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Multifunctionality and Durability of Cellulosic Fiber Reinforced Polymer Composites
Luleå University of Technology, Department of Engineering Sciences and Mathematics, Material Science.ORCID iD: 0000-0001-5550-2962
2022 (English)Doctoral thesis, comprehensive summary (Other academic)Alternative title
Multifunktionalitet och beständighet hos cellulosabaserade fiberkompositer (Swedish)
Abstract [en]

The overall objective of this thesis is to develop and evaluate cellulose-based fiber composites with added multifunctionality for advanced applications. In the strive towards sustainable societies and industries, materials as well as production processes need to be assessed against the sustainability criteria and selected accordingly. Cellulosic fibers reinforced polymer composites are being increasingly used in applications where weight saving, and environmental friendliness is as important as structural performance. Nonetheless, these materials have their limitations regarding durability and stability of the properties, but their potential in use for advanced applications can be expanded if functionalized and considered beyond their structural performance. Such multi-functionality of composites can be achieved by the coating of fibers and/or modifying the matrix with functional reinforcement, or by both of these routes combined. Coating of fibers and modifying the matrix with nano-reinforcement are two selected approaches for imparting functionality to the cellulosic fiber composites in the current study. 

Conductive Regenerated Cellulose Fibers (RCFs) were produced by coating commercial RCFs with copper via electroless plating process. Electrical conductivity and mechanical performance were evaluated, and the coated fibers were transformed into an embedded strains sensor-like assembly that could be used as structural health monitoring system in composites structures. A noticeable degradation in the mechanical strength of fibers was realized and it was attributed to the influence of the chemicals of the final plating step of process on the chains of cellulose as well as the loss of crystalline order in the RCF. 

In order to obtain modified matrix (nanocomposites) for multifunctional wood polymer composites (WPC), the commercial masterbatches based on Graphene Nanoplatelets (GNPs) were utilized by melt extrusion process. Effect of the processing parameters in terms of change in screw configurations and the change in composition of the constituents on the structure and mechanical performance of the nanocomposites was studied.  Results showed that there is insignificant effect of the change in the screw configuration in comparison with the effect of increasing the content of the GNPs. Stronger shear forces did not result in better dispersion of the nanoparticles. Addition of the compatibilizer, on the other hand, resulted in an adverse effect on the properties compared to the formulations where it is absent. The use of GNPs with larger aspect ratio resulted in much better improvement in the mechanical performance. Addition of the nanoparticles did not only improve mechanical performance but also resulted in increased thermal conductivity and diffusivity, especially when micro-scale reinforcement was added because of synergy between wood fibers and the GNPs. This synergy was reflected also in the significant 99% improved wear resistance and the >80% reduction in the creep strains of wood and graphene reinforced composites. 

During the design and selection of materials, quasi-static properties are often used as a selection criterion. However, in reality structures in use are often loaded during lengthy periods of time which are followed by multiple steps of unloading/reloading, depending on the service conditions.  In such cases their time-dependent response becomes more crucial than instantaneous mechanical response. Typically, characterization of these properties requires a lot of time, but it may be significantly shortened if proper modeling and analysis are employed. The effect of addition of GNPs to the polymer and wood composites has been studied experimentally by short term creep tests. The materials showed highly nonlinear response even at very low loading stresses, but the addition of the nanoparticles resulted in a decrease in the nonlinearity and in the irreversible strains due to plasticity. Modelling approaches have been used to extract parameters from experimental data that could be used in predicting long term performance using Zapas model for viscoplasticity and Schapery’s model for nonlinear viscoelasticity. 

Overall, the results of the performed work contribute to enriching the research field with the potential the bio-based composites have to offer in the advanced application and how nano-scale reinforcement can interact synergistically with the micro-sized fibers to improve the overall performance of WPC and under different loading scenarios.  

