Preparation and characteristics of poly(benzoxazine-urethane)/graphene oxide composites: Toughness,mechanical and thermal properties

Poly(benzoxazine-urethane)/graphene oxide [poly(Bz-PU)/GO] composites were successfully prepared by blending benzoxazine (Bz) with graphene oxide (GO) and isocyanato (NCO)-terminated polyurethane prepolymer (PU), followed by thermally activated polymerization of the blends. The network was formed via the mutual reaction and intermolecular interaction among the hydroxyl of GO, NCO groups of PU and phenolic hydroxyl of Bz. The toughness shown from SEM images and tensile properties of polybenzoxazine (PBz) plastic composites can effectively be improved by alloying with PU and GO. The onset curing temperature and exothermic peak maximums of the polymerization obtained from differential scanning calorimetry decreased resulted from the GO addition. The thermogravimetric analysis showed that the incorporation of 0.5 wt% of GO slightly improved the thermal stability of poly(Bz-PU)/GO composites. Additionally, the storage modulus improved and the glass transition temperature (Tg) increased gradually as the increasing GO content not beyond a certain amount. Finally, the exothermic peaks of the polymerization were shifted to lower temperature, and the thermal stability increased for the ternary composites as the number average molecular weights (Mn) of polyol decreased.     

Synergistic effect of functional carbon nanotubes and graphene oxide on the anti‐corrosion performance of epoxy coating

In this work, we reported the synergistic effect of functional carbon nanotubes (CNTs) and graphene oxide (GO) on the anticorrosion performance of epoxy coating. For this purpose, the GO and CNTs were firstly modified by the 3‐aminophenoxyphthalonitrile to realize the nitrile functionalized graphene oxides (GO‐CN) and carbon nanotubes (CNTs‐CN). As modified GO‐CN and CNTs‐CN were characterized and confirmed by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and gravimetric analyzer. It was found that about 19 and 24 wt% of 3‐aminophenoxyphthalonitrile were grafted onto the surface of the GO and CNTs, respectively. The electrochemical impedance spectroscopy results showed that the GO‐CN&CNTs‐CN hybrid materials exhibit a remarkable superiority in enhancing the anticorrosion performance of epoxy coatings. Significant synergistic effect of the lamellar structural GO‐CN and CNTs‐CN on the anticorrosion performance of epoxy composite coatings was designed. Besides, the epoxy coating with 1 wt% of the GO‐CN&CNTs‐CN hybrid exhibited the best anticorrosion performance, in which the impedance showed the largest one (immersion in 3.5 wt% of NaCl solution for 168 hr). Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation and properties of 3-aminopropyltriethoxysilane functionalized graphene/polyurethane nanocomposite coatings

Silicone-modified graphene was successfully synthesized by treating graphene oxide with 3-aminopropyltriethoxysilane (AMEO) and then reduced by hydrazine hydrate. Subsequently, the AMEO-functionalized graphene was incorporated into polyurethane (PU) matrix to prepare AMEO-functionalized graphene/PU nanocomposite coatings. The functionalized graphene could disperse homogenously by means of a covalent connection with PU. AMEO-functionalized graphene (AFG)-reinforced PU nanocomposite coatings showed more excellent mechanical and thermal properties than those of pure PU. A 227 % increase in tensile strength and a 71.7 % improvement of elongation at break were obtained by addition 0.2 wt% of AFG. Meanwhile, thermogravimetric analysis reveals that thermal degradation temperature was enhanced almost 50 °C higher than that of neat PU, and differential scanning calorimetry analysis demonstrates that glass transition temperature decreased by around 9 °C. The thermal conductivity of AFG/PU nanocomposite coatings also increased by 40 % at low AFG loadings of 0.2 wt%.     

Potential of zinc based-graphene oxide composite coatings on mild steel in acidic solution

This study introduces varying concentrations of graphene oxide (GO) as a filler into zinc chromate in forming composite coatings to improve the corrosion protection of mild steel. The purity of synthesized GO was inferred through the application of complementary characterization techniques, including FT-IR, XRD, Raman, SEM-EDX, and TEM analyses. GO doped zinc chromate coatings were deposited on the surface of mild steel through the brushing method. Electrochemical studies, i.e., electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PD) were conducted to elucidate the anticorrosion properties of the coated mild steel exposed to 0.5 ​M HCl solution. It was revealed that the highest anticorrosion protection was attained at low doping amount of 0.5% of GO with a corrosion rate of 0.036 mpy. Surface analyses revealed that incorporating GO into zinc chromate coating can effectively improve the anticorrosion properties and adhesion strength.     

