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Conceptual approach to renewable barrier film design based on wood hydrolysate
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.ORCID iD: 0000-0002-1631-1781
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
2011 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 12, no 4, 1355-1362 p.Article in journal (Refereed) Published
Abstract [en]

Biomass is converted to oxygen barriers through a conceptually unconventional approach involving the preservation of the biomass native interactions and macromolecular components and enhancing the effect by created interactions With a co-component. A combined calculation/assessment model is elaborated to understand, quantify, and predict which compositions that provide an intermolecular affinity high enough to mediate the molecular packing needed to create a functioning barrier. The biomass used is a wood hydrolysate, a polysaccharide-rich but not highly refined mixture where a fair amount of the native intermolecular and intramolecular hernicelluloses-lignin interactions are purposely preserved, resulting in barriers with very low oxygen permeabilities (OP) both at 50 and 80% relative humidity and, considerably lower OPs than coatings based on the corresponding highly purified spruce hemicellulose, O-acetyl galactoglucomannan (AcGGM). The component interactions and, mutual affinities effectively mediate an immobilization of the chain segments in a dense disordered structure, modeled through the Hansen's solubility parameter concept and quantified on the nanolength scale by positron annihilation lifetime spectrum (PALS).

Place, publisher, year, edition, pages
2011. Vol. 12, no 4, 1355-1362 p.
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-31287DOI: 10.1021/bm200128sISI: 000289223500058PubMedID: 21366288Scopus ID: 2-s2.0-79953872797OAI: oai:DiVA.org:kth-31287DiVA: diva2:403236
Note
Uppdaterad från submitted till published 20110506 QC 20110311Available from: 2011-03-11 Created: 2011-03-11 Last updated: 2017-12-11Bibliographically approved
In thesis
1. Wood Hydrolysate for Renewable Products
Open this publication in new window or tab >>Wood Hydrolysate for Renewable Products
2011 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

Renewable biomass has been used by mankind for a long time for different purposes, from simply food to industrial products. Among a large family of polysaccharides, hemicellulose is non-edible but has shown a potential in many industrial fields such as medicine, agriculture and packaging. However, a complicated process is usually required to extract highly purified hemicellulose for further applications, which makes it not practical and economical for real industrial applications.

This thesis presents the utilization of a wood hydrolysate which was simply upgraded and recovered instead of being highly purified from the liquid by-product in the pulp industry. This softwood hydrolysate is rich in hemicellulose, O-acetyl galactoglucomannan (AcGGM), and also contains some lignin.

Films and coatings were produced based on this wood hydrolysate by blending with two other polysaccharide co-components, carboxymethyl cellulose (CMC) and chitosan. Different recipes with a variety of concentrations and compositions were prepared. For comparison, highly purified AcGGM-based films and coatings were also produced.

Mechanical properties and water vapor and oxygen barrier properties of the films and coatings were investigated. It was found that as a co-component, chitosan improved the mechanical properties best, and CMC gave better oxygen barrier properties at both 50% and 80% relative humidity. The wood-hydrolysate-based films gave much lower oxygen permeability (OP) values than AcGGM-based films.

In order to reveal why the less purified wood hydrolysate gave a better oxygen barrier, both theoretical and experimental studies were carried out. A group calculation based on Hansen’s Solubility parameter theory (HSP) showed that there were strong interactions between lignin and AcGGM in the wood hydrolysate and also that CMC was more compatible with wood hydrolysate/AcGGM than chitosan. These led to an affinity between components and gave a more compact molecular structure, and thus a smaller free volume in the matrix. This interpretation was in agreement with the Positron annihilation lifetime spectra (PALS) data, which showed that wood-hydrolysate-based films had a smaller free volume (hole size) and narrower distribution than AcGGM-based films. It also showed that CMC-co-component films had smaller hole radii in the matrix than chitosan-co-component films. Thermal properties and FTIR also shed light on the influence and nature of these interactions.

 

Abstract [sv]

 

Förnyelsebar biomassa har använts under lång tid för olika ändamål, från mat till industriprodukter. En stor familj av heteropolysackarider är hemicellulosa som har visat en potential i många applikationer, t. ex, inom medicin, jordbruket och förpackning industrin. För att utvinna renad hemicellulosa, krävs komplicerade processer, vilket är opraktiskt och för kostsant för många industriella tillämpningar. I detta arbete har vi använt ett hydrolysat som utvinns utan omfattande upprening från en flytande sidoström i massaindustrin. Detta barrveds hydrolysat är rikt på hemicellulosan, O-acetylerad galactoglucomannan (AcGGM) och innehåller även en del lignin.

