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1.
To have a better insight into the effect of interaction between polymer matrix and clay on the properties of nanocomposite, poly(methyl methacrylate)/clay nanocomposites were prepared by a heterocoagulation method. Using a reactive cationic emulsifier, methacryloyloxyethyltrimethyl ammonium chloride (METAC), a strong polymer–clay interaction was obtained with the advantage of keeping a consistent polymer matrix property. X‐ray diffraction and transmission electronic microscopy indicated an exfoliated structure in nanocomposites. The glass transition temperature (Tg) of the nanocomposites was measured by DSC and DMA. The DMA results showed that with a strong interaction, PMMA–METAC nanocomposite showed a 20 °C enhancement in glass transition temperature (Tg), whereas a slight increase in Tg was observed for PMMA–cetyl trimethylammonium bromide (CTAB)/clay nanocomposite with a weak interaction. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 733–738, 2010  相似文献   

2.
Polystyrene (PS)/clay nanocomposites were prepared with two different new intercalation organophilic clays, the phosphonium salt (APP) and the ammonium 4‐(4‐adamantylphenoxy)‐1‐butanamine (APB) salts, by emulsion polymerization technique. X‐ray diffraction and transmission electron microscopy were performed to characterize the layered structures of APB‐ and APP‐treated polymer–clay nanocomposites, and both resulted in exfoliated structures. Molecular weights of PS obtained from these nanocomposites are slightly lower than the virgin PS formed under similar polymerization conditions. Coefficient of thermal expansion showed approximately a 44–55% decrease for APB‐ and APP‐intercalated clay nanocomposites relative to the pure PS. Both Tg and thermal decomposition temperature of the PS component in the nanocomposite are higher than the virgin PS, implying that the presence of clay is able to enhance thermal stabilities of the PS. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1781–1787, 2007  相似文献   

3.
X‐ray diffraction methods and differential scanning calorimetry thermal analysis have been used to investigate the structural changes of syndiotactic polystyrene (sPS)/clay nanocomposites. sPS/clay nanocomposites have been prepared by the mixing of sPS polymer solutions with organically modified montmorillonite. X‐ray diffraction data and differential scanning calorimetry results indicate that the dominating crystal forms and their relative fractions in sPS and sPS/clay nanocomposites are different for various premelting temperatures (Tmax's). Higher Tmax's favor the formation of the thermodynamically more stable β‐crystalline form, and its relative fraction has been obtained from the X‐ray diffraction data in the range of 11.5–13°. The intensity of the X‐ray diffraction data in the range of 11.5–13° decreases as the thickness of sPS/clay nanocomposites decreases from 150 to 20 μm. At the same time, the intensity of the X‐ray data in the range of 6–7° becomes sharper as the thickness of sPS/clay nanocomposites decreases. The calculation ratio based on the peak intensities at 6.2 and 6.8° for sPS/clay nanocomposites of equal thickness and crystallinity in the pure β and α forms has also been determined in this study. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1730–1738, 2003  相似文献   

4.
The in situ polymerization of the anilinium‐intercalated synthetic mica clay can easily result in an intercalated polyaniline (PANI)/clay nanocomposite. The FT‐IR spectra demonstrated a significant shift for ν(C? N) at 1292 cm?1 of the templated polymerized and intercalated PANI molecules. A red shift of λmax for PANI was found from UV–vis spectra. The intercalated PANI also expanded the clay basal spacing seen from WAXD patterns. The degradation rate and temperature of the nanocomposites were found to alleviate and increase compared to neat PANI, respectively. The microscopic examinations including TEM, SEM, and AFM pictures of the nanocomposite demonstrated an entirely different and more compatible morphology. Conductivity of nanocomposite gradually increased with PANI and apparent increase was found when intercalated PANI content reached 40.6 wt %, the possible percolation threshold. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1800–1809, 2008  相似文献   