二维材料改性水性聚氨酯防腐涂料的研究进展

水性聚氨酯涂料作为一种新兴的环保涂料,在防腐领域得到了广泛应用。然而,水性聚氨酯涂料交联密度低,耐水性稍差,不利于其长效防腐性能。利用具有独特物理化学特性的二维材料作为水性聚氨酯的填料,可以有效改善其性能。本文主要介绍了三种二维材料(石墨烯、MXene和六方氮化硼)作为填料与水性聚氨酯进行复合,并重点介绍了石墨烯、MXene和六方氮化硼的改性方法,并对水性聚氨酯复合涂层的性能进行了阐述和比较,最后对未来二维材料/水性聚氨酯的复合材料的发展和应用进行了展望。     

Graphene-Oxide-Based Fluoro- and Chromo-Genic Materials and Their Applications

Composite materials and their applications constitute a hot field of research nowadays due to the fact that they comprise a combination of the unique properties of each component of which they consist. Very often, they exhibit better performance and properties compared to their combined building blocks. Graphene oxide (GO), as the most widely used derivative of graphene, has attracted widespread attention because of its excellent properties. Abundant oxygen-containing functional groups on GO can provide various reactive sites for chemical modification or functionalization of GO, which in turn can be used to develop novel GO-based composites. This review outlines the most recent advances in the field of novel dyes and pigments encompassing GO as a key ingredient or as an important cofactor. The interactions of graphene with other materials/compounds are highlighted. The special structure and unique properties of GO have a great effect on the performance of fabricated hybrid dyes and pigments by enhancing the color performance of dyes, the anticorrosion properties of pigments, the viscosity and rheology of inks, etc., which further expands the applications of dyes and pigments in dyeing, optical elements, solar-thermal energy storage, sensing, coatings, and microelectronics devices. Finally, challenges in the current development as well as the future prospects of GO-based dyes and pigments are also discussed. This review provides a reference for the further exploration of novel dyes and pigments.     

Testing new graphene oxide-coated glazing for papyrus manuscripts in museums: Part I

The display of papyrus and paper (as cellulosic materials) in the Egyptian museums is always critical due to the traditional placement of display of sensitive materials between two plates of glass, acrylic, or other types of glazing materials. The sensitivity of the glazing materials to abrasion, ultraviolet rays, dust adhesion, and high light reflectivity are considered concerning issues to conservators, curators, and visitors. In this paper, thin protective coatings of graphene oxide (GO) were synthesized by modified Hummers' method and deposited on selected museums' glazing materials (glass and acrylic) using spin coating. Multi-analytical techniques were employed to assess the applicability of GO-coated glazing including scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), Raman spectroscopy (RS), Fourier transform infrared spectroscopy (FTIR), microhardness testing, NIR VIS, and UV spectrophotometer and static potential measurements. The results showed that the glass glazing hardness was increased by ~10% due to the deposition of the GO coating. Moreover, according to glazing type, the reflectance values of the GO-coated glazing samples, compared with the uncoated samples, confirmed that the thin film of GO improved the UV rays blocking. As is evident in the GO-coated glass where approximately 27% of UV rays have been blocked, likewise, 19% of UV rays were blocked in GO-coated acrylic (TRU VUE). Considering VIS and NIR reflection spectra of GO-coated plexiglass, a higher reflectance is presented by 29%. Furthermore, the static potential measurements showed an energy decline in GO-coated glazing compared with the uncoated samples.     

Highly Dispersible and Stable Anionic Boron Cluster–Graphene Oxide Nanohybrids

An efficient process to produce boron cluster–graphene oxide nanohybrids that are highly dispersible in water and organic solvents is established for the first time. Dispersions of these nanohybrid materials in water were extraordinarily stable after one month. Characterization of hybrids after grafting of appropriate cobaltabisdicarbollide and closo‐dodecaborate derivatives onto the surface of graphene oxide (GO) was done by FT‐IR, XPS, and UV/Vis. Thermogravimetric analysis (TGA) clearly shows a higher thermal stability for the modified‐GO nanohybrids compared to the parent GO. Of particular note, elemental mapping by energy‐filtered transmission electron microscopy (EFTEM) reveals that a uniform decoration of the graphene oxide surface with the boron clusters is achieved under the reported conditions. Therefore, the resulting nanohybrid systems show exceptional physico‐chemical and thermal properties, paving the way for an enhanced processability and further expanding the range of application for graphene‐based materials.     

