Varvara Apostolopoulou KalkavouraPost Doc
Forskningsprojekt
Publikationer
I urval från Stockholms universitets publikationsdatabas
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Citrated cellulose nanocrystals from post-consumer cotton textiles
2023. Maria-Ximena Ruiz-Caldas (et al.). Journal of Materials Chemistry A
ArtikelLäs mer om Citrated cellulose nanocrystals from post-consumer cotton textilesWe propose a new method for the extraction of cellulose nanocrystals (CNCs) from post-consumer cotton textiles through surface functionalization followed by mechanical treatment. Cotton-based textiles were esterified using an 85 wt% solution of citric acid at 100 degrees C, then further fibrillated in a microfluidizer. The final product, citrated cellulose nanocrystals (CitCNCs), was a dispersion of needle-like nanoparticles with high crystallinity. Up to 78 wt% of the cotton fabric was converted to CitCNCs that exhibited higher yields and a higher surface group content than CNCs extracted through H2SO4 hydrolysis, although CitCNCs showed a broader size distribution and decreased thermal stability. Experimental data supported by DFT calculations showed that the carboxyl groups on the CitCNC surface are bonded to cellulose by mono or diester linkages. An early-stage life cycle assessment (LCA) was performed to evaluate the environmental impact of using discarded textiles as a source of cellulose and analyze the environmental performance of the production of CitCNCs. Our work showed a significant reduction in the environmental burden of CNC extraction using post-consumer cotton instead of wood pulp, making clothing a good feedstock. The environmental impact of CitCNC production was mainly dominated by citric acid. As a proof of concept, around 58 wt% of the citric acid was recovered through evaporation and subsequent crystallization, which could reduce climate impact by 40%. With this work, we introduce a catalyst-free route to valorize textiles with the extraction of CitCNCs and how conducting LCA in laboratory-scale processes might guide future development and optimization.
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A Stiff, Tough, and Thermally Insulating Air- and Ice-Templated Plant-Based Foam
2022. Tamara L. Church (et al.). Biomacromolecules 23 (6), 2595-2602
ArtikelLäs mer om A Stiff, Tough, and Thermally Insulating Air- and Ice-Templated Plant-Based FoamBy forming and directionally freezing an aqueous foam containing cellulose nanofibrils, methylcellulose, and tannic acid, we produced a stiff and tough anisotropic solid foam with low radial thermal conductivity. Along the ice-templating direction, the foam was as stiff as nanocellulose–clay composites, despite being primarily methylcellulose by mass. The foam was also stiff perpendicular to the direction of ice growth, while maintaining λr < 25 mW m–1 K–1 for a relative humidity (RH) up to 65% and <30 mW m–1 K–1 at 80% RH. This work introduces the tandem use of two practical techniques, foam formation and directional freezing, to generate a low-density anisotropic material, and this strategy could be applied to other aqueous systems where foam formation is possible.
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Effect of density, phonon scattering and nanoporosity on the thermal conductivity of anisotropic cellulose nanocrystal foams
2021. Varvara Apostolopoulou Kalkavoura (et al.). Scientific Reports 11 (1)
ArtikelLäs mer om Effect of density, phonon scattering and nanoporosity on the thermal conductivity of anisotropic cellulose nanocrystal foamsAnisotropic cellulose nanocrystal (CNC) foams with densities between 25 and 130 kg m−3 (CNC25 –CNC130) were prepared by directional ice-templating of aqueous dispersions. Estimates of the solid and gas conduction contributions to the thermal conductivity of the foams using a parallel resistor model showed that the relatively small increase of the radial thermal conductivity with increasing foam density can be attributed to interfacial phonon scattering. The foam wall nanoporosity and, to a lesser extent, the orientation of the CNC particles and alignment of the columnar macropores, also influence the insulation performance of the foams. The insight on the importance of phonon scattering for the thermal insulation properties of nanocellulose foams provides useful guidelines for tailoring nanofibrillar foams for super-insulating applications.
