聚丙烯/海泡石纳米复合材料的制备与研究

采用CTAB对海泡石进行化学修饰,制备了改性海泡石,将海泡石、改性海泡石分别与聚丙烯(PP)熔融共混制备了熔融插层纳米复合材料.用XRD、DSC、SEM等测试手段对复合材料的结构进行表征,同时对复合材料的力学性能进行测试.结果表明,经过改性的海泡石亲油性增强;XRD结果表明PP大分子已经进入海泡石层间,形成插层型复合材料;DSC结果表明,一定量的改性海泡石的加入起到了异相成核作用,使复合材料的结晶更加完善;力学性能表明,改性海泡石使材料的冲击强度提高;SEM显示,改性海泡石呈两维纳米级均匀分散在PP基体中且与基体的界面结合良好.     

Preparation,structure and thermal properties of polylactide/sepiolite nanocomposites with and without organic modifiers

Polylactide-based nanocomposites containing unmodified and organic modified sepiolite were prepared through a solution casting method. The structure and properties of materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). From the results it can be concluded that the bundles of sepiolite have been dispersed into small aggregates containing several nanorods without destroying the crystal structure. Sepiolite nanofibers were well dispersed in the PLA matrix, exhibiting a randomly orientation with the contact among them in all cases. But the thermal stability of nanocomposites has been improved more by introducing unmodified sepiolite than that with organic modified sepiolite, which has also been confirmed by molecular dynamics simulation results that hydrophobic parts of organic modifiers could prevent the interaction between PLA molecules and sepiolite surface.     

PBAT based nanocomposites for medical and industrial applications

Poly(butylene adipate-co-terephthalate) (PBAT) based nanocomposites were prepared by melt blending PBAT with 5 and 10 wt.% of clay nanoparticles (unmodified and modified montmorillonites, unmodified and modified fluoro-hectorites, and unmodified sepiolites). All nanocomposites showed a good level of clay distribution and dispersion into PBAT, especially nanocomposites with high clay chemical affinity with the polymer matrix. DSC results showed that addition of layered silicates slightly hindered kinetics and extent of crystallization of PBAT; however, sepiolite particles were able to promote polymer crystallization kinetics and the transformation of the PBAT crystal structure to a more ordered form.Similar increases in the thermal stability of PBAT in nitrogen and air were obtained upon addition of all clays, due to a barrier effect of the clays toward polymer decomposition product ablation.Preliminary biocompatibility tests indicated that PBAT based materials with 10% clay content have good biological safety and display almost no cytotoxicity.The addition of all nanofillers increased the hardness of PBAT matrix. The DMA analysis showed that all nanocomposites presented higher E′ values than neat PBAT, indicating that addition of clays improved the mechanical properties of PBAT. For layered silicate nanocomposites, the main influencing factors on the thermo-mechanical properties appeared to be the aspect ratio and dispersion of clay nanoplatelets, rather than polymer/clay chemical affinity. The highest E′ values of sepiolite based nanocomposites make this nanoparticle the most attractive material for tissue engineering and environmental industrial applications.     

Morphology/behaviour relationship of nanocomposites based on natural rubber/epoxidized natural rubber blends

In order to analyze the effect of an epoxidized natural rubber (ENR) and filler treatment on the morphology and behavior of natural rubber (NR) nanocomposites, blends of these polymers have been prepared. The nature and extent of the clay dispersions in the filled samples were evaluated by X-ray diffraction. In the presence of ENR, an exfoliated structure was obtained which suggests that enough rubbery polymer was incorporated into the interlayer spacing. The effect of clay in rubber compounds was analyzed through rheological, mechanical and swelling characterization. A sensible improvement in the nanocomposite properties was observed by the addition of organoclay. It has been deduced that the properties of the compounds strongly depend on the extent of the silicate nanolayers dispersion into the rubber matrices as well as on the organoclay type and elastomer compatibility.     

Poly(lactic acid)/clay nanocomposites: effect of nature and content of clay on morphology,thermal and thermo-mechanical properties

Nanocomposites were prepared by melt blending Poly(lactic acid) with 5 and 7 wt% of an organically modified montmorillonite or an organically modified magnesium sodium fluoro-hectorite or unmodified sepiolite.All nanocomposites show a good level of clay dispersion into the polymer matrix as well as a considerable thermal and thermo-mechanical properties improvement. According to thermal analysis, the clays seem to act as nucleating agents inducing a higher degree of crystallinity of the polymer and rate of crystallization. Similar increases in the thermal stability of Poly(lactic acid) were obtained for all clays. Concerning layered silicate nanocomposites, it was found that the main influencing factors on the thermo-mechanical properties appear to be the aspect ratio and dispersion of clay nanoplatelets, rather than polymer/clay chemical compatibility. Needle like sepiolite shows thermo-mechanical improvements comparable to some layered silicates and an interesting ability to maintain high storage modulus values at increasing temperatures, due to its good dispersion within the polymer without the need of organic modifiers as instead necessary for layered clays used in this work.     

