Preparation and properties of compatibilized LDPE/organo-modified montmorillonite nanocomposites

Nanocomposites based on low density polyethylene, containing of 3 or 6 wt.% of organo-modified montmorillonite nanoclay (MMT-ODA) and maleic anhydride grafted low density polyethylene as a compatibilizer were prepared by melt mixing and characterized. Exfoliation of silicate layers was achieved, as confirmed by X-ray diffraction and transmission electron microscopy. The compatibilized nanocomposites exhibit improved thermal stability in air as compared to neat polyethylene and nonexfoliated MMT-ODA composite. The crystallinity and crystallization kinetics of polyethylene matrix is not affected significantly by the presence of MMT-ODA clay. Drawability of the compatibilized nanocomposite with 6 wt.% of MMT-ODA is similar to neat polyethylene, whereas the composition having the same amount of MMT-ODA, without compatibilizer, exhibits poorer drawability. Scanning electron microscopy and density measurements of drawn samples indicate the existence of pores in noncompatibilized composite while no pores and good adhesion to MMT-ODA are found in compatibilized nanocomposites.     

Preparation, structure, and properties of styrene-ethylene-butylene-styrene block copolymer/clay nanocomposites: Part II fracture behaviors

Styrene-ethylene-butylene-styrene block copolymer (SEBS)/clay nanocomposites were prepared via a melt mixing technique. Various amounts of two types of maleated compatibilizers, styrene-ethylene-butylene-styrene block copolymer grafted maleic anhydride (SEBS-g-MA) and polypropylene grafted maleic anhydride (PP-g-MA), were incorporated to improve the dispersion of commercial organoclay (denoted as 20A), respectively. PP-g-MA compatibilized system conferred higher tensile strength and tear strength (initiation condition) than SEBS-g-MA compatibilized system. At a fixed content of compatibilizers, the above mechanical properties were improved with increasing clay content as well. By relating tensile strength to tear strength (arrest condition), the average depth of flaw was in the range of 33.8 ± 3.4 μm, which successfully confirmed the extension of Rivlin and Thomas’s theory for conventional elastomers to thermoplastic elastomer/clay nanocomposites for the first time. Cutting strength of SEBS/clay nanocomposites gave an intermediate value when compared with crystalline plastics and conventional amorphous elastomers, which further signified the importance of micro-yielding of styrene domains, crystalline yielding of compatibilizer, and filler reinforcement even in the nano-fracture zone of deformation.     

Fractionated crystallization of compatibilized LDPE/PA6 blends

The paper presents differential scanning calorimetry and electron microscopy of the fractionated crystallization and polydispersity of the dispersed PA6 phase in compatibilized LDPE/PA6 75/25 w/w blends. The compatibilizers used were (i) an acrylic acid functionalized polyethylene, Escor 5001 (EAA); (ii) an ethylene-glycidylmethacrylate copolymer, Lotader GMA AX8840 (EGMA); (iii) a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer comprising 2 wt.% maleic anhydride grafts, Kraton FG 1901X (SEBS-g-MA). The compatibilizer SEBS-g-MA has the strongest reduction effect upon the size of PA-6 droplets. Its implementation provides the best fractionated crystallization. The fractionated crystallization has not been observed for the blend compatibilized with EGMA. The results show that the degree of compatibilization could be evaluated qualitatively by the progress of the fractionated crystallization. So, the three compatibilizers could be rated according to their effectiveness as follows: SEBS-g-MA > EAA > EGMA. The self-nucleation experiments have demonstrated that the lack of active nuclei in the finely dispersed PA6 droplets is the determining factor for the fractionated crystallization at high supercooling, and not the considered absolute particle size. The measurement of the Vickers microhardness of the compatibilized blends confirms that the compatibilizing activity of SEBS-g-MA and EAA is stronger than that of EGMA.     