采用层层自组装与光化学修饰法在聚氨酯表面固定生物多糖衍生物

采用层层自组装技术与光化学修饰方法相结合在聚氨酯材料表面固定生物多糖衍生物,首先合成具有光反应活性的叠氮壳聚糖,再在聚氨酯基材表面进行叠氮壳聚糖与香菇多糖硫酸酯的层层自组装,然后通过光化学反应对自组装多层膜修饰层进行交联,制备得到生物多糖衍生物层层自组装与光化学表面修饰的聚氨酯材料.通过红外光谱、X射线光电子能谱、水接触角测量仪、抗菌活性测试、溶血试验和血小板黏附测试等方法对被修饰聚氨酯材料的表面性能和生物性能进行了分析,测试结果表明修饰后的聚氨酯材料表面的亲水性和血液相容性得到改善,并且被修饰材料对大肠杆菌具有良好的抑制效果.     

Polylactic acid-based polyurethane/polyamide 6,12 and graphene nanocomposite: Structure and physical property study for packaging application

This effort reports on novel polylactic acid-derived polyurethane (PU) and polyamide 6,12 (PA6,12)-based blends and graphene-reinforced nanocomposite. PU/PA6,12 (50:50) blend was opted as matrix based on molecular weight and shear stress performance. PU/PA6,12 with 5?wt% graphene (PU/PA6,12/graphene 3) showed improved T₀ and T_max of 515 and 541°C relative to neat blend. PU/PA6,12/graphene 3 also revealed significantly high tensile (53?MPa) and flexural strength (1,711?MPa). For Eschericia coli, Staphylococcus, and Pseudomonas bacterial strains, nanocomposite with higher graphene loading produced significant inhibitory effects. Novel nanocomposites displayed fine antimicrobial and barrier properties against O₂ and H₂O to be used as a packaging material.     

Sunlight helps self-healing of liquid-crystalline gels of lignin-graft PMMA doped with GO and azobenzene

ABSTRACT

Self-healing soft matters have attracted much attention because of their extraordinary performance for extending working life of materials. To utilise sunlight to help self-healing of liquid-crystalline gels composed of one low-mass liquid crystal (5CB) and one hyperbranched polymer (lignin-graft-PMMA), a low content of graphene oxide (GO) and one azobenzene compound are doped as photoresponsive additives. Upon irradiation of UV light, the azobenzene can induce gel-sol transition due to the photoinduced molecular cooperative motion, thus surface dents can be repaired. On the other hand, GO functions as the nanoscale heat source because of the photothermal effect under exposure of visible (VIS) or NIR light, heating the gel to undergo gel-sol transition for mending surface cracks. In addition, the mechanical properties of the gels are also improved by addition of GO. This NIR-VIS-UV light responsive liquid-crystalline gel shows highly effective gel-sol transition upon direct solar radiation because of the coexistence of both photochemical and photothermal effect. Furthermore, these sunlight-assistant self-healing gels also show anisotropy and orientation just like other liquid-crystalline materials, enabling them to find various advanced applications with longer service life.     

光/潮气双重固化聚氨酯涂层的制备及性能研究

以甲苯-2,4-二异氰酸酯(TDI)和二乙醇胺(DEOA)为原料一步法合成了超支化聚氨酯,对其改性制备了光固化超支化聚氨酯丙烯酸酯(HPUA)和一系列双重固化(UV/潮气)超支化聚氨酯丙烯酸酯(DHPUA),使用傅立叶红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)和碳谱(13C-NMR)以及凝胶色谱(GPC)对其分子结构进行了表征.并以其为预聚物制备光固化涂层,通过对双重固化涂层的表面形貌、热性能和物理性能的研究,结果表明,超支化双重固化涂层经过潮气固化后,涂层表面的粗糙度随着树脂中硅氧烷端基的含量的增加先下降后上升;超支化双重固化涂层的物理性能和热稳定性都随着树脂中硅氧烷端基的含量的增加而提升.     

