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Bulk and interfacial properties of cellulose ethers
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This work summarizes several studies that all concern cellulose ethers of the types methylcellulose (MC) hydroxypropylmethylcellulose (HPMC) and ethyl(hydroxyethyl)cellulose (EHEC). They share the feature of negative temperature response, as they are soluble in water at room temperature but phase separate and sometimes form gels at high temperatures. The different types of viscosity transitions occurring in these three cellulose ethers are well-known. However, earlier studies have not solved the problem of why both HPMC and EHEC, as the temperature increases, exhibit a viscosity decrease just before the viscosity increases, whereas MC only has one transition temperature where the viscosity increases. With our investigations we have aimed to compare the effect of temperature on bulk solutions and on adsorbed layers of the different polymers using a range of techniques.

Light scattering and cryo transmission electron microscopy (cryo-TEM) was employed to study aggregation of MC, HPMC and EHEC in solution. The solvent quality of water is reduced for all three polymers in solution as the temperature increases, and this infers an onset of aggregation at a certain temperature. The aggregation rate follows the order EHEC > HPMC > MC. Cryo-TEM pictures of solutions frozen from high temperatures showed closely packed fibrils forming dense networks in MC solution. Some fibrils were also found in HPMC solution above the transition temperature, but they did not interconnect readily. This is explained by the bulky and hydrophilic hydroxypropyl groups attached to HPMC. EHEC has similar substituents, while MC only has short and hydrophobic methyl groups attached to the main chain.

An amphiphilic liquid, diethyleneglycolmonobutylether (BDG) was used as an additive to change the properties of MC solutions in water. With 10 wt% BDG added, the effect was similar in viscosity and light scattering measurements as well as cryo-TEM pictures, inducing a temperature response resembling that of HPMC in pure water. 5 wt% of BDG was enough to change the aggregation type and induce a transition temperature with viscosity decrease. The effect of the additive is rationalized by BDG acting as a hydrophobic and bulky substituent in MC, similar to the large substituents in HPMC and EHEC.

Two instruments, a quartz crystal microbalance with dissipation (QCM-D) and an ellipsometer, were used in parallel to determine the changes with temperature on an adsorbed layer of MC and HPMC on silica kept in water and in polymer solution. The silica needed to be hydrophobized for significant adsorption to take place. Adsorption was similar for both polymers at low temperatures, whereas a sharp transition in several layer properties occurred for HPMC, but not for MC, close to the solution viscosity transition temperature. Atomic force microscopy (AFM) was used to measure attractive and repulsive forces and also friction forces between MC layers in polymer solution. The small changes in normal forces with temperature infer that the hydrophobic groups in MC are mostly depleted from the surface. The surface–polymer interactions increase with increasing temperature and the layer becomes more cohesive, which induces a higher load bearing capacity and lower friction when measured at high loads. AFM imaging was employed to obtain the height distribution in MC adsorbed layers. These images indicate that fibril-like structures were formed at a lower temperature in the surface layer than in bulk solution.

The different preferences for adsorption and for aggregation in MC and HPMC above the solution transition temperatures are explained by the fibril formation in MC shielding hydrophobic parts of the polymer from the solution, and thus counteracting adsorption, but also fast aggregation. The viscosity decrease in HPMC and EHEC is conferred to intra-chain contraction and aggregation into less extended structures.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. , 41 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2012:22
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-95379ISBN: 978-91-7501-347-3 (print)OAI: oai:DiVA.org:kth-95379DiVA: diva2:527992
Public defence
2012-06-01, D3, Lindstedtsvägen 5, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20120523

Available from: 2012-05-23 Created: 2012-05-23 Last updated: 2012-09-25Bibliographically approved
List of papers
1. Aggregation and network formation of aqueous methylcellulose and hydroxypropylmethylcellulose solutions
Open this publication in new window or tab >>Aggregation and network formation of aqueous methylcellulose and hydroxypropylmethylcellulose solutions
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2010 (English)In: Colloids and Surfaces A: Physicochemical and Engineering Aspects, ISSN 0927-7757, Vol. 354, no 1-3, 162-171 p.Article in journal (Refereed) Published
Abstract [en]

