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Degradation of acrylonitrile butadiene rubber and fluoroelastomers in rapeseed biodiesel and hydrogenated vegetable oil
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. (Polymeric Materials)ORCID iD: 0000-0002-7348-0004
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Biodiesel and hydrotreated vegetable oil (HVO) are currently viewed by the transportation sector as the most viable alternative fuels to replace petroleum-based fuels. The use of biodiesel has, however, been limited by the deteriorative effect of biodiesel on rubber parts in automobile fuel systems. This work therefore aimed at investigating the degradation of acrylonitrile butadiene rubber (NBR) and fluoroelastomers (FKM) on exposure to biodiesel and HVO at different temperatures and oxygen concentrations in an automated ageing equipment and a high-pressure autoclave. The oxidation of biodiesel at 80 °C was promoted by an increase in the oxygen partial pressure, resulting in the formation of larger amounts of hydroperoxides and acids in the fuel. The fatty acid methyl esters of the biodiesel oxidized less at 150 °C on autoclave aging, because the termination reactions between alkyl and alkylperoxyl radicals dominated over the initiation reactions. HVO consists of saturated hydrocarbons, and remained intact during the exposure. The NBR absorbed a large amount of biodiesel due to fuel-driven internal cavitation in the rubber, and the uptake increased with increasing oxygen partial pressure due to the increase in concentration of oxidation products of the biodiesel. The absence of a tan δ peak (dynamical mechanical measurements) of the bound rubber and the appearance of carbon black particles devoid of rubber suggested that the cavitation was caused by the detachment of bound rubber from particle surfaces. A significant decrease in the strain-at-break and in the Payne-effect amplitude of NBR exposed to biodiesel was explained as being due to the damage caused by biodiesel to the rubber-carbon-black network. During the high-temperature autoclave ageing, the NBR swelled less in biodiesel, and showed a small decrease in the strain-at-break due to the cleavage of rubber chains. The degradation of NBR in the absence of carbon black was due only to biodiesel-promoted oxidative crosslinking. The zinc cations released by the dissolution of zinc oxide particles in biodiesel promoted reduction reactions in the acrylonitrile part of the NBR. Heat-treated star-shaped ZnO particles dissolved more slowly in biodiesel than the commercial ZnO nanoparticles due to the elimination of inter-particle porosity by heat treatment. The fuel sorption was hindered in HVO-exposed NBR by the steric constraints of the bulky HVO molecules. The extensibility of NBR decreased only slightly after exposure to HVO, due to the migration of plasticizer from the rubber. The bisphenol-cured FKM co- and terpolymer swelled more than the peroxide-cured GFLT-type FKM in biodiesel due to the chain cleavage caused by the attack of biodiesel on the double bonds formed during the bisphenol curing. The FKM rubbers absorbed biodiesel faster, and to a greater extent, with increasing oxygen concentration. It is suggested that the extensive biodiesel uptake and the decrease in the strain-at-break and Young’s modulus of the FKM terpolymer was due to dehydrofluorination of the rubber by the coordination complexes of biodiesel and magnesium oxide and calcium hydroxide particles. An increase in the CH2-concentration of the extracted FKM rubbers suggested that biodiesel was grafted onto the FKM at the unsaturated sites resulting from dehydrofluorination.

Place, publisher, year, edition, pages
Stockholm, Sweden: KTH Royal Institute of Technology, 2017. , p. 63
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2017:9
Keyword [en]
Degradation; Acrylonitrile butadiene rubber; Fluoroelastomers; Biodiesel; Hydrotreated vegetable oil; Cavitation; Bound rubber; Dehydrofluorination.
National Category
Polymer Technologies
Research subject
Fibre and Polymer Science
Identifiers
URN: urn:nbn:se:kth:diva-202422ISBN: 978-91-7729-274-6 (print)OAI: oai:DiVA.org:kth-202422DiVA: diva2:1076862
Public defence
2017-03-31, F3, 10:00 (English)
Opponent
Supervisors
Note

QC 20170227

Available from: 2017-02-27 Created: 2017-02-24 Last updated: 2017-06-26Bibliographically approved
List of papers
1. Deterioration of automotive rubbers in liquid biofuels: A review
Open this publication in new window or tab >>Deterioration of automotive rubbers in liquid biofuels: A review
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2015 (English)In: Renewable & sustainable energy reviews, ISSN 1364-0321, E-ISSN 1879-0690, Vol. 43, p. 1238-1248Article, review/survey (Refereed) Published
Abstract [en]

