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1.
Phase separation and mechanical responses of polyurethane nanocomposites   总被引:2,自引:0,他引:2  
Nanocomposites of a diamine-cured polyurethane with nanofillers of different kinds, sizes, and surfaces were studied. Atomic force microscopy, scanning electron microscopy, X-ray diffraction, tensile tests, and dynamic mechanical thermal analysis were employed in the experiments. Experimental results suggest that mechanical properties are strongly correlated to polymer phase separation, which depends on the nature of the interface between the polymer and the nanoparticles. Two stages of phase separation were observed: the first stage involves the self-assembly of the hard segments into small hard phases of about 10 nm in width; the second stage involves the assembly of the 10 nm wide hard phases into larger domains of about 40-100 nm in width. In the case of polyurethane/ZnO nanocomposites with 5 wt% (less than 1 vol%) 33 nm ZnO nanoparticles, the covalent bonds that were formed between the polymer and ZnO surface hydroxyl groups constrain both stages of phase separation in polyurethane, resulting in approximately 40% decrease in the Young's modulus, 80% decrease in the strain at fracture, and 11 °C increase in the glass transition temperature of the soft segments. In the case of polyurethane/Al2O3 nanocomposites with 5 wt% 15 nm Al2O3 nanoparticles, hydrogen bonds between the particles and the polymer mainly constrain the second step of the phase separation, resulting in about 30% decrease in the Young's modulus and 12 °C increase in the glass transition temperature, but only a moderate decrease in the strain at fracture. The most striking results come from polyurethane/clay composites, where only van der Waals type interactions exist between polyurethane and the organically modified clay (Cloisite 20A). With the addition of 5 wt% surface modified clay (Cloisite 20A), both the Young's modulus and the strain at fracture decrease more than 80%, but the glass transition temperature increases by about 13 °C. Adding 10 wt% Cloisite 20A into polyurethane almost totally disrupts the phase separation, resulting in a very soft composite that resembles a “viscous liquid” rather than a solid.  相似文献   

2.
Toughening mechanisms of nanoparticle-modified epoxy polymers   总被引:3,自引:0,他引:3  
An epoxy resin, cured with an anhydride, has been modified by the addition of silica nanoparticles. The particles were introduced via a sol-gel technique which gave a very well-dispersed phase of nanosilica particles which were about 20 nm in diameter. Atomic force and electron microscopies showed that the nanoparticles were well-dispersed throughout the epoxy matrix. The glass transition temperature was unchanged by the addition of the nanoparticles, but both the modulus and toughness were increased. The measured modulus was compared to theoretical models, and good agreement was found. The fracture energy increased from 100 J/m2 for the unmodified epoxy polymer to 460 J/m2 for the epoxy polymer with 13 vol% of nanosilica. The fracture surfaces were inspected using scanning electron and atomic force microscopies, and the results were compared to various toughening mechanisms proposed in the literature. The toughening mechanisms of crack pinning, crack deflection and immobilised polymer were discounted. The microscopy showed evidence of debonding of the nanoparticles and subsequent plastic void growth. A theoretical model of plastic void growth was used to confirm that this mechanism was indeed most likely to be responsible for the increased toughness that was observed due to the presence of the nanoparticles.  相似文献   

3.
Jiawen Xiong  Xiumin Qin  Huiqing Li 《Carbon》2006,44(13):2701-2707
A polyurethane/multi-walled carbon nanotube elastomer composite was synthesized. The microstructure of the composite was examined by field-emission scanning electron microscopy and transmission electron microscopy. The thermal and mechanical properties of the composite were characterized by dynamic mechanical thermal analysis, thermogravimetric analysis and tensile testing. The chemical linkage of carbon nanotubes with polyurethane matrix was confirmed by Fourier transform infrared spectra. The study on the structure of the composite showed that carbon nanotubes could be dispersed in the polymer matrix well apart from a few of clusters. The results from thermal analysis indicated that the glass transition temperature of the composite was increased by about 10 °C and its thermal stability was obviously improved, in comparison with pure polyurethane. The investigation on the mechanical properties showed that the modulus and tensile strength could be obviously increased by adding 2 wt% (by weight) CNT to the matrix.  相似文献   

