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1.
Purification of montmorillonite rich bentonite followed by surface modification using organic salts was performed. The bentonite was purified by sedimentation and then surface modified by ion exchange using alkyl‐ and aryl‐based phosphonium salts. The thermal stability, morphology, melt flow, and mechanical properties of the poly(ethylene terephthalate) (PET) nanocomposites prepared with these organoclays were studied with and without using a reactive elastomeric compatibilizer. TEM results showed that the alkyl based organoclay exhibited better dispersion and thus, higher tensile strength and elongation at break in the PET/organoclay/elastomer ternary nanocomposites than the aryl‐based organoclay did. The notched Charpy impact strength of PET increased from 2.9 to 4.7 kJ m?2 and 3.4 kJ m?2 for alkyl and aryl phosphonium organoclay‐based ternary nanocomposites, respectively. Upon compounding PET with alkyl and aryl phosphonium organoclays, the onset decomposition temperature of PET increased from 413°C to 420°C and 424°C, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

2.
F. Chavarria 《Polymer》2006,47(22):7760-7773
A series of alkyl ammonium/MMT organoclays were carefully selected to explore structure-property relationships for thermoplastic polyurethane (TPU) nanocomposites prepared by melt processing. Each organoclay was melt-blended with a medium-hardness, ester-based TPU, while a more limited number of organoclays was blended with a high-hardness, ether-based TPU. Wide-angle X-ray scattering, transmission electron microscopy, particle analysis, and stress-strain behavior were used to examine the effects of organoclay structure and TPU chemical structure on morphology and mechanical properties. Specifically, the following were observed: (a) one long alkyl tail on the ammonium ion rather than two, (b) hydroxy ethyl groups on the amine rather than methyl groups, and (c) a longer alkyl tail as opposed to a shorter one leads to higher clay dispersion and stiffness for medium-hardness TPU nanocomposites. Overall, the organoclay containing hydroxy ethyl functional groups produces the best dispersion of organoclay particles and the highest matrix reinforcement, while the one containing two alkyl tails produces the poorest. The two TPU's exhibit similar trends with regard to the effect of organoclay structure. The high-hardness TPU nanocomposites showed a slightly higher number of particles and clay dispersion. The organoclay structure trends are analogous to what has been observed for nylon 6-based nanocomposites; this suggests that polar polymers like polyamides, and apparently polyurethanes, have a relatively good affinity for the polar clay surface; and in the case of polyurethanes, the high affinity of the matrix for the hydroxy ethyl functional groups in the organoclay aids clay dispersion and exfoliation.  相似文献   

3.
Novel organoclays were synthesized by several kinds of phosphonium cations to improve the dispersibility in matrix resin of composites and accelerate the curing of matrix resin. The possibility of the application for epoxy/clay nanocomposites and the thermal, mechanical, and adhesive properties were investigated. Furthermore, the structures and morphologies of the epoxy/clay nanocomposites were evaluated by transmission electron microscopy. Consequently, the corporation of organoclays with different types of phosphonium cations into the epoxy matrix led to different morphologies of the organoclay particles, and then the distribution changes of silicate layers in the epoxy resin influenced the physical properties of the nanocomposites. When high‐reactive phosphonium cations with epoxy groups were adopted, the clay particles were well exfoliated and dispersed. The epoxy/clay nanocomposite realized the high glass‐transition temperature (Tg) and low coefficient of thermal expansion (CTE) in comparison with those of neat epoxy resin. On the other hand, in the case of low‐reactive phoshonium cations, the dispersion states of clay particles were intercalated but not exfoliated. The intercalated clay did not influence the Tg and CTE of the nanocomposite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