Place, publisher, year, edition, pages
Luleå University of Technology, 2022.
Series
Doctoral thesis / Luleå University of Technology 1 jan 1997 → …, ISSN 1402-1544
National Category
Composite Science and Engineering
Research subject
Polymeric Composite Materials
Identifiers
URN: urn:nbn:se:ltu:diva-90138ISBN: 978-91-8048-057-4 (print)ISBN: 978-91-8048-058-1 (electronic)OAI: oai:DiVA.org:ltu-90138DiVA, id: diva2:1650797
Public defence
2022-06-09, E632, Universitetsområdet Porsön, Luleå, 12:30 (English)
Opponent
Supervisors
Available from: 2022-04-08 Created: 2022-04-08 Last updated: 2022-05-19Bibliographically approved
List of papers
1. Conductive Regenerated Cellulose Fibers by Electroless Plating
Open this publication in new window or tab >>Conductive Regenerated Cellulose Fibers by Electroless Plating
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2019 (English)In: Fibers, ISSN 2079-6439, Vol. 7, no 5, article id 38Article in journal (Refereed) Published
Abstract [en]

Continuous metallized regenerated cellulose fibers for advanced applications (e.g. multi-functional composites) are produced by electroless copper plating. Copper is successfully deposited on the surface of cellulose fibers using commercial cyanide-free electroless copper plating package commonly available for manufacturing of printed wiring boards. The deposited copper is found to enhance the thermal stability, electrical conductivity and resistance to moisture uptake of the fibers. On the other hand, involved chemistry results in altering the molecular structure of the fibers as is indicated by the degradation of their mechanical performance (tensile strength and modulus).

Place, publisher, year, edition, pages
Basel: MDPI, 2019
Keywords
cellulose fibers, functionalization, copper coating, electroless plating, continuous fibers
National Category
Materials Engineering Other Electrical Engineering, Electronic Engineering, Information Engineering Composite Science and Engineering
Research subject
Polymeric Composite Materials; Industrial Electronics
Identifiers
urn:nbn:se:ltu:diva-73739 (URN)10.3390/fib7050038 (DOI)000470958000002 ()2-s2.0-85070398485 (Scopus ID)
Funder
The Swedish Foundation for International Cooperation in Research and Higher Education (STINT), IB2017-7389
Note

Validerad;2019;Nivå 2;2019-07-01 (johcin)

Available from: 2019-04-24 Created: 2019-04-24 Last updated: 2022-04-08Bibliographically approved
2. Conductive Regenerated Cellulose Fibers for Multi-Functional Composites: Mechanical and Structural Investigation
Open this publication in new window or tab >>Conductive Regenerated Cellulose Fibers for Multi-Functional Composites: Mechanical and Structural Investigation
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2021 (English)In: Materials, E-ISSN 1996-1944, Vol. 14, no 7, article id 1746Article in journal (Refereed) Published
Abstract [en]

Regenerated cellulose fibers coated with copper via electroless plating process are investigated for their mechanical properties, molecular structure changes, and suitability for use in sensing applications. Mechanical properties are evaluated in terms of tensile stiffness and strength of fiber tows before, during and after the plating process. The effect of the treatment on the molecular structure of fibers is investigated by measuring their thermal stability with differential scanning calorimetry and obtaining Raman spectra of fibers at different stages of the treatment. Results show that the last stage in the electroless process (the plating step) is the most detrimental, causing changes in fibers’ properties. Fibers seem to lose their structural integrity and develop surface defects that result in a substantial loss in their mechanical strength. However, repeating the process more than once or elongating the residence time in the plating bath does not show a further negative effect on the strength but contributes to the increase in the copper coating thickness, and, subsequently, the final stiffness of the tows. Monitoring the changes in resistance values with applied strain on a model composite made of these conductive tows show an excellent correlation between the increase in strain and increase in electrical resistance. These results indicate that these fibers show potential when combined with conventional composites of glass or carbon fibers as structure monitoring devices without largely affecting their mechanical performance.

