Preparation and properties of thermoplastic starch/montmorillonite nanocomposites using N,N‐bis(2‐hydroxyethyl)formamide as a new additive

N,N‐Bis(2‐hydroxyethyl)formamide (BHF) was synthesized efficiently and used as a new additive to prepare thermoplastic starch/montmorillonite (TPS/MMT) nanocomposites. Here, BHF acted as both plasticizer for TPS and swelling agent for MMT. The hydrogen bond interaction among BHF, starch, and MMT was proven by Fourier transform infrared (FTIR) spectroscopy. By scanning electron microscope (SEM), starch granules were completely disrupted. Atomic force microscopy demonstrated that partially exfoliated TPS/MMT nanocomposites were formed. The crystallinity of corn starch, MMT, BHF‐plasticized TPS (BTPS), and TPS/MMT nanocomposites was characterized by X‐ray diffraction (XRD), XRD demonstrated that partially intercalated TPS/MMT nanocomposites were formed. The water resistance of TPS/MMT nanocomposites increased compared with that of pure BTPS. Mechanical properties of BTPS and TPS/MMT nanocomposites were examined. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Effect of polymer matrix/montmorillonite compatibility on morphology and melt rheology of polypropylene nanocomposites

In this study, Ca²⁺‐montmorillonite (Ca²⁺‐MMT) and organo‐montmorillonite (OMMT) were modified by three compatibilizers with different degrees of polarity [poly(ethylene glycol) (PEG), alkyl‐PEG, and polypropylene (PP)‐g‐PEG]. PP/MMT nanocomposites were prepared by melt blending and characterized using X‐ray diffraction and transmission electron microscopy. The results showed the degree of dispersion of OMMT in the PP/PP‐g‐PEG/OMMT (PMOM) nanocomposite was considerably higher than those in the PP/PEG/OMMT and PP/alkyl‐PEG/OMMT nanocomposites, which indicated that the dispersion was relative to the compatibility between modified OMMT and PP matrix. Linear viscoelasticity of PP/MMT nanocomposites in melt states was investigated by small amplitude dynamic rheology measurements. With the addition of the modified MMT, the shear viscosities and storage modulus of all the PP/MMT nanocomposites decreased. It can be attributed to the plasticization effect of PEG segments in the three modifiers. This rheological behavior was different from most surfactant modified MMT nanocomposites which typically showed an increase in dynamic modulus and viscosity relative to the polymer matrix. The unusual rheological observations were explained in terms of the compatibility between the polymer matrix and MMT. In addition, the mechanical properties of PP/MMT nanocomposites were improved. A simultaneous increase in the tensile strength and toughness was observed in PP/PMOM nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Processing and properties of PLA/thermoplastic starch/montmorillonite nanocomposites

Thermoplastic starch (TPS) and polylactic acid (PLA) were compounded with natural montmorillonite (MMT) using a twin‐screw extrusion process to investigate the structure and properties of these nanocomposites and to examine the use of water to enhance clay exfoliation. Tensile and essential work of fracture measurements were performed on standard dumbbell shape samples and on double notched samples to determine the effect of MMT and PLA/TPS interfacial modification on the mechanical and fracture properties of the materials. The nanocomposite structure was investigated using X‐Ray diffraction, transmission electron microscopy, and atomic force microscopy. Differential scanning calorimetric analysis was performed on the materials to determine the effect of TPS and MMT on PLA crystallization and physical aging. It was found that the TPS can intercalate the clay structure and that the clay was preferentially located in the TPS phase or at the blend interface. This led to an improvement in tensile modulus and strength and to a reduction in fracture toughness. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Enhanced breakdown strength and electrical tree resistance properties of MMT/SiO2/LDPE multielement composites

