Fundamental research plays a pivotal role in the development of sustainable solutions that benefit both our environment and everyday lives. Cellulose, as an abundant and renewable resource, holds immense potential for sustainable applications. However, navigating the complexities of molecular and supramolecular structure of cellulose poses significant challenges in harnessing its full potential. By delving into fundamental research, we aim to uncover the underlying mechanisms governing cellulose interactions, paving the way for innovative advancements in sustainable material development.This thesis uncovers the intricate relationship between fundamental research and applied methodologies by showing how molecular contact and structure at the interface of cellulose-rich materials will control the development of the macroscopic mechanical properties of networks from cellulose-rich fibres. The study encompasses various facets, ranging from the development of model materials for studying interfacial interactions to the preparation of fibrous networks with tailored properties.In the initial part of the work the research delves into the development of model materials to investigate interactions at smooth interfaces of regenerated cellulose. The study reveals the crucial role of the making and breaking of cellulose interface, or sometimes interphase, in the development of adhesive joints. Experimental findings demonstrate how chemical additives influence the interactions between cellulose surfaces, thereby modulating the structural and adhesive properties at the interface. Furthermore, by utilizing model materials, insights are gained into fibre-fibre interactions and the influence of surface treatments on network formation and mechanical performance. Lastly, the research focused on investigating the preparation of fibrous networks at different densities and amount of adsorbed additives, providing a comprehensive understanding of how network density and composition affect mechanical properties of the networks.This work not only exemplifies a synergistic approach, where fundamental insights into molecular contacts and interface structures are translated into practical applications for enhancing macroscopic properties but also highlights the importance of integrating fundamental and applied methodologies in molecular engineering, offering novel strategies for advancing sustainable paper production practices and contributing to the attainment of sustainable development goals.

Grundläggande forskning spelar naturligtvis en avgörande roll i utvecklingen av hållbara materiallösningar och processer som gynnar både vår miljö och vårt vardagsliv. Cellulosa, som är en förnyelsebar och rikligt tillgänglig råvara, har också en enorm användnings potential i olika typer av hållbara material. Cellulosan har dock en avancerad och komplicerad molekylär och över molekylärstruktur och det är därför svårt att till fullo utnyttja den inneboende potentialen hos denna fascinerande råvara. Genom att fördjupa oss i och klarlägga de molekylära mekanismer som ligger till grund för växelverkan mellan cellulosarika ytor har vi skapat en grundförutsättning för att kunna utnyttja cellulosans inneboende egenskaper i olika typer av fiberbaserade nätverk . Resultaten i avhandlingen understryker den komplicerade och användbara kopplingen som finns mellan grundläggande förståelse och praktiska tillämpningar genom att visa hur den molekylära kontakten och strukturen i gränsytan mellan två cellulosa-rika ytor kommer att kontrollera de makroskopiska egenskaperna hos nätverk ifrån cellulosa rika fibrer. Studierna i avhandlingen omfattar olika aspekter, allt ifrån utvecklingen av väldefinierade och nm-jämna modellmaterial, för att studera molekylära växelverkai gränsytan mellan två cellulosa ytor, till framställningen av fibrösa nätverk med skräddarsydda egenskaper.I den första delen av arbetet har fokus legat på att utveckla väl karakteriserade modellmaterial och väldefinierade metoder för att klarlägga växelverkan i gränsytan eller gränsfasen mellan två cellulosa ytor. Resultaten visar också hur tillsats kemikalier påverkar växelverkan mellan cellulosa ytor och hur valet av kemikalier kan användas för att styra de strukturella och adhesiva egenskaperna hos gränsytan. Genom att använda våra modellmaterial har det också varit möjligt att bättre förstå de grundläggande mekanismerna som kontrollerar fiber-fiberväxelverkningar och därigenom hur tillsatskemikalier eller fibermodifieringar påverkar bildandet av en fiber/fiberfog och hur det i sin tur kontrollerar de makroskopiska mekaniska egenskaperna hos fibernätverket. I den sista delen av arbetet undersöktes hur olika mängder av fysikaliskt adsorberade styrkekemikalier och nätverks densiteter påverkar slutegenskaperna hos fibernätverk ifrån olika typer av fibrer. Resultaten visar att tillsatskemikalierna fortfarande har relativt sett stor positiv påverkan på de mekaniska egenskaperna hos nätverken, trots höga densiteter, vilket igen understryker vikten att klarlägga molekylära växelverkningar i gränsytan mellan fibrerna i ett fibernätverk.Sammantaget visar detta arbete inte bara hur grundläggande insikter om molekylära växelverkningar och gränsytsstrukturer har direkta praktiska tillämpningar för att förbättra makroskopiska egenskaper hos fibernätverk, utan det betonar också vikten av att integrera grundläggande och tillämpade metoder för skapa nya eller förbättrade biobaserade och recirkulerbara material.

