Nano-enabled microtechnology: polysulfone nanocomposites incorporating cellulose nanocrystals

Microchannel devices hold the potential to transform many separation processes. This preliminary study investigated the feasibility of incorporating cellulose nanocrystals (CNXLs) into polysulfone, a commonly used ultrafiltration membrane polymer. Incorporating CNXLs into non-water soluble polymers without aggregation has been problematic. A solvent exchange process was developed that successfully transferred an aqueous CNXL dispersion into the organic solvent N-methylpyrrolidone (NMP), which is a solvent for polysulfone (PSf). Films were prepared from the solution of PSf in NMP with dispersed CNXLs by a phase inversion process. Films were then examined by scanning electron microscopy and tested for their transport and mechanical properties. The interaction between the polymer matrix and the CNXL filler was studied by means of thermogravimetric analysis (TGA), which suggested a close interaction between the polymer and filler at the 2% filler loading. The tensile modulus showed a large increase beyond 1% filler loading, which could be due to a percolation effect. The water vapor transport rate increased with increase in filler loading. Agglomeration of the CNXLs seemed to be taking place at filler loadings >7%.     

Preparation of epoxy composite material containing natural aluminosilicate filler

The conditions for preparing epoxy composite material in which rock containing analcime and montmorillonite serves as a filler have been investigated. The introduction of filler in amounts of up to 1 wt % has increased strength characteristics and thermal stability of the material by 20–25%.     

尼龙66/蒙脱土复合材料结晶行为的研究

在密炼机中采用熔融共混法制备蒙脱土重量分数为 2 5 %、4 5 %的尼龙 6 6 /蒙脱土复合材料 .通过DSC法对非等温结晶行为及在 2 2 8～ 2 4 0℃范围内的等温结晶行为进行研究 ,并与纯尼龙 6 6进行比较 .从其等温和非等温结晶行为的研究表明 ,蒙脱土起成核剂的作用 ,它的填入使尼龙 6 6结晶速率提高 ,但填料与基体间的相互作用使其链段运动困难 ,结晶活化能提高 ;在研究的填料含量变化范围内 ,结晶行为变化不大 ,并且找到该复合材料在 2 2 8～ 2 34℃范围结晶对温度的不敏感区 ;对非等温结晶过程分析 ,刘结平 莫志深方程是适用的 ,而Ozawa方程则是不适用的 .     

Plasticized polylactide/clay nanocomposites. II. The effect of aging on structure and properties in relation to the filler content and the nature of its organo‐modification

Plasticized polylactide (PLA) – layered silicate nanocomposites were obtained by melt blending PLA with polyethylene glycol as plasticizer (20 wt %) and with different montmorillonite fillers: Cloisite® 20A, Cloisite® 25A, and Cloisite® 30B (from 1 to 10 wt %). Comparative samples of melt‐blended polylactide (without filler) and plasticized PLA with 20 wt % PEG were considered as well. Samples have been aged for 1 and 4 years and their chemical and physical characteristics were compared with not aged reference ones. It was found that molecular weight of the PLA decreased upon melt‐processing and aging, particularly when the Cloisite content increased, without a clear relation to the nature of the organo‐modifier. On the contrary, the PEG plasticizer was practically undegraded upon melt processing and aging. Structural studies revealed that plasticized PLA and plasticized PLA‐based nanocomposites are unstable in time of aging and undergo deplasticization. They showed, after aging, the presence of a thin PEG crystalline layer at the surface of the samples and improved the order in the PLA matrix to a higher extent in plasticized polylactide than in plasticized nanocomposite (due to clay stabilization effect). The amount of PEG diffusing toward sample surface was correlated with aging time, molecular weight of PLA matrix, and Cloisite® type, in clear relation to the extent of intercalation with PLA and PEG. Some modifications of the viscoelastic properties of PLA matrix, induced by the presence of both the nanoparticlate filler and the plasticizer, as well as a deterioration of the mechanical properties upon aging were observed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 312–325, 2006     

Properties of rubber filled with montmorillonite with various surface modifications

Layered silicate/natural rubber composites were prepared by direct polymer melt intercalation. Na‐montmorillonite Kunipia‐F and its organic derivates (organo‐clays) prepared by ion exchange were used as clay fillers. Silica (SiO₂) Ultrasil VN3, a filler commonly used in the rubber industry, was used in combination with clay fillers. The effect of clay or organo‐clay loading from 1 up to 10 phr without (0 phr) or with silica (15 phr) showed significant improvement of the tensile properties (stress at break, strain at break and modulus M100). Modification of montmorillonite by three alkylammonium cations with the same length of alkylammonium chain (18 carbons) and different structure resulted in altered reinforcing and plasticizing effects of the filler in composites with rubber matrix. Copyright © 2011 John Wiley & Sons, Ltd.     

