Degradation mechanisms of Silicone Rubber (SiR) by accelerated ageing for cables of nuclear power plant

Shimada, Akihiko; Sugimoto, Masaki; Kudo, Hisaaki*; Tamura, Kiyotoshi*; Seguchi, Tadao*

IEEE Transactions on Dielectrics and Electrical Insulation, 21(1), p.16 - 23, 2014/02

https://doi.org/10.1109/TDEI.2014.6740721

The thermal and radiation ageing behaviors and degradation mechanisms of SiR for the cable insulation of nuclear power plants were studied. The thermal ageing and radiation ageing in air were conducted up to 235C and 195C, respectively. The dose rate of radiation ageing is 1 kGy/h. Thermal ageing in vacuum as well as in air was also conducted. The degraded SiR is evaluated by tensile test, gel fraction measurement, swelling ratio measurement and weight measurement, and then the results are analyzed. It is appeared that the radiation degradation of SiR at high temperature is much more severe than that of SiR at low temperature at the same dose. Focusing on the molecular structure, it is supposed that crosslinking reagents which are included in SiR are removed, oxygen atom is attached instead of the reagents and new crosslinking is foamed. Their behaviors are different from the polymer of hydrocarbon.

Product analysis for polyethylene degradation by radiation and thermal ageing

Sugimoto, Masaki; Shimada, Akihiko; Kudo, Hisaaki*; Tamura, Kiyotoshi; Seguchi, Tadao*

Radiation Physics and Chemistry, 82, p.69 - 73, 2013/01

https://doi.org/10.1016/j.radphyschem.2012.08.009

The oxidation products formed by thermal and radiation ageing of crosslinked polyethylene for cable insulation were analyzed by FTIR-ATR spectrometry. The most of products were composed of carboxylic acid, carboxylic ester, and carboxylic anhydride. The carboxylic acid was the primal product, and the others were the secondary products by the thermal reaction of carboxylic acids. The carboxylic acid as the primal oxidation product supports the proposed new oxidation mechanisms that the main chain scission should occur directly by oxidation of polyethylene radicals.

Mechanism of antioxidant interaction on polymer oxidation by thermal and radiation ageing

Seguchi, Tadao*; Tamura, Kiyotoshi; Shimada, Akihiko; Sugimoto, Masaki; Kudo, Hisaaki*

Radiation Physics and Chemistry, 81(11), p.1747 - 1751, 2012/11

https://doi.org/10.1016/j.radphyschem.2012.06.011

The mechanism of polymer oxidation by radiation and thermal ageing was investigated for the life evaluation of cables installed in radiation environments. The antioxidant as a stabilizer was much effective for thermal oxidation with a small content in polymers, but was not effective for radiation oxidation. The ionizing radiation induced the oxidation to result chain scission even at low temperature, because the free radicals were produced and the antioxidant could not stop the oxidation of radicals with the chain scission. A new mechanism of antioxidant effect for polymer oxidation was proposed. The effect of antioxidant was not the termination of free radicals in polymer chains such as peroxy radicals, but was the depression of initial radical formation in polymer chains by thermal activation. The antioxidant molecule was assumed to delocalize the activated energy in polymer chains by Boltzmann statics (distribution) to result decrease the probability of radical formation at a given temperature. The interaction distance (delocalization area) by one antioxidant molecule was estimated to be 5-10 nm in polymer matrix, though the value would depend on the chemical structure of antioxidant.

Ageing research of cable insulation materials

Seguchi, Tadao*; Tamura, Kiyotoshi; Kudo, Hisaaki*; Shimada, Akihiko; Sugimoto, Masaki; Idesaki, Akira; Oshima, Takeshi; Yoshikawa, Masahito

JAEA-Review 2012-027, 46 Pages, 2012/08

JAEA-Review-2012-027.pdf:5.87MB

The research on cable degradation mechanisms was conducted for 5 years in 2006 - 2010 as the project research of plant life management for nuclear power plant by NISA (Nuclear and Industrial Safety Agency) of METI (Ministry of Economy, Trade, and Industry). At the finish of above research, the degradation mechanisms were reviewed on the analysis of many reports on cable degradation. The reports published after 1970 were mainly surveyed and the facts or data containing the experimental accuracy were selected. The verified facts, the reasonable interpretation of the facts, unresolved aspects were checked on the view points of recent techniques or analysis, and proposed the new model of degradation mechanisms was proposed.

Development of function-graded proton exchange membrane for PEFC using heavy ion beam irradiation

Shiraki, Fumiya*; Yoshikawa, Taeko*; Oshima, Akihiro*; Oshima, Yuji*; Takasawa, Yuya*; Fukutake, Naoyuki*; Oyama, Tomoko*; Urakawa, Tatsuya*; Fujita, Hajime*; Takahashi, Tomohiro*; et al.

Nuclear Instruments and Methods in Physics Research B, 269(15), p.1777 - 1781, 2011/08

https://doi.org/10.1016/j.nimb.2011.04.117

The graded energy deposition of heavy ion beam irradiation to polymeric materials was utilized to synthesize a novel proton exchange membrane (PEM) with the graded density of sulfonic acid groups toward the thickness direction. Stacked Poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) films were irradiated by Xe ion beam with the energy of 6 MeV/u under a vacuum condition. Irradiated films were grafted with styrene monomer and then sulfonated. The membrane electrode assembly (MEA) fabricated by the function graded PEM showed improved fuel cell performance in terms of voltage stability. It was expected that the function-graded PEM could control the graded concentration of sulfonic acid groups in PEM.

