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.     

Doping of Zinc Oxide with Selected First Row Transition Metals for Photocatalytic Applications

ZnO doped with Cr, Mn, Fe, Co, Ni and Cu was prepared by homogeneous hydrolysis of sulfates with urea. The samples were annealed at various temperatures and characterized by X‐ray powder diffraction, UV/VIS reflectance spectroscopy, BET (Brunauer‐Emmet‐Teller) surface area and porosity measurements. The photocatalytic activity of the samples was evaluated by measuring the degradation of an organic dye Reactive Black 5. The morphology of the samples was determined by scanning electron microscopy and atomic force microscopy. For the Cu‐doped ZnO sample, EPR spectra were obtained. All samples annealed at 800°C contained hexagonal ZnO. In the VIS region, the best photocatalytic performance had the ZnO samples doped with Cr, Fe and Cu.     

Fabrication of Micro‐ and Nanoscale Crystals and Thin Films of a Phthalocyanine

Micro‐ and nanosized crystals of 1, 4, 8, 11, 15, 18, 22, 25–octabutoxy–29H, 31H–phthalocyanine (Pc) were successfully fabricated through the reprecipitation approach followed by ultrasonication treatment from acetone solution. Phthalocyanine thin films were prepared by vacuum sublimation, spin‐coating and drop‐cast methods, respectively. Field emission scanning electron microscopy (FESEM), UV/VIS/NIR spectroscopy, polarizing optical microscopy and luminescence spectrometry were applied to study phthalocyanine crystal's surface morphology, electronic absorption, birefringence and light emission properties accordingly. The electronic absorption maximum of Pc nanocrystals shifts to longer wavelength compared to that in acetone solution. Birefringence phenomena exist for Pc crystals with different sizes. Fluorescence is observed for both the Pc in acetone solution and thin film.     

Zeolitic imidazolate framework-67 (ZIF-67) rhombic dodecahedrons as full-spectrum light harvesting photocatalyst for environmental remediation

The inferior utilization efficiency of light is the main obstacle to the practical application of traditional photocatalysts such as TiO₂ and ZnO. In this regard, the development of novel photocatalysts with the capability of harvesting full spectrum light (from ultraviolet (UV) to near-infrared (NIR)) energy is a promising solution for solar energy conversion and environmental remediation. Here, we report the discovery of a single material that can harvest UV, visible (VIS), and NIR radiations to decompose heavy metal contaminants in aqueous solution. Zeolitic imidazolate framework-67 (ZIF-67) rhombic dodecahedrons were synthesized through a facile solution approach and employed in the reduction of Cr(VI) under UV−VIS−NIR pulsed laser irradiation, which was generated from the fundamental, second and third harmonics of Nd:YAG laser, respectively. The nanostructures showed efficient Cr(VI) reduction under UV, VIS and NIR laser irradiation and the measured reduction efficiency (%) was 71.22%, 69.52%, and 40.79%, respectively after 120 min. A possible explanation for the photocatalytic activity in Cr(VI) reduction was proposed. This is the first study of its kind where pulsed laser and ZIF-67 rhombic dodecahedrons capable of harvesting full spectrum light energy have been employed for the removal of Cr(VI) from water. The extraordinary capacity of harvesting full-spectrum light and long-term stability make ZIF-67 a potential photocatalyst for environmental remediation.     

Measurement of the percentage volume particle size distribution of powdered microcrystalline cellulose using reflectance near-infrared spectroscopy

This is the first reported method for determining the percentage volume particle size distribution of a powder (microcrystalline cellulose) by near-infrared (NIR) reflectance spectroscopy. A total of 113 samples of powdered microcrystalline cellulose were used from six different commercially available grades, with different moisture contents (range: 0.9-4.8% m/m). NIR reflectance measurements of these samples were made in narrow soda glass vials. Reference particle size data for the samples were acquired by laser diffraction. The NIR data were then calibrated to measure particle size by partial least squares regression. The effects of a range of different NIR data pre-treatments on calibration and prediction precision were investigated. Overall, simple absorbance data were found to produce regression models with the best predictive ability (root mean square error of prediction = 0.90%). The method was also found to be insensitive to moisture content.     