Montmorillonite (MMT)/low-density polyethylene (LDPE) nanocomposites have excellent partial discharge resistance and electrical tree resistance compared with pure LDPE. However, the MMT/LDPE nanocomposites have low breakdown strength due to the poor compatibility between nano-MMT and LDPE. In order to improve the breakdown strength of the MMT/LDPE composites without changing the LDPE matrix, an MMT/SiO₂/LDPE multielement composite was prepared by melt blending, and its breakdown strength and electrical tree resistance properties were investigated. The results show that the MMT/SiO₂/LDPE multielement composite has excellent breakdown strength and electrical tree resistance properties compared with the MMT/LDPE composite. The reasons for the excellent insulation properties of the MMT/SiO₂/LDPE multielement composites were analyzed by exploring the effects of MMT and SiO₂ on the microstructure and trap characteristics of LDPE. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47364.     

The effect of clay modification on the mechanical properties of poly(methyl methacrylate)/organomodified montmorillonite nanocomposites prepared by in situ suspension polymerization

Poly(methylmethacrylate) (PMMA)/montmorillonite (MMT) nanocomposites were prepared by in situ suspension polymerization. MMT was previously organically modified by different modification agents [dioctadecyl dimethyl ammonium chloride (DODAC) and methacrylatoethyltrimethyl ammonium chloride (MTC)] and different modification method (cation‐exchange reaction and grafting reaction), ultimately giving rise to five kinds of organomodified MMT (OMMT). The structure of the OMMT was studied by Wide angle X‐ray diffraction (WAXD) and Fourier transform infrared spectroscopy (FTIR). Meanwhile, the structure of the PMMA/MMT nanocomposites microspheres was also investigated by WAXD. The molecular weight of the polymers extracted from PMMA/MMT nanocomposites was measured by gel permeation chromatograph (GPC). Finally, the mechanical properties of these PMMA/MMT nanocomposites were studied in detail. It was found that large interlayer spacing (d₀₀₁) of OMMT could not entirely ensure an exfoliated structure of resultant PMMA/MMT nanocomposites, while OMMT with relative small d₀₀₁ could still yield exfoliated structure as long as the compatibility between OMMT and polymer matrix was favorable. In addition, the results of mechanical investigation indicated that the compatibility between OMMT and PMMA matrix turned out to be the dominant factor deciding the final mechanical properties of PMMA/MMT nanocomposites. POLYM. COMPOS., 37:1705–1714, 2016. © 2014 Society of Plastics Engineers     

Polypropylene/organically modified Sabah montmorillonite nanocomposites: Surface modification and nanocomposites characterization

The aim of the work is to extract, purify, and organically modify montmorillonite (MMT) of Lahad Datu, Sabah bentonite. The octadecylamine treated Sabah MMT (S‐OMMT) (2–8 wt%) was then melt blended with polypropylene (PP) and maleated polypropylene (PPgMAH) (10 wt%) via single screw nanomixer extruder followed by injection molding into test samples to examine the mechanical, thermal, and morphological properties of PP/S‐OMMT nanocomposites. Unmodified Sabah MMT (S‐MMT) and commercial grade MMT (Nanomer 1.30P) filled PP nanocomposites were also characterized for comparison purpose. X‐ray diffraction results showed that the interlayer spacing of S‐MMT increased after organic modification as Fourier transform infra‐red and elemental analysis evidenced the presence of octadecylamine. PP/S‐OMMT nanocomposites showed a better dispersion and strength compared to PP/Nanomer 1.30P nanocomposites due to its smaller MMT platelet size. differential scanning calorimetry and Thermogravimetry analysis revealed that the thermal stability and crystallinity of neat PP improved with the addition of all types of MMT. Dynamic mechanical analyzer showed that PP nanocomposites have higher storage modulus (E′) values than the neat PP over the whole temperature range. The new PP/S‐OMMT nanocomposites showed a comparable performance with PP/Nanomer 1.30P nanocomposites exhibiting promising future applications of S‐MMT in polymer/MMT nanocomposites. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Study on the properties of polyethylene/montmorillonite nanocomposites prepared by a novel vane mixer