Place, publisher, year, edition, pages
Basel, Switzerland: MDPI, 2021
Keywords
regenerated cellulose fibers (RCFs), electroless copper plating, conductive cellulose fibers, mechanical properties, molecular structure, functional composites
National Category
Composite Science and Engineering
Research subject
Polymeric Composite Materials; Machine Elements; Cyber-Physical Systems; Experimental Physics
Identifiers
urn:nbn:se:ltu:diva-83555 (URN)10.3390/ma14071746 (DOI)000638717200001 ()33916305 (PubMedID)2-s2.0-85104353403 (Scopus ID)
Funder
The Swedish Foundation for International Cooperation in Research and Higher Education (STINT), IB2017-7389European Regional Development Fund (ERDF)Interreg Nord
Note

Validerad;2021;Nivå 2;2021-04-12 (alebob)

Available from: 2021-04-09 Created: 2021-04-09 Last updated: 2024-07-04Bibliographically approved
3. Mechanical Performance of PE Reinforced with Graphene Nanoplatelets (GNPs): Effect of Composition and Processing Parameters
Open this publication in new window or tab >>Mechanical Performance of PE Reinforced with Graphene Nanoplatelets (GNPs): Effect of Composition and Processing Parameters
2024 (English)In: Nanocomposites, E-ISSN 2055-0332, Vol. 10, no 1, p. 418-429Article in journal (Refereed) Published
Abstract [en]

Processing parameters of melt mixing (one of the most conventional techniques in polymer processing) play a significant role in the quality and properties of the resulting material, especially when nanoreinforcements are involved. The current study investigates varying processing temperature, rotation speed and elements of the screw extruder, aiming to enhance mechanical properties of polyethylene (PE) nanocomposites by improving dispersion of nanoparticles from a commercial masterbatch in two grades of PE. The study investigates the effect of a common compatibilizer (MAPE) and shearing forces at varying amounts of graphene nanoplatelets (GNPs) in polyethylene. A comparison is made on mechanical properties, morphology, and changes in the microstructure. Results show that increasing amounts of GNPs lead to expected continuous increase of mechanical properties with reference to the base polymer. Addition of MAPE did not result in significant improvement in the performance of the studied systems. Use of stronger shear forces resulted in mostly negative impact on the properties.

Place, publisher, year, edition, pages
Taylor & Francis, 2024
Keywords
PE nanocomposites, graphene nanoplatelets, compatibilizer, twin-screwextruder, mechanicalproperties
National Category
Composite Science and Engineering
Research subject
Machine Elements; Polymeric Composite Materials
Identifiers
urn:nbn:se:ltu:diva-90136 (URN)10.1080/20550324.2024.2407693 (DOI)001325255900001 ()2-s2.0-85205761675 (Scopus ID)
Funder
Interreg Nord, Smart-WPCNorrbotten County Council, Smart-WPCEU, Horizon 2020, Nano2DayLuleå University of Technology
Note

Validerad;2024;Nivå 2;2024-11-22 (sarsun);

Full text license: CC BY 4.0;

This article has previously appeared as a manuscript in a thesis.

Available from: 2022-04-08 Created: 2022-04-08 Last updated: 2024-12-05Bibliographically approved
4. Characterization of Wood and Graphene Nanoplatelets (GNPs) Reinforced Polymer Composites
Open this publication in new window or tab >>Characterization of Wood and Graphene Nanoplatelets (GNPs) Reinforced Polymer Composites
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2020 (English)In: Materials, E-ISSN 1996-1944, Vol. 13, no 9, article id 2089Article in journal (Refereed) Published
Abstract [en]

This paper investigates the utilization of commercial masterbatches of graphene nanoplatelets to improve the properties of neat polymer and wood fiber composites manufactured by conventional processing methods. The effect of aspect ratio of the graphene platelets (represented by the different number of layers in the nanoplatelet) on the properties of high-density polyethylene (HDPE) is discussed. The composites were characterized for their mechanical properties (tensile, flexural, impact) and physical characteristics (morphology, crystallization, and thermal stability). The effect of the addition of nanoplatelets on the thermal conductivity and diffusivity of the reinforced polymer with different contents of reinforcement was also investigated. In general, the mechanical performance of the polymer was enhanced at the presence of either of the reinforcements (graphene or wood fiber). The improvement in mechanical properties of the nanocomposite was notable considering that no compatibilizer was used in the manufacturing. The use of a masterbatch can promote utilization of nano-modified polymer composites on an industrial scale without modification of the currently employed processing methods and facilities.

