Graft co-polymerization of maleic acid and vinyl acetate onto poly（vinylidene fluoride） powder by pre-irradiation technique

Binary monomers of maleic acid and vinyl acetate are grafted onto poly(vinylidene fluoride) (PVDF) powder by pre-irradiation induced graft polymerization technique in emulsion solution. The co-grafting of binary monomers is successfully proved by FT-IR spectroscopy analysis. The influences of the absorbed dose, reaction temperature, reaction time, total concentration of monomers, and feed ratio of binary monomers on the degree of grafting are investigated. The thermal property of grafted PVDF powder was characterized by differential scanning calorimetry (DSC) and thermo-gravimetry analysis (TGA).     

Radiation grafting of poly(vinyl acetate) onto wheat straw and properties of the product

Poly(vinyl acetate)(PVAc) was grafted onto wheat straw by γ-irradiation to improve the compatibility between wheat straw and high-density polyethelene(PE).The grafting was proved by Fourier transform infrared(FTIR) spectroscopy. The compact structure of wheat straw was loosened because the chemical bonds and crystalline structure were destructed by the γ-rays. The modified wheat straw needed less energy for thermal transition, as revealed by differential scanning calorimetry(DSC).Thermal analysis revealed that grafted PVAc acted as a protective barrier for the wheat straw and leads to an increase in maximum pyrolysis temperature. The crystallite size of grafted wheat straw decreased to 5.33 nm from 5.63 nm before irradiation. There were holes in melted form appeared on the surface of the grafted wheat straws.Both the grafted PVAc and irradiation are beneficial to lower the torque of wheat straw/PE melts and improve its mechanical properties by 36%. Possible mechanism of irradiation grafting was proposed.     

Determination of boron concentration in uranium fuel samples by ICP-OES following a separation step by cation exchange resin

The boron content of uranium fuel samples with boron concentrations in the range of 0.05–10 μg/g was determined using inductively coupled plasma optical emission spectrometry(ICP-OES) after the uranium was separated by cation exchange. The samples were dissolved in 3 M HNO_3 on a hot plate at 150℃ and evaporated to near dryness. The residues were redissolved in 0.2 M HNO-_3 and passed through a column loaded with Dowex 50WX8-400 resin. Uranium was adsorbed on the resin,while boron was easily eluted with 0.2 M HNO_3. The boron content of the effluent was determined using ICPOES. Several strategies were employed to improve the reliability of the experimentally determined boron content.The addition of mannitol and proper control of the evaporation process were shown to be effective in preventing boron loss during sample dissolution and evaporation. The memory effect was eliminated by flushing the system with 1.5% ammonia for 30 s between successive sample runs,and the matrix match method was used to eliminate the matrix effect arising from mannitol during the ICP-OES analysis. The accuracy of the results of the analysis was determined by addition recovery tests and by comparison with the results of three Chinese certified reference materials(GBW04242, GBW04243, and GBW04232). Using the method we developed, the limit of detection for boron was as low as 0.05 μg/g in uranium fuel samples, and the relative standard deviations for 0.1–0.5 g uranium samples with 0.05–2 μg/g of boron were within 9%.     

Provenance studies of archaeological ceramics from Mar-Takla(Ain-Minin,Syria)using radioisotope X-ray fluorescence method

The radioisotope X-ray fluorescence method was applied to studies of the provenance of the ceramics fragments originated from the Mar-Takla site in Syria.The samples were irradiated 1000s by a ^109Cd radioisotope source and 13 elements (Ca,Ti,Mn,Fe,Zn,Ga,As,Rb,Sr,Y,Zr,Nb,and Pb)were determined in 35 samples.The data were subjected to two multivariate statistical methods,cluster and principal components analysis(PCA).It was shown from the combination of the statistical techniques and the determination of elemental composition of the samples that 94% of the ceramic samples analyzed can be considered to be manufactured using two sources of raw materials.     

