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1.
Poly(methyl methacrylate) (PMMA) was γ‐irradiated (5–20 kGy) by a 137Cs source at room temperature in air. The changes in the molecular structure attributed to γ‐irradiation were studied by mechanical testing (flexure and hardness), size‐exclusion chromatography, differential scanning calorimetry, thermal gravimetric analysis, and both Fourier transform infrared and solution 13C‐NMR spectroscopy. Scanning electron microscopy was used to investigate the influence of the dose of γ rays on the fracture behavior of PMMA. The experimental results confirm that the PMMA degradation process involves chain scission. It was also observed that PMMA presents a brittle fracture mechanism and modifications in the color, becoming yellowish. The mechanical property curves show a similar pattern when the γ‐radiation dose increases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 886–895, 2002  相似文献   

2.
This article investigates the effects of electron beam (EB) radiation on poly(D ,L ‐lactic acid)‐b‐poly (ethylene glycol) copolymer (PLA‐b‐PEG‐b‐PLA). The copolymer films were EB irradiated at doses from 0 to 100 kGy. The degradation of these films was studied by measuring the changes in their molecular weight, mechanical and thermal properties. The dominant effect of EB radiation on PLA‐b‐PEG‐b‐PLA is chain‐scission. With increasing irradiation dose, recombination reactions or partial crosslinking may occur in addition to chain scission. The degree of chain scission Gs and crosslinking Gx of sample are calculated to be 0.213 and 0.043, respectively. A linear relationship is also established between the decreases in molecular weight with increasing irradiation dose. Elongation at break of the irradiated sample decreases significantly, whereas its tensile strength decreases slightly. The glass transition temperature (Tg) is basically invariant as a function of irradiation dose. Thermogravimetric analysis shows that its thermal stability decreases with increasing dose. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

3.
The sensitivity to radiation of mixtures of poly(methyl methacrylate) (PMMA) and polystyrene-co-acrylonitile) (SAN) was studied over the entire range of composition. Polystyrene-co-acrylonitrile, like polystyrene, is highly resistant to ionizing radiation, having a small Gx value for crosslinking (0.077) and an even smaller Gs value for main chain scission (0.055). In contrast, PMMA degrades readily under irradiation (with Gs = 1.2). In γ-irradiated blends, the behavior of each polymer is largely influenced by the presence of the other component. Gel formation in SAN is impeded by PMMA, as a result of a decrease in Gx, and a concomitant increase in the ratio Gs/Gx. Flexural strength measurements, along with molecular weight determinations by gel permeation chromatography, demonstrated that SAN had a marked protective effect on PMMA by decreasing Gs (chain scission). This protective effect was not observed in earlier experiments with PMMA–PS blends, in spite of its chemical similarity to the system PMMA–SAN. The difference in behavior between PMMA–PS and PMMA–SAN may be explained on the basis of polymer compatibility. PMMA and SAN form a compatible pair, whereas PMMA and PS are incompatible; thus the short range protective effect of the phenyl groups in PS is inhibited.  相似文献   

4.
The γ irradiation of poly(methacrylate)s with various ester groups at room temperature was investigated by gel permeation chromatography and NMR techniques. The G values for scission and crosslinking for each of the polymers were estimated from the changes in the molecular weights and molecular weight distributions. The new structures formed during γ irradiation were examined by 1H-NMR spectroscopy. All of the investigated poly(alkanemethacrylate)s were found to produce the alkane formates during γ irradiation, and for poly(2-methyl heptyl methacrylate) G(S) was less than 4G(X), indicating gel formation in this polymer. In the investigation of poly(benzyl methacrylate), no formate ester was found, but some small molecule compounds formed from the benzyl radical were detected. The benzyl group was also found to stabilize the polymer against radiation damage. © 1996 John Wiley & Sons, Inc.  相似文献   

5.
For medical applications, 4,4′‐dicyclohexyl methane diisocyanate (HMDI)‐based poly(carbonate urethane)s were synthesized from HMDI and 1,4‐butanediol as hard segments and poly(carbonate diol) (number‐average molecular weight = 2000 g/mol) as soft segments. The effects of wide‐range γ irradiation on the samples were examined through a series of analytical techniques. Scanning electron microscopy revealed that γ irradiation etched and roughened the surfaces of the irradiated samples. The gel content and crosslinking density measurements confirmed that crosslinking occurred along with degradation at all of the investigated irradiation doses and the degree of both crosslinking and degradation increased with increasing irradiation dose. Fourier transform infrared spectroscopy demonstrated that chain scission in the γ‐irradiated samples occurred at the carbonate and urethane bonds. The decreasing molecular weight and tensile strength indicated that the degradation increased with the γ‐irradiation dose. Differential scanning calorimetry and dynamic mechanical thermal analysis indicated that γ irradiation had no significant effect on the phase‐separation structures. There was a slight reduction in the contact angle. An evaluation of the cytotoxicity demonstrated the nontoxicity of the nonirradiated and irradiated polyurethanes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41049.  相似文献   

