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1.
Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) was irradiated by 60Co γ‐rays (doses of 50, 100 and 200 kGy) under vacuum. The thermal analysis of control and irradiated PHBV, under vacuum was carried out by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The tensile properties of control and irradiated PHBV were examined by using an Instron tensile testing machine. In the thermal degradation of control and irradiated PHBV, a one‐step weight loss was observed. The derivative thermogravimetric curves of control and irradiated PHBV confirmed only one weight‐loss step change. The onset degradation temperature (To) and the temperature of maximum weight‐loss rate (Tp) of control and irradiated PHBV were in line with the heating rate (°C min?1). To and TP of PHBV decreased with increasing radiation dose at the same heating rate. The DSC results showed that 60Co γ‐radiation significantly affected the thermal properties of PHBV. With increasing radiation dose, the melting temperature (Tm) of PHBV shifted to a lower value, due to the decrease in crystal size. The tensile strength and fracture strain of the irradiated PHBV decreased, hence indicating an increased brittleness. Copyright © 2004 Society of Chemical Industry  相似文献   

2.
The energetic material, 3‐nitro‐1,5‐bis(4,4′‐dimethyl azide)‐1,2,3‐triazolyl‐3‐azapentane (NDTAP), was firstly synthesized by means of Click Chemistry using 1,5‐diazido‐3‐nitrazapentane as main material. The structure of NDTAP was confirmed by IR, 1H NMR, and 13C NMR spectroscopy; mass spectrometry, and elemental analysis. The crystal structure of NDTAP was determined by X‐ray diffraction. It belongs to monoclinic system, space group C2/c with crystal parameters a=1.7285(8) nm, b=0.6061(3) nm, c=1.6712(8) nm, β=104.846(8)°, V=1.6924(13) nm3, Z=8, μ=0.109 mm−1, F(000)=752, and Dc=1.422 g cm−3. The thermal behavior and non‐isothermal decomposition kinetics of NDTAP were studied with DSC and TG‐DTG methods. The self‐accelerating decomposition temperature and critical temperature of thermal explosion are 195.5 and 208.2 °C, respectively. NDTAP presents good thermal stability and is insensitive.  相似文献   

3.
A systematic protocol to fabricate self‐assembly deoxycholate‐chitosan nanospheres (DC‐CsNS) by γ‐ray pre‐irradiation and chemical modification was studied. Hydrophobic deoxycholic acid moieties were chemically conjugated to pre‐irradiated chitosan. The influences of chitosan physical forms (i.e., colloid and flake) during irradiation, radiation doses, and the reaction system (heterogeneous or homogeneous) on the chemical modification and the particle shape and size were investigated. Pre‐irradiation of chitosan in colloidal form produced smaller DC‐CsNS particle size than that of flake form. In the heterogeneous reaction, the pre‐irradiated dose influenced the DC‐CsNS particle size, whereas in the homogeneous reaction all pre‐irradiation doses gave an identical average size range of 30–50 nm. By pre‐irradiation (10 kGy) of chitosan in colloidal form before heterogeneous chemical conjugation, it is possible to obtain DC‐CsNS with an average size of 46 nm. DC‐CsNS of about 50 nm in size could also be synthesized using homogeneous chemical conjugation onto non‐irradiated chitosan with the addition of N‐hydroxysuccinimide (NHS). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

4.
In the medical industry, ionizing radiation has attracted increasing interest in recent years for the sterilization of biomedical materials due to its high effectiveness at relatively low cost and simple operation. In the study reported here, silk fibroin (SF) fiber was used to prepare novel reinforced poly(ε‐caprolactone) (PCL) biocomposites, and the effect of electron beam irradiation on both non‐isothermal and isothermal crystallization kinetics of the SF/PCL biocomposites was investigated. The models of Ozawa treatment, Avrami analysis and regime theory of crystal growth are applicable for describing the non‐isothermal and isothermal crystallization kinetics of the irradiated PCL and SF/PCL composites. Compared with non‐irradiated PCL and SF/PCL composites, the irradiated specimens exhibit the same crystallization regime (regime II) and similar lateral surface free energy (σ), except for smaller fold surface free energy (σe) and work of chain folding (q). The crosslinked PCL network formed in the irradiation process can act as a nucleation agent and accelerate the primary crystallization of PCL. However, the restriction effect of the crosslinked PCL network on the molecular chain mobility will reduce the overall crystallization rate of PCL, and this restriction effect appears stronger in the non‐isothermal crystallization process than in the isothermal crystallization process. Copyright © 2009 Society of Chemical Industry  相似文献   

