane/out-of-plane orientation of hexagonally packed (HEX) cylinders but also promotes epitaxial order-order transitions from HEX cylinders to either face-centered orthorhombic or body-centered cubic spheres without modifying the volume fraction of both blocks. This general approach paves the way for the controlled self-assembly of other high-χ BCP systems.

Anchoring polyamide active layer to improve the thermal stability of polyacrylonitrile composite forward osmosis membrane through interfacial enthalpic effect

Traditional composite polymer membranes suffer from deteriorated rejection when operation temperature exceed 60 °C, which is attributed to the decrease in glass transition temperature of polymer in cross-linked active layer. To address this issue and fabricate thermally stable composite membranes, primary amino group was successfully introduced to polyacrylonitrile (PAN) through reaction between cyan group and diethylenetriamine to firmly anchor polymer chains of active layer on surface of support layer. This not only restrained the movement of polymer chains in the active layer but also the movement of polymer chains in the cross-linked support layer. The resulting thermally stable membrane was used to improve water flux of forward osmosis (FO) process. All the modified FO membranes exhibited substantial thermal stability compared to FO membrane based on original PAN support layer. Taking 1 mol/L NaCl as draw solution and deionized water as feed solution, the water flux of PAN-C3 reached 103.0 ± 8.2 L/(m2·h) at 90 °C, which was three times the value at 25 °C, with a constant JS/JW of 0.35 g/L. Furthermore, the rejection was stable at 93.4 %. This method can be further applied to fabricate thermally stable reverse osmosis and nanofiltration membranes.

Efficient Pervaporation for Ethanol Dehydration: Ultrasonic Spraying Preparation of Polyvinyl Alcohol (PVA)/Ti3C2Tx Nanosheet Mixed Matrix Membranes.

Polyvinyl alcohol (PVA) pervaporation (PV) membranes have been extensively studied in the field of ethanol dehydration. The incorporation of two-dimensional (2D) nanomaterials into the PVA matrix can greatly improve the hydrophilicity of the PVA polymer matrix, thereby enhancing its PV performance. In this work, self-made MXene (Ti3C2Tx-based) nanosheets were dispersed in the PVA polymer matrix, and the composite membranes were fabricated by homemade ultrasonic spraying equipment with poly(tetrafluoroethylene) (PTFE) electrospun nanofibrous membrane as support. Due to the gentle coating of ultrasonic spraying and following continuous steps of drying and thermal crosslinking, a thin (~1.5 μm), homogenous and defect-free PVA-based separation layer was fabricated on the PTFE support. The prepared rolls of the PVA composite membranes were investigated systematically. The PV performance of the membrane was significantly improved by increasing the solubility and diffusion rate of the membranes to the water molecules through the hydrophilic channels constructed by the MXene nanosheets in the membrane matrix. The water flux and separation factor of the PVA/MXene mixed matrix membrane (MMM) were dramatically increased to 1.21 kg·m-2·h-1 and 1126.8, respectively. With high mechanical strength and structural stability, the prepared PGM-0 membrane suffered 300 h of the PV test without any performance degradation. Considering the promising results, it is likely that the membrane would improve the efficiency of the PV process and reduce energy consumption in the ethanol dehydration.

Multifunctional asymmetric electrolyte membrane encouraging durable lithium-metal batteries in wide temperature variations

The progress of high-performance lithium-metal batteries (LMBs) has been greatly impeded by lithium dendrite growth and electrolyte performance defects. Herein, an ultra-thin asymmetric multilayer composite electrolyte with a total thickness of 19 μm is designed. The rigid metal-organic framework (MOF) tier with Li+ conductivity towards the anode side adjusts the even deposition of Li+, owns high elasticity modulus (6.4 GPa) to restrain lithium dendrite formation, and improves the thermostability of the membrane. The in-situ cross-linked polymer layer on the cathode side achieves good electrode-electrolyte interface contact. Consequently, the functional asymmetric multilayer composite electrolyte displays a superior ionic conductivity (0.68 mS cm−1) and a high-efficiency Li+ transference (tLi+ = 0.47). The assembled Li||Li symmetric cells can cycle steadily for 1500 h at a high current density of 3 mA cm−2 at 30 °C and 1000 h at 1 mA cm−2 at 100 °C. The assembled LMBs with different cathodes show high rate capability and long-period cycling stability at room temperature. More impressively, the batteries display excellent electrochemical performance within −15 °C-100 °C and do not cause a short circuit even at 170 °C, showing high thermal safety. This work frames a neoteric strategy for the practical application of LMBs.

