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Effects of plasticizing and crosslinking on coatings based on blends of starch-PVOH and starch-lignin
Karlstad University, Faculty of Health, Science and Technology (starting 2013), Department of Engineering and Chemical Sciences (from 2013).
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

A barrier material is usually needed on a fiber-based food package to protect the packed food from gases and moisture and thus maintain its quality. Barrier materials presently used in food packaging applications are mostly petroleum-based polymers. Over the last few decades, efforts have been made to replace petroleum-based materials with bio-based materials. The present work has focused on the possibility of using a natural barrier material on a fiber-based food package and the  effects of plasticizing and cross-linking on the mechanical and barrier properties, and the stability in water of coatings based on starch-poly(vinyl alcohol) (PVOH) and starch-lignin blends.

The flexibility of the starch films was increased by adding PVOH further by adding a plasticizer. It was shown that citric acid can act as a compatibilizer and cross-linker for starch and PVOH, and the use of citric acid may slow down the diffusion of both oxygen and water vapor if a multilayer coating strategy is used. The addition of polyethylene glycol to the pre-coating recipe resulted in a lower oxygen transmission rate through polyethylene-extruded board than when citric acid was added to the pre-coating. The flexibility of the barrier coatings and the properties of the base substrate affect the cracking tendency of the barrier coatings during the creasing and folding of a barrier-coated board.

The addition of lignin to the starch reduced the migration of starch from the starch-lignin films and the addition of ammonium zirconium carbonate as a cross-linker reduced the migration of both starch and lignin from the films. The addition of starch to the lignin solution increased the solubility of lignin at low pH, and the pilot-coated board showed a significant decrease in migration of lignin from the coatings containing ammonium zirconium carbonate when the pH of the coating solution was decreased.

Abstract [en]

A barrier material is usually needed on a fiber-based food package to maintain quality by protecting packed food from gases and moisture. Over the last few decades, efforts have been made to replace petroleum-based materials with bio-based materials. The present work has focused on the possibility of using a natural barrier material on fiber-based food packaging materials, and the effects of plasticizing and cross-linking on the mechanical and barrier properties and on the stability in water of coatings based on starch-PVOH and starch-lignin blends have been evaluated.

Citric acid can act as a compatibilizer and cross-linker for starch and PVOH, and the use of citric acid may retard the diffusion of both oxygen and water vapor if a multilayer coating strategy is used. A polyethylene extrusion coating on a board pre-coated with a recipe containing polyethylene glycol resulted in a greater reduction in the rate of oxygen transmission than through a board pre-coated with a recipe containing citric acid. The addition of lignin to the starch solution decreased the migration of starch from the starch-lignin films, and the addition of ammonium zirconium carbonate as a cross-linker decreased the migration of both starch and lignin from the films. 

Place, publisher, year, edition, pages
Karlstads universitet, 2018. , p. 69
Series
Karlstad University Studies, ISSN 1403-8099 ; 2018:14
Keywords [en]
Citric acid, Glycerol, Polyethylene glycol, Barrier coatings, Starch, Lignin, Mechanical properties, Poly(vinyl alcohol), Creasing, Adhesion, Cross-linking, Extrusion coating
National Category
Chemical Engineering
Research subject
Chemical Engineering
Identifiers
URN: urn:nbn:se:kau:diva-66853ISBN: 978-91-7063-844-2 (print)ISBN: 978-91-7063-939-5 (electronic)OAI: oai:DiVA.org:kau-66853DiVA, id: diva2:1193256
Public defence
2018-05-16, 1B306, Fryxellsalen, Karlstad, 10:15 (English)
Opponent
Supervisors
Note

Artikel 4 och 5 ingick som manuskript i avhandlingen

Available from: 2018-04-25 Created: 2018-03-26 Last updated: 2021-06-14Bibliographically approved
List of papers
1. Study of starch and starch-PVOH blends and effects of plasticizers on mechanical and barrier properties of coated paperboard
Open this publication in new window or tab >>Study of starch and starch-PVOH blends and effects of plasticizers on mechanical and barrier properties of coated paperboard
2016 (English)In: Nordic Pulp & Paper Research Journal, ISSN 0283-2631, E-ISSN 2000-0669, Vol. 31, no 3, p. 499-510Article in journal (Refereed) Published
Abstract [en]