6.
Miscible polymer blends based on various ratios of poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) were prepared in film form by the solution casting technique using benzene as a common solvent. The thermal decomposition behavior of these blends and their individual homopolymers before and after γ‐irradiation at various doses (50–250 kGy) was investigated. The thermogravimetric analysis technique was utilized to determine the temperatures at which the maximum value of the rate of reaction (Tmax) occurs and the kinetic parameters of the thermal decomposition. The rate of reaction curves of the individual homopolymers or their blends before or after γ‐ irradiation displayed similar trends in which the Tmax corresponding to all polymers was found to exist in the same position but with different values. These findings and the visual observations of the blend solutions and the transparency of the films gave support to the complete miscibility of these blends. Three transitions were observed along the reaction rate versus temperature curves; the first was around 100–200°C with no defined Tmax, which may arise from the evaporation of the solvent. The second Tmax was in the 340–380°C range, which depended on the polymer blend and the γ‐irradiation condition. A third transition was seen in the rate of reaction curves only for pure PVAc and its blends with PMMA with ratios up to 50%, regardless of γ‐ irradiation. We concluded that γ‐irradiation improved the thermal stability of PVAc/PMMA blends, even though the PMMA polymer was degradable by γ irradiation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1773–1780, 2006  相似文献   

7.
Brush type of poly (3‐hydroxy butyrate), PHB, copolymer synthesis has been reported. Natural PHB was chlorinated by passing chlorine gas through PHB solution in CHCl3/CCl4 mixture (75/25 v/v) to prepare chlorinated PHB, PHB‐Cl, with the chlorine contents varying between 2.18 and 39.8 wt %. Toluene solution of PHB‐Cl was used in the atom transfer radical polymerization (ATRP) of methyl methacrylate, MMA, in the presence of cuprous bromide (CuBr)/2,2′‐bipyridine complex as catalyst, at 90°C. This “grafting from” technique led to obtain poly (3‐hydroxybutyrate)‐g‐poly(methylmethacrylate) (PHB‐g‐PMMA) brush type graft copolymers (cylindrical brush). The polymer brushes were fractionated by fractional precipitation methods and the γ values calculated from the ratio of the volume of nonsolvent to volume of solvent of brushes were ranged between 2.8 and 9.5 depending on the molecular weight, grafting density, and side chain length of the brushes, while the γ values of PHB, PHB‐Cl, and homo‐PMMA were 2.7–3.8, 0.3–2.4, and 3.0–3.9, respectively. The fractionated brushes were characterized by gel permeation chromatography, 1H‐NMR spectrometry, thermogravimetric analysis (TGA), and differential scanning calorimetry techniques. PHB‐g‐PMMA brush type graft copolymers showed narrower molecular weight distribution (mostly in range between 1.3 and 2.2) than the PHB‐Cl macroinitiator (1.6–3.5). PHB contents in the brushes were calculated from their TGA thermograms and found to be in range between 22 and 42 mol %. The morphologies of PHB‐g‐PMMA brushes were also studied by scanning electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

8.
This article investigated the effects of electron beam (EB) irradiation on poly(D ,L ‐lactic acid)‐b‐poly(ethylene glycol) copolymer (PLEG) and poly(L ‐lactic acid) (PLLA). The dominant effect of EB irradiation on both PLEG and PLLA was chain scission. With increasing dose, recombination reactions or partial crosslinking of PLEG can occur in addition to chain scission, but there was no obvious crosslinking for PLLA at doses below 200 kGy. The chain scission degree of irradiated PLEG and PLLA was calculated to be 0.213 and 0.403, respectively. The linear relationships were also established between the decrease in molecular weight with increasing dose. Elongation at break of the irradiated PLEG and PLLA decreased significantly, whereas the tensile strength and glass transition temperature of PLLA decreased much more significantly compared with PLEG. The presence of poly(ethylene glycol) (PEG) chain segment in PLEG was the key factor in its greater stability to EB irradiation compared with PLLA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