ESR study on radiation-induced radicals in carboxymethyl cellulose aqueous solution

Saiki, Seiichi; Nagasawa, Naotsugu; Hiroki, Akihiro; Morishita, Norio; Tamada, Masao; Kudo, Hisaaki*; Katsumura, Yosuke*

Radiation Physics and Chemistry, 80(2), p.149 - 152, 2011/02

https://doi.org/10.1016/j.radphyschem.2010.07.024

Carboxymethyl cellulose (CMC), one of polysaccharide derivatives, at highly concentrated aqueous solution undergoes radiation-crosslinking reactions. In this topic, CMC radical, formed by reaction with OH radical attributed to radiation-induced crosslinking reaction, were studied by ESR method to understand the radiation-induced reaction mechanism of CMC aqueous solution. At first, it was succeeded to observe ESR spectra of the CMC radical using photolysis of hydrogen peroxide as the origin of OH radical. Observed ESR spectra were identified as radicals located on the secondary carbon of carboxymethyl groups. Secondly, NO saturated CMC aqueous solution 6 min after electron beam irradiation was measured by ESR method. The spectra were almost same shape as the case of photolysis of hydrogen peroxide, and were assigned as long-lived radicals located on carboxymethyl groups. Next, in the case of N and O saturation, spectra intensity become half or 0. This means that these long-lived radicals are produced by reaction with OH radical.

Changes to the chemical structure of isotactic-polypropylene induced by ion-beam irradiation

Oka, Toshitaka; Oshima, Akihiro*; Motohashi, Ryota*; Seto, Naoto*; Watanabe, Yuji*; Kobayashi, Ryoji*; Saito, Koki*; Kudo, Hisaaki*; Murakami, Takeshi*; Washio, Masakazu*; et al.

Radiation Physics and Chemistry, 80(2), p.278 - 280, 2011/02

https://doi.org/10.1016/j.radphyschem.2010.07.047

The chemical structures of various ion-beam irradiated isotactic-polypropylene samples were studied. Results of micro-Fourier transform infrared spectroscopy and ultraviolet-visible spectroscopy suggest not only the linear energy transfer, but also the fluence is effective in local transformation of the isotactic-polypropylene.

ESR study on carboxymethyl chitosan radicals in an aqueous solution

Saiki, Seiichi; Nagasawa, Naotsugu; Hiroki, Akihiro; Morishita, Norio; Tamada, Masao; Muroya, Yusa*; Kudo, Hisaaki*; Katsumura, Yosuke*

Radiation Physics and Chemistry, 79(3), p.276 - 278, 2010/03

https://doi.org/10.1016/j.radphyschem.2009.08.043

Carboxymethyl chitosan (CMCTS) is one kind of polysaccharide derivatives and has a good water-solubility. At a high concentrated aqueous solution, CMCTS forms gel by ionizing irradiation, though polysaccharide derivatives are generally radiation-degradation type. In general, OH radical, which is one of main water radiolysis products and very oxidative species, is said to induce crosslinking reaction of polymer solution. The purpose of this study is to understand the radiation-crosslinking mechanism of CMCTS at a high concentrated aqueous solution. In this study, identification of CMCTS radical produced by reaction with OH radical was introduced. CMCTS radical in an aqueous solution was observed directly by ESR method using photolysis of hydrogen peroxide. The ESR spectra have a large doublet split and small triplet split like [Triplet Doublet]. However, some species seemed to be overlapped on ESR spectra, because right-and-left triplet spectra are not equiform. Compared with some radicals, which have analogical structure to CMCTS, about hyperfine coupling constant, [Triplet Doublet], assigned as radical on carboxymethyl group linked to C6, and [Doublet], assigned as radical on carboxymethyl group linked to C2 or C3, were isolated from ESR spectra of experimental results. In conclusion, these spectra were identified as radicals located on secondary carbon of carboxymethyl groups.

Pulse radiolysis study on reaction kinetics and pK value of hydroxyl radical at high temperatures

Muroya, Yusa*; Takahashi, Hiroyuki*; Katsumura, Yosuke; Lin, M.; Kumagai, Yuta; Kudo, Hisaaki*

Proceedings of Symposium on Water Chemistry and Corrosion in Nuclear Power Plants in Asia 2009, p.71 - 75, 2009/10

Hydroxyl radical is one of the most important water decomposition products because it has strong oxidative property. However, its property higher than 200C has not yet been clarified well. In this work, reaction kinetics and pK value of OH radical at elevated temperature over 300C have been investigated by means of nanosecond pulse radiolysis. Transient absorption spectra of formed radical and rate constants for the reaction with some solutes in aqueous solutions of benzoate, nitrobenzene, and carbonate etc., have been investigated. In addition, temperature dependent pK value (OH/O) up to 300C has also been evaluated by direct trace and indirect competitive reaction method.

Localized-impact damage caused by proton bombarding in mercury target

Futakawa, Masatoshi; Kogawa, Hiroyuki; Ishikura, Shuichi*; Kudo, Hisaaki*; Soyama, Hitoshi*

Journal de Physique, IV, 110, p.583 - 588, 2003/09

A liquid-mercury target system for the MW-scale target is being developed in the world. The moment the proton beams bombard the target, pressure waves will be generated in the mercury by the thermally shocked heat deposition. Provided that the negative pressure generates through its propagation in the mercury target and causes cavitation in the mercury, there is the possibility for the cavitation bubbles collapse to form pits on the interface between the mercury and the target vessel wall. In order to estimate the cavitation erosion damage, Split Hopkinson Pressure Bar (SHPB) tests impact tests were performed to impose the impact pressure to the interface between mercury and solid metals. In particular, the surface hardening treated samples: Kolsterising, some coatings are investigated. As results, it is confirmed that the pitting damage is suppressed by surface hardening treatments and relative hardness appeared to be a good correlating parameter on impact erosion resistance.