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1.
Exfoliated and intercalated polyurethane (PU) nanocomposites were prepared by in situ polymerization of polyol/organoclay mixture, chain extender and diisocyanate. Wide‐angle X‐ray diffraction and transmission electron microscopy confirmed an exfoliated structure for clay C30B and an intercalated structure for C20A in polyol and PU. The realization of exfoliated state for clay C30B in polyol during the mixing stage can provide an effective approach for controlling the exfoliation degrees by adjusting the content of intercalated and exfoliated organoclay C20A and C30B before polymerization. The effect of exfoliation degree on the mechanical and viscoelastic properties of PU was investigated. The addition of organoclay improved the tensile strength, modulus and elongation, but the hysteresis loss ratio and relaxation rate increased, and the relaxation time distribution became broad. The effect of organoclay on PU properties varied with the hard segment content. By increasing the exfoliation degree, the tensile strength and modulus increased, whereas the elongation decreased. The exfoliated PU nanocomposite had a lower relaxation rate and hysteresis loss ratio than the intercalated PU. Copyright © 2005 Society of Chemical Industry  相似文献   

2.
Biodegradable poly(ester)urethane (PU) elastomer‐based nanocomposite films incorporated with organically modified nanoclay were prepared with melt‐extrusion compounding followed by a casting film process. These films were intended for application as biodegradable food packaging films, with their enhanced gas barrier, mechanical, and thermal properties and good flexibility. From both X‐ray diffraction measurements and transmission electron microscopy observations, the coexistence of intercalated tactoids and exfoliated silicate layers in the compounded PU/clay nanocomposite films was confirmed. In addition, the morphology exhibited a clay dispersion state in the matrix and was influenced by the incorporated nanoclay content. The effects of the nanoclay loading level on the thermal, mechanical, and barrier properties of the compounded nanocomposites were also investigated. As a result, it was revealed that the addition of nanoclay up to a certain level resulted in a remarkable improvement in the thermal properties in terms of thermal stability and the degree of thermal shrinkage; mechanical properties, including dynamic storage modulus and tensile modulus; and oxygen/water‐vapor barrier properties of the nanocomposite films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

3.
Preparation and characterization of nylon 11/organoclay nanocomposites   总被引:1,自引:0,他引:1  
Tianxi Liu 《Polymer》2003,44(12):3529-3535
Nylon 11/organoclay nanocomposites have been successfully prepared by melt-compounding. X-ray diffraction and transmission electron microscopy indicate the formation of the exfoliated nanocomposites at low clay concentrations (less than 4 wt%) and a mixture of exfoliated and intercalated nanocomposites at higher clay contents. Thermogravimetric and dynamic mechanical analyses as well as tensile tests show that the degree of dispersion of nanoclay within polymer matrix plays a vital role in property improvement. The thermal stability and mechanical properties of the exfoliated nylon 11/clay nanocomposites (containing lower clay concentrations) are superior to those of the intercalated ones (with higher clay contents), due to the finer dispersion of organoclay among the matrix.  相似文献   

4.
Xia Cao  Tomy Widya 《Polymer》2005,46(3):775-783
Polyurethane (PU)/montmorillonite (MMT) nanocomposites were synthesized with organically modified layered silicates (organoclays) by in situ polymerization and foams were prepared by a batch process. Clay dispersion of polyurethane nanocomposites was investigated by X-ray diffraction and transmission electron microscopy. The morphology and properties of PU nanocomposites and foams greatly depend on the functional groups of the organic modifiers, synthesis procedure, and molecular weight of polyols because of the chemical reactions and physical interactions involved. Silicate layers of organoclay can be exfoliated in the PU matrix by adding hydroxyl and organotin functional groups on the clay surface. The presence of clay results in an increase in cell density and a reduction of cell size compared to pure PU foam. In the polyurethane with high molecular weight polyol, a 6 °C increase in Tg, 650% increase in reduced compressive strength, and 780% increase in reduced modulus were observed with the addition of 5% organically treated clays. Opposite effects were observed in PU nanocomposite foams with highly crosslinked structure. The interference of the H-bond in the presence of clay is probably the reason.  相似文献   