5.
Montmorillonite (MMT) was modified with the acidified cocamidopropyl betaine (CAB) and the resulting organo‐montmorillonite (O‐MMT) was dispersed in an epoxy/methyl tetrahydrophthalic anhydride system to form epoxy nanocomposites. The intercalation and exfoliation behavior of the epoxy nanocomposites were examined by X‐ray diffraction and transmission electron microscopy. The curing behavior and thermal property were investigated by in situ Fourier transform infrared spectroscopy and DSC, respectively. The results showed that MMT could be highly intercalated by acidified CAB, and O‐MMT could be easily dispersed in epoxy resin to form intercalated/exfoliated epoxy nanocomposites. When the O‐MMT loading was lower than 8 phr (relative to 100 phr resin), exfoliated nanocomposites were achieved. The glass‐transition temperatures (Tg's) of the exfoliated nanocomposite were 20 °C higher than that of the neat resin. At higher O‐MMT loading, partial exfoliation was achieved, and those samples possessed moderately higher Tg's as compared with the neat resin. O‐MMT showed an obviously catalytic nature toward the curing of epoxy resin. The curing rate of the epoxy compound increased with O‐MMT loading. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1192–1198, 2004  相似文献   

6.
This investigation reports the preparation of tailor‐made poly(2‐ethylhexyl acrylate) (PEHA) prepared via in situ living radical polymerization in the presence of layered silicates and characterization of this polymer/clay nanocomposite. Being a low Tg (?65 °C) material, PEHA has very good film formation property for which it is used in paints, adhesives, and coating applications. 2‐Ethylhexyl acrylate was polymerized at 90 °C using CuBr and Cu(0) as catalyst in combination with N,N,N′,N″,N″‐pentamethyl diethylenetriamine (PMDETA) as ligand. A tremendous enhancement in reaction rate and polymerization data was achieved when acetone was added as additive to increase the efficiency of the catalyst system. PEHA/clay nanocomposite was prepared at 90 °C using CuBr as catalyst in combination with PMDETA as ligand. Different types of clay with same loading were also used to study the effect on reaction rate. The molecular weight (Mn) and polydispersity index of the prepared nanocomposites were characterized by size exclusion chromatography. The active end group of the polymer chain was analyzed by 1H NMR analysis and by chain extension experiment. Polymer/clay interaction was studied by Fourier Transform Infrared spectrometry and wide‐angle X‐ray diffraction analyses. Distribution of clay in the polymer matrix was studied by the transmission electron microscopy. Thermogravimetric analysis showed that thermal stability of PEHA/clay nanocomposite increases on addition of nanoclay. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

7.
Poly(styrene‐co‐butyl acrylate) copolymers were prepared by free‐radical random copolymerization of styrene and butyl acrylate in emulsion in the presence of 10% of surface‐modified sodium montmorillonite (Na‐MMT). The objective of this work was to evaluate the impact of the clay organic modifier in terms of its chemical structure, its degree of interaction within the clay galleries surface, and its ability to copolymerize with monomers, on the morphology and properties of the final nanocomposite prepared. Na‐MMT was modified using different organic modifiers, namely: sodium 1‐allyloxy‐2‐hydroxypropyl (Cops), 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS), N‐isopropylacrylamide (NIPA), and sodium 11‐methacryloyloxy‐undecan‐1‐yl sulfate (MET), respectively. The morphology and properties of the nanocomposites obtained were found to be dependant on the clay organic modifier. X‐ray diffraction (XRD) and transmission electron microscopy indicated that, nanocomposites at 10% clay loading with Cops‐, NIPA‐, and MET‐modified clays, yielded intercalated to partially exfoliated structures, whereas AMPS‐modified clay gave a nanocomposite with a fully exfoliated structure. All polymer–clay nanocomposites were found to be more thermally stable than neat poly(S‐co‐BA) as were determined by TGA. However, nanocomposites with intercalated structures exhibited greater thermal stability relative to fully exfoliated ones. Furthermore, nanocomposites with exfoliated structures exhibited higher storage moduli (GI) than partially exfoliated once, whereas intercalated structure showed the lowest GI values. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3619–3628, 2008  相似文献   

