Morphological and rheological characterization of multi-walled carbon nanotube/PLA/PBAT blend nanocomposites

Biodegradable poly (lactic acid) (PLA)/poly (butyleneadipate-co-butyleneterephthalate) (PBAT)/multi-walled carbon nanotube (MWNT) polymer blend nanocomposites were prepared by using a laboratory-scale twin-screw extruder. Fractured surface morphology of the polymer blend/MWNT nanocomposites were examined via SEM. Furthermore, cross sectioned samples obtained using an ultramicrotome was observed via TEM. In addition, effects of both MWNT reinforcement and phase affinity of MWNT on thermal and rheological properties of the PLA/PBAT blends were investigated by TGA and rotational rheometer. Immiscible PLA/PBAT blend with MWNT nanocomposites showed two-step thermal degradation. The onset temperature of thermal degradation started in the PLA much earlier than in the PBAT. Nonetheless, based on TGA data, it was found that the MWNT enhanced thermal property of the PLA/PBAT blend/MWNT nanocomposites. Rheological properties revealed that both shear and complex viscosities showed unique shear thinning behavior due to selectively localized MWNT dispersion state.     

Study on the preparation and characterization of biodegradable polylactide/multi-walled carbon nanotubes nanocomposites

In this study, polylactide/multi-walled carbon nanotubes (PLA/MWNTs) hybrids were prepared by means of a melt blending method. To enhance the compatibility between PLA and MWNTs, the acrylic acid grafted polylactide (PLA-g-AA) and the multihydroxyl-functionalized MWNTs (MWNTs-OH) were used to replace PLA and MWNTs, respectively. The crude MWNTs were chemically oxidized by a mixture of H₂SO₄ and HNO₃ and then reacted with thionyl chloride to functionalize them with chlorocarbonyl groups (MWNTs-COCl). The MWNTs-OH was finally obtained by the reaction of MWNTs-COCl and 1,6-hexanediol. The resulting products have been characterized by FTIR, ¹³C solid-state NMR, TGA, DMA, SEM, TEM, and Instron mechanical tester. Due to the formation of ester groups through the reaction between carboxylic acid groups of PLA-g-AA and hydroxyl groups of MWNTs-OH, results demonstrated dramatic enhancement in thermal and mechanical properties of PLA, for example, 77 °C increase in initial decomposition temperature with the addition of only 1 wt%. Based on the result of thermal and mechanical examinations, it was found that the optimal amount of MWNTs-OH was 1 wt% because excess MWNTs-OH caused separation of the organic and inorganic phases and lowered their compatibility.     

碳纳米管/丙烯酸酯橡胶复合材料的制备及性能研究

采用自制的大分子表面改性剂对多壁碳纳米管(MWNTs)进行表面改性,制备改性MWNTs/丙烯酸酯橡胶(ACM)复合材料,研究改性MWNTs用量对复合材料性能的影响,并与炭黑补强的ACM性能进行对比.结果表明:用MWNTs填充ACM制备的材料,其性能远优于炭黑补强的ACM橡胶的性能;随着改性MWNTs用量的增大,复合材料...     

Structure and conductivity of multi-walled carbon nanotube/poly(3-hexylthiophene) composite films

This work reports a structure-property investigation of a conjugated polymer nanocomposite with enhanced conductivity. Regioregular poly(3-hexylthiophene) (rrP3HT) was used to prepare composites with thin, short, multi-walled carbon nanotube (MWNT) addition over a wide range of concentrations. Scanning and transmission electron microscopies demonstrated an excellent dispersion and good wetting properties within the carbon nanotube composites. Coated MWNTs showed superstructures of P3HT self-organized on nanotube surfaces. Changes in the long range order and on the self-ordered mesophase of the bulk material were investigated by infrared and Raman spectroscopies, differential scanning calorimetry and X-ray diffraction. Interplay between charge transport through the semiconducting polymer and carbon nanotube network increased the composite's conductivity after percolation to values close to 10⁻² S cm⁻¹.     

Preparation and thermal properties of multiwalled carbon nanotube/polybenzoxazine nanocomposites

In this study, we prepared nanocomposites comprising multiwalled carbon nanotubes (MWCNTs) and polybenzoxazine (PBZ). The MWCNTs were purified through microwave digestion to remove most of the amorphous carbon and metal impurities. After purification, MWCNTs were treated with H₂SO₄/HNO₃ (3 : 1) to introduce hydroxyl and carboxyl groups onto their surfaces. Raman spectroscopy revealed the percentage of nanotube content improved after prolonged microwave treatment, as evidenced by the decrease in the ratio of the D (1328 cm^?1) and G (1583 cm^?1) bands. For the untreated MWCNTs, the I_D/I_G ratio was 0.56. After microwave treatment for 40 min, the value decreased to 0.29, indicating that the percentage of nanotube content improved. Dynamic mechanical analyses (DMAs) revealed that the storage moduli and the T_gs of the MWCNTs/PBZ nanocomposites were higher than that of the pristine PBZ. This is due to the nanometer‐scale MWCNTs restricting the motion of the macromolecular chains in the nanocomposites. Transmission electron microscopy (TEM) image revealed that the MWCNTs were well dispersed within the PBZ matrix on the nanoscale when the MWCNT content was less than 2.0 phr. The coefficient of thermal expansion (CTE) of the nanocomposites decreased on increasing the MWCNTs content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystallization and melting behavior of three biodegradable poly(alkylene succinates). A comparative study