4.
Epoxy-nanocomposite resins filled with 12-nm spherical silica particles were investigated for their thermal and mechanical properties as a function of silica loading. The nanoparticles were easily dispersed with minimal aggregation for loadings up to 25 wt% as determined using transmission electron microscopy (TEM) and ultra-small-angle X-ray scattering (USAXS). A proportional decrease in cure temperatures and glass transition temperature (for loadings of 10 wt% and above) was observed with increased silica loading. The morphology determined by USAXS is consistent with a zone around the silica particles from which neighboring particles are excluded. The “exclusion zone” extends to 10× the particle diameter. For samples with loadings less than 10 wt%, increases of 25% in tensile modulus and 30% in fracture toughness were obtained. More highly loaded samples continued to increase in modulus, but decreased in strength and fracture toughness. Overall, the addition of nanosilica is shown as a promising method for property enhancement of aerospace epoxy composite resins.  相似文献   

5.
E. Shivakumar  E. Segal 《Polymer》2005,46(10):3363-3371
Dynamic mechanical analysis was performed to characterize the viscoelastic properties of binary and ternary blends of fluorocarbon elastomer (FKM), acrylic elastomer (ACM) and liquid crystalline polymer (LCP). The results showed that the storage and loss modulus of all the blends increased significantly with the weight percentage of the LCP. The glass transition temperature evaluated at the loss modulus peak, were in the range of −10-+5 °C for all the blends. The time temperature superposition principle was applied for the FKM/ACM and 20% LCP filled FKM/ACM blend in order to evaluate the changes in the viscoelastic properties of FKM/ACM blend by the addition of LCP. The Arrhenius and William-Landel-Ferry (WLF) equations were used to quantify the viscoelastic behaviour at the glass transition region. Both the blends exhibited a single relaxation, which is glass transition, observed as a peek in the loss modulus at 1 Hz. The glassy moduli of these two systems were found to be comparable, but the rubbery moduli of the LCP filled FKM/ACM was much higher than the LCP unfilled system. However, the viscoelastic behaviour of these two systems and their sensitivity to time temperature may be considered to be quite similar.  相似文献   

6.
Topcoat constituting multi-layer coatings for wood furniture used in high humidity environments, like bathrooms, must have not only good barrier properties, but also good mechanical properties. Three different types of commercial organoclays, namely Cloisite 10A (C10A), Cloisite 15A (C15A) and Cloisite 30B (C30B), were chosen in this study as reinforcing agents. These nanoparticles were dispersed (1 and 3 wt% into the formulation) into a commercial epoxy acrylate oligomer by means of a three roll mill. Samples obtained from free standing UV-cured coatings were used for mechanical assessments. Mechanical tests were performed in both dynamic and static mode in order to investigate the viscoelastic behavior and tensile properties of coatings. Results from dynamic mechanical analysis have shown that all nanocomposite coatings have higher (72–75 °C) glass transition temperature compared to that observed (71 °C) in unreinforced coatings. The restriction of polymer chains mobility, due to the presence of layered silicate nanoparticles, has been used to explain the increase of glass transition temperature related to the decrease of the free volume. The storage modulus for nanocomposites containing 3 wt% of C10A, C15A and C30B was found to be slightly higher than that observed in pure coatings. The analysis of tensile stress–strain curves has revealed that tensile properties are affected by relative humidity (RH) due to the plasticization effect of humidity. In fact, results have shown that regardless of the organoclay type, the increase of RH decreases both Young's modulus and tensile strength while increasing maximum strain. We believe that low interfaces between photocrosslinked polymer chains and organoclays explain the lack of any effect of organoclays on both storage and Young's moduli. Among samples from each type of UV-cured coating tested at 0, 20 and 80% of RH, regardless of the organoclay type and content, only samples tested (tensile tests in static mode) at RH = 80% were broken. SEM images obtained from the fractured surface of these samples have shown that unreinforced UV-cured coatings and nanocomposite coatings are respectively characterized by smooth and rough fracture surface.  相似文献   