Design of polymer-based nanoreactors for efficient acid/base cascade catalysis: A comparative study of site isolation strategies

Cascade catalysis carries out two or more consecutive catalytic reactions without separation and purification of intermediate products, which is of great significance in chemical production. Acid/base cascade catalysis in one-pot is widely studied, but it still faces great challenges due to the incompatibility of the two catalysts. In this study, three catalytic systems for acid/base cascade catalysis, the mixture of two separated acid and base micelles, acid and base isolated micelles with/without an intermediate cross-linking layer as catalytic nanoreactors were fabricated by utilizing RAFT polymerization technique respectively. Comparative study of the three site isolation strategies were carried out through investigating their catalytic activities for the deacetalization-Knoevenagel cascade reactions. The results disclosed that intermediate cross-linking layer of core-shell micelle could effectively hamper the contact of acid and base catalysts, presenting good catalytic activities. The study may provide new ideas and fabrication approaches for other cascade catalysis with incompatible catalysts.

Cross-Linkable Polymer-Based Multi-layers for Protecting Electrochemical Glucose Biosensors against Uric Acid, Ascorbic Acid, and Biofouling Interferences.

The lifetime of implantable electrochemical glucose monitoring devices is limited due to the foreign body response and detrimental effects from ascorbic acid (AA) and uric acid (UA) interferents that are components of physiological media. Polymer coatings can be used to shield biosensors from these interferences and prolong their functional lifetime. This work explored several approaches to protect redox polymer-based glucose biosensors against such interferences by designing six targeted multi-layer sensor architectures. Biological interferents, like cells and proteins, and UA and AA interferents were found to have individual effects on the current density and operational stability of glucose biosensors, requiring individual protection and treatment. Protection against biofouling can be achieved using a poly(2-methacryloyloxyethyl phosphorylcholine-co-glycidyl methacrylate) (MPC) zwitterionic polymer coating. An enzyme-scavenging approach was compared to electrostatic repulsion by negatively charged polymers for protection against AA and UA interferences. A multi-layer novel polymer design (PD) system consisting of a cross-linkable negatively charged polyvinylimidazole-polysulfostyrene co-polymer inner layer and a cross-linkable MPC zwitterionic polymer outer layer showed the best protection against AA, UA, and biological interferences. The sensor protected using the novel PD shield displayed the lowest mean absolute relative difference between the glucose reading without the interferent and the reading value with the interferent present and also displayed the lowest variability in sensor readings in complex media. For sensor measurements in artificial plasma, the novel PD extends the linear range (R2 = 0.99) of the sensor from 0-10 mM for the control to 0-20 mM, shows a smaller decrease in sensitivity, and retains high current densities. The application of PD multi-target coating improves sensor performance in complex media and shows promise for use in sensors operating in real conditions.

Nanovehicle-assisted monomer shuttling enables highly permeable and selective nanofiltration membranes for water purification

Fabricating nanofiltration membranes with high water permeance and selectivity is crucial to efficient water purification. However, achieving such a goal with a simple and cost-effective approach that is compatible with existing membrane manufacturing infrastructure remains a substantial technical challenge. Here we show a strategy of nanoemulsion-regulated interfacial polymerization (NERIP) based on nanovehicle-assisted monomer shuttling for fabricating highly permeable and selective nanofiltration membranes. In NERIP, the nanovehicles, which are surfactant-stabilized oil droplets (in water) enriched with piperazine (PIP), enter and merge into the hexane phase to initiate the polymerization between PIP and trimesoyl chloride. This nanovehicle-assisted monomer shuttling results in the formation of polyamide ‘bubbles’ that later collapse into nanocraters. The nanocrater structure substantially increases the surface area and void fraction of the polyamide layer. The PIP shuttling also accelerates the polymerization reaction, enabling the formation of a thin and highly cross-linked polyamide layer with a more uniform pore size distribution. These structural superiorities yield an unprecedentedly high performance with a water permeance of 36.8 ± 1.9 l m−2 h−1 bar−1 and a Na2SO4 rejection of 99.6 ± 0.1%. NERIP creates a new dimension to fabricate highly permeable and selective nanofiltration membranes for desalination and water purification. The development of advanced nanofiltration membranes should be compatible with existing manufacturing process to be practically useful. A process based on nanoemulsion-regulated interfacial polymerization allows the fabrication of low-cost and high-performance membranes.

