电子辐照改性PAN/PEO基体凝胶电解质对染料敏化太阳电池性能的提高

采用电子束（EB）对聚丙烯腈/聚氧化乙烯（PAN/PEO）凝胶电解质进行了剂量为13～260 kGy的辐照, 并对辐照改性的电解质组装的染料敏化太阳电池(DSSC)进行了性能测量。 结果表明, 改性后的DSSC的光电转化效率比改性前的高; 并且随EB辐照剂量的增加, DSSC效率先迅速增加(0～65 kGy), 然后缓慢减小(65～130 kGy)直至趋于一个平衡值(130～260 kGy)。 提升DSSC效率的最佳辐照剂量为65 kGy, 此时效率提高了约36%。 对比DSSC短路电流、 开路电压和填充因子随辐照剂量的变化, 发现DSSC效率的提高主要是由短路电流的提高引起的。 测量表明, 辐照改性后的DSSC时间稳定性得到了改善, 并且辐照剂量越高, 稳定性的改善越明显。 In this work, PAN/PEO (polyacrylonitrile/polyethylene oxide) based gel electrolyte was irradiated by electron beam (EB) with dose from 13 to 260 kGy. Then, DSSC (dye sensitized solar cell) was fabricated by the irradiated electrolyte and characterized. The results show that the efficiency of the DSSC fabricated by irradiated electrolyte is promoted comparing with DSSC fabricated by un irradiated electrolyte. And with irradiation dose increasing, the DSSC efficiency increases rapidly at first (0～65 kGy), then, drops down slowly (65～130 kGy), finally trends to a stable value (130～260 kGy). It indicates that there is an optimal irradiation dose, at which the promotion of DSSC efficiency is the highest, approximate 36%. Observed from the change of short circuit current, open circuit voltage and fill factor, short circuit current promotion by EB irradiation is found to be the main reason of DSSC performance promotion. The time stability measurement of the DSSC indicates that EB irradiation on PAN/PEO electrolyte reduces the loss of efficiency and the limiting effects become more apparent as the irradiation dose increases.     

含氟聚合物交联度的XPS表征

本文研究了用X-光电子能谱(XPS)求F-46(四氟乙烯—六氟丙烯共聚物),含氟聚酰亚胺和聚偏氟乙烯的凝胶化剂量(Rg),并表征其交联度。目前交联的含氟聚合物的XPS研究,特别是用它表征交联度还未见文献报告。实验结果表明这些含氟聚合物的辐射交联是通过脱氟原子进行的,其F/C(氟原子与碳原子比)必然随交联度的增加而下降,从而与其交联度相关。以交联样品的logF/C对logR(辐照剂量)做图,或以logⅠ(含氟原子碳基团的Cls峰的相对强度)对logR做图,可以求得Rg值。用XPS方法和凝胶含量方法求得的Rg值较一致。     

Ionic conductivity study on electron beam irradiated polyacrylonitrile-polyethylene oxide gel

Different mass percent polyacrylonitrile (PAN)-polyethylene oxide (PEO) gels were prepared and irradiated by an electron beam (EB) with energy of 1.0 MeV to the dose ranging from 13 kGy to 260 kGy.The gels were analysed by using Fourier transform infrared spectrum,gel fraction and ionic conductivity (IC) measurement.The results show that the gel is crosslinked by EB irradiation,the crosslinking degree rises with the increasing EB irradiation dose (ID) and the mass percents of both PAN and PEO contribute a lot to the crosslinking;in addition,EB irradiation can promote the IC of PAN-PEO gels.There exists an optimum irradiation dose,at which the IC can increase dramatically.The IC changes of the PAN-PEO gels along with ID are divided into three regions:IC rapidly increasing region,IC decreasing region and IC balanced region.The cause of the change can be ascribed to two aspects,gel capturing electron degree and crosslinking degree.By comparing the IC-ID curves of different mass percents of PAN and PEO in gel,we found that PAN plays a more important role for gel IC promotion than PEO,since addition of PAN in gel causes the IC-ID curve sharper,while addition of PEO in gel causes the curve milder.     

