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Wood Hydrolysate Barriers: Performance Controlled via Selective Recovery
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.ORCID iD: 0000-0002-0626-0802
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.
2012 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 13, no 2, 466-473 p.Article in journal (Refereed) Published
Abstract [en]

Films and coatings were produced from a noncellulosic polysaccaride-rich wood hydrolysate (WH) and the resulting oxygen barrier performance was improved by a selective choice of upgrading conditions. The WH was obtained from process water in the hydrothermal treatment of hardwood and subjected to one of three alternative upgrading treatments, resulting in xylan-rich fractions with significant differences in structure, composition, and properties of the recovered WH fractions, which in turn had a major impact on their performance with respect to tensile and oxygen barrier properties. The WH in the least upgraded state, the crudest fraction, produced films with the best performance in terms of oxygen permeability and was superior to corresponding films based on highly purified hemicellulose.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2012. Vol. 13, no 2, 466-473 p.
Keyword [en]
RENEWABLE SOURCES, FILMS, HEMICELLULOSES, SPRUCE, POLYSACCHARIDES, HYDROGELS, XYLAN
National Category
Biochemistry and Molecular Biology
Identifiers
URN: urn:nbn:se:kth:diva-90911DOI: 10.1021/bm201518dISI: 000300115900021Scopus ID: 2-s2.0-84856915601OAI: oai:DiVA.org:kth-90911DiVA: diva2:507811
Note

QC 20120306

Available from: 2012-03-06 Created: 2012-03-05 Last updated: 2017-12-07Bibliographically approved
In thesis
1. Wood hydrolysate Barriers
Open this publication in new window or tab >>Wood hydrolysate Barriers
2012 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

Wood hemicellulose is an abundant but fairly unexploited renewable feedstock. Recent studies have shown that hemicelluloses have a large potential for use in the food packaging industry as a sustainable alternative to the conventional oxygen-barrier materials used today. Such hemicelluloses are the main components of wood hydrolysates (WH), which are released in large quantities in many forestry process side streams. Recovering these hemicellulose-rich WH fractions and turning them into food packaging materials would be beneficial from both, an environmental and an economic point of view. However, in the development of packaging materials for large-scale applications, the high production costs to obtain the highly purified hemicellulose and their high moisture sensitivity are considered to be the two main limiting factors.In this study, a selective choice of the upgrading conditions during the recovery of WH and the incorporation of layered silicate particles in WH-based films and coating formulations are used as tools to control and tailor the barrier and tensile performances of the materials, enabling the design of renewable oxygen-barrier materials that are cost-effective and with improved properties. The WH originated from the aqueous liquor from hardwood hydrothermal treatment and upgraded according to one of three alternative routes (ultrafiltration, ultrafiltration followed by diafiltration, and ethanol precipitation) resulting in hemicellulose-rich fractions with different structures, compositions, and properties, which in turn resulted in different performances in terms of mechanical and oxygen-permeability properties. WH in its crudest form gave rise to coatings with the best oxygen-barrier performance, higher than the oxygen-barrier performance of pure hemicellulose coatings. The addition of montmorillonite or talc layered silicates as mineral additives in the WH-based films resulted in better water-vapor-barrier properties, and considerably improved oxygen barrier performance at a relative humidity as high as 80 %. The application of the WH-based films was therefore extended to a wider range of relative humidity conditions.

Abstract [sv]

Hemicellulosorna utgör en rikligt förekommande men underutnyttjad förnyelsebar råvara. Hemicellulosorna har en stor potential att kunna användas som material i matförpackningar som ett hållbart alternativ till de konventionella syrgasbarriärer som används idag. Hemicellulosor är huvudkomponenter i vedhydrolysat (WH) som frisätts i stora mängder i många träindustriella processvattenströmmar. Att utvinna dessa hemicellulosa-rika WH-fraktioner och omvandla dem till förpackningsmaterial skulle vara fördelaktigt, från såväl ett miljömässigt som ett ekonomiskt perspektiv. I utvecklingen av förpackningsmaterial i stor skala utgör dock de höga produktionskostnader som renframställning av hemicellulosa kräver, samt deras höga fuktkänslighet, de två viktigaste begränsande faktorerna.I detta arbete har två strategier utarbetats och tillämpats för att kontrollera och skräddarsy barriär- och mekaniska egenskaper hos framställda WH-baserade film- och bestrykningsmaterial; selektiva uppgraderingsförhållanden samt inkorporering av skiktade silikatpartiklar. Dessa strategier möjliggör design av syrgasbarriärer som är kostnadseffektiva och har förbättrade egenskaper. Det WH som användes var ett processvatten från en hydrotermisk behandling av lövved. Tre olika upparbetningsstrategier tillämpades och jämfördes (ultrafiltrering, ultrafiltrering följd av diafiltrering, samt fällning i etanol) och de hemicellulosa-rika fraktioner som erhölls från respektive upparbetning skilde sig åt i struktur, sammansättning och egenskaper, vilket i sin tur resulterade i material med olika prestanda i fråga om mekaniska egenskaper och syrgasbarriärförmåga. Den minst upparbetade WH-fraktionen gav upphov till beläggningar med bäst syrgasbarriärförmåga, bättre än beläggningar baserade på renframställd hemicellulosa. En tillsats av mineraladditiv i form av montmorillonit-lera eller talksilikater i de WH-baserade filmerna resulterade i förbättrad ångbarriärförmåga och markant förbättra syrgasbarriärförmåga vid relativa luftfuktigheter så höga som 80%. Applikationsområdet för WH-baserade filmer kan därmed utökas till att gälla ett bredare fuktighetsintervall.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. 43 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2012:50
Keyword
wood hydrolysate, xylan, hemicellulose, layered silicates, oxygen barrier, packaging, film, coaing, birch.
National Category
Textile, Rubber and Polymeric Materials Composite Science and Engineering
Identifiers
urn:nbn:se:kth:diva-104821 (URN)978-91-7501-503-3 (ISBN)
Presentation
2012-10-29, E36, lindstedtsvägen 3, KTH, Stockholm, 13:00 (English)
Opponent
Supervisors
Funder
Vinnova, 2009-04311
Note