4.
Rhutesh K. Shah 《Polymer》2006,47(11):4075-4084
Melt processed nanocomposites were formed from low-density polyethylene, LDPE, and organoclays over a wide range of processing temperatures. These composites show limited exfoliation, and hence, their X-ray analysis reveals a distinct peak corresponding to the interplatelet distances in the unexfoliated clay galleries. The degradation of the quaternary ammonium surfactant of the organoclay in these systems was characterized by examining the change in the position of these peaks as a function of the melt processing temperature. Upon degradation, the mass of the surfactant within the clay galleries decreases, which causes the platelets to collapse and shifts the WAXS peak to lower d-spacings. The results of the WAXS analysis suggest that a significant portion of the surfactant is lost from the organoclays when the melt processing temperature is increased from 180 to 200 °C or higher. The extent of surfactant degradation in these composites was determined to be independent of the organoclay content. Organoclay degradation appears to limit the extent of exfoliation or dispersion in LDPE as revealed by stress-strain analyses of nanocomposites processed at different temperatures. The amount of surfactant lost during thermogravimetric analysis of various organoclays indicates that surfactants with multiple alkyl tails have greater thermal stability than those with a single alkyl tail. A comparison of the mass of surfactant lost during melt processing of nanocomposites and during thermogravimetric analysis of organoclays (in the absence of polymer) indicated that at a given time, a larger surfactant loss from the clay galleries occurs during extrusion than during the TGA experiment. This is attributed to the greater ease with which the degradation products (predominantly α-olefins) are solubilized in polyethylene for the composites as opposed to evaporated from the organoclay during TGA.  相似文献   

5.
Youngjae Yoo 《Polymer》2008,49(17):3795-3804
An amorphous polyamide (a-PA) and three organoclays, M3(HT)1, M2(HT)2 and (HE)2M1T1, were melt processed to explore the effect of the organoclay structure on the extent of exfoliation and properties of these nanocomposites. Wide angle X-ray scattering, transmission electron microscopy, and stress-strain behavior were used to determine the degree of exfoliation of the nanocomposites. For quantitative assessment of the structure of the nanocomposites, a detailed particle analysis was made to provide various averages of the clay dimensions and aspect ratio. The results evaluated from different methods were generally consistent with each other. Nanocomposites based on the organoclays with one alkyl tail and hydroxyl ethyl groups gave well-exfoliated structures and high matrix reinforcement while nanocomposites from two-tailed organoclay contain a considerable concentration of intercalated stacks. Nanocomposites from the organoclays with one alkyl tail showed slightly better exfoliation and matrix reinforcement than those from the organoclays with hydroxyl ethyl groups. The organoclay structure trends for a-PA are analogous to what has been observed for nylon 6; this suggests that a-PA, like nylon 6, has good affinity for the pristine silicate surface of the clay leading to better exfoliation and enhanced mechanical properties with one-tailed organoclay than multiple-tailed organoclay. Furthermore, heat distortion temperatures were predicted from the dynamic mechanical properties of nanocomposites.  相似文献   

6.
Polyethylene‐based ternary nanocomposites were prepared with different clay structures, obtained by the modification of purified Resadiye bentonite as the reinforcement, a random terpolymer of ethylene, butyl acrylate, and maleic anhydride with the trade name Lotader3210 as the compatibilizer, and linear low‐density polyethylene (LLDPE) as the polymer matrix in an intensive batch mixer. The quaternary ammonium/phosphonium salts used for the modification of bentonite were dimethyldioctadecyl ammonium (DMDA) chloride (Cl), tetrakisdecyl ammonium (TKA) bromide (Br), and tributylhexadecyl phosphonium (TBHP) Br. The effects of the physical properties and structure of the organoclay on the clay dispersion were studied at different clay contents (2 and 5 wt %) and at a compatibilizer/organoclay ratio of 2.5. The extent of organoclay dispersion was determined by X‐ray diffraction (XRD) and was verified by transmission electron microscopy (TEM), mechanical testing, and rheological analysis. XRD analysis showed that the nanocomposite with the organoclay DMDA contained intercalated silicate layers, as also verified by TEM. The TEM analysis of the nanocomposites with TBHP exhibited intercalated/partially exfoliated clay dispersion. TKA, with a crowded alkyl environment, sheltered and hindered the intercalation of polymer chains through the silicate layers. In comparison to pure LLDPE, nanocomposites with a 33–41% higher Young's modulus, 16–9% higher tensile strength, and 75–144% higher elongation at break were produced with DMDA and TBHP, respectively (at 5 wt % organoclay). The storage modulus increased by 807–1393%, and the dynamic viscosity increased by 196–339% with respect to pure LLDPE at low frequencies for the samples with DMDA and TBHP (at 5 wt % organoclay). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