Effect of organic modification of sepiolite for PA 6 polymer/organoclay nanocomposites

Polyamide 6 nanocomposites based on sepiolite needle-like clay were prepared via melt extrusion. Sepiolite was organomodified with trimethyl hydrogenated tallow quaternary ammonium (3MTH) by using different amounts of modifier respect to the sepiolite. The effect of modifier/sepiolite ratio on the final nanocomposite properties and the catalytic effect of the sepiolite on the polymeric matrix were evaluated. The presence of organomodified sepiolite on the polymer matrix favoured the crystallinity of the PA 6. The catalytic effect of the sepiolite was reduced as the modifier amount increased. The elastic modulus and Heat Deflection Temperature (HDT) in PA 6/organosepiolite nanocomposites increased ∼2.5 times respect to the neat PA 6 matrix. The higher the modification grade the better the dispersion and orientation of needle-like sepiolite clay were attained. This effect supported the reinforcement efficiency of organosepiolites with high modifier content.     

Natural rubber latex/potato starch nanocrystal nanocomposites: Correlation morphology/electrical properties

This paper discusses the preparation and characterization of nanocomposites obtained with potato starch nanocrystals, and their use as fillers in order to realize nanocomposites with a natural rubber latex matrix. The preparation of potato starch nanocrystals was done by hydrolysis of potato starch powder using sulfuric acid. The synthesized potato starch nanocrystal suspensions were mixed with natural rubber latex by latex stage mixing process using a magnetic stirrer. In this way, composites containing up to 20% w/w of fillers have been obtained. Morphological studies indicated a relatively uniform dispersion of starch nanocrystals in the nanocomposites until 15% w/w filler loading. Dielectric measurements confirm the existence of a threshold at a composition close to 15% w/w of filler at which the fillers become agglomerated.     

Intercalation/Exfoliation mechanism of hybrid formation in polypropylene/lamellar mesostructured silica nanocomposites

Understanding the optimal processing conditions for the fabrication of polymer nanocomposites is of fundamental importance in designing materials with balance of properties. To understand these conditions in the case of maleic anhydride grafted polypropylene (PP-g-MA)/layered mesostructured silica (LMS) nanocomposites, the effect of temperature, shear rate, and residence time during processing on the structure of the nanocomposites were studied. The results showed that the combination of temperature, residence time, and mechanical shears have strong effect on the structure of the nanocomposites, rather than just interfacial interactions between the polymer matrix and silicate layers. However, interfacial interactions between the polymer matrix and silicate layers primarily play an important role to the intercalation of polymer chains into the silicate galleries. On the basis of our experimental results, a first explanation of the formulation mechanism of PP-g-MA/LMS nanocomposites is proposed. Finally, a general concept of processing conditions for manufacturing of polymer nanocomposites by melt-compounding process in a batch-mixer is described.     

剥离型环氧树脂/蒙脱土纳米复合材料研究

采用阳离子交换的方法对蒙脱土进行了有机化处理,使蒙脱土由亲水性变成亲油性,并且使其层间距由原来的1.2nm扩大到2.2nm.采用X-射线衍射仪研究了有机蒙脱土在环氧树脂中的剥离行为,制备了环氧树脂/蒙脱土纳米复合材料并测试了其性能.实验结果表明,环氧树脂与有机蒙脱土的相容性好,蒙脱土在环氧树脂中完全剥离;环氧树脂/蒙脱土纳米复合材料的力学性能、热性能以及阻隔性能与纯环氧树脂固化物相比均有不同程度的提高和改善.     

Polyimide/sepiolite nanocomposite films: Preparation, morphology and properties

Polyimide/sepiolite nanocomposite films have been prepared via an in situ polymerization method. The process involves the dispersion of sepioite in N,N-dimethylacetamide, polycondensation of 2,2′-bis [4-(3,4-dicarboxyphenoxy) phenyl] propane dianhydride and 4,4′-oxydianiline in the presence of sepiolite suspension to form poly(amic acid), and the thermal imidization of poly(amic acid)/sepiolite nanocomposite. The morphology, thermal and mechanical performance, and water absorption of nanocomposite films were systematically studied with various sepiolite contents. The results indicated that sepiolite was dispersed homogeneously at a nanometer scale in polyimide matrix. Owing to such nanodispersion of sepiolite, the polyimide/sepiolite nanocomposite films exhibit dramatic improvements on the mechanical properties and the coefficient of thermal expansion while fine thermal stability and low water absorption capacity were also maintained. When the sepiolite content increased to 16% the polyimide/sepiolite nanocomposite film achieved as much as 41% and 94% increase on the tensile strength and modulus respectively, and 50% decreased in coefficient of thermal expansion.     