5.
Nanocomposites based on cyclic olefin copolymer/linear low density polyethylene blends (COC/LLDPE) with various contents of three different modified organoclays (20A, 10A, and I28E) compatibilized with polyethylene grafted maleic anhydride (PEgMA) were prepared by met mixing. The influence of content and type of organoclay and compatibilizer on nanocomposite morphology, thermal, and mechanical properties as well as on oxygen and water vapour barrier properties was determined. X‐ray diffraction (XRD) and transmission microscopy (TEM) were used to investigate the clay dispersion, which showed a strong dependence on compatibilizer and type of organoclay. An exfoliated–intercalated morphology was obtained for compatibilized samples of C20A and I28E organoclays at 5 wt%. A less intercalated structure was obtained for samples with C10A. The exfoliated–intercalated structure was influenced both by the compatibilizer and the increase on the nanocomposite viscosity due to the COC incorporation as was determined by Rheological measurements. Mechanical analysis gave an evidence of increasing stiffness after nanoclay was added into COC/LLDPE blend matrix observing higher Young modulus for the compatibilized samples. A notorious decrease of Oxygen and Water vapour permeation rate was observed for COC/LLDPE blend films nanocomposites only when using C20A and I28E clays. These results can be useful in the design of sustainable flexible films for the packaging requirements of specific types of food. POLYM. COMPOS., 37:3167–3174, 2016. © 2015 Society of Plastics Engineers  相似文献   

6.
Acrylonitrile–butadiene–styrene (ABS)–clay composite and intercalated nanocomposites were prepared by melt processing, using Na‐montmorillonite (MMT), several chemically different organically modified MMT (OMMT) and Na‐laponite clays. The polymer–clay hybrids were characterized by WAXD, TEM, DSC, TGA, tensile, and impact tests. Intercalated nanocomposites are formed with organoclays, a composite is obtained with unmodified MMT, and the nanocomposite based on synthetic laponite is almost exfoliated. An unintercalated nanocomposite is formed by one of the organically modified clays, with similar overall stack dispersion as compared to the intercalated nanocomposites. Tg of ABS is unaffected by incorporation of the silicate filler in its matrix upto 4 wt % loading for different aspect ratios and organic modifications. A significant improvement in the onset of thermal decomposition (40–44°C at 4 wt % organoclay) is seen. The Young's modulus shows improvement, the elongation‐at‐break shows reduction, and the tensile strength shows improvement. Notched and unnotched impact strength of the intercalated MMT nanocomposites is lower as compared to that of ABS matrix. However, laponite and overexchanged organomontmorillonite clay lead to improvement in ductility. For the MMT clays, the Young's modulus (E) correlates with the intercalation change in organoclay interlayer separation (Δd001) as influenced by the chemistry of the modifier. Although ABS‐laponite composites are exfoliated, the intercalated OMMT‐based nanocomposites show greater improvement in modulus. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

7.
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   

8.
Cheon Il Park  O Ok Park 《Polymer》2004,45(4):1267-1273
The fabrication of a syndiotactic polystyrene (sPS)/organoclay nanocomposite was conducted via a stepwise mixing process using poly(styrene-co-vinyloxazolin) (OPS), i.e. melt intercalation of OPS into organoclay followed by blending with sPS. The effects of several parameters, including type of organoclay and mixing temperature on the microstructure of the nanocomposite were investigated through X-ray diffraction patterns and rheological properties. The microstructure of the nanocomposite mainly depended on the arrangement type of the organic modifiers in the clay gallery. Using organoclays having lateral a bilayer arrangement exfoliated structure was obtained, whereas intercalated structure were obtained when organoclay with a paraffinic monolayer arrangement was employed in our sPS/OPS/organoclay system. In this work, a simple heat treatment on a previously prepared OPS/organoclay nanocomposite induced microstructural evolution with a favorable direction from intercalation to exfoliation. This phenomenon is attributed to a strong interaction between OPS and the clay surfaces, which is revealed by plateau behavior of the storage modulus in rheological properties. When heat is applied to the OPS/organoclay, the OPS chains and clay layers move together by promoted thermal motion of OPS chains, which results in disordering of stacked clay layers and exfoliation.  相似文献   