Solution properties of methylcellulose (MC) and hydroxypropylmethylcellulose (HPMC) have been investigated as a function of temperature and concentration using a broad range of experimental techniques. Novelties include the extensive comparison between MC and HPMC solutions as well as the combination of techniques, and the use of Cryo transmission electron microscopy (Cryo-TEM). The correlation between rheology and light scattering results clearly demonstrates the relation between viscosity change and aggregation. Cryo-TEM images show the network structures formed. Viscosity measurements show that for both MC and HPMC solutions sudden changes in viscosity occur as the temperature is increased. The onset temperature for these changes depends on polymer concentration and heating rate. For both MC and HPMC solutions the viscosity on cooling is very different compared to on heating, demonstrating the slow equilibration time. The viscosity changes in MC and HPMC solutions are dramatically different; for MC solutions the viscosity increases by several orders of magnitude when a critical temperature is reached, whereas for HPMC solutions the viscosity decreases abruptly at a given temperature, followed by an increase upon further heating. Light and (SAXS) small-angle X-ray scattering shows that the increase in viscosity, for MC as well as for HPMC solutions, is due to extensive aggregation of the polymers. Light scattering also provides information on aggregation kinetics. The SAXS measurements allow us to correlate aggregation hysteresis to the viscosity hysteresis, as well as to extract some structural information. Cryo-TEM images give novel information that a fibrillar network is formed in MC solutions, and the strong viscosity increase occurs when this network spans the whole solution volume. For HPMC solutions the behaviour is more complex. The decrease in viscosity can be related to the formation of compact objects, and the subsequent increase to formation of fibrillar structures, which are more linear and less entangled than for MC.

National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-19299 (URN)10.1016/j.colsurfa.2009.09.040 (DOI)000275351300024 ()2-s2.0-73249124118 (Scopus ID)
Funder
Swedish Research Council
Note
QC 20110114Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2012-05-23Bibliographically approved
2. Temperature responsive surface layers of modified celluloses
Open this publication in new window or tab >>Temperature responsive surface layers of modified celluloses
2011 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 13, no 10, 4260-4268 p.Article in journal (Refereed) Published
Abstract [en]

The temperature-dependent properties of pre-adsorbed layers of methylcellulose (MC) and hydroxypropylmethylcellulose (HPMC) were investigated on silica and hydrophobized silica surfaces. Three different techniques, quartz crystal microbalance with dissipation monitoring, ellipsometry, and atomic force microscopy imaging, were used, providing complementary and concise information on the structure, mass and viscoelastic properties of the polymer layer. Adsorption was conducted at 25 degrees C, followed by a rinsing step. The properties of such pre-adsorbed layers were determined as a function of temperature in the range 25 degrees C to 50 degrees C. It was found that the layers became more compact with increasing temperature and that this effect was reversible, when decreasing the temperature. The compaction was more prominent for MC, as shown in the AFM images and in the thickness data derived from the QCM analysis. This is consistent with the fact that the phase transition temperature is lower, in the vicinity of 50 degrees C, for MC than for HPMC. The water content of the adsorbed layers was found to be high, even at the highest temperature, 50 degrees C, explored in this investigation.

Keyword
QUARTZ-CRYSTAL MICROBALANCE, ETHYL HYDROXYETHYL CELLULOSE, AQUEOUS-SOLUTIONS, THERMAL GELATION, HYDROXYPROPYL METHYLCELLULOSE, VISCOELASTIC PROPERTIES, OPTICAL-PROPERTIES, IONIC SURFACTANT, DEPENDENT FORCES, POLYMER LAYERS
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-31311 (URN)10.1039/c0cp02074e (DOI)000287584700010 ()2-s2.0-79951941383 (Scopus ID)
Funder
Swedish Research Council
Note
QC 20110318Available from: 2011-03-18 Created: 2011-03-14 Last updated: 2012-05-23Bibliographically approved
3. Temperature-dependent adsorption of cellulose ethers on silica and hydrophobized silica immersed in aqueous polymer solution
Open this publication in new window or tab >>Temperature-dependent adsorption of cellulose ethers on silica and hydrophobized silica immersed in aqueous polymer solution
2011 (English)In: RSC ADVANCES, ISSN 2046-2069, Vol. 1, no 2, 305-314 p.Article in journal (Refereed) Published
Abstract [en]

