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Novel oil resistant cellulosic materials
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. (Fibertechnology)
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The aim of this study has been to prepare and characterise oil resistant cellulosic materials, ranging from model surfaces to papers and aerogels. The cellulosic materials were made oil resistant by chemical and topographic modifications, based on surface energy, surface roughness and barrier approaches. Detailed wetting studies of the prepared cellulosic materials were made using contact angle measurements and standardised penetration tests with different alkanes and oil mixtures.

A significant part of the activities were devoted to the development of model cellulosic surfaces with different degrees of crystalline ordering for the wetting studies. Crystalline cellulose I, II and amorphous cellulose surfaces were prepared by spin-coating of cellulose nanocrystal or microfibrillated cellulose (MFC) dispersions, with Langmuir-Schaefer (LS) films or by a layer-by-layer (LbL) deposition technique. The formation of multilayers consisting of polyethyleneimine (PEI)/anionic MFC or cationic MFC/anionic MFC was further studied and optimized in terms of total layer thickness and adsorbed amount by combining Dual Polarization Interferometry (DPI) or Stagnation Point Adsorption Reflectrometry (SPAR) with a Quartz Crystal Microbalance with Dissipation (QCM-D).

The smooth cellulosic surfaces prepared had different molecular and mesostructure properties and different surface energies as shown by X-ray diffraction, Atomic Force Microscopy (AFM) imaging, ellipsometry measurements and contact angle measurements.

The cellulose model surfaces were found to be ideal for detailed wetting studies, and after the surface has been coated or covalently modified with various amounts of fluorosurfactants, the fluorinated cellulose films were used to follow the spreading mechanisms of different oil mixtures. The viscosity and surface tension of the oil mixtures, as well as the dispersive surface energy of the cellulose surfaces, were found to be essential parameters governing the spreading kinetics. A strong correlation was found between the surface concentration of fluorine, the dispersive surface energy and the measured contact angle of the oil mixtures.

Silicon surfaces possessing structural porous characteristics were fabricated by a plasma etching process. The structured silicon surfaces were coated with sulfate-stabilized cellulose I nanocrystals using the LbL technique. These artificial intrinsically oleophilic cellulose surfaces were made highly oleophobic when coated with a thin layer of fluorinated silanes. By comparison with flat cellulose surfaces, which are oleophilic, it is demonstrated that the surface energy and the surface texture are essential factors preventing oil from spreading on the surface and, thus, inducing the observed macroscopic oleophobic properties.

The use of the MFC for surface coating on base papers demonstrated very promising characteristics as packaging materials. Environmental-Scanning Electron Microscopy (E-SEM) micrographs indicated that the MFC layer reduced the sheet porosity, i.e. the dense structure formed by the nanofibers resulted in superior oil barrier properties. Attempts were made to link the procedure for preparation of the MFC dispersions to the resulting microstructure of the coatings, and film porosity and the film moisture content to the resulting permeability properties.

Finally, MFC aerogels were successfully prepared by freeze-drying. The surface texture of the porous aerogels was carefully controlled by adjusting the concentration of the MFC dispersion used for the freeze-drying. The different scales of roughness of the MFC aerogels were utilised, together with the very low surface energy created by fluorination of the aerogel, to induce highly oleophobic properties.

Place, publisher, year, edition, pages
Stockholm: KTH , 2009. , ix, 55 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2009:57
Keyword [en]
oleophobic, MFC, cellulose, oil resistant, contact angle, XPS, SEM
National Category
Paper, Pulp and Fiber Technology
Identifiers
URN: urn:nbn:se:kth:diva-11494ISBN: 978-91-7415-476-4 (print)OAI: oai:DiVA.org:kth-11494DiVA: diva2:277300
Public defence
2009-12-04, F3, Lindstedtvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20100623Available from: 2009-11-17 Created: 2009-11-17 Last updated: 2012-03-13Bibliographically approved
List of papers
1. Wetting kinetics of oil mixtures on fluorinated model cellulose surfaces
Open this publication in new window or tab >>Wetting kinetics of oil mixtures on fluorinated model cellulose surfaces
Show others...
2008 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 317, 556-567 p.Article in journal (Refereed) Published
Abstract [en]