用傅立叶变换红外光谱法研究核辐照对三七粉成分的影响

本文采用红外光谱法对经不同剂量核辐照的三七粉进行了对比研究, 比较了它们红外光谱的异同。三七粉的红外光谱主要由淀粉吸收带及碳水化合物的吸收带组成, 低辐照剂量(低于15 kGy)处理的三七粉组成成分的化学结构及含量几乎未发生变化; 较高辐照剂量(高于18 kGy)处理的三七粉组成成分中少数成分的化学结构及含量可能已经发生了变化。表明采用适当核辐照剂量杀灭三七粉中污染微生物和各种寄生虫卵是可取的。辐照剂量高于15 kGy后, 糖类(主要是多糖、庶糖)增加, 增加的糖可能是淀粉转化而来的。     

傅里叶变换红外光谱法研究核辐照对丹参粉成分的影响

采用红外光谱法对经不同剂量核辐照的丹参粉样品进行了对比研究,比较了它们红外光谱的异同。丹参粉的红外光谱主要由蔗糖、葡萄糖及含C=O的各种化合物的吸收带组成。低辐照剂量(不高于12kGy)处理的丹参粉的组成成分的化学结构及含量几乎未发生变化;较高辐照剂量(等于或大于15kGy)处理的丹参粉的部分药用有效成分(丹酚酸、丹参素、丹参酮ⅡA 3种有效成分)的化学结构及含量已经发生了变化。表明采用适当剂量(不高于12kGy)的~(60)Coγ射线核辐照杀灭丹参粉中污染微生物和各种寄生虫卵是可取的。     

60Co-γ-射线辐照法修饰玉米淀粉

采用60Co-γ-射线辐照法修饰玉米淀粉.随着60Co-γ-射线辐照剂量的增加(10-30kGy),扫描电镜(SEM)显示玉米淀粉的分子粒径逐渐变小;X射线衍射法(XRD)表明,玉米淀粉的结晶度逐渐降低.傅里叶红外光谱(FTIR)表明,60Co-γ-射线的辐照能够破坏玉米淀粉分子的缔合氢键,产生羰基和羧基.随着辐照剂量的增加,羰基和羟基的数量增加,玉米淀粉的溶解度从0.29％(原始玉米淀粉)增加到7.8％(30kGy).     

用傅立叶变换红外光谱法研究核辐照对人参粉成分的影响

本文采用傅立叶变换红外光谱(吸收光谱、二阶导数谱及差谱)法对经不同剂量核辐照的人参粉进行了对比研究.辐照剂量不高于9 kGy时,人参粉样品的化学成分几乎没有发生变化;人参粉样品经15kGy及以上的辐照剂量辐照后,可能产生新的化学成分,表明采用辐照剂量不高于9 kGy的核辐照杀灭人参粉污染的微生物和各种寄生虫卵是可行的;...     

离子液体中聚氧化乙烯(PEO)相变过程中的氢键效应

我们把Flory-Huggins模型推广应用到聚合物/离子液体体系,研究聚氧化乙烯(PEO)在离子液体[EMIM][BF_4]中相变过程中的氢键效应,理论模型考虑了三种类型氢键(Ⅰ型:PEO-[EMIM]~+氢键,Ⅱ型:PEO-[BF_4]~-氢键和Ⅲ型:[EMIM]~+-[BF_4]~-氢键)的形成,分析了三种类型的氢键分数随温度、 PEO体积分数的变化.研究发现,三种类型的氢键分数随温度的升高而减少.在较小PEO体积分数条件下,增加PEO体积分数,Ⅰ型、Ⅱ型氢键分数轻微地减小;在较大PEO体积分数条件下,增加PEO体积分数,Ⅰ型、Ⅱ型氢键分数急剧减少.Ⅲ型氢键分数随着PEO体积分数的增加而急剧降低.由于三种氢键效应,第二维里系数A_2随温度的增加而减小.通过计算分析不同分子量的PEO在[EMIM][BF_4]中的相图发现,在PEO体积分数较低的条件下,Ⅰ型、Ⅱ型和Ⅲ型氢键是PEO相变的主要驱动力;在PEO体积分数较高的条件下,Ⅰ型和Ⅱ型氢键在PEO相变过程中起到主导作用.     

傅里叶变换红外光谱法研究核辐照对三七总皂苷粉成分的影响

采用傅里叶变换红外光谱(卷积谱)法对经不同剂量y-射线核辐照的三七总皂苷粉进行了对比研究.辐照剂量不高于9kGy时,三七总皂苷粉样品的化学成分几乎没有发生变化;三七总皂苷粉样品经15kGy及以上的辐照剂量辐照后,可能产生新的化学成分;经21kGy的剂量辐照,三七总皂苷粉产生了人参、三七粉所含的普通成分(非三七总皂苷成分...     