8.
A new class of polybenzoxazine/montmorillonite (PBz/MMT) nanocomposites has been prepared by the in situ polymerization of the typical fluid benzoxazine monomer, 3‐pentyl‐5‐ol‐3,4‐dihydro‐1,3‐benzoxazine, with intercalated benzoxazine MMT clay. A pyridine‐substituted benzoxazine was first synthesized and quaternized by 11‐bromo‐1‐undecanol and then used for ion exchange reaction with sodium ions in MMT to obtain intercalated benzoxazine clay. Finally, this organomodified clay was dispersed in the fluid benzoxazine monomers at different loading degrees to conduct the in situ thermal ring‐opening polymerization. Polymerization through the interlayer galleries of the clay led to the PBz/MMT nanocomposite formation. The morphologies of the nanocomposites were investigated by both X‐ray diffraction and transmission electron microscopic techniques, which suggested the partially exfoliated/intercalated structures in the PBz matrix. Results of thermogravimetric analysis confirmed that the thermal stability and char yield of PBz nanocomposites increased with the increase of clay content. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

9.
Synthesis of poly(styrene‐block‐tetrahydrofuran) (PSt‐b‐PTHF) block copolymer on the surfaces of intercalated and exfoliated silicate (clay) layers by mechanistic transformation was described. First, the polystyrene/montmorillonite (PSt/MMT) nanocomposite was synthesized by in situ atom transfer radical polymerization (ATRP) from initiator moieties immobilized within the silicate galleries of the clay particles. Transmission electron microscopy (TEM) analysis showed the existence of both intercalated and exfoliated structures in the nanocomposite. Then, the PSt‐b‐PTHF/MMT nanocomposite was prepared by mechanistic transformation from ATRP to cationic ring opening polymerization (CROP). The TGA thermogram of the PSt‐b‐PTHF/MMT nanocomposite has two decomposition stages corresponding to PTHF and PSt segments. All nanocomposites exhibit enhanced thermal stabilities compared with the virgin polymer segments. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2190–2197, 2009  相似文献   

10.
The thermophysical and mechanical properties of a nanocomposite material composed of amine‐cured diglycidyl ether of bisphenol A (DGEBA) reinforced with organomontmorillonite clay are reported. The storage modulus at 100 °C, which was above the glass‐transition temperature (Tg), increased approximately 350% with the addition of 10 wt % (6.0 vol %) of clay. Below the Tg, the storage modulus at 30 °C increased 50% relative to the value of unfilled epoxy. It was determined that the Tg linearly increased as a function of clay volume percent. The tensile modulus of epoxy at room temperature increased approximately 50% with the addition of 10 wt % of clay. The reinforcing effect of the organoclay nanoplatelets is discussed with respect to the Tandon–Weng and Halpin–Tsai models. A pseudoinclusion model is proposed to describe the behavior of randomly oriented, uniformly dispersed platelets in nanocomposite materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4391–4400, 2004  相似文献   

11.
The continuous‐multilayer model introduced in our previous study for the Tg behavior of thin films is adapted to nanocomposite systems. Tg enhancement in both thin films and nanocomposites with attractive interfacial interactions can be explained by the same model. Various shapes of nanoparticles are proposed to rationalize the adaptation of the one‐dimensional model for the Tg behavior of thin film to three‐dimensional system such as nanocomposite. The tendency of predicted Tg enhancements in poly(methyl methacrylate) and P2VP nanocomposites with silica particles are qualitatively fit to experimental data in literatures. For the further quantitative fitting, the model is partially modified with the consideration for other factors affecting Tg deviation in nanocomposite. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2281–2287, 2009  相似文献   