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Humidity-Dependent Thermal Boundary Conductance Controls Heat Transport of Super-Insulating Nanofibrillar Foams
2021. Varvara Apostolopoulou-Kalkavoura (et al.). Matter 4 (1), 276-289
ArtikelLäs mer om Humidity-Dependent Thermal Boundary Conductance Controls Heat Transport of Super-Insulating Nanofibrillar FoamsCellulose nanomaterial (CNM)-based foams and aerogels with thermal conductivities substantially below the value for air attract significant interest as super-insulating materials in energy-efficient green buildings. However, the moisture dependence of the thermal conductivity of hygroscopic CNM-based materials is poorly understood, and the importance of phonon scattering in nanofibrillar foams remains unexplored. Here, we show that the thermal conductivity perpendicular to the aligned nanofibrils in super-insulating ice-templated nanocellulose foams is lower for thinner fibrils and depends strongly on relative humidity (RH), with the lowest thermal conductivity (14 mW m−1 K−1) attained at 35% RH. Molecular simulations show that the thermal boundary conductance is reduced by the moisture-uptake-controlled increase of the fibril-fibril separation distance and increased by the replacement of air with water in the foam walls. Controlling the heat transport of hygroscopic super-insulating nanofibrillar foams by moisture uptake and release is of potential interest in packaging and building applications.
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Moisture uptake in nanocellulose: the effects of relative humidity, temperature and degree of crystallinity
2021. Mohit Garg (et al.). Cellulose 28 (14), 9007-9021
ArtikelLäs mer om Moisture uptake in nanocelluloseFoams made from cellulose nanomaterials are highly porous and possess excellent mechanical and thermal insulation properties. However, the moisture uptake and hygroscopic properties of these materials need to be better understood for their use in biomedical and bioelectronics applications, in humidity sensing and thermal insulation. In this work, we present a combination of hybrid Grand Canonical Monte Carlo and Molecular Dynamics simulations and experimental measurements to investigate the moisture uptake within nanocellulose foams. To explore the effect of surface modification on moisture uptake we used two types of celluloses, namely TEMPO-oxidized cellulose nanofibrils and carboxymethylated cellulose nanofibrils. We find that the moisture uptake in both the cellulose nanomaterials increases with increasing relative humidity (RH) and decreases with increasing temperature, which is explained using the basic thermodynamic principles. The measured and calculated moisture uptake in amorphous cellulose (for a given RH or temperature) is higher as compared to crystalline cellulose with TEMPO- and CM-modified surfaces. The high water uptake of amorphous cellulose films is related to the formation of water-filled pores with increasing RH. The microscopic insight of water uptake in nanocellulose provided in this study can assist the design and fabrication of high-performance cellulose materials with improved properties for thermal insulation in humid climates or packaging of water sensitive goods.
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Thermal Conductivity of Hygroscopic Foams Based on Cellulose Nanomaterials
2021. Varvara Apostolopoulou-Kalkavoura.
Avhandling (Dok)Läs mer om Thermal Conductivity of Hygroscopic Foams Based on Cellulose NanomaterialsBiobased super-insulating materials could mitigate climate change by minimizing the use of petroleum-based materials, creating artificial carbon sinks and minimizing the energy needed to maintain pleasant interior conditions. Cellulose nanomaterials (CNM) produced from abundantly available cellulose sources constitute versatile, highly anisotropic raw materials with tunable surface chemistry and high strength. This thesis includes the evaluation of the thermal conductivity of isotropic and anisotropic CNM-based foams and aerogels and analysis of the dominant heat transfer mechanisms.
