IPN’s of acrylic acid and N-isopropylacrylamide by gamma and electron beam irradiation

Interpenetrating networks (IPN) of temperature sensitive N-isopropylacrylamide (NIPAAm) and pH sensitive acrylic acid (AAc) monomer were prepared in two consecutive steps. Hydrogels of AAc were synthesized by gamma radiation from a ⁶⁰Co gamma source and an electron beam from a Van de Graaff accelerator. A second hydrogel of NIPAAm was synthesized within the first AAc hydrogel by polymerization and cross-linking with a redox initiator and cross-linking agent. The thermal and pH sensitivity of the hydrogels were determined by measuring the swelling, and the morphology and composition by SEM.     

Development of novel hydrogels by modification of sterculia gum through radiation cross-linking polymerization for use in drug delivery

In order to modify the sterculia gum polysaccharide, to develop the hydrogels meant for the drug delivery, we have prepared sterculia gum, 2-hydroxyethylmethacrylate (HEMA) and acrylic acid (AAc) based hydrogels by radiation-induced crosslinking polymerization. Polymeric networks (hydrogels) thus formed were characterized with SEMs, FTIR,TGA and swelling studies which were carried out as a function monomers concentration, radiation dose, amount of sterculia contents in the polymer matrix and nature of the swelling medium. This paper discusses the swelling kinetics of the hydrogels and release dynamics of anti-diarrhea model drug ornidazole from the hydrogels to evaluation of swelling and drug release mechanism. Diffusion exponent ‘n’ have 0.73, 0.56 and 0.61 values and gel characteristic constant ‘k’ have 1.28 × 10⁻², 2.95 × 10⁻² and 2.14 × 10⁻² values in distilled water, pH 2.2 buffer and pH 7.4 buffer. The release of drug from the polymer matrix occurred through non-Fickian diffusion mechanism. The values for the late time diffusion coefficients have been lower than the values of initial and average diffusion coefficients. It reflects that in the initial stages rate of release of drug from polymer matrix was higher as compared to the late stages, it means after certain time the drug release occurred in controlled manner.     

Gamma-radiation-induced grafting of binary mixture of methacrylic acid and 4-vinyl pyridine onto Teflon-FEP film as an effective polar membrane for separation processes

Ionic bifunctional membranes have been synthesized by grafting binary mixture of methacrylic acid (MAAc) and 4-vinyl pyridine (4-VP) onto Teflon-FEP film by pre-irradiation method. Optimum conditions pertaining to maximum percentage of grafting were evaluated as a function of different reaction parameters. Maximum percentage of grafting of binary mixture (MAAc-co-4-VP) (71.29%) was obtained at an optimum total dose of 54.48 kGy and the total concentration was 9.49 mol/L ([4-VP] = 0.07 mol/L and [MAAc ] = 9.42 mol/L) in 5 ml of water. The effect of alcohols as additives to the reaction medium on percent grafting of the binary mixture has also been studied. The membranes were characterized by FTIR spectroscopy, scanning electron microscopy and thermogravimetric analysis. Swelling studies of the membranes were performed in different solvents such as water, benzene, carbon tetrachloride and dimethyl formamide (DMF). Maximum swelling was observed in DMF with minimum swelling in benzene. Metal ion (Cu²⁺, Ni²⁺ and Fe²⁺) uptake studies show better affinity for Fe²⁺ ions. Conductance measurements in different aqueous salt solution showed that these membranes have affinity for Na⁺/K⁺ ions and Cl⁻ ions and hence can be used in desalination/separation processes for the separation of both type of cationic and anionic ions.     

Radiation synthesis of PVP/CMC hydrogels as wound dressing

Carboxymethyl cellulose (CMC) and poly(N-vinyl pyrrolidone) (PVP) were blended to synthesize hydrogels by ⁶⁰Co γ-ray irradiation. A series of hydrogels were prepared with three compositions, i.e. PVP:CMC = 5:5, 6:4 and 7:3. The properties of the hydrogels such as gel fraction, gel strength, swelling behavior and moisture retention were investigated. Compared with pure PVP and CMC hydrogels, PVP/CMC blend hydrogels possessed improved gel strength, flexibility and transparency. As the content of PVP in PVP/CMC blend hydrogels increased, the gel fraction increased while the swelling rate decreased. The hydrogels with optimal properties were obtained in a composition of PVP/CMC = 6/4 with sterilization dose (25 kGy) and further characterized by FT-IR and SEM. Properties concerning the application of wound dressing were performed by comparison with a commercial hydrogel wound dressing to find a similar moisture retention capability and improved swelling rate. The improved properties as well as the cheapness of the materials suggest that PVP/CMC blend hydrogel can be good candidate as wound dressing.     

