石墨烯/棉织物制备及其电热性能研究

采用丝网印刷方式将氧化石墨烯浆料印制在棉织物表面,再经还原方法得到了电热性能优良的石墨烯棉织物。综合分析织物表面形貌、表面电阻及发热性能,探究了印制次数、还原浓度、还原时间及还原剂种类对石墨烯棉织物发热性能影响。结果表明,印制次数为10次,还原浓度为5 mg/mL,时间6 h,施加在两端电压为24 V时,织物的表面电阻为4.0 kΩ/cm,表面温度为46.8℃,电热性能达到最佳。     

碳纳米管/石墨烯协同改性碳纤维复合材料的制备及性能

利用偶联剂（KH570）改性的石墨烯（GO）和酸化的多壁碳纳米管(MWCNTs)协同改性聚丙烯腈（PAN）基碳纤维制备得到PAN/MWCNTs/GO基碳纤维（MPG）,以此为原料,采用湿法造纸技术,制备PAN/MWCNTs/GO基碳纤维复合材料（MPG P）。利用傅里叶变换红外光谱仪、扫描电子显微镜,对MPG纤维进行表征,并利用四探针测试仪、万能试验机和多孔材料分析仪,研究了MPG-P材料的导电性能、力学性能、孔径分布以及孔隙率。结果表明,当MWCNTs/GO含量为0.2 %（质量分数,下同）时,MPG P表现出最佳的拉伸强度(37.21 MPa),电阻率为13.17 mΩ·cm,孔隙率为63.7 %;当MWCNTs/GO=1/2（质量比,下同）时,表现出最佳的拉伸强度(40.13 MPa),比纯PAN复合材料(30.18 MPa)提高了32.97 %,电阻率为13.52 mΩ·cm,孔隙率为65.2 %。     

Multifunctional cotton fabrics with graphene/polyurethane coatings with far-infrared emission,electrical conductivity,and ultraviolet-blocking properties

In order to introduce multifunctional properties into flexible cotton fabric, graphene and waterborne anionic aliphatic polyurethane composites were prepared and then deposited on the surface of the fabric substrate through facile pad-dry-cure process. The fabrics thus obtained were characterized by scanning electron microscopy and Fourier transform infrared spectroscopy, and their functional properties such as far-infrared emission, electrical conductivity, and ultraviolet (UV) blocking were studied. The coating process enhanced the far-infrared emissivity up to 0.911 in the wavelength range of 4–18 μm. In addition, the ultraviolet protection factor (UPF) of the fabric with 0.8-wt% graphene could reach 500, up to 60-fold higher than that of pristine cotton fabric (UPF 8.19), and its electrical resistivity was decreased from 1.15 × 10⁷ to 2.94 × 10⁻¹ Ω m, which is almost 8 orders of magnitude. The fabrics have also been found to be stable even after 10 cycles of laundering.     

Discussion of aqueous urethane acrylate oligomers with sulfoisophthalate on the antistatic hydrophilic finishing of different fabrics

In this study, PEG(SE) containing sulfonic acid group was produced by transesterification of dimethyl 5‐sulfoisophthalate sodium salt (SIP) with PEG. The reactive urethane acrylate oligomers were synthesized by using SE as soft segment, isophorone diisocyanate (IPDI) as hard segment, and hydroxyethyl methacrylate (HEMA) as blocking agent. Their solution properties and thermal properties were investigated. Dipping process was carried out on polyethylene terephthalate (PET) fabric, polyamide (nylon) fabric, and cotton fabric for hydrophilic finishing and the effects of processing condition on the fixation behavior and hydrophilic property of treated fabric have been discussed. The conclusions are as follows: the particle size of oligomer solutions are about 45–90 μm, surface tension of solutions are below 43 dyn/cm, and they have smaller contact angle than water. The particle size, particle variance, and streaming current reading decreased, but the surface tension and contact angle enhanced upon increasing PEG molecular weight. The melting point of oligomer is 38°C–52°C and the glass transition point is −18°C to −25°C. In comparison with the fabric finishing, the add‐on of PET fabric is the highest, followed by nylon, then cotton. The durability of treated cotton fabric is the highest, followed by PET, then nylon. The hydrophilicity is most stable for nylon fabric with PEG molecular weight of 2,000, and cotton and PET fabric with molecular weight of 1,000. POLYM. COMPOS., 29:45–57, 2008. © 2007 Society of Plastics Engineers     

Ionic liquid assisted fabrication of cellulose-based conductive films for Li-ion battery