The influence of temperature on adsorption and the adsorbed layer properties of methylcellulose (MC) and hydroxypropylmethylcellulose (HPMC) were investigated on silica and hydrophobized silica surfaces immersed in aqueous polymer solution. To achieve a concise understanding a quartz crystal microbalance with dissipation, ellipsometry, and atomic force microscopy imaging were employed. These techniques provide complimentary information on the structure, mass and viscoelastic properties of the polymer layers. Adsorption was first allowed at 25 degrees C. Next, the temperature was increased step-wise up to 50 degrees C and then decreased again. This procedure highlights the temperature dependence of the adsorbed material, as well as the hysteresis in the adsorption due to temperature cycling. A change in temperature not only affects the adsorbed amount, but also the properties of the layer as illustrated by measurements of its water content, thickness and viscoelasticity.

Keyword
quartz-crystal microbalance, air-water-interface, hydroxypropyl methylcellulose, surface-properties, optical-properties, thermal gelation, solid interfaces, ionic-strength, ellipsometry, ethyl(hydroxyethyl)cellulose
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-46836 (URN)10.1039/c1ra00235j (DOI)000295852200017 ()2-s2.0-84859346718 (Scopus ID)
Funder
Swedish Research Council
Note
QC 20111107Available from: 2011-11-07 Created: 2011-11-07 Last updated: 2012-05-23Bibliographically approved
4. Temperature-Dependent Competition between Adsorption and Aggregation of a Cellulose Ether-Simultaneous Use of Optical and Acoustical Techniques for Investigating Surface Properties
Open this publication in new window or tab >>Temperature-Dependent Competition between Adsorption and Aggregation of a Cellulose Ether-Simultaneous Use of Optical and Acoustical Techniques for Investigating Surface Properties
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2012 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 28, no 25, 9515-9525 p.Article in journal (Refereed) Published
Abstract [en]

Adsorption of the temperature-responsive polymer hydroxypropylmethylcellulose (HPMC) from an aqueous solution onto hydrophobized silica was followed well above the bulk instability temperature (T-2) in temperature cycle experiments. Two complementary techniques, QCM-D and ellipsometry, were utilized simultaneously to probe the same substrate immersed in polymer solution. The interfacial processes were correlated with changes in polymer aggregation and viscosity of polymer solutions, as monitored by light scattering and rheological measurements. The simultaneous use of ellipsometry and QCM-D, and the possibility to follow layer properties up to 80 degrees C, well above the T-2 temperature, are both novel developments. A moderate increase in adsorbed amount with temperature was found below T-2, whereas a significant increase in the adsorbed mass and changes in layer properties were observed around the T-2 temperature where the bulk viscosity increases significantly. Thus, there is a clear correlation between transition temperatures in the adsorbed layer and in bulk solution, and we discuss this in relation to a newly proposed model that considers competition between aggregation and adsorption/deposition. A much larger temperature response above the T-2 temperature was found for adsorbed layers of HPMC than for layers of methyl cellulose. Possible reasons for this are discussed.

Keyword
Ellipsometry, Ethers, Silica, Surface properties
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-95333 (URN)10.1021/la301114f (DOI)000305661400041 ()2-s2.0-84862849443 (Scopus ID)
Note
QC 20120731Available from: 2012-05-22 Created: 2012-05-22 Last updated: 2017-12-07Bibliographically approved
5. Aggregation of Modified Celluloses in Aqueous Solution: Transition from Methylcellulose to Hydroxypropylmethylcellulose Solution Properties Induced by a Low-Molecular-Weight Oxyethylene Additive
Open this publication in new window or tab >>Aggregation of Modified Celluloses in Aqueous Solution: Transition from Methylcellulose to Hydroxypropylmethylcellulose Solution Properties Induced by a Low-Molecular-Weight Oxyethylene Additive
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2012 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 28, no 38, 13562-13569 p.Article in journal (Refereed) Published
Abstract [en]