12.
The exfoliated montmorillonite (MMT) nanoplatelets tended to re‐stack with each other after casting the MMT/poly(methylacrylate‐co‐methylmethacrylate) P(MA‐co‐MMA) latex solutions fabricated by soap‐free emulsion polymerization into films as revealed by X‐ray diffraction and transmission electron microscopy. As the content of MMT was increased from 0 to 20 wt %, the Tg measured by differential scanning calorimetry was slightly decreased from 19.2 to 17.2 °C, whereas that measured by dynamic mechanical analysis was increased from 22 to 32 °C, indicating that the local motion of polymer segments has been retarded by MMT nanoplatelets. Besides, the elongated elliptical voids appeared during stretching of 1 wt % MMT/P(MA‐co‐MMA) film to cracking also illustrated the pinning effect provided by the exfoliated MMT. As the content of MMT was increased more than 10 wt %, the mechanical behavior of MMT/P(MA‐co‐MMA) nanocomposite films was changed from ductile to brittle nature with significant increase of Young's modulus and tensile strength owing to the restacking of exfoliated MMT nanoplatelets. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1064–1069, 2010  相似文献   

13.
The nonisothermal cold crystallization behavior of intercalated polylactide (PLA)/clay nanocomposites (PLACNs) was studied using differential scanning calorimetry, polarized optical microscope, X‐ray diffractometer, dynamic mechanical thermal analysis, and Fourier transform infrared spectrometer. The results show that both the cold crystallization temperature (Tcc) and melting point (Tm) of PLA matrix decreases monotonously with increasing of clay loadings, accompanied by the decreasing degree of crystallinity (Xc%) at the low heating rates (≤5 °C/min). However, the Xc% of PLACNs presents a remarkable increase at the high heating rate of 10 °C/min in contrast to that of neat PLA. The crystallization kinetics was then analyzed by the Avrami, Jezioney, Ozawa, Mo, Kissinger and Lauritzen–Hoffman kinetic models. It can be concluded that at the low heating rate, the cold crystallization of both the neat PLA and nanocomposites proceeds by regime III kinetics. The nucleation effect of clay promote the crystallization to some extent, while the impeding effect of clay results in the decrease of crystallization rate with increasing of clay loadings. At the high heating rate of 10 °C/min, crystallization proceeds mainly by regime II kinetics. Thus, the formation of much more incomplete crystals in the PLACNs with high clay loadings due to the dominant multiple nucleations mechanism in regime II, may have primary contribution to the lower crystallization kinetics, also as a result to the higher degree of crystallinity and lower melting point in contrast to that of neat PLA. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1100–1113, 2007  相似文献   

14.
Polybenzoxazine (PBZ), which has a structure similar to that of phenolic resin, is formed through the thermal self‐curing of benzoxazine, that is through a heterocyclic ring opening reaction that requires no catalyst and releases no condensation byproducts. We have used the solvent blending method to prepare PBZ/clay nanocomposites possessing various clay contents. We synthesized a monofunctional benzoxazine monomer (MBM) and then treated the clay with this intercalation agent. The results of X‐ray diffraction (XRD) analysis indicated that MBM intercalated into the galleries of the clay; the nanocomposite possessed an exfoliated structure at 3% clay content. To better understand the curing kinetics of the PBZ/clay nanocomposites, we performed dynamic and isothermal differential scanning calorimetry (DSC) measurements. We describe the thermodynamics of the curing process, using all three of the Kissinger, Ozawa, and Kamal models. The Kissinger and Ozawa methods gave fairly close results for the calculated activation energies, which decreased upon increasing the clay content. The Kamal method, based on an autocatalytic model, suggested a total reaction order of between 2.4 and 2.8. The glass transition temperature (Tg) decreased upon increasing the clay content. Thermogravimetric analysis (TGA) indicated that the nanocomposites have higher decomposition temperatures than does the pristine PBZ; this finding suggests an enhancement in their thermal stability. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 347–358, 2006  相似文献   