Gln-Lys isopeptide bond and boroxine synergy to develop strong, anti-mildew and low-cost soy protein adhesives

The development of renewable soy protein (SP) adhesives has aroused growing interest in the wood industry. This research aims to develop a low-cost, sustainable, and high-performance SP adhesive without a petrochemical crosslinker. The hard skin barrier benefits from the dense cross-linked layer of cuticle cells constructed by the peptide bonds between membrane proteins and the dehydration condensation reaction between adjacent hydroxyl groups of polysaccharides. Inspired by the above skin mechanism, a biomimetic strategy of commercially available transglutaminase (TGase) was applied, which constructed Gln-Lys isopeptide bonds within the SP chains. The covalent boroxine structure formed by dehydration of the hydroxyl groups of boronic acid engineered a dense and robust network like skin barrier, converting the SP into a strong, water-resistant, anti-mildew, and flame-retardant adhesive. The resultant adhesive showed outstanding wet shear strength of 1.55 MPa, about 138.5% greater than the pure SP adhesive, and the residual rate increased from 86.19% to 95.99%. The small content of TGase achieved satisfactory performances and low-cost SP adhesive, establishing its usefulness as a crosslinker to replace the petroleum-based modifiers. Notably, the boronic acid mounted on the SP chains by TGase protected proteins from microbial consumption, thus extending the anti-mildew shelf-life of the liquid adhesives from 2 to 15 days. Moreover, the dense and rigid structure containing Gln-Lys isopeptide bonds and boroxine network effectively improved the flame resistance of the cured adhesives, which reduced the peak heat release rate (PHRR) from 95.1 to 84.2 W/g. Therefore, this simple bionic strategy achieved the goal of formulating green, low-cost, high-performance, and multifunctional SP-based adhesives.

Stimuli-responsive SERS biosensor for ultrasensitive tetracycline sensing using EDTA-driven PEI@CaCO3 microcapsule and CS@FeMMs

In this work, a stimuli-responsive SERS biosensor was fabricated for tetracycline (TTC) by “signal-on” strategy using (EDTA)-driven polyethyleneimine grafted calcium carbonate (PEI@CaCO3) microcapsule and chitosan-Fe magnetic microbeads (CS@FeMMs). Initially, aptamer conjugated magnetic-bead CS@FeMMs@Apt with superparamagnetism and excellent biocompatibility was employed as capture probe, which facilitated the rapid and easy magnetic separation. Subsequently, the PEI cross-linked layer and aptamer network layer were constructed onto the outer layer of CaCO3@4-ATP microcapsule to form sensing probes (PEI@CaCO3@4-ATP@Apt) via the layer-by-layer assembly method. In the presence of TTC, a sandwich SERS-assay was exploited by aptamer recognition induced target-bridged strategy. When the solution of EDTA was added, the core layer of CaCO3 would be dissolved quickly, destroying the microcapsule to release 4-ATP. The released 4-ATP could be quantitatively monitored by dripping the supernatant onto the AuNTs@PDMS SERS platform, resulting in a strong Raman “signal-on”. Under the optimal conditions, a good linear relationship was established with a correlation coefficient (R2) of 0.9938 and a LOD of 0.03 ng/mL. Additionally, the application capacity of the biosensor to detect TTC was also affirmed in food matrixes, and the results were consistent with the standard ELISA method (P > 0.05). Hence, this SERS biosensor affords extensive application prospects for TTC detection with multiple merits such as high sensitivity, environment friendliness, and high stability.