纳米有机蛭石/天然橡胶复合材料的制备及性能

以十六烷基三甲基溴化铵为插层剂, 用球磨法对蛭石进行了快速有机插层, 用过熔融共混法制备出纳米有机蛭石/ 天然橡胶复合材料。用XRD、SEM、TEM 对其微观结构进行了表征与分析, 证明蛭石以纳米片层分散在天然橡胶基体中。力学性能测试表明: 复合材料拉伸强度、扯断伸长率、300 %定伸强度、邵氏A 硬度、撕裂强度得到明显的改善。DMA、DSC 测试表明: 复合材料的模量具有明显的提高, 而玻璃化转变温度无明显变化。可见有机插层蛭石对天然橡胶的综合性能具有较明显的改善作用。      

Mechanical,thermal and microstructural characteristics of cellulose fibre reinforced epoxy/organoclay nanocomposites

Epoxy nanocomposites reinforced with recycled cellulose fibres (RCFs) and organoclay platelets (30B) have been fabricated and investigated in terms of WAXS, TEM, mechanical properties and TGA. Results indicated that mechanical properties generally increased as a result of the addition of nanoclay into the epoxy matrix. The presence of RCF significantly enhanced flexural strength, fracture toughness, impact strength and impact toughness of the composites. However, the inclusion of 1 wt.% clay into RCF/epoxy composites considerably increased the impact strength and toughness. The presence of either nanoclay or RCF accelerated the thermal degradation of neat epoxy, but at high temperature, thermal stability was enhanced with increased char residue over neat resin. The failure micromechanisms and energy dissipative processes in these nanocomposites were discussed in terms of microstructural observations.     

Effect of layered silicate reinforcement on the structure and mechanical properties of spent polyamide-12 nanocomposites

The aim of this work was to study the structure and mechanical properties of spent polyamide-12 and spent polyamide-12/layered silicate reinforced novel nanocomposites. Layered silicate at 1, 3, 5 and 7 wt.% was incorporated in spent polyamide-12 and its nanocomposites were prepared using single screw injection moulding technique. The interlamellar structure and surface morphology were characterised by transmission electron microscope (TEM) and scanning electron microscope (SEM). Different levels of layered silicate dispersion (as characterised by TEM and SEM) correlated strongly with improvements in mechanical performance. The results showed that the tensile and flexural properties are found to be increased with the incorporation of layered silicate into spent PA-12 matrix. Comparison of tensile and flexural test results between virgin PA-12, spent PA-12 and spent PA-12 nanocomposites showed that spent PA-12 samples have retained 70% of its tensile and 80% of its flexural properties respectively, compared to virgin PA-12.     

Fibre-reinforced glass/silicate composites: effect of fibrous reinforcement on intumescence behaviour of silicate matrices as a fire barrier application

This paper is the third in series on fire-resistant laminated glass composites containing an intumescent silicate interlayer and studies the effect of reinforcing fibres on the intumescent behaviour of the silicate matrices. Two silicate matrices with different silica/metal oxide ratios (SiO₂:Na₂O) were reinforced by polypropylene (PP), polyamide 66 (PA66), AR-glass (ARG) and stainless steel (ST) fibres, selected because of their alkali and UVA resistant properties. Thermal degradative behaviour of fibre/silicate mixtures having 5/95 and 10/100 mass ratios were examined to understand the effect of each fibre type on the intumescence of each silicate. Fibre reinforcements of the silicate layer were either as a nonwoven web or as a woven mesh. The intumescent properties of silicates were studied by heating the composites in a furnace at 450 °C for five minutes and measuring the intumescent layer thickness. The results showed that all fibre types in nonwoven web reinforcements had a negative effect while inorganic glass fibre in a woven mesh form had a negligible effect on the overall intumescence of silicate matrices. It was proposed that while fibre type was of minor importance, the fabric structure played an important role in inhibiting intumescence. Preferred reinforcement should preferably have open mesh-like characteristics.     

