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Adhesive Interaction between Polyelectrolyte Multilayers of Polyallylamine Hydrochloride and Polyacrylic Acid Studied Using Atomic Force Microscopy and Surface Force Apparatus
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0001-7496-1101
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0001-8622-0386
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.

Place, publisher, year, edition, pages
2009. Vol. 25, no 5, 2887-2894 p.
Keyword [en]
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: urn:nbn:se:kth:diva-9460DOI: 10.1021/la803628wISI: 000263770800054Scopus ID: 2-s2.0-65249127948OAI: oai:DiVA.org:kth-9460DiVA: diva2:114067
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: 2016-05-16Bibliographically approved
In thesis
1. On the Adhesive Properties of Polyelectrolyte Multilayers
Open this publication in new window or tab >>On the Adhesive Properties of Polyelectrolyte Multilayers
(English)Licentiate thesis, comprehensive summary (Other scientific)
Identifiers
urn:nbn:se:kth:diva-9462 (URN)978-91-7415-138-1 (ISBN)
Presentation
2008-10-31, STFI-Salen, Drottning Kristinas väg 61, KTH, Stockholm, 10:00 (English)
Supervisors
Available from: 2008-11-07 Created: 2008-11-05 Last updated: 2010-08-23
2. On the Adhesion Between Substrates Covered with Polyelectrolyte Multilayers
Open this publication in new window or tab >>On the Adhesion Between Substrates Covered with Polyelectrolyte Multilayers
2008 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis examines the formation of Polyelectrolyte Multilayers (PEM) on cellulose fibres as a new way of influencing the fibre surface and the adhesion between wood fibres. The aim of the study was to enhance the fundamental understanding of the adsorption mechanisms behind the formation of Polyelectrolyte Multilayers on cellulose fibres; to study how the properties of the layers can be influenced and to show how the properties of the layers influence the adhesion between the fibres and the strength of paper sheets made from the PEM treated fibres.

Different polyelectrolyte systems are known to form PEMs with different properties, and in this work two different polymer systems were extensively studied: poly(dimethyldiallylammonium chloride) (PDADMAC) / poly(styrene sulphonate) (PSS), which are both strong polylectrolytes (i.e. are highly charged over a wide range of pH) and poly allylaminehydrochloride (PAH) /poly acrylic acid (PAA), which are both weak polyelectorlytes (i.e. sensitive to pH changes). PEMs were also formed from PAH/ poly(3,4-ethylenedioxythiophene):PSS (PEDOT:PSS), in order to form electrically conducting PEMs on fibres and PEM-like structures were formed from polyethylene oxide (PEO) and polyacrylic acid (PAA).

In order to study the influence of the PEM on adhesion and paper strength, fibres were treated and used to form sheets which were physically tested according to determine the tensile index and strain at break. Both these systems were studied using different molecular mass fractions. High molecular mass PDADMAC/PSS (>500k/1000k) had a significantly greater influence as a function of the number of layers than low molecular mass PDADMAC/PSS (30k/80k). In contrast, sheets made from high molecular mass PAH/PAA (70k/240k) showed a significantly lower increase in strength than sheets made from low molecular PAH/PAA investigated earlier. Both these systems had a greater influence on paper strength when the cationic polyelectrolyte was adsorbed in the outermost layer. The amount of polyelectrolytes adsorbed on the fibres was determined using polylectrolyte titration (PET) and destructive analytical methods. Adsorption to model surfaces of silicon oxide was studied before the adsorption on fibres, in order to understand the influence on PEM properties of parameters such as salt concentration and adsorption time.

Adhesion studies of surfaces coated with PAH/PAA using AFM, showed an increase in adhesion as a function of the number of adsorbed layers. The adhesion was higher when PAH was adsorbed in the outermost layers. Individual fibres were also partly treated using a Dynamic Contact Angle analyser (DCA) and were studied with regard to their wettability. In general, the wettability was lower when the cationic polymer was outermost. The level of adhesion and paper strength are discussed in terms of rigidity and wettability and the PEMs demonstrating a large number of free chain ends, a large chain mobility and a low wettability was found to have the greatest influence to adhesion and paper strength.

Place, publisher, year, edition, pages
Stockholm: KTH, 2008. viii, 60 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2008:27
Keyword
fibre, polyelectorlyte, multilayer, wettability, contact angle, paper strength, atomic force microscopy, surface force apparatus
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-4825 (URN)978-91-7178-955-6 (ISBN)
Public defence
2008-05-16, F3, Flodissalen, Lindstedtsvägen 26, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20100823Available from: 2008-06-13 Created: 2008-06-13 Last updated: 2010-08-23Bibliographically approved
3. Molecular Interactions in Thin Films of Biopolymers, Colloids and Synthetic Polyelectrolytes
Open this publication in new window or tab >>Molecular Interactions in Thin Films of Biopolymers, Colloids and Synthetic Polyelectrolytes
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
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:nbn:se:kth:diva-41023 (URN)978-91-7501-098-4 (ISBN)
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

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Blomberg, EvaWågberg, Lars

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