The wetting of two different model cellulose surfaces has been studied; a regenerated cellulose (RG) surface prepared by spin-coating, and a novel multilayer film of poly(ethyleneimine) and a carboxymethylated microtibrillated cellulose (MFC). The cellulose films were characterized in detail using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). AFM indicates smooth and continuous films on a nanometer scale and the RMS roughness of the RG cellulose and MFC surfaces was determined to be 3 and 6 nm, respectively. The cellulose films were modified by coating with various amounts of an anionic fluorosurfactant, perfluorooctadecanoic acid, or covalently modified with pentadecafluorooctanyl chloride. The fluorinated cellulose films were used to follow the spreading mechanisms of three different oil mixtures. The viscosity and surface tension of the oils were found to be essential parameters governing the spreading kinetics on these surfaces. XPS and dispersive surface energy measurements were made on the cellulose films coated with perfluorooctadecanoic acid. A strong correlation was found between the surface concentration of fluorine, the dispersive surface energy and the contact angle of castor oil on the surface. A dispersive surface energy less than 18 mN/m was required in order for the cellulose surface to be non-wetting (theta(e) > 90 degrees) by castor oil.

Keyword
MFC; adsorption; fluorosurfactant; XPS; AFM; multilayer; wetting; oil resistance; cellulose surface; contact angle
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-7850 (URN)10.1016/j.jcis.2007.09.096 (DOI)000251556100023 ()2-s2.0-36148995487 (Scopus ID)
Note
QC 20100623Available from: 2007-12-18 Created: 2007-12-18 Last updated: 2010-11-03Bibliographically approved
2. Buildup of Polyelectrolyte Multilayers of Polyethyleneimine and Microfibrillated Cellulose Studied by in situ Dual Polarization Interferometry and Quartz Crystal Microbalance with Dissipation
Open this publication in new window or tab >>Buildup of Polyelectrolyte Multilayers of Polyethyleneimine and Microfibrillated Cellulose Studied by in situ Dual Polarization Interferometry and Quartz Crystal Microbalance with Dissipation
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2008 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 24, no 6, 2509-2518 p.Article in journal (Refereed) Published
Abstract [en]

Polyethyleneimine (PEI) and Microfibrillated cellulose (MFC) have been used to buildup polyelectrolyte multilayers (PEM) on silicone oxide and silicone oxynitride surfaces at different pH values and with different electrolyte and polyelectrolyte/colloid concns. of the components.  Consecutive adsorption on these surfaces was studied by in situ dual-polarization interferometry (DPI) and quartz crystal microbalance measurements.  The adsorption data obtained from both the techniques showed a steady buildup of multilayers.  High pH and electrolyte concn. of the PEI soln. was found to be beneficial for achieving a high adsorbed amt. of PEI, and hence of MFC, during the buildup of the multilayer.  On the other hand, an increase in the electrolyte concn. of the MFC dispersion was found to inhibit the adsorption of MFC onto PEI.  The adsorbed amt. of MFC was independent of the bulk MFC concn. in the investigated concn. range (15-250 mg/L).  At. force microscopy measurements were used to image a MFC-treated silicone oxynitride chip from DPI measurements.  The surface was found to be almost fully covered by randomly oriented microfibrils after the adsorption of only one bilayer of PEI/MFC.  The surface roughness expressed as the rms-roughness over 1 μm2 was calcd. to be 4.6 nm (1 bilayer).  The adsorbed amt. of PEI and MFC and the amt. of water entrapped by the individual layers in the multilayer structures were estd. by combining results from the two anal. techniques using the de Feijter formula.  These results indicate a total water content of ca. 41% in the PEM.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2008
Keyword
PAPER STRENGTH PROPERTIES; ADSORPTION PROPERTIES; SILICA SURFACES; WOOD FIBERS; THIN-FILMS; PROTEIN; ELLIPSOMETRY; KINETICS; GROWTH
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-70183 (URN)10.1021/la7032884 (DOI)000253941000036 ()2-s2.0-42149121363 (Scopus ID)
Note
QC 20120207Available from: 2012-02-07 Created: 2012-01-30 Last updated: 2017-12-08Bibliographically approved
3. Nanoscale Cellulose Films with Different Crystallinities and Mesostructures: Their Surface Properties and Interaction with Water
Open this publication in new window or tab >>Nanoscale Cellulose Films with Different Crystallinities and Mesostructures: Their Surface Properties and Interaction with Water
2009 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 25, no 13, 7675-7685 p.Article in journal (Refereed) Published
Abstract [en]