Polyesters based on succinic acid and respective aliphatic diols, with 2–4 methylene groups were synthesized by melt polycondensation. Crystallization and melting behaviour of samples having the same molecular weight were studied. The odd–even effect was observed for the melting temperatures of these polymers. Poly(propylene succinate) exhibited the slower crystallization rates and lower degree of crystallinity, among these polyesters. In contrast poly(butylene succinate) showed the faster crystallization rates and higher degree of crystallinity. Multiple melting of the isothermally crystallized samples was attributed to partial melting re-crystallization and re-melting, as was revealed by MTDSC measurements and observations at fast DSC heating scans. The equilibrium melting points were found to be 114, 133.5 and 58 °C for PESu, PBSu and PPSu respectively. Also, the corresponding values for enthalpy of fusion were 180, 210 and 140 J/g. Spherulitic growth rates were analysed and the regime transition of PESu and PBSu was studied.     

Grafting of alkoxyamine end-capped (co)polymers onto multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWNTs) have been successfully modified by polystyrene, poly(?-caprolactone), and their block copolymers by addition reaction of the alkoxyamine-terminated precursors. Polymer-modified MWNTs are easily dispersed in good solvents for the grafted polymer, such as toluene and THF. This observation has been confirmed by TEM analysis. The grafting ratio of polystyrene chains at the surface of MWNTs depends on the polymer molecular weight.     

Multiwalled carbon nanotube/polybenzoxazine nanocomposites: Preparation, characterization and properties

A novel nanocomposite composed of polybenzoxazine (PBZ) and multiwalled carbon nanotubes (MWNT) was prepared successfully. The surface modification of MWNT, including nitric acid modification followed by toluene-2,4-diisocyanate (TDI) treatment, introduced hydroxyl, carboxyl, and isocyanate groups on the MWNT surface. The surface carboxyl groups catalyzed the ring-opening reaction of benzoxazine and thus decreased the curing temperature of the system. The isocyanate groups reacted with the phenolic hydroxyl groups generated by the ring opening of benzoxazine resulting in the significant improvement of the adhesion between PBZ and MWNT. Dynamic mechanical analyses indicated the increase of storage modulus as well as T_g by the addition of MWNT into PBZ. A well dispersed modified-MWNT on nanoscale level inside PBZ matrix was observed by TEM and SEM.     

Preparation and properties of multiwalled carbon nanotube/polycaprolactone nanocomposites

Multiwalled carbon nanotube/polycaprolactone nanocomposites (MWNT/PCL) were prepared by in situ polymerization, whereby as‐received MWNTs (P‐MWNTs) and purified MWNTs (A‐MWNTs) were used as reinforcing materials. The A‐MWNTs were purified by nitric acid treatment, which introduced the carboxyl groups (COOH) on the MWNT. The micrographs of the fractured surfaces of the nanocomposites showed that the A‐MWNTs in A‐MWNT/PCL were better dispersed than P‐MWNTs in PCL matrix (P‐MWNT/PCL). Percolation thresholds of the P‐MWNT/PCL and A‐MWNT/PCL, which were studied by rheological properties, were found at ～2 wt % of the MWNT. The conductivity of the P‐MWNT/PCL was between 10^?1 and 10^?2 S/cm by loading of 2 wt % of MWNT although that of the A‐MWNT/PCL reached ～10^?2 S/cm by loading of 7 wt % of MWNT. The conductivity of the P‐MWNT/PCL was higher than that of the A‐MWNT/PCL at the entire range of the studied MWNT loading, which might be due to the destruction of π‐network of the MWNT by acid treatment, although the A‐MWNT/PCL was better dispersed than the P‐MWNT/PCL. The amount of the MWNT at which the conductivity of the nanocomposite started to increase was strongly correlated with the percolation threshold. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1957–1963, 2007     

Rheological and electrical properties of polycarbonate/multi-walled carbon nanotube composites