Place, publisher, year, edition, pages
MDPI, 2020
Keywords
graphene nanoplatelets (GNPs), nanocomposites masterbatch, wood polymer composites (WPC), energy transport, high density polyethylene (HDPE)
National Category
Composite Science and Engineering Tribology (Interacting Surfaces including Friction, Lubrication and Wear)
Research subject
Polymeric Composite Materials; Machine Elements
Identifiers
urn:nbn:se:ltu:diva-73740 (URN)10.3390/ma13092089 (DOI)000535941100083 ()32369956 (PubMedID)2-s2.0-85085253513 (Scopus ID)
Funder
Interreg NordNorrbotten County Council
Note

Validerad;2020;Nivå 2;2020-05-12 (alebob)

Available from: 2019-04-24 Created: 2019-04-24 Last updated: 2024-07-04Bibliographically approved
5. Tribological Study on Wood and Graphene Reinforced High Density Polyethylene
Open this publication in new window or tab >>Tribological Study on Wood and Graphene Reinforced High Density Polyethylene
2022 (English)In: ECCM 2022 - Proceedings of the 20th European Conference on Composite Materials: Composites Meet Sustainability / [ed] Vassilopoulos, Anastasios; Michaud, Véronique, Lausanne: EPFL Lausanne, Composite Construction Laboratory , 2022, Vol. 1, p. 585-592Conference paper, Published paper (Other academic)
Abstract [en]

Wear rate (WR) and coefficient of friction (COF) for high-density polyethylene (HDPE)and its composites of wood flour (WF) and/or graphene nanoplatelets (GNPs) are studied. Theinvestigation is performed by pin-on-disc test configuration on samples with different moisturecontents (dry, and samples saturated at RH of 33% and 79% in room temperature). The effect ofthe different scales of reinforcement (GNPs and WF) on these properties is discussed. Themorphological/microstructural changes in the materials induced by the motion in contact and/ormoisture content are investigated by differential scanning calorimetry (DSC). Results show thatreinforcing the polymer with WF or GNPs reduces the WR significantly, compared to neat HDPE.The hybrid reinforcements contribute to maximum improvement in wear resistance (>98%) andin the reduction of COF (>11%). The improvement in the tribological behavior of bio-basedmaterials has a significant impact on sustainable development through the improved design,durability, and environmental impact.

Place, publisher, year, edition, pages
Lausanne: EPFL Lausanne, Composite Construction Laboratory, 2022
Keywords
Tribology, WPC, graphene, functional composites, hybrid composites
National Category
Composite Science and Engineering Tribology (Interacting Surfaces including Friction, Lubrication and Wear)
Research subject
Machine Elements; Polymeric Composite Materials
Identifiers
urn:nbn:se:ltu:diva-90133 (URN)10.5075/epfl-298799_978-2-9701614-0-0 (DOI)2-s2.0-85149170413 (Scopus ID)978-2-9701614-0-0 (ISBN)
Conference
20th European Conference on Composite Materials (ECCM20), June 26-30, 2022, Lausanne, Switzerland
Available from: 2022-04-08 Created: 2022-04-08 Last updated: 2023-03-14Bibliographically approved
6. Time‐dependent properties of graphene nanoplatelets reinforced high‐density polyethylene
Open this publication in new window or tab >>Time‐dependent properties of graphene nanoplatelets reinforced high‐density polyethylene
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2021 (English)In: Journal of Applied Polymer Science, ISSN 0021-8995, E-ISSN 1097-4628, Vol. 138, no 30, article id 50783Article in journal (Refereed) Published
Abstract [en]