5.
The energetic material 3‐(4‐aminofurazan‐3‐yl)‐4‐(4‐nitrofurazan‐3‐yl)furazan (ANTF) with low melting‐point was synthesized by means of an improved oxidation reaction from 3,4‐bis(4′‐aminofurazano‐3′‐yl)furazan. The structure of ANTF was confirmed by 13C NMR spectroscopy, mass spectrometry, and the crystal structure was determined by X‐ray diffraction. ANTF crystallized in monoclinic system P21/c, with a crystal density of 1.785 g cm−3 and crystal parameters a=6.6226(9) Å, b=26.294(2) Å, c=6.5394(8) Å, β=119.545(17)°, V=0.9907(2) nm3, Z=4, μ=0.157 mm−1, F(000)=536. The thermal stability and non‐isothermal kinetics of ANTF were studied by differential scanning calorimetry (DSC) with heating rates of 2.5, 5, 10, and 20 K min−1. The apparent activation energy (Ea) of ANTF calculated by Kissinger's equation and Ozawa's equation were 115.9 kJ mol−1 and 112.6 kJ mol−1, respectively, with the pre‐exponential factor lnA=21.7 s−1. ANTF is a potential candidate for the melt‐cast explosive with good thermal stability and detonation performance.  相似文献   

6.
Branched poly(butylene succinate) (PBS) copolymers were synthesized, from succinic acid (SA), 1,4‐butanediol (1,4‐BD), and 1,2‐octanediol (1,2‐OD) through a two‐step process containing esterification and polycondensation, with different mole fractions of 1,2‐OD segments. The branched PBS copolymers were characterized with 1H‐NMR, differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), thermogravimetric analysis (TGA), dynamic rheological testing, and tensile properties analysis. The results of DSC and WAXD show that, with the increasing of the 1,2‐OD segments content, the glass transition temperature (Tg), melting temperature (Tm), crystallization temperature (Tc), and the degree of crystallinity (Xc) decrease. While the crystal structure of PBS does not change by introducing 1,2‐OD segments. The results of TGA and dynamic rheological testing indicate that the thermal stability of neat PBS is improved with the addition of 1,2‐OD segments. The incorporation of 1,2‐OD segments has some effects on the rheological properties of PBS, such as complex viscosities (|η*|), storage modulus (G′), and loss modulus (G″). Tensile testing demonstrates that the elongation at break is improved significantly with increasing 1,2‐OD segments content, but without a notable decrease of tensile strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

7.
The protection of some poly(methyl methacrylate) (PMMA) samples against γ rays was investigated in the absence and presence of poly(p‐sulfanilamide). Pure PMMA (without additives) and PMMA–poly(p‐sulfanilamide) blend samples were irradiated with γ rays for different exposure doses (5, 15, 25, 35, 50, 75, and 100 kGy). The viscosity‐average molecular weights were determined and thin‐layer chromatography measurements were carried out after each irradiation dose. The maximum protection against γ rays was found when 1% poly(p‐sulfanilamide) was used. The radiation chemical yield for main scission (Gs) was calculated and had lower values in the case of 1% poly(p‐sulfanilamide). The energy absorption per scission was maximum for 1% poly(p‐sulfanilamide), and this confirmed the obtained Gs data. From thin‐layer chromatography studies, it was observed that both the retention factor (Rf) values and polydispersity of the PMMA samples increased with an increasing exposure dose. The effect of γ irradiation on PMMA films doped with 1% poly(p‐sulfanilamide) was investigated with UV spectroscopy after the extraction of the additives. A change in the intensity of the absorption bands with an increasing irradiation dose was recorded. It is suggested that PMMA films doped with this type of polymer can be used as dosimeters. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

8.
We conducted this study to examine the changes in the molecular structure and physiological activities of silk sericin after γ irradiation. Sericin from Bombyx mori was extracted with an Na2CO3 solution. The molecular weight distribution of sericin increased in the gel permeation chromatography and sodium dodecyl sulfate/polyacrylamide gel electrophoresis results as the irradiation dose increased. Circular dichroism data also revealed that the α‐helix contents decreased with the irradiation dose. Ultraviolet absorption was shown a different pattern between the irradiated and unirradiated sericin. However, the Fourier transform infrared spectrum was not changed in all of the groups. Furthermore, the irradiated sericin was significantly increased in 2,2‐diphenyl‐1‐picryl‐hydrazil radical scavenging, and the tyrosinase inhibitory activities increased with irradiation dose. Therefore, γ irradiation was an effective method for producing high‐molecular‐weight sericin and for developing functional foods and cosmetics. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