Concerns over the fast depletion of fossil fuels, environmental issues and stringent legislation associated with petroleum-based fuels have triggered a shift to bio-based fuels, as an alternative to meet the growing energy demand in the transportation sector. However, since conventional automobile fuel systems are adapted to petroleum-based fuels, switching to biofuels causes a severe deterioration in the performance of currently used rubber components. The degradation of the rubber materials in biofuels is complicated by the presence of different additives in biofuels and rubber compounds, by oxidation of biofuels and by the effects of thermomechanical loadings in the engine. This paper presents a comprehensive review of the effects of different types of biofuels, particularly biodiesel and bioethanol, on the physical, mechanical, morphological and thermal properties of elastomers under different exposure conditions. In addition, the literature data available on the variation of rubbers' resistance to biofuels with the changes in their monomer type and composition, cure system and additives content was also studied. The review essentially focuses on the compatibility of biofuels with acrylonitrile butadiene rubber, fluoroelastomers, polychloroprene rubber and silicon rubber, as the most commonly used automotive rubbers coming into contact with fuels during their service. The knowledge summarized in this study can help to develop a guideline on the selection of rubber for automotive parts designed to withstand biofuels.

Keyword
Biofuels, Rubbers, Automobile fuel system, Degradation
National Category
Energy Engineering
Identifiers
urn:nbn:se:kth:diva-161100 (URN)10.1016/j.rser.2014.11.096 (DOI)000348880600097 ()2-s2.0-84919799253 (Scopus ID)
Funder
Swedish Energy Agency, 2011-006737
Note

QC 20150318

Available from: 2015-03-18 Created: 2015-03-09 Last updated: 2017-12-04Bibliographically approved
2. Deterioration of acrylonitrile butadiene rubber in rapeseed biodiesel
Open this publication in new window or tab >>Deterioration of acrylonitrile butadiene rubber in rapeseed biodiesel
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2015 (English)In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 111, p. 211-222Article in journal (Refereed) Published
Abstract [en]

The deterioration of acrylonitrile butadiene rubber (NBR) exposed to rapeseed biodiesel at 90 degrees C was studied. The oxidation of biodiesel and NBR during ageing was monitored by H-1 NMR and infrared spectroscopy, HPLC and titration methods. The oxidation of biodiesel was impeded in the presence of NBR, but promoted in biodiesel-exposed rubber. This was explained as being due to the migration of stabilizer from the rubber to biodiesel, the diffusion of dissolved oxygen from biodiesel into NBR and the absorption of oxidation precursors of biodiesel by the rubber. The resemblance between the anomalous sorption kinetics of biodiesel in NBR and the equilibrium benzene uptake by the aged rubbers revealed that biodiesel caused a network defect in NBR, resulting in a gradual increase in the equilibrium swelling. The cleavage of crosslinks was implausible since the Young's modulus of the rubber at low strains, disregarding an initial decrease, increased with increasing exposure time. The appearance of 'naked' carbon black particles in the scanning electron micrographs of the aged rubbers and a drastic decrease in the strain-at-break of NBR after exposure to biodiesel suggests that internal cavitation was caused by the attack of biodiesel on the acrylonitrile units of NBR.

Keyword
Biodiesel, Acrylonitrile butadiene rubber, Oxidation, Degradation mechanism
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-161639 (URN)10.1016/j.polymdegradstab.2014.11.012 (DOI)000348949000025 ()2-s2.0-84919779987 (Scopus ID)
Note

QC 20150317

Available from: 2015-03-17 Created: 2015-03-13 Last updated: 2017-12-04Bibliographically approved
3. Degradation of carbon-black-filled acrylonitrile butadiene rubber in alternative fuels: Transesterified and hydrotreated vegetable oils
Open this publication in new window or tab >>Degradation of carbon-black-filled acrylonitrile butadiene rubber in alternative fuels: Transesterified and hydrotreated vegetable oils
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2016 (English)In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 123, p. 69-79Article in journal (Refereed) Published
Abstract [en]

The deterioration of acrylonitrile butadiene rubber (NBR), a common sealing material in automobile fuel systems, when exposed to rapeseed biodiesel and hydrotreated vegetable oil (HVO) was studied. The fuel sorption was hindered in HVO-exposed rubber by the steric constraints of bulky HVO molecules, but it was promoted in biodiesel-exposed rubber by fuel-driven cavitation in the NBR and by the increase in diffusivity of biodiesel after oxidation. The absence of a tan δ peak of the bound rubber and the appearance of carbon black particles devoid of rubber suggested that the cavitation was made possible in biodiesel-aged rubber by the detachment of bound rubber from particle surfaces. The HVO-exposed NBR showed a small decrease in strain-at-break due to the migration of plasticizer from the rubber, and a small increase in the Young’s modulus due to oxidative crosslinking. A drastic decrease in extensibility and Payne-effect amplitude of NBR on exposure to biodiesel was explained as being due to the damage caused by biodiesel to the continuous network of bound rubber-carbon black. A decrease in the ZnO crystal size with increasing exposure time suggested that the particles are gradually dissolved in the acidic components of oxidized biodiesel. The Zn2+ cations released from the dissolution of ZnO particles in biodiesel promoted the hydrolysis of the nitrile groups of NBR.