7.
Organic nucleating agents and inorganic nanoparticles, as well as their hybrid composites, affect the crystallization temperature and morphology of the monoclinic α-form of isotactic polypropylene (iPP). Techniques such as differential scanning calorimetry, hot-stage optical microscopy with cross polars, wide angle X-ray diffraction, and transmission electron microscopy were employed. Nanoparticles of zinc oxide function as efficient supports for 1,3,5-benzene tricarboxylic-(N-2-methylcyclohexyl)triamine because the temperature at which the maximum rate of iPP crystallization occurs during 10 °C/min cooling from the molten state increases from 111 °C for the pure polymer to 125 °C at low concentrations of this hybrid nucleating agent. In the absence of zinc oxide, 0.06 wt% of this aliphatic triamine recrystallizes near 165 °C and increases the crystallization temperature of iPP by 7 °C, relative to the pure polymer. Fluorinated aromatic triamines, such as 1,3,5-benzene tricaboxylic-(N-4-fluorophenyl)triamine, are weak nucleating agents that reduce spherulite size in isotactic polypropylene but only increase the crystallization temperature marginally when the polymer is cooled from the molten state. Both micro- and nanoparticles of zinc oxide reduce spherulite size in isotactic polypropylene, but smaller spherulites are observed when the inorganic nanoparticles exhibit dimensions on the order of 40-150 nm relative to micron-size particles. In contrast, 0.06 wt% of the aliphatic triamine in iPP yields a distorted birefringent texture under cross polars that is not spherulitic. Non-spherulitic birefringent textures in iPP are also observed when the aliphatic triamine nucleating agent is coated onto micro- or nanoparticles of zinc oxide. This study demonstrates that the nonisothermal crystallization temperature of isotactic polypropylene increases by an additional 7 °C when an aliphatic triamine is distributed efficiently within the polymeric matrix by coating this nucleating agent onto zinc oxide nanoparticles.  相似文献   

8.
As a continuation of previous work involving synthesis of an allyl-functionalized hyperbranched polyimide, AT-PAEKI, we have studied the use of this reactive polymer as a modifier of bisphenol-A based bismaleimide resin (BPA-BMI). This was pursued in anticipation of improvements in processability as well as physical properties including glass transition temperature, elastic modulus, and fracture toughness. Apparent miscibility, indicated by optical clarity with a single Tg, was observed for compositions containing up to 16 wt% AT-PAEKI. Additionally, we observed complete suppression of monomer crystallization and a slight increase in the overall cure exotherm. By rheological characterization, blends containing 4 wt% AT-PAEKI were found to feature a dramatic (65-fold) reduction in the viscosity minimum during heating. Dynamic mechanical analysis (DMA) showed that the addition of 2, 4, 8 wt%. AT-PAEKI increases the cured modulus by approximately 10% from a base value of 3.4 GPa, while adding 16 wt% AT-PAEKI decreases the modulus slightly to 3.3 GPa. DMA also revealed that the cured glass transition temperature increases monotonically with the addition of AT-PAEKI. Fracture toughness was gauged using the single edge notched beam methodology to yield the critical stress intensity factor, KIC. Our results showed a modest toughening effect (from 0.48 to 0.55 MPa m1/2) upon the addition of AT-PAEKI. We conclude that AT-PAEKI may serve as an effective reactive processing aid with slight improvements in Tg, modulus, and fracture toughness.  相似文献   

9.
The molecular dynamics of a series of poly(dimethylsiloxane) networks filled with silica nanoparticles synthesized in situ was investigated using thermally stimulated depolarization currents, broadband dielectric relaxation spectroscopy and differential scanning calorimetry. The techniques used cover together a broad frequency range (10−3-109 Hz), thus allowing to gain a more complete understanding of the effects of the nanoparticles on the chain dynamics. In addition to the α relaxation associated with the glass transition of the polymer matrix, we observe in dielectric measurements a slower α relaxation which is assigned to polymer chains close to the polymer/filler interface whose mobility is restricted due to interactions with the filler surface. The thickness of the interfacial layer is estimated to be about 2.1-2.4 nm. Differential scanning calorimetry shows a change in the shape of the glass transition step, as well as a decrease in both the degree of crystallinity and the crystallization rate by the addition of silica.  相似文献   