A novel mixer‐vane mixer which is based on elongation flow was used to prepare high‐density polyethylene (HDPE)/montmorillonite (MMT) nanocomposites without any additives. The effect of elongation flow on MMT intercalating in HDPE matrix was studied in terms of rotor speed and mixing time. X‐ray diffraction and transmission electron microscope analyses showed that exfoliated and intercalated nanostructures were obtained when the rotor speed was 40 and 50 rpm, and mixing time was 6 minutes. For all samples prepared by vane mixer, MMT layers showed fine intercalation in the nanocomposites. Differential scanning calorimetry and thermogravimetric analysis were used to study the thermal properties of the nanocomposites. The results showed that the addition of MMT can improve the crystallization of the HDPE. Tensile test revealed the relationships between the mechanical properties and process parameters. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42600.     

Effect of length of hydroxyalkyl groups in the clay modifier on the properties of thermoplastic polyurethane/clay nanocomposites

Polyether‐ and polyester‐based thermoplastic polyurethane (TPU) nanocomposites containing the montmorillonite modified with quaternary ammonium salts having a relatively long hydroxyalkyl branch (MMT‐OH) were prepared via solution mixing. Quaternary ammonium salts with dimethyl, octyl, hydroxyundecyl branches were synthesized by the addition reaction of dimethyloctylamine and 11‐bromo‐1‐undecanol and were used for the preparation of MMT‐OH. In this MMT‐OH clay, hydroxyl groups are located at the outer end of the relatively long undecyl branch, which may make the hydroxyl groups more exposed to the matrix polymers compared to the clays with the modifiers having shorter hydroxyalkyl chain such as C30B. Actually, more hydroxyl groups in MMT‐OH's are thought to be exposed outside the modified clay, since MMT‐OH's were observed to be somewhat dispersed in water, while clays with shorter alkyl chains were not. From XRD and TEM results, the silicate layers of MMT‐OH were shown to be very well dispersed in ether‐TPU and ester‐TPU nanocomposites prepared from dimethyl acetamide solution. In the case of ester‐TPU nanocomposites, much better clay dispersion was observed for nanocomposites containing MMT‐OH than the ones with C30B in the TEM images. The tensile properties measurement showed the similar trend. Although MMT‐OH has only one hydroxyl group while C30B has two, above results of better tensile properties and water dispersibility of MMT‐OH than C30B having two hydroxyls indicate that the position of hydroxyls may be a important factor in determining the properties of TPU/clay nanocomposites. Fourier transform infrared spectroscopy analyses showed that the long hydroxyalkyl chain modifiers may provide more hydrogen bonding sites than short hydroxyalkyl chain modifiers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Flame retardance of montmorillonite/rubber composites

The effect of dispersion of clay in rubber on the mechanical properties and flame retardance of rubber/montmorillonite (MMT) nanocomposites and rubber/MMT microcomposites were investigated in the present article, and the results were compared with the performance of silica reinforced rubber composites. Cone calorimeter test and limiting oxygen index test were employed to evaluate the flame retardance. From the results, it could be seen that the rubber/MMT nanocomposites always possessed the best flame retardance, such as lower peak heat release rate and higher fire performance index value. In addition, the rubber/MMT nanocomposites also showed better mechanical properties than the pure rubber and the other composites, especially in tear strength. With the rubber/silica composites, as expected, the silica could appropriately endow the rubber with flame retardance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fabrication and properties of thermoplastic starch/montmorillonite composite using dialdehyde starch as a crosslinker

