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1.
In this study, poly(l ‐lactide) (PLA) is melt‐blended with thermoplastic polyurethane (TPU) to modify the brittleness of PLA. An aliphatic ester‐based TPU was selected in order to have an ester sensitivity for degradation and an inherent biocompatibility. Using this compatible TPU, there was no need to apply problematic compatibilizers, so the main positive properties of PLA such as biocompatibility and degradability were not challenged. The detected microstructure of PLA/TPU blends showed that when the TPU content was lower than 25 wt %, the structure appeared as sea‐islands, but when the TPU content was increased, the morphology was converted to a cocontinuous microstructure. A higher interfacial surface area in the blend with 25 wt % TPU (PLA25) resulted in a higher toughness and abrasion resistance. The various analyses confirmed interactions and successful coupling of two phases and confirmed that melt‐blending of PLA with the aliphatic ester‐based TPU is a convenient, cost‐effective, and efficient method to conquer the brittleness of PLA. The prepared blends are general‐purpose plastics, but PLA25 showed an optimum mechanical strength, toughness, and biocompatibility suitable for a wide range of applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43104.  相似文献   

2.
The poly(l ‐lactide)‐b‐poly(ethylene glycol)‐b‐poly(l ‐lactide) block copolymers (PLLA‐b‐PEG‐b‐PLLA) were synthesized in a toluene solution by the ring‐opening polymerization of 3,6‐dimethyl‐1,4‐dioxan‐2,5‐dione (LLA) with PEG as a macroinitiator or by transterification from the homopolymers [polylactide and PEG]. Two polymerization conditions were adopted: method A, which used an equimolar catalyst/initiator molar ratio (1–5 wt %), and method B, which used a catalyst content commonly reported in the literature (<0.05 wt %). Method A was more efficient in producing copolymers with a higher yield and monomer conversion, whereas method B resulted in a mixture of the copolymer and homopolymers. The copolymers achieved high molar masses and even presenting similar global compositions, the molar mass distribution and thermal properties depends on the polymerization method. For instance, the suppression of the PEG block crystallization was more noticeable for copolymer A. An experimental design was used to qualify the influence of the catalyst and homopolymer amounts on the transreactions. The catalyst concentration was shown to be the most important factor. Therefore, the effectiveness of method A to produce copolymers was partly due to the transreactions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40419.  相似文献   

3.
Four‐armed star poly(l ‐ lactide)‐grafted multiwalled carbon nanotubes (CNTs‐g‐4PLLA) were synthesized through the nucleophilic substitution reaction between 4PLLA and acryl chloride of CNTs and then characterized by transmission electron microscope, X‐ray photoelectron spectroscopy, thermal gravimetric analysis (TGA), and ultraviolet visible spectrophotometer. The results indicated that 4PLLA was successfully grafted onto CNTs, and CNTs‐g‐4PLLA contained 37.7 wt% of 4PLLA. PLLA/CNTs‐g‐4PLLA nanocomposites were prepared by solution casting with different CNTs‐g‐4PLLA content. Rheological behavior of PLLA/CNTs‐g‐4PLLA nanocomposites was measured using a rheometer. The result showed that CNTs‐g‐4PLLA formed a network structure at percolation concentration, which improves obviously rheological properties of PLLA in the molten state. The crystallization behavior and crystal structure of the nanocomposites were comprehensive evaluated through differential scanning calorimetry, X‐ray diffraction, and polarizing optical microscope. The results found that CNTs‐g‐4PLLA played two roles in PLLA crystallization. The addition of CNTs‐g‐4PLLA acted as nucleating agent and obviously accelerated the spherulites growth under percolation concentration, while it inhibited the movement of PLLA chains at above percolation concentration, resulting in the decrease of crystallinity. Thermal stability and mechanical properties of the nanocomposites were also investigated using TGA, dynamic mechanical analysis, and tensile test. These results indicated that the incorporation of CNT‐g‐4PLLA into the PLLA matrix improved the thermal stability, storage modulus, and tensile strength of the nanocomposites. POLYM. COMPOS., 37:2744–2755, 2016. © 2015 Society of Plastics Engineers  相似文献   