The mechanical properties of self-supporting films based on starch-plasticizer and starch-PVOH-plasticizer and the barrier properties of paperboard coated with solutions of these polymers have been studied. The plasticizers used were glycerol, polyethylene glycol and citric acid. It was shown that the addition of a plasticizer and PVOH to starch substantially increases the flexibility of starch films. It was seen that curing the self-supporting films led to a decrease in flexibility. After heat-treatment, a substantial increase in storage modulus was observed only in the starch-PVOH-citric-acid blend films. Tensile tests on the films indicate that citric acid did not cause any noticeable phase separation. Citric acid acted as a compatibilizer for starch-PVOH blends even though a similar enrichment of PVOH at the air-solid interface was observed with both citric acid and polyethylene glycol as plasticizer. The properties of barrier coatings greatly reflected the compatibility of starch-PVOH blends containing citric acid. The only plasticizer that resulted in a lower water vapour transmission rate through the starch and starch-PVOH coatings was citric acid, which suggests that cross-linking took place. With four layers, coatings based of starch-PVOH possessed the same oxygen-transmission rate with citric acid as without citric acid.

Place, publisher, year, edition, pages
AB SVENSK PAPPERSTIDNING, 2016
Keywords
Citric acid; Glycerol; Polyethylene glycol; Barrier coatings; Starch; Mechanical properties
National Category
Chemical Engineering
Research subject
Chemical Engineering
Identifiers
urn:nbn:se:kau:diva-38334 (URN)000387976000010 ()
Available from: 2015-11-06 Created: 2015-11-06 Last updated: 2019-07-10Bibliographically approved
2. Effects on Oxygen-barrier Properties of Pretreating Paperboard with a Starch–Poly(Vinyl Alcohol) Blend before Polyethylene Extrusion
Open this publication in new window or tab >>Effects on Oxygen-barrier Properties of Pretreating Paperboard with a Starch–Poly(Vinyl Alcohol) Blend before Polyethylene Extrusion
2016 (English)In: Packaging technology and science, ISSN 0894-3214, Vol. 30, no 8, p. 399-410Article in journal (Refereed) Published
Place, publisher, year, edition, pages
John Wiley & Sons, 2016
National Category
Chemical Engineering
Research subject
Chemical Engineering
Identifiers
urn:nbn:se:kau:diva-38336 (URN)10.1002/pts.2210 (DOI)000406002100004 ()
Note

ej publicerats än

Available from: 2015-11-06 Created: 2015-11-06 Last updated: 2020-05-13Bibliographically approved
3. Crack analysis of barrier coatings based on starch and starch-PVOH with and without plasticizer
Open this publication in new window or tab >>Crack analysis of barrier coatings based on starch and starch-PVOH with and without plasticizer
2018 (English)In: Nordic Pulp & Paper Research Journal, ISSN 0283-2631, E-ISSN 2000-0669, Vol. 33, no 2, p. 336-347Article in journal (Refereed) Published
Abstract [en]

Barrier coatings based on starch and starch-PVOH plasticized with glycerol and without plasticizer were applied to two different paperboard substrates, a triple coated board and duplex board, in order to investigate the tendency for cracks to develop in the barrier coating layers during creasing and folding. Tensile properties of films based on the starch and starch-PVOH blend were determined to investigate the relationship between the flexibility of the films and the cracking in the barrier coating layers. Furthermore, the oxygen transmission rate through the barrier-coated paperboard was measured before and after creasing and folding. The oxygen transmission rate through the barrier-coated samples was over the measurable range i. e. OTR>10000cm3/m2day after creasing and folding, which indicated failure in the barrier coating layers. Optical microscopy revealed small cracks in the barrier coating layers, probably related to an increase in flexibility of the barrier coating layers. It was observed in scanning electron micrographs that cracks in the barrier coating layers seemed to follow the fibers when the barrier coating was applied on the rear side of the duplex board. Scanning electron micrographs and surface profiler images revealed that cracks in the barrier coating layers might have originated from the mineral coating layer when the starch and starch/PVOH coating layers were applied on the mineral-coated side of the triple coated board. An increase in the thickness of the barrier coating layer did not seem to increase the resistance to failure.