辐照还原法制备Au掺杂MF气凝胶（英文）

利用辐照还原法在500kGy辐照剂量下制备了Au掺杂MF有机气凝胶。通过X射线衍射(XRD)、能量色散光谱仪(EDX)和透射电子显微镜(TEM)测试证实了辐照法成功地制备出Au掺杂MF有机气凝胶复合物。EDX和TEM照片表明辐照处理后Au纳米颗粒均匀地分布在MF气凝胶骨架中,并且Au纳米颗粒的平均尺寸为5.8nm。N2吸附数据分析表明掺入Au纳米颗粒后,MF气凝胶的比表面积、总孔体积、微孔体积和介孔体积都有所下降。     

Ionic conductivity study on electron beam irradiated polyacrylonitrileben polyethylene oxide gel

Different mass percent polyacrylonitrile (PAN)—polyethylene oxide (PEO) gels were prepared and irradiated by an electron beam (EB) with energy of 1.0 MeV to the dose ranging from 13 kGy to 260 kGy. The gels were analysed by using Fourier transform infrared spectrum, gel fraction and ionic conductivity (IC) measurement. The results show that the gel is crosslinked by EB irradiation, the crosslinking degree rises with the increasing EB irradiation dose (ID) and the mass percents of both PAN and PEO contribute a lot to the crosslinking; in addition, EB irradiation can promote the IC of PAN—PEO gels. There exists an optimum irradiation dose, at which the IC can increase dramatically. The IC changes of the PAN—PEO gels along with ID are divided into three regions: IC rapidly increasing region, IC decreasing region and IC balanced region. The cause of the change can be ascribed to two aspects, gel capturing electron degree and crosslinking degree. By comparing the IC—ID curves of different mass percents of PAN and PEO in gel, we found that PAN plays a more important role for gel IC promotion than PEO, since addition of PAN in gel causes the IC—ID curve sharper, while addition of PEO in gel causes the curve milder.     

Metal adsorption of gamma-irradiated carboxymethyl cellulose/polyethylene oxide blend films

Blend films of different ratios of carboxymethyl cellulose (CMC)/polyethylene oxide (PEO) were prepared by the solution casting method. To investigate the effect of irradiation on all properties of prepared blend, it was exposed to different gamma irradiation doses (10, 20, and 30?kGy). Physical properties such as gel fraction (GF) (%) and swelling (SW) (%) were investigated. It was found that the GF (%) increases with increasing irradiation dose up to 20?kGy, while SW (%) decreases with an increase in the irradiation doses for all blend compositions. Moreover, the structural and mechanical properties of the prepared films were studied. The results of the mechanical properties obtained showed that there is an improvement in these properties with an increase in both CMC and irradiation dose up to 20?kGy. The efficiency of metal ions uptake was measured using a UV spectrophotometer. The prepared films showed good tendency to absorb and release metal ions from aqueous media. Thus, the CMC/PEO film can be used in agricultural domain.     

Development of dry polymer electrolyte based on polyethylene oxide with co-bridging agent crosslinked by electron beam

Polyethylene oxide (PEO)-based electrolytes were crosslinked using electron beam (EB) irradiation. The gel contents of a polymer film were increased after irradiation doses of 0, 140, 280, and 420 kGy, with ionic conductivities of 0.831, 1.55, 6.08, and 7.95 (× 10^? 5) S cm^? 1 at 40 °C, respectively. The slight decrease in conductivity at higher temperatures after irradiation is due to the retardation of polymer motion by crosslinking. The electrolyte with higher EB dose amount exhibits higher conductivity due to stabilization of the amorphous state. The EB crosslinking with a co-bridging agent shows enhanced conductivities of 4.71, 6.59, and 7.18 (× 10^? 5) S cm^? 1 at 40 °C, after irradiation with 140, 280, and 420 kGy. Addition of the co-bridging agent is effective for developing a crosslinked structure with a smaller EB dose. Tensile strength becomes two to three times higher with irradiation compared to the non-treated polymer. Combination of the EB technique with a co-bridging agent is a simple and effective method to prepare strong dry polymer electrolyte films with improved room temperature conductivity.     

X-ray irradiation-induced structural modifications in PM-355 polymeric nuclear track detector film

Samples from sheets of the polymeric material PM-355 have been exposed to X-rays from a 50 kV X-ray tube in the dose range of 10–300 kGy. The resultant effect of X-ray irradiation on the structural properties of PM-355 has been investigated using different techniques such as X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Vickers hardness and refractive index measurements. The results indicate that the X-ray irradiation of PM-355 in the dose range of 10–20 kGy causes initially chain scission. Above 20 and up to 100 kGy, the active free radicals produced from scission contribute to chemical reactions that lead to the crosslinking. Thus, the X-ray irradiation in the dose range of 20–100 kGy leads to a more compact structure of the PM-355 polymer, resulting in an enhancement of its Vickers hardness and refractive index. Moreover, the irradiation in the dose range of 100–300 kGy leads to the predominance of the degradation. This degradation is reported by FTIR spectroscopy and enhances the degree of ordering in the degraded samples as revealed by XRD technique. Additionally, it decreases both the Vickers hardness and refractive index of the PM-355 samples.     

