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Chitosan and chitosan/wheat gluten blends: properties of extrudates, solid films and bio-foams
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis presents four different studis describing the characteristics and processing opportunities of two widely available biopolymers: chitosan and wheat gluten. The interest in these materials is mainly because they are bio-based and obtained as co- or by-products in the fuel and food sector

In the first study, high solids content chitosan samples (60 wt.%) were successfully extruded. Chitosan extrusion has previously been reported but not chitosan extrusion with a high solids content, which decreases the drying time and increases the production volume. An orthogonal experimental design was used to assess the influence of formulation and processing conditions, and the optimal formulation and conditions were determined from the orthogonal experimental analysis and the qualities of the extrudates. The mechanical properties and processing-liquid mass loss of the optimized extrudates showed that the extrudates became stable within three days. The changes in the mechanical properties depended on the liquid mass loss.

In a separate study, monocarboxylic (formic, acetic, propionic, and butyric) acid uptake and diffusion in chitosan films were investigated. It is of importance in order to be able to optimize the production of this material with the casting technique. The time of the equilibration uptake in the chitosan films exposed to propionic and butyric acid was nine months. This long equilibration time encouraged us study the exposed films further. The uptake and diffusivity of acid in the films decreased with increasing acid molecular size. A two-stage absorption curve was observed for the films exposed to propionic acid vapour. The films at the different stages showed different diffusivities. The acid transport was also affected by the structure of the chitosan films. X-ray diffraction suggested that the crystal structure of the original films disappeared after the films had been dried from their acid-swollen state, and that the microstructure of the dried films depended on the molecular size of the acid. Compared with the original films, the dried films retained their ductility, although a decrease in the molecular weight of the chitosan was detected. The water resistance of the acid-exposed films was increased, even though the crystallinity of these films was lower.

The third study was devoted to chitosan/wheat gluten blend films cast from aqueous solutions. Different solvent types, additives and drying methods were used to examine their effects on the microstructures of the blended films. Chitosan and wheat gluten were immiscible in the aqueous blend, and the wheat gluten formed a discrete phase, and the homogeneity of the films was improved by using a reducing agent, compared with films prepared using only water/ethanol as cast media. Adding urea and surfactants resulted in a medium homogeneity of the films compared to those prepared with the reducing agents or with only water/ethanol. An elongated wheat gluten phase was observed in a film using glyoxal, in contrast to pure chitosan/wheat gluten blends. The opacity of the different films was studied. The mechanical properties and humidity uptake of the films increased with increasing chitosan content. The films containing 30 wt.% of wheat gluten showed the most promising mechanical properties, close to those of the pristine chitosan films.

The final part describes the preparation and properties of a bio-foam composed of a blend of chitosan and wheat gluten. This foam was prepared without any porogen or frozen liquid phase to create porosity. A unique phase distribution of the chitosan and wheat gluten solutions formed without any agitation, and the foam was obtained when the liquid phase were withdrawn under vacuum. These foams showed high mass uptake of n-hexane and water in a short time due to their open pores and high porosity. The maximum uptake of n-hexane measured was 20 times the initial mass of the foam. The foams showed a high rebound resilience (94 % at 20 % compression strain) and they were not broken when subjected to bending.  

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2015. , viii, 67 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2015:41
National Category
Textile, Rubber and Polymeric Materials
Identifiers
URN: urn:nbn:se:kth:diva-172435ISBN: 978-91-7595-657-2 (print)OAI: oai:DiVA.org:kth-172435DiVA: diva2:848170
Public defence
2015-09-11, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20150825

Available from: 2015-08-25 Created: 2015-08-24 Last updated: 2015-12-31Bibliographically approved
List of papers
1. Chitosan extrusion at high solids content: An orthogonal experimental design study
Open this publication in new window or tab >>Chitosan extrusion at high solids content: An orthogonal experimental design study
2014 (English)In: Polymers from Renewable Resources, ISSN 2041-2479, Vol. 5, no 1, 1-12 p.Article in journal (Refereed) Published
Abstract [en]

For economic reasons and to save time there is a need to shorten the drying operation associated with the production of chitosan materials. Hence it is of interest to extrude chitosan at as high a solids content as possible. This is, to our knowledge, the first systematic study of the extrusion of chitosan at high solids content (60 wt%). An orthogonal experimental design was used to evaluate the effect of processing conditions and material factors on the extrudability of chitosan. This, together with the examination of the evenness and surface finish of the extrudate, made it possible to determine the best conditions for obtaining a readily extrudable high quality material. It was observed that a 1/1 ratio of chitosans with molar masses of 12 and 133 kDa, a process liquid containing 30 wt% acetic acid and 70 wt% water, and extrusion at 50 rpm and 50°C were the optimal material and processing conditions. Materials processed under these conditions were evaluated mechanically at different times after extrusion (stored at 50% RH) in order to see when the properties stabilized. Most mass loss occurred within the first three days after extrusion and this governed the mechanical properties (stiffness and extensibility), which also exhibited the largest changes within these three days (an increase in modulus from 18 to 830 MPa and a decrease in elongation at break from 17 to 3%).