7.
In the current study, in order to prepare poly(ethylene terephthalate) (PET)/organoclay nanocomposite fibers, a slurry‐compounding method (SCM) was applied and compared to conventional melt‐compounding method (CMM) in terms of the dispersion of organoclays and the performance of the spun and or drawn fibers. The organoclays were synthesized by using three different alkyl phosphonium salts and compared with commercially available alkyl ammonium‐modified organoclays in terms of thermal stability and basal spacing. It was found that the alkyl phosphonium salts exhibited higher thermal stability and basal spacing with respect to commercial alkyl ammonium organoclays. Among them, tributylhexadecylphosphonium bromide resulted in superior properties; therefore, it was used to prepare the nanocomposite PET fibers. The organoclay content of 0.1–1 wt% was taken as the material parameter. It was demonstrated that the SCM yielded better dispersion of organoclays with respect to CMM. The drawn nanocomposite fibers prepared via SCM exhibited improved tensile strength and modulus in comparison to the neat‐PET. The maximum tensile properties for fibers were obtained at 0.5% organoclay loading in SCM. The thermal properties and the percentage of crystallinity were investigated by differential scanning calorimetry analysis. In addition, Fourier transform infrared spectroscopy was utilized to obtain the percentage of crystallinity of the fibers. POLYM. COMPOS., 34:887–896, 2013. © 2013 Society of Plastics Engineers  相似文献   

8.
S. Hotta 《Polymer》2004,45(22):7639-7654
Polyethylene-clay nanocomposites were prepared by melt compounding various combinations of a maleic anhydride grafted linear low density polyethylene (LLDPE-g-MA), a linear low density polyethylene (LLDPE), and two organoclays. The two types of organoclay were selected to show the effect of the number of alkyl groups attached to the nitrogen of the organic modifier on exfoliation and improvement of mechanical properties. Nanocomposites derived from the organoclay having two alkyl tails, M2(HT)2, exhibited better dispersion and improvement of mechanical properties than nanocomposites based on the organoclay having one alkyl tail M3(HT)1. This result is the opposite of what is observed for nylon-6 nanocomposites. In addition, the rheological properties and gas permeability of the nanocomposites derived from the organoclay having two alkyl tails, M2(HT)2 were investigated. Both melt viscosity and melt tension (melt strength) increased with increased content of clay (MMT) and LLDPE-g-MA. Gas permeability was decreased by the addition of MMT.  相似文献   

9.
Lili Cui  Yefim Brun  P.J. Yoon 《Polymer》2009,50(11):2492-5343
This paper explores the possible advantages of the more thermally stable imidazolium-based organoclay over a more conventional ammonium-based organoclay for facilitating exfoliation and minimizing polymer matrix degradation in melt blended polyamide 6 (PA-6) and polycarbonate (PC) nanocomposites. The thermal stability of the two organoclays was evaluated by TGA analyses. The extent of clay exfoliation was judged by analysis of the morphology and tensile modulus of these nanocomposites formed using a DSM Microcompounder, while the extent of color formation and molecular weight change were used to evaluate polymer matrix degradation. For PA-6 and PC nanocomposites, the use of the imidazolium organoclay only produced slight differences in both exfoliation and molecular weight change, although the imidazolium organoclay is remarkably more thermally stable than the ammonium organoclay.  相似文献   

