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High-Temperature and Chemically Resistant Foams from Sustainable Nanostructured Protein
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymeric Materials.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymeric Materials.ORCID iD: 0000-0002-2073-7005
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0001-9577-6845
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymeric Materials.ORCID iD: 0000-0001-5454-3316
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2021 (English)In: Advanced sustainable systems, ISSN 2366-7486, Vol. 5, no 9, article id 2100063Article in journal (Refereed) Published
Abstract [en]

Covalently crosslinked protein networks produced from whey protein nanofibrils (PNFs) are demonstrated to be sustainable high‐performance foams that show chemical resistance and mechanical strength, stiffness, and toughness on harsh aging at 150 °C. The aged foams are able to retain their properties at 180 °C for as long as 24 h, far exceeding the properties of most classical petroleum‐based thermoplastics. The foams are further developed into soft foams by the addition of glycerol as a plasticizer. The improvement in the mechanical performance of the foams with aging, which is equivalent to an increase by one order of magnitude in modulus and yield strength, is confirmed to be associated with (iso)peptide crosslinks. The results open the way for using protein‐based foam materials in severe/corrosive environments such as filtration, thermal insulation, and fluid absorption. The protein foams produced are suggested as suitable alternatives to petroleum‐based porous polymers.

Place, publisher, year, edition, pages
Wiley , 2021. Vol. 5, no 9, article id 2100063
Keywords [en]
aging, foams, mechanical properties, protein nanofibrils, thermal stability, whey protein
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-300412DOI: 10.1002/adsu.202100063ISI: 000652518800001Scopus ID: 2-s2.0-85106222305OAI: oai:DiVA.org:kth-300412DiVA, id: diva2:1589207
Note

QC 20250330

Available from: 2021-08-30 Created: 2021-08-30 Last updated: 2025-03-30Bibliographically approved
In thesis
1. Materials Based on Protein Nanofibrils
Open this publication in new window or tab >>Materials Based on Protein Nanofibrils
2021 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Protein nanofibrils (PNFs) prepared from whey protein isolate (WPI) at low pH and elevated temperature were processed into materials, i.e. hydrogels, films, foams, and fibres, for different applications where they could potentially be sustainable alternatives to petroleum-based polymers. WPI was chosen as the starting material due to the high accessibility of whey as an industrial side-stream product from cheese manufacturing, and its ability to easily grow PNFs.

PNFs grown in the presence of different metal ions were generally curved and short, and they formed hydrogels, in contrast to the straight ones fibrillated without metal ions. The effect of metal ions with different acidity was systematically studied with respect to fibrillation kinetics and gelation behaviour. The protein fibrillation was accelerated by the addition of metal ions. The strength of the hydrogel increased with increasing acidity of the metal ion at the same ion concentration, as long as the ion did not precipitate as hydroxide/oxide. 

Protein nanocomposite films were prepared by adding separately grown PNFs into a non-fibrillar protein matrix from the same WPI starting material. The glycerol-plasticized composite films obtained an increased elastic modulus and decreased strain at break with increasing content of PNFs. 

The produced PNF foams showed high-temperature resistance during aging at 150 °C for as long as one month (maximum testing time), far exceeding the properties of many petroleum-based thermoplastics. The aged foams were also able to retain their properties in different solutions that normally degrade/dissolve protein materials.

PNFs were also organized into microfibres using a flow-focusing method. Genipin was added as a natural crosslinker to improve the mechanical properties of the obtained fibre. The crosslinked fibre (using only 2% genipin) obtained a significantly higher stiffness and strength at break as compared to the fibre assembled without genipin. 

Abstract [sv]

Protein-nanofibriller (PNF) framställda av vassleproteinisolat (WPI) vid lågt pH och förhöjd temperatur användes här för att göra material, dvs. hydrogeler, filmer, skum och fibrer, för olika applikationer som möjliga hållbara alternativ till petroleumbaserade polymerer. WPI valdes som utgångsmaterial på grund av vasslets stora tillgänglighet då det erhålles som sidoström vid osttillverkning, och dessutom dess förmåga att lätt bilda PNF.

PNF som framställts i närvaro av olika metalljoner var i allmänhet krökta och bildade hydrogeler, i motsats till de raka, som framställs utan metalljoner. Effekten av metalljoner med olika surhetsgrad studerades systematiskt vad gäller fibrilleringskinetik och gelningsbeteende. Hydrogelens styrka ökade med ökande surhetsgrad hos metalljonen vid samma jonkoncentration, så länge jonen inte fälldes ut som hydroxid/oxid. 

Protein-nanokompositfilmer framställdes genom tillsats av separat framställda PNF i en icke-fibrillär proteinmatris från samma utgångsmaterial (WPI). De glycerol-mjukgjorda kompositfilmerna erhöll en ökad elastisitetsmodul och minskad brott-töjningen med ökande innehåll av PNF. 

De tillverkade PNF-skummen visade sig klara tuffa miljöer, det vill säga en temperatur på 150 °C i luft så länge som en månad (maximal testtid), vilket var betydligt bättre än för många klassiska petroleumbaserade termoplaster. De åldrade skummen behöll dessutom sina egenskaper i olika vätskor som normalt bryter ned/löser upp proteinmaterial. 

Med hjälp av en flödesfokuseringsmetod tillverkades här också PNF mikrofibrer. Genipin, en naturligt förekommande tvärbindare, tillsattes till för att förbättra de mekaniska egenskaperna hos den erhållna fibern. Den tvärbundna fibern (med endast 2% genipin) erhöll en signifikant högre styvhet och brottstyrka jämfört med fibern utan genipin. 

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2021. p. 73
Series
TRITA-CBH-FOU ; 2021:31
Keywords
protein nanofibrils, whey protein, hydrogel, film, microfibre, protein structure, mechanical properties
National Category
Textile, Rubber and Polymeric Materials Composite Science and Engineering Materials Engineering
Identifiers
urn:nbn:se:kth:diva-300416 (URN)978-91-7873-960-8 (ISBN)
Public defence
2021-10-08, F3, Lindstedsvägen 26, https://kth-se.zoom.us/webinar/register/WN_g08XJhazQ2OR2jf0GmjLTg, Stockholm, 10:00 (English)
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Note

QC 2021-08-31

Available from: 2021-08-31 Created: 2021-08-30 Last updated: 2022-06-25Bibliographically approved

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Ye, XinchenCapezza, Antonio JoseGowda, VasanthaOlsson, Richard T.Lendel, ChristoferHedenqvist, Mikael S.

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