A facile and easily industrialized approach for preparing highly dispersed MMT/polymer nanocomposites is developed by combining the latex compounding method and a spray‐drying process. Clay particles are successfully delaminated into layers, and layer re‐stacking is effectively prevented. HR‐TEM and XRD results confirm that MMT layers achieve exfoliated or nearly exfoliated dispersion in both MMT/styrene‐butadiene rubber and MMT/PS nanocomposites. Compared with melt‐blended MMT/SBR composites, MMT/SBR nanocomposites prepared by this new strategy exhibit extremely high dynamic modulus.
Summary: To improve the interfacial interaction in MMT‐SBR nanocomposites, one type of UOAC was introduced to in‐situ modified MMT before latex compounding with SBR. The influence of the UOAC/MMT ratio on the structure and properties of MMT/SBR nanocomposites were carefully studied by XRD, TEM, and mechanical testing. It was found that through the in‐situ organic modification, a rubber‐intercalated structure of MMT was obtained in the nanocomposites, and the amount of rubber‐intercalated structure strongly depended on the UOAC/MMT ratio. The tensile strength of MMT‐SBR nanocomposites was enhanced dramatically from 4 to 18 MPa by in‐situ organic modification of MMT.
Stress‐strain diagram of SBR/clay nanocomposites. 相似文献
Fully exfoliated PS/clay nanocomposites were prepared via FRP in dispersion. Na‐MMT clay was pre‐modified using MPTMS before being used in a dispersion polymerization process. The objective of this study was to determine the impact of the clay concentrations on the monomer conversion, the polymer molecular weight, and the morphology and thermal stability of the nanocomposites prepared via dispersion polymerization. DLS and SEM revealed that the particle size decreased and became more uniformly distributed with increasing clay loading. XRD and TEM revealed that nanocomposites at low clay loading yielded exfoliated structures, while intercalated structures were obtained at higher clay loading.
Two novel cationic RAFT agents, PCDBAB and DCTBAB, were anchored onto MMT clay to yield RAFT‐MMT clays. The RAFT‐MMT clays were then dispersed in styrene where thermal self‐initiation polymerization of styrene to give rise to exfoliated PS/clay nanocomposites occurred. The RAFT agents anchored onto the clay layers successfully controlled the polymerization process resulting in controlled molecular masses and narrow polydispersity indices. The nanocomposites prepared showed enhanced thermal stability, which was a function of the clay loading, clay morphology, and slightly on molecular mass.
Summary: It is a big challenge to improve simultaneously both the flame retardancy and the melt‐dripping resistance of polymeric materials such as PET. In this paper, a novel intumescent flame retardant, DPSPB, was synthesized and blended with copolyester PET‐co‐DDP/O‐MMT nanocomposites, which were synthesized by polycondensation of TPA, EG, DDP, and O‐MMT. The resulting PET‐co‐DDP/O‐MMT/DPSPB nanocomposites exhibit very good flame retardance and dripping resistance, e.g., LOI = 29, UL‐94 V‐0. SEM, XRD, and XPS were used to investigate the relationships between the structures and properties of the composites. It is proved that DPSPB offers excellent protection for the structure of nanocomposites, which is responsible for the good anti‐dripping properties of the nanocomposites.
Residues of copolyesters after combustion: common nanocomposite residue of PDMN (left) and the novel nanocomposite residue of PDMN/DPSPB (right). 相似文献
PSU/MMT nanocomposites are prepared by dispersing MMT nanolayers in a PSU matrix via in situ photoinduced crosslinking polymerization. Intercalated methacrylate‐functionalized MMT and polysulfone dimethacrylate macromonomer are synthesized independently by esterification. In situ photoinduced crosslinking of the intercalated monomer and the PSU macromonomer in the silicate layers leads to nanocomposites that are formed by individually dispersing inorganic silica nanolayers in the polymer matrix. The morphology of the nanocomposites is investigated by XRD and TEM, which suggests the random dispersion of silicate layers in the PSU matrix. TGA results confirm that the thermal stability and char yield of PSU/MMT nanocomposites increases with the increase of clay loading.
Summary: Styrene‐isoprene‐butadiene rubber/montmorillonite nanocomposites were synthesized by the addition of toluene into clay and living anionic polymerization. These silicate layers (B‐M) were exfoliated within 30 min after polymerization initiation, whereas the layers in the nanocomposites prepared without using toluene (A‐M) were only partially exfoliated and not well‐dispersed in the matrix. The results of TEM and X‐ray diffraction revealed disperse silicates and a strong interaction between the terpolymer matrix and clay in the B‐M nanocomposites. The B‐M‐exfoliated nanocomposites exhibited higher decomposition and glass transition temperatures, storage moduli, tensile strengths and elongations at the break than those of the pure terpolymer and A‐M. With an organophilic montmorillonite (OMMT) content of 3 wt.‐%, the exfoliated nanocomposite exhibited the best thermal stability and mechanical properties. In addition, GPC and 1H NMR results showed that the introduction of OMMT caused a slight increase in the of terpolymer, but hardly affected the microstructure of the terpolymer independent of the preparation method. Thus, the addition of toluene plays an important role in enhancing the dispersion of OMMT, which leads to the improvement of the structure and properties of the B‐M nanocomposites.