10.
A sol–gel chemical route was adopted to prepare the zinc oxide (ZnO) nanoparticles as small as 4 nm. UV-curable ZnO-acrylic nanocomposites were then prepared by employing 3-(trimethoxysilyl)propyl methacrylate (TPMA) as the surface modification agent of ZnO particles. UV–vis analysis revealed a high optical transparency (>95%) in visible light region for nanocomposite thin films with ZnO contents up to 20 wt.%. The addition of ZnO nanoparticles also enhanced the dielectric constants of nanocomposites and the dielectric constants greater than 4 in frequencies ranging from 1 to 600 MHz was obtained in the samples containing 10 wt.% of ZnO nanoparticles. A comparison of experimental results and theoretical calculation indicated that the interfacial polarizations in between ZnO nanoparticles and polymer matrix may play an important role in the enhancement of dielectric properties of nanocomposites.  相似文献   

11.
In this study a nanocomposite monofilament composed of a nematic thermotropic liquid crystalline polymer (TLCP) mixed with 1.5 wt.% of carbon nanoparticles (CNP) was prepared by melt extrusion. The nanoparticles had either a fibrous (VGCF) or layered (GNP) geometry. The tensile strength and modulus of the fibers increased with the draw down ratio of the filament; a positive effect on the tensile modulus is displayed by fibrous CNP, achieving values higher than those of high property organic fibers utilized as reinforcement for composite materials. Thermotropic transitions were characterized by DSC and in situ synchrotron WAXD. In particular, it was shown that the breadth of the temperature span of the crystalline-nematic transition correlated inversely with the draw down ratio. At high draw down ratio, addition of CNP also increased the relative amount of oriented polymer chains and contributed to sharpening of the mesomorphic transition.  相似文献   

12.
Fa-Ai Zhang  Dong-Keun Lee 《Polymer》2009,50(20):4768-9934
PMMA-mesoporous silica nanocomposites were prepared for the first time through in situ batch emulsion polymerization of methyl methacrylate in the presence of large pore MSU-F silica with a mesocellular foam structure (24.8 nm average cavity size) and subsequent compression molding of the polymer-silica nanoparticle mixtures. For composites containing 5.0 wt % silica, the onset decomposition temperature and the temperature at 10% weight loss for the nanocomposite increased 41 °C and 50 °C, respectively, in comparison to pure PMMA. The glass transition temperature of the nanocomposite increased 9.3 °C, as determined by differential scanning calorimetry. In addition, the storage modulus determined by dynamic mechanical analysis increased 17% and 80% at 50 °C and 100 °C, respectively. Substantial improvements in tensile strength (+50%) and modulus (+72%), were achieve at 10 wt % nanoparticle loading. Composites made by compression molding of physical mixtures of PMMA and MSU-F silica powders provide less improvement in thermal stability, glass transition temperature and mechanical properties in comparison to the composites made through in situ batch emulsion polymerization. Unlike previously reported composites made from nanoclays, the silica composites reported here show improvements in both thermal stability and mechanical reinforcement.  相似文献   

13.
Shape memory polymer composites based on a blend of thermoplastic polyurethane (TPU) segmented block copolymer and poly(ε-caprolactone) (PCL) with weight ratio of 70/30 and various nanomagnetite contents (0–5 wt%) were prepared by melt blending of TPU and PCL, together with a masterbatch of TPU/nanomagnetite. The samples were compounded for 10 min at 200 °C using an internal mixer. Synthesized nanomagnetite powder was introduced to the masterbatch via a solution mixing method using a high-intensity ultrasonic horn. Subsequently, thermal, mechanical, rheological and electrical properties of the TPU/PCL/nanomagnetite shape memory composites were investigated through various tests. The degree of crystallization of the PCL component in the composite structure was inspected by differential scanning calorimetry (DSC) and X-ray diffraction measurements. The results revealed that the percentage of crystallinity and the melting temperature of the PCL component changed in the presence of magnetite nanoparticles, which was related to the nanoparticles acting as nucleants. Observing a single glass transition temperature (T g) in DSC thermograms of the samples was indicative of good compatibility of the TPU and PCL components in the composite structure. This was also confirmed by dynamic-mechanical analysis in which the loss modulus curves showed a single glass transition temperature. Moreover, the loss modulus peak at glass transition was lowered and broadened by addition of nanomagnetite, by which it was assumed that introducing nanoparticles into the system changed the mechanism of glass transition due to particle–matrix interactions. The dynamic rheological and electrical resistivity experiments verified the existence of a low percolation threshold at about 2 wt% nanomagnetite. The state of nanomagnetite dispersion in the masterbatch and the microstructure of the ternary composites were characterized by scanning electron microscopy. Finally, adding nanomagnetite led to weakening of shape recovery of the polymer blend, with shape recovery dropping to 70 % at 5 % of nanomagnetite.  相似文献   