层状壳聚糖水凝胶的制备与性能

通过两步低温辐射和冷冻/解冻循环相结合的方法制备聚乙烯醇/聚氧乙烯(PVA/PEO)为基层,聚乙烯醇/壳聚糖(PVA/CS)为上层抗菌功能层的层状壳聚糖水凝胶。通过对吸收剂量、电子束流、聚合物溶液浓度等的研究确定最佳制备工艺,并通过溶胀性能、力学性能、抗菌性能及红外光谱和扫描电镜表征所得层状水凝胶的结构与性能。结果表明,该方法制备的层状壳聚糖水凝胶具有明显的层状结构,层间结合紧密,壳聚糖结构未改变;层状水凝胶的溶胀性能随着壳聚糖含量增大而逐渐增大,60%CS含量平衡溶胀度达到2 200%;层状水凝胶力学强度随着壳聚糖含量增加而先增大后减小,40%CS含量下层状水凝胶从PVA/PEO凝胶的0.35MPa提高到0.47 MPa;抗菌性能测试表明层状水凝胶对大肠杆菌和金黄色葡萄球菌均具有明显的抑菌效果,抑菌性能随着壳聚糖含量的提高而增大。     

Removal of Co2+ from radioactive wastewater by polyvinyl alcohol (PVA)/chitosan magnetic composite

Cobalt is one of the toxic radioactive elements and the removal of Co²⁺ from radioactive wastewater has received increasing attention in recent years. In this paper, polyvinyl alcohol (PVA)/chitosan magnetic composite was prepared and used for Co²⁺ removal. The effect of initial pH, contact time and initial Co²⁺ concentration on Co²⁺ adsorption was investigated. The kinetics, thermodynamic and isotherms of Co²⁺ sorption onto the composite were determined. The results showed that pseudo second-order equation could be used to describe the Co²⁺ removal process. The maximum sorption capacity was calculated to be 14.39 mg/g at pH 6.0 and 30 °C using the Langmuir model. The analysis of FTIR and SEM-EDAX were performed before and after Co²⁺ sorption onto the PVA/chitosan magnetic beads, revealing that the functional groups –NH₂ and –OH played main role in Co²⁺ sorption process. PVA/chitosan magnetic composite is promising adsorbent for removing Co²⁺ radioactive wastewater.     

Effect of maleic acid content on the thermal stability, swelling behaviour and network structure of gelatin-based hydrogels prepared by gamma irradiation

The highly swelling Poly (acrylamide/maleic acid/gelatin) P(AAm/MA/G) hydrogels were prepared by gamma-irradiation at low dose rate (0.94 kGy/h) and moderate dose rate (3.84 kGy/h). The hydrogels were confirmed by FTIR. The effect of copolymer composition, dose and dose rate on the swelling behaviour was discussed. Increasing of MA content and G in the initial mixture leads to an increase in the amount of MA and G in the gel system and decrease in the gelation %. The swelling behaviours of the hydrogel prepared at moderate dose rate increased with increasing MA mole content in the gel system but, there is no systematic dependence of swelling on MA content was observed for the hydrogels obtained at low dose rate. Pore structure of the hydrogels was monitored by using scanning electron microscopy. Thermogravimetric analysis (TGA) and the rate of the thermal decomposition of P(AAm/MA/G) hydrogels has been evaluated to give a better understanding of the thermal stability of polymers, The X-ray data of P(AAm/MA/G) hydrogels was discussed to investigate some features namely the degree of ordering and crystallite size.     

Radiation-induced grafting of N-isopropylacrylamide and acrylic acid onto polypropylene films by two step method

Binary graft copolymerization of pH sensitive acrylic acid (AAc) and thermosensitive N-isopropylacrylamide (NIPAAm) monomers onto pre-irradiated polypropylene films (PP) was carried out by two individual steps using a Co⁶⁰ gamma radiation source. The influence of preparation conditions, such as pre-irradiation dose and reaction time on grafting yield was studied. The swelling behavior and FTIR-ATR study for PP films grafted films were investigated.     

