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Molecular Interactions in Thin Films of Biopolymers, Colloids and Synthetic Polyelectrolytes
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The development of the layer-by-layer (LbL) technique has turned out to be an efficient way to physically modify the surface properties of different materials, for example to improve the adhesive interactions between fibers in paper. The main objective of the work described in this thesis was to obtain fundamental data concerning the adhesive properties of wood biopolymers and LbL films, including the mechanical properties of the thin films, in order to shed light on the molecular mechanisms responsible for the adhesion between these materials.

LbLs constructed from poly(allylamine hydrochloride) (PAH)/poly(acrylic acid) (PAA), starch containing LbL films, and LbL films containing nanofibrillated cellulose (NFC) were studied with respect to their adhesive and mechanical properties. The LbL formation was studied using a combination of stagnation point adsorption reflectometry (SPAR) and quartz crystal microbalance with dissipation (QCM-D) and the adhesive properties of the different LbL films were studied in water using atomic force microscopy (AFM) colloidal probe measurements and under ambient conditions using the Johnson-Kendall-Roberts (JKR) approach. Finally the mechanical properties were investigated by mechanical buckling and the recently developed SIEBIMM technique (strain-induced elastic buckling instability for mechanical measurements).

From colloidal probe AFM measurements of the wet adhesive properties of surfaces treated with PAH/PAA it was concluded that the development of strong adhesive joints is very dependent on the mobility of the polyelectrolytes and interdiffusion across the interface between the LbL treated surfaces to allow for polymer entanglements.

Starch is a renewable, cost-efficient biopolymer that is already widely used in papermaking which makes it an interesting candidate for the formation of LbL films in practical systems. It was shown, using SPAR and QCM-D, that LbL films can be successfully constructed from cationic and anionic starches on silicon dioxide and on polydimethylsiloxane (PDMS) substrates. Colloidal probe AFM measurements showed that starch LbL treatment have potential for increasing the adhesive interaction between solid substrates to levels beyond those that can be reached by a single layer of cationic starch. Furthermore, it was shown by SIEBIMM measurements that the elastic properties of starch-containing LbL films can be tailored using different nanoparticles in combination with starch.

LbL films containing cellulose I nanofibrils were constructed using anionic NFC in combination with cationic NFC and poly(ethylene imine) (PEI) respectively. These NFC films were used as cellulose model surfaces and colloidal probe AFM was used to measure the adhesive interactions in water. Furthermore, PDMS caps were successfully coated by LbL films containing NFC which enabled the first known JKR adhesion measurements between cellulose/cellulose, cellulose/lignin and cellulose/glucomannan. The measured adhesion and adhesion hysteresis were similar for all three systems indicating that there are no profound differences in the interaction between different wood biopolymers. Finally, the elastic properties of PEI/NFC LbL films were investigated using SIEBIMM and it was shown that the stiffness of the films was highly dependent on the relative humidity.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2011. , ix, 56 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2011:50
Keyword [en]
Polyelectrolyte multilayers, Layer-by-Layer assembly, Adhesion, Adsorption, Young's modulus, Mechanical buckling, AFM, JKR, SPAR, QCM-D, SIEBIMM, PAH, PAA, Starch, NFC, Nanocellulose
National Category
Materials Chemistry Paper, Pulp and Fiber Technology Nano Technology
Identifiers
URN: urn:nbn:se:kth:diva-41023ISBN: 978-91-7501-098-4 (print)OAI: oai:DiVA.org:kth-41023DiVA: diva2:443056
Public defence
2011-10-14, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20110923

Available from: 2011-09-23 Created: 2011-09-23 Last updated: 2014-10-03Bibliographically approved
List of papers
1. Adhesive Interaction between Polyelectrolyte Multilayers of Polyallylamine Hydrochloride and Polyacrylic Acid Studied Using Atomic Force Microscopy and Surface Force Apparatus
Open this publication in new window or tab >>Adhesive Interaction between Polyelectrolyte Multilayers of Polyallylamine Hydrochloride and Polyacrylic Acid Studied Using Atomic Force Microscopy and Surface Force Apparatus
2009 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 25, no 5, 2887-2894 p.Article in journal (Refereed) Published
Abstract [en]

