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1.
With the use of thermomechanical spectrometry in two modes, coaxial, when the load application vector is coplanar with the compacting pressure vector (semicrystalline copolymer) during the measurement of the deformation of a copolymer of tetrafluoroethylene with perfluoro(propyl vinyl ether), and mutually perpendicular (completely amorphous copolymer), it has been established that the axial compression of the copolymer brought its topological structure to an absolutely anisotropic state. After γ-irradiation, the semicrystalline structure of the copolymer was retained regardless of the radiation dose. The minimum values of the glass transition temperature of the amorphous block and the degree of crystallinity were observed in the copolymer irradiated to a dose of 150 kGy. The molecular weight distribution functions of interjunction chains in the networks of the amorphous blocks of the initial copolymer and its γ-irradiated analogs are bimodal.  相似文献   

2.
The molecular–topological structure of a copolymer of tetrafluoroethylene and perfluoro(propyl vinyl ether) before and after γ-irradiation has been studied for the first time. The pseudo-network structure of the copolymer contains an amorphous block and the crystalline segments of macromolecules serve as branching points. After γ-irradiation to a dose of 15 to 2380 kGy, polyassociative cluster-type entities have appeared in the initial copolymer in place of the crystalline branching points with simultaneous structure amorphization and a decrease in the onset temperature of molecular flow.  相似文献   

3.
彭静 《高分子科学》2004,(5):439-444
INTRODUCTIONChitosan, poly-β-(1 -?4)-D-glucosamine, can be obtained from chitin by deacetylation with alkali. It is soluble indilute acidic medium due to the presence of amino groups. The use of chitosan in many areas, such as foodprocessing, biochemistry, Pharmaceuticals, medicine, and agriculture has been developed over the pastdecades[1,2].In recent years, it has been reported that many properties of chitosan depend on the molecular weight[3]. Thechitosan oligomers possess better fun…  相似文献   

4.
The molecular–topological structure of a tetrafluoroethylene copolymer with ethylene after γ-irradiation and thermal annealing has been studied. The pseudo-network structure of the copolymer contains, in addition to the amorphous block, crystalline segments of macromolecules in the role of branching sites. Topologically, the diblock structure of the copolymer after thermal annealing at 538 K is transformed into a three-block structure with the appearance of a high-temperature amorphous block. Irradiation of the copolymer with γ-rays to a dose of 150 kGy does not lead to appreciable changes in its molecular–topological structure.  相似文献   

5.
The molecular–topological structure of a copolymer of tetrafluoroethylene and perfluoromethylvinyl ether has been studied for the first time before and after irradiation with 1- and 4-MeV protons. The pseudo-network structure of the copolymer contains an amorphous block and crystalline segments of macromolecules as branching points. After bombardment with protons, a high-temperature amorphous block is formed in the copolymer with simultaneous complete amorphization of the copolymer structure and a decrease in its molecular flow temperature. The surface of a target plate with a thickness of 500 μm that has not been directly exposed to proton bombardment preserves the molecular–topological structure of the initial copolymer.  相似文献   

6.
In this paper, pork fat peroxidation by γ-irradiation and the possible effects of oxygen, UV-irradiation and storage after the γ-irradiation have been investigated. It has been found that the level of peroxides in irradiated pork increases linearly with the increasing absorbed dose. The chemical yield of peroxides formed in the irradiated fat is about 4.2 and independent on the sample temperature or absorbed dose rate, but dependent on storage time of sample before γ-irradiation. The irradiated pork exhibits some unusual features as following: 1) the peroxide content in irradiated pork is higher than that in unirradiated one; 2) the peroxide content in irradiated pork increases gradually on storage and is essentially constant in unirradiated one, which is very useful for the detection of irradiated pork; 3) the further peroxidation in irradiated pork is much more susceptible to UV radiation than that in unirradiated pork.  相似文献   