The deformation of polymers at constant applied stress is one of their major drawbacks, limiting their use in advanced applications. The study of this property using classical techniques requires extensive testing over long periods of time. It is well known that reinforced polymers show improved behavior over time compared to their neat counterparts. In this study, the effect of adding different amounts of graphene nanoplatelets (GNPs) on the time‐dependent properties of high‐density polyethylene (HDPE) is investigated using short‐term creep tests and load/unload recovery tests. The results are discussed in terms of the test profile and the influence of loading history. Viscoplasticity/viscoelasticity analysis is performed using Zapas model and by comparing creep, creep compliance and pure viscoelasticity curves. The results show that the reinforcement of 15 wt% GNP have the most significant effect on the time‐dependent behavior, reducing the strain by more than 50%. The creep compliance curves show that nano‐reinforced HDPE behaves nonlinearly viscoelastically even at very low stresses. In addition to demonstrating the effect of nano‐reinforcement, the discussion of the results concludes that the influence of loading history can be quite significant and should not be neglected in the design and evaluation of material behavior.

Place, publisher, year, edition, pages
John Wiley & Sons, 2021
Keywords
graphene and fullerenes, mechanical properties, theory and modeling, thermoplastics, viscosity and viscoelasticity
National Category
Composite Science and Engineering
Research subject
Polymeric Composite Materials; Machine Elements
Identifiers
urn:nbn:se:ltu:diva-83561 (URN)10.1002/app.50783 (DOI)000636776700001 ()2-s2.0-85103565338 (Scopus ID)
Funder
EU, Horizon 2020, 777810Interreg NordLuleå University of Technology
Note

Validerad;2021;Nivå 2;2021-06-10 (alebob);

An image from this article was selected for the cover image of the issue, it can be found here: https://doi.org/10.1002/app.50972

This article has previously appeared as a manuscript in a thesis.

Available from: 2021-04-09 Created: 2021-04-09 Last updated: 2023-03-16Bibliographically approved
7. Time-dependent properties of high-density polyethylene with wood/graphene nanoplatelets reinforcement
Open this publication in new window or tab >>Time-dependent properties of high-density polyethylene with wood/graphene nanoplatelets reinforcement
2023 (English)In: Polymer Composites, ISSN 0272-8397, E-ISSN 1548-0569, Vol. 44, no 1, p. 465-479Article in journal (Refereed) Published
Abstract [en]

The effect of graphene nanoplatelets (GNPs) on the long-term performance of wood fiber/high-density polyethylene (HDPE) composite is investigated by using short-term creep tests with an efficient, faster data analysis approach. Previously, it was shown that the addition of GNPs at 15 wt% into HDPE reduces the viscoplastic (VP) strain developed during 2 h creep by ~50%. The current study shows that 25 and 40 wt% wood content in HDPE reduce the VP strains developed during 2 h creep time by >75% with no noticeable effect of the increased wood content. However, further addition of GNPs results in more than 90% total reduction in the VP strains. The current study shows that the development of the VP strains in the hybrid composites follows Zapas model. Viscoelastic (VE) response of these composites is nonlinear and thus is described by Schapery's model. Parameters for VP and VE models are obtained from the creep experiments and were validated in a separate loading-unloading test sequence. Results show a very good agreement between experiments and predictions for the studied materials as long as the micro-damage is not present.

Place, publisher, year, edition, pages
John Wiley & Sons, 2023
Keywords
creep, graphene nanoplatelets, multiscale composites, time-dependent properties, viscoelasticity, viscoplasticity, wood fibers
National Category
Composite Science and Engineering
Research subject
Polymeric Composite Materials; Machine Elements
Identifiers
urn:nbn:se:ltu:diva-90137 (URN)10.1002/pc.27110 (DOI)000877029700001 ()2-s2.0-85141407844 (Scopus ID)
Funder
European Regional Development Fund (ERDF), 1.1.1.2/VIAA/4/20/646EU, Horizon 2020, 777810 Nano2Day
Note

Validerad;2023;Nivå 2;2023-04-19 (hanlid);

Available from: 2022-04-08 Created: 2022-04-08 Last updated: 2023-04-19Bibliographically approved

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