A novel model is presented for predicting the phase selective filler localization in an equilibrium state for ternary rubber blends of SBR, NBR, and NR. It is based on surface tension data of the rubber components and the filler. Phase‐selective filler localization in ternary rubber blends is determined experimentally by means of FTIR spectroscopy on the basis of the wetting concept. It is found that by preparation of ternary blends with certain silica loadings, pre‐mixed in each blend phase using the masterbatch technology, silica transfer processes between blend phases take place until the equilibrium filler distribution is reached. The sequence of the silica transfer processes can be explained by taking into consideration the formation of a phase‐in‐phase morphology of the ternary blend.
Summary: An original direct melt extrusion processing of nylon 6/clay nanocomposites was reported based on pristine (Na+‐based) montmorillonite as well as a simple approach using a typical two‐screw extruder. By the application of intercalation agents as the thermodynamic assistants, this method is as an appropriate procedure for industrialized manufacture together with much lowered production cost. Interestingly enough, the synergistic effects of montmorillonite with other inorganic particulates was observed for the first time here.
X‐ray diffraction patterns of pristine MMT and nylon 6/MMT composites with grouped intercalation agents. 相似文献
To improve the physical properties of poly(trimethylene terephthalate) (PTT), a series of nanocomposites based on PTT and exfoliated graphite (EG) are prepared via melt compounding and their structures, thermal stabilities, mechanical, and electrical properties are studied. XRD and SEM show that graphene nanosheets are well dispersed in the PTT matrix without forming crystalline aggregates even at high EG content. Thermal stability and dynamic mechanical moduli of the nanocomposites are substantially improved by EG addition, and a pronounced increase in electrical volume resistivity from an insulator to almost a semiconductor is observed with increasing EG content. The electrical percolation threshold of the nanocomposites is found to be formed at the EG concentration between 3.0 and 5.0 wt.‐%.
PA6 nanocomposite films with different nanoclay dispersion degrees are prepared by melt compounding and cast extrusion. The dispersion of the MMT platelets (homogeneity and degree of exfoliation) is evaluated qualitatively by TEM and quantitatively by rheology and NMR; it ranges from microcomposites to highly exfoliated nanocomposites. Compared to neat PA6, the optical properties (clarity, gloss, haze) are worse for the microcomposites and better for the nanocomposites. The mechanical properties depend strongly on the exfoliation level. Better exfoliation leads to higher stiffness. The strain at break decreases compared to neat PA6 films even in the case of highly exfoliated nanocomposites films. At low MMT content, the microcomposite has a higher ductility than well exfoliated nanocomposites films.
To understand the effect of the percolated clay network structure formed by the exfoliated clay layers in nanocomposites, the clay network structure in nylon‐6‐based nanocomposites is characterized using TEM and FFT analyses. A MMT volume fraction between 0.013 and 0.014 is the percolation threshold for strong network formation. The volume spanning MMT network leads to a very high flow activation energy as compared with that of neat nylon 6, resulting in the pseudo‐solid like response under molten state in N6CNs. A canonical NVT‐MD simulation was conducted in the system made up by nylon 6 molecules/Si(OH)4 molecules. The formation of the strong interfacial interaction between nylon 6 molecules and Si(OH)4 molecules induced by OH groups is suggested.
Hyperbranched PEI and urea‐functionalized PEI amphiphiles are employed as additives in NBR compounding. Polarity design governing phase separation, PEI migration and PEI‐mediated self‐healing of NBR is demonstrated. The compatibility of PEI and NBR decreases with increasing molecular weight of PEI and with decreasing degree of substitution. Microphase‐separated NBR/PEI blends are prepared with varying PEI molecular architectures. Thermal self‐healing of NBR/PEI is monitored by applying tests combining crack initiation with annealing under compression. All PEI additives show complete crack‐healing upon annealing at 100 °C for 12 h. In contrast to neat NBR, the NBR/PEI‐2 blend afforded a self‐healing efficiency of 44% after cutting and re‐joining by compression and annealing.
Poly(ε‐caprolactone) nanocomposites, PCLOC25A and PCLOC30B, with organoclays (OCs) having nonpolar and polar organic modifiers, respectively, were prepared by the melt mixing method and additional heat treatment. WXRD analysis revealed that both nanocomposites were exfoliated, irrespective of the OC polarity. However, WXRD failed to show the degree of exfoliation of the nanocomposites, because the d001 peaks disappeared. Thus, dynamic mechanical analysis (DMA) was carried out to compare the degree of exfoliation of the PCL nanocomposites. From DMA, PCLOC30B showed higher elasticity, storage moduli, viscosity, and activation energy than PCLOC25A, indicating that PCLOC30B had a more exfoliated structure than PCLOC25A. This is due to the polar interaction in PCLOC30B, as verified by the plots of aT versus temperature. Thus, it was confirmed that DMA provides an alternative approach to evaluating the degree of exfoliation of nanocomposites.