14.
Epoxy/vapor grown carbon nanofiber composites (VGCF) with different proportions of VGCF were fabricated by the in situ process.The VGCFs were well dispersed in both of the low and high viscosity epoxy matrices, although occasional small aggregates were observed in a high viscosity epoxy of 20 wt.%. The dynamic mechanical behavior of the nanocomposite sheets was studied. The storage modulus and the glass transition temperature (Tg) of the polymer were increased by the incorporation of VGCFs.The electrical and mechanical properties of the epoxy-VGCFs nanocomposite sheets with different weight percentages of VGCFs were discussed. The results were that both had maximum tensile strength and Young’s modulus at 5 wt.% for both materials and reduced the fracture strain with increasing filler content. The electrical resistivity was decreased with the addition of filler content. Mechanical, electrical and thermal properties of low viscosity epoxy composites were resulted better than that of the high viscosity composites.  相似文献   

15.
Semi-interpenetrating polymer networks (SIPNs) and polymer mixtures (1:1 mass ratio) based on segmented polyester polyurethane (PU) with carboxylic groups and methacrylic copolymer (PM) with tertiary amine groups were studied by the electron spin resonance (ESR) spin label method. The concentration of functional groups varied from 0 to 0.45 mmol g−1 in both prepolymers. The ESR spectra of spin labelled PM component were used to characterise the heterogeneity of segmental motion and transitions due to the additional polymer interactions imposed by complementary functional groups. The results were deduced from the temperature dependent ESR spectra. Two component spectra reflect the effect of PU chains on segmental motion of the PM component below the macroscopic glass transition temperature, Tg. The ratio of the fast and slow component was related to the complex polymer-polymer interaction or extent of miscibility. Restrictions of segmental motion of PM chains increase with functional groups concentration and above certain concentration (0.25 mmol g−1) PM segments in the network assess faster motion suggesting a change in the local packing density and domain structure. An increased miscibility and disorganisation of the ordered domains are confirmed by the loss of spherulitic morphology and crystallinity at higher functional groups concentration. PU/PM mixtures reveal similar motional behaviour as SIPNs of the same composition. However, the differences in the fractional amount of fast and slow motions confirm better interpenetration and interaction of the two polymers in the SIPNs. The results of motional heterogeneity and polymer interactions were complemented with the Tgs.  相似文献   

16.
Hiroaki Miyagawa 《Polymer》2004,45(15):5163-5170
The thermo-physical properties and the impact strength of diglycidyl ether of bisphenol F (DGEBF) epoxy nanocomposites reinforced with fluorinated single-wall carbon nanotubes (FSWCNT) are reported. A sonication technique was used to disperse FSWCNT in the glassy epoxy network resulting in nanocomposites having large improvement in modulus with extremely small amount of FSWCNT. The glass transition temperature decreased approximately 30 °C with an addition of 0.2 wt% (0.14 vol%) FSWCNT, without adjusting the amount of the anhydride curing agent. This was because of non-stoichiometry of the epoxy matrix that was caused by the fluorine on the single-wall carbon nanotubes. The correct amount of the anhydride curing agent needed to achieve stoichiometry was experimentally examined by dynamic mechanical analysis (DMA). The storage modulus of the epoxy at room temperature (which is below the glass transition temperature of the nanocomposites) increased up to 0.63 GPa with the addition of only 0.30 wt% (0.21 vol%) of FSWCNT, representing an up to 20% improvement compared with the neat epoxy. The Izod impact strength slightly decreased when the amount of FSWCNT was increased to 0.3 wt%. The excellent improvement in the storage modulus was achieved without sacrificing impact strength.  相似文献   