Thiophene‐Fused‐Heteroaromatic Diones as Promising NIR Reflectors for Radiative Cooling

Developing appropriate NIR‐reflective materials to combat near–infrared (NIR) heat radiation (700–2500 nm) from sunlight, avoiding energy accumulation and reduce energy consumption, is important and highly desirable. In this research, four thiophene‐fused‐heteroaromatic diones were used as basic reflectors to investigate the relationship between their intrinsic molecular structures and NIR‐reflective properties. The reflectance intensity can be readily tuned by adjusting the length of the appended aliphatic side chains, as well as the strength of the electron‐donating groups. A methoxy‐substituted thiophene‐fused‐heteroaromatic dione showed the best performance in reflecting NIR, and it was used as a coating for a model glass house. The comparison of the internal temperature difference relative to a control house was measured and the maximum temperature was 12 °C lower than that in the control house.     

Novel UV-protective formulations for cotton, PET fabrics and their blend utilizing irradiation technique

A novel coating formulation to impart ultraviolet (UV) protection property to cotton, Polyethylene trephethalate (PET) and cotton/PET fabrics was prepared and gamma rays as an ionizing radiation was utilized for surface curing. Natural occurring aluminum potassium sulfate (Alum) was used individually and in binary coat with Zinc Oxide (ZnO), to induce the UV-blocking properties. It was found that using Alum (0.3 g/ml) caused a prompt increase in ultraviolet protection factor (UPF) over the uncoated fabrics. Moreover, the incorporated ZnO in the binary coat increased the UPF for two to threefold than the stand-alone Alum coating, specially in case of PET coated fabric. Water absorbance and moisture regain of ZnO and Alum/ZnO coated fabrics showed a decrease over the blank samples, due to the usage of oligomer/monomer combination. On contrary, Alum showed a hydrophilic effect with the increase in its content in the formulation. Surface Electron Microscope showed the homogenous coating of fibers. X-ray diffraction (XRD), energy dispersive X-ray (EDX) and water vapor permeability were also tested for coated samples.     

纳米SiO2改性苯基缩水甘油醚丙烯酸酯的紫外光固化性能研究

以苯基缩水甘油醚（PGE）和丙烯酸（AA）为原料,三苯基膦为催化剂,4-甲氧基苯酚为抑制剂,合成了一种新型光敏预聚物苯基缩水甘油醚丙烯酸酯（PGEA）。然后用十六烷基三甲基溴化铵处理纳米SiO₂,并用硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH-570）进行表面改性,并加入到预聚物PGEA中,制成紫外纳米复合涂层。用扫描电子显微镜（SEM）发现涂层含量小于5%时,改性纳米SiO₂的分散效果较好。用扫描原子力显微镜（AFM）观察到固化膜表面光滑。而适量的改性纳米SiO₂可以提高紫外光固化材料的拉伸强度、伸长率和冲击强度。     

UV Curable Hard Transparent Hybrid Coating Materials on Polycarbonate Prepared by the Sol-Gel Method

UV curable, hard, transparent inorganic/organic composites with covalent links between the inorganic and the organic networks were prepared by the sol-gel method. These hybrid coating materials were synthesized using a commercially available, acrylate end-capped polyester or polyurethane oligomeric resin (EBC80, EBC284), hexanedioldiacrylate (HDDA) as a reactive solvent, 3-(trimethoxysilyl)propoxymethacrylate (TMSPM) as a coupling agent between the organic and inorganic phase, and a metal alkoxide, tetraethylorthosilicate (TEOS). The materials were applied on primer or oxygen plasma pretreated polycarbonate sheets and UV cured, followed by a thermal treatment to give a transparent coating with a good adhesion and abrasion resistance. The high transmission and the thermogravimetric behavior indicate the presence of a nanoscale hybrid composite, as is confirmed by SAXS and TEM measurements. In a Taber Abrasion Test, uncoated polycarbonate sheets exhibit a 48% decrease in light transmittance at 600 nm after 300 wear cycles, whereas the EBC80 hybrid coating system containing 9 wt% SiO₂ (EBC80/25Si) shows only 28% decrease in light transmittance. A maximal improvement of the abrasion resistance is achieved when 23 wt% SiO₂ is incorporated (EBC80/60Si, EBC284/60Si) with only 20% decrease in light transmittance. The abrasion resistance of glass is not yet encountered. For optimal results, it is essential that the rate of condensation of the silanol groups is sufficiently high to form a dense three-dimensional network.     