QC 20121113

Available from: 2012-11-13 Created: 2012-11-13 Last updated: 2012-11-13Bibliographically approved
2. Strategies for Renewable Barriers with Enhanced Performance
Open this publication in new window or tab >>Strategies for Renewable Barriers with Enhanced Performance
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Forest biomass is expected to play an increasingly important role in tomorrow´s global bio-economy as one of the main renewable sources of materials, chemicals and energy. In the framework of the biorefinery concept, the forestry industry is looking for new processes to utilize several fractions in the biomass (cellulose, hemicelluloses, lignin etc.), thereby generating value-added by-products, an economically sustainable process, and new market opportunities. The work presented in this thesis aims to develop oxygen barrier films and coatings based on the hemicelluloses-rich biorefinery fraction, referred to as wood hydrolysate (WH). These WHs were obtained from the aqueous process liquor after the hydrothermal treatment of hardwood. The WH-based films and coatings are intended to meet the increasing demand of bio-based and biodegradable barrier materials in multi-layered laminates for the food-packaging sector. This work has employed four strategies to provide control and enhancement of the mechanical and barrier properties of WH: I) a selective choice of up-grading pre-treatments of the WH aqueous liquor, II) the incorporation of layer silicates into the barrier formulation, III) chain-extension of the hemicellulose chains present in the WH via reductive amination, and IV) the development of wood hydrolysate polyelectrolyte complexes (PEC) with quaternized cellulose (QC). It has been demonstrated that the crude WH, with almost no upgrading pre-treatment, produced coatings with the best performance in terms of low oxygen permeability. Furthermore, the addition of naturally occurring layered silicates into the WH-based film formulations led to a decrease in water vapor permeability, and a considerably lower oxygen permeability at 80% relative humidity. Moreover, the chain-extension approach was shown to significantly enhance the formability and mechanical performance of WH-based films, making it possible to produce cohesive films with a higher proportion of WH, 70–85% (w/w) and to reduce the content of co-components in the films. The WH/QC-PEC-based films exhibited by far the best tensile properties, better than those previously obtained with carboxymethyl cellulose as a co-component in an equal amount, with a tensile strain-at-break as high as 7 %.

Abstract [sv]

Vedbiomassa väntas spela en viktig roll i framtidens bioekonomi som en förnybar råvara för material, baskemikalier och energi. Genom att betrakta skogindustriella processer som ett bioraffinaderi och utnyttja fler vedfraktioner i biomassan (cellulosa, lignin och hemicellulosor m.fl.) via nya processer och metoder kan mervärdesprodukter och en ekonomiskt hållbar process skapas och nya inkomstkällor och marknader genereras. Avhandlingsarbetes mål har varit att skapa barriärfilmer och –bestrykningar baserade på hemicellulosa-rika så kallade vedhydrolysat (WH), vattenbaserade fraktioner som generats vid hydrotermisk extraktion av lövved. De WH-baserade filmerna och bestrykningarna är avsedda att utgöra biobaserade och nedbrytbara barriärskikt i flerskiktade matförpackningslaminat. Avhandlingsarbetet har resulterat i fyra strategier som kontrollerar och förbättrar barriär- och mekaniska egenskaper hos WH: I) selektiv upprening av förbehandling av hydrolysaten, II) inblandning av skiktade silikatpartiklar i formuleringarna, III) kedjeförlängning av hemicellulosapolymererna i WH via reducerande aminering, samt IV) skapandet av polyelektrolytkomplex (PEC) mellan WH och katjonisk cellulosa (QC). 

Den WH som förbehandlades minst gav upphov till bättre syrgasbarriärer än WH som upprenades i högre grad. Tillsats av silikatpartiklar till filmformuleringarna resulterade i filmer med lägre permeabilitet för vattenånga och i synnerhet en förbättring av syrgasbarriäregenskaperna vid 80% relativ fuktighet. Kedjeförlängning förbättrade signifikant filmbildningsegenskaperna liksom de mekaniska egenskaperna vilket gjorde det möjligt att skapa koherenta filmer med en högre andel WH, 70 – 85% (w/w) och en lägre andel tillsats. PEC-baserade filmer uppvisade de överlägset bästa mekaniska egenskaperna, med en töjbarhet på upp till 7%, jämfört med tidigare WH-baserade filmer där lika delar karboxymetylcellulosa använts som tillsats.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2015. 69 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2015:17
Keyword
Wood hydrolysate, xylan, birch, layered silicates, oxygen barrier, packaging, film, coating, reductive amination, chain-extension, cationic cellulose, polyelectrolyte complexes, hemicellulose, vedhydrolysat, xylan, björk, silikat, syrgasbarriär, förpackningar, film, bestrykning, reducerande aminering, kedjeförlängning, katjonisk cellulosa, polyelektrolytkomplex, hemicellulosa
National Category
Polymer Technologies Paper, Pulp and Fiber Technology Textile, Rubber and Polymeric Materials
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-164098 (URN)978-91-7595-510-0 (ISBN)
Public defence
2015-05-08, Kollegiesalen, Brinellvägen 8, Stockholm, 13:00 (English)
Opponent
Supervisors
Funder
VINNOVA, 2009-04311
Note

QC 20150414

Available from: 2015-04-14 Created: 2015-04-13 Last updated: 2015-04-14Bibliographically approved

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