A facile rheological approach for the evaluation of “super toughness point” of compatibilized HDPE / MWCNT nanocomposites

Fast and efficient determination of the optimal mechanical property of a polymer/CNT nanocomposite is crucial to develop polymer conductive nanocomposites. This work establishes a rheological approach to evaluate the super-toughness point of compatibilized high density polyethylene (HDPE)/multi-walled carbon nanotube (MWCNT) nanocomposites. Results illustrate that three types of HDPE/MWCNT nanocomposites exhibit obvious gel plateaus in the dynamic rheological curves and the gel points of nanocomposites with compatibilizer shift to the low MWCNTs loading. The super-toughness points of HDPE/MWCNT nanocomposites with compatibilizers show the correspondence with the gel points acquired from the rheological data, indicating that dynamic rheology is an effective way to determine the super-toughness points of HDPE/MWCNT nanocomposites with compatibilizers. Furthermore, unique network structure at the gel points is directly observed and the new mechanism of toughness is proposed. This study provides new insights for effective control of the structures and properties of polymer/CNT nanocomposites.     

Properties and preparation of compatibilized nylon 6 nanocomposites/ABS blends: Part II – Physical and thermal properties

The physical and thermal properties of nanoclay filled nylon 6 (nano-nylon 6) blended with poly(acrylonitrile–butadiene–styrene)terpolymers (ABS) were investigated using metallocene polyethylene grafted maleic anhydride (POE-g-MA) or polybutadiene grafted maleic anhydride (PB-g-MA) as a compatibilizer. Cooling conditions significantly affected the crystalline structure of nano-nylon 6. No clear effect of both compatibilizers on the dispersion of clay has been observed via transmission electron microscope analysis. Through morphology observation, the ABS particle sizes tended to decrease with the addition of compatibilizers, especially in PB-g-MA cases, suggesting a good interfacial bonding between nano-nylon 6 matrix and ABS dispersed phase. Non-isothermal crystallization results indicated that the crystallization temperatures slightly changed with increasing content of compatibilizers. In addition, melting behaviors with different crystal forms varied widely with cooling conditions. The crystallization kinetics under isothermal conditions reflected that introduced compatibilizers impeded the growth rate, especially for PB-g-MA compatibilized system.     

Flammability, microhardness and transparency of nanocomposites based on functionalized polyethylenes

The flammability, microhardness and transparency of nanocomposites based on poly(ethylene-co-acrylic acid) copolymers having different concentration of acrylic acid and different molar mass, their Zn ionomer and ethylene-glycidylmethacrylate copolymer as matrixes and on organically modified montmorillonite as a nanofiller have been investigated. The presence and the increase in the content of the clay lead to the increase in the limiting oxygen index and to significant reduction of the burning rate of all materials. The results from the Vickers microhardness measurements have shown that the addition of the clay to matrixes of polar functionalized polyethylenes leads to a significant increase in the microhardness of the materials, while the creep constant does not decrease significantly. The UV spectra show that the light transmittance of the materials does not change significantly in the presence of the clay, i.e., the nanocomposite films preserve the polymer transparency. The results have been interpreted by the intercalated structures of the nanocomposites investigated.     

Flammability and morphology of HDPE/clay nanocomposites

High-density polyethylene/modified bentonite clay/polar compatibilizer nanocomposites were prepared through the melt intercalation process. The clay was organophilizated using different percentages of quaternary ammonium salt 100, 125, and 150 % based cation exchange capacity of the clay. The nanocomposites were prepared in a counter-rotating twin-screw extruder and then specimens were injection molded. For the evaluation of flammability of the test system was used for burning in the horizontal position according to the norm (Underwriters Laboratories, UL94HB) and to the method of cone calorimeter. The thermal behavior of nanocomposites was evaluated by thermogravimetry and X-ray diffraction techniques, and transmission electron microscopy were used to characterize the morphology and analyze the degree of expansion of the clays prepared and the degree of exfoliation of nanocomposites. It was observed that the percentage of ammonium salt and the compatibilizer polar influence on the final properties of the systems and consequently improving the thermal stability and reducing the flammability of the matrix.     