Polyethersulfone-TPU blend membrane coated with an environmentally friendly sabja seed mucilage-Cu2 + cross-linked layer with outstanding separation performance and superior antifouling

In this study, membranes were prepared by blending polyethersulfone (PES) with thermoplastic polyurethane (TPU) in order to enhance the mechanical properties of PES membranes. The membranes were fabricated using the vapor-induced phase separation coupled with non-solvent induced phase separation (VIPS-NIPS method) for the purpose of preventing the formation of macro-voids and enhancing the mechanical stability. After the formation of the PES-TPU membranes, a layer of Sabja seed mucilage (SSM), as an eco-friendly low-cost polysaccharide, was fabricated on the membranes surface, and then chelated via Cu2+ ions, in order to enhance the rejection performance of the prepared membranes. The PES-TPU coated with Sabja seed mucilage-Cu2+ (PES-TPU@SSM/Cu) exhibited not only high permeance of 7.97 L/m2.h.bar, but also extraordinary dye and pharmaceutical residue rejection performance of 98.4% methylene blue, 99.5% crystal violet, 98.2% ceftriaxone and 97.6% amoxicillin, arising from the formation of the cross-linked dense SSM/Cu layer. Moreover, all the antifouling parameters of the fabricated membrane were boosted by SSM/Cu coating on the membrane surface and the long-term durability of the membrane was also investigated after 10 days, exhibiting no significant changes in the membrane performance. Furthermore, mechanical properties were remarkably meliorated by TPU addition.

Interfacial Ultraviolet Cross-Linking of Green Bilayer Dielectrics.

Electronic waste is a growing challenge which needs to be addressed through the integration of high-performance sustainable materials. Green dielectric polymers such as poly(vinyl alcohol) (PVA) have favorable electrical properties but are challenging to integrate into thin film electronics due to their physical properties. For example, PVA suffers from poor film formation and is hygroscopic. Bilayer dielectrics with interfacial cross-linking can enable the use of high-performance PVA with favorable surface chemistry by using a hydrophobic poly(caprolactone) (PCL) layer. In this study, we developed a benzodioxinone-terminated PCL layer, which can be UV cross-linked to the hydroxy groups of the PVA dielectric. This air-stable UV-cross-linking PCL dielectric was able to effectively cross-link with PVA, leading to high-performance capacitors and single-walled carbon nanotube-based thin film transistors. This UV cross-linking PCL dielectric led to significant improvements in shelf-life, ease of processing, and similar device performance compared to our previously reported thermally cross-linking PCL layer. The UV cross-linking at the interface between these bilayers can allow for the integration of high-speed roll-to-roll processing, which enables low-cost, sustainable, and high-performance electronics.

Solution-processed high efficiency OLED harnessing a thermally cross-linked hole-transporting layer and exciplex-forming emission layer

Solution-processed light-emitting device was feasibly achieved by a new exciplex-forming BCz3Ph : PO-T2T blend as the emitting layer casted on top of a thermally polymerized hole-transporting layer formed by a dicarbazole-based monomer BCzC4Sy.

Tung oil-based phosphorus-containing polyol as a flame retardant for bamboo

A novel method for preparing a tung oil-based flame retardant polyol (MTTO) is described. An epoxidized tung oil methyl ester was initially prepared using green nontoxic phosphotungstate (Ag3O40PW12·xH2O) as the catalyst. The MTTO was then produced from epoxidized transesterified tung oil (ETOME) using diethyl phosphate and ring-opening. The MTTO molecular structure was analyzed using FTIR, 1H, 31P, 13C NMR, and HR-MS. Both MTTO and MTTO-coated melamine-modified bamboo showed excellent flame retardation, with a UL-94 rating of V-0, increased LOI from 28.3 % to 36.4 % and 38.7 %, and significant reductions in the PHRR and THR of the untreated bamboo of 42.7 % and 50.6 % and 37.5 % and 42.1 %, respectively. MTTO was effective in both the gas and condensed phases, preventing bamboo degradation through the release of non-flammable small molecules and the formation of a cross-linked phosphorus-oxygen network carbon layer. Moreover, the addition of melamine led to the release of more non-flammable gases, expansion of the char layer, and increased density of the nitrogen-phosphorus-oxygen cross-linked network carbon layer during combustion, resulting in reduced PHRR and THR.