9.
The compounds 1,4‐butanediol, succinic anhydride, and nanocellulose (NCC) were used to synthesize poly(butylene succinate)‐grafted Nanocrystalline Cellulose (PBS‐g‐NCC) nanocomposites via polymerization in situ. The resulting structures were examined by transmission electron microscopic (TEM), scanning electron microscope (SEM), 1H and 13C‐nuclear magnetic resonance spectroscopic (NMR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and X‐ray diffraction (XRD) analyses. TEM showed the cellulose to be nanoscale and SEM analysis indicated that 3 wt% NCC dispersed well in PBS matrix. 1H and 13C‐NMR analyses indicated the product to possess peaks characteristic of PBS. DSC analysis clearly showed that the NCC increased the PBS crystallinity when 3 wt% NCC was introduced into PBS matrixes by polymerization in situ, compared to pure PBS. TGA illustrated that the thermal stability of PBS‐g‐NCC was better than that of pure PBS, when 3 wt% NCC was added. XRD analysis suggested that 3 wt% NCC improved PBS crystallinity, which was in good agreement with the present DSC results. POLYM. ENG. SCI., 59:928–934, 2019. © 2018 Society of Plastics Engineers  相似文献   

10.
Samples of polyacrylamide (PAAm), poly(acrylic acid) (PAA), and their complex were γ‐irradiated at different doses, namely 48, 96, and 144 KGy. The examination of the infrared spectra of these samples showed that there are no significant observable changes in their spectral features apart from slight changes in the intensities of the absorption bands. The analysis of the absorbances ratios (A 1700 cm?1/A 1450 cm?1) and (A 1650 cm?1/A 1450 cm?1), denoted as R1 and R2, respectively, showed that these ratios depend on γ‐doses. It was found that in the case of PAA, R1 assumed linear increase with increasing the dose to 96 KGy and then showed marked decrease. For the complex, R1 increased slightly by increasing the dose to 96 KGy and then decreased. For PAAm, although irradiation with 48 KGy increases the values of R2, irradiation with 96 and 144 KGy decreases its value. On the other hand, for the complex, R2 suggested slight decrease on irradiation with 48 KGy followed by continued increases with increasing the dose up to 144 KGy. The increase in R1 and R2 may be due to crosslinking as a result of the formation of free radicals. The decrease in these ratios after irradiation with 96 KGy may be due to degradation. It was concluded that γ‐irradiation has a lower effect on the complex (i.e., the complex has a structure which is different from those of PAA and PAAm). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1619–1623, 2002  相似文献   

11.
Blown films of bimodal‐high‐density polyethylene (HDPE) (BPE) and its blend containing 40 wt% of linear low‐density polyethylene (LLDPE) are prepared in various neck‐heights (NHs). The crystal structures of both films are investigated in detail using small‐angle X‐ray scattering and wide‐angle x‐ray diffraction techniques. The results show that the blending of LLDPE notably modifies the crystal structure of BPE, including crystal density (ρc), crystallite size of the 110 plane (〈L110〉), thickness of the lamellar crystal (Lc), and grain widths of the lamellae. The relationships between NH, crystal structure, and the resistance of dart‐drop impact (DDI) are investigated for both BPE and BPE/LLDPE films. The results indicate that the reorientation of lamellae might be a primary factor responsible for the DDI property. However, large values of ρc, Lc, and 〈L110〉 are required for the film to achieve high DDI.  相似文献   

12.
3,4,5‐Triamino‐1,2,4‐triazolium 5‐nitrotetrazolate ( 2 ) was synthesized in high yield from 3,4,5‐triamino‐1,2,4‐triazole (guanazine) ( 1 ) and ammonium 5‐nitrotetrazolate. The new compound 2 was characterized by vibrational (IR and Raman) and multinuclear NMR spectroscopy (1H, 13C, 15N), elemental analysis and single crystal X‐ray diffraction (triclinic, P(‐1), a=0.7194(5), b=0.8215(5), c=0.8668(5) nm, α=75.307(5), β=70.054(5), γ=68.104(5)°, V=0.4421(5) nm3, Z=2, ϱ=1.722 g cm−1, R1=0.0519 [F>4σ(F)], wR2(all data)=0.1154). The 15N NMR spectrum and X‐ray crystal structure (triclinic, P‐1, a=0.5578(5), b=0.6166(5), c=0.7395(5) nm, α=114.485(5)°, β=90.810(5)°, γ=97.846(5)°, V=0.2286(3) nm3, Z=2, ϱ=1.658 g cm−1, R1=0.0460 [F>4σ(F)], wR2(all data)=0.1153) of 1 were also determined.  相似文献   