Compatibilized polyethylene—thermally reduced graphene nanocomposites: Interfacial interactions and hyperspectral mapping for component distribution

Ethylene-co-acrylic acid (EAA) and ethylene-co-methacrylic acid ionomer (EMAZ) copolymers were used as compatibilizers for polyethylene-graphene nanocomposites generated by melt mixing. At 5 wt% content, the EAA compatibilizer enhanced the tensile modulus of PE by 40 % and shear modulus by >300 % (1 rad/s) due to efficient dispersion of graphene platelets which helped in effective stress transfer. These also resulted in enhanced thermal stability for PE-EAA-G nanocomposite as compared to nanocomposite with EMAZ. The properties of the nanocomposites were significantly better than the conventional nanocomposites based on layered silicate materials. Mapping of the component distribution in the nanocomposites was demonstrated by using hyperspectral imaging. The nanocomposite with EAA exhibited higher extent of spectral signal mixing due to better mixing of filler and compatibilizer in PE matrix. On the other hand, nanocomposite with EMAZ had no spectral mixing as the components did not mix optimally with each other. The DSC thermogram for this nanocomposite also exhibited a small shoulder at low temperature probably due to immiscibility of the compatibilizer with the matrix polymer. The hyperspectral imaging and mapping was thus demonstrated to be a useful method for determination of component distribution in complex nanocomposite systems.     

The effect of various compatibilizers on thermal,mechanical, and morphological properties of polystyrene/polypropylene blends

The effects of various compatibilizers on thermal, mechanical and morphological properties of 50/50 polypropylene/polystyrene blends were investigated. Various compatibilizers, polystyrene-(ethylene/butylenes/ styrene) (SEBS), ethylene vinyl acetate (EVA), polystyrene-butylene rubber (SBR) and blend of compatibilizers SEBS/PP-g-MAH, EVA/PP-g-MAH, and SBR/PP-g-MAH were used. Differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray scattering, scanning electron microscopy, microhardness, and Izod impact strength were adopted. It was found that the influence of various compatibilizers was appeared on all the properties studied. The properties of the blends compatibilized with SEBS, EVA, and SBR are very distinct from those of blends compatibilized with blend of compatibilizers. Results show that compatibilized blends with the blend of compatibilizers EVA/PP-g-MAH, SBR/PP-g-MAH, and SEBS/PP-g-MAH or SBR were relatively more stable than the uncompatibilized blend and blend compatibilized with SEBS or EVA. The compatibilizer does not only reduce the interfacial tension or increase the phase interfacial adhesion between the immiscible polymers, but greatly affects the degree of crystallinity of blends.

     

Microhardness and thermal stability of compatibilized LDPE/PA6 blends

Microhardness tests, water absorption and thermogravimetric measurements have been performed on blends of low density polyethylene (LDPE) with different molar mass and polyamide 6 (PA6) compatibilized with 2 pph poly(ethylene-co-acrylic acid) (Escor 5001 by Exxon). The negative deviation of Vickers microhardness from the additivity has been interpreted by changes in the crystallinity of the blend components. The hardness values of the compatibilized blends that are lower than those of the corresponding uncompatibilized blends have been explained by the decrease of the degree of crystallinity of PA6 phase in the presence of Escor. The molar mass of LDPE almost does not influence on the hardness values. The lower water absorption of the compatibilized blends, caused by the formation of a copolymer between PA6 and the compatibilizer leads to microhardness values of the wet compatibilized blends higher than those of the corresponding uncompatibilized blends. The thermogravimetric measurements demonstrate that the thermal stability of blends increases in the presence of 2 pph Escor 5001. The results confirm the compatibilizing efficiency of Escor 5001 towards LDPE/PA6 blends in a wide composition range.     

Influence of gamma irradiation on high density polyethylene/ethylene‐vinyl acetate/clay nanocomposites

The study of high density polyethylene (HDPE)/ethylene‐vinyl acetate (EVA)/and organically‐modified montmorillonite (OMT) nanocomposites prepared by melt intercalation followed by exposure to gamma‐rays have been carried out. The morphology and properties of the nanocomposites were studied using X‐ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and cone calorimetry. The purpose of the study focuses on the influence of gamma irradiation on the morphology, thermal stability and flammability properties of the nanocomposites. XRD studies and TEM images verified that the ordered intercalated nanomorphology of the nanocomposites was not disturbed by gamma irradiation. TGA data showed that the nano‐dispersion of clay throughout the polymer inhibited the irradiation degradation of HDPE/EVA blend, which led to the nanocomposites exhibiting superior irradiation‐resistant properties than that of the pure blend. Cone calorimetry results indicated that the improvement in heat release rate (HRR) for irradiated HDPE/EVA blend was suppressed efficiently when clay was present. Increasing clay loading from 2 to 10% was beneficial by improving the flammability properties of the nanocomposites, but promoted a rapid increase in the sub‐peak HRR at high irradiation dose level. Copyright © 2004 John Wiley & Sons, Ltd.     