4.
To modify the mechanical properties of a poly(l ‐lactide) (PLLA)/poly(para‐dioxanone) (PPDO) 85/15 blend, poly(para‐dioxanone‐co‐l ‐lactide) (PDOLLA) was used as a compatibilizer. The 85/15 PLLA/PPDO blends containing 1–5 wt % of the random copolymer PDOLLA were prepared by solution coprecipitation. Then, the thermal, morphological, and mechanical properties of the blends with different contents of PDOLLA were studied via differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and tensile testing, respectively. The DSC result revealed that the addition of PDOLLA into the blends only slightly changed the thermal properties by inhibiting the crystallization degree of the poly(l ‐lactide) in the polymer blends. The SEM photos indicated that the addition of 3 wt % PDOLLA into the blend was ideal for making the interface between the PLLA and PPDO phases unclear. The tensile testing result demonstrated that the mechanical properties of the blends containing 3 wt % PDOLLA were much improved with a tensile strength of 48 MPa and a breaking elongation of 214%. Therefore, we concluded that the morphological and mechanical properties of the PLLA/PPDO 85/15 blends could be tailored by the addition of the PDOLLA as a compatibilizer and that the blend containing a proper content of PDOLLA had the potential to be used as a medical implant material. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41323.  相似文献   

5.
Well‐defined poly(l ‐lactide‐b‐ethylene brassylate‐b‐l ‐lactide) (PLLA‐b‐PEB‐b‐PLLA) triblock copolymer was synthesized by using double hydroxyl‐terminated PEBs with different molecular weights. Gel permeation chromatography and NMR characterization were employed to confirm the structure and composition of the triblock copolymers. DSC, wide‐angle X‐ray diffraction, TGA and polarized optical microscopy were also employed to demonstrate the relationship between the composition and properties. According to the DSC curves, the cold crystallization peak vanished gradually with decrease of the PLLA block, illustrating that the relatively smaller content of PLLA may lead to the formation of a deficient PLLA type crystal, leading to a decrease of melting enthalpy and melting temperature. Multi‐step thermal decompositions were determined by TGA, and the PEB unit exhibited much better thermal stability than the PLLA unit. Polarized optical microscopy images of all the triblock samples showed that spherulites which develop radially and with an extinction pattern in the form of a Maltese cross exhibit no ring bond. The growth rate of the spherulites of all triblock samples was investigated. The crystallization capacity of PLLA improved with incorporation of PLLA, which accords with the DSC and wide‐angle X‐ray diffraction results. © 2019 Society of Chemical Industry  相似文献   

6.
The enhancement of mechanical properties were achieved by solution blending of poly(d ‐lactide) (PDLA) and 5‐arm poly(l ‐lactide) (5‐arm PLLA). Differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD) results indicated almost complete stereocomplex could be obtained when 5‐arm PLLA exceeded 30wt %. Tensile test results showed that the addition of 5‐arm PLLA in linear PDLA gave dramatically improvement both on tensile strength and elongation at break, which generally could not be increased simultaneously. Furthermore, this work transformed PDLA from brittle polymer into tough and flexible materials. The mechanism was proposed based on the TEM results: the stereocomplex crystallites formed during solvent evaporation on the blends were small enough (100–200 nm), which played the role of physical crosslinking points and increased the interaction strength between PDLA and 5‐arm PLLA molecules, giving the blends high tensile strength and elongation at break. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42857.  相似文献   