辐射合成法合成明胶类水凝胶及其性能研究

采用辐射法合成了明胶/羧甲基纤维素钠（CMC-Na）/聚乙烯吡咯烷酮（PVP）水凝胶,利用索氏提取器、紫外-可见分光光度计以及原子光谱仪分别对其溶胀性、pH值敏感性、凝胶含量及其对Cr（Ⅵ）的吸附性能进行了测试分析。在剂量率约为83 Gy/min,吸收剂量为15、25、35和45 kGy条件下,明胶/CMC-Na/PVP质量比为4∶1∶2、4∶1∶5和2∶1∶5的明胶/CMC-Na/PVP水溶液经辐照均能交联合成水凝胶。在高纯水中,该类水凝胶溶胀率分布于11～56之间;在pH=1的高氯酸溶液中,所有凝胶的溶胀率较之水溶液中均有所下降,说明这类水凝胶对pH值敏感。不同原料比例生成的水凝胶,其溶胀率并未随吸收剂量的增大而呈现出明显的增加。比例为4∶1∶5的水凝胶溶胀性能最为优良,其溶胀率最大值为56。合成的明胶/CMC-Na/PVP水凝胶可在1个月内完全腐化分解,说明在PVP中添加明胶和CMC-Na后,引入了天然高分子材料优良的降解性能,加速了凝胶分解,缩短了降解时间。同时,发现该类凝胶具有极强的吸Cr（Ⅵ）能力,可达0.539 g/g。     

Resistance to void formation of Cu-Ni alloys

Cu-Ni alloys were found by Brimhall and Kissinger to be void-resistant in a low-dose neutron irradiation experiment. This fact was investigated at much higher damage doses by means of irradiations at various temperatures between 300°C and 600°C with Ni⁺, Cu⁺ or C⁺ at 0.1 MeV, or Ni⁶⁺ at 46.5 MeV. Only the 2% Cu and 2% Ni alloys showed voidage whilst those containing 20, 50, 80% Ni were found to be completely free from voids at atom displacement levels well in excess of 30 dpa. It is proposed that fine-scale clusters having a different composition from the solid-solution matrix may be acting as traps for displaced interstitials and vacancies, so inhibiting vacancy agglomeration into voids.     

Radiation-chemical synthesis of poly(vinyl alcohol) hydrogel containing dicyclohexano-18-crown-6

Radiation-chemical synthesis of poly(vinyl alcohol) hydrogels containing physically immobilized dicyclohexano-18-crown-6 was carried out. Remarkable gel fraction of 40-70% was observed at absorbed dose of about 5 kGy. Increasing degree of poly(vinyl alcohol) crosslinking led to growth of the efficiency of crown ether immobilization. Post-irradiation thermal annealing of the hydrogel samples at 120 °C for 0.5-5 h resulted in an increase of crown ether retention as compared with non-annealed samples by approximately 20% at the same absorbed dose. Preliminary results on a sorption behavior of the crown-containing hydrogels with respect to Sr²⁺ cations in 2.4 M HNO₃ solution are presented.     

PNIPAM/蒙脱土复合水凝胶辐射合成与表征

采用辐射聚合方法合成了PNIPAM/蒙脱土(MMT)复合水凝胶;研究了蒙脱土对PNIPAM/MMT复合水凝胶溶胀性能和压缩性能的影响.结果表明,虽然MMT能提高复合水凝胶的初始溶胀速率和平衡溶胀率,但它不改变凝胶原有的环境响应性能和溶胀机理.PNIPAM水凝胶和PNIPAM/MMT复合水凝胶均具有温度敏感性,低临界溶解温度(LCST)均在32℃左右,溶胀机理均遵循Fickian扩散模式,即水分子的扩散成为水凝胶溶胀的决定过程.使用MMT能改善PNIPAM/MMT复合水凝胶的压缩性能;且复合水凝胶的压缩性能随MMT含量的增加而提高.     