We have developed a customized measurement cell for hygroscopic materials in which the humidity and temperature are carefully controlled while the thermal conductivity is measured. Anisotropic cellulose nanofibrils (CNF) foams with varying diameters showed a super-insulating behavior perpendicular (radial) to the nanofibril direction, that depended non-linearly on the relative humidity (RH) and foam density. Molecular simulations revealed that the very low thermal conductivity is related to phonon scattering due to the increase of the inter-fibrillar gap with increasing RH that resulted in a 6-fold decrease of the thermal boundary conductance. The moisture-induced swelling exceeds the thermal conductivity increase due to water uptake at low and intermediate RH and resulted in a minimum thermal conductivity of 14 mW m-1 K-1 at 35% RH and 295 K for the foams based on the thinnest CNF.
The density-dependency of the thermal conductivity of cellulose nanocrystal (CNC) foams with densities of 25 to 129 kg m-3 was investigated and a volume-weighted modelling of the solid and gas thermal conductivity contributions suggested that phonon scattering was essential to explain the low radial thermal conductivity, whereas the replacement of air with water and the Knudsen effect related to the nanoporosity in the foam walls had a small effect. Intermediate-density CNC foams (34 kg m-3) exhibited a radial thermal conductivity of 24 mW m-1 K-1 at 295 K and 20% RH, which is below the value for air.
The moisture uptake of foams based on CNMs with different degree of crystallinity and surface modifications decreased significantly with increasing crystallinity and temperature. Molecular simulations showed that the narrow pore size distribution of the amorphous cellulose film, and the relatively low water adsorption in the hydration cell around the oxygen of the carboxyl group play an important role for the moisture uptake of amorphous and crystalline CNM-based materials.
Isotropic CNF- and polyoxamer based foams as well as CNF-AL-MIL-53 (an aluminum‑based metal-organic framework) foams were both moderately insulating (>40 mW m-1 K-1) and comparable with commercial expanded polystyrene. The thermal conductivity of CNF and polyoxamer foams displayed a very strong RH dependency that was modelled with a modified Künzel’s model. The presence of hydrophobic AL-MIL-53 decreased the moisture uptake of CNF-AL-MIL-53 aerogels by 42% compared to CNF-polyoxamer foams.
Solid and gas conduction are the main heat transfer mechanisms in hygroscopic nanofibrillar foams and aerogels that depend on the interfacial phonon scattering, Knudsen effect and water uptake. It is essential that the thermal conductivity measurements of hygroscopic CNM-based foams and aerogels are determined at controlled RH and that parameters such as the temperature, density, nanoporosity, fibril dimensions and alignment are characterized and controlled for systematic development and upscaling of biobased foams for applications in building insulation and packaging.
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Thermally Insulating Nanocellulose-Based Materials
2021. Varvara Apostolopoulou-Kalkavoura, Pierre Munier, Lennart Bergström. Advanced Materials 33 (28)
ArtikelLäs mer om Thermally Insulating Nanocellulose-Based MaterialsThermally insulating materials based on renewable nanomaterials such as nanocellulose could reduce the energy consumption and the environmental impact of the building sector. Recent reports of superinsulating cellulose nanomaterial (CNM)-based aerogels and foams with significantly better heat transport properties than the commercially dominating materials, such as expanded polystyrene, polyurethane foams, and glass wool, have resulted in a rapidly increasing research activity. Herein, the fundamental basis of thermal conductivity of porous materials is described, and the anisotropic heat transfer properties of CNMs and films with aligned CNMs and the processing and structure of novel CNM-based aerogels and foams with low thermal conductivities are presented and discussed. The extraordinarily low thermal conductivity of anisotropic porous architectures and multicomponent approaches are highlighted and related to the contributions of the Knudsen effect and phonon scattering.
