Effect of solvent on electrical conductivity and gas sensitivity of PEDOT: PSS polymer composite films

Poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS) was blended with polyethylene oxide (PEO) and polyvinyl alcohol (PVA) and composite film was cast. Additional solvents of dimethyl sulfoxide (DMSO) and ethylene glycol (EG) were mixed and their effects on electrical conductivity and structural changes were investigated. The electrical conductivity increased in response to the additional solvent, leading to an increase in the PEDOT ratio relative to the control. PEDOT:PSS/PEO composite film had a much higher electrical conductivity than PEDOT:PSS/PVA. When blended with PEO, the quinoid structure revealed by Raman spectroscopy increased relative to the PVA‐blended case, indicating higher electrical conductivity. The current–voltage response and gas sensitivity showed much better performance in PEDOT:PSS/PEO/DMSO composite film. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42628.     

羧甲基纤维素钠/凹凸棒石纳米复合材料的制备与表征

以羧甲基纤维素钠(CMC-Na)为基体,凹凸棒石(AT)为增强材料,采用溶液共混法制备了标题物。研究了凹凸棒石用量对纳米复合材料结构和性能的影响。通过FT-IR、TG、SEM对复合材料进行了表征。试验结果表明,当凹凸棒石用量为羧甲基纤维素钠质量的0.22%时,复合材料的力学性能最佳。由于纳米凹凸棒石的引入,CMC-Na分子某些特征峰的波数发生了变化,复合材料的形貌也发生了改变;羧甲基纤维素钠/凹凸棒石纳米复合材料的热稳定性高于纯羧甲基纤维素钠膜。     

糠醛渣制备羧甲基纤维素的研究

以糠醛渣为原料,采用Milox法提取纤维素,经漂白处理后制备羧甲基纤维素(CMC),对纤维素提取工艺、漂白工艺及CMC的合成进行了初步研究。实验结果表明,纤维素提取工艺优化条件:甲酸80mL,过氧化氢14mL,反应时间2.5h—2.5h—2.5h,反应温度80℃—95℃—80℃;漂白工艺条件:可选择过氧化氢10mL,氢氧化钠质量浓度2.5g/L,反应温度45℃,反应时间60min。制得的CMC的取代度为0.901 2,黏度为45mPa·s。     

Synthesis and characterization of fluorine‐containing polyurethane–acrylate core–shell emulsion

Fluorinated polyurethane–acrylate (FPUA) hybrid emulsion was prepared by copolymerization of polyurethane, methyl methacrylate, and 1H,1H,2H,2H‐heptadecafluorooctyl acrylate (FA) via emulsion polymerization in the presence of a perfluoronated reactive surfactant. The polyurethane was synthesized from isophorone diisocyanate, poly(propylene glycol)‐1000, dimethylolpropionic acid, 1,4‐butanediol, and 2‐hydroxyethyl methylacrylate. The influence of the monomer on the surface properties, wetting behaviors, particle size, and viscosity of the emulsion was investigated. The mechanical properties of FPUA latex films were improved, and water absorption and contact angle were improved with the addition of methyl methacrylate and FA. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43357.     

Preparation and characterization of sodium carboxymethyl cellulose from cotton stalk using microwave heating

BACKGROUND: This paper describes the use of cotton stalk, an agricultural waste, for the preparation of sodium carboxymethyl cellulose (CMC) using microwave heating. The study includes the optimization of pre‐treatment and preparation processes, and the characterization of product. RESULTS: The optimal cotton stalk pre‐treatment condition involved the addition of 12% alkali to extract cellulose for 6 min at a microwave power of 200 W using the ratio of cotton stalk to solvent 1:9, giving 87.52% cellulose. Response surface methodology was applied to optimize the preparation of CMC, with the best conditions for preparation predicted by the model: $m_{\rm {cotton stalk cellulose}}:m_{\rm {sodium hydroxide}}:m_{\rm {sodium chloroacetate}} = {1.0:1.1:1.2}$ with etherification at 195.5 W of microwave power for 1.97 min. Under these conditions, CMC with degree of substitution (DS) 0.77, viscosity 498.0 cps and purity 92% was produced. The results of Fourier transform infrared (FT‐IR) spectroscopy indicated that the product had the characteristics of a high DS. Scanning electron microscopy showed that the particles were nearly clava in shape with length ranging from about 12–100 µm. The product met the quality standards of GB/T1904‐2005. CONCLUSION: Preparation of CMC from cotton stalk using microwave heating can shorten the processing time and may be considered a feasible alternative, contributing to solving environmental problems resulting from cotton stalk. Copyright © 2011 Society of Chemical Industry     

Cellulose‐Derived Carbon Fibers with Improved Carbon Yield and Mechanical Properties