7.
Poly(l ‐lactide) in its l ‐form has promising mechanical properties. Being a semicrystalline polymer, it can be subjected to strain‐induced crystallization at temperatures above Tg and can thereby become oriented. Following a simultaneous (SIM) biaxial strain process or a sequential (SEQ) biaxial strain process, the mechanical properties of biaxially strained tubes can be further improved. This study investigated these properties in relation to their morphology and crystal orientation. Both processes yield the same mechanical strength and modulus, yet exhibit different crystal orientation. Through further wide angle X‐ray scattering analysis it was found that the SEQ biaxial strain yields larger interplanar spacing and distorted crystals and looser packing of chains. However, this does not influence the mechanical properties negatively. A loss of orientation in SEQ biaxially strained samples at high degrees of strain was detected, but was not seen for SIM biaxial strain and did not correlate with mechanical performance in either case. However, post‐annealing reduced the orientation to the same level in both cases, and the modulus and strength decreased for both SIM and SEQ biaxial strain. It is therefore concluded that mechanical properties after biaxial strain are related to strain‐induced amorphous orientation and the packing of crystals, rather than strain‐induced crystallinity. © 2015 Society of Chemical Industry  相似文献   

8.
Poly(l ‐lactide) (PLLA) nanofibers were prepared by melt extrusion of immiscible blends of PLLA/low density polyethylene (LDPE) and subsequent removal of the LDPE matrix from the blend fibers. The effect of blends composition and draw ratio on the phase structure of the blend fibers, crystallization, mechanical properties, and the diameter of the PLLA nanofibers was investigated. It is found that the diameter of the PLLA phase gradually increases with the increase of PLLA content. With the variation of PLLA content from 50 to 60 wt %, the average diameter of acquired PLLA nanofibers changes from 119 to 153 nm under the draw ratio of 1.5. When further increasing the content of PLLA to 65%, it is difficult to acquire PLLA nanofibers due to the poor dissolving properties between PLLA and LDPE components. Oriented PLLA nanofibers with the average diameter of 92 nm can be fabricated from PLLA/LDPE (50/50, wt %) blends under the draw ratio of 2. The present results suggest that it is possible to acquire polymer nanofibers with high output using blend sea‐island melt spinning. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41228.  相似文献   

9.
Effect of Poly(l ‐lactide)/Poly(d ‐lactide) (PLLA/PDLA) block length ratio on the crystallization behavior of star‐shaped poly(propylene oxide) block poly(d ‐lactide) block poly (l ‐lactide) (PPO–PDLA–PLLA) stereoblock copolymers with molecular weights (Mn) ranging from 6.2 × 104 to 1.4 × 105 g mol?1 was investigated. Crystallization behaviors were studied utilizing differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide‐angle X‐ray diffraction (WAXD). Only stereocomplex crystallites formed in isothermal crystallization at 140 to 156°C for all samples. On one hand, the overall crystallization rate decreased as PLLA/PDLA block length ratio increased. As PLLA/PDLA block length ratio increased from 7:7 to 28:7, the value of half time of crystallization (t1/2) delayed form 2.85 to 5.31 min at 140°C. On the other hand, according to the Lauritzen–Hoffman theory, the fold‐surface energy (σe) was calculated. σe decreased from 77.7 to 73.3 erg/cm2 with an increase in PLLA/PDLA block length ratio. Correspondingly increase in nucleation density was observed by the polarized optical microscope. Results indicated that the PLLA/PDLA block length ratio had a significant impact on the crystallization behavior of PPO–PDLA–PLLA copolymers. POLYM. ENG. SCI., 55:2534–2541, 2015. © 2015 Society of Plastics Engineers  相似文献   

10.
This paper aims to evaluate the potential of totally bioresorbable composites as cardiovascular stent material. Copolymers were synthesized by ring‐opening polymerization of L ‐lactide (LLA) and 1,3‐trimethylene carbonate (TMC) with LLA‐TMC ratios of 3/1, 4/1, and 5/1 and characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). Wt. 5% of poly(L ‐lactide)‐co‐(glycolide) (PLGA) fibers are used to reinforce PTMC‐LLA copolymer matrices to prepare totally bioresorbable composites. Heat treatment under vacuum and oxygen plasma treatment are applied to improve the mechanical performance of the composites in terms of eliminating the imperfections inside, enhancing interfacial affinity, surface roughness, and enriching surface oxidative chemical bonds. After plasma treatment, the viscosity and tensile strength of the fibers decrease, but the surface chemical bonds are enriched and surface roughness is increased. The composites with 15‐min plasma‐treated fibers and 2 h heat treatment exhibit the highest tensile strength of 46 MPa, i.e., very close to that of PLLA (48 MPa), which is usually used as biodegradable stent material. Moreover, the tensile modulus of the above composite is 1711 MPa, which is only 34% of PLLA's modulus (4985 MPa). Therefore, novel composites with sufficient tensile strength and better flexibility are obtained as promising cardiovascular stent material. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers  相似文献   