Cr-Zn/Ni-Containing Nanocomposites as Effective Magnetically Recoverable Catalysts for CO2 Hydrogenation to Methanol: The Role of Metal Doping and Polymer Co-Support

CO2 hydrogenation to methanol is an important process that could solve the problem of emitted CO2 that contributes to environmental concern. Here we developed Cr-, Cr-Zn-, and Cr-Ni-containing nanocomposites based on a solid support (SiO2 or Al2O3) with embedded magnetic nanoparticles (NPs) and covered by a cross-linked pyridylphenylene polymer layer. The decomposition of Cr, Zn, and Ni precursors in the presence of supports containing magnetic oxide led to formation of amorphous metal oxides evenly distributed over the support-polymer space, together with the partial diffusion of metal species into magnetic NPs. We demonstrated the catalytic activity of Cr2O3 in the hydrogenation reaction of CO2 to methanol, which was further increased by 50% and 204% by incorporation of Ni and Zn species, respectively. The fine intermixing of metal species ensures an enhanced methanol productivity. Careful adjustment of constituent elements, e.g., catalytic metal, type of support, presence of magnetic NPs, and deposition of hydrophobic polymer layer contributes to the synergetic promotional effect required for activation of CO2 molecules as well. The results of catalytic recycle experiments revealed excellent stability of the catalysts due to protective role of hydrophobic polymer.

In situ formed cross-linked polymer networks as dual-functional layers for high-stable lithium metal batteries

Lithium-metal anodes (LMAs) have been recognized as the ultimate anodes for next-generation batteries with high energy density, but stringent assembly-environment conditions derived from the poor moisture stability dramatically hinder the transformation of LMAs from laboratory to industry. Herein, an in situ formed cross-linked polymer layer on LMAs is designed and constructed by a facile thiol-acrylate click chemistry reaction between poly(ethylene glycol) diacrylate (PEGDA) and the crosslinker containing multi thiol groups under UV irradiation. Owing to the hydrophobic nature of the layer, the treated LMAs demonstrate remarkable humid stability for more than 3 h in ambient air (70% relative humidity). The coating humid-resistant protective layer also possesses a dual-functional characterization as solid polymer electrolytes by introducing lithium bis(trifluoromethanesulfonyl)imide in the system in advance. The intimate contact between the polymer layer and LMAs reduces interfacial resistance in the assembled Li/LiFePO4 or Li/LiNi0.8Co0.1Mn0.1O2 full cell effectively, and endows the cell with an outstanding cycle performance.

Graphene oxide dispersion in epoxy resin prepared by direct phase transfer from ethanol: Rheology and aging

Graphene oxide addition to epoxy still presents challenges related to attaining optimized dispersion in scale-up production. Herein, the synthesis of high-quality GO by exfoliation in ethanol enabled the spontaneous phase transfer of GO from solvent to epoxy resin to produce a masterbatch with 1.5 wt.% GO content. Nanocomposites with 0.25 wt.%, 0.50 wt.% and 0.75 wt.% nanofiller contents were obtained by masterbatch dilution in epoxy resin. The results reveal the presence of a partial cross-linked network in these nanocomposites associated with the presence of GO, even without the use of a hardener. Thermogravimetric analysis showed the influence of GO on the oxidative decomposition mechanism of epoxy resin, whose behavior was assigned to strong interactions in the GO-epoxy interphase. Furthermore, the rheological behavior changes demonstrate the high quality of the GO dispersion in the resin obtained in this work. The nanocomposites showed high viscosity increases over time and pseudoplastic behavior, which was completely different from the neat epoxy resin. Aged nanocomposites without hardener present a first chemically cross-linked layer of epoxy to GO (∼ 10% for nanocomposite at 0.50 wt.% GO content) and a supramolecular coating interacting and entangled with these structures (> 40% of epoxy chains for EP-GO50).