Effect of potassium permanganate on morphological,structural and electro-optical properties of graphene oxide thin films

This work investigated the effect of Potassium Permanganate (KMnO₄) on graphene oxide (GO) properties, especially on electrical properties. The GO thin films were deposited on a glass substrate using drop casting technique and were analysed by using various type of spectroscopy (e.g. Scanning Electron Microscopy (SEM), Ultra- Violet Visible (UV–VIS), Fourier Transform Infrared (FTIR), X-Ray Diffraction (XRD), optical band gap, Raman Spectroscopy). Furthermore, the electrical experiments were carried out by using current–voltage (I-V) characteristic. The GO thin film with 4.5 g of KMnO₄ resulted in higher conductivity which is 3.11 × 10^?4 S/cm while GO with 2.5 g and 3.5 g of KMnO₄ achieve 2.47 × 10^?9 S/cm and 1.07 × 10^?7 S/cm, respectively. This further affects the morphological (SEM), optical (band gap, UV–Vis, FTIR, and Raman), and crystalline structural (XRD) properties of the GO thin films. The morphological, elemental, optical, and structural data confirmed that the properties of GO is affected by different amount of KMnO₄ oxidizing agent, which revealed that GO can potentially be implemented for electrical and electronic devices.     

钒酸银/氧化石墨烯复合物的制备和可见光催化性能

通过改进Hummers法制备了氧化石墨烯(GO),采用液相沉淀法合成了Ag₃VO₄/GO复合物,利用X射线衍射(XRD)、扫描电子显微镜(SEM)和紫外-可见(UV-Vis)漫反射光谱等技术手段对样品进行了测试表征;并在可见光辐射下(λ≥420 nm)考察了复合物催化剂中GO含量对Ag₃VO₄光催化降解甲基橙溶液(MO)的性能影响。 结果表明,掺杂质量分数2%的GO复合物光催化活性提高最显著,30 min内对MO的降解率可达到89%以上,是纯Ag₃VO₄光催化活性的3倍。     

Effect of alkali and ultraviolet aging on physical,thermal, and mechanical properties of fibers for potential use as reinforcing elements in glass/silicate composites

This work reports the effect of an alkaline environment and ultraviolet (UV) radiation on the physical, thermal, and tensile properties of different fibers selected as potential reinforcing elements to enhance the impact properties of brittle glass/silicate composites. The fibers, which included regenerated cellulosic (viscose and rayon), synthetic (ultrahigh molecular weight polyethylene, polypropylene, polyamide, acrylic), glass, ceramic, and steel, were aged in different alkaline solutions with pH ranging from 11.1 to 13.6 at 70°C for different periods of time and exposed to UV radiation for 330 h. The physical and thermal properties of aged fibers were studied using tensile testing, scanning electron microscopy, and simultaneous differential and thermogravimetric analysis. Results showed that the regenerated cellulosic fibers, acrylic, E‐glass, and A‐glass fibers could not withstand the highly alkaline environment. Overall, ultrahigh molecular weight polyethylene, UV‐stable polypropylene, polyamide 6.6, AR‐glass, ceramic (alumino borosilicate), and steel fibers performed very well under all conditions, indicating that they have the potential to be used as reinforcing elements in glass/silicate composites. Copyright © 2011 John Wiley & Sons, Ltd.     

A novel pyrophosphate BaCr2(P2O7)2 as green pigment with high NIR solar reflectance and durable chemical stability

A novel pyrophosphate BaCr₂(P₂O₇)₂ was synthesized by the conventional solid-state reaction. The X-ray diffraction (XRD), FTIR spectrum, scanning electron microscopy (SEM) and ultraviolet–visible (UV–Vis) near infrared (NIR) reflectance spectra were applied to characterize the powders. The refractive indexes and nature of the VB and CB were determined. The structure, color properties and application were investigated. The results reveal that the anomalist bodies with smooth surfaces were obtained at 1200 °C with a mean size of 3 μm. A high reflectance peak at 535 nm was observed in the visible region, which is associated with the brilliant and deep green color of this pigment. With all the acids, alkali and deionized water treatment, the polycrystalline pigment BaCr₂(P₂O₇)₂ was found to be durable in chemical stability. The significantly high NIR solar reflectance of BaCr₂(P₂O₇)₂ is 90.0%, a higher cooling ability, so it has been selected to be tested as cool green pigment in ceramics. Moreover, this novel pyrophosphate pigment has great potential as cool pigment for surface coating applications.     