Effect of helium preinjection and prior thermomechanical treatment on the microstructure of type 316 SS

Samples of 316 SS were preinjected with 15 appm helium either hot (650°C) or cold (room temperature) and irradiated with 3 MeV Ni⁺ ions to a dose level of 25 dpa at 625°C in order to test the validity of helium preinjection as a means of simulation of transmutant helium production. Results for preinjected and single-ion irradiated samples were compared to samples irradiated at 625°C to a 25 dpa dose level with 3 MeV Ni⁺ and simultaneously injected with helium at a rate of 15 appm He/dpa (dual-ion irradiated samples). Preinjected samples exhibited bimodal cavity size distributions. Preinjected samples of solution annealed or solution annealed and aged material showed lower swelling than dual-ion irradiated samples. However, He preinjected 20% cold worked samples showed greater swelling than dual-ion irradiated samples.     

Void formation in solution-treated aisi 316 and 321 stainless steels under 46.5 mev ni6+ irradiation

The swelling and radiation damage structure developed in solution-treated 316 and 321 stainless steels bombarded by 46.5 MeV Ni⁶⁺ ions in the Variable Energy Cyclotron (VEC) have been determined. Foils were pre-injected with 10^?5 a/a He at room temperature and subsequently bombarded by Ni⁶⁺ ions in the temperature range 450–750°C at a damage rate of 1–3 × 10^?3 dpa per second to doses up to 300 dpa and specimens from the foils were examined by transmission electron microscopy. The data obtained were compared with data from other experiments aimed at simulating the fast-neutron irradiation of 316 and 321 steels, in particular previous work with 20 MeV C²⁺ ions and with data on fast-reactor bombarded material. The swelling rates in Ni-ion bombarded specimens were about a factor two less than those in C-ion bombarded specimens and in good agreement with swelling rates in 5 MeV Ni⁺- and neutron-bombarded material. The peak swelling temperature after a dose of 40 dpa was 650°C in 316 steel and 625°C in 321 steel where the swelling was about 5.8% and 4.6% respectively.     

Metal ion implantation in inert polymers for strain gauge applications

Metal ion implantation in inert polymers may produce ultra-thin conducting films below the polymer surface. These subsurface films are promising structures for strain gauge applications. To this purpose, polycarbonate substrates were irradiated at room temperature with low-energy metal ions (Cu⁺ and Ni⁺) and with fluences in the range between 1 × 10¹⁶ and 1 × 10¹⁷ ions/cm², in order to promote the precipitation of dispersed metal nanoparticles or the formation of a continuous thin film. The nanoparticle morphology and the microstructural properties of polymer nanocomposites were investigated by glancing-incidence X-ray diffraction and transmission electron microscopy (TEM) measurements. At lower fluences (<5 × 10¹⁶ ions/cm²) a spontaneous precipitation of spherical-shaped metal nanoparticles occurred below the polymer top-surface (∼50 nm), whereas at higher fluences the aggregation of metal nanoparticles produced the formation of a continuous polycrystalline nanofilm. Furthermore, a characteristic surface plasmon resonance peak was observed for nanocomposites produced at lower ion fluences, due to the presence of Cu nanoparticles. A reduced electrical resistance of the near-surface metal-polymer nanocomposite was measured. The variation of electrical conductivity as a function of the applied surface load was measured: we found a linear relationship and a very small hysteresis.     

Radiation effects on hydroxypropyl methylcellulose phthalate in aqueous system

A water-insoluble cellulose derivative, hydroxypropyl methylcellulose phthalate (HPMCP) hydrogels, was converted to Na type to form hydrogel in paste-like status by radiation crosslinking. Mechanism for radiation crosslinking of cellulose-derivatives in paste-like status was discussed. Crosslinkers, i.e. methyl N,N-bis-acrylamide (MBA) or ethyleneglycol dimethacrylate (EGDMA) has been used to decrease gelation dose (Dg) of synthesis HPMCP hydrogels and improve its mechanical properties. HPMCP-MBA hydrogels were found to be more rigid and HPMCP-EGDMA hydrogels were more flexible. Swelling degree of HPMCP hydrogel in many kinds of salt solutions followed Hofmeister series, which is ubiquitous in polyelectrolyte hydrogel. Specific reswelling was observed in concentrated KF solution, implying a very strong F⁻ binding ability of benzyl group. The comprehensive results obtained in this study will be utilized on the design of HPMCP-based controlled release system.     