An imidazolium-based ionic liquid, 1-ethyl-3-methylimidazolium diethyl phosphate ([Emim]DEP) was used to dispense graphene nanoplates (GN) and multiwalled carbon nanotubes (MWCNTs) as well as dissolve cellulose for fabricating composite conductive films. The effects of GN, MWCNTs, and cellulose mass ratios on the electrical conductivity and morphology of the films were investigated. The interaction between GN, MWCNTs, and cellulose was analyzed by SEM, X-ray diffraction (XRD), TGA, and Raman spectroscopy. The results indicate that [Emim]DEP plays a vital and irreplaceable role in GN and MWCNTs dispersion, cellulose dissolution, and porous formation during the regeneration and drying processes. MWCNTs linked flaky GN and a hybrid structure was constructed elaborately to form a better conductive path and improve the conductivity as well as increase the film stability. For the XRD result, the carbonized GN-MWCNTs-cellulose films exhibited the graphitic peaks, showing that the films still retained the structure of carbon atoms or molecules. Besides, the maximum conductivity of carbonized GN-MWCNTs-cellulose (7:3:2) composite film was up to 9,009 S m⁻¹, due to the small carbon clusters formation and the high degree of graphitization. Further, the carbonized films were applied as anodes in Li-ion battery and showed good electrochemical performance. The best cyclic stability (i.e., discharge/charge capacity) of 438/429 mA h g⁻¹ and coulomb efficiency of 50.2% were obtained. This novel and sustainable design is a promising approach to obtain cellulose-based conductive films and anodes for Li-ion battery applications.     

20%啶虫脒可溶液剂在棉花和土壤中的残留及消解动态

[目的]评价啶虫脒在棉花和土壤中使用的安全性,建立其使用规范。[方法]采用田间试验及液质联用检测方法,研究了啶虫脒在棉花和土壤中的残留消解动态,并对其在棉花上使用的安全性提出了建议。[结果]啶虫脒在棉花和土壤中的消解较快。棉叶中半衰期为2.14～5.37 d,土壤中半衰期0.88～8.87 d。20%啶虫脒可溶液剂防治棉花蚜虫,用药量30～45 g a.i./hm2,棉花收获前49 d开始施药,末次施药后7、14、21 d采集棉籽及土壤样品,检测的棉籽及土壤中啶虫脒的残留量均低于0.05 mg/kg。[结论]拟推荐我国啶虫脒在棉花和土壤中的最大残留限量为0.2 mg/kg。     

Flameproofing of cellulose and several synthetic polymers by substituted N-[(phosphinyl) methyl]-2-imidazolidinones

Substituted 1-[(phosphinyl)methyl]-2-imidazolidinones were used for development of a novel finishing process referring cotton fabric fire and crease resistant. The process involves treatment of cotton fabric with an acidic solution of substituted 1-[(phosphinyl)methyl]-3-hydroxymethyl-2-imidazolidinones and tris (N-hydroxymethyl) melamine followed by curing. The fire resistance, the crease resistance, and the mechanical strength of the treated fabric were determined in order to evaluate the process. Particularly, the fire resistance of the specimens was determined by measuring their char length, the afterflame time, and the afterglow time. All treated specimens were selfextinguishing. The crease resistance and the mechanical strength of the specimens were determined by measuring their recovery angle and breaking load, respectively. In addition, substituted 1,3-bis[(phosphinyl)methyl]-2-imidazolidinones were used as fire retardant additives in several synthetic polymers such as nylon 66 and polyethylene with significant increase of their limiting oxygen index (LOI) value.     

Tribological behaviors of hybrid PTFE/nomex fabric/phenolic composite reinforced with multiwalled carbon nanotubes

Modification of composites was a general method to improve their tribological behaviors. On the way to explore composites with enhanced tribological behaviors, we have successfully prepared hybrid PTFE/Nomex fabric/phenolic composite filled with multiwalled carbon nanotubes (MWCNTs) or MWCNTs modified by polystyrene (PS) with a grafting to method. The results of pin‐on‐disc type wear tests indicated tribological behaviors were improved both for hybrid PTFE/Nomex fabric/phenolic composite filled with MWCNTs and MWCNTs‐PS, especially for that of filled with MWCNTs‐PS. And the probable reason was also discussed based on the characterization results. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Aqua-mediated in situ synthesis of highly potent phosphorous functionalized flame retardant for cotton fabric