Keyword
Acetic acid, Chitosan, Extrusion, High solids content, Orthogonal experimental design, Water
National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-161685 (URN)2-s2.0-84901837844 (Scopus ID)
Note

QC 20150317

Available from: 2015-03-17 Created: 2015-03-13 Last updated: 2015-08-25Bibliographically approved
2. Unusual Effects of Monocarboxylic Acids on The Structure and on The Transport and Mechanical Properties of Chitosan Films
Open this publication in new window or tab >>Unusual Effects of Monocarboxylic Acids on The Structure and on The Transport and Mechanical Properties of Chitosan Films
Show others...
2015 (English)In: Carbohydrate Polymers, ISSN 0144-8617, E-ISSN 1879-1344, Vol. 132, 419-429 p.Article in journal (Refereed) Published
Abstract [en]

The purpose of this study was to study the transport of monocarboxylic acids in chitosan films, since this is important for understanding and predicting the drying kinetics of chitosan from aqueous solutions. Despite the wealth of data on chitosan films prepared from aqueous monocarboxylic acid solutions, this transport has not been reported. Chitosan films were exposed to formic, acetic, propionic and butyric acid vapours, it was found that the rate of uptake decreased with increasing molecular size. The equilibration time was unexpectedly long, especially for propionic and butyric acid, nine months. A clear two-stage uptake curve was observed for propionic acid. Evidently, the rate of uptake was determined by acid-induced changes in the material. X-ray diffraction and infrared spectroscopy indicated that the structure of the chitosan acetate and buffered chitosan films changed during exposure to acid and during the subsequent drying. The dried films previously exposed to the acid showed less crystalline features than the original material and a novel repeating structure possibly involving acid molecules. The molar mass of the chitosan decreased on exposure to acid but tensile tests revealed that the films were always ductile. The films exposed to acid vapour (propionic and butyric acid) for the longest period of time were insoluble in the size-exclusion chromatography eluent, and they were also the most ductile/extensible of all samples studied.

Keyword
Chitosan, Monocarboxylic acids, Uptake, Diffusivity, Mechanical properties
National Category
Textile, Rubber and Polymeric Materials
Identifiers
urn:nbn:se:kth:diva-172432 (URN)10.1016/j.carbpol.2015.06.050 (DOI)26256366 (PubMedID)2-s2.0-84936864765 (Scopus ID)
Note

QC 20150825

Available from: 2015-08-24 Created: 2015-08-24 Last updated: 2017-12-04Bibliographically approved
3. Wheat gluten/chitosan blends: A new biobased material
Open this publication in new window or tab >>Wheat gluten/chitosan blends: A new biobased material
Show others...
2014 (English)In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 60, 186-197 p.Article in journal (Refereed) Published
Abstract [en]

Wheat gluten and chitosan are renewable materials that suffer from some poor properties that limit their use as a potential replacement of petroleum-based polymers. However, polymer blends based on wheat gluten and chitosan surprisingly reduced these shortcomings. Films were cast from acidic aqueous or water/ethanol solutions of wheat gluten and chitosan. Wheat gluten was the discontinuous phase in the 30-70 wt.% wheat gluten interval investigated. The most homogeneous films were obtained when reducing agents were used (alone or together with urea or glycerol). They consisted mainly of 1-2 mu m wheat gluten particles uniformly distributed in the continuous chitosan phase. Slightly smaller particles were also observed in the water/ethanol solvent system, but together with significantly larger particles (as large as 200 mu m). Both small and large particles were observed, albeit in different sizes and contents, when surfactants (both with and without a reducing agent) or urea (without a reducing agent) were used. The particles were often elongated, and preferably along the film, the most extreme case being observed when the glyoxal crosslinker was used together with sodium sulfite (reducing agent), showing particles with an average thickness of 0.6 mu m and an aspect ratio of 4.2. This film showed the highest transparency of all the blend films studied. For one of the most promising systems (with sodium sulfite), having good film homogeneity and small particles, the mechanical and moisture solubility/diffusivity properties were studied as a function of chitosan content. The extensibility, toughness and moisture solubility increased with increasing chitosan content, and the moisture diffusivity was highest for the pristine chitosan material. It is noteworthy that the addition of 30 wt.% wheat gluten to chitosan reduced the moisture uptake, while the extensibility/toughness remained unchanged.

Keyword
Wheat gluten, Chitosan, Blend, Reducing agent, Surfactant
National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-159396 (URN)10.1016/j.eurpolymj.2014.09.007 (DOI)000346883800021 ()2-s2.0-84907774269 (Scopus ID)
Note

QC 20150130

Available from: 2015-01-30 Created: 2015-01-29 Last updated: 2017-12-05Bibliographically approved
4. A Novel Chitosan/Wheat Gluten Biofoam Fabricated by Mixing and Vacuum-drying
Open this publication in new window or tab >>A Novel Chitosan/Wheat Gluten Biofoam Fabricated by Mixing and Vacuum-drying
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Textile, Rubber and Polymeric Materials
Identifiers
urn:nbn:se:kth:diva-172463 (URN)
Note

QS 2015

Available from: 2015-08-25 Created: 2015-08-25 Last updated: 2015-08-25Bibliographically approved

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