Place, publisher, year, edition, pages
Elsevier, 2016
Keyword
Acrylonitrile butadiene rubber, Biodiesel, Bound rubber degradation, HVO
National Category
Other Chemistry Topics Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-181471 (URN)10.1016/j.polymdegradstab.2015.11.019 (DOI)000368204100007 ()2-s2.0-84949575368 (Scopus ID)
Note

QC 20160202

Available from: 2016-02-02 Created: 2016-02-02 Last updated: 2017-11-30Bibliographically approved
4. Degradation of fluoroelastomers in rapeseed biodiesel at different oxygen concentrations
Open this publication in new window or tab >>Degradation of fluoroelastomers in rapeseed biodiesel at different oxygen concentrations
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2017 (English)In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 136, p. 10-19Article in journal (Refereed) Published
Abstract [en]

The degradation of fluoroelastomers (FKM) based on different monomers, additives and curing systems was studied after exposure to rapeseed biodiesel at 100 °C and different oxygen partial pressures. The sorption of fuel in the carbon black-filled FKM terpolymer was promoted by the fuel-driven cavitation in the rubber. The bisphenol-cured rubbers swelled more in biodiesel than the peroxide-cured FKM, presumably due to the chain cleavage caused by the attack of biodiesel on the double bonds formed during the bisphenol curing. With any of the selected types of monomer, the FKM rubbers absorbed biodiesel faster and to a greater extent with increasing oxygen partial pressure due to the increase in concentration of the oxidation products of biodiesel. Water-assisted complexation of biodiesel on magnesium oxide and calcium hydroxide particles led to dehydrofluorination of FKM, resulting in an extensive fuel uptake and a decrease in the strain-at-break and the Young's modulus of the rubbers. An increase in the CH2-concentration determined by infrared spectroscopy, and the appearance of biodiesel flakes in scanning electron micrographs of the extracted rubbers, were explained as being due to the presence of insoluble biodiesel grafted onto FKM on the unsaturated sites resulting from dehydrofluorination. The extensibility of the GFLT-type FKM was the least affected on exposure to biodiesel because this rubber contained less unsaturation and metal oxide/hydroxide particles.

Place, publisher, year, edition, pages
Elsevier, 2017
Keyword
Degradation; Fluoroelastomers; Biodiesel; Chain cleavage; Dehydrofluorination
National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-202419 (URN)10.1016/j.polymdegradstab.2016.12.006 (DOI)000393531300002 ()2-s2.0-85007236838 (Scopus ID)
Note

QC 20170228

Available from: 2017-02-24 Created: 2017-02-24 Last updated: 2017-11-29Bibliographically approved
5. Effects of ageing conditions on degradation of acrylonitrile butadiene rubber filled with heat-treated ZnO star-shaped particles in rapeseed biodiesel
Open this publication in new window or tab >>Effects of ageing conditions on degradation of acrylonitrile butadiene rubber filled with heat-treated ZnO star-shaped particles in rapeseed biodiesel
Show others...
2017 (English)In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321Article in journal (Refereed) Published
Abstract [en]

The degradation of acrylonitrile butadiene rubber (NBR) after exposure to biodiesel at different oxygen partial pressures in an automated ageing equipment at 80 °C, and in a high-pressure autoclave at 150 °C was studied. The oxidation of biodiesel was promoted by an increase in oxygen concentration, resulting in a larger uptake of fuel in the rubber due to internal cavitation, a greater decrease in the strain-at-break of NBR due to the coalescence of cavity, and a faster increase in the crosslinking density and carbonyl index due to the promotion of the oxidation of NBR. During the high-temperature autoclave ageing, less fuel was absorbed in the rubber, because the formation of hydroperoxides and acids was impeded. The extensibility of NBR aged in the autoclave decreased only slightly due to the cleavage of rubber chains by the biodiesel attack. The degradation of NBR in the absence of carbon black was explained as being due to oxidative crosslinking. The dissolution of ZnO crystals in the acidic components of biodiesel was retarded by removing the inter-particle porosity and surface defects through heat treating star-shaped ZnO particles. The rubber containing heat-treated ZnO particles swelled less in biodiesel than a NBR filled with commercial ZnO nanoparticles, and showed a smaller decrease in the strain-at-break and less oxidative crosslinking.

Place, publisher, year, edition, pages
Elsevier, 2017
Keyword
Acrylonitrile butadiene rubber; Biodiesel; Degradation; Oxidation; Heat treatment; Zinc oxide
National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-202418 (URN)10.1016/j.polymdegradstab.2017.02.011 (DOI)000400222500004 ()2-s2.0-85014171938 (Scopus ID)
Note

QC 20170228

Available from: 2017-02-24 Created: 2017-02-24 Last updated: 2017-05-23

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