Flame retardancy in various materials is becoming an increasingly important performance feature. In the textile industries, fire-related problems have become an important concern over the decade. Herein, the polyvinyl alcohol (PVA) and graphene-supported material were functionalized with trimethyl phosphate (TMP) for the synthesis of flame retardant (FR) composite material [graphene polymer functionalized trimethyl phosphate (GPTMP)] in the aqueous medium, which improves the stability of cotton fabric against flame. Graphene and PVA fabricated with phosphorus functional groups make the fabric more comfortable against fire and help to avoid further spreading of fire. The composite-coated fabric sustains for a long time on continuous flame with maintaining its initial shape and size. The GPTMP-coated fabric shows flame retardancy for up to 540 s on constant flame exposure, whereas control samples such as PVA-, graphene oxide-, and TMP-coated fabrics resist for up to 15, 20, and 14 s, respectively. The limiting oxygen index (LOI) and vertical flammability test (VFT) for synthesized composites were performed to confirm and support the flame retardancy property of GPTMP. The GPTMP shows the 35% LOI value and forms the char length of 2.6 cm during VFT. This work provides a simple and eco-friendly method to obtain novel GPTMP, which has a high potential as a FR for different fabrics, including cotton.     

Synthesis and Characterization of Multifunctional Cotton Containing Cyclodextrin and Butylacrylate Moieties

Herein we report new approaches for multifunctionalization of cotton fabric using reactive cyclodextrin (RCD), butylacrylate (BuA) and a newly developed initiator which is based on potassium persulphate/ammonium persulphate (KPS/APS) mixture. The first approach involves preparation of reactive preformed polymer and thus obtained polymer is grafted to cotton fabric in subsequent steps. The second approach addresses concurrent in situ grafting of cotton fabric using the same initiator in presence of RCD, and BuA. Indeed, occurence of the three types of grafting occurs, as evidenced by FTIR and SEM analysis. The presence of BuA moieties in the molecular structure of cotton renders it soft. Also presence of RCD moieties with tours-shaped cavity of cyclodextrin provides several possibilities for imparting new and significantly improved properties to cotton fabric. This would depend upon nature and amount of guest compounds accommodated in cyclodextrin cavities. Characterization of the products were monitored to SEM, FTIR, ¹H-NMR.     

Preparation of graphene/multi-walled carbon nanotube hybrid and its use as photoanodes of dye-sensitized solar cells

This study employed a solution-based method to prepare a 3-D hybrid material comprising graphene and acid-treated multi-walled carbon nanotubes (MWCNTs). The adsorption of MWCNTs on graphene reduces the π–π interaction between graphene sheets resulting from steric hindrance, providing a subsequent reduction in aggregation. Optimal proportions of MWCNTs to graphene (2:1) enabled the even distribution of individual MWCNTs deposited on the surface of the graphene. The hybrid 3-D material was incorporated within a TiO₂ matrix and used as a working electrode in dye-sensitized solar cells (DSSCs). The hybrid material provides a number of advantages over electrodes formed of either MWCNTs or graphene alone, including a greater degree of dye adsorption and lower levels of charge recombination. In this study, DSSCs incorporating 3-D structured hybrid materials demonstrated a conversion efficiency of 6.11%, which is 31% higher than that of conventional TiO₂-based devices.     

Effect of carbonaceous counter electrodes on the performance of ZnO-graphene nanocomposites based dye sensitized solar cells

With many advantages like low-cost preparation, excellent electrical properties, and high catalytic activity; carbon allotropes are the most expected carbon materials to substitute the expensive Platinum (Pt) as counter electrodes (CEs) for dye-sensitized solar cells (DSSCs). In the present study, the photovoltaic behaviors of DSSCs fabricated with graphene, multiwalled carbon nanotubes (MWCNTs), and Pt films CEs, respectively, were compared. The graphene and MWCNTs CEs films were prepared by doctor blading the graphene and MWCNTs pastes on Indium tin oxides (ITOs) glass substrates. The structural, morphological, and compositional properties of these carbon CEs viz. graphene and MWCNTs were investigated by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), and energy dispersive X-ray (EDX), respectively. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed for the examination of electrochemical and catalytic properties of Pt as well as carbonaceous CEs. These low-cost graphene and MWCNTs CEs were employed in the sandwich-structured DSSCs having ZnO-graphene nanocomposite films as photoanodes. The photoconversion efficiency (η) values of as prepared DSSCs were measured under AM 1.5 illumination (100?mW?cm^?2). The DSSCs with graphene CE and MWCNTs CE performed with efficiency values of 2.26% and 2.04%, respectively. The performance of these carbonaceous CEs are comparative to that of Pt CE which indicates the practicability of carbon based nanomaterials in DSSCs as low cost alternatives to the expensive Pt.     