In the present work, the adhesion between substrates treated with identical polyelectrolyte multilayers (PEM) from polyallylamine hydrochloride (PAR) and poly(acrylic acid) (PAA) was studied using atomic force microscopy (AFM) and the Surface force apparatus (SFA). The AFM measurements, conducted under wet conditions for PEMs formed at pH 7.5, showed a higher adhesion (pull-off force) when PAH was adsorbed in the outermost layers. There was also a difference depending on the Molecular mass of the polymers, demonstrating a greater adhesion for the low molecular mass combination of polyelectrolytes. Furthermore, die time in contact showed to be of importance, with increasing pull-off forces with contact time at maximum load. The SFA measurements were conducted under dry conditions, at 100% RH, and under wet conditions for PEMs adsorbed at pH 7.5/3.5. The SFA adhesion measurements showed that under dry conditions, the adhesive forces between two high energetic mica substrates were lowered when they were covered by PEMs before the measurements. The thickness of the adsorbed layers was also measured using SFA. This showed that there was a significant swelling when the dry layers were exposed to 100% RH or to wet conditions. The swelling was higher, indicating a less rigid layer, when PAH was adsorbed in the outermost layer than when the PEM was capped with PAA.

Keyword
Adhesion measurements; Adhesive forces; Adhesive interactions; Adsorbed layers; AFM; Atomic forces; Atomic-force microscopies; Contact time; Dry conditions; Low molecular mass; Maximum loads; Mica substrates; Polyacrylic acids; Polyallylamine hydrochlorides; Polyelectrolyte multilayers; Pull-off forces; Surface force apparatus; Wet conditions
National Category
Paper, Pulp and Fiber Technology Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-9460 (URN)10.1021/la803628w (DOI)000263770800054 ()2-s2.0-65249127948 (Scopus ID)
Note

QC 20100823. Uppdaterad från manuskript till artikel (20100823). Tidigare titel: The Adhesive Interaction between Polyelectrolyte Multilayers of Polyallylamine Hydrochloride and Polyacrylic Acid studied using Atomic Force Microscopy (AFM) and Surface Force Apparatus (SFA)

Available from: 2008-11-05 Created: 2008-11-05 Last updated: 2017-12-14Bibliographically approved
2. Adsorption Behavior and Adhesive Properties of Biopolyelectrolyte Multilayers formed from Cationic and Anionic Starch
Open this publication in new window or tab >>Adsorption Behavior and Adhesive Properties of Biopolyelectrolyte Multilayers formed from Cationic and Anionic Starch
2009 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 10, no 7, 1768-1776 p.Article in journal (Refereed) Published
Abstract [en]

Cationic starch (D.S. 0.065) and anionic starch (D.S. 0.037) were used to form biopolyelectrolyte multilayers. The influence of the solution concentration of NaCl on the adsorption of starch onto silicon oxide substrates and on the formation of multilayers was investigated using stagnation point adsorption reflectometry (SPAR) and quartz crystal microbalance with dissipation (QCM-D). The wet adhesive properties of the starch multilayers were examined by measuring pull-off forces with the AFM colloidal probe technique. It was shown that polyelectrolyte multilayers (PEM) can be successfully constructed from cationic starch and anionic starch at electrolyte concentrations of 1 mM NaCl and 10 mM NaCl. The water content of the PEMs was approximately 80% at both electrolyte concentrations. However, the thickness of the PEMs formed at 10 mM NaCl was approximately twice the thickness formed at I mM NaCl. The viscoelastic properties of the starch PEMs, modeled as Voigt elements, were dependent on the polyelectrolyte that was adsorbed in the outermost layer. The PEMs appeared to be more rigid when capped by anionic starch than when capped by cationic starch. The wet adhesive pull-off forces increased with layer number and were also dependent oil the polyelectrolyte adsorbed in the outermost layer. Thus, starch PEM treatment has a large potential for increasing the adhesive interaction between solid substrates to levels higher than can be reached by a single layer of cationic starch.

Keyword
Adhesive interaction; Adhesive properties; Adsorption behavior; AFM; Anionic starch; Cationic starches; Colloidal probe techniques; Electrolyte concentration; Layer number; Polyelectrolyte multilayer; Pull-off forces; Quartz crystal microbalance with dissipation; Silicon oxide substrates; Single layer; Solid substrates; Solution concentration; Stagnation point adsorption reflectometry; Viscoelastic properties; Voigt elements; Wet adhesives
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-9461 (URN)10.1021/bm900191s (DOI)000268139300013 ()2-s2.0-67650497882 (Scopus ID)
Note
QC 20100826. Uppdaterad från manuskript till artikel (20100826)Available from: 2008-11-05 Created: 2008-11-05 Last updated: 2017-12-14Bibliographically approved
3. Polyelectrolyte Multilayers from Cationic and Anionic Starch: Influence of Charge Density and Salt Concentration on the Properties of the Adsorbed Layers
Open this publication in new window or tab >>Polyelectrolyte Multilayers from Cationic and Anionic Starch: Influence of Charge Density and Salt Concentration on the Properties of the Adsorbed Layers
2010 (English)In: Starke (Weinheim), ISSN 0038-9056, E-ISSN 1521-379X, Vol. 62, no 2, 102-114 p.Article in journal (Refereed) Published
Abstract [en]