A systematic study of the degree of molecular ordering and swelling of different nanocellulose model films has been conducted. Crystalline cellulose II surfaces were prepared by spin-coating of the precursor cellulose solutions onto oxidized silicon wafers before regeneration in water or by using the Langmuir-Schaefer (LS) technique. Amorphous cellulose films were also prepared by spin-coating of a precursor cellulose solution onto oxidized silicon wafers. Crystalline cellulose I surfaces were prepared by spin-coating wafers with aqueous suspensions of sulfate-stabilized cellulose nanocrystals and low-charged microfibrillated cellulose (LC-MFC). In addition, a dispersion of high-charged MFC was used for the buildup of polyelectrolyte multilayers with polyetheyleneimine on silica with the aid of the layer-by-layer (LbL) technique. These preparation methods produced smooth thin films on the nanometer scale Suitable for X-ray diffraction and swelling measurements. The surface morphology and thickness of the cellulose films were characterized in detail by atomic force microscopy (AFM) and ellipsometry measurements, respectively. To determine the surface energy of the cellulose surfaces, that Is, their ability to engage in different interactions with different materials, they were characterized through contact angle measurements against water, glycerol, and methylene iodide. Small incidence angle X-ray diffraction revealed that the nanocrystal and MFC films exhibited a cellulose I crystal structure and that the films prepared from N-methylmorpholine-N-oxide (NMMO), LiCl/DMAc solutions, using the LS technique, possessed a cellulose II structure. The degree of crystalline ordering was highest in the nanocrystal films (similar to 87%), whereas the MFC, NMMO, and LS films exhibited a degree of crystallinity of about 60%. The N,N-dimethylacetamide(DMAc)/LiCl film possessed very low crystalline ordering (<15%). It was also established that the films ha different mesostructures, that is, structures around 10 nm, depending on the preparation conditions. The LS and LiCl/DMAc films are smooth without any clear mesostructure, whereas the other films have a clear mesostructure in which the dimensions are dependent oil the size of the nanocrystals, fibrillar cellulose, and electrostatic charge of the MFC. The swelling of the films was studied using a quartz crystal microbalance with dissipation. To understand the swelling properties of the films, it was necessary to consider both the difference in crystalline ordering and the difference in mesostructure of the films.

Keyword
QUARTZ-CRYSTAL MICROBALANCE; INVERSE GAS-CHROMATOGRAPHY; POLYELECTROLYTE MULTILAYERS; MODEL FILMS; THIN-FILMS; QCM-D; NATIVE CELLULOSE; MICROFIBRILLATED CELLULOSE; ULTRATHIN FILMS; SILICON-WAFERS
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-11498 (URN)10.1021/la900323n (DOI)000267533800074 ()2-s2.0-67650089781 (Scopus ID)
Note
QC 20100623Available from: 2009-11-17 Created: 2009-11-17 Last updated: 2010-12-03Bibliographically approved
4. Adsorption behaviour, structural and adhesive properties of microfibrillated cellulose-based multilayers
Open this publication in new window or tab >>Adsorption behaviour, structural and adhesive properties of microfibrillated cellulose-based multilayers
(English)Article in journal (Refereed) Submitted
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-13665 (URN)
Note
QC 20100623Available from: 2010-06-23 Created: 2010-06-23 Last updated: 2010-07-19Bibliographically approved
5. Oxygen and oil barrier properties of microfibrillated cellulose films and coatings
Open this publication in new window or tab >>Oxygen and oil barrier properties of microfibrillated cellulose films and coatings
2010 (English)In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 17, no 3, 559-574 p.Article in journal (Refereed) Published
Abstract [en]