The poor mechanical properties and high water solubility of biodegradable thermoplastic starch (TPS) represent the main disadvantages of TPS in many applications. In this work, TPS film was prepared from a water solution of corn starch modified by 5 wt% dialdehyde starch (DAS) as crosslinking agent and 3 wt% montmorillonite (MMT) as reinforcing additive. Interactions occurring in the TPS films were investigated by Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, XRD, DSC, dynamic mechanical thermal analysis (DMTA) and TGA. The results obtained fom FTIR spectroscopy and DSC suggest the formation of hydrogen bond interactions between the hydroxyl group of starch, DAS, the MMT layers and glycerol. DMTA indicated that the relaxation of films with DAS and MMT appears in a higher and broader temperature range due to the starch backbone stiffness; the extreme increase in the storage modulus confirmed the suggested interactions. The determination of the weight loss of the films in water indicated a significant increase of the water resistance of TPS due to incorporation of DAS and MMT. Changes in mechanical properties of the films containing DAS and clay were determined, showing a substantial increase in tensile strength from 2.7 to 6.7 MPa, while Young's modulus increased by 15 times for TPS modified with 5% DAS and 3% MMT. Therefore, the outcomes of this study confirmed that DAS is a suitable biomacromolecule crosslinker for starch and can significantly enhance TPS and TPS/MMT properties. © 2019 Society of Chemical Industry     

聚氨酯/蒙脱土纳米复合材料

综述了聚氨酯／蒙脱土纳米复合材料的制备、结构表征和热力学性能，对制备过程进行了热力学分析，并对其发展前景进行了讨论。聚氨酯／蒙脱土纳米复合材料是一种新型的有机／无机纳米复合材料。在无机材料含量远低于常规填充量的情况下复合材料就可以具有较好的力学性能、阻隔性，热稳定性能也显著提高。     

The Effect of Spray-Freeze Drying of Montmorillonite on the Morphology,Dispersion, and Crystallization in Polypropylene Nanocomposites

The spray-freeze drying (SFD) technique was applied to sonicated aqueous suspensions of spray-dried montmorillonite clay (MMT) to produce highly porous agglomerates (SFD-MMT). Both MMT (used as a reference) and SFD-MMT were subsequently incorporated in polypropylene (PP) via melt compounding to produce 2 wt % nanocomposites with and without maleic anhydride grafted polypropylene (PP-g-MA). Polypropylene nanocomposites containing SFD-MMT exhibited thinner silicate flake layers compared to large agglomerates in PP/MMT nanocomposites. SFD-MMT particles became even more finer in the presence of PP-g-MA (i.e., in PP/PP-g-MA /SFD-MMT) where it hindered PP crystallization instead of serving as nucleation sites for the PP crystallization during rapid cooling. SFD-MMT improved the thermal stability of PP/PP-g-MA by 30°C compared to only 5–8°C for MMT/nanocomposites. MMT acts as a heterogeneous nucleating agent in the nucleation-controlled PP nanocomposites, but the hindrance effect was observed for the PP/PP-g-MA with SFD-MMT. PP/PP-g-MA/SFD-MMT exhibited twice the edge surface energy as compared to PP/PP-g-MA/MMT. The incorporation of both types of MMT raised the tensile moduli of PP and PP/PP-g-MA, with no improvement in their tensile strength and a decrease in the elongation at break. The PP/PP-g-MA/SFD-MMT showed brittle failure. POLYM. ENG. SCI., 60:168–179, 2020. © 2019 Society of Plastics Engineers     

PET/MMT纳米复合材料的制备

采用烷基季铵盐对蒙脱土(MMT)进行有机化处理,采用插层聚合法制备PET/MMT纳米复合材料。探讨了不同的MMT来源、添加量及聚合条件对PET/MMT纳米复合材料耐热性能的影响。结果表明: MMT的添加质量分数为2.5%,缩聚反应终温250℃时,PET/MMT纳米复合材料具有较好的综合性能。     

Preparation and Properties of Biodegradable Thermoplastic Starch/Clay Hybrids

Biodegradable thermoplastic starch (TPS)/clay hybrids were prepared by melt intercalation. Three organically modified montmorillonite (MMT) with different ammonium cations and one unmodified Na⁺ MMT (Cloisite Na⁺) were used. Cloisite Na⁺ showed the best dispersion in the TPS matrix. It was observed that the TPS/Cloisite Na⁺ hybrid showed an intercalation of TPS in the silicate layer due to the matching of the surface polarity and interactions of the Cloisite Na⁺ and the TPS, which gives higher tensile strength and better barrier properties to water vapor as compared to the other TPS/organoclay hybrids as well as the pristine TPS. It was found that the dynamic mechanical properties of the TPS/clay hybrids were also affected by the polar interactions.     