Radiation synthesis of low swelling acrylamide based hydrogels and determination of average molecular weight between cross-links

A comparative analysis of determination of cross-link density (ν_e) of hydrogels by using swelling tests and mechanical measurements has been made. Poly(acrylamide/methacrylamide) P(AAm/MAAm) and poly(acrylamide/hydroxyethyl methacrylate) P(AAm/HEMA) hydrogels were prepared by using gamma rays and used as model hydrogel systems. The uniaxial compression test was applied to cylindrical gel samples in the swollen state at pH 7. Stress-strain curves of hydrogels were evaluated to calculate the shear modulus values. The average molecular weight between cross-links and ν_e obtained from mechanical measurements were significantly different than the values obtained from swelling experiments. Large differences were attributed to the uncertainty on the value of the χ parameter used in the Flory-Rehner equation. ±1% change in this parameter doubled or reduced the value of hydrogel to half value.     

含药聚氧化乙烯共聚水凝胶膜的制备及其性能研究

应用冻融循环和辐射交联技术,制备了含有醋酸氨苄磺胺的的聚氧化乙烯共聚水凝胶膜,并对其理化性能和药物释放进行了研究。实验结果显示,与未经冻融循环处理的聚氧化乙烯共聚水凝胶膜比较,增强的了矣氧化乙烯共聚水凝胶膜抗强度明显增加（Ｐ〈０．０１）,凝胶分数和断裂伸长率亦稍有增加,表明冻融循环处理可明显地改善该膜的机械性能,使该膜作为伤口敷料具有理想的柔韧性、交联度和伸缩性。溶用蔗研究显示,该水凝胶膜的平衡水     

Physicochemical study of radiation-grafted LDPE copolymer and its use in metal ions adsorption

Graft copolymerization of (acrylonitrile-co-N-vinylpyrrolidone) AN/NVP binary monomer onto (low density polyethylene) LDPE film was achieved using simultaneous irradiation method. The influence of grafting conditions such as solvent type, comonomer composition and comonomer concentration on the grafting process were investigated. The prepared grafted films were chemically modified into amidoximated form using hydroxyl amine hydrochloride (NH₂OH · HCl). The untreated and amidoximated grafted films were characterized by studying their FT-IR spectroscopy, swelling behavior and mechanical properties. The ability of the amidoximated grafted films to adsorbed metal ions such as Cr³⁺, Ni²⁺, Cd²⁺, Ag⁺ and Pb²⁺ was evaluated. The parameters that might influence the metal ions adsorption capacity of treated grafted LDPE films such as comonomer compositions, the degree of grafting, the feeding metal ions solution concentration and the pH were discussed. The obtained results illustrate that the amidoximated grafted films could be fruitful in the practical field of water treatment.     

聚丙烯腈-亚铁氰化钾钴/钛球形复合吸附剂制备及其对Cs+的吸附性能研究

本文合成了聚丙烯腈-亚铁氰化钾钴/钛球形复合吸附剂（PAN-KCoCF和PAN-KTiCF）,通过静态吸附实验,研究了接触时间、pH值、竞争离子、Cs⁺初始浓度等对PAN-KCoCF和PAN-KTiCF吸附Cs⁺效果的影响,分析了吸附过程的反应动力学和吸附等温线,并用扫描电镜（SEM）、傅里叶红外光谱（FT-IR）、X射线衍射仪（XRD）等对吸附剂进行了分析。结果表明,PAN-KCoCF和PAN-KTiCF对Cs⁺的吸附平衡时间均为16 h,随着pH值的增加,PAN-KTiCF对Cs⁺的吸附量先快速增大,随后趋于平缓,而PAN-KCoCF对Cs⁺的吸附量几乎不变,溶液中含K⁺、Na⁺、NH⁺₄、Ca²⁺或Mg²⁺等竞争离子时,PAN-KCoCF相比PAN-KTiCF对Cs⁺的选择性更高;PAN-KCoCF和PAN-KTiCF对Cs⁺的吸附动力学行为可用准二级动力学方程来描述,表面吸附为动力学控制的主要步骤;吸附过程符合Langmuir等温吸附模型,为单分子层吸附,PAN-KCoCF和PAN KTiCF对Cs⁺的饱和吸附量分别可达128.370、278.552 mg/g。