11.
Poly(l ‐lactide) (PLLA) is a bioabsorbable polymer with high stiffness and strength compared to the other commercially available bioabsorbable polymers. The properties of PLLA can be improved by straining, causing deformation‐mediated molecular orientation. PLLA tubes were biaxially strained above their Tg for improvement of their strength, in a two‐step process (sequential straining). Mechanical properties and crystal morphology were investigated as a function of processing strain rate and temperature. DSC revealed that a low processing strain rate allows molecular chain relaxation in the direction of strain and the crystallization is suppressed. Faster strain rates on the other hand suppress chain relaxation, and results in crystalline tubes. The mechanical properties are influenced by both processing strain rate and temperature. Low strain rates allow chain relaxation resulting in the lowest strength and stiffness, whereas a larger stiffness and strength is achieved by increasing strain rate and temperature. Isotropic mechanical properties are only observed at high processing strain rates. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45192.  相似文献   

12.
Collagen was extracted from Rana chensinensis skin supplied from byproducts via an acid enzymatic extraction method. The R. chensinensis skin collagen (RCSC) and poly(l ‐lactide) (PLLA) were blended at a 3:7 ratio in 1,1,1,3,3,3‐hexafluoroisopropanol (HFIP) at a concentration of 10% (g/mL) and electrospun to produce nanofibers in an aligned and random orientation. For comparison, pure PLLA nanofibrous membranes with aligned and random nanofiber orientations were also produced. The secondary structure of the RCSC nanofibers was investigated by circular dichroism to confirm that the extracted substance was collagen. The presence of collagen in the blend nanofiber was verified by LSCM. The blended nanofibers showed uniform, smooth, and bead‐free morphologies and presented a smaller fiber diameter (278 and and 259 nm) than the pure the ones of PLLA (559 and and 439 nm) nanofibers. It was found that the addition of RCSC and the modification of the nanofiber's orientation affected the fiber's diameter and the crystallization of PLLA. The cell viability studies with human fibroblast cells demonstrated that the RCSC/PLLA nanofibrous membranes formed by electrospinning exhibited good biocompatibility and that the aligned scaffolds could regulate the cell morphology by inducing cell orientation. The empirical results in this study indicated that the aligned RCSC/PLLA nanofibrous membrane is a potential wound dressing candidate for skin regeneration. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45109.  相似文献   

13.
Two series of copolymers were synthesized by emulsion polymerization: poly(styrene-co-acrylonitrile) P(S:AN) and P(S:AN-acrylic acid) P(S:AN-AA). The monomeric concentrations in both series were: 0:100, 20:80, 40:60, 50:50 (wt%:wt%), and 1 wt% of AA. The copolymers were dissolved in N,N-dimethylformamide (4–10 wt%) and were electrospun. Polymeric yarns were collected using a blade collector. The synthesized and fabricated materials were characterized by known techniques. Mechanical and electrical properties of polymeric yarns indicated a dependence of monomeric concentration. Elastic modulus increases as acrylonitrile concentration increases (up to 30 MPa). Yarns were submitted to degradation process into saline solution, where the acrylic acid content kept a constant elastic modulus at long times. The electrical current into yarns was higher when the concentration is 50:50 wt%:wt% (1.2 mA). The cytotoxicity results showed a cell viability close to 100% for yarns without AA.  相似文献   