The mechanical/thermal properties of microcellular injection‐molded poly‐lactic‐acid nanocomposites

This study investigated the influence of montmorillonite (MMT) content on the mechanical/thermal properties of microcellular injection‐molded polylactide (PLA)/clay nanocomposites. Carbon dioxide was the blowing agent. The PLA/MMT nanocomposites were prepared by twin screw extrusion. The results showed that as MMT content is increased, tensile strength, impact strength, and cell density decrease. This is caused by the speed degradation of PLA due to the addition of MMT. MMT decreases the crystallization temperature but increases the decomposition temperature of the nanocomposites. The XRD results showed that the layer spacing of the clay increases as MMT content increases. TEM pictures showed that the MMT is well dispersed within the PLA matrix. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers.     

Preparation and characterization of anionically polymerized butadiene‐isoprene copolymer/clay nanocomposites

Butadiene‐isoprene copolymer/montmorillonite (BIR/MMT) nanocomposites were synthesized successfully via in situ anionic polymerization. The results of transmission electron microscopy and X‐ray diffractometer showed that the clay layers were exfoliated and high reaction temperature benefited the exfoliation of layers in BIR/MMT. The polymerization still exhibited “living” characteristics with the addition of organophilic montmorillonite (OMMT). However, the contents of 1,2‐polybutadiene and 3,4‐polyisoprene of the copolymer decreased with the addition of OMMT, because of its absorption effect on N,N,N′,N′‐tetramethylethanediamine as revealed by ¹H NMR. Moreover, it was observed that the glass‐transition temperature of the BIR/MMT nanocomposites also decreased when compared with the BIR copolymers. The thermal stability of the nanocomposites was improved, because of the barrier property of exfoliated clay layers. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 1167–1172, 2006     

Synthesis and characterization of polyurethane cationomer/MMT hybrid composite

BACKGROUND: The development of polymeric nanocomposites incorporating intercalated or exfoliated layered silicate clays into the organic matrix has been substantially motivated by the significant improvements induced by the presence of the inorganic component. Moreover, understanding and controlling the dispersion of inorganic layers into segmented polyurethane matrices by means of ionic interactions, and exploiting these interactions to enhance physicomechanical behaviour, could be of great interest in the field of polymer nanocomposites. RESULTS: New cationic polyurethane elastomers were prepared starting from poly(butylene adipate)diol (M_n = 1000 g mol^?1), 4,4′‐diphenylmethane diisocyanate, 1,4‐butanediol and N‐methyldiethanolamine or N,N′‐β‐hydroxyethylpiperazine, used as potential quaternizable moieties. The characterization of the polymers was achieved using specific analyses employed for the macromolecular samples (Fourier transform infrared and ¹H NMR spectroscopy, thermogravimetric analysis (TGA), gel permeation chromatography). An extension of our research on polymers reinforced with organically modified montmorillonite (OM‐MMT) in order to prepare hybrid composites with improved properties was performed and the resulting materials were characterized using TGA, X‐ray diffraction, atomic force microscopy and scanning electron microscopy. Also, the mechanical properties of the cationic polyurethane/OM‐MMT composites were investigated in comparison with the pristine ionic/non‐ionic polymers and their composites containing non‐ionic polymer blended with OM‐MMT or ionic polymer and unmodified MMT. CONCLUSION: The insertion of the organically modified clay into the polymeric matrix gave an improvement of the mechanical properties of the polyurethane composites, especially the tensile strength and stiffness of the hybrid materials. Copyright © 2009 Society of Chemical Industry     