7.
The molecular-topological structure of powdered high-density polyethylene (PE) after its compression under an optimized pressure and γ-radiolysis was first analyzed. A semicrystalline structure composed of one amorphous block and three crystalline modifications was formed with different rates and different melting onset temperatures in unirradiated PE and in PE irradiated to a dose of 5.5 Mrad. This structure was retained to 242 Mrad; after such a dose, the amorphous block completely disappeared. The net crystallinity of PE at a dose of 5.5 Mrad reached a minimum value but was close to 100 wt % in the initial state or after irradiation to 242 Mrad.  相似文献   

8.
Irradiation of a polytetrafluoroethylene (PTFE) film with accelerated (1–5 MeV) helium ions at a fluence of 1015 ion/cm2 has been studied. The efficiency of carbonization, defined as a decrease in the fluorine content and an increase in the carbon content on the surface of the polymer, increases with the incident ion energy. A characteristic feature of the topological structure of PTFE is the presence of four high-meltingpoint crystalline modifications, the “branching points” of the pseudo-network of the amorphous matrix block, in addition to a low-melting-point modification with the melting onset temperature of 13°C. After bombardment with 3–5 MeV ions, only two crystalline blocks remain in the polymer and a cluster block, which was not present in the unirradiated polymer, appears. The overall mass fraction of the crystalline structure in the irradiated polymer (0.48) is below that in the initial polymer (0.66), indicating amorphization of its structure.  相似文献   

9.
Six topological structures (an amorphous and five crystalline blocks) have been detected in a polytetrafluoroethylene film with a pseudo-network structure. During the Γ-irradiation of the polymer in air, the crystalline fractions degrade and gradually convert into amorphous and cluster states with the increasing radiation dose. After irradiation at a dose of 90 kGy, the polymer loses its capability for crystallization and forms a completely amorphous topological structure. However, regardless of dose in the range of 3–90 kGy, the topological structure of the polymer irradiated in a vacuum remains unchanged and consists of amorphous, cluster, and crystalline blocks.  相似文献   

10.
利用凝胶渗透色谱(GPC)、傅里叶变换红外光谱(FTIR)和示差扫描量热(DSC)等手段对不同剂量γ射线辐照后等规聚丙烯(iPP)的分子链结构及结晶行为的变化进行了研究.结果表明,γ射线辐照使iPP的分子量下降,并在其分子链中产生羟基和羰基等极性基团,从而影响其结晶行为.在非等温结晶过程中,当辐照剂量≤50 kGy时,iPP的热结晶温度略有升高;增大辐照剂量,iPP的热结晶温度明显降低.iPP的熔融温度则随辐照剂量的增大而降低,且分裂成双峰.利用Avrami方程研究了辐照前后iPP的等温结晶动力学,发现辐照前后样品的Avrami指数n都在3左右,表明iPP的结晶遵循异相成核机理,且不受辐照剂量和等温结晶温度的影响,但总结晶速率随等温结晶温度和辐照剂量的升高而逐渐减小.探讨了iPP经过γ射线辐照后,分子链断裂、链结构变化和结晶速率之间的关系.  相似文献   

11.
The molecular-topological structure of polyethylene (PE) and a PE matrix in a glass-reinforced plastic (GRP) after γ-irradiation of the plastic was studied by means of thermomechanical spectroscopy. The four-block topological structure of unirradiated PE (one amorphous block and three crystalline phases with different initial melting temperatures) is transformed into a three-block structure in the GRP already at a minimal radiation dose of 25 kGy. The intermediate crystalline phase disappears under these conditions, the molecular relaxation characteristics in all topological blocks alter, and chemical branching points appear in the pseudonetwork structure of the amorphous matrix block.  相似文献   