Filmer och beläggningar skapades genom blandning av detta hydrolysat med två andra polysackarider samkomponenter; karboximetylcellulosa (CMC) och kitosan. Olika formuleringar med varierade koncentrationer och kompositioner utvecklades. Dessutom framställdes motsvarande formuleringar av AcGGM. Filmerna och beläggningarna analyserades med avseende på mekaniska egenskaper, kemisk struktur, vattenånga- och syrebarriäregenskaper. Kitosan, som samkomponent, förbättrade de mekaniska egenskaperna bäst medan CMC gav bäst syrebarriäregenskaper vid såväl 50% som 80% relativ fuktighet. Hydrolysat-baserade filmer hade betydligt lägre syrepermeabilitet (OP) än AcGGM-baserade filmer. För att förstå varför mindre renat hydrolysat gav bättre syrebarriäregenskaper än upprenad AcGGM, utvecklades en kombinerat teoretisk-analytisk modell. Beräkningar baserade på Hansens löslighetsparametersteori (HSP) visade att det finns starka interaktioner mellan lignin och hemicellulosorna i hydrolysatet, och även att CMC var mer kompatibel med hydrolysat/AcGGM än kitosan, vilket ger en starkare affinitet mellan komponenterna och en mer kompakt molekylstuktur, och därmed mindre fri volym i matrisen. Denna tolkning verifieras av positron annihilation lifetime spectra (PALS), som visar att hydrolysat-baserade filmer har en mindre fri volym (hålstorlek) och högre homogenitet än AcGGM-baserade filmer. Även termiska analyser och FTIR verifierade inflytandet och arten av dessa interaktioner.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2011. 49 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2011:20
Keyword
wood hydrolysate, hemicellulose, oxygen permeability, PALS, film, coating, CMC, chitosan, HSP
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-31134 (URN)978-91-7415-879-3 (ISBN)
Presentation
2011-04-04, D32, KTH, Lindstedtsv 5, Entreplan, 100 44 Stockholm, 09:00 (English)
Opponent
Supervisors
Note

QC 20110311

Available from: 2011-03-11 Created: 2011-03-09 Last updated: 2012-12-18Bibliographically approved
2. Wood hydrolysates- New concepts in renewable material design
Open this publication in new window or tab >>Wood hydrolysates- New concepts in renewable material design
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Wood hydrolysates (WHs) are biomasses obtained in processes involving hydrothermal treatments of wood. WHs are rich in hemicelluloses and lignin. Instead of complicated extraction processes, such as precipitation, or extensive purification, this work utilizes the crude WHs. These WHs were successfully developed into oxygen-barrier films and coatings and a conceptual model was established to predict biomass matrix performance from molecular structures and interactions.

Free standing films and coatings from blends of WHs and either chitosan or carboxylmethyl cellulose (CMC) as a co-component, were produced. The films had an excellent oxygen-barrier performance which was even better than the corresponding films prepared from highly purified hemicelluloses. From a fundamental point of view, the Hansen solubility parameter (HSP) theory revealed the interactions between molecules in WHs, as well as in WH-based blends, which shed light on the great barrier performance of WH-based films. The hypothesis was that these strong interactions increased the mutual molecular affinity in the matrix, which led to a denser molecular packing and hence a good oxygen-barrier performance. The positron annihilation lifetime spectroscopy (PALS) measurements quantified the free volumes in the WH-based matrices. The HSP results, free volume size and distribution and thermal analyses supported the hypothesis well.

The HSP model was then used as a tool for designing oxygen-barrier coatings from WH-based blends. Using the HSP model, the interactions between different WHs and CMC were calculated and quantified. According to our hypothesis, the oxygen-barrier performance could thus be predicted. The free volume from PALS, oxygen permeability (OP) results were generally in consistence with the prediction from HSP model, which shows the potential of the HSP model for designing formulations of WHs for oxygen-barrier coatings for food packaging. 