Toughening of ethylene-propylene random copolymer/clay nanocomposites: Comparison of different compatibilizers

Ethylene/propylene-random-copolymer(PPR)/clay nanocomposites were prepared by two-stage melt blending. Four types of compatibilizers,including an ethylene-octene copolymer grafted maleic anhydride(POE-g-MA) and three maleic-anhydride-grafted polypropylenes(PP-g-MA) with different melt flow indexes(MFI),were used to improve the dispersion of organic clay in matrix.On the other hand,the effects of organic montmorillonite(OMMT) content on the nanocomposite structure in terms of clay dispersion in PPR matrix,thermal behavior and tensile properties were also studied. The X-ray diffraction(XRD) and transmission electron microscopy(TEM) results show that the organic clay layers are mainly intercalated and partially exfoliated in the nanocomposites.Moreover,a PP-g-MA compatibilizer(compatibilizer B) having high MFI can greatly increase the interlayer spacing of the clay as compared with other compatibilizers.With the introduction of compatibilizer D(POE-g-MA),most of the clays are dispersed into the POE phase,and the shape of the dispersed OMMT appears elliptic,which differs from the strip of PP-g-MA.Compared with virgin PPR,the Young’s modulus of the nanocomposite evidently increases when a compatibilizer C(PP-g-MA) with medium MFI is used.For the nanocomposites with compatibilizer B and C,their crystallinities(X_c) increase as compared with that of the virgin PPR. Furthermore,the increase of OMMT loadings presents little effect on the melt temperature(T_m) of the PPR/OMMT nanocomposites,and slight effect on their crystallization temperature(T_c).Only compatibilizer B can lead to a marked increases in crystallinity and T_c of the nanocomposite when the OMMT content is 2 wt%.     

Intercalated linear low density polyethylene (LLDPE)/clay nanocomposites prepared with oxidized polyethylene as a new type compatibilizer: Structural, mechanical and barrier properties

In this study, the use of low molecular weight oxidized polyethylenes (OxPE) with different molecular weight and acid number as a new type of compatibilizer in low density polyethylene (LLDPE)/org-clay nanocomposite preparation was examined. Nanocomposites having 5 phr (part per hundred) org-clay were prepared by melt processing. The effect of compatibilizer polarity and clay dispersion on the thermal, mechanical and barrier properties of the nanocomposites was investigated. It was observed that oxidized polyethylenes created a strong interfacial interaction between the clay layers and polymer phase based on the analysis of the linear viscoelastic behavior of the samples by small amplitude oscillatory rheometry. We showed that physical performance of the nanocomposites is not only affected by clay dispersion but also both melt viscosity and polarity of the oxidized polyethylene compatibilizers. It was found that oxygen permeability values of the nanocomposite samples prepared with the oxidized polyethylenes were lower than that of a sample prepared with conventional compatibilizer, maleic anhydride grafted polyethylene (PE-g-MA).     

Morphology and properties of polypropylene/ethylene–octene copolymer/clay nanocomposites with double compatibilizers