15.
Novel fluorinated coating containing well‐dispersed silicate nanolayers is successfully produced via in‐situ free radical polymerization of 2,2,2‐trifluoroethyl methacrylate in the presence of vinylbenzyl‐functionalized montmorillonite with different loading. The organic modification of sodium montmorillonite is achieved through an ion exchange reaction with triphenylvinylbenzylphosphonium chloride as surfactant prepared before use by reaction with vinylbenyl chloride and phosphine. The following in‐situ polymerization in the presence of organomodified clay leads to fluorinated nanocomposites with of partially exfoliated and intercalated morphologies, as determined via XRD and TEM analysis. The nanoscale dispersion of clay layers is also evidenced by thermal analysis; a moderate decrease of the glass transition temperature about 2–8 °C compared to their virgin PMATRIF and an improvement of their thermal stability as evidenced by TGA. The wettability of the nanocomposite films is also studied by contact angle measurements with water. The incorporation of organomodified clays not only increases the hydrophobicity of the fluorinated polymers but also improves the surface properties of obtained nanocomposites. Compared the virgin homopolymer, the mechanical properties of the nanocomposites are reduced by addition of organomodifed clay at temperature from 30 to 60 °C, whereas this trend is gradually decreased at higher temperature. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 411–418  相似文献   

16.
The relationships between the microstructure and the fracture behavior of three polymer/clay nanocomposites were studied. Two different polymer matrices were chosen, namely polyamide‐6 and polyethylene (compatibilized with PE‐g‐MA or PE‐g‐PEo), to reach very different clay dispersion states. The microstructure was characterized in terms of polymer crystallinity, orientation of the polymer crystalline lamellae, clay dispersion state, and orientation of the clay tactoids. The mechanical behavior was characterized by tensile tests. The essential work of fracture (EWF) concept was used to determine the fracture behavior of the nanocomposites. Both tensile and EWF tests were performed in two perpendicular directions, namely longitudinal and transversal. It is shown that the fracture behaviors of the matrices mainly depend on the polymer crystalline lamellae orientation. For the nanocomposites, the relationships between the matrix orientation, the clay dispersion states, the values of the EWF parameters (we and βwp), and their anisotropy are discussed. The results show that the lower the average clay tactoid thickness, the lower is the decrease of fracture performance for the nanocomposite and the more consumed energy as longer the path of the crack. Besides, a linear dependence of the anisotropy of the EWF parameters of the nanocomposites on the average clay aspect ratio is found. The more exfoliated the structure is, the less pronounced the anisotropy of the EWF parameters. Interestingly, it is thought that the average clay aspect ratio is the parameter representing the clay dispersion state that governs the fracture anisotropy of the nanocomposites (as the elastic properties determined by tensile tests). © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1820–1836, 2008  相似文献   

17.
The processing of nanocomposite materials composed of amine‐cured diglycidyl ether of bisphenol A (DGEBA) reinforced with organomontmorillonite clay is reported. A novel sample preparation scheme was used to process the modified clay in the glassy epoxy network, resulting in nanocomposites where the clay was both exfoliated and intercalated by the epoxy network. The processing scheme involves sonication of the constituent materials in a solvent, followed by solvent extraction to generate a composite with homogeneous dispersions of the nanoclay. Fourier transform infrared spectroscopy (FTIR) and Fourier transform (FT‐)Raman spectroscopy confirmed that the chemical structure of the epoxy network was not affected by the use of solvents in this processing scheme. The glass‐transition temperature, Tg, linearly increased with an increased weight ratio of the nanoclay. The microstructure of clay nanoplatelets in the composites was observed with transmission electron microscopy (TEM), wide‐angle X‐ray scattering (WAXS), and small‐angle X‐ray scattering (SAXS). It was found that the clay nanoplatelets were well‐dispersed, and were intercalated as well as exfoliated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4384–4390, 2004  相似文献   

