Study of rheological properties of polypropylene/organoclay hybrid materials

Polypropylene nanocomposites reinforced with organic modified montmorillonite clay have been fabricated by melt compounding using extrusion. The morphology of the composites is studied with transmission electron microscopy and X-ray diffraction. The melt-state rheological properties of the nanocomposites have been investigated as a function of temperature and organoclay loading. It is found that the organoclays are intercalated and dispersed evenly in the matrix. The storage and loss moduli of the hybrid composites decrease with temperature and increase with organoclay concentration. Both polypropylene and its composites demonstrate a melt-like rheological behavior, indicating the low degree of exfoliation of the organoclay. A shear thinning behavior is found for both polypropylene and its composites, but the onset of shear thinning for organoclay composites occurs at lower shear rates.     

Exfoliation of clay layers in polypropylene matrix using potassium succinate-g-polypropylene as compatibilizer

The efficiency of potassium succinate-g-polypropylene (KPPSA) as compatibilizer for the dispersion of clay in a high molecular weight polypropylene during melt mixing for the preparation of nanocomposites was evaluated and compared with maleic anhydride-g-polypropylene (PPMA). Nanocomposites were prepared by direct melt mixing and by masterbatch methods and the structure obtained was characterized by WAXD and TEM. The exfoliation and better dispersion of the organoclay was observed with KPPSA than PPMA. The dispersion of clay was found to be dependent on the method of preparation, type and the amount of compatibilizer used. The dispersion was better when the nanocomposites were prepared by two step masterbatch route than the single step direct mixing method. Flexural moduli and crystallization behavior were studied and correlated with the dispersion of organoclay in the PP matrix.     

Investigation of the nanostructure and mechanical properties of polypropylene/polyamide 6/layered silicate ternary nanocomposites

This work aims to investigate the structure–property relationship in ternary nanocomposites consisting of polypropylene as the matrix, nanoclay as the reinforcement and polyamide 6 as the intermediate phase. In this regard, composites of polypropylene/organoclay, polyamide/organoclay, blends of polypropylene/polyamide, and ternary nanocomposites of polypropylene/polyamide/layered silicate with and without compatibilizer were produced via melt compounding. Nanostructure was investigated by wide-angle X-ray diffraction and transmission electron microscopy. Scanning electron microscopy was employed to study the microstructure. Modulus of elasticity and yield strength were measured by uniaxial tensile test. Results show that silicate layers can only be observed inside polyamide particles. Moreover, polypropylene was unable to intercalate the grade of organoclay used in this study. While polyamide/organoclay system exhibited an exfoliated structure, the nanostructure of ternary nanocomposites was chiefly intercalated, due to the high concentration of silicate layers inside polyamide particles. Incorporation of organoclay into the polypropylene/polyamide system was seen to have a noticeable effect on the shape and size of polyamide particles. In addition, elastic modulus and yield strength were observed to be directly affected by incorporation of nanoclay and compatibilizer into the polypropylene matrix, respectively. The simultaneous presence of the two constituents in the system resulted in samples with superior mechanical properties in the elastic as well as the plastic deformation regime.     

Mechanical and thermal properties of carbon fiber/polypropylene composite filled with nano-clay

The effect of organoclay on the mechanical and thermal properties of woven carbon fiber (CF)/compatibilized polypropylene (PPc) composites is investigated. Polypropylene–organoclay hybrids nanocomposites were prepared using a maleic anhydride-modified PP oligomer (PP-g-MA) as a compatibilizer. Different weight percentages of Nanomer® I-30E nanoclay were dispersed in PP/PP-g-MA (PPc) using a melt mixing method. The PPc/organoclay nanocomposite was then used to manufacture plain woven CF/PPc nanocomposites using molding compression process. CF/PPc/organoclay composites were characterized by different techniques, namely; dynamic mechanical analysis (DMA), fracture toughness and scanning electron microscope. The results revealed that at filler content 3% of organoclay, initiation and propagation interlaminar fracture toughness in mode I were improved significantly by 64% and 67% respectively, which could be explained by SEM at given weight as well; SEM images showed that in front of the tip, fibers pull out during initiation delamination accounting for fracture toughness improvement. Dynamic mechanical analysis showed enhancement in thermomechanical properties. With addition 3 wt.% of organoclay, the glass transition temperature increased by about 6 °C compared to neat CF/PPc composite indicating better heat resistance with addition of organoclay.     