Place, publisher, year, edition, pages
Walter de Gruyter, 2018
Keywords
Starch, Glycerol, Barrier coatings, Mechanical properties, Creasing, Folding
National Category
Chemical Engineering
Research subject
Chemical Engineering
Identifiers
urn:nbn:se:kau:diva-66849 (URN)10.1515/npprj-2018-3039 (DOI)000450922400018 ()
Available from: 2018-03-26 Created: 2018-03-26 Last updated: 2024-02-07Bibliographically approved
4. Lignin-containing coatings for packaging materials
Open this publication in new window or tab >>Lignin-containing coatings for packaging materials
2018 (English)In: Nordic Pulp & Paper Research Journal, ISSN 0283-2631, E-ISSN 2000-0669, Vol. 33, no 3, p. 548-556Article in journal (Refereed) Published
Abstract [en]

The mechanical properties and chemical stability in water of self-supporting films made from aqueous solutions of starch and lignin, and the barrier properties of paperboard coated with solutions of these polymers have been studied. The dissolution of starch from the starch-lignin films in contact with the model liquids was decreased significantly when lignin was added to the starch films. The addition of ammonium zirconium carbonate (AZC) to the formulations as a crosslinking agent substantially increased the storage modulus of the starch-lignin films, which indicated that crosslinking had occurred. The addition of AZC to the formulations also led to a decrease in dissolution of both starch and lignin from the starch-lignin films in contact with model liquids. The effect of AZC on the water stability of the films was greater when the pH of the starch-lignin-AZC solution was adjusted with ammonia rather than NaOH. The addition of NH4Cl solution as a presumed catalyst to the recipe when the pH adjustment was performed with NaOH did not improve the effect of AZC on the water stability of the films. The water vapour transmission rate of the coated paperboard decreased slightly when AZC was added to the coating formulation.

Place, publisher, year, edition, pages
Walter de Gruyter, 2018
Keywords
barrier coatings, glycerol, lignin, mechanical properties, starch
National Category
Chemical Engineering
Research subject
Chemical Engineering
Identifiers
urn:nbn:se:kau:diva-66852 (URN)10.1515/npprj-2018-3042 (DOI)000450923900021 ()
Note

Artikeln ingick som manuskript i Javeds doktorsavhandling Effects of plasticizing and crosslinking on coatings based on blends of starch-PVOH and starch-lignin

Available from: 2018-03-26 Created: 2018-03-26 Last updated: 2024-02-07Bibliographically approved
5. Lignin-containing coatings for packaging materials: Pilot trials
Open this publication in new window or tab >>Lignin-containing coatings for packaging materials: Pilot trials
2021 (English)In: Polymers, E-ISSN 2073-4360, Vol. 13, no 10, article id 1595Article in journal (Refereed) Published
Abstract [en]

One severe weakness of most biopolymers, in terms of their use as packaging materials, is their relatively high solubility in water. The addition of kraft lignin to starch coating formulations has been shown to reduce the water solubility of starch in dry coatings. However, lignin may also migrate into aqueous solutions. For this paper, kraft lignin isolated using the LignoBoost process was used in order to examine the effect of pH level on the solubility of lignin with and without ammonium zirconium carbonate (AZC). Machine-glazed (MG) paper was coated in a pilot coating machine, with the moving substrate at high speed, and laboratory-coated samples were used as a reference when measuring defects (number of pinholes). Kraft lignin became soluble in water at lower pH levels when starch was added to the solution, due to the interactions between starch and lignin. This made it possible to lower the pH of the coating solutions, resulting in increased water stability of the dry samples; that is, the migration of lignin to the model liquids decreased when the pH of the coating solutions was reduced. No significant difference was observed in the water vapor transmission rate (WVTR) between high and low pH for the pilot-coated samples. The addition of AZC to the formulation reduced the migration of lignin from the coatings to the model liquids and led to an increase in the water contact angle, but also increased the number of pinholes in the pilot-coated samples.

Place, publisher, year, edition, pages
MDPI, 2021
Keywords
barrier coatings, glycerol, lignin, starch
National Category
Chemical Engineering
Research subject
Chemical Engineering; Chemical Engineering
Identifiers
urn:nbn:se:kau:diva-66850 (URN)10.3390/polym13101595 (DOI)000655155600001 ()2-s2.0-85106576528 (Scopus ID)
Funder
Knowledge Foundation, 20100268Vinnova, 2015-05023
Note

Artikeln ingick som manuskript i Javeds (2018) doktorsavhandling Effects of plasticizing and crosslinking on coatings based on blends of starch-PVOH and starch-lignin. 

Available from: 2018-03-26 Created: 2018-03-26 Last updated: 2024-01-17Bibliographically approved

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