18.
This article reports the synthesis and the properties of novel thermoplastic elastomers of A‐B‐A type triblock copolymer structure, where the hard segment A is poly(l ‐lactide) (PLLA) and the soft segment B is poly(ε‐caprolactone‐stat‐d ,l ‐lactide) (P(CL‐stat‐DLLA)). The P(CL‐stat‐DLLA) block with DLLA content of 30 mol % was applied because of its amorphous nature and low glass transition temperature (Tg = approximately ?40 °C). Successive polymerization of l ‐lactide afforded PLLA‐block‐P(CL‐stat‐DLLA)‐block‐PLLAs, which exhibited melting temperature (Tm = approximately 150 °C) for the crystalline PLLA segments and still low Tg (approximately ?30 °C) of the soft segments. The triblock copolymers showed very high elongation at break up to approximately 2800% and elastic properties. The corresponding d ‐triblock copolymers, PDLA‐block‐P(CL‐stat‐DLLA)‐block‐PDLAs (PDLA = poly(d ‐lactide)) were also prepared with the same procedure using d ‐lactide in place of l ‐lactide. When the PLLA‐block‐P(CL‐stat‐DLLA)‐block‐PLLA was blended with PDLA‐block‐P(CL‐stat‐DLLA)‐block‐PDLA, stereocomplex crystals were formed to enhance their Tm as well as tensile properties. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 489–495  相似文献   

19.
We synthesized organosoluble, thermoplastic elastomer/clay nanocomposites by making a jelly like solution of ethylene vinyl acetate containing 28% vinyl acetate (EVA‐28) and blending it with organomodified montmorillonite. Sodium montmorillonite (Na+‐MMT) was made organophilic by the intercalation of dodecyl ammonium ions. X‐ray diffraction patterns of Na+‐MMT and its corresponding organomodified dodecyl ammonium ion intercalated montmorillonite (12Me‐MMT) showed an increase in the interlayer spacing from 11.94 to 15.78 Å. However, X‐ray diffraction patterns of the thermoplastic elastomer and its hybrids with organomodified clay contents up to 6 wt % exhibited the disappearance of basal reflection peaks within an angle range of 3–10°, supporting the formation of a delaminated configuration. A hybrid containing 8 wt % 12Me‐MMT revealed a small hump within an angle range of 5–6° because of the aggregation of silicate layers in the EVA‐28 matrix. A transmission electron microscopy image of the same hybrid showed 3–5‐nm 12Me‐MMT particles dispersed in the thermoplastic elastomer matrix; that is, it led to the formation of nanocomposites or molecular‐level composites with a delaminated configuration. The formation of nanocomposites was reflected through the unexpected improvement of thermal and mechanical properties; for example, the tensile strength of a nanocomposite containing only 4 wt % organophilic clay was doubled in comparison with that of pure EVA‐28, and the thermal stability of the same nanocomposite was higher by about 34 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2065–2072, 2002  相似文献   

20.
《中国化学会会志》2017,64(12):1399-1407
Here we investigate a new type of highly flame retardant poly(methyl methacrylate) (PMMA) nanocomposite by bulk polymerization of methyl methacrylate (MMA) in the presence of organic nano carboncapsule (OCNC/NCNC)‐incorporated modified montmorillonites (CL120, CL42). The morphology of the modified clay was confirmed by X‐ray diffraction (XRD), and Fourier transform infrared (FT‐IR) spectroscopy was used to identify the functional groups in the clay. The nano morphological characterization of the clay in the PMMA matrix was confirmed by XRD and transmission electron microscopy (TEM). The thermal and mechanical properties of the PMMA nanocomposites were investigated by thermogravimetry and dynamic mechanical analysis, respectively. PMMA containing organo nano carboncapsule‐doped CL42 modified cocoamphodipropionate (K2) (P‐O‐CL42) could achieve very high thermal stability compared to pristine PMMA. The 5% thermal decomposition temperature (T 5d) increased by 63.2°C. Storage modulus of PMMA nanocomposites measured by DMA analysis. An enhancement of storage modulus and significant reduction in the peak heat release (PHR) rate were observed in the almost all PMMA nanocomposites as compared to pristine PMMA. Moreover, these results suggest that PMMA nanocomposites can have potential applications in the building industry and the medical field.  相似文献   

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