Preparation of a new anion exchanger by pre-irradiation grafting technique and its adsorptive removal of rhenium(Ⅶ) as analogue to ~(99)Tc

A new anion exchanger with pyridine groups was prepared by grafting of 2-vinyl pyridine onto polypropylene(PP) nonwoven fabrics by pre-irradiation grafting technique, followed by quaternization of pyridine rings in grafted chains in reaction with bromoethane. The results showed that the grafting yield increased with the monomer concentration and conversion ratio of quaternization increased with the time. The grafted and quaternized fabrics were characterized by FT-IR, DSC, SEM and ICP. The possibility of adsorption of perrhenate(ReO–4), a nonradioactive analogue to pertechnetate(99TcO–4), from aqueous solution by anion exchanger was investigated. The experiments performed at pH= 0.1–6 showed that p H = 2.2 was the optimal acidity for ReO–4adsorption, and an adsorption equilibrium was achieved in 30 min. The reaction enthalpy was-12.55 k J/mol,indicating that the adsorption process is exothermic. XPS tests indicated that the Re O–4uptake was a typical ion exchange between Cl–on anion exchanger and ReO–4.     

Creep damage characterization of UNS N10003 alloy based on a numerical simulation using the Norton creep law and Kachanov–Rabotnov creep damage model

The calculation of inelastic creep damage is important for the structural integrity evaluation of the elevated temperature structure in a thorium molten salt reactor(TMSR). However, a creep damage theory model and numerical simulation method have not been proposed for the key materials(UNS N10003 alloy) in the TMSR. In this study, creep damage characterization of UNS N10003 alloy is investigated using the Norton creep law and Kachanov–Rabotnov(K–R) creep damage model. First, the creep experimental data of the UNS N10003 alloy at 650 °C were adopted to fit the material constants of the two models. Then, the creep damage behavior of the UNS N10003 alloy was analyzed and discussed under uniaxial and multi-axial stress states. The results indicated that the K–R creep damage model is more suitable for the UNS N10003 alloy than the Norton model. Finally, the numerical simulation method was developed by a user-defined UMAT subroutine and subsequently verified through a finite element analysis(FEA). The FEA results were in agreement with the theoretical solutions. This study provides an effective method for the inelastic creep damage analysis of the elevated temperature structure in the TMSR.     

Degradation of phenol using a combination of granular activated carbon adsorption and bipolar pulse dielectric barrier discharge plasma regeneration

A combined method of granular activated carbon (GAC) adsorption and bipolar pulse dielectric barrier discharge (DBD) plasma regeneration was employed to degrade phenol in water. After being saturated with phenol, the GAC was filled into the DBD reactor driven by bipolar pulse power for regeneration under various operating parameters. The results showed that different peak voltages, air flow rates, and GAC content can affect phenol decomposition and its major degradation intermediates, such as catechol, hydroquinone, and benzoquinone. The higher voltage and air support were conducive to the removal of phenol, and the proper water moisture of the GAC was 20％. The amount of H2O2 on the GAC was quantitatively determined, and its laws of production were similar to phenol elimination. Under the optimized conditions, the elimination of phenol on the GAC was confirmed by Fourier transform infrared spectroscopy,and the total removal of organic carbons achieved 50.4％. Also, a possible degradation mechanism was proposed based on the HPLC analysis. Meanwhile, the regeneration efficiency of the GAC was improved with the discharge treatment time, which attained 88.5％ after 100 min of DBD processing.     

A method of laser focusing control in microlaser-induced breakdown spectroscopy

This paper presents a method for the automatic adjustment of the laser defocusing amount in micro-laser-induced breakdown spectroscopy. A microscopic optical imaging system consisting of a CCD camera and a 20× objective lens was adopted to realize the method. The real-time auto-focusing of the system was achieved by detecting the effective pixels of the light spot generated by the laser pointer. The focusing accuracy of the method could achieve 3 μm. The element concentrations of Mn and Ni in low-alloy steels were analyzed at a crater diameter of about 35 μm using the presented method. After using the presented method, the determination coefficients of Mn and Ni both exceeded 0.997, with the root-mean-square errors being 0.0133 and 0.0395, respectively. Scanning analysis was performed on the inclined plane and the curved surface by means of focusing control and non-focusing control. Ten characteristic spectral lines of Fe were selected as the analysis lines. With the focusing control, the average relative standard deviations obtained on the inclined plane and curved surface were both less than 5%, and much less than the values without focusing control, 14.6% and 40.39%.     

Fast neutron radiation inactivation of Bacillus subtilis:Absorbed dose determination

In this paper,fast neutron inactivation effects of Bacillus subtilis were investigated with fission fast neutrons from CFBR-Ⅱreactor of INPC(Institute of Nuclear Physics and Chemistry)and mono-energetic neutrons from the Van de Graaff accelerator at Peking University.The method for determining the absorbed dose in the Bacillus subtilis suspension contained in test tubes is introduced.The absorbed dose,on account of its dependence on the volume and the form of confined state,was determined by combined experiments and Monte Carlo method.Using the calculation results of absorbed dose,the fast neutron inactivation effects on Bacillus subtilis were studied.The survival rates and absorbed dose curve was constructed.     