Fabrication of flexible carbon dioxide gas sensor with conductive polymer/reduced graphene oxide hybrids: Effects of substrate type and mass ratio

Flexible gas sensors made of polyaniline (PANI)-reduced graphene oxide (rGO) nanocomposite were prepared using three different substrates, namely filter paper, cotton fabric, and weighing paper, through in-situ reduction of GO and in-situ polymerization of aniline. Preliminary analysis showed that the PANI/rGO coated on filter paper possesses a superior electrical conductance than PANI/rGO coated on cotton fabric and weighing paper. Such observation was attributed to the good attachment of the PANI/rGO nanocomposites onto the high-density mesh-like structure of the filter paper with rough surfaces. In contrast, PANI/rGO coated onto weighing paper and cotton fabric of different surface structures presented lower-to-almost negligible conductance. Accordingly, PANI/rGO filter paper was selected for the subsequent evaluation of gas sensing properties. The gas-sensing performances of the PANI/rGO filter paper sensors indicated that the 5 wt% PANI/rGO (i.e., 5 wt% rGO) sample exhibited the best response of 306% for 500 ppm carbon dioxide (CO₂) gas at room temperature with a recovery rate of 41.5%. On the other hand, the optimum recovery rate of 59.5% was identified at 0.5 wt% PANI/rGO sample which exhibited a response of 155%. Owing to the synergy effect, the PANI/rGO sensor outperformed the sensor made of pure PANI or pure rGO.     

Thermal analyses of flame-retardant twills containing cotton,polyester and wool

Medium weight twill fabrics constructed from cotton and cotton blended with polyester and/or wool were analyzed under nitrogen by three thermoanalytical techniques. Fabrics were tested both before and after treatment with [tetrakis(hydroxymethyl)phosphonium] sulfate (THPS), urea, and trimethylolmelamine. The presence of all fibers was distinguishable in differential scanning calorimetric analysis (DSC) of untreated fabrics; the relative positions of the endothermic, decomposition peak temperatures were only slightly changed. After flame-retardant (FR) treatment, the blended cotton and wool fibers were altered. Both fibers decomposed as exotherms during DSC analysis. These data supported earlier microscopical, X-ray evidence that wool fibers were actually reacting with the FR treatment. The two DSC peaks for polyester polymer melting and decomposing remained unaffected by either blending with other fibers or the presence of the FR finish on the fabric. There was excellent agreement between DSC peak temperatures and the temperature of maximum rate of weight loss obtained from thermogravimetric analysis (TGA). Blending cotton with either of these fibers increased the residue measured after TGA. The increased residue correlated with increased flame resistance as measured by the 45° angle, edge-ignition burning rate test.     

Flame retardant finishing of cotton fleece fabric: Part V. Phosphorus‐containing maleic acid oligomers

The high flammability of cotton fleece makes it necessary to apply a flame retardant system on cotton fleece so that it can meet the federal regulation ‘Standard for the Flammability of Clothing Textiles’ (16 CFR 1610). The objective of this research was to reduce the flammability of cotton fleece using the phosphorus‐containing maleic acid oligomers (PMAO) synthesized by aqueous free radical polymerization of maleic acid. We found that PMAO can be bound to cotton fleece by esterifying with cotton cellulose with sodium hypophosphite as the catalyst. Both the 45^° flammability and limiting oxygen index data indicated that the treatment of cotton using PMAO reduced the flammability of cotton fleece. The micro‐scale combustion calorimetric data revealed that PMAO reduced the peak heat release rate and heat release capacity of the treated cotton woven fabric. The cotton fleece treated with PMAO/NaH₂PO₂ passed the federal flammability test (16 CFR Part 1610) and achieved ‘Class 1’ flammability. The PMAO bound to cotton was durable to multiple home laundering cycles. The treated fleece also showed high strength retention with little change in fabric whiteness. The use of triethanolamine as an additive modestly enhanced the performance of PMAO with no significant changes in fabric physical properties. Copyright © 2009 John Wiley & Sons, Ltd.     

棉织物无甲醛防皱整理剂MA-IA-AA共聚物的合成及性能

国内首次以马来酸(MA)、衣康酸(IA)和丙烯酸(AA)为单体,采用水相聚合工艺制备了MA/IA/AA共聚物,目标产物得到红外光谱检测证实。产物用作无甲醛纺织品防皱整理剂,研究了聚合条件对共聚物溴值和抗皱整理效果的影响。结果表明,在n(MA)∶n(IA)∶n(AA)=1∶1∶1、温度85℃、引发剂滴加时间为2 5h、m(引发剂)/m(总单体)=0 09时,制备的聚合多元羧酸的溴值低于43mg/g,单体转化率达到94%,聚合物相对分子质量为871。用该聚合物整理后,棉织物折皱回复角(WRA)可达到286°,提高率为83 3%,与公认效果最好的丁烷四羧酸(BTCA)整理后棉织物折皱回复角289°几乎一样。整理后的棉织物经水洗50次后,WRA仍可保持在263°,比水洗前的286°仅仅下降8%。整理后棉织物白度为77 6%。     