Rheological and electrical properties of the polycarbonate (PC)/multi-walled carbon nanotube (MWNT) were studied. The MWNT was funtoinalized by treating with the hydrogen peroxide (H₂O₂). The H₂O₂ treated MWNT was dried by thermal and freeze drying methods. From the morphological studies, the degree of entanglement of the MWNT was decreased after treating with the H₂O₂. For the H₂O₂ treated MWNT (thermal drying), the length of the MWNT was shortened compared that of the H₂O₂ treated MWNT (freeze drying). The rheological and electrical properties of the PC/MWNT (H₂O₂ treated) composites increased compared that of the PC/MWNT (untreated) composites. Also, the electrical conductivity showed higher value for the PC/MWNT (H₂O₂ treated, freeze drying) composites compared that of the PC/MWNT (H₂O₂ treated, thermal drying) composites. From the results of the morphological, rheological, and electrical properties of the PC/MWNT composites, it is suggested that the electrical and rheological properties of the PC/MWNT composites are affected by the MWNT-MWNT network structure, which is related with the MWNT morphologies such as the degree of aggregation and aspect ratio of the MWNT.     

Dynamic mechanical and morphological properties of polycarbonate/multi-walled carbon nanotube composites

Dynamic mechanical and morphological properties of the polycarbonate (PC)/multi-walled carbon nanotube (MWNT) composites were studied by dynamic mechanical thermal analysis (DMTA) and X-ray diffractometry, respectively. For the without annealed PC/MWNT composites containing the higher content of the MWNT (≥7.0 wt%), double tan δ peaks were observed, which could be explained by the phase separation morphology model. For the annealed PC/MWNT composites, a broad single tan δ peak was observed. From the X-ray diffraction of the annealed PC/MWNT composites, it was observed that more regular structure of the PC was obtained, which was consistent with the result of the thermal analysis of the annealed PC/MWNT composites. From the dynamic mechanical properties, thermal analysis, and X-ray diffraction of the annealed PC/MWNT composites, it is suggested that PC/MWNT composites show a broad single tan δ peak and partially crystalline structure of the PC in the PC/MWNT composites by annealing.     

PBS/PHB共混合金的制备及其性能

采用双螺杆挤出机将聚羟基丁酸酯(PHB)与聚丁二酸丁二酯(PBS)熔融共混,制备了PBS/PHB合金,并研究了其性能.结果表明:PBS与PHB组成了热力学互容体系;随着PHB用量的增加,PBS/PHB合金的晶体形态为尺寸逐渐减小的环带球晶,合金的拉伸强度与韧性显著增加;PBS/PHB合金在紫外光老化后的抗冲击性能下降,...     

Facile approach to prepare multi-walled carbon nanotubes/graphene nanoplatelets hybrid materials

A facile approach was developed to prepare multi-walled carbon nanotubes/graphene nanoplatelets hybrid materials through covalent bond formation. First, poly(acryloyl chloride) was grafted onto oxidized multi-walled carbon nanotubes through the reaction between the acyl chloride groups of poly and the hydroxyl groups of oxidized multi-walled carbon nanotubes. Second, the remaining acyl chloride groups of poly were allowed to react with the hydroxyl groups of hydroxylated graphene nanoplatelets. Scanning electron microscopy and transmission electron microscopy data showed that the multi-walled carbon nanotubes and graphene nanoplatelets were effectively connected with each other. And Fourier transform infrared spectroscopy data indicated the formation of covalent bonds between carbon nanotubes and graphene nanoplatelets. Conformational changes were monitored by Raman spectroscopy. This novel kind of carbon hybrid materials may have the potential application in a wide field, especially in increasing the toughness and strength of the matrix resin.     

可生物降解PBS包膜尿素缓释肥料的制备与性能研究

研究可生物降解PBS包膜尿素缓释肥料的制备与性能。以可生物降解PBS为包膜材料,通过循环流化床工艺制备PBS包膜尿素缓释肥料,经过对制备工艺进行优化,确定包膜剂PBS质量分数为5%、二次流化时间为20 min、包膜率为10%的PBS包膜尿素具有良好的缓释效果,其初期释放率为10%,第28天时累积释放率为72%,基本符合缓释肥料标准。     

Preparation and characterization of alkylated carbon nanotube/polyimide nanocomposites

BACKGROUND: The development of carbon nanotube‐reinforced composites has been impeded by the difficult dispersion of the nanotubes in polymers and the weak interaction between the nanofiller and matrices. Efficient dispersion of carbon nanotubes is essential for the formation of a functional nanotube network in a composite matrix. RESULTS: Multiwalled carbon nanotubes (MWNTs) were incorporated into a polyimide matrix to produce MWNT/polyimide nanocomposites. To disperse well the MWNTs in the matrix and thus improve the interfacial adhesion between the nanotubes and the polymer, ‘branches’ were grafted onto the surface of the nanotubes by reacting octadecyl isocyanate with carboxylated MWNTs. The functionalized MWNTs were suspended in a precursor solution, and the dispersion was cast, followed by drying and imidization to obtain MWNT/polyimide nanocomposites. CONCLUSION: The functionalized MWNTs appear as a homogeneous dispersion in the polymer matrix. The thermal stability and the mechanical properties are greatly improved, which is attributed to the strong interactions between the functionalized MWNTs and the polyimide matrix. Copyright © 2009 Society of Chemical Industry     