The manufacture of high mechanical strength cellulose‐based carbon fibers (CFs) is accomplished in a continuous process at comparably low temperatures and with high carbon yields. Applying a sulfur‐based carbonization agent, i.e., ammonium tosylate (ATS), carbon yields of 37% (83% of theory), and maximum tensile strengths and Young's moduli up to 2.0 and 84 GPa are obtained already at 1400 °C. For comparison, the use of the well‐known carbonization aid ammonium dihydrogenphosphate ((NH₄)H₂PO₄), ADHP, is also investigated. Both the precursor and the CFs are characterized via elemental analysis, wide‐angle X‐ray scattering, Raman spectroscopy, scanning electron microscopy, and tensile testing. Thermogravimetric analysis coupled with mass spectrometry/infrared spectroscopy discloses differences in structure formation between ATS and ADHP‐derived CFs during pyrolysis.     

羧甲基纤维素钠和羟乙基纤维素在日化产品中的应用

羧甲基纤维素钠(CMC)和羟乙基纤维素(HEC)是纤维素醚类产品中使用范围最广的产品,它们是纤维素链上葡萄酐单元的羟基与醚化基团(氯乙酸或环氧乙烷)反应而成的。其水溶液是非牛顿性流体,黏度随剪切速率变化而与时间无关。溶液的黏度随浓度增大迅速增加,是使用范围最广的增稠剂和流变助剂。介绍了CMC和HEC的分子结构、合成制备、溶液特性和在日化产品应用的配方。     

农作物秸杆制备羧甲基纤维素工艺的研究

本文以玉米秸秆为原料,讨论了制备羧甲基纤维素的工艺。它的最佳条件为;NaOH用量为8g,碱化温度30℃～35℃,碱化时间50min;醚化剂(一氯乙酸)用量为11g,醚化时间120min,醚化温度65℃;乙醇质量分数75%,其产品质量符合纺织行业上浆标准。     

Preparation and characterization of thermoplastic water‐borne polycarbonate‐based polyurethane dispersions and cast films

Stable water‐borne polyurethane dispersions (PUDs) were prepared from bifunctional aliphatic polycarbonate‐based macrodiol, 2,2‐bis(hydroxymethyl)propionic acid (DMPA), 1,6‐diisocyanatohexane, 1,4‐butanediol (BD), and triethylamine. Water‐borne dispersion particles are thus solely formed from self‐assembled linear PU chains. Both PUDs and PUD‐based films were characterized with regards to the concentration of DMPA (ionic species content) and BD (hard‐segment content). Average particle size of PUDs decreased and their long‐term stability increased with increasing DMPA and decreasing BD concentration. Functional properties of cast films made from PUDs are substantially influenced by the character of the original colloidal particle dispersions. The swelling behavior of the films, their surface morphology, and mechanical properties are more influenced by DMPA than BD contents. At DMPA concentrations higher than 0.2 mmol g^?1 of the solid mass of polyurethane, distinct self‐organization of individual nanoparticles into fibril‐like structures was detected by atomic force microscopy and scanning electron microscopy. PU films made from PUD containing high BD as well as high DMPA concentrations have the best utility properties namely sufficient tensile properties and a very low swelling ability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42672.     

Preparation of sodium carboxymethyl cellulose from paper sludge

BACKGROUND: This paper describes the reuse of paper sludge, an industrial solid waste, for the preparation of sodium carboxymethyl cellulose (CMC). The process includes pretreatment, basification and etherification. RESULTS: The optimal pretreatment condition involved the addition of 6.7% hydrochloric acid to the paper sludge for 30 min at 70 °C. The order of factors influencing the effect of reaction was: etherification temperature > sodium hydroxide dose > basification temperature > etherification time > sodium chloroacetate dose. The optimal preparation condition of CMC was: m_papersludge: m_{sodiumhydroxide}: m_{sodiumchloroacetate} = 0.9:0.8:1.15; basification at 40 °C; etherification at 60 °C for 1 h. Under these conditions, certified CMC with viscosity less than 20 mPa· s, DS more than 0.50 and purity more than 90% was produced. The results of Fourier transform infrared (FTIR) and X‐ray diffraction (XRD) spectra analyses indicated that the product has characteristics of high degree of substitution (DS) and low crystallinity. The coated paper using CMC prepared from paper sludge as a water retention agent can meet the quality standards of GB/T 10335.1‐2005. CONCLUSION: Preparation of CMC from paper sludge can be considered a feasible alternative, generating value‐added product and contributing to solving environmental problems resulting from paper sludge. Copyright © 2008 Society of Chemical Industry     

Preparation and characterization of innovative cellulose diacetate/epoxy resin blends modified by isophorone diamine