12.
In the present work, electron spin resonance (ESR) identification of γ-irradiated cefadroxil monohydrate (CM), duricef capsule (DC) and duricef suspension (DS) and their potential use as normal and/or accidental dosimetric materials were investigated in the dose range of 1–25 kGy. Although unirradiated samples did not exhibit any ESR signals, irradiated samples were observed to present ESR spectra with many resonance lines originating from radiation induced radical or radicals. Dose-response curves associated with the resonance peak heights of CM (I1, I2) and DS (I3, I4, I5, I6) were found to follow linear and power functions of applied radiation dose, respectively. Simulation calculations were performed to determine the structure and spectral parameters of the radiation-induced radicalic species involved in the formation of experimental ESR spectrum of CM using, as input, the room temperature signal intensity data obtained for a sample irradiated at dose of 10 kGy. Kinetic behaviors and activation energies of the radicalic species were also calculated using the data obtained from annealing studies performed at five different temperatures. The presence of detectable signal intensities even after a storage period of 100 days was considered as providing an opportunity in the discrimination of irradiated CM and DS from unirradiated ones. Basing on room temperature signal intensity decay and dose–response data, it was concluded that CM and DS present the features of a good dosimetric material.  相似文献   

13.
The molecular-topological structure of polytetrafluoroethylene (PTFE) has been studied in the range of ?100 to +450°C by thermomechanical spectrometry. Revealed in this temperature range is a fourblock topological structure composed of one amorphous (T g = 16°C) and three crystalline (low-melting (T m = 315°C), intermediate (T m 1 = 355°C), and high-melting (T m 2 = 388°C)) polymorphs. At a dose of 1 kGy, the long-range orientation of chains in the intermediate and high-melting crystalline blocks of PTFE is replaced by short-range orientation of the cluster association structure. At doses of 100?C500 kGy, the latter structure transitions to the amorphous state and the irradiated samples acquire a semicrystalline structure of the two-block type. The molecular-mass distribution function of interjunction chains of the pseudo-network of the amorphous block is bimodal in character and its maxima are noticeable shifted toward lower masses with an increase in the radiation dose. As the dose increases, the crystallinity decreases and the molecular mobility of amorphized chains is enhanced. As a result, both the glass transition and the molecular flow onset temperatures of the polymer are reduced.  相似文献   

14.
Thermoluminescence (TL) response of contaminating minerals from six samples of pulses commonly consumed in Pakistan has been studied for identification of irradiation treatment. The samples were irradiated by Co-60 gamma rays at 0.3, 0.5 and 1.0 kGy, or by 10 MeV electrons using an accelerator at 0.75 and 2.2. kGy. Generally, the TL intensity for minerals separated from irradiated samples was higher than for unirradiated samples. To normalize the results, separated minerals deposited on stainless steel discs were re-irradiated by a normalizing dose and TL response was redetermined. The ratio of the area of the first glow curve to the second glow curve was more than 0.8 for all irradiated samples and less than 0.33 for most of the unirradiated samples. For those unirradiated samples where the ratio of the glow curves was more then 0.03, the shapes of the glow curves were compared. Taking this criterion into consideration, all 21 unirradiated and irradiated samples of pulses were identified correctly. Therefore, a normalization procedure by re-irradiation of minerals and analysis of TL glow curve shapes lead to unequivocal identification of radiation treatment of pulses.  相似文献   

15.
The mechanical properties and heat shrinkability of electron beam crosslinked polyethylene–octene copolymer were studied. It was found that gel content increases with increased radiation dose. The analysis of results by the Charlesby–Pinner equation revealed that crosslinking was dominant over chain scission upon irradiation. Formation of a crosslinked structure in the electron beam irradiated sample was confirmed by the presence of a plateau of dynamic storage modulus above the melting point of the polymer. Wide-angle X-ray diffraction revealed that there was little change in crystallinity for the irradiated samples, indicating that radiation crosslinking occurs in the amorphous region of the polymer. The tensile modulus increases, whereas the elongation at break decreases with increased radiation dose. The heat shrinkability of the material increased with an increased radiation dose because the radiation-induced crosslinks serve as memory points during the shrinking process.  相似文献   

16.
Five topological units: low- and high-temperature amorphous blocks and three crystalline modifications that act as branching points in the networks of both amorphous blocks, have been detected for the first time in the pseudo-network structure of the unirradiated fluoroelastomer SKF-32 by means of thermomechanical spectrometry (TMS). When the rubber is γ-irradiated to a dose of 10 kGy, the structures of the intermediate and high-melting crystalline fractions degrade and their amorphized chains along with interjunction chains of both amorphous blocks assimilate into one amorphous block, and the latter is the block of the chemically crosslinked rubber already with a topologically diblock semicrystalline structure. A radiothermoluminescence (RTL) curve of the irradiated rubber shows four relaxation transitions (emissions peaks), with only the transition at–25°C almost coinciding with the glass transition temperature observed in thermomechanical analysis curve of the crosslinked rubber.  相似文献   