Effects of maleination and heat treatment on morphology and dynamic mechanical thermal behavior of polypropylene/organoclay nanocomposites

Effects of maleinated compatibilizer and heat treatment on the internal structure and physical properties of PP/organoclay nanocomposites were investigated by using various measurements, e.g., SAXS, TEM, DSC and DMTA, and rotational rheometer. Experimental results showed that maleination and heat treatment affected the internal structure and dynamic mechanical properties of PP/organoclay nanocomposites. Storage modulus and loss tangent of PP/organoclay nanocomposites were strongly related to the compatibilizer loadings and heat treatment conditions because the interfacial structure between PP molecular chains and organoclay particles had been changed by the addition of compatibilizer to PP/organoclay nanocomposites. DSC and DMTA results of the compatibilized nanocomposites and effects of heat treatment on crystallization and dynamic mechanical thermal properties demonstrated that there is a small change in the glass transition temperature because the chain mobility and free volume in the amorphous region are increased by heat treatment. It was found that heat treatment imposed influence on both amorphous and crystalline regions of PP/organoclay nanocomposites.     

Dispersion and rheology of polypropylene/organoclay nanocomposites: effect of cation exchange capacity and number of alkyl tails

Nanocomposites of montmorillonite organoclays and polypropylene (PP) were prepared via direct melt intercalation using maleic anhydride functionalized polypropylene (PP-g-MA) as a compatibilizer. Two montmorillonite clays (MMT) with different cation exchange capacities (CEC) were exchanged with alkyl ammonium ions, in which one or two octadecyl chains are attached to the nitrogen atom. The role of alkyl chain numbers and CEC value on the dispersion of clay and rheology of PP nanocomposites under shear and extensional flow was evaluated by X-ray diffraction, scanning electron microscopy, and rheologic techniques. It was found that the low-CEC organoclay with one alkyl chain could only form a conventional composite. However, the low-CEC organoclay with two alkyl chains or high-CEC organoclay with one alkyl chain can disperse finely in the matrix. Nanocomposites containing these two organoclays showed typical shear rheologic properties of intercalated nanocomposites, but only the former showed a mild strain-hardening behavior in uniaxial extensional flow. When using an intercalant with two tails, the high-CEC clay would lead the organoclay to form mixed structures which further resulted in an inferior dispersion quality. It was proposed that the dispersion quality and rheologic properties of nanocomposites were related to the arrangement of modifier molecules in the clay galleries, which was determined by the CEC of clay and the structure of alkyl ammonium ions.     

Investigation of physical and chemical properties of polypropylene hybrid nanocomposites

Hybrid nanocomposites fabricated based on an optimized physical and chemical properties modified polypropylene (PP)/polypropylene grafted maleic anhydride (PP-g-MA) with varied concentrations (1–7 wt% at a step of 2 wt%) of organoclay, montmorillonite (MMT). The morphology of the nanocomposites was studied by scanning electron microscopy (SEM), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). It was found that partly intercalated and partly exfoliated structure (intercalated–exfoliated structures) existed in the system. The degree of exfoliation is a key factor to determine the reinforcement efficiency. The ratio of exfoliation to intercalation plays an important role in determining the properties of PP nanocomposites and only completely exfoliated silicate layers can significantly improve the properties. PP hybrid nanocomposites showed good thermal stability in the thermogravimetric analysis (TGA). Introduction of ∼3% MMT in the nanocomposites increased the onset temperature of degradation by 27.5 °C compared to that of pure PP, while the 5 wt% MMT resulted the maximum hardness in these nanocomposites. The solvent resistance of PP hybrid nanocomposites slightly increased with increasing the clay content.     

Effect of organoclay platelets on morphology and properties of LLDPE/EMA blends

Blends of linear low density polyethylene (LLDPE) and ethylene-co-methyl acrylate (EMA) and their nanocomposites with two types of modified montmorillonite (organoclay) were explored in order to achieve an improved balance between stiffness and toughness. The nanocomposites were prepared in a HAAKE RHEOMIX at three different mixing sequences. The compression molded nanocomposites were utilized to evaluate the morphology and the properties like mechanical, dynamic mechanical and thermal. The results reveal that the morphology and the properties of the nanocomposites are dependent on the blending sequence as well as the type of nanoclay used. The addition of organoclay slightly increases the tensile modulus for all the nanocomposites. On the other hand, a drastic improvement of the impact strength was observed when the organoclay located at the dispersed EMA phase. The effects of clay concentration on the properties of the nanocomposites were also studied. The optimum dispersion as well as property was found for the nanocomposite at 5 wt% of the nano clay.     