The purpose of the present work was for identify limits for the formation of stable polyelectrolyte multilayers (PEMs) from cationic and anionic starches (with degrees of substitution of 0.04-0.09) on SiO2 surfaces, taking account of the effect of the charge density of the starches and the salt concentration in the surrounding water phase. The experiments were performed at a pH of 6.3 using stagnation point adsorption reflectometry (SPAR) and quartz crystal microbalance with dissipation (QCM-D). From these experiments it was concluded that it is possible to form PEMs by the adsorption of oppositely charged starches on SiO2 surfaces; it was also found that adsorption of the first layer is controlled both by electrostatic, non-ionic interactions and by pure steric restrictions, Le, geometrical restrictions, at the surface. The results also indicate that the charge density of the starch must exceed a certain value to allow multilayer formation and that this critical charge density increases with increasing salt concentration. The combination of charge densities of the cationic/anionic starches was also found to influence the adsorption behaviour, and the formed polyelectrolyte multilayers had a high water content of 69-92%.

Keyword
Model surfaces, Polyelectrolyte multilayer, Stagnation point adsorption, reflectometry, Starch, Quartz crystal microbalance, paper strength properties, wood fibers, adhesive properties, ionic-strength, adsorption, size, flow
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-19287 (URN)10.1002/star.200900176 (DOI)000275242000005 ()2-s2.0-77249173310 (Scopus ID)
Note
QC 20100525, QC 20110930.Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
4. Tailoring the mechanical properties of starch-containing layer-by-layer films
Open this publication in new window or tab >>Tailoring the mechanical properties of starch-containing layer-by-layer films
2012 (English)In: Colloids and Surfaces A: Physicochemical and Engineering Aspects, ISSN 0927-7757, E-ISSN 1873-4359, Vol. 394, 14-22 p.Article in journal (Refereed) Published
Abstract [en]

The Young's modulus of layer-by-layer (LbL) films containing starch was determined using the recently developed SIEBIMM (strain-induced elastic buckling instability for mechanical measurements) technique. By using cationic starch (CS) in combination with anionic starch (AS), silica nanoparticles (SNP), and nanofibrillated cellulose (NFC), the mechanical properties of these sub-micrometer starch-containing LbL films could be tailored. At 50% relative humidity (RH), the Young's modulus of CS/AS, CS/SNP, and CS/NFC was 0.6 GPa, 0.9 GPa, and 1.8 GPa, respectively, in the 25-85-nm thickness range. As expected for these hygroscopic starch-containing LbL films, the mechanical properties depended on RH. At 0% RH, the Young's modulus was 2-4.5 times higher than at 50% RH. The LbL buildup on polydimethylsiloxane (PDMS) was studied in situ using quartz crystal microgravimetry with dissipation (QCM-D), and atomic force microscopy (AFM) was used to characterize the surface morphology and thickness of the films.

Place, publisher, year, edition, pages
Elsevier, 2012
Keyword
Cationic starch, Anionic starch, Nanofibrillated cellulose, Silica nanoparticles, Layer-by-layer assembly, Young's modulus
National Category
Materials Chemistry Paper, Pulp and Fiber Technology Nano Technology
Identifiers
urn:nbn:se:kth:diva-41020 (URN)10.1016/j.colsurfa.2011.11.017 (DOI)000300867800003 ()2-s2.0-84855285311 (Scopus ID)
Note

QC 20120326

Available from: 2011-09-23 Created: 2011-09-23 Last updated: 2017-12-08Bibliographically approved
5. Self-Organized Films from Cellulose I Nanofibrils Using the Layer-by-Layer Technique
Open this publication in new window or tab >>Self-Organized Films from Cellulose I Nanofibrils Using the Layer-by-Layer Technique
2010 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 11, no 4, 872-882 p.Article in journal (Refereed) Published
Abstract [en]