17.
Jianwen Xu  Wenmin Pang 《Polymer》2006,47(1):457-465
A series of novel Si-O-Si cross-linked organic/inorganic hybrid polyurethanes (HYPUs) with shape memory effect were prepared from isophorone diisocyanate (IPDI), poly(ethylene oxide) (PEO), and a newly synthesized hybrid diol (HD) containing hydrolysable Si-OEt groups. After hydrolyzation and condensation of Si-OEt groups, the resulted films were characterized using wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and shape recovery test to get the insight into the relationship between shape memory behaviors and polymeric structures. The glass transition temperatures (Tg) and storage modulus increased with Si-O-Si cross-linking increasing in the hybrid polyurethanes. The hybrid polyurethanes can recover to their original shapes almost completely in less than 40 s in atmosphere and in less than 10 s in water, respectively, when heated at 25 °C above Tg. The shape memory mechanism is coming from the freezing at low temperature and activation at high temperature of micro-Brownian movement of amorphous molecular chains since the temperature ranges at which the sharpest changes of recovered curvature happened are found to be around their glass transition range. The high ratio of storage modulus below and above accounted for the temporary shape fixing at low temperature. The samples with more Si-O-Si cross-linking have higher storage modulus at high temperature, resulting in faster shape recovery speed but lower temporary shape fixing.  相似文献   

18.
In this review, potential and properties of carbon nanotube, graphite, graphene oxide, and clay nanofiller have been deliberated with reference to aerospace application. The polymers discussed as matrices are polypropylene, polyaniline, polyurethane, polystyrene, and polyamide. Main focus of the review is to converse space competency of polymer/carbon nanotube, polymer/graphite, polymer/graphene oxide, and polymer/clay nanocomposite. The effect of nanofiller addition on the desired aerospace properties of polymeric nanocomposite has been conversed. Attractive features are high glass transition temperature, thermal stability, high modulus, chemical resistance, and nonflammability. Toward the end, challenges in the enhancement of materials’ properties for aerospace relevance have been considered.  相似文献   

19.
A series of amorphous polyphosphazenes containing carbazole-based multifunctional chromophores were synthesized. These polymers show low glass transition temperature (20-65 °C) and can easily be fabricated into optically transparent films with long-term stability. As an unambiguous evidence of photorefractive effect, preliminary two-beam-coupling experiments were performed at 633 nm under room temperature. All of these single-component polymers exhibited photorefractive performance without external electric field or prepoling, and gain coefficient of 91 cm−1 was observed in a polymer with the lowest glass transition temperature. The influence of the alkylene spacer length between the side group and the polymer backbone on the glass transition temperature, chromophore loading, as well as the optical gain was discussed. The steady-state photorefractive performance of a polyphosphazene with the shortest alkylene spacer was enhanced significantly by adding a photoconductive plasticizer N-ethyl-carbazole to lower the glass transition temperature and a gain of 198 cm−1 and a diffraction efficiency of 46% were achieved at zero electric field.  相似文献   

20.
The high concentration triblock copolymer poly(ethylene oxide)99-poly(propylene oxide)69-poly(ethylene oxide)99 (Pluronic F127) aqueous solutions with the addition of different components commonly used in physiologically relevant applications were characterized by rheological measurements, differential scanning calorimetry (DSC) and small angle X-ray/neutron scattering. The sol-gel transition temperature, as well as the storage modulus of the F127 solution depend both on the concentration of polymer and of clay. Above the gel transition, the storage modulus of the solutions increased with clay concentration. Yield strain is independent of polymer and clay concentrations. Two different kinds of inorganic salts, sodium chloride (NaCl) and calcium chloride (CaCl2) were added into the polymer and polymer-clay solutions. The sol-gel transition temperature decreased noticeably, but the storage modulus decreased only a small amount with increasing concentration of inorganic salts. Addition of salts to polymer-clay solutions resulted in precipitation of the clays which decreased the modulus. No effect on the mechanical properties was observed with the addition of common serum proteins. However, addition of 0.5-10% glucose decreased the transition temperature between 3° and 7°, without significantly affecting the modulus. The depression of the transition temperature by glucose was similar to that found with salts and indicated that the mechanism, namely competition for water, may be similar.  相似文献   

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