Structure and properties of linear polyethylene-montmorillonite nanocomposites

Nanocomposites based on PE and three types of montmorillonite are prepared by melt blending on a Brabender plastograph. The structure of hybrid materials is studied with the use of X-ray diffraction analysis and transmission electron microscopy. The type of modifier and the polarity of the polyolefin matrix affect the character of the filler structure (intercalated and exfoliated) formed during blending with the polymer. A correlation is found between the parameters of structural organization and the mechanical and barrier properties of nanocomposites. The tensile modulus of the nanocomposites containing 3?C5 wt % modified montmorillonite is 75% higher than that of the unfilled PE, whereas the time of combustion and the rate of flame propagation are 20 and 10% smaller, respectively.     

The Impact of Filler Geometry on Polylactic Acid-Based Sustainable Polymer Composites

Recently, biocomposites have emerged as materials of great interest to the scientists and industry around the globe. Among various polymers, polylactic acid (PLA) is a popular matrix material with high potential for advanced applications. Various particulate materials and nanoparticles have been used as the filler in PLA based matrix. One of the extensively studied filler is cellulose. However, cellulose fibres, due to their hydrophilic nature, are difficult to blend with a hydrophobic polymer matrix. This leads to agglomeration and creates voids, reducing the mechanical strength of the resulting composite. Moreover, the role of the various forms of pure cellulose and its particle shape factors has not been analyzed in most of the current literature. Therefore, in this work, materials of various shapes and shape factors were selected as fillers for the production of polymer composites using Polylactic acid as a matrix to fill this knowledge gap. In particular, pure cellulose fibres (three types with different elongation coefficient) and two mineral nanocomponents: precipitated calcium carbonate and montmorillonite were used. The composites were prepared by a melt blending process using two different levels of fillers: 5% and 30%. Then, the analysis of their thermomechanical and physico-chemical properties was carried out. The obtained results were presented graphically and discussed in terms of their shape and degree of filling.     

Morphology and physical properties of polyethylene/silicate nanocomposite prepared by melt intercalation

Maleated polyethylene (PEMA)/silicate nanocomposites with a different aspect ratio of silicate and maleated PEMA/SiO₂ composite were prepared by melt intercalation. The nanocomposites with a high aspect ratio silicate (montmorillonite) showed a faster decrease in the terminal slope of the storage modulus and a steeper increase in complex viscosity than those with a low aspect ratio silicate (laponite) and SiO₂. The addition of montmorillonite increases the crystallization and the melting temperature of PEMA but decreases above 3 vol % of the silicate content because of the increased viscosity. The nanocomposite with montmorillonite showed the highest yield strength and secant modulus among the composites because of the highest aspect ratio of the filler. It also revealed strong interfacial adhesion with the matrix and orientation during tensile deformation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1454–1463, 2002     

The Properties of Epoxy Binders Modified by Furan Resin and Polysulfone

The joint effect of furfuralacetone and a thermoplastic polysulfone on the properties of an epoxydiane oligomer in the viscous-flow and cured state has been studied. The addition of 10 wt % furfuralacetone to the epoxy oligomer involving polysulfone allows one to reduce the viscosity of the binder by more than two times, which favors an improved impregnation of fibrous fillers, while using modified binders in the production of reinforced plastics. The joint effect of two modifiers results in a 1.75-fold enhancement of crack resistance once the binder is cured along with the retention of heat resistance of the matrix. The improvement of crack resistance of the modified matrix is due to the phase separation of the multicomponent binder in the course of curing.     

A brief survey on CLAYPEN and Nanocomposites based on unmodified PE and organo-pillared clays

New clay fillers are mixed with linear low-density polyethylene at 160 °C for 10 min to obtain clay-PE nanocomposites (CLAYPEN) by melt intercalation. Raw montmorillonite (Mt) was pillared (PMt) with partially hydrolyzed Al and Fe salt solutions and further reacted with hexadecyl trimethylammonium bromide (OPMt). For comparison, the hexadecyl trimethylammonium-montmorillonite (OMt) was prepared as a reference material. PE is not intercalated by organoclay. In investigating the pillared clay-PE nanocomposites, XRD is not an appropriate indicator of intercalation of PE, which penetrates into the mesoporous OPMt as shown by TEM. All the nanocomposites have higher Young modulus values than the pristine PE. The best compromise between the other mechanical properties (tensile strength and elongation at break) is obtained with the OPMt-PE nanocomposite. Cone-calorimeter study shows that peak heat release rate value of PE decreases substantially (34%) on addition of 5 phr of this novel OPMt filler.     