用于脑电图监测的石墨烯/聚丙烯酸共聚酯/织物复合电极的制备与性能

为制备脑电检测用聚合物基柔性复合电极片，以石墨烯、丙烯酸(AA)、丙烯酸甲酯(MA)和丙烯酸乙酯(EA)为原料，通过原位聚合的方法制得了系列聚丙烯酸共聚酯/石墨烯复合乳液，并通过与织物浸渍的方法制备了复合电极片。研究了石墨烯含量变化对复合电极片电阻的影响、各单体含量对电极片柔性的影响，以及复合电极片用于脑电监测的性能。结果表明，当石墨烯的质量分数约为46.5%、反应温度80 ℃，反应时间3 h，AA、MA与EA的体积投料比为0.2∶1∶1.8，织物采用聚丙烯无纺布并与聚丙烯酸共聚酯复合乳液浸渍后，制备的复合电极片在室温下具有良好的柔性、导电及力学强度，适合用于脑电图监测，脑电信号强度及其稳定性与商用电极（Ag/AgCl）相比性能相近，且不需要涂抹导电膏，使用方便，不会污染皮肤及对皮肤造成损伤。     

Frictional dependence of graphene and carbon nanotube in diamond-like carbon/ionic liquids hybrid films in vacuum

The use of graphene and multi-walled carbon nanotubes (MWCNTs) additives as lubricants has received considerable interest because of their excellent mechanical and frictional properties. Given their structural differences, both carbon nano-additives are expected to have different synergistic effects at various conditions (from boundary to mixed lubrication). For applications in space, the tribological properties of graphene and MWCNTs additives in diamond-like carbon/ionic liquids hybrid films in different lubricating states at high vacuum were compared. The wear surfaces, transfer films, wear debris, and microstructures of the hybrid films were analyzed via Raman spectroscopy, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. The results showed that MWCNTs and graphene present the different nano-scale tribological mechanisms and produce different lubricating effect on the hybrid films at different lubricating states.     

Modification of carbon black pigment: Cotton fabric colouring and anti‐bacterial finishing

Functional polymer modified carbon black (CB) pigment (P‐(DMC‐co‐CHPMA)‐g‐MPTS/CB) with reactive epoxy and quaternary ammonium groups was designed and prepared via a thiol‐ene click chemistry reaction, and its dispersion ability in the aqueous phase, as well as its colouring and anti‐bacterial properties for cotton fabrics, were investigated. In considering both dispersion ability and reactive ability to cotton fabric, the mole ratio of the monomers (methacrylatoethyl trimethyl ammonium chloride [DMC] and 3‐chloro‐2‐hydroxypropyl methacrylate [CHPMA]) was discussed. Morphology and chemical properties of P‐(DMC‐co‐CHPMA)‐g‐MPTS/CB were tested by scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis and X‐ray photoelectron spectroscopy, resulting in a weight content of copolymer (DMC‐co‐CHPMA) in P‐(DMC‐co‐CHPMA)‐g‐MPTS/CB of ca. 18%. P‐(DMC‐co‐CHPMA)‐g‐MPTS/CB was fixed onto cotton fabric via a nucleophilic‐substituted reaction between reactive epoxy groups on the CB surface and the hydroxyl groups of cotton fabric, which endowed good fastness to cotton fabric without either a fixing or an adhesive agent. Also, coloured cotton fabric demonstrated excellent anti‐bacterial activity towards Staphylococcus aureus and Escherichia coli O157:H7.     

Thin films of carbon nanotubes and chemically reduced graphenes for electrochemical micro-capacitors

We report the making of chemically reduced graphene (CRG) sheets separated by layer-by-layer-assembled multi-walled carbon nanotubes (MWCNTs) for electrochemical micro-capacitor applications. Submicron thin films of amine-functionalized MWCNTs (MWCNT-NH₂) and CRG derived from graphene oxides, were shown to be cross-linked with amide bonds having high packing densities of ∼70%. These carbon-only electrodes were found to have large volumetric capacitance of in an acidic electrolyte (0.5 M H₂SO₄). The electrode capacitance in a neutral electrolyte (1 M KCl) was found much lower, which supported the hypothesis that the observed high capacitances in the acidic electrolyte can be attributed primarily to redox reactions between protons and surface oxygen-containing groups on carbon.