Compatibilizing effect of acrylic acid modified polypropylene on the morphology and permeability properties of polypropylene/organoclay nanocomposites

This work dealt with the morphology and permeability properties of polypropylene/organoclay nanocomposites prepared using an acrylic acid grafted polypropylene (PP-g-AA) as compatibilizing agent. Two PP-g-AA containing the same acrylic acid content (6 wt.%) and having different molar masses were tested. The o-MMT content was 0, 1 or 5 wt.% and the PP-g-AA/o–MMT mass ratio was 0/1, 1/1, 2/1 or 5/1. Results of wide angle X-ray scattering (WAXS) and transmission electron microscopy (TEM) showed that without the PP-g-AA, the o-MMT was dispersed in the PP/o-MMT in a micrometer scale, similar to a conventional microcomposite. With the PP-g-AA, the o-MMT was much better dispersed and its interlayers were intercalated and partly exfoliated by the polymer chains. CO₂ permeability values decreased for all samples with the incorporation of the organoclay. The compatibilized samples showed a more significant reduction in CO₂ permeability, up to 50% when compared to the neat PP. In general, the PP-g-AA acted satisfactorily in compatibilizing PP/organoclay nanocomposites. Moreover, samples prepared with the compatibilizer/organoclay ratio of 5/1 had better barrier properties.     

Organoclay effect on transverse compressive strength of glass/epoxy nanocomposites

This research focuses on the fabrication of glass fiber/epoxy nanocomposites containing organoclay as well as understanding the organoclay effect on the transverse compressive strength of nanocomposites. To demonstrate the organoclay effect, three different loadings of organoclay were dispersed, respectively, in the epoxy resin using a mechanical mixer followed by sonication. The corresponding glass/epoxy nanocomposites were produced by impregnating dry glass fiber with organoclay epoxy compound through a vacuum hand lay-up procedure. Unidirectional block specimens were employed for transverse compression tests on a hydraulic MTS machine. Experimental observations indicate that glass/epoxy nanocomposites containing organoclay exhibit higher transverse compressive strength than conventional composites. Furthermore, the failure mechanisms for all tested specimens were found to be fiber and matrix debonding. Therefore, results indicate that the increasing characteristic in transverse failure stress may be ascribed to the enhanced fiber/matrix adhesion modified by the organoclay.     

Morphology development and stability of polypropylene/organoclay nanocomposites

A series of polypropylene (PP)/organoclay nanocomposites with varied concentrations of clay, from 1 to 7 wt%, was successfully prepared via melt intercalation using a PP functionalized with maleic anhydride as compatibilizer. The morphology/property relationships of the nanocomposites were investigated by XRD, TGA and DSC analyses. Two distinct groups of composites, from a quasi-exfoliated to an intercalated/flocculated morphology, were identified. In particular, intercalated/flocculated morphologies were obtained for those composites with an organoclay concentration beyond the threshold (3 wt%), as evidenced by XRD analysis and confirmed by the increase of the glass transition temperature. This last effect was related to the confinement of polymer chains between the silicate layers, generating a reduction of the chain mobility. The variable increase of the thermal stability of the nanocomposites was also likely related to the different degree of exfoliation/intercalation of the samples. The toluene extraction of composites was used as a powerful methodology to distinguish between polymer phases differently interacting with the inorganic surface: composites having a semi-exfoliated structure were split into two fractions having a similar morphology. For those samples having the higher organoclay concentration and intercalated morphology, a toluene-residue fraction was obtained containing almost all the clay present in the pristine composite. Furthermore, in this case the morphological analysis of the residue fraction evidenced a collapse of the inorganic structure compared to that of the unextracted composite. A careful characterization of both soluble and residue fractions is reported and the results are discussed considering the interactions at the interface between the functionalized PP chains and silicate layers and their effects on the organoclay dispersion degree and stability.     