生物可降解共聚物PBST和PBS的结构与结晶性能

利用核磁共振氢谱和广角X射线衍射法研究了生物可降解共聚物聚对苯二甲酸-共-丁二酸丁二醇酯(PBST)的结构及结晶性能,并与聚丁二酸丁二醇酯(PBS)进行比较。结果表明:PBST为无规共聚物,其晶体结构为三斜晶系,PBS为均聚物,为单斜晶系,PBST的结晶度和结晶尺寸均比PBS的小。     

Design of a multi-walled carbon nanotube field emitter with micro vacuum gauge

The variation of vacuum level inside a field emission device when electron is emitted from multi-walled carbon nanotubes (MWCNTs) by electric field was measured where MWCNT gauge packaged with a vacuum device was used to measure the degree of a vacuum until the end of the vacuum device life. It was found that the electrical properties of MWCNTs altered with the degree of a vacuum. We fabricated MWCNT gauge which were printed and pasted by the screen printer. In this paper, we report the successful detection of the ionization of gases in vacuum state.     

Preparation and characterization of poly[Ni(salen)(crown receptor)]/multi-walled carbon nanotube composite films

Nanocomposite films comprising multi-walled carbon nanotubes (MWCNTs) embedded within poly[Ni(3-Mesalophen-b15-c5)] were deposited on Pt and ITO electrode surfaces by the potentiodynamic polymerisation of [Ni(3-Mesalophen-b15-c5)] from solutions containing dispersed MWCNTs. Composites incorporating carbon nanotubes subject to a range of oxidising pre-treatments were compared with those incorporating untreated carbon nanotubes and with the pure polymer. In both cases, the use of CH₃CN and CH₂Cl₂ as fabrication and characterization media were explored. Films were characterized by voltammetry, electrochemical impedance spectroscopy and scanning electron microscope (SEM). The coating of the carbon nanotubes with polymer varied significantly with pre-treatment and solvent medium; this influenced the final composite morphology and electrical properties. Performance enhancement of the polymer component by the presence of the carbon nanotubes was manifested through the ability to store charge and the ease with which this could be accomplished; these were parameterized via increased redox capacitance and decreased charge-transfer resistance, respectively. Correlation of impedance parameters with SEM images provided a morphological rationale for composite electrical properties.     

Electrical, mechanical, and glass transition behavior of polycarbonate-based nanocomposites with different multi-walled carbon nanotubes

Five commercially available multi-walled carbon nanotubes (MWNTs), with different characteristics, were melt mixed with polycarbonate (PC) in a twin-screw micro compounder to obtain nanocomposites containing 0.25-3.0 wt.% MWNT. The electrical properties of the composites were assessed using bulk electrical conductivity measurements, the mechanical properties of the composites were evaluated using tensile tests and dynamic mechanical analysis (DMA), and the thermal properties of the composites were investigated using differential scanning calorimetry (DSC). Electrical percolation thresholds (p_cs) were observed between 0.28 wt.% and 0.60 wt.%, which are comparable with other well-dispersed melt mixed materials. Based on measurements of diameter and length distributions of unprocessed tubes it was found that nanotubes with high aspect ratios exhibited lower p_cs, although one sample did show higher p_c than expected (based on aspect ratio) which was attributed to poorer dispersion achieved during mixing. The stress-strain behavior of the composites is only slightly altered with CNT addition; however, the strain at break is decreased even at low loadings. DMA tests suggest the formation of a combined polymer-CNT continuous network evidenced by measurable storage moduli at temperatures above the glass transition temperature (T_g), consistent with a mild reinforcement effect. The composites showed lower glass transition temperatures than that of pure PC. Lowering of the height of the tanδ peak from DMA and reductions in the heat capacity change at the glass transition from DSC indicate that MWNTs reduced the amount of polymer material that participates in the glass transition of the composites, consistent with immobilization of polymer at the nanotube interface.     

吹膜级PBS/PLA复合材料的制备与性能研究

利用熔融共混法制备了综合性能优良的吹膜级聚丁二酸丁二酯/聚乳酸(PBS/PLA)复合材料,并通过万能试验机、差示扫描量热分析仪、热重分析仪、透气透湿分析仪分别测试了PBS/PLA复合材料及其薄膜的力学性能、热性能、阻隔性能。结果表明,制备的PBS/PLA复合材料较纯PBS树脂具有更好的刚性,且所吹塑的薄膜与包装用低密度聚乙烯膜各项性能相当。