• Title/Summary/Keyword: Chain scission

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Characterization on the Thermal Oxidation of Raw Natural Rubber Thin Film using Image and FT-IR Analysis

  • Kim, Ik-Sik;Cho, Hwanjeong;Sohn, Kyung-Suk;Choi, Hwa-Soon;Kim, Sung-Uk;Kim, Sinkon
    • Elastomers and Composites
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    • v.55 no.1
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    • pp.51-58
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    • 2020
  • In this study, the thermal oxidation of raw natural rubber (NR) was investigated under controlled conditions by optical image and fourier transform infrared (FT-IR) analysis. The thermal oxidation was performed on a transparent thin film of raw NR coated on a KBr window in a dark chamber at 80℃ under low humidity conditions to completely exclude moisture and restrict light oxidation. Images of the thin film of raw NR were obtained before and after thermal oxidation. FT-IR absorption spectra were measured in the transmission mode at different thermal exposure times. The thermal oxidation of NR was examined by the changes in the absorption peaks at 3449, 1736, 1447, 1377, 1242, 1072, and 833 cm-1, which corresponded to a hydroxyl group (-OH), a carbonyl group (-C=O) from an aldehyde and a ketone, a methylene group (-CH2-), a methyl group (-CH3), a carbon-oxygen single bond (-C-O) from an epoxide, a carbon-oxygen bond (-C-O) from an ether, an alcohol, a peroxide, or a cyclic peroxide, and a cis-methine group (cis-CCH3=CH-), respectively. In the initial stage of thermal oxidation, two different types of free radicals were produced quickly and randomly by the homolytic cleavage of a double bond and allylic hydrogen abstraction. Aldehydes and ketones were formed from chain scissions of the double bonds and alcohols were produced from allylic hydrogen abstraction at the methylene or methyl groups. Two reactions seemed to proceed competitively with each other. At a later stage, oxidative crosslinks seemed to dominate through the combination of free radicals such as an allyl radical (CH=CHCH2·), alkoxy radical (RO·), and peroxy radical (ROO·) and the reaction of a hydroperoxide (-ROOH) with a double bond. The image obtained after thermal oxidation showed hardening without cracks. Based on these observations, a plausible two-step mechanism was suggested for chain hardening caused by the thermal oxidation.

A Study on the Tracking Characteristics of Silicone Rubber Degraded by Accelerated UV Exposure (자외선 가속열화에 의한 실리콘 고무의 트래킹 특성 변화에 관한 연구)

  • Kim, Suk-Cheol;Lee, Jun-Ho;Hwang, Bo-Seung;Lee, Dong-Yeong;Han, Min-Gu
    • The Transactions of the Korean Institute of Electrical Engineers C
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    • v.49 no.5
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    • pp.302-309
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    • 2000
  • The tracking characteristics of silicone rubber degraded by accelerated outdoor exposure employing a weather-o-meter were investigated. The tracking test was performed according to ICE Publ.587 method but the concentration of conductive solution was two times higher than IEC standard in order to accelerate the tracking failure. The number of large effective scintillation and the current of high voltage circuit were measured simultaneously. It was shown that the number of effective scintillation had valuable information of the tracking degradation state of silicone rubber, while the average current between electrodes could not provide information enough for diagnosis. Based upon the experimental results, it could be said that the key factor accelerating tracking failure was not Joule heating by current but pyrolysis by burning of silicone rubber, and that reduction of contact angle was due to chain scission which resulted in the free radicals of low molecules.

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The Thermal Degradation Mechanism of Polymethyl Methacrylate Blend (Polymethyl Methacrylate Blend의 열화에 따른 분해기구 해석에 관한 연구)

  • Kim, Dong-Keun;Moon, Myeong-Ho;Seul, Soo-Duk;Sohn, Jin-Eon
    • Elastomers and Composites
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    • v.23 no.2
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    • pp.125-133
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    • 1988
  • The thermal degradation of polymethyl methacrylate(PMMA) blend namely polymethyl methacrylate-polycarbonate(PMMA-PC) blend and polymethyl methacrylate-polystyrene(PMMA-PS) blend were carried out by isothermal method under air at several heating temperature from 220 to $270^{\circ}C$. Molecular weight changes during the thermal decomposition were monitored by means of the viscosity average molecular weight($\bar{M}v$). The viscosity average molecular weight was determined by Gel Permeation Chromatography(GPC). The dominant process in the degradation of PMMA-PC and PMMA-PS blend were main chain scission randomly due to weak links that may be distributed along the polymer backbone and the initial rate which the bonds are broken is not sustained. The infra-red spectra of degraded PMMA-PS blend show that the presence of aromatic ketone band at $1685cm^{-1}$. However, the infra-red spectra of degraded PMMA-PC blend show that the presence of hydroperoxide band at $3450cm^{-1}$. Thus indicating that the weak links are attacked by oxygen from the air and produce hydroperoxide or ketone. The activation energies of PMMA-PC blend and PMMA-PS blend were 18.2 and 17.9 Kcal/mol, respectively.