Temperature effects on the viscosity and aggregation behavior of aqueous solutions of three different cellulose ethers-methylcellulose (MC), hydroxypropylmethylcellulose (HPMC), and ethyl(hydroxyethyl)cellulose (EHEC)-were investigated using viscosity and dynamic light scattering measurements as well as cryo-TEM. In all cases, increasing temperature reduces the solvent quality of water, which induces aggregation. It was found that the aggregation rate followed the order EHEC > HPMC > MC, suggesting that cellulose ethers containing some bulky and partially hydrophilic substituents assemble into large aggregates more readly than methylcellulose. This finding is discussed in terms of the organization of the structures formed by the different cellulose ethers. The temperature-dependent association behavior of cellulose ethers was also investigated in a novel way by adding diethyleneglycolmonobutylether (BDG) to methylcellulose aqueous solutions. When the concentration of BDG was at and above 5 wt %, methylcellulose adopted HPMC-like solution behavior. In particular, a transition temperature where the viscosity was decreasing, prior to increasing at higher temperatures, appeared, and the aggregation rate increased. This observation is rationalized by the ability of amphiphilic BDG to accumulate at nonpolar interfaces and thus also to associate with hydrophobic regions of methylcellulose. In effect, BDG is suggested to act as a physisorbed hydrophilic and bulky substituent inducing constraints on aggregation similar to those of the chemically attached hydroxypropyl groups in HPMC and oligo(ethyleneoxide) chains in EHEC.

Keyword
Cellulose, Ethers, Hydrophilicity, Viscosity, Water quality
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-95376 (URN)10.1021/la301704f (DOI)000309040800004 ()2-s2.0-84866673236 (Scopus ID)
Note

QC 20121029. Updated from manuscript to article in journal.

Available from: 2012-05-23 Created: 2012-05-23 Last updated: 2017-12-07Bibliographically approved
6. Surface forces and friction between non-polar surfaces coated by temperature-responsive methylcellulose
Open this publication in new window or tab >>Surface forces and friction between non-polar surfaces coated by temperature-responsive methylcellulose
2014 (English)In: Colloids and Surfaces A: Physicochemical and Engineering Aspects, ISSN 0927-7757, E-ISSN 1873-4359, Vol. 441, 701-708 p.Article in journal (Refereed) Published
Abstract [en]

Methylcellulose is a heterogeneous polymer that exposes both methyl groups and -OH-groups to the solution, and the solvent quality of water for methylcellulose deceases with increasing temperature. In bulk solution this leads to aggregation into fibrils at high temperatures. In this report we address how temperature affects adsorbed layers of methylcellulose on hydrophobized silica surfaces in contact with an aqueous methylcellulose solution. The layers were imaged using PeakForce tapping mode atomic force microscopy, in order to determine how the additional adsorption that occurs with increasing temperature affects the layer structure. Surface force and friction measurements were carried out using the AFM colloidal probe method. The data demonstrate that the normal surface forces were rather insensitive to temperature, whereas the friction forces changed significantly with increasing temperature. At low loads the friction increases with increasing temperature, whereas at high loads the reverse is observed. These findings are discussed in terms of how the worsening of the solvent condition affects the aggregation state in the adsorbed layer, and the polymer-surface affinity.

Keyword
Temperature-responsive polymer, Cellulose ethers, Methylcellulose friction, Load bearing capacity, Atomic force microscopy, Surface forces
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-95377 (URN)10.1016/j.colsurfa.2013.10.038 (DOI)000329260800090 ()2-s2.0-84887548022 (Scopus ID)
Funder
VinnovaSwedish Foundation for Strategic Research
Note

QC 20140131. Updated from manuscript to article in journal.

Available from: 2012-05-23 Created: 2012-05-23 Last updated: 2017-12-07Bibliographically approved

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