Hot press transferring of graphene nanoplatelets on polyurethane block copolymers film for electroactive shape memory devices

We report a transferring method of graphene nanoplatelets (GNPs) on polyurethane (PU) block copolymers film. We polymerized PU block copolymer films, and then, a GNP layer, deposited on glossy paper by drop casting, was transferred by hot press from the glossy surface to the synthetized PU substrate. Nanoindentation test showed that GNP coated PU substrate exhibits improved mechanical properties with respect to the neat PU film. When an electric bias was applied to the GNP coating, the heat generated by Joule effect was transferred to the PU substrate showing an electroactive shape recovery effect. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1100–1106     

UV-Vis-NIR Light-deformable Shape-memory Polyurethane Doped with Liquid-crystal Mixture and GO towards Biomimetic Applications

Nature has been inspiring material researchers to fabricate biomimetic functional devices for various applications, and shape-memory polymer materials(SMPMs) have received tremendous attention since the promising intelligent materials possess more advantages over others for the fabrication of biomimetic functional devices. As is well-known, SMPMs can be stimulated by heat, electricity, magnetism, pH, solvent and light. From the viewpoint of practical applications, ultraviolet(UV)-visible(Vis)-near infrared(NIR) light-responsive SMPMs are undoubtedly more advantageous. However, up to now, UV-Vis-NIR light-deformable SMPMs by combining photothermal and photochemical effects are still rarely reported. Here we designed a UV-Vis-NIR light-deformable SMP composite film via incorporating a liquid crystal(LC) mixture and graphene oxide(GO) into a shape-memory polyurethane matrix. The elongated composite films exhibited interesting photomechanical bending deformations with different light-triggered mechanisms,(1) photochemically induced LC phase transition upon UV exposure,(2) photochemically and photothermally induced LC phase transition upon visible-light irradiation,(3) photothermally triggered LC phase transition and partial stress relaxation upon low-intensity NIR exposure. All the deformed objects could recover to their original shapes by high-intensity NIR irradiation.Moreover, the biomimetic circadian rhythms of acacia leaves and the biomimetic bending/spreading of fingers were successfully achieved, which could blaze a way in the field of biomimetic functional devices due to the excellent light-deformable and shape-memory properties of the SMP composite films.     

Green synthesis of nickel oxide particles and its integration into polyurethane scaffold matrix ornamented with groundnut oil for bone tissue engineering

Physiochemical properties of the fabricated scaffolds play a crucial role in influencing the cellular response for the new tissue growth. In this study, electrospun polyurethane (PU) scaffolds incorporated with green synthesized nickel oxide nanoparticles and groundnut oil (GO) were fabricated using electrospinning technique. First, synthesis of nickel oxide (NiO) was done using leaf extract of Plectranthus amboinicus (PA) via microwave-assisted technique. Synthesized nanoparticles were confirmed through Energy-dispersive X-ray spectroscopy (EDX) analysis and size of the particles were in the range of 800–950?nm. Fiber morphology of the fabricated scaffolds was analyzed using scanning electron microscope (SEM) which showed decrease in fiber diameter for the fabricated composites compared to the pristine PU. The wettability studies showed an increase in contact angle for developed composites than the pure PU. Thermal analysis depicted an increase in thermal behavior for the PU/GO/NiO compared to the pristine PU. Surface roughness values were obtained through atomic force microscopy (AFM) which showed a decrease in roughness while adding GO and NiO to the PU. Finally, the fabricated composites showed enhanced deposition of calcium content than the pristine PU. These results corroborated that the developed composites have a significant effect on the fiber morphology, wettability, thermal behavior, surface roughness, and mineral deposition depicting its versatility for bone regeneration.     

Hybrid polypyrrole/copper/graphene oxide nanocomposite films synthesized via potentiostatic deposition with enhanced photovoltaic properties

Novel ternary nanocomposites films of Polypyrrole/copper/graphene oxide (PPy/Cu/GO) showed enhanced optical and electronic properties. In this study, PPy/Cu/GO films were synthesized with different GO load (0.0, 0.4, 0.6, and 0.8 wt%) using electrochemical deposition technique. The structural, optical and electrical properties of the composites were evaluated using X-Ray Diffraction (XRD) spectroscopy, UV–visible spectroscopy, Scanning electron microscopy (SEM), Energy dispersive X-ray spectroscopy (EDX), and four-point probe methods. XRD results reveal that the GO was completely intercalated and dispersed uniformly in the nanocomposites. The results also revealed that the nanocomposite films are crystalline in nature, with distinct peaks corresponding to indexed miller indices. UV-visible analysis revealed that all of the nanocomposites showed good UV absorbance which was significant in the UV–Vis region of ≈450 nm. The energy band gap decreased with increase in GO load and was found within 3.46 to 2.25 eV, across the range of GO load which fall within the range of energy band gap for photovoltaic applications. The SEM results revealed that the nanocomposite films showed unevenly shaped structures with porous surface which increases with increasing GO loading, while the EDX result revealed the presence of carbon, oxygen nitrogen and copper as fundamental elements deposited. The nanocomposites' four-point probe analysis revealed slight increase in conductivity with low GO content. The incorporation of Cu and GO nanoparticles in PPy matrix provides a better balance and thus improved the photovoltaic properties of PPy/Cu/GO making them suitable for photovoltaic applications.     