13.
Poly(vinyl alcohol)/poly(ethylene glycol) (PVA/PEG) copolymer was prepared using casting technique. The obtained PVA/PEG thin films have been irradiated with gamma rays with doses ranging from 1.5 to 20 Gy. The resultant effect of gamma irradiation on the thermal properties of PVA/PEG has been investigated using thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The onset temperature of decomposition To and activation energy of thermal decomposition Ea were calculated, results indicating that the PVA/PEG thin film decomposes in one main weight loss stage. Also, the gamma irradiation in dose range 4–12 Gy led to a more compact structure of PVA/PEG copolymer, which resulted in an improvement in its thermal stability with an increase in the activation energy of thermal decomposition. The variation of transition temperatures with gamma dose has been determined using DTA. The PVA/PEG thermograms were characterized by the appearance of an endothermic peak due to melting of crystalline phase. In addition, structural property studies using X‐ray diffraction and infrared spectroscopy were performed on both nonirradiated and irradiated samples. Furthermore, the transmission of the PVA/PEG samples and any color changes were studied. The color intensity (E was greatly increased with increasing the gamma dose and was accompanied by a significant increase in the blue and green color components. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

14.
Latex films were prepared by annealing pyrene (Py)‐labeled poly(methyl methacrylate) particles at glass‐transition temperature (100°C). These films were then irradiated by γ‐rays from 60Co in a gamma cell at room temperature at the same dose rate (rad/h) for 30 min. Before dissolution films were annealed at elevated temperatures for a 30‐min time interval to complete the film formation process. Steady‐state fluorescence (SSF) technique were used to monitor the dissolution of these irradiated latex films. The dissolution of films in chloroform–heptane (80–20%) mixture was monitored in real time by the Py fluorescence intensity change. Relaxation constants k0 and desorption coefficients Dd of polymer chains were measured. It was observed that both Dd and k0 values first increased and then decreased by increasing the annealing temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 129–137, 2002  相似文献   

15.
Self‐assembled binuclear complexes of Pd2L′2L2 and Pd2L4 type formulations have been achieved by combining the cis‐protected palladium(II) component i. e., [PdL′]2+ (where L′ stands for tmeda) and naked palladium(II) separately with a 3‐pyridyl appended non‐chelating bidentate ligand, L under suitable conditions. Supramolecular fusion of the Pd2L4 and PdL′2 type complexes have been demonstrated that provided the corresponding Pd2L′2L2 type complex. One pot synthesis of the binuclear Pd2L′2L2 type complex is achieved by combining palladium(II), L′ and L at equimolar ratio, however, along with an unidentified trap. The crystal structure of a Pd2L4 type complex confirmed the binuclear architecture of the cage. Intermolecular H‐bonding and π‐π stacking interactions are analyzed from the crystal structure and the extended intermolecular interactions apparently generated a grid pattern.  相似文献   

16.
Naturally amorphous biopolyester poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P3/4HB) containing 21 mol % of 4HB was blended with semi‐crystal poly(butylene succinate) (PBS) with an aim to improve the properties of aliphatic polyesters. The effect of PBS contents on miscibility, thermal properties, crystallization kinetics, and mechanical property of the blends was evaluated by DSC, TGA, FTIR, wide‐angle X‐ray diffractometer (WAXD), Scanning Electron Microscope (SEM), and universal material testing machine. The thermal stability of P3/4HB was enhanced by blending with PBS. When PBS content is less than 30 wt %, the two polymers show better miscibility and their crystallization trend was enhanced by each other. The optimum mechanical properties were observed at the 5–10 wt % PBS blends. However, when the PBS content is more than 30 wt %, phase inversion happened. And the two polymers give lower miscibility and poor mechanical properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