A “green” processing method, dual‐melt extrusion, was used to prepare thermoplastic starch/montmorillonite nanocomposites without organic reactions in the solution. XRD demonstrates that sorbitol enlarged the interlayer distance of MMT during the first step. MMT‐sorbitol, formamide and starch were used to obtain TPS/MMT nanocomposites in the second step. XRD and TEM reveal that TPS intercalated the layers of MMT. With increasing MMT content, improvements in thermal stability, tensile strength, Young's modulus and energy break, and a slight decrease of elongation at break, appeared. The effect of water content on the tensile strength and elongation at break was also studied.
PIB/MMT nanocomposite films containing UHP are fabricated and characterized for potential applications in wounded‐skin oxygen delivery and/or tooth cleaning. The UHP acts as a source of oxygen, whereas MMT creates a pathway for water molecules penetrating the film in order to generate a controlled release of H2O2 molecules. Most UHP particles are uniformly dispersed throughout the entire thickness of the films. DMA measurements indicate that the material retains most of its structural characteristics when exposed to water. SEM measurements show that no interface exists between individually spread multilayers. SAXS measurements indicate that the clay platelets are predominantly exfoliated and randomly oriented within the film. Controlled release of H2O2 is found over a period of ≈90–100 min.
Summary: Binary and ternary blends of PVC mixed with α‐methylstyrene/acrylonitrile‐butadiene‐styrene copolymer (AMS‐ABS) and ethylene/vinyl acetate/carbon monoxide terpolymer (EVA‐CO) are investigated, with the aim to obtain a new PVC based material with an improved heat distortion temperature and good processability. Dynamic Mechanical Thermal Analysis (DMTA) reveals that ternary PVC/AMS‐ABS/EVA‐CO blends exhibit two glass transition temperatures: the lower Tg corresponds to a PVC/EVA‐CO phase and the higher one to a PVC/AMS‐ABS phase. An analysis of PVC respective interactions with AMS‐ABS and EVA‐CO leads to assert that the distribution of PVC in the ternary PVC/AMS‐ABS/EVA‐CO system is basically controlled by the binary immiscible blend composition, taken as Φ AMS‐ABS/Φ EVA‐CO ratio. The inclusion of AMS‐ABS and EVA‐CO to form ternary blends based on PVC, allows to improve heat distortion temperature (owed to the presence of AMS‐ABS), maintaining a low viscosity in the molten state, due to the plasticizing effect of EVA‐CO.
Viscosity function obtained at T = 170 °C from extrusion capillary measurements. 相似文献
The traditional PA 6.6 production route, i.e. solution melt polymerization followed by extrusion, is applied to the in situ intercalation of PA 6.6/clay nanocomposites. Organoclays of different types are tested and the derived nanocomposites are thoroughly characterized in terms of molecular weight, thermal properties and morphology. Reaction acceleration is found in the presence of fully exchanged organoclays, which is attributed to a chain extension mechanism based on clay SiOH groups. Analysis of the nanocomposites' nanostructure indicates that the applied solution melt polymerization process results in some flocculation of the tested organoclays, which is improved in some cases after extrusion and leads to partially exfoliated nanocomposites.
Summary: One of the important applications of PUEs is as damping materials such as the spring aids used in cars, which need to have excellent cyclic fatigue durability. Our results show that the fatigue durability of PUE can be significantly improved by incorporating organoclay. The best result was obtained for 3 wt.‐% organoclay, and the fatigue durability of the PUE‐organoclay nanocomposites was increased on an average to about ten times that of pure PUE. The addition of organoclay resulted in a reduction in the size of hard‐segment domains. The organoclay nanoplatelets show reversible deformation behaviour during a fatigue test confirmed by WAXD and computer simulation. These could benefit in stopping crack propagation, releasing concentrated stress and giving rise to fatigue resistance.
Schematic diagram of d‐spacing on nanoscale change during stretching. 相似文献
SBS nanocomposites based on a SBS triblock copolymer containing different weight fractions of a commercial Cloisite 20A organoclay were prepared by melt‐processing. Extensive electron microscopy as well as WAXS and static tensile and tensile creep tests were used to evaluate the resulting morphological and mechanical properties of the nanocomposites. The nanocomposite morphology is characterized by a combination of intercalated and partly exfoliated clay platelets with occasional clay aggregates present at higher clay contents; nanocomposite features that are reflected by the results of both the static tensile as well as the tensile creep tests at room temperature. For this particular thermoplastic elastomer nanocomposite system, well dispersed nanoclays lead to an enhanced stiffness and ductility; effects that induce promising improvements in nanocomposite creep performance.