14.
In this work, stereocomplex‐poly(l ‐ and d ‐lactide) (sc‐PLA) was incorporated into poly(ε‐caprolactone) (PCL) to fabricate a novel biodegradable polymer composite. PCL/sc‐PLA composites were prepared by solution casting at sc‐PLA loadings of 5–30 wt %. Differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD) demonstrated the formation of the stereocomplex in the blends. DSC and WAXD curves also indicated that the addition of sc‐PLA did not alter the crystal structure of PCL. Rheology and mechanical properties of neat PCL and the PCL/sc‐PLA composites were investigated in detail. Rheological measurements indicated that the composites exhibited evident solid‐like response in the low frequency region as the sc‐PLA loadings reached up to 20 wt %. Moreover, the long‐range motion of PCL chains was highly restrained. Dynamic mechanical analysis showed that the storage modulus (E′) of PCL in the composites was improved and the glass transition temperature values were hardly changed after the addition of sc‐PLA. Tensile tests showed that the Young's modulus, and yield strength of the composites were enhanced by the addition of sc‐PLA while the tensile strength and elongation at break were reduced. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40208.  相似文献   

15.
The effect of the final melting temperature (Tf) on the crystallization of poly(l ‐lactide) (PLLA)/poly(d ‐lactide) (PDLA) was studied via a combination of differential scanning calorimetry, wide‐angle X‐ray scattering, polarized optical microscopy, and Fourier transform infrared (FTIR) spectroscopy. We observed that a residual stereocomplex (SC) crystal induced the formation of SC crystals during cooling from a Tf (230°C) just above the melting peak of the SC crystals. On cooling from a Tf (240°C) just above the endset temperature of SC crystal melting [Tm(S)(E)], the possible order structure and the strong interchain interaction promoted the preferential crystallization of SC crystals; this enhanced the formation of α crystals. During cooling from a Tf (≥250°C) far above Tm(S)(E), the crystallization peaks of α and SC crystals converged. The FTIR results indicated that the residual SC crystals, possible ordered structure, and interchain interactions in the melt might have been the key factors for the different crystallization of PLLA/PDLA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43015.  相似文献   

16.
A thermosensitive amphiphilic triblock copolymer, poly(d,l ‐lactide) (PLA)‐b‐poly(N‐isopropyl acrylamide) (PNIPAAM)‐b‐PLA, was synthesized by the ring‐opening polymerization of d,l ‐lactide; the reaction was initiated from a dihydroxy‐terminated poly(N‐isopropyl acrylamide) homopolymer (HO‐PNIPAAM‐OH) created by radical polymerization. The molecular structure, thermosensitive characteristics, and micellization behavior of the obtained triblock copolymer were characterized with Fourier transform infrared spectroscopy, 1H‐NMR, gel permeation chromatography, dynamic light scattering, and transmission electron microscopy. The obtained results indicate that the composition of PLA‐b‐PNIPAAM‐b‐PLA was in good agreement with what was preconceived. This copolymer could self‐assemble into spherical core–shell micelles (ca. 75–80 nm) in aqueous solution and exhibited a phase‐transition temperature around 26 °C. Furthermore, the drug‐delivery properties of the PLA‐b‐PNIPAAM‐b‐PLA micelles were investigated. The drug‐release test indicated that the synthesized PLA‐b‐PNIPAAM‐b‐PLA micelles could be used as nanocarriers of the anticancer drug adriamycin (ADR) to effectively control the release of the drug. The drug‐delivery properties of PLA‐b‐PNIPAAM‐b‐PLA showed obvious thermosensitive characteristics, and the release time of ADR could be extended to 50 h. This represents a significant improvement from previous PNIPAAM‐based drug‐delivery systems. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45304.  相似文献   