The influence of nanoclay on the morphology and properties of the polypropylene (PP)/ethylene–octene block copolymer (EOC) blend with double compatibilizers of maleated PP (PP‐g‐MA) and maleated EOC (EOC‐g‐MA) was investigated and compared with the nanocomposites containing either PP‐g‐MA or EOC‐g‐MA as a compatibilizer. X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy were utilized for morphological characterization in conjunction with dynamic mechanical thermal analysis, mechanical testing, and rheological evaluation of these nanocomposites. The results suggested that in the nanocomposite including both compatibilizers of PP‐g‐MA and EOC‐g‐MA, clay was dispersed as a mixed structure of intercalation and exfoliation in both phases of the polymer blend. Comparing the mechanical properties of the studied nanocomposite with nanocomposites of PP/EOC/PP‐g‐MA/clay and PP/EOC/EOC‐g‐MA/clay also indicated that the nanocomposite containing mixed compatibilizers displayed higher tensile modulus, tensile strength, and complex viscosity because of the better dispersion of clay in both phases. The results also confirmed the increased structural stability and reduced dispersed phase size of PP/EOC/PP‐g‐MA/EOC‐g‐MA blend in the presence of clay that proposed the compatibilization role of clay in this nanocomposite. Copyright © 2014 John Wiley & Sons, Ltd.     

Future trends of plastic bottle recycling: Compatibilization of PET and PLA

We improved the recyclability of mixed poly(ethylene-terephthalate) (PET) and poly(lactic acid) (PLA) bottle waste. We made uncompatibilized and compatibilized PET/PLA blends of different weight ratios with a twin-screw extruder. Then, we analysed the mechanical properties, the miscibility and the thermal stability of the blends with and without compatibilizers. From the change in intrinsic viscosities (IV), we concluded that different reactions occur between the polymer chains due to the compatibilizers. We observed that when ethylene-butyl acrylate-glycidyl methacrylate (E-BA-GMA) as compatibilizer was added, the blends became tougher; elongation at break and Charpy impact strength increased, but Young's modulus of the blends decreased. In addition, the compatibilizers improved the thermal stability of the blends and this may have been caused by a number of mechanisms.     

Morphology and thermal properties of a PC/PE blend with reactive compatibilization

Reactive compatibilization of immiscible polymers is becoming increasingly important and hence a representative study of a polycarbonate/high density polyethylene (PC/HDPE) system is the focus of this paper. A grafted copolymer PC‐graft‐ethylene‐co‐acrylic acid (PC‐graft‐EAA) was generated as a compatibilizer in situ during processing operation by ester and acid reaction between PC and ethylene‐acrylic acid (EAA) in the presence of the catalyst dibutyl tin oxide (DBTO). As the polyethylene (PE) matrix does not play any part during the synthesis of the copolymer and since PC and EAA are also immiscible, to simplify the system, the influence of this copolymer formation at the interface between PC and EAA on rheological properties, phase morphology, and crystallization behavior for EAA/PC binary blends was first studied. The equilibrium torque increased with the DBTO content increasing in EAA/PC blends on Haake torque rheometer, indicating the in situ formation of the graft copolymer. Scanning electron microscopy (SEM) studies of cryogenically fractured surfaces showed a significant change at the distribution and dispersion of the dispersed phase in the presence of DBTO, compared with the EAA/PC blend without the catalyst. Differential scanning calorimetry (DSC) studies suggested that the heat of fusion of the EAA phase in PC/EAA blends with or without DBTO reduced with the formation of the copolymer compared with pure EAA. Then morphological studies and crystallization behavior of the uncompatibilized and compatibilized blends of PC/PE were studied as functions of EAA phase concentration and DBTO content. Morphological observations in PC/PE blends also revealed that on increasing the EAA content or adding the catalyst DBTO, the number of microvoids was reduced and the interface was intensive as compared to the uncompatibilized PC/PE blends. Crystallization studies indicated that PE crystallized at its bulk crystallization temperature. The degree of crystallinity of PE phase in PC/PE/EAA blends was also reduced with the addition of EAA and DBTO compared to the uncompatibilized blends of PC/PE, indicating the decrease in the degree of crystallinity was more in the presence of PC‐graft‐EAA. Copyright © 2007 John Wiley & Sons, Ltd.     

利用~1H-NMR研究HDPE/PET/EVA共混体系的酯交换反应

本文在选用EVA作为HDPE/PET共混体系增容剂的基础上 ,通过双螺杆反应挤出熔融加工过程 ,促使EVA侧基上的酯基官能团与PET组分主链上的酯基在适当催化剂———有机金属化合物存在的条件下发生酯交换反应 .1H NMR结果表明 ,酯交换反应的产生在共混体系界面原位形成接枝或交联的PET EVA共聚物 ,且主要是以生成接枝共聚物的反应为主 .     