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A Study on Thermal Stability of Chlorinated Polyethylene (함염소 폴리에틸렌의 열안정성에 관한 연구)

  • Seul S. D.;Lee N. W.
    • Journal of the Korean Institute of Gas
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    • v.1 no.1
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    • pp.120-126
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    • 1997
  • The thermal decomposition of low density polyethylene(LDPE) and $25\%{\~}48\%$ chlorinated polyethylene(CPE) were studied using a dynamic thermogravimetry in the stream of nitrogen gas with 20ml/min. The mathematic method, differential (Friedman) and Integral (Ozawa) method were used to obtain value of activation energy of decomposition energy on the reaction. The activation energies evaluated by the above methods agree with each other very well. The maximum average activation energy calculated was 71.71kcal/mol. The thermal decomposition of LDPE and CPE were considered to be carried out by main chain scission and the thermogravimetric trace curve agree with the theoretical equation.

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A Study of Thermal Decomposition Characteristics and Toxicity of Product on PS/SAN/ABS (PS/SAN/ABS의 열분해특성과 생성물의 독성에 관한 연구)

  • Kang Yun Jin;Lee Nae Woo;Seul Soo Duk
    • Journal of the Korean Institute of Gas
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    • v.4 no.1 s.9
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    • pp.16-25
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    • 2000
  • To estimate the thermal characteristics and toxic parameters on styrene copolymers, We have investigated the activation energy, physical features and generation possibility of toxic material like narcotic gases. The activation energy was 25${\~}$50 Kcal/mol by the Kissinger's and DSC method at high temperature decomposition. It will be good information to estimate the possibility of fire occurrence. From calculations of FED, the values of $LC_{50}$ for PS, SAN and ABS were checked as 8,580, 265 and 308 $mg/m^3$ The mechanisms of thermal decomposition were mainly estimated by main chain scission, not by side group on FT-IR analysis.

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Effects of Heat Treatment on Electrical and Mechanical Properties of Glass Fiber Reinforced Epoxy (열처리가 유리섬유 강화 복합재료의 전기적 및 기계적 성질에 미치는 영향)

  • 이백수;이덕출
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.11 no.3
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    • pp.174-180
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    • 1998
  • In this work, the properties of FRP, which is applied recently in the composite insulating materials, by thermal treatment were investigated. The specimens were epoxy glass laminates fabricated by thermal press method and had the volume content of 46[%] cutted $45^{\circ}C$ in the fiber direction and 1.0[mm] thickness. The experimental results showed that the amount of weight loss, wettability, surface potential, and surface resistivity increased up to 200[$^{\circ}C$] as a function of temperature. Usually, most degradations caused the hydrophilic to decrease the contact angle. But, in this work on thermal-degradated FRP, we can confirm the introduction of hydrophobic properties by cross-linking and the ablation of polar small-molecules rather than chain scission and oxidation. Finally, weight loss and contact angle increased. These phenomena show the existence of hydrophobic surface. With the change to the hydrophobic surface and the electrical potential and resistivity on FRP surface increased. But, the dielectric properties and tensile stength are decreased.

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Mechanical Degradation of Polymers in Dilute Solution (III). The Influence of the Mixed Solvents (稀薄溶液에서의 Polymer의 機械的 切斷 (제3보). 混合溶媒의 영향)

  • Yeong Moo Won
    • Journal of the Korean Chemical Society
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    • v.17 no.3
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    • pp.207-212
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    • 1973
  • The mechanical degradation of poly (-vinylacetate) in several mixed solvents (dioxane-n-butanol, dioxane-sec-butanol, dioxane-ethyleneglycol, dioxane-kerosene.) was studied using the capillary flow method. The velocity constant of scission reaction (k) and the limited degree of polymerization (g) were compared at the same value of [${\eta}$], which is considered as the parameter of molecular dimension of polymers in solution. As result, (k) did not change much, even if the species and the volume fraction of poor (non-) solvents changed, while the value of (g) changed according to the species of poor solvents and the value of [${\eta}$]. From the facts described above, It follows that the limited degree of polymerization (g) were affected by the composition and distribution of mixed solvent molecules around the polymer chain, and the value of $\alpha$ (at [${\eta}$] = $KM^a$) in the polymer solution.