10.
The vulcanization behavior and mechanical properties of clay/fluoroelastomer nanocomposites produced by melt‐mixing of Dyneon FPO 3741 (a terpolymer of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene) with 10 phr of unmodified montmorillonite (CloisiteNA) or di(hydrogenated tallow‐alkyl) dimethyl ammonium‐modified montmorillonites (Cloisite15A and Cloisite20A) were studied. The properties of clay/FKM nanocomposites were compared with composites prepared using 10 and 30 phr of carbon black. The effects of clay surfactant and surfactant concentration on the vulcanization behavior, mechanical, and dynamical properties of peroxide cured composites were studied. XRD results of cured composites showed a decrease in d‐spacing and indicated deintercalation of the clays after the vulcanization process. It was also found that organoclays retard the FKM peroxide vulcanization process. Significantly, higher maximum torque on vulcanization was obtained with organoclays versus unmodified clay and carbon black. Although the morphologies of organoclay/FKM nanocomposites studied by XRD and TEM suggest similar intercalated/exfoliated structures, the organoclay with the lowest concentration of surfactant (95 meq/100 g clay) resulted in the highest increase in torque, modulus, hardness, and tear strength in the clay/FKM nanocomposites. It was also found that organoclays can increase both the hydrodynamic reinforcement and hysteresis loss of FKM nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

11.
A carefully selected series of organic amine salts were ion exchanged with sodium montmorillonite to form organoclays varying in amine structure or exchange level relative to the clay. Each organoclay was melt-mixed with a high molecular grade of nylon 6 (HMW) using a twin screw extruder; some organoclays were also mixed with a low molecular grade of nylon 6 (LMW). Wide angle X-ray scattering, transmission electron microscopy, and stress-strain behavior were used to evaluate the effect of amine structure on nanocomposite morphology and physical properties. Three surfactant structural issues were found to significantly affect nanocomposite morphology and properties in the case of the HMW nylon 6: decreasing the number of long alkyl tails from two to one tallows, use of methyl rather than hydroxy-ethyl groups, and use of an equivalent amount of surfactant with the montmorillonite, as opposed to adding excess, lead to greater extents of silicate platelet exfoliation, increased moduli, higher yield strengths, and lower elongation at break. LMW nanocomposites exhibited similar surfactant structure-nanocomposite behavior. Overall, nanocomposites based on HMW nylon 6 exhibited higher extents of platelet exfoliation and better mechanical properties than nanocomposites formed from the LMW polyamide, regardless of the organoclay used. This trend is attributed to the higher melt viscosity and consequently the higher shear stresses generated during melt processing.  相似文献   

12.
Sodium montmorillonite (MMT) was modified with several organic phosphonium salts. Organoclays with water soluble surfactants were prepared by the traditional cation exchange reaction. An alternative procedure was used to prepare organoclays with water insoluble salts. The effect of chemical composition and molecular weight of the salts on the thermal stability and basal spacing were evaluated. The phosphonium montmorillonites exhibit higher thermal stability than conventional ammonium organoclays. The basal spacing is generally larger for the phosphonium montmorillonites. These properties provide a good potential for the use of phosphonium organoclays for the synthesis of polymer/clay nanocomposites by melt processing.  相似文献   

13.
采用3种有机改性剂分别对无机粘土进行改性,然后通过熔融共混制得了天然橡胶(NR)/有机粘土纳米复合材料。通过热重分析(TGA)和X-射线衍射(XRD)表征了粘土的有机改性程度。用扫描电镜(SEM)和流变手段表征了纳米复合材料的形态和流变特性。结果表明,含有2条长烷基链和含有2个羟乙基官能团的改性剂对粘土具有更好的改性效果,但由于羟乙基官能团具有强极性,与非极性的NR相容性差,导致有机粘土在基体中大量团聚。各纳米复合材料的储能模量在低频区表现出不同程度的"二次平台"或者"上翘",在时间扫描过程中随着时间变化表现出不同的结构演变。  相似文献   