To realize an industrially feasible and efficient process for WH-based barrier coating layers, some new approaches were attempted. Previously, coatings were prepared manually from WH-based blends. Now, a creative spray drying (SPD) coating technique was developed for a reproducible, efficient coating process of WHs with no additives or second components. Also, glyoxal crosslinking improved the ductility of the WH-based coatings which in turn improved the quality and oxygen-barrier performance of the coatings. Finally, scanning electron microscopy (SEM) integrated with a micro-tensile test device made it possible the real-time observation of coating surfaces during the deformation process. This can successfully analyze the mechanical performance of the coatings without being influenced by substrate.

In summary, the WHs present a viable and very promising resource for green barrier design.

Abstract [sv]

Hydrolysat är processvätskor från träindustrin. Istället för komplicerade utvinningsprocesser av ren hemicellulosa från processvätskor, används här det oförädlade hydrolysatet, som innehåller till största delen hemicellulosa och en del lignin. Den här avhandlingen beskriver hur vi framgångsrikt utvecklade detta hydrolysat till syrgasbarriärfilmer och bestrykningar som kan användas till matförpackningar samt hur modellering av strukturerna och interaktionerna mellan hydrolysatets komponenter kan förutsäga deras prestanda som barriärmaterial.

Fristående filmer och bestrykningar skapades från blandningar av vedhydrolysat och en samkomponent: antingen kitosan eller karboximetylcellulosa (CMC). Filmerna hade utmärkta syrgasbarriäregenskaper som till och med var bättre än filmer beredda av motsvarande renade hemicellulosa. Hansens löslighetsparametersteori (HSP) påvisade och kvantifierade interaktioner mellan molekylerna i både hydrolysat och hydrolysat-baserade blandningar vilket ger en förståelse för de goda barriäregenskaperna. Vår hypotes var att dessa starka interaktioner ökade affiniteten i matrisen vilket leder till tät molekylär packning och därmed bra syrgasbarriäregenskaper. Med Positron annihiliation lifetime spectroscopy (PALS) uppmättes de fria volymerna i de hydrolysat-baserade matriserna. HSP resultaten, storlek och fördelning av fri volym, samt termisk analys, verifierade hypotesen väl.

HSP-modellen användes sedan för att prediktera kompositionen hos syrgasbarriärbestrykningar från hydrolysat-baserade blandningar. Genom att använda HSP-modellen, kan interaktionerna mellan olika hydrolysat och CMC beräknas och interaktionerna i matrisen utvärderas. De fria volymerna uppmätta med PALS, syrepermeabilitet (OP)-resultaten var generellt överensstämmande med förutsägelserna från HSP-modellen, vilket visar potentialen för HSP- modellen som verktyg i formuleringen av barriärbestrykningarr för matförpackningar.

För att utveckla en industriellt realistisk och effektiv process för produktion av hydrolysat-baserade bestrykningar provades flera angreppssätt. Först gjordes bestrykningar manuellt från hydrolysat-baserade blandningar och dessa hade utmärkta syrebarriäregenskaper. Sedan utvecklades en spraytorkningsbeläggningsteknik (SPD) som en reproducerbar, effektiv bestrykningsprocess för hydrolysat utan tillsatser eller andra samkomponenter. Dessutom förbättrade töjbarheten hos bestrykningarna genom tvärbindning med glyoxal vilket i sin tur förbättrade kvalitet och syrgasbariäregenskaperna för bestrykningen. SEM integrerat med en dragprovutrustning gjorde det möjligt att i realtid observeraytan av bestrykningen under deformationsprocessen. Detta gjorde det möjligt att studera de mekaniska egenskaperna för beläggningarna utan inverkan av substratet.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. 74 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2013:26
Keyword
wood hydrolysate, oxygen barrier, coatings, films, hemicellulose, lignin, CMC, chitosan, HSP, PALS, spray drying, SEM with tensile test, glyoxal crosslinking., vedhydrolysat, syrebarriäregenskaper, ytbeläggningar, filmer, hemicellulosa, lignin, CMC, kitosan, HSP, PALS, spraytorkning, SEM med dragprovning, glyoxal tvärbindning.
National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-122167 (URN)978-91-7501-743-3 (ISBN)
Public defence
2013-06-04, K2, Teknikringen 28, KTH, 100 44 Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Formas, 243-2008-129Vinnova, 2009-04311
Note

QC 20130515

Available from: 2013-05-15 Created: 2013-05-13 Last updated: 2013-05-15Bibliographically approved

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