The possibility of forming self-organized films using only charge-stabilized dispersions of cellulose I nanofibrils with opposite charges is presented, that is, the multilayers were composed solely of anionically and cationically modified microfibrillated cellulose (MFC) with a low degree of substitution. The build-up behavior and the properties of the layer-by-layer (LbL)-constructed films were studied using a quartz crystal microbalance with dissipation (QCM-D) and stagnation point adsorption reflectometry (SPAR). The adsorption behavior of cationic/anionic MFC was compared with that of polyethyleneimine (PEI)/anionic MFC. The water contents of five bilayers of cationic/anionic MFC and PEI/anionic MFC were approximately 70 and 50%, respectively. The MFC surface coverage was studied by atomic force microscopy (AFM) measurements, which clearly showed a more dense fibrillar structure in the five bilayer PEI/anionic MFC than in the five bilayer cationic/anionic MFC. The forces between the cellulose-based multilayers were examined using the AFM colloidal probe technique. The forces on approach were characterized by a combination of electrostatic and steric repulsion. The wet adhesive forces were very long-range and were characterized by multiple adhesive events. Surfaces covered by PEU/anionic MFC multilayers required more energy to be separated than surfaces covered by cationic/anionic MFC multilayers.

Keyword
quartz-crystal microbalance, dual-polarization interferometry, polyelectrolyte multilayer films, atomic-force microscope, microfibrillated cellulose, silica surfaces, paper strength, cationic, polyelectrolytes, viscoelastic properties, adhesive properties
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-19390 (URN)10.1021/bm100075e (DOI)000276557300006 ()2-s2.0-77950843535 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
6. Direct Adhesive Measurements between Wood Biopolyrner Model Surfaces
Open this publication in new window or tab >>Direct Adhesive Measurements between Wood Biopolyrner Model Surfaces
2012 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 13, no 10, 3046-3053 p.Article in journal (Refereed) Published
Abstract [en]

For the first time the dry adhesion was measured for an all-wood biopolymer system using Johnson-Kendall-Roberts (JKR) contact mechanics. The polydimethylsiloxane hemisphere was successfully surface-modified with a Cellulose I model surface using layer-by-layer assembly of nanofibrillated cellulose and polyethyleneimine. Flat surfaces of cellulose were equally prepared on silicon dioxide substrates, and model surfaces of glucomannan and lignin were prepared on silicon dioxide using spin-coating. The measured work of adhesion on loading and the adhesion hysteresis was found to be very similar between cellulose and all three wood polymers, suggesting that the interaction between these biopolymers do not differ greatly. Surface energy calculations from contact angle measurements indicated similar dispersive surface energy components for the model surfaces. The dispersive component was dominating the surface energy for all surfaces. The JKR work of adhesion was lower than that calculated from contact angle measurements, which partially can be ascribed to surface roughness of the model surfaces and overestimation of the surface energies from contact angle determinations.

Keyword
Adhesion, Angle measurement, Biomolecules, Biopolymers, Cellulose, Contact angle, Deformation, Interfacial energy, Loading; Silica, Silicones, Surface roughness
National Category
Chemical Sciences Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-104696 (URN)10.1021/bm300762e (DOI)000309488600005 ()2-s2.0-84867475444 (Scopus ID)
Note

QC 20121112. Updated from Manuscript to Article

Available from: 2012-11-12 Created: 2012-11-09 Last updated: 2017-12-07Bibliographically approved
7. Determination of Young's Modulus for Nanofibrillated Cellulose Multilayer Thin Films Using Buckling Mechanics
Open this publication in new window or tab >>Determination of Young's Modulus for Nanofibrillated Cellulose Multilayer Thin Films Using Buckling Mechanics
Show others...
2011 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 12, no 4, 961-969 p.Article in journal (Refereed) Published
Abstract [en]

The Young's modulus of multilayer films containing nanofibrillated cellulose (NFC) and polyethyleneimine (PEI) was determined Using the strain-induced elastic buckling instability for mechanical measurements (SLEBIMM) technique.(1) Multilayer films were built up on polydimethylsiloxane substrates using electrostatic layer-by-layer assembly. At 50% relative humidity, SIEBIMM gave a constant Young's modulus of 1.5 +/- 0.2 GPa for 35-75 run thick films. Conversely, in vacuum, the Young's modulus was 10 times larger, at 17.2 +/- 1.2 GPa. A slight decrease in buckling wavelength with increasing strain was observed by scanning electron microscopy with in situ compression, and above 10% strain, extensive cracking parallel to the compressive direction occurred. We conclude that whereas PEI acts as a "glue" to hold multiple layers of NFC together, it prevents full development of hydrogen bonding and specific fibril-fibril interactions, and at high humidity, its hygroscopic nature decreases the elastic modulus when compared with pure NFC films.

National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-33242 (URN)10.1021/bm101330w (DOI)000289223500013 ()2-s2.0-79953860258 (Scopus ID)
Note
QC 20110506Available from: 2011-05-06 Created: 2011-05-02 Last updated: 2017-12-11Bibliographically approved

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