9.
Poly(lactic acid) (PLA)/organoclay nanocomposites were prepared by melt compounding in a co‐rotating twin screw extruder. Two types of commercialized organoclay (dimethyl benzyl stearyl ammonium ion and dimethyl distearyl ammonium ion intercalated between clay platelets named as Clay A and Clay B, respectively) and two grades of poly(ethylene glycol) (PEG) with different molecular weight (Mw = 2,000 and 300,000–500,000 named as PEG2k and PEG500k, respectively) were used in this study. The Young's modulus improved by the addition of organoclay to PLA matrix. The Young's modulus decreased with the addition of PEG to PLA/organoclay nanocomposites. The tensile strength and elongation of PLA/Clay B nanocomposites increased with the addition of PEG2k. The effect of the addition of PEG on d‐spacing of PLA/organoclay nanocomposites is dependent upon the kind of organoclay. The sizes of clay agglomerations in PLA/PEG/organoclay nanocomposites are larger than those of PLA/organoclay ones in the same organoclay. Addition of PEG to PLA/organoclay nanocomposites during melt compounding will not be useful for the preparation of PLA/organoclay having fully exfoliated clay platelets. The shear thinning properties of the nanocomposites are independent of the addition of PEG. On the whole, PEG2k is good plasticizer for PLA/organoclay nanocomposites. POLYM. COMPOS. 27:256–263, 2006. © 2006 Society of Plastics Engineers  相似文献   

10.
Y.W. Chen-Yang  Y.K. Lee  Y.T. Chen  J.C. Wu 《Polymer》2007,48(10):2969-2979
In this work, a stable de-aggregated solvent-swollen organic modified clay, ALA-MMT, suspension is prepared by an efficient solvent swelling process using a home-made shaking mixer. It is found that the estimated average size of the as-prepared organoclay particles in the suspension is reduced to about 155 nm, which has not been reported before. The X-ray diffraction (XRD) patterns confirm that the d-spacing of the silicate layers of the solvent-swollen ALA-MMT expands from 1.4 nm to about 2.1 nm. The de-aggregated solvent-swollen ALA-MMT suspension is then used with polyurethane (PU) to prepare a series of highly exfoliated and high-organoclay-loading nanocomposites, PU/ALA-MMT. Both the XRD patterns and the TEM photographs of the as-prepared PU/ALA-MMT nanocomposites indicate that the organoclay is uniformly dispersed in the PU matrix with a highly exfoliated morphology structure of up to 7 wt% loading. Meanwhile, the TEM photographs give the first report for PU/clay nanocomposites which are almost completely exfoliated, and ∼1-nm thin silicate nanolayers are homogeneously dispersed in the polymer matrix with a high aspect ratio of 30-100. The thermal, mechanical, and anti-corrosion properties are all tremendously enhanced for the as-prepared nanocomposites. The results obtained for the PU nanocomposite with 7 wt% ALA-MMT loading (PUC7) reveal a 19 °C increment in Tg, a 48 °C increment in T5%, a 248% increase in the tensile strength, and a 123% increase in the elongation. The stainless steel disk (SSD) coated with PUC7 shows the lowest corrosion rate of 2.01 × 10−6 mm/year, which is 469% lower than that of the SSD coated with pure PU. The reinforcements are much greater than the previously reported PU/clay nanocomposites with comparable clay loadings ascribed to the exceptional homogeneity of as-prepared nanocomposites, which are accredited largely to the stable de-aggregated solvent-swollen organoclay suspension generated by the efficient solvent swelling process.  相似文献   

11.
The effect of the reaction media on clay dispersion and mechanical properties in poly(butylene succinate) (PBS, a biodegradable aliphatic thermoplastic polyester)/organoclay nanocomposites was investigated in this article. The results suggested that the most dispersed structures can be observed for organoclay modified in supercritical carbon dioxide (scCO2), which was used as solvent in the modification of montmorillonite in this study known for its environmentally benign, inexpensive, and nonflammable solvent, high diffusivity like a gas, near‐zero surface tension, low viscosity and density like a liquid, and high‐solvency power tunable by adjusting pressure and then organoclay modified in ethanol, while the least for organoclay was modified in distilled water. The results also confirmed intercalation‐predominate structures were obtained for nanocomposites of PBS with organoclay modified in ethanol, the mixture of intercalated and exfoliated structures for nanocomposites of PBS with organoclay modified in distilled water, but when clay was modified in scCO2, exfoliation‐predominate structures were observed for the nanocomposites. The storage modulus was significantly enhanced below the glass transition temperature, and the glass transition temperature shifted to a higher temperature compared with pure PBS and the maximum for PBS‐based nanocomposite of pretreated grafted montmorillonite via modification with trihexyltetradecylphosphonium chloride in scCO2 (OGMMTc). The mechanical properties including tensile strength and notched impact strength first decreased and then increased, whereas flexural strength and flexural modulus steadily and nearly linearly increased, maximum for PBS/OGMMTc nanocomposite, owing to the strong interaction between matrix and clay, which ultimately led to better overall dispersion. J. VINYL ADDIT. TECHNOL., 22:423–432, 2016. © 2015 Society of Plastics Engineers  相似文献   