可生物降解性聚合物-层状硅酸盐纳米复合材料的研究进展

可生物降解性聚合物一层状硅酸盐纳米复合材料比聚合物基体有更好的力学强度、热稳定性、热变形温度、气体阻隔特性和更快的降解速率，表现出剪切变稀、模量升高、似固体行为等流变特性。文中综述了可生物降解性聚合物纳米复合材料的制备方法、表征手段、性能测试及其应用等方面的研究进展。     

Influence of morphology on the dynamic mechanical characteristics of PP-EP/EVA/organoclay nanocomposites

A study on the dynamic mechanical properties of polypropylene copolymer/ethylene–vinyl acetate/organoclay (PP-EP/EVA/C20A) nanocomposites is presented. Nanocomposites were obtained by melt blending. Morphology consisting of intercalated–exfoliated clay nanolayers preferentially located within the EVA phase was observed by transmission electron microscopy (TEM) and wide angle X-ray diffraction (WAXD). Polar groups of vinyl acetate in the EVA facilitated the polymer–clay interactions. Changes in the glass transition temperature (T_g) were correlated with changes in the clay intercalation–exfoliation levels. The highly reinforced with intercalated–exfoliated clay layers EVA phase was considered as the origin of the improvement on mechanical properties of the ternary nanocomposites and is associated with the increase on viscosity, heat deflection temperature (HDT), and storage modulus.     

Thermal, mechanical and vibration characteristics of epoxy-clay nanocomposites

Diglycidyl ether of bisphenol-A (DGEBA) epoxy resin system filled individually with organoclay (OC) and unmodified clay (UC) were synthesized by mechanical shear mixing with the addition of diamino-diphenylmethane (DDM) hardener. The unmodified clay used was Na⁺-Montmorillonite (MMT) and the organoclay was alkyl ammonium treated MMT clay. The reinforcement effect of OC and UC in the epoxy polymer on thermal, mechanical and vibration properties were studied. X-ray diffraction (XRD) and Transmission electron microscopy (TEM) were used to study the structure and morphology of nanocomposites. Curing study shows that the addition of OC in epoxy resin aids the polymerization by catalytic effect, and UC addition does not show any effect in the curing behavior of epoxy polymer. Thermogravimetry analysis (TGA) shows enhanced thermal stability for epoxy with OC fillers than that of epoxy with UC fillers. The epoxy with OC fillers shows considerable improvement on tensile and impact properties over pure epoxy polymer and epoxy with UC fillers. The improvement in tensile and impact properties of nanocomposites is supported with the fracture surface studies. Epoxy with OC fillers shows enhanced vibration characteristics than that of the pure epoxy polymer and epoxy with UC fillers.     

Micro- and nano-scale deformation behavior of nylon 66-based binary and ternary nanocomposites

The primary aim of this paper is to provide an insight on the effect of the location of organoclay on the micro- and nano-scale deformation processes in melt-compounded nylon 66/organoclay/SEBS-g-MA ternary nanocomposites prepared by different blending sequences. In addition, the deformation processes of the ternary nanocomposites were compared to the binary nanocomposites (nylon 66/organoclay and nylon 66/SEBS-g-MA) and neat nylon 66. The incorporation of SEBS-g-MA particles toughened nylon 66 markedly; but the flexural modulus and strength were both reduced. Conversely, the use of organoclay increased the modulus but decreased the fracture toughness of nylon 66. Nylon 66/SEBS-g-MA/organoclay ternary nanocomposites exhibited balanced elastic stiffness and toughness. Stress-whitening studies of the fracture surfaces in terms of gray level were also performed and an attempt was made to correlate the optical reflectivity characteristics with fracture toughness. It was concluded that the capability of SEBS-g-MA particles to cavitate was decreased by the presence of organoclay in the SEBS-g-MA phase, resulting in reduced toughening efficiency. The best micro-structure for toughness and other mechanical properties is thus to maximize the amount of exfoliated organoclay in the nylon 66 matrix rather than to have it embedded in the finely dispersed SEBS-g-MA particles.     