9.
The miscibility and crystallization kinetics of the blends of random poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [P(HB‐co‐HV)] copolymer and poly(methyl methacrylate) (PMMA) were investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). It was found that P(HB‐co‐HV)/PMMA blends were miscible in the melt. Thus the single glass‐transition temperature (Tg) of the blends within the whole composition range suggests that P(HB‐co‐HV) and PMMA were totally miscible for the miscible blends. The equilibrium melting point (T°m) of P(HB‐co‐HV) in the P(HB‐co‐HV)/PMMA blends decreased with increasing PMMA. The T°m depression supports the miscibility of the blends. With respect to the results of crystallization kinetics, it was found that both the spherulitic growth rate and the overall crystallization rate decreased with the addition of PMMA. The kinetics retardation was attributed to the decrease in P(HB‐co‐HV) molecular mobility and dilution of P(HB‐co‐HV) concentration resulting from the addition of PMMA, which has a higher Tg. According to secondary nucleation theory, the kinetics of spherulitic crystallization of P(HB‐co‐HV) in the blends was analyzed in the studied temperature range. The crystallizations of P(HB‐co‐HV) in P(HB‐co‐HV)/PMMA blends were assigned to n = 4, regime III growth process. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3595–3603, 2004  相似文献   

10.
A complex of Eu(C10H8N2O2)2 (NO3)3, in different amounts [0.1, 0.3, 0.5, 1, 2 wt % with respect to the poly(methyl methacrylate) (PMMA)], was doped into PMMA matrix and the resulting formulation deposited by a solvent casting technique. Each complex‐doped PMMA composition was characterized by UV‐visible spectroscopy, fluorescence spectroscopy, fluorescence lifetime analysis, X‐ray diffraction and infrared spectroscopy. The structural properties of the composites are discussed on the basis of the results from these analyses. The chelate‐doped PMMA shows good luminescence properties with relatively long life times. It has been shown that the fluorescence life time of the complex‐doped PMMA composites varies with the amount of the chelate molecule in the composite. The results from the fluorescence analyses suggest that, in the doped systems, the microenvironment around the central metal ion changes with composition. The optical properties of the system vary with composition. The observations should be of value to the development of superior luminescent materials. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers  相似文献   

11.
The thermal degradation kinetics of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [poly(HB–HV)] under nitrogen was studied by thermogravimetry (TG). The results show that the thermal degradation temperatures (To, Tp, and Tf) increased with an increasing heating rate (B). Poly(HB–HV) was thermally more stable than PHB because its thermal degradation temperatures, To(0), Tp(0), and Tf(0)—determined by extrapolation to B = 0°C/min—increased by 13°C–15°C over those of PHB. The thermal degradation mechanism of PHB and poly(HB–HV) under nitrogen were investigated with TG–FTIR and Py–GC/MS. The results show that the degradation products of PHB are mainly propene, 2‐butenoic acid, propenyl‐2‐butenoate and butyric‐2‐butenoate; whereas, those of poly(HB–HV) are mainly propene, 2‐butenoic acid, 2‐pentenoic acid, propenyl‐2‐butenoate, propenyl‐2‐pentenoate, butyric‐2‐butenoate, pentanoic‐2‐pentenoate, and CO2. The degradation is probably initiated from the chain scission of the ester linkage. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1530–1536, 2003  相似文献   

12.
Infrared (IR) spectroscopy studies were performed for poly(methyl methacrylate) (PMMA) samples doped with an organic ligand or its cobalt(II) complex after the extraction of the dopant during γ‐radiolysis. There were no drastic changes in the IR absorption band position, but noticeable changes in the intensities were found. The relative transmission of IR absorption bands, such as those at 750, 840, 1065, and 1388 cm?1, were measured according to the transmission of the carbonyl group band at 1717 cm?1. The degradation and recombination mechanism of different groups in the polymeric chain or backbone during radiolysis could be explained by the behavior of the relative transmission data for each group with increasing exposure dose. The tacticity of the PMMA samples was unchanged during radiolysis, and they were found to be syndiotactic. This was confirmed by the IR J values for different PMMA samples before and after irradiation. The protection efficiency of the organic ligand and its cobalt(II) complex was also investigated, and it was found that the organic ligand was more protective than the cobalt(II) complex for PMMA samples against γ‐rays. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1937–1950, 2004  相似文献   