17.
The technological exploitation of polylactide in fields requiring wide range of operating conditions is limited by the low crystallization rate of the polymer and therewith the low thermomechanical stability. Here we report the crystallization and consequent improvement of the thermomechanical properties of originally amorphous poly(d,l ‐lactide) (d : l ratio 11 : 89) loaded with cellulose nanocrystals (CNCs). Isothermal treatment of samples with different CNC contents and at various temperatures, showed up to 6 wt % crystalline phase formation, as confirmed by differential scanning calorimetry and X‐ray diffraction measurements. Under a particular set of annealing conditions, CNCs promote the formation of a lamellar structure. This provides the system with higher order and cohesion which in combination with stress‐transfer between CNCs, led to an increase of the storage modulus in the rubbery plateau up to 30 times (from 2.7 MPa up to 79 MPa), a rise of the melting temperature up to 50°C, and an improvement of the Young's modulus up to 40%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41607.  相似文献   

18.
Nanocomposites of poly(lactide) (PLA) and the PLA plasticized with diglycerine tetraacetate (PL‐710) and ethylene glycol oligomer containing organo‐modified montmorillonites (ODA‐M and PGS‐M) by the protonated ammonium cations of octadecylamine and poly(ethylene glycol) stearylamine were prepared by melt intercalation method. In the X‐ray diffraction analysis, the PLA/ODA‐M and plasticized PLA/ODA‐M composites showed a clear enlargement of the difference of interlayer spacing between the composite and clay itself, indicating the formation of intercalated nanocomposite. However, a little enlargement of the interlayer spacing was observed for the PLA/PGS‐M and plasticized PLA/PGS‐M composites. From morphological studies using transmission electron microscopy, a finer dispersion of clay was observed for PLA/ODA‐M composite than PLA/PGS‐M composite and all the composites using the plasticized PLA. The PLA and PLA/PL‐710 composites containing ODA‐M showed a higher tensile strength and modulus than the corresponding composites with PGS‐M. The PLA/PL‐710 (10 wt %) composite containing ODA‐M showed considerably higher elongation at break than the pristine plasticized PLA, and had a comparable tensile modulus to pure PLA. The glass transition temperature (Tg) of the composites decreased with increasing plasticizer. The addition of the clays did not cause a significant increase of Tg. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006  相似文献   

19.
Electrospun fibrous membranes have been used frequently in biomedical applications, but their simultaneous use as antibacterial agents and in the prevention of cell adhesion on repaired tendons after injury has not been investigated. In this study, silver‐nanoparticle (SN)‐loaded poly(L ‐lactide) (PLLA) fibrous membranes were prepared by the electrospinning of SNs into PLLA fibers. Micrograph results showed that these membranes were composed of electrospun fibers and that the fibers were incorporated with SNs. From the results of X‐ray diffraction and thermogravimetry, we concluded that the SNs were physically mixed into the fibers at the desired content. The mechanical properties were not significantly changed. The preliminary antibacterial effects on Staphylococcus epidermidis and Staphylococcus aureus and the synergistic antiproliferative effects of the SN‐loaded PLLA fibrous membranes were observed. Taken together, these results demonstrate that SNs can be directly loaded onto a biodegradable PLLA fibrous membrane via electrospinning to achieve proper material properties with preliminary potential as antibacterial antiadhesion barriers for tendon injury. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

20.
Poly(vinyl acetate) (PVAc) was added to the crystalline blends of poly(ethylene oxide) (PEO) and poly(L ‐lactide) (PLLA) (40/60) of higher molecular weights, whereas diblock and triblock poly(ethylene glycol)–poly(L ‐lactide) copolymers were added to the same blend of moderate molecular weights. The crystallization rate of PLLA of the blend containing PVAc was reduced, as evidenced by X‐ray diffraction measurement. A ringed spherulite morphology of PLLA was observed in the PEO/PLLA/PVAc blend, attributed to the presence of twisted lamellae, and the morphology was affected by the amount of PVAc. A steady increase in the elongation at break in the solution blend with an increase in the PVAc content was observed. The melting behavior of PLLA and PEO in the PEO/PLLA/block copolymer blends was not greatly affected by the block copolymer, and the average size of the dispersed PEO domain was not significantly changed by the block copolymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3618–3626, 2001  相似文献   

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