14.
P.J. YoonD.L. Hunter  D.R. Paul 《Polymer》2003,44(18):5341-5354
Polycarbonate nanocomposites were prepared using two different twin screw extruders from a series of organoclays based on sodium montmorillonite, with somewhat high iron content, exchanged with various amine surfactants. It seems that a longer residence time and/or broader residence time distribution are more effective for dispersing the organoclay. The effects of organoclay structure on color formation during melt processing were quantified using colorimeter and UV-Vis spectroscopy techniques. Color formation in the PC nanocomposites depends on the type of organoclay and the type of pristine clay employed. Double bonds in the hydrocarbon tail of the surfactants lead to more darkly colored materials than saturated surfactants. The most severe color was observed when using a surfactant containing hydroxy-ethyl groups and a hydrocarbon tail derived from tallow. Molecular weight degradation of the PC matrix during melt processing produces phenolic end groups which were tracked by UV-Vis spectroscopy. Greater dispersion of the clay generally led to higher reduction in molecular weight due to the increased surface area of clay exposed; however, for color, the situation is far more complex. Hydroxy-ethyl groups and tallow unit on the surfactant lead to more degradation. A selected series of organoclays based on synthetic clay Laponite® and calcium montmorillonite from Texas (TX-MMT) were also prepared to explore the effects of the clay structure. Laponite® and TX-MMT produce less color formation in PC nanocomposites than montmorillonite probably due to lower content of iron. Dynamic rheological properties support the trends of molecular weight degradation and dispersion of clay.  相似文献   

15.
Novel biodegradable aliphatic polyester (APES)/organoclay nanocomposites were prepared through melt intercalation method. Two kinds of organoclays, Cloisite 30B and Cloisite 10A with different ammonium cations located in the silicate gallery, were chosen for the nanocomposites preparation. The dispersion of the silicate layers in the APES hybrids was characterized by using X-ray diffraction (XRD) and transmission electron microscopy (TEM). Tensile properties and the biodegradability of the APES/organoclay nanocomposites were also studied. APES/Cloisite 30B hybrids showed higher degree of intercalation than APES/Cloisite 10A hybrids due to the strong hydrogen bonding interaction between APES and hydroxyl group in the gallery of Cloisite 30B silicate layers. This leads to higher tensile properties and lower biodegradability for APES/Cloisite 30B hybrids than for the APES/Cloisite 10A hybrids.  相似文献   

16.
Polymer‐clay nanocomposites are a newer class of flame retardant materials of interest due to their balance of mechanical, thermal and flammability properties. Much more work has been done with natural clays than with synthetic clays for nanocomposite flammability applications. There are advantages and disadvantages to both natural and synthetic clay use in a nanocomposite, and some of these, both fundamental and practical, will be discussed in this paper. To compare natural and synthetic clays in regards to polymer flammability, two clays were used. The natural clay was a US mined and refined montmorillonite, while the synthetic clay was a fluorinated synthetic mica. These two clays were used as inorganic clays for control experiments in polystyrene, and then converted into an organoclay by ion exchange with an alkyl ammonium salt. The organoclays were used to synthesize polystyrene nanocomposites by melt compounding. Each of the formulations was analysed by X‐ray diffraction (XRD), thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). Flammability performance was measured by cone calorimeter. The data from the experiments show that the synthetic clay does slightly better at reducing the heat release rate (HRR) than the natural clay. However, all the samples, including the inorganic clay polystyrene microcomposites, showed a decreased time to ignition, with the actual nanocomposites showing the most marked decrease. The reason for this is postulated to be related to the thermal instability of the organoclay (via the quaternary alkyl ammonium). An additional experiment using a more thermally stable organoclay showed a time to ignition identical to that of the base polymer. Finally, it was shown that while polymer‐clay nanocomposites (either synthetic or natural clay based) greatly reduce the HRR of a material, making it more fire safe, they do not provide ignition resistance by themselves, at least, at practical loadings. Specifically, the cone calorimeter HRR curve data appear to support that these nanocomposites continue to burn once ignited, rather than self‐extinguish. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

17.
In this study, the preparation of organoclays via a new process using supercritical carbon dioxide is described. This method turns out to be very efficient with various surfactants, in particular nonwater-soluble alkylphosphonium salts. The influence of the surfactant as well as of the clay nature on the thermal stability of the organoclay is evaluated by thermogravimetric analysis. Phosphonium-based montmorillonites are up to 90 °C more stable than ammonium-based montmorillonites. Moreover, the use of hectorite adds another 40 °C of thermal stability to the phosphonium-modified clays. These organomodified clays have been melt-blended with polyamide 6 and morphology as well as fire properties of the nanocomposites are discussed, in terms of influence of the stability of organoclays. For the first time, comparison of nanocomposites based on clay organomodified by ammonium and phosphonium salts of the very same structure is reported.  相似文献   