聚丙烯/抗老化剂复合体系的γ-射线辐照降解研究

研究了聚丙烯(PP)及含有受阻酚类抗氧剂和受阻胺类光稳定剂复合体系的PP复合物经过γ-射线辐照后发生的结构变化及抗老化剂所起作用。实验利用红外光谱(FTIR)和示差扫描量热法(DSC)对PP的结构变化进行了系统表征。研究结果表明,当辐照剂量较小(50 kGy)时,纯PP及其复合物体系均未发生明显降解;当辐照剂量较大(≥50 kGy)时,PP及其复合物的羰基指数迅速提高,二者的结晶温度和熔融温度大幅度降低,说明PP发生了严重降解。在相同γ-射线辐照剂量条件下(≥50 kGy),PP复合物的羰基指数高于纯PP,而结晶温度以及熔融温度低于纯PP,表明高辐照剂量下抗老化剂复合物的存在不但没有阻止聚丙烯的降解,反而加快了降解的速率。     

Gamma induced changes in the structural and optical properties of Makrofol LS 1–1 polycarbonate

ABSTRACT

Samples from sheets of the polymeric material Makrofol LS 1–1 have been exposed to gamma radiation in the dose range 10–250?kGy. The modifications induced in Makrofol samples due to gamma irradiation have been studied through different characterization techniques such as intrinsic viscosity as a measure of the average molecular mass, Fourier Transform Infrared spectroscopy FTIR, refractive index and color difference studies. The results indicate that the crosslinking dominates at the dose range 50–250?kGy. The crosslinking reported by viscosity measurements is supported by the trend of the function groups present in the sample with the gamma dose. Also, the increase in intrinsic viscosity indicating an increase in the average molecular mass was associated with an increase in the refractive index. Additionally, the non-irradiated Makrofol samples showed significant color sensitivity towards gamma irradiation. The color intensity ΔE, which is the color difference between the non-irradiated sample and those irradiated with different gamma doses, increased (0–5.56) with increasing the dose up to 250?kGy, convoyed by an increase in the red and yellow color components.     

Defects generated by irradiation with gamma rays in lead doped KCl–KBr mixed single crystals

In this work we report the behavior of solid solutions of lead-doped KCl–KBr mixed single crystals subjected to gamma irradiation. Various composition of KCl_1−xBr_x (x=0.02, 0.35, 0.50, 0.65, 0.85) doped with 20–40 ppm of Pb²⁺ were used and exposed to ionizing radiation. The defect production seems to be correlated with the observed increasing integrated thermoluminescence glow curve as a function of irradiation at high 10 kGy dose as well as in the low 2.2–130 dose Gy range. The analysis shows the potential use of these mixed crystals as radiation detector. The defects generated by irradiation were monitored by the optical absorption spectrum and the thermally stimulated luminescence.     

Electron beam induced modifications in crystalline structure of polyvinylidene fluoride/nanoclay composites

PVDF/nanoclay nanocomposites were prepared via melt mixing method. The intercalated dispersion of the nanoclay in PVDF matrix was confirmed by XRD. According to FTIR, DSC and XRD results, the presence of nanoclay facilitated transition from α-to-β crystalline phase. Electron beam irradiation decreased the melting point of the nanocomposites. The decrease in melting point of the nanocomposites was about 11 °C at 500 kGy. The crystallinity of nanocomposites increased at an irradiation dose of 100 kGy and decreased at higher irradiation doses. The extent of crosslinking of the nanocomposites increased significantly with irradiation up to 300 kGy. The nanoclay intensified the increase in yield strength with irradiation doses up to 300 kGy. The combination of nanoclay and irradiation had a synergistic effect on the increase of yield strength.     

Structural and optical modifications in gamma-irradiated polyimide/silica nanocomposite

The structural and optical properties of thin films of polyimide composites with nanosilica particle content of 15?wt%, prepared via sol–gel process, were studied as a function of the gamma dose. The resultant effect of gamma irradiation on the properties of polyimide/silica nanocomposite has been investigated using X-ray diffraction and UV spectroscopy. Absorption and reflectance spectra were collected by a spectrophotometer giving UV-radiation of wavelength range 200–800?nm. The optical data obtained were analyzed and the calculated values of the optical energy gap exhibited gamma dose dependence. The direct optical energy gap for the nonirradiated polyimide/silica nanocomposite is about 2.41?eV, and increases to a value of 2.65?eV when irradiated with gamma doses up to 300?kGy. It was found that the calculated refractive index of the polyamide/silica increases with the gamma dose in the range 50–300?kGy.