Cellulose diacetate (CA)/epoxy resin (EP) blends with excellent mechanical performance were prepared with simple blending followed by curing with isophorone diamine (IPDA). The reaction between the amino groups of IPDA and epoxide groups of EP was confirmed by Fourier transform infrared spectroscopy. Scanning electron microscopy revealed that the cured EP particles gradually became larger and closer to each other to form semi‐interpenetrating polymer networks in the CA matrix; this contributed to the improved mechanical properties of the CA/EP blends. Dynamic rheological experiments indicated that the CA/EP blends with semi‐interpenetrating polymer networks retained processability. After the introduction of a low content (5–10 phr) of IPDA, the mechanical properties of the CA/EP blends were significantly enhanced. With the addition of 20–30‐phr IPDA, the CA/EP blend exhibited a tensile strength of 77 MPa, a flex strength of 65 MPa, a flex modulus of 2.6 GPa, and a hardness of 94 HD; these values were much higher than those of the pristine CA/EP binary blend. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44151.     

Effects of Polymer Additives and Dispersion State on the Mechanical Properties of Cellulose Nanocrystal Films

Films produced from colloidal and nanomaterial dispersions such as aqueous cellulose nanocrystal (CNC) dispersions tend to crack above a critical cracking thickness; this issue limits the ability to produce flow‐aligned CNC films at thicknesses above ≈50 μm. This research explores the effects of adding polyethylene oxide (PEO), flocculation with hydrochloric acid (HCl), and the combination of both methods on film cracking, mechanical properties, and mechanical anisotropy. Most research on CNC polymer composites focuses on composites where the polymer is the majority component. To the authors' knowledge there has been only one investigation of CNC films' mechanical anisotropy and no studies of using HCl flocculation to flocculate CNC dispersions prior to shear casting. PEO addition significantly reduces Young's modulus, tensile strength, and toughness, but enhances the Young's modulus anisotropy. Flocculation results in little property deterioration but nearly eliminates mechanical anisotropy. The combination of both techniques results in similar properties as flocculation alone. These findings highlight the trade‐offs between these two approaches and can be used to help guide further research on obtaining robust shear cast CNC films over a range of thicknesses.

     

废纸制备羧甲基纤维素的研究

以废纸为原料制备羧甲基纤维素(CMC),探讨了分散剂组成、碱化温度、时间、碱用量和醚化剂用量、醚化温度、时间对产品粘度的影响。结果表明,当废纸、氢氧化钠和醚化剂的质量比为1 0∶0 9∶1 2,以85%的乙醇水溶液为分散剂,35℃碱化90min,75℃醚化150min时,生成的CMC质量最好,取代度>0.6,有效成分>85%,水分<10%,氯化物<4%,其2%水溶液的粘度>500mPa·s。     

Correlation between interlamellar amorphous structure and gas permeability in poly(lactic acid) films

We have investigated the relationship between amorphous structure and its gas permeability of poly(lactic acid) (PLA) using differential scanning calorimetry, wide‐angle X‐ray scattering, and small‐angle X‐ray scattering measurements. We focused on the hierarchical interlamellar amorphous structure of various gas‐permeable PLA films. The films crystallized just above T_g did not have any long‐spacing period peaks at the room temperature even with the existence of crystals; conversely, peaks could be observed from long spacing periods with heating. Therefore, the interlamellar amorphous density became as high as crystalline region one at the room temperature. These high‐density amorphous regions, the so‐called rigid‐amorphous phase, reduced the gas diffusion and permeation. In the case of samples crystallized above 90°C, the long spacing period peaks could be observed even at the room temperature. The amorphous region did not develop the rigid‐amorphous phase, and the gas permeability depended only on crystallinity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40626.     

毛竹笋壳制备羧甲基纤维素

以废弃毛竹笋壳为原料,经过4次加碱法制备出了羧甲基纤维素,并通过FTIR、XRD、TGA、SEM手段对原料与产品进行了表征。实验结果表明,制备羧甲基纤维素的最佳工艺条件为精制竹笋壳5 g,氢氧化钠5 g,氯乙酸6 g,85%乙醇溶液为溶剂,第1次碱化温度和时间分别为30 ℃和90 min,加入氢氧化钠总质量的80%,后3次碱化是在醚化过程中平均加入剩余20%的碱,醚化最终温度为70 ℃,醚化总时间为3 h。在此工艺条件下,所得到的羧甲基纤维素的取代度为0.9341,黏度为35 mPa?s。     

Multilayer films ageing under ultraviolet radiations: Complementary study by dielectric spectroscopy