13.
Poly (ethylene terephthalate) (PET) was irradiated in air by gamma rays at dose rate of 28 kGy/h for doses up to 3500 kGy. The influences of gamma irradiation on the glass transition and degree of crystallinity were investigated by differential scanning calorimetry. For amorphous PET, the observed glass transition temperature Tg and step of heat capacity ΔCp decreased with absorbed dose. These decreases were attributed to a predominant chain scission process. The glass transition temperature may be useful as an indicator of radiation to the PET. The results also showed that such chain scission increases in mobility lead to a greater crystallizability. POLYM. ENG. SCI. 46:1374–1377, 2006. © 2006 Society of Plastics Engineers  相似文献   

14.
In this study, γ rays were used for the first time to cure dental‐base material. The effect of the radiation dose on the thermal and rheological properties of poly(methyl methacrylate) (PMMA) used as a dental‐base material was investigated. The commercial powder and liquid material (heat‐curing‐grade) were mixed and polymerized at 60 and 70°C in a constant‐temperature water bath for 30 min and then were cured by γ rays, with total doses of 7.5, 15, 22.5, 30, 45, 52.5, 360, and 2160 krad. For each sample, the viscosity‐average molecular weights were measured, and no significant differences were observed of total dose on molecular weights. A thermal investigation with differential scanning calorimetry showed an exothermic peak in the thermograms of samples that were not completely polymerized and crosslinked. The rheological nature of the samples was studied with dynamic mechanical analysis. A comparison of properties of γ‐ray‐cured samples and those cured by other methods revealed γ curing to be a superior method for producing high‐molecular‐weight homogenous polymers with low porosity and crosslinking. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1291–1296, 2001  相似文献   

15.
A new graft copolymers poly(aryl ether sulfone)‐graft‐polystyrene (PSF‐g‐PS) and poly(aryl ether sulfone)‐graft‐[polystyrene‐block‐poly(methyl methacrylate)] (PSF‐g‐(PS‐b‐PMMA)) were successfully prepared via atom transfer radical polymerisation (ATRP) catalyzed by FeCl2/isophthalic acid in N,N‐dimethyl formamide. The products were characterized by GPC, DSC, IR, TGA and NMR. The characterization data indicated that the graft copolymerization was accomplished via conventional ATRP mechanism. The effect of chloride content of the macroinitiator on the graft copolymerization was investigated. Only one glass transition temperature (Tg) was detected by DSC for the graft copolymer PSF‐g‐PS and two glass transition temperatures were observed in the DSC curve of PSF‐g‐(PS‐b‐PMMA). The presence of PSF in PSF‐b‐PS or PSF‐g‐(PS‐b‐PMMA) was found to improve thermal stabilities. © 2002 Society of Chemical Industry  相似文献   

16.
Specimens of poly(vinylidene fluoride) (PVDF)–poly(methyl methacrylate) (PMMA)–polystyrene (PS) polyblends with different weight percentage ratios of the three polymers were prepared with the solution cast technique. The effect of γ irradiation on the Vicker's microhardness was studied. Among the three pure polymers, PVDF, PMMA, and PS, the γ irradiation imparted crosslinking in PVDF, thereby causing radiational hardening. In the cases of PMMA and PS, the effect of irradiation exhibited a predominance of both the scissioning and crosslinking processes in different ranges of doses. Moreover, at a dose of 5 Mrad, in both PMMA and PS, maximum radiational crosslinking was observed. The effect of γ irradiation seemed to stabilize beyond 15 Mrad in PVDF and beyond 20 Mrad in PMMA and PS. Microhardness measurements on ternary blends of PVDF, PMMA, and PS revealed that the blend with low contents of PMMA, that is, up to 5 wt %, yielded softening, whereas increasing the content of PMMA beyond 5 wt % produced a hardened material because of radiational crosslinking, and a higher content of PMMA in the blend facilitated this crosslinking. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3107–3111, 2004  相似文献   