In this work we have investigated the effect of surface modification of fibres on the overall mechanical properties of high-density papers. Paper sheets were prepared by a combination of heat-pressing and polyelectrolyte Layer-by-Layer (LbL) modification of different softwood fibres. LbLs of Polyallylamine Hydrochloride (PAH) and Hyaluronic Acid (HA) were adsorbed onto unbleached kraft fibres and bleached Chemo-ThermoMechanical Pulp (CTMP) to improve the strength of the fibre–fibre joints in papers made from these fibres. Additionally, different sheet-making procedures were used to prepare a range of network densities with different degrees of fibre–fibre interaction in the system. The results demonstrate that interfacial adhesion within fibre–fibre joints plays a pivotal role in the network's performance, even at higher paper densities. Hygroexpansion measurements and fracture zone imaging with Scanning Electron Microscopy (SEM) further support the claim that stronger interactions between the fibres allow for a better utilisation of the inherent fibre properties. Surface treatments and network densification significantly improved the paper sheets' mechanical properties. Specifically, LbL-treatments alone increased specific stiffness up to 60% and specific strength by over 100%. This improvement is linked to the build-up of residual stresses during drying. Due to a high interaction between the fibres during water removal the fibres become constrained, leading to increased stretching of fibre segments. Strengthened fibre joints intensify this constraint, further increasing the stretch and, consequently, the paper's strength.

The growing demand for sustainable products has spurred research into renewable materials, with cellulose-based materials emerging as prominent candidates due to their exceptional properties, abundance, and wide-ranging applications. In this context, there is a need to develop a better fundamental understanding of cellulose interactions such that we can continue to design and improve sustainable materials. Individual interactions can be difficult to assess in bulk fibre-based materials and therefore cellulose model materials have become indispensable tools for researchers as they can facilitate the study of cellulose interactions at a molecular level enabling the design of sustainable materials with enhanced properties. This study presents a new methodology for studying the effects of surface treatments on the individual fibre–fibre joint strength using wet-spun cellulose nanofiber (CNF) filaments as model materials. The Layer-by-Layer assembly technique is used to modify the surface chemistry of the model materials as well as bleached and unbleached hardwood Kraft fibres, demonstrating its potential to enhance adhesive properties and overall mechanical performance of papers made from these fibres. The study further explores the impact of increasing network density through wet-pressing during paper preparation, showcasing a comprehensive approach to molecularly tailor fibre-based materials to achieve superior mechanical properties. The proposed methodology provides a time-efficient evaluation of chemical additives in paper preparation.

Interactions between dry cellulose were studied using model systems, cellulose beads, and cellulose films, usingcustom-built contact adhesion testing equipment. Depending on the configuration of the substrates in contact,Polydimethylsiloxane (PDMS) film, cellulose films spin-coated either on PDMS or glass, the interaction showsthree distinct processes. Firstly, molecular interlocking is formed between cellulose and cellulose when there is asoft PDMS thin film backing the cellulose film. Secondly, without backing, no initial attraction force between thesurfaces is observed. Thirdly, a significant force increase, ΔF, is observed during the retraction process for cel­lulose on glass, and there is a maximum in ΔF when the retraction rate is increased. This is due to the kinetics of acontacting process occurring in the interaction zone between the surfaces caused by an interdigitation of a finefibrillar structure at the nano-scale, whereas, for the spin-coated cellulose surfaces on the PDMS backing, there isa more direct adhesive failure. The results have generated understanding of the interaction between cellulose-rich materials, which helps design new, advanced cellulose-based materials. The results also show thecomplexity of the interaction between these surfaces and that earlier mechanisms, based on macroscopic materialtesting, are simply not adequate for molecular tailoring.

Despite extensive research on biobased and fiber-basedmaterials, fundamental questions regarding the molecular processesgoverning fiber−fiber interactions remain unanswered. In this study, weintroduce a method to examine and clarify molecular interactions withinfiber−fiber joints using precisely characterized model materials, i.e.,regenerated cellulose gel beads with nanometer-smooth surfaces. Byphysically modifying these materials and drying them together to createmodel joints, we can investigate the mechanisms responsible for joiningcellulose surfaces and how this affects adhesion in both dry and wet statesthrough precise separation measurements. The findings reveal a subtlebalance in the joint formation, influencing the development ofnanometer-sized structures at the contact zone and likely inducingbuilt-in stresses in the interphase. This research illustrates how model materials can be tailored to control interactions betweencellulose-rich surfaces, laying the groundwork for future high-resolution studies aimed at creating stiff, ductile, and/or tough jointsbetween cellulose surfaces and to allow for the design of high-performance biobased materials.

The nano- to microscale structures at the interface between materials can define the macroscopic material properties. These structures are extremely difficult to investigate for complex material systems, such as cellulose-rich materials. The development of new model cellulose materials and measuring techniques has opened new possibilities to resolve this problem. We present a straightforward approach combining micro-focusing grazing-incidence small-angle X-ray scattering and atomic force microscopy (AFM) to investigate the structural rearrangements of cellulose/cellulose interfaces in situ during drying. Based on the results, we propose that molecular interdiffusion and structural rearrangement play a major role in the development of the properties of the cellulose/cellulose interphase; this model is representative of the development of the properties of joint/contact points between macroscopic cellulose fibers.