The effect of ultraviolet (UV) irradiation on a multilayer film made of poly(ethylene terephthalate)/Polyamide 6/poly(ethylene terephthalate) was investigated by uniaxial tractions, UV‐visible‐NIR and Fourier transformed infra‐red‐attenuated total reflection spectroscopy, differential scanning calorimetry ( DSC), and dynamic dielectric spectroscopy (DDS). The multilayer was exposed to ultraviolet radiations (filtered at 270 nm) for 7 days, in air. The complexity of the multilayer thermograms recorded by DSC and DDS has required the study of each film constituting the multilayer to assess each the contribution of each one of them. A deterioration in mechanical properties and a decrease in UV transmission for low wavelengths are observed. These evolutions seem to result to the photo‐oxidation of the poly(ethylene terephthalate) film mainly localized at the exposed layer. This layer acts as a UV protection filter for the other layers. However, the DDS analyses show a plasticization effect of the primary mode in the Polyamide 6, which is evidence of photo‐oxidation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Facile preparation for robust and freestanding silk fibroin films in a 1‐butyl‐3‐methyl imidazolium acetate ionic liquid system

Silk fibroin film (SFF) with excellent mechanical properties was prepared for the first time with Bombyx mori silk fibroin as the material and 1‐butyl‐3‐methyl imidazolium acetate ([Bmim]OAc) ionic liquid (IL) as the solvent. The aim was to understand whether the microstructure of SFF could be modified and whether the mechanical properties were improved when [Bmim]OAc IL was used as a solution. With this new system, the obtained SFF was easily peeled off of the substrate, and the silk fibroin proteins retained the α‐helix secondary structure (silk I). Further test results show that the tensile strength (126.8–129.7 MPa) and anti‐UV performance were stronger than the silk fibroin regenerated by traditional ways. Therefore, this study provided and identified a new method with [Bmim]OAc to obtain SFF with strong mechanical properties. This facile preparation and related SFF with excellent mechanical strength could have potential applications in biocompatible implants, synthetic coatings for artificial skin, and many other areas. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42822.     

Co‐extruded polymeric films for gas separation membranes

In recent years, gas separation has become an important step in many production process streams and part of final products. Through the use of melt co‐extrusion and subsequent orientation methods, gas separation membranes were produced entirely without the use of solvents, upon which current methods are highly dependent. Symmetric three layer membranes were produced using poly(ether‐block‐amide) (PEBA) copolymers, which serve as a selective material that exhibits a high CO₂ permeability relative to O₂. Thin layers of PEBA are supported by a polypropylene (PP) layer that is made porous through the use of two methods: (1) inorganic fillers or (2) crystal phase transformation. Two membrane systems, PEBA/(PP + CaCO₃) and PEBA/β‐PP, maintained a high CO₂/O₂ selectivity while exhibiting reduced permeability. Incorporation of an annealing step either before or after orientation improves the membrane gas flux by 50 to 100%. The improvement in gas flux was a result of either elimination of strain induced crystallinity, which increases the selective layer permeability, or improvement of the PP crystal structure, which may increase pore size in the porous support layer. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39765.     

Thermal properties and miscibility of semi‐crystalline and amorphous PLA blends

The focus of this research is the study of the microstructures and miscibility at the interface between semi‐crystalline and amorphous PLAs [poly (l ‐lactic acid)(PLLA) with poly (l ,d ‐lactic acid)(PDLLA), respectively]. The blends are prepared through thermal processing (extrusion and hot‐pressing). To increase the area of interface between PDLLA and PLLA, the fibers from PLLA and PDLLA are used. Thermal and microstructures of the blends were studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), dynamic thermogravimetric analysis(DMA), small‐angle X‐ray diffraction(SAXS) and wide‐angle X‐ray diffraction (WAXD). The two PLAs are miscible in molten state. However, phase separation is detected after various thermal treatments, with PDLLA being excluded from the regions of interlamellar PLLA regions when PDLLA content is low, as determined from X‐ray diffraction studies. The compatibility between the two PLAs is not perfect in the molten state, since enthalpies of the various blends at T_g are lower than any pure PLA material. The semi‐crystalline PLLA fiber can recrystallize alone in the molten amorphous PDLLA, and a higher nuclei density is observed at the interface. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41205.     

疏水改性羧甲基纤维素及其pH敏感水凝胶的研究

通过羧甲基纤维素钠( CMC -Na)与脂肪酰氯在正庚烷介质中酯化反应制备疏水改性羧甲基纤维素(Ln-CMC -Na),讨论了物料比、温度和时间对反应的影响,确定了适宜的反应条件.根据Ln-CMC -Na的水溶性,确定在脂肪酰氯与CMC -Na摩尔比为0.08时,分别用十、十二、十四、十六和十八酰氯制备出系列改性产品,并测定了其HLB值、表面张力和临界胶束浓度.以三氯化铝为交联剂,Ln-CMC -Na作配体制得pH敏感水凝胶.