Preparation and characterization of UV-cured acrylic nanocomposites based on modified organophilic montmorillonites

UV-cured nanocomposites have been prepared through the photopolymerization of the acrylic resin BEMA (Bisphenol A ethoxylate dimethacrylate) added with organophifilic montmorillonites. Two types of commercially available nanoclays namely Cloisite 30B and Cloisite Na⁺ were further modified with organic compatibilizers (dodecylsuccinic anhydride, octadecylamine, octadecanoic alcohol and octadecanoic acid) in order to increase their basal spacing and improve the dispersion in the acrylic matrix. The modification with the organic compatibilizers determined an increase of the interlayer distance, as revealed by XRD (X-Ray Diffraction) analysis. The different types of the modified nanoclays were then dispersed in BEMA monomer at 5% m/m concentration and UV-cured in order to prepare the nanocomposites. XRD measurements performed on the nanocomposites showed a slight increase of the interlayer distance indicating the formation of intercalated structures. The photopolymerization reaction was monitored through real-time FT-IR (Fourier Transform Infrared Spectroscopy) in order to check any influence of the nanofillers on the cure kinetics. The nanocomposites were investigated by DSC (Differential Scanning Calorimetry) and TG (Thermogravimetric) analyses and compared to the neat UV-cured resin. The presence of the nanofillers did not influence the glass transition temperature (T_g) of the acrylic resin; in addition an increase of the thermal stability in air of the nanocomposites was evidenced through TG analysis.     

The role of interfacial compatibilization upon the microstructure and electrical conductivity threshold in polypropylene/expanded graphite nanocomposites

Attempts have been made to evaluate the effect of interface and degree of interfacial interaction upon electrical conductivity threshold in polypropylene/expanded graphite (PP/EG) nanocomposites, and dispersion state of graphite nanosheets. For this purpose, maleic anhydride grafted polypropylene (PPgMA) and maleic anhydride grafted EPDM (EPDMgMA) were used as compatibilizer. Nanocomposite samples containing 1–5 vol% of EG were prepared by melt mixing method using laboratory scale internal mixer. Characterization was carried out by using X‐ray diffraction (XRD), differential scanning calorimeter (DSC), thermo‐gravimetric analysis (TGA), scanning electron microscope (SEM), transmission electron microscope (TEM), and rheo‐mechanical spectroscopy (RMS). The conductivity measurements were carried out by using four point probe method according to ASTM D991. Results showed that the conductivity threshold is controlled by the extent of interfacial interaction between PP and EG. So, better conductivity was obtained using PPgMA as compatibilizer which causes higher level of interaction between PP and EG, and therefore better dispersion of the EG nanolayers in the polymer matrix. On the other hand, high levels of compatibilizers, especially EPDMgMA, caused formation of separated aggregates of EG shelled with the compatibilizer, which results in the reduction of conductivity of the nanocomposites. This finding has been verified by SEM, RMS, and conductivity measurements. Effects of EG nanolayers on crystalline structure and thermal decomposition temperature of the nanocomposites have also been investigated by DSC and TGA, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

纳米CaCO_3/相容剂/PP中的界面相互作用研究

采用不同相容剂(PP-g-MAH、POE-g-MAH和EVA-g-MAH)制备了不同界面相互作用的纳米CaCO3(CC)/相容剂/PP体系,研究了相容剂/PP和相容剂/CC界面相互作用对PP/CC的结晶形态、结晶行为、熔融特性和力学性能的影响.观察到PP/CC界面相互作用提高PP结晶温度和PP/CC的模量和冲击强度,但降低了屈服强度.相容剂/CC界面相互作用进一步提高了PP/CC的结晶温度.PP/相容剂界面相互作用取决于PP与相容剂相容性.PP/PP-g-MAH相容性高有利于提高PP/CC的异相成核作用和PP/CC屈服强度和模量,但降低冲击强度.PP/POE-g-MAH部分相容对相容剂/CC界面的异相成核作用、PP/CC屈服强度和模量影响不大,可明显提高冲击强度.但PP/EVA-g-MAH不相容导致PP/CC冲击强度明显降低.