Doping of TiO2–GO and TiO2–rGO with Noble Metals: Synthesis,Characterization and Photocatalytic Performance for Azo Dye Discoloration

The nanocomposites of titania coupled with graphene oxide (GO) and reduced graphene oxide (rGO), respectively, were prepared by homogeneous hydrolysis with urea. Graphene was obtained by effect of high‐intensity cavitation field on natural graphite in the presence of strong aprotic solvents in pressurized ultrasonic reactor. The morphology of TiO₂–GO and TiO₂–rGO composites was assessed by scanning electron microscopy and atomic force microscopy. The nitrogen adsorption–desorption was used for determination of surface area (BET) and porosity. Raman and IR spectroscopy were used for qualitative analysis and diffuse reflectance spectroscopy was employed to estimate band‐gap energies. Further enhancement of the photocatalytic activity was attained by codoping of composites with noble metals—Au, Pd and Pt. The photocatalytic activity of TiO₂–GO and TiO₂–rGO were assessed by photocatalytic decomposition of Orange II dye in an aqueous slurry under UV and visible light irradiation. The photocatalytic activity of noble metals codoped samples was determined with decomposition of Reactive Black 5 azo dye.     

Broad-band antireflection coating at near-infrared wavelengths by a breath figure

We prepared a porous thin film by spin-coating of a cellulose acetate butyrate (CAB) solution in tetrahydrofuran under a humid environment. Due to evaporative cooling during spin-coating, condensed water droplets were formed by a breath figure on the CAB solution, and these developed a porous structure after complete drying. By varying the solution concentration and rotating speeds, two distinct morphologies were generated: top and bottom layers with higher and lower porosities, respectively. We found that the two-layer porous film coated on glass exhibited low reflectance of less than 1% in the near-infrared (NIR) regime corresponding to wavelengths between 900 and 2200 nm. Since the porous structure was very uniform over a large area, the film could be easily employed for broad-band antireflection coating at NIR wavelengths.     

Surface properties,adherence, and photocatalytic activity of sol–gel dip-coated TiO2–ZnO films on glass plates

In this study, TiO₂–ZnO nanostructured films prepared from different Ti/water mole ratios were deposited on glass plates by a sol–gel dip-coating method. The structural and surface properties, adherence, and photoactivity of synthesized TiO₂–ZnO coatings in methylene blue degradation were investigated. Among the as-prepared TiO₂–ZnO coatings from sols with different Ti/water mole ratios (1, 0.66, 0.5, and 0.4), the highest sol concentration (Ti/water mole ratio of 1) showed the highest methylene blue photodegradation of almost 80% after 400 min of UV irradiation. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), Energy-dispersive X-ray (EDX), and UV-vis diffuse reflectance spectra (DRS) confirmed that at high sol concentrations (Ti/water mole ratios of 1 and 0.66), a mixed phase of anatase and rutile is formed, whereas at a Ti/water mole ratio of 0.5, just pure rutile is formed. In detail, decreasing the sol concentration increases the cracks, degree of agglomeration, and the thickness of coatings. UV-vis DRS studies also confirm that decreasing the sol concentration in synthesized TiO₂–ZnO films leads to a shift in the absorption region of the coating to the UV region. Moreover, decreasing the sol concentration declines the coating adherence onto glass plates. TEM images of the TiO₂–ZnO coating synthesized from sol with a Ti/water mole ratio of 1 revealed the formation of ZnO nanorods around a spherical TiO₂, which indicates the presence of strong interaction between TiO₂ and ZnO nanoparticles. The TiO₂–ZnO coating synthesized from sol with a Ti/water mole ratio of 1 was then evaluated at different methylene blue concentrations, pH values, and number of coatings. After five consecutive runs, no significant decrease in the photodegradation efficiency was observed. Scanning electron microscopy (SEM) picture of used coating showed a smooth and stable layer without any detachment. Thermogravimetric analysis (TG) and sonication test confirmed thermal and mechanical stabilities of this coating as well.     