12.
P.J. YoonD.L. Hunter  D.R. Paul 《Polymer》2003,44(18):5323-5339
Polycarbonate nanocomposites were prepared by melt processing from a series of organoclays based on sodium montmorillonite exchanged with various amine surfactants. To explore the effects of matrix molecular weight on dispersion, an organoclay was melt-mixed with a medium molecular weight polycarbonate (MMW-PC) and a high molecular weight polycarbonate (HMW-PC) using a twin screw extruder. The effects of surfactant chemical structure on the morphology and physical properties were explored for nanocomposites formed from HMW-PC. Wide angle X-ray scattering, transmission electron microscopy, and stress-strain behavior were employed to investigate the nanocomposite morphology and physical properties. The modulus enhancement is greater for nanocomposites formed from HMW-PC than MMW-PC. This trend is attributed to the higher shear stress generated during melt processing. A surfactant having both polyoxyethylene and octadecyl tails shows the most significant improvement in modulus with some of the clay platelets fully exfoliated. However, the nanocomposites formed from a range of other organoclays contained both intercalated tactoids and collapsed clay particles with few, if any, exfoliated platelets.  相似文献   

13.
The main objective of this study was to synthesize and characterize the properties of ethylene–propylene–diene terpolymer (EPDM)/clay nanocomposites. Pristine clay, sodium montmorillonite (Na+–MMT), was intercalated with hexadecyl ammonium ion to form modified organoclay (16Me–MMT) and the effect of intercalation toward the change in interlayer spacing of the silicate layers was studied by X‐ray diffraction, which showed that the increase in interlayer spacing in Na+–MMT by 0.61 nm is attributed to the intercalation of hexadecyl ammonium ion within the clay layers. In the case of EPDM/16Me–MMT nanocomposites, the basal reflection peak was shifted toward a higher angle. However, gallery height remained more or less the same for different EPDM nanocomposites with organoclay content up to 8 wt %. The nanostructure of EPDM/clay composites was characterized by transmission electron microscopy, which established the coexistence of intercalated and exfoliated clay layers with an average layer thickness in the nanometer range within the EPDM matrix. The significant improvement in thermal stability and mechanical properties reflects the high‐performance nanocomposite formation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2429–2436, 2004  相似文献   

14.
《国际聚合物材料杂志》2012,61(13):1035-1049
Epoxy resin/layered silicate nanocomposites with various clay contents were prepared. The structural studies showed the intercalation of epoxy polymer chains into the clay galleries. The adhesion analysis of nanocomposite coating films on metallic substrates showed the excellent adhesion of epoxy-based nanocomposite coatings on iron plates, especially in lower clay loadings. According to the hardness test results, the organoclay minerals caused the increasing of the hardness of epoxy nanocomposites. The thermal properties of nanocomposites were evaluated by means of DSC and TGA analysis. The tensile and compression strengths of cured epoxy/clay systems were also investigated.  相似文献   

15.
Understanding the complex mechanism of dispersion and intercalation of the clay tactoids can allow us to control the final morphology, homogeneity, and the macroscopic properties of clay nanocomposites. The objective of this work is a multiscale study of the dispersion state of PP/organoclay and PP‐g‐MA/organoclay composite. The microscopic investigation, WAXS diffractograms, rheological analysis, and mechanical properties were used to characterize the dispersion of organoclay in PP and PP‐g‐MA matrices during melt blending in two different shear rates. The morphological results show a system of aggregating intercalated clay particles which disperse by increasing mixing time with a strain‐controlled process and a very quick intercalation process in early mixing times for PP‐g‐MA/organoclay nanocomposite, while PP/organoclay samples only form microcomposites. The relative network modulus of these intercalated particles as a function of mixing time was obtained; and the tensile modulus of nanocomposite samples were compared with Halpin‐Tsai model prediction. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers  相似文献   