Plasma-induced grafting of acrylic acid on bentonite for the removal of U(VI) from aqueous solution

Fabrication of reusable adsorbents with satisfactory adsorption capacity and using environmentfriendly preparation processes is required for the environment-related applications. In this study,acrylic acid(AA) was grafted onto bentonite(BT) to generate an AA-graft-BT(AA-g-BT)composite using a plasma-induced grafting technique considered to be an environment-friendly method. The as-prepared composite was characterized by scanning electron microscopy, x-ray powder diffraction, thermal gravity analysis, Fourier transform infrared spectroscopy and Barrett–Emmett–Teller analysis, demonstrating the successful grafting of AA onto BT. In addition, the removal of uranium(VI)(U(VI)) from contaminated aqueous solutions was examined using the as-prepared composite. The influencing factors, including contact time,p H value, ionic strength, temperature, and initial concentration, for the removal of U(VI) were investigated by batch experiments. The experimental process fitted best with the pseudo-secondorder kinetic and the Langmuir models. Moreover, thermodynamic investigation revealed a spontaneous and endothermic process. Compared with previous adsorbents, AA-g-BT has potential practical applications in treating U(VI)-contaminated solutions.     

Preparation and characterization of proton exchange membranes from polystyrene grafted poly（vinylidene fluoride） powder

Proton exchange membranes(PEMs) were prepared in three steps:graRing of polystyrene onto PVDF powder using pre-irradiation graft polymerization technique, processing the grafted PVDF powder into membranes of around 50-μm thickness, and sulfonating them with cholorosulfonic acid to form poly(vinylidene fluoride)-g-poly(styrene sulfonic acid) membranes. Kinetics of the graft polymerization was studied. The existing of polystyrene side-chains in the grafted PVDF powders, and PSSA groups in PEMs, were proved by FT-IR. Properties of the PEMs, i.e. the ion exchange capacity, water uptake, proton conductivity, thermal property and oxidative stability,were characterized. Dependence of properties on the degree of grafting was investigated, too.     

粉体PVDF辐射接枝苯乙烯

以聚偏氟乙烯（PVDF）粉体为基材,采用预辐射接枝方法,在PVDF粉体上接枝聚合苯乙烯单体。并通过红外光谱、元素分析、差示扫描量热分析、热重分析对接枝后粉体进行了表征。红外光谱证明苯乙烯被成功接枝到PVDF粉体上,DSC图谱反映出结晶度随接枝率的增大而减小,接枝苯乙烯后粉体的热重图与接枝前的粉体比较也有明显的变化,进一步佐证了苯乙烯的成功接枝。     

预辐射接枝丙烯酰胺改性PVDF粉体及其亲水性滤膜的制备

通过γ射线预辐射接枝方法将丙烯酰胺(Acryl amide,AAm)单体接枝到聚偏氟乙烯Poly(vinylidene fluoride),PVDF]粉体上,通过测定粉体接枝前后氟元素含量的变化来计算接枝率.研究了同一单体浓度下,接枝率随反应时间的变化规律,并将具有不同接枝率的改性粉体溶解在N-甲基吡咯烷酮(N-met...     

PVDF粉体预辐照接枝甲基丙烯酸缩水甘油酯制备锂离子二次电池隔膜研究

以聚偏氟乙烯（PVDF）粉体为基材,采用预辐照接枝方法,在PVDF粉体上用乳液聚合接枝甲基丙烯酸缩水甘油酯（GMA）,并采用溶液铸膜的方法制备了PVDF-g-PGMA膜。利用红外光谱（FTIR）,扫描电子显微镜（SEM）,压汞仪,电导率测试等分析表征手段对制备的PVDF—g-PGMA膜进行了表征。在氩气手套箱中组装成扣式电池,在电池测试系统上测试扣式电池的充放电循环性能。测试结果表明,在相同制备条件下,以PVDF-g-PGMA作为隔膜的锂离子电池性能优于以PVDF作为隔膜的锂离子电池性能。     

Characteristics of poly(vinylidene difluoride) modified by plasma-based ion implantation