氧化石墨烯水热还原前后的发光光谱

分别采用改进Hummers方法和水热还原法制备了氧化石墨烯(GO)和还原氧化石墨烯(RGO)。 GO和RGO经透射电子显微镜(TEM)、紫外-可见吸收光谱(UV-Vis)、红外光谱(IR)、荧光发射和激发光谱(PL、PLE)等技术手段进行了表征。 荧光发射光谱显示,氧化石墨烯(GO)在可见光的激发下可以得到波长在600~800 nm范围内的宽谱近红外荧光。 通过比较氧化石墨烯水热还原前后的光谱变化,发现氧化石墨烯近红外荧光起源于氧化石墨烯的表面含氧基团,如C=O、COOH。 近红外荧光穿透性好、对生物组织损坏小,非常适合于生物成像,预示着氧化石墨烯在生物成像方面的应用潜力。     

Epoxy resins and epoxy blends studied by near infra-red spectroscopy

The cure and the final network of epoxy resins have been investigated by numerous techniques, nevertheless a clear understanding of this network structure has not yet been achieved. FTIR analysis of polymeric materials provides highly precise measurements that are widely interpretable in terms of chemical structure. Yet the high absorption of fundamental bands requires careful sample preparation to reduce the thickness of the sample or special reflection techniques are needed. Furthermore, the occurrence of overlapping bands for epoxy resin (N-H and O-H vibrations in the 3000 cm⁻¹ region) renders the quantitative analysis in the region mid IR particularly difficult. However, the overtone and combination bands are 10–100 times weaker than the fundamental ones and are observed in near infrared (NIR) region. Longer pathlengths than Mid IR ones can be used allowing transmission analysis of thick samples (1-20 mm) without special preparation. NIR absorption bands have different intensities depending on the anharmonicity of vibrations. The strongest absorption bands are due to protons connected to carbon, nitrogen, oxygen. Hydrogen bonding due to inter- and intramolecular interactions can cause band broadening, peak position shifts and intensity variations. NIR spectroscopy is therefore a useful technique to investigate polymeric materials and was used to study the cure reactions of various epoxy resins cured with amine hardener. Using different NIR techniques (reflectance, transmission and microscopy) we will briefly present some results concerning hydrogen bonding between epoxy and amine hardener before curing, epoxy resins, glass/epoxy composites and epoxy/PES (polyethersulfone) blends.     

水性纸品上光涂料的研究进展

水性纸品上光涂料是用于印刷品的精加工及包装材料的表面整饬的一种涂料,具有成本低、无污染、无毒无害、性能优良,运输方便等优点,是当前印刷上光涂料的主要发展方向。目前,国内的水性纸品上光涂料生产技术多样化,质量参差不齐,且成本高,耐水、耐磨、光泽度性能都达不到高档印刷品的上光要求,70%的高档水性纸品上光涂料需要依靠进口。本文系统地介绍了目前国内外水性纸品上光涂料的研究进展,总结了水性纸品上光涂料的各自特点与应用,并提出一种水性纸品上光涂料制备的新方法。     

AgBr@TiO<Subscript>2</Subscript>/GO ternary composites with enhanced photocatalytic activity for oxidation of benzyl alcohol to benzaldehyde

AgBr@TiO₂/GO (graphene oxide) ternary composite photocatalyst was synthesized by fabricating core–shell-structured AgBr@TiO₂ and anchoring it onto the surface of GO. The obtained samples were characterized by transmission electron microscopy, X-ray diffraction analysis, X-ray photoelectron spectroscopy, ultraviolet–visible (UV–Vis) diffuse reflectance spectrum, and photoluminescence (PL) spectroscopy. It was found that the AgBr nanoparticles were prone to aggregation while the core–shell-structured AgBr@TiO₂ possessed excellent dispersity. PL analysis revealed that the ternary-structured AgBr@TiO₂/GO could effectively promote the separation rate of electron–hole pairs. Photocatalytic oxidation of benzyl alcohol to benzaldehyde under visible-light irradiation was selected as probe reaction to evaluate the photocatalytic activity of the different samples. It was found that the AgBr@TiO₂/GO ternary composite exhibited evidently improved photocatalytic activity compared with AgBr, AgBr@TiO₂, and AgBr/GO. On the basis of the experiment results, the photocatalytic oxidation mechanism of benzyl alcohol over AgBr@TiO₂/GO is tentatively discussed.