16.
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   

17.
Polypropylene nanocomposites were prepared with organic‐modified montmorillonite, by blending the polymer and the organoclay (direct addition), or by blending the polymer with an organoclay/silicone copolymer masterbatch. The effect of the organoclay/silicone copolymer masterbatch on the morphology and properties of polypropylene was compared with that nanocomposite obtained with the direct organoclay addition. The results showed that the morphology of both polypropylene nanocomposites is constituted by clay tactoids together with some few individual platelets and clay aggregates. Smaller tactoids were observed for the nanocomposite prepared with the masterbatch, in which the silicone copolymer remained intercalated in the clay or adjacent to tactoids. The introduction of the organoclay in the polymer matrix resulted only in an increase in the Young's modulus (28%), while yielding stress, elongation at break and Izod impact strength remained practically unchanged. On the other hand, the incorporation of organoclay by using the masterbatch resulted in a marked improvement (111%) in the elongation at break and in Izod impact strength (85%). The improvement in the elongation at break came with the reduction of the modulus and the yielding stress, by 25 and 15%, respectively. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers  相似文献   

18.
Organically modified montmorrillonite clay, containing a long chain aliphatic quarternary ammonium cation, was used to prepare polyimide/organoclay hybrids. Several approaches were examined in an attempt to achieve fully exfoliated nanocomposites. These included simple mixing of the clay in a pre-made high molecular weight poly(amide acid) solution; simple mixing followed by sonication of the organoclay/poly(amide acid) solutions; and the preparation of high molecular weight poly(amide acid)s in the presence of the organoclay dispersed in N-methyl-2-pyrrolidinone (NMP). The best results were obtained using the in-situ polymerization approach. The resulting nanocomposite films (both amide acid and imide), containing 3-8% by weight of organoclay, were characterized by differential scanning calorimetry (DSC), dynamic thermogravimetric analysis (TGA), transmission electron microscopy (TEM), X-ray diffraction (XRD) and thin film tensile properties. A significant degree of dispersion was observed in the nanocomposite films of the amide acid and the imide. After thermal treatment of amide acid films to effect imidization, in both air and nitrogen, the films were visually darker than control films without clay and the level of clay dispersion appeared to have decreased. In the latter case, the separation between the layers of the clay decreased to a spacing less than that present in the original organoclay. These observations suggest that thermal degradation of the aliphatic quarternary ammonium cation occurred likely during thermal treatment to effect imidization and solvent removal. These thermal degradation effects were less pronounced when thermal treatment was performed under nitrogen. The polyimide/organoclay hybrid films exhibited higher room temperature tensile moduli and lower strength and elongation to break than the control films.  相似文献   

19.
Thermoplastic polyurethane (TPU) nanocomposites based on organophilic-layered silicates were prepared via melt blending. Wide angle X-ray diffraction (WAXD) and transmission electron microscope (TEM) were employed to investigate the state and mechanism of exfoliation of the layered silicate within TPU matrix. The TPU nanocomposites were found to have a partially exfoliated morphology at lower clay loading, whereas the morphology changed to an intercalated nanostructure at higher clay loadings. The effect of the state of dispersion of organoclay on rheological properties of the nanocomposites were carried out by rubber process analyzer (RPA), which exhibited more pronounced shear thinning behavior, and increased storage and loss modulus with the increase in organoclay content. The pseudo-plastic like behavior was observed due to change in liquid-like to solid-like behavior of nanoclay-filled systems.  相似文献   

20.
The tensile and impact properties of amine‐cured diglycidyl ether of bisphenol A based nanocomposites reinforced by organomontmorillonite clay nanoplatelets are reported. The sonication processing scheme involved the sonication of the constituent materials in a solvent followed by solvent extraction to generate nanocomposites with homogeneous dispersions of the organoclay nanoplatelets. The microstructure of the clay nanoplatelets in the nanocomposites was observed with transmission electron microscopy, and the clay nanoplatelets were well dispersed and were intercalated and exfoliated. The tensile modulus of epoxy at room temperature, which was above the glass‐transition temperature of the nanocomposites, increased approximately 50% with the addition of 10 wt % (6.0 vol %) clay nanoplatelets. The reinforcing effect of the organoclay nanoplatelets was examined with respect to the Tandon–Weng and Halpin–Tsai models. The tensile strength was improved only when 2.5 wt % clay nanoplatelets were added. The Izod impact strength decreased with increasing clay content. The failure surfaces of the nanocomposites were observed with environmental scanning electron microscopy and confocal laser scanning microscopy. The roughness of the failure surface was correlated with the tensile strength. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 281–287, 2005  相似文献   

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