Polymer Nanocomposites Using Urchin‐Shaped Carbon Nanotube‐Silica Hybrids as Reinforcing Fillers

Summary: Carbon nanotubes (CNTs) have been grown on MCM‐41 supported Fe nanoparticles and the as‐prepared (no further purification) CNT‐silica hybrid was directly incorporated into nylon‐6 (PA6) by simple melt‐compounding. The urchin‐shaped CNT‐silica hybrid filler was observed to be homogeneously dispersed throughout the matrix by scanning electron and transmission electron microscopy. Compared with neat PA6, the tensile modulus and strength of the composite are greatly improved by about 110%, with incorporation of only 1 wt.‐% CNT‐silica filler.

SEM image and schematic representation showing polymer chains wrapping around the urchin‐shaped CNT‐silica hybrid filler.     

聚苯乙烯/蒙脱土熔融插层复合的研究

用熔融法制备了聚苯乙烯／蒙脱土插层复合材料，用Ｘ 射线衍射、ＤＳＣ等手段研究了复合材料的结构与性能．聚苯乙烯熔体不能插层于钠基蒙脱土中，但能插层于经有机化合物处理过的蒙脱土中．     

Effect of the Mixture Composition on Shear and Extensional Rheology of Recycled PET and ABS Nanocomposites

Summary: Recycled PET as well as ABS - organomodified montmorillonite nanocomposites were prepared via melt compounding in a counter-rotating twin screw extruder. The topological changes in polymer matrices as dependency on clay modification have been evaluated from dynamic experiments in the shear flow using low amplitude oscillatory measurements. Flow characteristics of all studied organoclay nanocomposites showed shear-thinning behavior at low frequencies. Filling of PET with some organoclays led to degradation reactions, which were reflected by lower magnitudes of viscosity and storage modulus in the range of higher frequencies as compared to unfilled polymer matrix. On the contrary, no degradation during the processing of different organoclays with recycled ABS has been observed.     

多壁碳纳米管/聚乙烯复合材料的制备及其导电行为

多壁碳纳米管/聚乙烯复合材料的制备及其导电行为;碳纳米管;高密度聚乙烯;渗流阈值;导电行为;V-PTC特性     

Effect of polysulfone modification techniques on the properties of polymer-silicate nanocomposites

An effect of different methods of structural modification of the heat-resistant amorphous polysulfone with layered silicate montmorillonite on the properties of the resulting polymer-silicate nanocomposites has been studied. Comparative evaluation of the technological, physical, mechanical, thermal, and rheological properties of the nanocomposites has been performed.     

Effect of processing consitions on the development of morphology in clay nanoparticle filled nylon 6 fibers

The effect of melt temperature on the phase behavior and preferential orientation development in Nylon 6/montmorillonite nanocomposites were investigated at melt spinning temperatures ranging from 230° to 250°C. The fibers were found to exhibit mostly γ crystalline form that is typical of Nylon 6 filled with montmorillonite nanoparticles. At higher take-up speeds α-crystals begin to appear in the crystalline phase. The presence of nanoparticles was found to impart substantial chain orientation levels even at low to moderate take up speeds reaching a plateau at moderate take up speeds. This was attributed to the increased spin line stress in the presence of nanoparticles that increase the overall viscosity due to their large contact areas with the polymer chains. This increased spinline tension was found to cause fiber breakup at moderate speeds. Increasing melt temperature from 230° to 250°C alleviated this problem.     

聚乳酸/矿物填料复合材料的示差扫描量热研究

通过熔融共混法制备了一系列聚乳酸(PLA)/矿物填料复合材料.采用示差扫描量热(DSC)研究了含有碳酸钙(CaCO3)、蒙脱土(MMT)和凹凸棒土(AT)的聚乳酸复合材料在不同热历程中的结晶和熔融行为.研究发现,MMT和AT对PLA的慢速降温结晶无明显影响,而碳酸钙在慢速降温过程中能够有效促进PLA结晶;在2.5 K/min的降温速率下,结晶热焓随碳酸钙含量增加而增加;填料种类和含量会对复合材料升温过程的冷结晶和熔融产生较大影响,低含量矿物填料主要对PLA的冷结晶起成核作用,其中MMT成核效果最好.较高含量下不同填料会对PLA晶体形态产生影响,从而得到多样的DSC曲线变化.     