Preparation and properties of polyethylene/montmorillonite nanocomposites formed via ethylene copolymerization

BACKGROUND: In situ formation of polyethylene/clay nanocomposites is one of the prevalent preparation methods that include also solution blending and melt blending with regard to process simplification, economy in cost, environment protection and marked improvement in the mechanical properties of the polymeric matrix. In the work reported here, the preparation of linear low‐density polyethylene (LLDPE) and fabrication of polymer/clay nanocomposites were combined into a facile route by immobilizing pre‐catalysts for ethylene oligomerization on montmorillonite (MMT). RESULTS: [(2‐ArN?C(Me))₂C₅H₃N]FeCl₂ (Ar = 2,4‐Me₂(C₆H₃)) was supported on MMT treated using three different methods. The MMT‐supported iron complex together with metallocene compound rac‐Et(Ind)₂ZrCl₂ catalyzed ethylene to LLDPE/MMT nanocomposites upon activation with methylaluminoxane. The oligomer that was formed between layers of MMT promoted further exfoliation of MMT layers. The LLDPE/MMT nanocomposites were highly stable upon heating. Detailed scanning electron microscopy analysis revealed that the marked improvement in impact strength of the LLDPE/MMT nanocomposites originated from the dispersed MMT layers which underwent cavitation upon impact and caused plastic deformation to absorb most of the impact energy. In general, the mechanical properties of the LLDPE/MMT nanocomposites were improved as a result of the uniform dispersion of MMT layers in the LLDPE matrix. CONCLUSION: The use of the MMT‐supported iron‐based diimine complex together with metallocene led to ethylene copolymerization between layers of MMT to form LLDPE/MMT nanocomposites. The introduction of exfoliated MMT layers greatly improved the thermal stability and mechanical properties of LLDPE. Copyright © 2009 Society of Chemical Industry     

Novel preparation and properties of EPDM/montmorillonite nanocomposites

This article reports on a novel route to develop ethylene–propylene–diene rubber (EPDM)/montmorillonite nanocomposites Modification of the MMT was carried out with maleic anhydride (MA), which acts as the intercalation agent for MMT and the vulcanizing agent for EPDM matrix, as well as the compatibilizer for the EPDM and MMT phases. The effect of MA‐modified MMT in nanocomposites was investigated by focusing on three major aspects: structural analysis, thermal properties, and material properties. The d‐spacings of both the MA modified MMT and exfoliated nanocomposites were investigated by X‐ray diffraction (XRD), and the morphology of these nanocomposites was examined by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Dynamic mechanical analysis confirms the constraint effect of exfoliated MMT layers on EPDM chains, which benefited the increased storage modulus, increased glass transition temperature. Thermogravimetric analysis indicates that there is some enhancement in degradation behavior between the nanocomposites and EPDM matrix. The nanocomposites exhibit great improvement in tensile strength and modulus, as well as elongation‐at‐break. The effects of MA addition on the formation of nano‐metric reinforcement and on the mechanical properties of nanocomposites are discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 2578–2585, 2006     

淀粉对蒙脱土/丁腈橡胶纳米复合材料结构和性能的影响

采用蒙脱土水悬浮液/橡胶乳液共混-共凝复合技术制备蒙脱土/丁腈橡胶纳米复合材料时,在蒙脱土水悬浮液和丁腈胶乳的混合体系中加入淀粉,考察了淀粉用量对蒙脱土/丁腈橡胶纳米复合材料结构和性能的影响。结果表明,淀粉的加入有利于蒙脱土片层形成剥离型结构。当蒙脱土用量为5份、淀粉用量为10份时,蒙脱土几乎呈完全剥离状态;随着淀粉用量的增加,该复合材料的邵尔A硬度、100%定伸应力、拉伸强度、扯断伸长率和撕裂强度均有所提高。