17.
The thermal degradation of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [P(HB‐HV)] was studied using thermogravimetry (TG). In the thermal degradation of PHB, the temperature at the onset of weight loss (To) was derived by To = 0.97B + 259, where B represents the heating rate (°C/min). The temperature at which the weight loss rate was maximum (Tp) was Tp = 1.07B + 273, and the final temperature (Tf) at which degradation was completed was Tf = 1.10B + 280. The percentage of the weight loss at temperature Tp (Cp) was 69 ± 1% whereas the percentage of the weight loss at temperature Tf (Cf) was 96 ± 1%. In the thermal degradation of P(HB‐HV) (7:3), To = 0.98B + 262, Tp = 1.00B + 278, and Tf = 1.12B + 285. The values of Cp and Cf were 62 ± 7 and 93 ± 1%, respectively. The derivative thermogravimetric (DTG) curves of PHB confirmed only one weight loss step change because the polymer mainly consisted of the HB monomer only. The DTG curves of P(HB‐HV), however, suggested multiple weight loss step changes; this was probably due to the different evaporation rates of the two monomers. The incorporation of 10 and 30 mol % of the HV component into the polyester increased the various thermal temperatures (To, Tp, andTf) by 7–12°C (measured at B = 20°C/min). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2237–2244, 2001  相似文献   

18.
A novel copolymer of polybenzimidazoles was prepared by copolymerization of 3,3′‐diaminobenzidine tetrahydrochloride, 3,4‐diaminobenzoic acid and isophthalic acid in polyphosphoric acid at 200 °C. The polymerization could be performed within 90–110 min with the assistance of microwave irradiation. The solubility of the copolymer obtained in N,N‐dimethylacetamide (DMAc) was improved compared with those of poly[2,2′‐(m‐phenylene)‐5,5′‐bibenzimidazole] and poly(2,5‐benzimidazole). Thus copolymer membranes could be readily prepared by dissolving the copolymer powders in DMAc with refluxing under ambient pressure. The decomposition temperature of the copolymer was about 520 °C in air according to thermogravimetric analysis data. The proton conductivity and mechanical strength of the phosphoric acid‐doped copolymer membranes were investigated at elevated temperatures. A conductivity of 0.09 S cm?1 at 180 °C and a tensile stress at break of 5.9 MPa at 120 °C were achieved for the acid‐doped copolymer membranes by doping acids in a 75 wt% H3PO4 solution. Copyright © 2010 Society of Chemical Industry  相似文献   

19.
The purpose of this study was to improve the physical properties and to expand the application range of starch‐based blend films added nano‐sized TiO2/poly(methyl methacrylate‐co‐acrylamide) (PMMA‐co‐AM). Starch‐based blend films were prepared by using corn starch, polyvinyl alcohol (PVA), nano‐sized PMMA‐co‐AM, nano‐sized TiO2/PMMA‐co‐AM particles, and additives, i.e., glycerol (GL) and citric acid (CA). Nano‐sized PMMA‐co‐AM was synthesized by emulsion polymerization and TiO2 nanoparticles were also prepared by using sol–gel method. Nano‐sized TiO2/PMMA‐co‐AM particles were synthesized by wet milling for 48 h. The morphology and crystallinity of TiO2, nano‐sized PMMA‐co‐AM and TiO2/PMMA‐co‐AM particles were investigated by using the scanning electron microscope (SEM) and X‐ray diffractometer (XRD). In addition, the functional groups of the TiO2/PMMA‐co‐AM particles were characterized by IR spectrophotometry (FTIR). The physical properties such as tensile strength (TS), elongation at break (%E), degree of swelling (DS), and solubility (S) of starch‐based films were evaluated. It was found that the adding of nano‐sized particles can greatly improve the physical properties of the prepared films. The photocatalytic degradability of starch/PVA/nano‐sized TiO2/PMMA‐co‐AM composite films was evaluated using methylene blue (MB) and acetaldehyde (ATA) as photodegradation target under UV and visible light. The degree of decomposition (C/C0) of MB and ATA for the films containing TiO2 and CA was 0.506 and 0.088 under UV light irradiation and 0.586 (MB) and 0.631 (ATA) under visible light irradiation, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

20.
The major degradative process in γ-irradiated cellulose acetate is chain scission. For the dry powder the Gs value (number of scissions per 100 eV of energy absorbed) was found to be 7.1. The water-swollen material was found to degrade at the higher rate of Gs = 9.45. Additions of ethanol and methanol to the water brought about reductions in Gs, whereas dissolved nitrous oxide produced an increase in Gs. The useful life of cellulose acetate reverse osmosis membranes exposed to γ radiation was estimated by observations of the water permeation rate during irradiation. Membrane breakdown occurred at 15 Mrad in pure water, but the dose to breakdown was extended to 83 Mrad in the presence of 4% methanol.  相似文献   

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