Bi-hybrid coatings: polyaniline-montmorillonite filler in organic-inorganic polymer matrix

A bi-hybrid composite is represented by an organic-inorganic (O-I) filler dispersed in an O-I matrix. Polyaniline-montmorillonite, as a nanocomposite filler, was synthesised by two independent processes: (1) montmorillonite was surface-modified with a conducting polymer, polyaniline, during the in-situ oxidation of aniline or (2) montmorillonite was pre-treated with aniline, then the aniline was polymerised and the polyaniline subsequently produced penetrated the montmorillonite structure. The organic-inorganic polymer matrix was formed in two independent steps: (1) inorganic building units were formed in situ by the sol-gel process, (2) followed by organic polymeric matrix formation by polyaddition reactions of epoxy groups with amines. Polyaniline-montmorillonite filler was added to the reaction system between these two steps, i.e. when the inorganic structures of the O-I matrix have already been formed but prior to formation of the organic polymeric matrix. Two different O-I matrices were prepared from functionalised organosilicon precursors and oligomeric amines. 3-[(Glycidyloxy)propyl]trimethoxysilane reacted with α,ω-oligo(propylene oxide) diamine and diethoxy[3-(glycidyloxy)propyl]-methylsilane reacted with α,ω-oligo(propylene oxide) triamine. The resulting bi-hybrid coatings, the O-I filler dispersed in the O-I matrix, were characterised by atomic-force and optical microscopies, and also by tensile tests. The filler composition affected both the mechanical and surface properties of the coatings.     

Kinetics of the thermal degradation of poly(lactic acid) obtained by reactive extrusion: Influence of the addition of montmorillonite nanoparticles

A reactive extrusion-calendering process was used in order to manufacture sheets with a nominal thickness of 1 mm of poly(lactic acid) and its nanocomposite with 2.5% of an organo-modified montmorillonite. During processing, the properties of the melt were stabilized and enhanced by the addition of 0.5% of a styrene-acrylic multi-functional-epoxide oligomeric reactive agent. The general analytical equation has been used in order to evaluate the kinetic parameters of the thermal degradation of poly(lactic acid) obtained by reactive extrusion and its nanocomposite. Various empirical and theoretical solid-state mechanisms have been tested to elucidate the best kinetic model. In order to reach this goal, master plots have been constructed by means of standardized conversion functions. Given that it is not always easy to visualize the best accordance between experimental and theoretical values of standardized conversion functions, a new index has been developed to quantitatively discern the best mechanism. By doing that, it has been possible to determine the right activation energy of the thermal degradation. It has been demonstrated that the best theoretical mechanism was the random scission of macromolecular chains within the polymer matrix. This was also in accordance with an empirical kinetic model based on an autocatalytic kinetic model. The presence of montmorillonite nanoparticles has been beneficial and has enhanced the thermal stability of poly(lactic acid).     

Polylactide compositions. II. Correlation between morphology and main properties of PLA/calcium sulfate composites

Starting from calcium sulfate (gypsum) as fermentation by‐product of lactic acid production process, high performance composites have been produced by melt‐blending polylactide (PLA, L/D isomer ratio of 96:4) and β‐anhydrite II (AII) filler, that is, calcium sulfate hemihydrate previously dehydrated at 500 °C. Characterized by attractive mechanical and thermal properties due to good filler dispersion throughout the polyester matrix, these composites are interesting for potential use as biodegradable rigid packaging. Physical characterization of selected composites filled with 20 and 40 wt % AII has been performed and compared to processed unfilled PLA with similar amorphous structure. State of dispersion of the filler particles and interphase characteristic features have been investigated using light microscopy (LM) and scanning electron microscopy (SEM). Addition of AII did not decrease PLA thermal stability as revealed by thermogravimetry analyses (TGA) and allowed reaching a slight increase of PLA crystallizability during melt crystallization and upon heating from the glassy, amorphous state (DSC). It was found by thermomechanical measurements (DMTA) that the AII filler increased pronouncedly storage modulus (E′) of the composites in comparison with PLA in a broad temperature range. The X‐ray investigations showed stable/unchanged crystallographic structure of AII during processing with molten PLA and in the composite system. The notable thermal and mechanical properties of PLA–AII composites are accounted for by the good filler dispersion throughout the polyester matrix confirmed by morphological studies, system stability, and favorable interactions between components. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2770–2780, 2007