胍盐键合型聚氨酯涂料的制备及其抗菌防霉性能

采用化学键合的方式将聚六亚甲基盐酸胍(PHMG)键合到聚氨酯(PU)分子链上,制得抗菌PU涂料PU-PHMG。利用红外光谱(FT-IR)、阿贝折射仪、原子力显微镜(AFM)等对其结构与性能进行了表征,用振荡法、抑菌圈法等对其抗菌性能进行了测试,同时探究了PHMG的质量分数对PU涂料各项性能的影响。研究表明:当PHMG的质量分数为1.0%时,PHMG的键合效率达到93.59%,对大肠杆菌和金黄色葡萄球菌的抑菌率达到99.5%以上,证明PU-PHMG具有优异持久的抗菌性能。此外,该涂料还兼具优异的防霉性能和力学性能。     

Effect of walnut shells and silanized walnut shells on the mechanical and thermal properties of rigid polyurethane foams

In the study walnut shells (WS) and silanized walnut shells (S_WS) were used as cellulosic fillers for novel polyurethane (PU) composite foams. The impact of 1, 2 and 5 wt% of WS and S_WS on the foaming parameters, mechanical and thermo-mechanical properties of obtained materials were evaluated. The results have shown that compared to untreated WS filler, the application of S_WS leads to PU foams with more regular structure and improved physico-mechanical behavior of PU materials. For example, compared to controlled WS_0 foam, PU foams enhanced with 1 wt% of the S_WS exhibited better mechanical properties, such as higher compressive strength (~15% of improvement), better impact strength (~6% of improvement), and improved tensile strength (~9% of improvement). The addition of S_WS improved the thermomechanical stability of PU foams. This work provides a better understanding of a relationship between the surface modification of the walnut shell filler and the mechanical, insulating and thermal properties of the PU composites. Due to these positive and beneficial effects, it can be stated that the use of WS and S_WS as natural fillers in PU composite foams can promote a new application path in converting agricultural waste into useful resources for creating a new class of green materials.     

Synthesis and properties of silanized waterborne polyurethane/graphene nanocomposites

A series of silanized waterborne polyurethane (WPU)/graphene oxide (GO) chemical hybrids were synthesized from polycaprolactone diol, isophorone diisocyanate, dimethylol butanoic acid, and (3-aminopropyl) triethoxysilane with GO as multifunctional crosslink as well as reinforcing filler. With the addition of GO, dispersion size greatly decreased due to the increased water phase viscosity, while it increased after chain extension reaction due to the migration of GO into the PU particles. The GO covalently bonded to WPU via the sol–gel type reaction augmented contact angle, glass transition temperature (Tg), hardness, and Young’s modulus of the cast film up to 1 %. However, the effects were less pronounced at high content (1.5 %) due to the agglomeration of GO particles.     

Recent progress in applications of graphene oxide for gas sensing: A review

This paper is a review of the recent progress on gas sensors using graphene oxide (GO). GO is not a new material but its unique features have recently been of interest for gas sensing applications, and not just as an intermediate for reduced graphene oxide (RGO). Graphene and RGO have been well known gas-sensing materials, but GO is also an attractive sensing material that has been well studied these last few years. The functional groups on GO nanosheets play important roles in adsorbing gas molecules, and the electric or optical properties of GO materials change with exposure to certain gases. Addition of metal nanoparticles and metal oxide nanocomposites is an effective way to make GO materials selective and sensitive to analyte gases. In this paper, several applications of GO based sensors are summarized for detection of water vapor, NO₂, H₂, NH₃, H₂S, and organic vapors. Also binding energies of gas molecules onto graphene and the oxygenous functional groups are summarized, and problems and possible solutions are discussed for the GO-based gas sensors.