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Plasticizing and crosslinking effects of borate additives on the structure and properties of poly(vinyl acetate)
Luleå University of Technology, Department of Engineering Sciences and Mathematics, Material Science.ORCID iD: 0000-0003-1776-2725
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Chemical Engineering.ORCID iD: 0000-0003-3652-7798
Luleå University of Technology, Department of Engineering Sciences and Mathematics, Material Science.
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Chemical Engineering.ORCID iD: 0000-0003-1067-7990
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Number of Authors: 52017 (English)In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 7, no 13, p. 7483-7491Article in journal (Refereed) Published
Abstract [en]

As an environmentally friendly, low-cost and widely used polymer, poly(vinyl acetate) (PVAc) is worth modifying to achieve better properties. Here, we report on the influence of borate additives on the structure and properties of partially hydrolysed PVAc. In addition to the general crosslinking function of borate additives, an extraordinary plasticizing effect was found. By controlling the pH from 4 to 11 during sample preparation, the plasticizing and crosslinking effects can be shifted. In alkaline conditions, the degree of crosslinking in the PVAc/borate sample is increased; however, this increase declines gradually with an increase in the borate additive content, which impacts the morphology of the PVAc latex particles, as well as the mechanical and thermal properties of the PVAc/borate films. In contrast, in acidic conditions, the PVAc/borate films are plasticized by borate additives; thus, their ultimate mechanical strength, elastic moduli and thermal stabilities decrease, while the water diffusivities increase.

Place, publisher, year, edition, pages
2017. Vol. 7, no 13, p. 7483-7491
National Category
Physical Chemistry Bio Materials
Research subject
Wood and Bionanocomposites; Chemistry of Interfaces
Identifiers
URN: urn:nbn:se:ltu:diva-61616DOI: 10.1039/C6RA28574KISI: 000393757100006Scopus ID: 2-s2.0-85010648470OAI: oai:DiVA.org:ltu-61616DiVA, id: diva2:1068198
Note

Validerad; 2017; Nivå 2; 2017-02-13 (andbra)

Available from: 2017-01-24 Created: 2017-01-24 Last updated: 2018-08-15Bibliographically approved
In thesis
1. Cellulose-based Nanocomposites – The Relationship between Structure and Properties
Open this publication in new window or tab >>Cellulose-based Nanocomposites – The Relationship between Structure and Properties
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Nanocellulose materials extracted from various types of biomass have recently attracted significant attention. Due to their remarkable mechanical properties, large surface area and biodegradability, they can be promising reinforcements in nanocomposites. Cellulose-based nanocomposites constitutive of nanocellulose reinforcements and biodegradable polymer matrices have great potential to be used in environmentally friendly applications to replace fossil-based materials. However, the challenge of controlling their nanoscale structure, especially achieving good dispersion of nanocellulose in hydrophobic polymer matrices, still poses significant obstacles to producing high-performance nanocomposites. Therefore, this thesis reports several methods for structural modification of cellulose-based nanocomposites toward the objectives of improving the dispersion of nanocellulose and enhancing the properties of the nanocomposites. The methods include in situ emulsion polymerization in the presence of nanocellulose, crosslinking of polymer matrix, grafting of polymer brushes to nanocellulose and drawing of nanocomposites to obtain aligned structures. The resulting mechanical, thermal and other related properties are investigated, and the relationship between structure and properties of the nanocomposites are discussed.

To address the challenge of achieving good dispersion of nanocellulose in hydrophobic matrices, in situ emulsion polymerization of vinyl acetate monomer in the presence of cellulose nanocrystals has been developed. Microscopy results show that the in situ method improves the compatibility between nanocellulose and hydrophobic polymers, which consequently improves the dispersion of nanocellulose in the nanocomposites. Compared with direct mixed polymer/nanocellulose composites, the in situ synthesized nanocomposites exhibit higher stiffness and strength arising from their superior interphase volume, which is confirmed theoretically and experimentally. Crosslinking of partially hydrolyzed poly(vinyl acetate) by borate additives under different pH conditions has been studied to further enhance mechanical properties of the nanocomposites. Moreover, the “grafting to” modification method also helps to overcome this challenge. It is revealed that poly(ethylene glycol)-grafted cellulose nanofibers disperse better in poly(lactic acid) matrix than unmodified cellulose nanofibers, which is attributed to the improved compatibility and steric effect provided by the covalently grafted poly(ethylene glycol) brushes.

To substantially enhance the unidirectional mechanical properties of cellulose-based nanocomposites, a highly aligned structure in the materials is obtained through the drawing process. Drawing conditions including temperature, speed and draw ratio show considerable effects on the mechanical and thermal properties of the nanocomposites. Furthermore, the aligned nanocomposites consisting of poly(lactic acid) matrix and ultra-low weight fraction of poly(ethylene glycol)-grafted cellulose nanofibers demonstrate competitive strength, superb toughness and interesting optical behaviors compared with other aligned nanocellulose-based materials reported in the literature, indicating their potential to be further developed for large-scale environmentally friendly applications.

Place, publisher, year, edition, pages
Luleå: Luleå University of Technology, 2018
Series
Doctoral thesis / Luleå University of Technology 1 jan 1997 → …, ISSN 1402-1544
Keywords
Nanocellulose; Nanocomposite; Dispersion; Poly(vinyl acetate); Poly(lactic acid); Alignment; Mechanical characteristics
National Category
Composite Science and Engineering Nano Technology Bio Materials
Research subject
Wood and Bionanocomposites
Identifiers
urn:nbn:se:ltu:diva-70411 (URN)978-91-7790-182-2 (ISBN)978-91-7790-183-9 (ISBN)
Public defence
2018-09-19, E632, Luleå, 10:00 (English)
Opponent
Supervisors
Funder
Knut and Alice Wallenberg FoundationBio4Energy
Available from: 2018-08-16 Created: 2018-08-15 Last updated: 2018-09-04Bibliographically approved

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Geng, ShiyuShah, Faiz UllahLiu, PengAntzutkin, OlegOksman, Kristiina

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