17.
1,4‐Dimethyl‐5‐aminotetrazolium 5‐nitrotetrazolate ( 2 ) was synthesized in high yield from 1,4‐dimethyl‐5‐aminotetrazolium iodide ( 1 ) and silver 5‐nitrotetrazolate. Both new compounds ( 1, 2 ) were characterized using vibrational (IR and Raman) and multinuclear NMR spectroscopy (1H, 13C, 14N, 15N), elemental analysis and single crystal X‐ray diffraction. 1,4‐Dimethyl‐5‐aminotetrazolium 5‐nitrotetrazolate ( 2 ) represents the first example of an energetic material which contains both a tetrazole based cation and anion. Compound 2 is hydrolytically stable with a high melting point of 190 °C (decomposition). The impact sensitivity of compound 2 is very low (30 J), it is not sensitive towards friction (>360 N). The molecular structure of 1,4‐dimethyl‐5‐aminotetrazolium iodide ( 1 ) in the crystalline state was determined by X‐ray crystallography: orthorhombic, Fddd, a=1.3718(1) nm, b=1.4486(1) nm, c=1.6281(1) nm, V=3.2354(5) nm3, Z=16, ρ=1.979 g cm−1, R1=0.0169 (F>4σ(F)), wR2 (all data)=0.0352.  相似文献   

18.
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   

19.
The crystallization behavior and isothermal crystallization kinetics of neat poly(l ‐lactic acid) (PLLA) and PLLA blended with ionic liquid (IL), 1‐butyl‐3‐methylimidazolium dibutylphosphate, were researched by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and wide angle X‐ray diffraction (WXRD). Similar to the non‐isothermal crystallization behavior of neat PLLA, when PLLA melt was cooled from 200 to 20°C at a cooling rate of 10°C min?1, no crystallization peak was detected yet with the incorporation of IL. However, the glass transition temperature and cold crystallization temperature of PLLA gradually decreased with the increase of IL content. It can be attributed to the significant plasticizing effect of IL, which improved the chain mobility and cold crystallization ability of PLLA. Isothermal crystallization kinetics was also analyzed by DSC and described by Avrami equation. For neat PLLA and IL/PLLA blends, the Avrami exponent n was almost in the range of 2.5–3.0. It is found that t1/2 reduced largely, and the crystallization rate constant k increased exponentially with the incorporation of IL. These results show that the IL could accelerate the overall crystallization rate of PLLA due to its plasticizing effect. In addition, the dependences of crystallization rate on crystallization temperature and IL content were discussed in detail according to the results obtained by DSC and POM measurements. It was verified by WXRD that the addition of IL could not change the crystal structure of PLLA matrix. All samples isothermally crystallized at 100°C formed the α‐form crystal. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41308.  相似文献   

20.
Chitosan is a biodegradable polymer composed of randomly distributed β‐(1,4)‐linked D ‐glucosamine (deacetylated unit) and N‐acetyl‐D ‐glucosamine (acetylated unit). It is produced commercially by deacetylation of chitin, which is the structural element in the exoskeleton of crustaceans (such as crabs and shrimps) and the cell walls of fungi. In the work reported, we developed a facile technique for the preparation of chitosan by irradiating prawn shell at various intensities from 2 to 50 kGy. It was observed that γ‐irradiation of prawn shell increased the degree of deacetylation (DD) of chitin at a relatively low alkali concentration during the deacetylation process. Among the various irradiation doses applied to prawn shell, a dose of 50 kGy and 4 h heating in 50% NaOH solution yielded 84.56% DD while the chitosan obtained from non‐irradiated prawn shell with the same reaction conditions had only 74.70% DD. In order to evaluate the effect of γ‐irradiation on the various physicochemical, thermomechanical and morphological properties, the chitosan samples were again irradiated (2–100 kGy) with γ‐radiation. Molecular weight, DD, thermal properties with differential scanning calorimetry and thermogravimetric analysis, particle morphology by scanning electron microscopy, water binding capacity (WBC), fat binding capacity (FBC) and antimicrobial activity were determined and the effects of various γ‐radiation doses were assessed. The DD, WBC, FBC and antimicrobial activity of the chitosan were found to improve on irradiation. It was obvious that irradiation caused a decrease of molecular weight from 187 128 to 64 972 g mol?1 after applying a radiation dose of 100 kGy which occurred due to the chain scission of chitosan molecules at glycosidic linkages. The decrease of molecular weight increased the water solubility of the chitosan, the extent of which was explored for biomedical applications. Copyright © 2012 Society of Chemical Industry  相似文献   

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