Synthesis and characterization of thermoplastic polyurethane/montmorillonite nanocomposites produced by reactive extrusion

The novel polyurethane/montmorillonite (PU/MMT) nanocomposites based on poly (propylene oxide) glycol (POP), 4,4′-diphenymethylate diisocyanate (MDI), 1,4-butanediol (1,4-BD) and MMT has been synthesized using a one-step direct polymerization-intercalation technique by twin-screw extruder. Its structure and thermal properties are characterized by X-ray diffraction (XRD), Transmission electron microscopy (TEM) and High-resolution electron microscopy (HREM), Fourier-transform infrared spectroscopy (FTIR) and Thermogravimetry analysis (TGA), respectively. The results of XRD and HREM analyses show that the silicate layer is well dispersed in PU matrix and this mesostructure can be considered as a delaminated nanocomposites. The TGA analysis indicates that the thermal stability properties of the PU/MMT nanocomposites are increased slightly compared with the pristine PU, due to the increase of the char residue. The mechanical and flammability performances are examined by electronic Universal Tester and Cone calorimetry, respectively. The layered silicate, which acts as a high aspect ratio reinforcement, enhances tensile strength of the PU. Specifically, there is a 25% increase in the tensile strength of PU nanocomposites containing 4 wt.% MMT compared with that of pristine PU. However, the elongation at break of PU/MMT nanocomposites is lower than that of pristine PU. The loading of MMT leads to the remarkably decrease of heat release rate (HRR), contributing to the improvement of flammability performance.     

壳聚糖/无机物纳米复合材料在抗菌方面的研究进展

壳聚糖作为一种天然高分子有机物,具有良好的生物相容性、可降解性和抗菌性,在抗菌方面已有一定的应用,但其抗菌性能易受自身因素和外界条件的影响,因此如何巩固和加强壳聚糖的抗菌性能并进行应用成为了研究的热点。将壳聚糖与无机物纳米材料复合,有机和无机组分协同互补,能显著提高材料的抗菌性能,复合材料还具有优异的机械强度和生物相容性,可广泛应用于水处理、食品、纺织、化妆品和医学等领域,引起了科研人员的密切关注。本文总结了壳聚糖的抗菌机理和影响抗菌性能的因素,详细介绍了壳聚糖与金属、金属氧化物、层状硅酸盐和碳材料等无机物复合后的纳米材料在抗菌方面的应用,同时对其在抗菌领域的发展前景进行了展望。     

聚氯乙烯/聚丙烯酸丁酯-白泥纳米复合材料的冲击断面形态及流变性能

通过多步交换反应及扩散-聚合的方法,使聚丙烯酸丁酯(PBA)嵌入到改性层状结构的白泥层间,得到白泥-聚丙烯酸丁酯(PBA)纳米复合物的微米级粒子;然后将聚氯乙烯与白泥-聚丙烯酸丁酯进行熔融共混,制得具有一定特性的有机-无机纳米复合材料;并对复合材料的缺口冲击断面形态及流变性能进行了研究。结果表明,复合材料的冲击断面具有明显的网状结构和空洞化特征,属典型的韧性断裂;PVC/白泥-PBA(质量分数0.5%~7.0%)纳米复合材料基本上保持了纯PVC的加工性能。     

Environmentally friendly polymer hybrids Part I Mechanical, thermal, and barrier properties of thermoplastic starch/clay nanocomposites

As an attempt to develop environmentally friendly polymer hybrids, biodegradable thermoplastic starch (TPS)/clay nanocomposites were prepared through melt intercalation method. Natural montrorillonite (Na⁺ MMT; Cloisite Na⁺) and one organically modified MMT with methyl tallow bis-2-hydroxyethyl ammonium cations located in the silicate gallery (Cloisite 30B) were chosen in the nanocomposite preparation. TPS was prepared from natural potato starch by gelatinizing and plasticizing it with water and glycerol. The dispersion of the silicate layers in the TPS hybrids was characterized by using wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). It was observed that the TPS/Cloisite Na⁺ nanocomposites showed higher tensile strength and thermal stability, better barrier properties to water vapor than the TPS/Cloisite 30B nanocomposites as well as the pristine TPS, due to the formation of the intercalated nanostructure. The effect of clay contents on the tensile, dynamic mechanical, and thermal properties as well as the barrier properties of the nanocomposites were investigated.     

Nanocomposites of ABS and sepiolite: Study of different clay modification processes

Melt compounding of acrylonitrile–butadiene–styrene (ABS) matrix and nanocomposites have been studied in order to evaluate the optimal modification process for sepiolite. Different screw speeds were tested to elucidate possible degradations related to a high shear effect, and thermal stability of pristine and modified sepiolite was carried out. Both processes of modification, via quaternary ammonium salts and silane coupling agents, have been compared by means of morphological, thermal and mechanical experiments, working out that ammonium salt modified sepiolite provided the best results in the final properties.     

插层法制备聚合物/层状硅酸盐纳米复合材料的研究进展

插层法可制得性能优异的聚合物／层状硅酸盐纳米复合材料，其基体材料的力学性能、热稳定性、阻燃性及气体阻隔性等得到大幅度改善，近年来受到广泛的重视。文中从制备方法、材料性能及应用等方面较详细地综述了该领域的研究进展情况。