The preparation of carboxymethylated microfibrillated cellulose (MFC) films by dispersion-casting from aqueous dispersions and by surface coating on base papers is described. The oxygen permeability of MFC films were studied at different relative humidity (RH). At low RH (0%), the MFC films showed very low oxygen permeability as compared with films prepared from plasticized starch, whey protein and arabinoxylan and values in the same range as that of conventional synthetic films, e.g., ethylene vinyl alcohol. At higher RH's, the oxygen permeability increased exponentially, presumably due to the plasticizing and swelling of the carboxymethylated nanofibers by water molecules. The effect of moisture on the barrier and mechanical properties of the films was further studied using water vapor sorption isotherms and by humidity scans in dynamic mechanical analysis. The influences of the degree of nanofibrillation/dispersion on the microstructure and optical properties of the films were evaluated by field-emission scanning electron microscopy (FE-SEM) and light transmittance measurements, respectively. FE-SEM micrographs showed that the MFC films consisted of randomly assembled nanofibers with a thickness of 5-10 nm, although some larger aggregates were also formed. The use of MFC as surface coating on various base papers considerably reduced the air permeability. Environmental scanning electron microscopy (E-SEM) micrographs indicated that the MFC layer reduced sheet porosity, i.e., the dense structure formed by the nanofibers resulted in superior oil barrier properties.

Keyword
MFC, Barrier, Oil, Oxygen permeability, Nanofibers, Nanocellulose, Packaging, Films, SEM, Coating, X-RAY-SCATTERING, EDIBLE FILMS, SURFACE-PROPERTIES, HIGH TOUGHNESS, FREE-VOLUME, PERMEABILITY, STARCH, WATER, SUSPENSIONS, POLYOLS
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-13666 (URN)10.1007/s10570-009-9393-y (DOI)000277637100008 ()2-s2.0-77952430889 (Scopus ID)
Note
QC 20100623Available from: 2010-06-23 Created: 2010-06-23 Last updated: 2011-01-04Bibliographically approved
6. Design of Highly Oleophobic Cellulose Surfaces from Structured Silicon Templates
Open this publication in new window or tab >>Design of Highly Oleophobic Cellulose Surfaces from Structured Silicon Templates
2009 (English)In: Applied Materials and Interfaces, ISSN 1944-8244, Vol. 1, no 11, 2443-2452 p.Article in journal (Refereed) Published
Abstract [en]

Structured silicon surfaces, possessing hierarchical porous characteristics consisting of micrometer-sized cavities superimposed upon a network of nanometer-sized pillars or wires, have been fabricated by a plasma-etching process. These surfaces have superoleophobic properties, after being coated with fluorinated organic trichlorosilanes, on intrinsically oleophilic surfaces. By comparison with flat silicon surfaces, which are oleophilic, it has been demonstrated that a combination of low surface energy and the structured features of the plasma-etched surface is essential to prevent oil from penetrating the surface cavities and thus induce the observed macroscopic superoleophobic phenomena with very low contact-angle hysteresis and low roll-off angles. The structured silicon surfaces were coated with cellulose nanocrystals using the polyelectrolyte multilayer technique. The cellulose surfaces prepared in this way were then coated with a monolayer of fluorinated trichlorosilanes. These porous cellulose films displayed highly nonwetting properties against a number of liquids with low surface tension, including alkanes such as hexadecane and decane. The wettability and chemical composition of the cellulose/silicon surfaces were characterized with contact-angle goniometry and X-ray photoelectron spectroscopy, respectively. The nano/microtexture features of the cellulose/silicon surfaces were also studied with field-emission scanning electron microscopy. The highly oleophobic structured cellulose surfaces are very interesting model surfaces for the development of biomimetic self-cleaning surfaces in a vast array of products, including green constructions, packaging materials, protection against environmental fouling, sports, and outdoor clothing, and microfluidic systems.

Keyword
superoleophobic; cellulose; surface roughness; low surface energy; nanocrystals; polyelectrolyte multilayer; XPS; SEM; oil repellent; coating
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-11499 (URN)10.1021/am900394y (DOI)000272039700006 ()2-s2.0-77954574786 (Scopus ID)
Note

QC 20100623

Available from: 2009-11-17 Created: 2009-11-17 Last updated: 2015-06-08Bibliographically approved
7. Ultra light-weight microfibrillated cellulose aerogels with tunable oleophobicity
Open this publication in new window or tab >>Ultra light-weight microfibrillated cellulose aerogels with tunable oleophobicity
(English)Article in journal (Refereed) Submitted
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-13667 (URN)
Note
QC 20100623Available from: 2010-06-23 Created: 2010-06-23 Last updated: 2010-07-19Bibliographically approved

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