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Study on The Characteristics of UV Modified PET Surface and Effects in an Electroless Plating Solution (UV 전처리 후 PET 표면의 성질과 무전해 구리 도금액 내에서의 영향에 관한 연구)

  • Lee, Geon-Hyeong;Lee, Hong-Gi;Heo, Jin-Yeong
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2015.11a
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    • pp.176-177
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    • 2015
  • 본 실험에서 PET 위 무전해 구리 도금을 위한 전처리 방법 중 하나인 UV 조사를 통해 전처리를 한 후 PET 표면의 특성과 염기성 무전해 도금액이 개질된 표면에 미치는 영향에 관한 연구를 하였다. 일반적으로 PET 표면을 개질시키기 위해 UVC(254nm) 파장을 이용하여 PET bond break (Chain Scission)을 이루는 것으로 알려진다. 이때 공기 중의 산소와 UV 조사를 통해 생성된 PET 내의 free radical과 산화 반응을 통해 친수성이 높은 표면을 형성하게 된다. PET 표면의 친수성을 측정하기 위해 접촉각 측정기가 사용되었으며, 표면의 거칠기 및 형상을 관찰하기 위해 AFM과 FE-SEM를 각각 이용하였다. 또한 PET 표면의 구조 변화는 XPS를 통해 분석을 진행 하였다. UV 조사 후 표면의 거칠기 및 친수성은 높아졌지만, 무전해 도금은 이루어지지 않았다. 분석 결과, 이는 표면에 형성된 Low Molecular Weight Oxidation Compound(LMWOC)가 염기성 수용액 내에서 용해되어 모두 씻겨 나가 표면에 형성된 Sn/Pd을 모두 떨어트린 것으로 판단되며, 위와같은 이유로 UV 조사 후 습식 공정에 적용하기 위해 표면개질 된 PET를 염기성 수용액을 통해 전처리가 필요한 것으로 사료된다.

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Study on The Thermal Properties of Poly(methyl methacrylate) and Poly($\alpha$-methylstyrene-co-acrylonitrile) Mix tures (Poly(methyl methacrylate)와 Poly($\alpha$-methylstyrene-co-acrylonitrile) 혼합물의 열적특성에 관한 연구)

  • Moon, Deog-Ju;Kim, Byung-Chul;Kim, Dong-Keun;Seul, Soo-Duk;Sohn, Jin-Eon
    • Elastomers and Composites
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    • v.23 no.4
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    • pp.289-298
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    • 1988
  • The thermal degradation of poly(methyl methacrylate)(PMMA) and poly($\alpha$-methylstyrene-co-acrylonitrile)(SAN) mixtures were carried out using the thermogravimetry(TG) and differential scanning calorimetry(DSC) in the stream of nitrogen and air with 50 ml/min at the various heating rate from 4 to $20^{\circ}C/min$ and temperature from 20 to $500^{\circ}C$. The value of activation energies of thermal degradation determined by TG and DSC in the various PMMA/SAN mixtures were 34-54 kcal/mol in the stream of nitrogen. The value of activation energy of SAN 60% mixture were appeared high in comparison with addition rule. PMMA/SAN mixtures by the analysis of infrared spectrophotometer were decomposed by main chain scission in the stream of nitrogen.

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Kinetic Study on the Thermal Degradation of Poly(Methyl Methacrylate) and Poly(Acrylonitrile Butadiene Styrene) Mixtures (Poly(methyl methacrylate)와 Poly(acrylonitrile butadiene styrene)와의 혼합에 의한 열분해속도에 관한 연구)

  • Moon, Deok-Ju;Kim, Dong-Keun;Seul, Soo-Duk
    • Elastomers and Composites
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    • v.24 no.1
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    • pp.11-18
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    • 1989
  • The thermal degradation of Poly(methyl methacrylate) (PMMA) and poly(acrylonitrile butadiene styrene)(ABS) terpolymer as well as their mixtures were carried out using the thermogravimetry and differential scanning calorimetry(DSC) in the stream of nitrogen and air with 50 ml/min at the various heating rate from 4 to $20^{\circ}C/min$ and temperature from 200 to $300^{\circ}C$ The values of activation energies of thermal degradation determined by TG and DSC in the various PMMA/ABS mixtures were $34{\sim}58Kcal/mol,\;35{\sim}54Kcal/mol$ in the stream of nitrogen. The values of activation energy of ABS20% mixture was appeared high in camparison with addition rule. According to increasing the composition of ABS, the temperatures of glass transition and initial decomposition temperature were increased. PMMA/ABS mixtures by the analysis of infrared spectrophotometer were decomposed by main chain scission in the stream of nitrogen.

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