Effect of hygrothermal ageing on morphology and indentation modulus of injection moulded nylon 6/organoclay nanocomposites

The effect of water immersion on the morphology and indentation modulus of injection moulded nylon 6 and its organoclay nanocomposites was investigated. XRD analysis showed that at 70 °C water promoted further crystallization in the nylon matrix and aided the γ- to α-crystal phase transition in the skin region. However, the presence of organoclay deterred this transformation. The combined actions of water and heat (70 °C) did not further degrade nylon 6 and its nanocomposites compared to water ageing at room temperature (25 °C). In fact, there was relative enhancement of the indentation moduli owing to the beneficial morphological changes induced in the nylon matrix. The largest improvements were found in the skin region of the injection moulded bars.     

Effect of material and processing parameters on mechanical properties of Polypropylene/Ethylene–Propylene–Diene–Monomer/clay nanocomposites

Polypropylene/Ethylene–Propylene–Diene–Monomer (PP/EPDM) blends are well known for having a combination of favourable mechanical properties. In this paper, addition of organoclay to PP/EPDM to make PP/EPDM nanocomposites with enhanced mechanical properties is studied. PP/EPDM/organoclay nanocomposites were prepared using a lab scale twin-screw extruder. Maleic anhydride grafted polypropylene (PP-g-MA) was used to enhance the intercalation/exfoliation process and to create good adhesion at the polymer/polymer and polymer/filler interfaces. Taguchi method was employed to deign the experiments and optimize material and processing parameters for optimized mechanical properties. Organoclay (NC) and compatibilizer content were selected as material parameters and the main processing variables were feeding rate and average shear rate (RPM). X-ray diffraction (XRD), Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) were used to study the microstructure of the nanocomposites samples. It was observed that NC content and shear rate in extruder improved the tensile strength and modulus. Another important result was the insignificant effect of NC content on impact strength while increasing shear rate first increased and then decreased the impact strength.     

熔融挤出插层制备聚丙烯/蒙脱土纳米复合材料的探讨(Ⅰ)

通过双螺杆挤出机熔融挤出法制备出插层型聚丙烯/蒙脱土纳米复合材料。利用有机蒙脱土的预凝胶测试,复合材料的透射电子显微镜(TEM)观察,熔体流动指数测试(M I),力学性能测试,耐热性测试等方法进行了表征。结果表明,通过本方法制备的聚丙烯/蒙脱土复合材料是典型的插层型纳米复合材料。该复合材料在有机蒙脱土质量分数仅为4.0%时缺口冲击强度提高了103%,耐热性有所提高,而屈服强度、刚性基本不变,为研制PPR管等同时具有高韧性和高耐热性的聚丙烯产品开辟了一条崭新的途径。     

Polyolefin-based nanocomposites: the effect of organosilane on organoclay dispersion

This work dealt with the morphology and properties of polypropylene/organoclay (PP/OMMt) nanocomposites prepared using maleic anhydride-grafted polypropylene (PP-g-MA) or organosilane (OTMS) as a compatibilizing agent. The content of OMMt was 2 wt%, and different concentrations of OTMS were used to obtain OTMS/OMMt mass ratios of 0/1, 1/1, 0.5/1 or 0.25/1. The results of wide-angle X-ray scattering and transmission electron microscopy investigations showed that the OTMS promoted the total exfoliation of OMMt in the PP matrix, while the OMMt yielded a micrometer-scale dispersion when PP-g-MA was used. In general, the OTMS satisfactorily compatibilized the PP/OMMt nanocomposites, increasing the modulus of the PP matrix. When a hybrid compatibilizer of OTMS/PP-g-MA was used, better thermal and mechanical properties were achieved.     

Reinforcement of polyurethane composites with an organically modified montmorillonite

A clay with reactive activity prepared by treatment of natural montmorillonite with Methylene-bis-ortho-chloroaniline (MOCA) was incorporated into polyurethane matrix and a series of PU/clay nanocomposites were obtained by in situ polymerization. The microstructure of the nanocomposites with different content of the clay was examined by atomic force microscopy (AFM). The thermal and mechanical properties of the nanocomposites with different organic clay content were characterized by dynamic mechanical thermal analysis (DMTA) and thermogravimetric analysis (TGA). It was found that the moduli and thermal stability of the nanocomposites were improved with augment of clay, especially, for the PU/9 wt% MO-MMT nanocomposite, compared to pure PU, the storage modulus and the loss modulus were increased by about 300% and 667% at −45 °C, respectively.