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Elastic Aerogels of Cellulose Nanofibers@Metal-Organic Frameworks for Thermal Insulation and Fire Retardancy
2020. Shengyang Zhou (et al.). Nano-Micro Letters 12 (1)
ArtikelLäs mer om Elastic Aerogels of Cellulose Nanofibers@Metal-Organic Frameworks for Thermal Insulation and Fire RetardancyMetal-organic frameworks (MOFs) with high microporosity and relatively high thermal stability are potential thermal insulation and flame-retardant materials. However, the difficulties in processing and shaping MOFs have largely hampered their applications in these areas. This study outlines the fabrication of hybrid CNF@MOF aerogels by a stepwise assembly approach involving the coating and cross-linking of cellulose nanofibers (CNFs) with continuous nanolayers of MOFs. The cross-linking gives the aerogels high mechanical strength but superelasticity (80% maximum recoverable strain, high specific compression modulus of similar to 200 MPa cm(3) g(-1), and specific stress of similar to 100 MPa cm(3) g(-1)). The resultant lightweight aerogels have a cellular network structure and hierarchical porosity, which render the aerogels with relatively low thermal conductivity of similar to 40 mW m(-1) K-1. The hydrophobic, thermally stable MOF nanolayers wrapped around the CNFs result in good moisture resistance and fire retardancy. This study demonstrates that MOFs can be used as efficient thermal insulation and flame-retardant materials. It presents a pathway for the design of thermally insulating, superelastic fire-retardant nanocomposites based on MOFs and nanocellulose.
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Sclerotization-inspired aminoquinone cross-linking of thermally insulating and moisture-resilient biobased foams
2020. Konstantin Kriechbaum (et al.). ACS Sustainable Chemistry and Engineering 8 (47), 17408-17416
ArtikelLäs mer om Sclerotization-inspired aminoquinone cross-linking of thermally insulating and moisture-resilient biobased foamsThermally insulating foams and aerogels based on cellulose nanofibrils (CNFs) are promising alternatives to fossil-based thermal insulation materials. We demonstrate a scalable route for moisture-resilient lightweight foams that relies on sclerotization-inspired Michael-type cross-linking of amine-modified CNFs by oxidized tannic acid. The solvent-exchanged, ice-templated, and quinone-tanned cross-linked anisotropic structures were mechanically stable and could withstand evaporative drying with minimal structural change. The low-density (7.7 kg m–3) cross-linked anisotropic foams were moisture-resilient and displayed a compressive modulus of 90 kPa at 98% relative humidity (RH) and thermal conductivity values close to that of air between 20 and 80% RH at room temperature. Sclerotization-inspired cross-linking of biobased foams offers an energy-efficient and scalable route to produce sustainable and moisture-resilient lightweight materials.
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Strong silica-nanocellulose anisotropic composite foams combine low thermal conductivity and low moisture uptake
2020. Pierre Munier (et al.). Cellulose 27 (18), 10825-10836
ArtikelLäs mer om Strong silica-nanocellulose anisotropic composite foams combine low thermal conductivity and low moisture uptakeWe report the fabrication of anisotropic lightweight composite foams based on commercial colloidal silica particles and TEMPO-oxidized cellulose nanofibrils (TOCNF). The unidirectional ice-templating of silica-TOCNF dispersions resulted in anisotropic foams with columnar porous structures in which the inorganic and organic components were homogeneously distributed. The facile addition of silica particles yielded a significant enhancement in mechanical strength, compared to TOCNF-only foams, and a 3.5-fold increase in toughness at a density of 20 kg m−3. The shape of the silica particles had a large effect on the mechanical properties; anisotropic silica particles were found to strengthen the foams more efficiently than spherical particles. The water uptake of the foams and the axial thermal conductivity in humid air were reduced by the addition of silica. The composite foams were super-insulating at dry conditions at room temperature, with a radial thermal conductivity value as low as 24 mW m−1 K−1, and remained lower than 35 mW m−1 K−1 up to 80% relative humidity. The combination of high strength, low thermal conductivity and manageable moisture sensitivity suggests that silica-TOCNF composite foams could be an attractive alternative to the oil-based thermal insulating materials.