18.
Alkyl pyridinium, 1‐vinyl alkyl imidazolium, 1,3‐dialkyl imidazolium, and tetraalkyl phosphonium bromides were successfully used as intercalants for the preparation of highly thermally stable organophilic montmorillonites. Nanocomposites of linear low density polyethylene (LLDPE) and linear low density polyethylene grafted with maleic anhydride (LLDPE/LLDPE‐g‐MAH) were prepared from those organoclays. The micro‐ and nano‐dispersions were analyzed through X‐ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM): intercalation and/or partial exfoliation were found to occur only for formulations based on organoclays having an initial basal distance higher than 20 Å, suggesting the existence of a critical interfoliar distance for the delamination of silicate layers in a noninteracting polymer matrix. The properties of the nanocomposites were analyzed through differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and oscillatory rheometry. The dynamic crystallization of LLDPE was not significantly affected by the presence of clay. TGA in oxidative atmosphere proved to be very sensitive to the dispersion state of the organoclay: the thermal stability was drastically enhanced for intercalated and partially exfoliated formulations. However, the inherent thermal stability of the organoclay did not appear to influence significantly the overall thermal stability of the composite in the range of temperatures investigated (160–230°C). POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.  相似文献   

19.
The role of the type of organic modifier used with montmorillonite (MMT) on the formation of polymer/clay nanocomposites in the melt compounding process was investigated. Various organoclays including primary [12‐aminolauric acid (12ALA)], secondary [dioctylamine (DOA)], tertiary [trioctylamine (TOA)], and two commercial quaternary (Cloisite 30B and 20A) MMTs were melt compounded with carefully selected polymers including polypropylene, polystyrene, styrene–acrylonitrile copolymer, poly(methyl methacrylate), poly(vinylidene fluoride), and acrylonitrile–butadiene copolymer (NBR). X‐ray diffraction and transmission electron microscopy characterizations confirmed that the two quaternary ammonium organoclay (Cloisite 30B and 20A) have superior compatibility compared to the primary (12ALA), secondary (DOA), and tertiary (TOA) ammonium organoclay. DOA and TOA can form polymer/clay nanocomposites only with the most polar polymer (NBR). Cloisite Na+ and 12ALA can not form nanocomposite with any polymers. The large organic surface area of the quaternary ammonium organoclay could be the reason of the best compatibility with polar polymers. It is estimated that long alkyl ammonium chains of organic modifier can spread over the clay surface more effectively than short alkyl chains. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1888–1896, 2005  相似文献   

20.
Preparation of thermally stable recycled PET‐organoclay nanocomposites with improved processing and mechanical properties is a challenging task from the environmental as well as industrial and commercial point of view. In this work, both modification of sodium‐type montmorillonite with 1,2‐dimethyl‐3‐octadecyl‐1H‐imidazol‐3‐ium chloride and additional treatment with [3‐(glycidyloxy)propyl]trimethoxysilane was performed. Thermal stability of the organoclays and nanocomposites prepared by melt compounding was tested by thermogravimetric analysis, differential scanning calorimetry, and melt rheology. In comparison with the organoclays modified with quaternary ammonium compounds, the prepared clays showed substantial suppression of matrix degradation during melt mixing. The increase in interlayer distance of silicate platelets and homogeneity of dispersions in the recycled and virgin PET matrices have been evaluated by transmission electron microscopy and wide‐angle X‐ray scattering. The higher degree of delamination in the nanocomposites filled with imidazole organoclays was in a good agreement with improved rheological characteristics and led to significant enhancement in mechanical properties and thermal stability. A difference in structure (besides the level of delamination and homogeneity of silicate platelets) of recycled versus virgin PET nanocomposites was detected by X‐ray diffraction patterns. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

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