Surface modification of polymers using radiation effects has been studied in a variety of fields, such as gas barrier or biochemical applications. However, the mechanism of improvement or degradation of polymers induced by radiation has not been well understood. In this study, poly(vinylidene difluoride) (PVDF) of crystalline phase of II (alpha form) was modified by plasma-based ion implantation (PBII) to control its adsorption properties for protein. Helium ions with applied bias voltages ranging from ?1 to ?20 kV were irradiated to the PVDF substrate for one minute and protein adsorption properties on the modified PVDF substrates was evaluated by the Western blotting method. As a result, adsorption of PVDF decreased with increasing the applied bias voltage, whereas the modification with only plasma treatment did not cause a significant change in adsorption properties for protein. The PBII-induced decrease in adsorption can be used for monitoring or patterning the protein. In order to study the mechanism, chemical and physical properties of the modified surfaces were analyzed with X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR) in attenuated total reflection (ATR) mode. Contact angles on the modified surfaces were also measured and surface free energies were calculated by Owens–Wendt–Rabel–Kaeble method. The surface morphology observed AFM and SEM did not show a significant change after the modification but the concentration of fluorine decreased and the surface energy on the surface increased after the modification. The influential factors in adsorption properties of the modified PVDF for protein are discussed.     

黄原胶辐射接枝N-乙烯基吡咯烷酮及其物性研究

采用共辐射法制备了黄原胶-N-乙烯基吡咯烷酮接枝共聚物(XG-g-NVP).研究表明在黄原胶浓度及XG/NVP质量比一定的情况下,接枝率随吸收剂量的增加而增加,并逐步达到平衡:在吸收剂量和质量比一定时,接枝率住浓度为10g/L达到最大;在吸收剂量和黄原胶浓度一定时,接枝率在质量比为10:1达到最大值.红外光谱研究表明接...     

Grafting of PNIPAAm on PVDF submicroscopic tracks induced by the active sites remainders of the etching process

The present work is part of a systematic study that involves different polymeric substrates and monomers with the purpose to induce grafting on etched tracks. The residual active sites produced by heavy ion beams, remaining after the etching process, were used to start the grafting process. In order to produce tracks on foils of poly(vinylidene fluoride) (PVDF) they were irradiated with ²⁰⁸Pb of 25.62 MeV/n or with 115 MeV Cl ions. Then, they were etched and grafted with N-isopropylacrylamide (NIPAAm) monomers. Experimental curves of grafting yield as a function of fluence with the etching time as a parameter were measured. Also, the grafting yield as a function of the grafting and etching time was obtained. The replica method allowed the observation of the shape of the grafted tracks using transmission electron microscopy (TEM). In addition NIPAAm grafted foils were analyzed using Fourier transform infrared spectroscopy (FTIR).     

γ射线辐照聚偏氟乙烯接枝苯乙烯磺酸乙酯

以聚偏氟乙烯(Polyvinylidene fluoride,PVDF)树脂为基材,采用γ射线预辐射接枝法在PVDF树脂上接枝苯乙烯磺酸乙酯(Ethyl styrenesulfonate,ETSS),探讨吸收剂量、接枝温度、接枝反应时间及单体浓度对接枝率的影响。之后在95℃水解PVDF-g-PETSS聚合物得到PVDF接枝苯乙烯磺酸(PVDF-g-PSSA)离子交换树脂。红外光谱、X射线光电子能谱、热重分析证明PVDF-g-PETSS及PVDF-g-PSSA被成功制备。当接枝率为120%时,PVDF-g-PSSA的离子交换容量达到2.05 mmol/g。这种将带有磺酸基团的单体通过辐照接枝引入PVDF基材然后水解的方法简单、高效、污染小,有望在离子交换树脂及离子交换膜的制备中得到应用。     

γ共辐射接枝丙烯酸改善聚醚砜粉体亲水性的研究

利用γ射线共照射技术在聚醚砜（Polyethersulfone,PES）粉体上按枝了丙烯酸。研究了丙烯酸单体体积分数、接枝溶液pH值、吸收剂量、阻聚剂（Cu^2＋）浓度等对接枝率的影响规律。通过与称重法相结合,得到了利用红外光谱对接枝率进行定量分析的工作曲线。研究结果表明,当吸收剂量为25kGy、单体体积分数为30％、阻聚剂用量为0．004mol／L时,可以获得最高的接枝率。接枝溶液中盐酸的添加有利于提高接枝率。提高接枝率有助于改善PES的亲水性。