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Analysis of the Porous Architecture and Properties of Anisotropic Nanocellulose Foams: A Novel Approach to Assess the Quality of Cellulose Nanofibrils (CNFs)
2018. Konstantin Kriechbaum (et al.). ACS Sustainable Chemistry and Engineering 6 (9), 11959-11967
ArtikelLäs mer om Analysis of the Porous Architecture and Properties of Anisotropic Nanocellulose FoamsCellulose nanofibrils (CNFs) are a unique nanomaterial because of their abundant, renewable, and biocompatible origin. Compared with synthetic nanoparticles, CNFs are commonly produced from cellulose fibers (e.g., wood pulp) by repetitive high-shear mechanical disintegration. Yet, this process is still highly demanding in energy and costly, slowing down the large-scale production and commercialization of CNFs. Reducing the energy consumption during fibers fibrillation without using any chemical or enzymatic pretreatments while sustaining the CNF quality is challenging. Here, we show that the anisotropic properties of the CNF foams are directly connected to the degree of nanofibrillation of the cellulose fibers. CNFs were produced from wood pulps using a grinder at increasing specific energy consumptions. The anisotropic CNF foams were made by directional ice templating. The porous architecture, the compressive behavior of the foams, and the CNF alignment in the foam cell walls were correlated to the degree of fibrillation. A particular value of specific energy consumption was identified with respect to the highest obtained foam properties and CNF alignment. This value indicated that the optimal degree of fibrillation, and thus CNF quality, was achieved for the studied cellulose pulp. Our approach is a straightforward tool to evaluate the CNF quality and a promising method for the benchmarking of different CNF grades.
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Fire-Retardant and Thermally Insulating Phenolic-Silica Aerogels
2018. Zhi-Long Yu (et al.). Angewandte Chemie International Edition 57 (17), 4538-4542
ArtikelLäs mer om Fire-Retardant and Thermally Insulating Phenolic-Silica AerogelsEnergy efficient buildings require materials with a low thermal conductivity and a high fire resistance. Traditional organic insulation materials are limited by their poor fire resistance and inorganic insulation materials are either brittle or display a high thermal conductivity. Herein we report a mechanically resilient organic/inorganic composite aerogel with a thermal conductivity significantly lower than expanded polystyrene and excellent fire resistance. Co-polymerization and nanoscale phase separation of the phenol-formaldehyde-resin (PFR) and silica generate a binary network with domain sizes below 20 nm. The PFR/SiO2 aerogel can resist a high-temperature flame without disintegration and prevents the temperature on the non-exposed side from increasing above the temperature critical for the collapse of reinforced concrete structures.
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Thermal conductivity of hygroscopic foams based on cellulose nanofibrils and a nonionic polyoxamer
2018. Varvara Apostolopoulou-Kalkavoura (et al.). Cellulose 25 (2), 1117-1126
ArtikelLäs mer om Thermal conductivity of hygroscopic foams based on cellulose nanofibrils and a nonionic polyoxamerNanocellulose-based lightweight foams are promising alternatives to fossil-based insulation materials for energy-efficient buildings. The properties of cellulose-based materials are strongly influenced by moisture and there is a need to assess and better understand how the thermal conductivity of nanocellulose-based foams depends on the relative humidity and temperature. Here, we report a customized setup for measuring the thermal conductivity of hydrophilic materials under controlled temperature and relative humidity conditions. The thermal conductivity of isotropic foams based on cellulose nanofibrils and a nonionic polyoxamer, and an expanded polystyrene foam was measured over a wide range of temperatures and relative humidity. We show that a previously developed model is unable to capture the strong relative humidity dependence of the thermal conductivity of the hygroscopic, low-density nanocellulose- and nonionic polyoxamer-based foam. Analysis of the moisture uptake and moisture transport was used to develop an empirical model that takes into consideration the moisture content and the wet density of the investigated foam. The new empirical model could predict the thermal conductivity of a foam with a similar composition but almost 3 times higher density. Accurate measurements of the thermal conductivity at controlled temperature and relative humidity and availability of simple models to better predict the thermal conductivity of hygroscopic, low-density foams are necessary for the development of nanocellulose-based insulation materials.
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