17.
The gamma irradiation effects on the bulk etch rate, V b of an indigenously prepared new nuclear track detector which is a copolymer of allyl bis-(2-nitroxy-ethyl) carbomate (ABNEC) and allyl diglycol carbonate (ADC) [ABNEC:ADC (1:9)] were studied in the dose range of 25.0–250.0 kGy and etching temperature range of 60–80 °C. The bulk etch rates increase and the activation energy values for bulk etching of gamma-irradiated detectors decrease with the increase in gamma dose indicating the scission of the detector. UV–visible spectra of the unirradiated and the irradiated films were also taken to explore the possibility of using this new detector for gamma dose measurements.  相似文献   

18.
Dilute aqueous solution of cresol red has been evaluated spectrophotometrically as possible gamma rays dosimeter. A 0.10 mM solution of cresol red was irradiated by gamma rays using a cobalt-60 radiation source. The absorbance spectra of the unirradiated and irradiated solutions were recorded using double beam scanning spectrophotometer. The absorbance of the solution before and after irradiation was measured at 434 nm (λmax) as well as at other wavelengths (415, 448 and 470 nm). Various parameters, such as Absorbance (A), ΔA, %A, -log A and log Ao/Ai were plotted against radiation dose, in order to check the response of cresol red solution and its possible use as chemical dosimeter. The response plots of A, ΔA, and %A versus absorbed dose showed that the solution can be used as a radiation dosimeter in a dose range up to 0.82 kGy. Using response plots of -log A and log Ao/Ai, the useful dose range can be extended up to 1.65 kGy; which are useful dose ranges for food irradiation applications. Stability studies of cresol red solution at different light and temperature conditions for pre- and post-irradiated storage of the dosimetric solutions suggested that aqueous solution of cresol red is highly stable in dark, under fluorescence light and at room temperature up to 150 days  相似文献   

19.
Electrical conductivity and dielectric parameters of the (BuA/MMA) copolymer films irradiated with 1.5 MeV electron beam (EB) have been studied. The samples were irradiated with different doses of the electron beam: 5, 10, 50, 125 and 200 kGy. The electrical conductivity of the samples was found to decrease as the irradiation dose increases. The temperature dependence of the direct current (dc) conductivity for unirradiated and irradiated samples has been obtained over a temperature range from 293 to 373 K. The activation energy values were calculated for all samples. Moreover, measurements of the dielectric constant, dielectric loss and alternating current (ac) conductivity were performed at a frequency range from 100 Hz to 5 MHz at room temperature. The results indicated that the EB irradiation has formed some traps in the energy gap, which reduce the movement of the charge carriers. Furthermore, a direct proportional relationship between the activation energy and the irradiation dose was estimated in two regions: below and above the glass transition temperature of the polymer. Dipole relaxation was observed in the samples, and the dose effect was found to shift this relaxation towards higher frequencies.  相似文献   

20.
The molecular–topological structure of polyamide before and after γ-irradiation has been first studied by thermomechanical spectrometry. The γ-irradiation with a dose up to 300 kGy does not change the topological structure of the polymer, the four-block pseudo-network structure of which contains crystalline segments of macromolecules and polyassociative entities of the cluster type in addition to low-and high-temperature amorphous blocks. During irradiation, only interblock mass transfer of the chain segments occurs, resulting in different dose-dependent values for the molecular weight of the chains, their weight fraction in each topological block, and the glass transition and molecular flow temperatures of the polymer. Radiothermoluminescence curves exhibit three maxima at 152, 200, and 330 K, of which the last one is detected in a temperature region close to the glass transition temperature of the high-temperature amorphous block on the thermomechanical analysis curve of the polymer.  相似文献   

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