| 1. |
- Dahlström, Christina
(författare)
-
Quantitative microscopy of coating uniformity
- 2012
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Print quality demands for coated papers are steadily growing, and achieving coating uniformity is crucial for high image sharpness, colour fidelity, and print uniformity. Coating uniformity may be divided into two scales: coating thickness uniformity and coating microstructure uniformity, the latter of which includes pigment, pore and binder distributions within the coating layer. This thesis concerns the investigation of both types of coating uniformity by using an approach of quantitative microscopy.First, coating thickness uniformity was analysed by using scanning electron microscope (SEM) images of paper cross sections, and the relationships between local coating thickness variations and the variations of underlying base sheet structures were determined. Special attention was given to the effect of length scales on the coating thickness vs. base sheet structure relationships.The experimental results showed that coating thickness had a strong correlation with surface height (profile) of base sheet at a small length scale. However, at a large length scale, it was mass density of base sheet (formation) that had the strongest correlation with coating thickness. This result explains well the discrepancies found in the literature for the relationship between coating thickness variation and base sheet structure variations. The total variance of coating thickness, however, was dominated by the surface height variation in the small scale, which explained around 50% of the variation. Autocorrelation analyses were further performed for the same data set. The autocorrelation functions showed a close resemblance of the one for a random shot process with a correlation length in the order of fibre width. All these results suggest that coating thickness variations are the result of random deposition of particles with the correlation length determined by the base sheet surface textures, such as fibre width.In order to obtain fundamental understandings of the random deposition processes on a rough surface, such as in paper, a generic particle deposition model was developed, and systematic analyses were performed for the effects of particle size, coat weight (average number of particles), levelling, and system size on coating thickness variation. The results showed that coating thickness variation3grows with coat weight, but beyond a certain coat weight, it reaches a plateau value. A scaling analysis yielded a universal relationship between coating thickness variation and the above mentioned variables. The correlation length of coating thickness was found to be determined by average coat weight and the state of underlying surfaces. For a rough surface at relatively low coat weight, the correlation length was typically in the range of fibre width, as was also observed experimentally.Non-uniformities within the coating layer, such as porosity variations and binder distributions, are investigated by using a newly developed method: field emission scanning electron microscopy (FESEM) in combination with argon ion beam milling technique. The combination of these two techniques produced extremely high quality images with very few artefacts, which are particularly suited for quantitative analyses of coating structures. A new evaluation method was also developed by using marker-controlled watershed segmentation (MCWS) of the secondary electron images (SEI).The high resolution imaging revealed that binder enrichment, a long disputed subject in the area, is present in a thin layer of a 500 nm thickness both at the coating surface and at the base sheet/coating interface. It was also found that the binders almost exclusively fill up the small pores, whereas the larger pores are mainly empty or depleted of binder.
|
|
| 2. |
- Eivazihollagh, Alireza
(författare)
-
Metal-Chelate Complexes in Alkaline Solution : On Recovery Techniques and Cellulose-based Hybrid Material Synthesis
- 2018
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- For decades, aminopolycarboxylate chelating agents have been extensively used in various industrial applications. The ability of chelating agents to form stable metal-chelate complexes is the main reason for using them to manage metal ions within water-based industrial processes. Considerable quantities of industrial effluent containing chelating agents and heavy metals are produced and often discharged into the environment. The toxicity of heavy metals and the non-biodegradability of the chelating agents, as well as their accumulation in the environment, has become cause for concern. The main purpose of this thesis was to evaluate and develop processes for recovery of chelated metal complexes from aqueous solution. In this regard, the membrane electrolysis technique was evaluated for recovery of copper and aminopolycarboxylic chelating ligands such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), and a surface-active derivative of DTPA, 2-dodecyldiethylenetriaminepentaacetic acid (C12-DTPA) from aqueous solution. By using this method, it was possible to simultaneously recover the chelating ligand for further reuse and collect the metals by electrodeposition, making the process more cost-effective and hindering the discharge of copper ions and chelating ligands as pollutants into the environment. In addition, the ion flotation technique with the chelating surfactant C12-DTPA could be employed to separate metal ions, especially from their dilute solutions, and concentrate them in a foam phase. This is because C12-DTPA has a purpose-built functionality; besides forming strong coordination complexes with metal ions, it is also surface-active and will readily adsorb at air-water interfaces. In this study, C12-DTPA was effectively used in combination with foaming agents for the removal of toxic metal ions such as Cd2+, Zn2+, and Sr2+ from aqueous solution using ion flotation. From an economical perspective, this method could be combined with the membrane electrolysis technique to recover metal and regenerate chelating surfactant so that it can be reused.The present work also shows the synthesis of metal and metal oxide(s) nanoparticles (NPs) in alkaline aqueous solution containing chelated metal ions, in order to fabricate metal NPs–cellulose hybrid materials. Cellulose is the most abundant renewable material, with good mechanical performance and chemical resistivity in a wide range of solvents, which makes it a promising material to support metal NPs. In this respect, we developed a rapid and inexpensive one-pot synthesis of spherical copper NPs in a cellulose matrix. The hybrid material displayed antibacterial properties for both the gram-negative and gram-positive bacteria. The synthesis was further developed by studying the influence of various chelating ligands and surfactants on the NPs’ morphology and chemical composition. According to the results, DDAO, a zwitterionic surfactant, was found to mediate the formation of pure octahedral Cu2O NPs. In addition, a hybrid material film composed of regenerated cellulose and synthesized Cu2O nano-octahedrons was fabricated by spin-coating.
|
|
| 3. |
- Forsberg, Viviane, 1981-
(författare)
-
Liquid-Phase Exfoliation of Two-Dimensional Materials : Applications, deposition methods and printed electronics on paper
- 2019
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- After the unprecedented success of graphene research, other materials that can also be exfoliated into thin layers, like Transition metal dichalcogenides (TMDs) such as molybdenum disulfide (MoS2), have also become the subjects of extensive studies. As one of the most promising methods for large scale production of such materials, liquid-phase exfoliation (LPE) has also been the subject of extensive research and is maturing as a field to the point that devices using additive manufacturing and printed nanosheets are often reported. The stability of the nanosheets in environmentally friendly solvents, particularly in water, with or without stabilizers, is still a focus of great interest for sustainable and commercial production. In this thesis, different methods of LPE in water with and without stabilizers are investigated and discussed. Stabilizers such as surfactant sodium dodecyl sulfate (SDS) and modified cellulose2-hydroxyethyl cellulose (HEC), were employed. Because waterdoes not have surface energy parameters that match those of2D materials, the dispersions in water do not usually have a high yield. Therefore, to circumvent the use of organic solvents that are known to be able to successfully exfoliate and stabilize nanosheets of two-dimensional materials, this thesis focuses on water as the solution-process medium for exfoliation and the assisting stabilizers used to keep the exfoliated nanomaterials in dispersion with a long half-time. Surfactant-assisted dispersions are discussed together with test-printing resultsusing inkjet to deposit the material. Process parameters for the LPE method using HEC as a stabilizer are presented together with thin nanosheets characterized by Raman spectroscopy. Dispersions using HEC presented the longest half-time among the studied methods, higher than previously reported values for methods using mixed low-boiling-point solvents. Devices using exfoliated nanosheets have been fabricated and presented in the present study. The photoconductivity of MoS2 using a device fabricated with LPE MoS2 nanosheets and the cathodoluminescence of LPE MoS2 are discussed. Although fabricated with mechanically exfoliated nanosheets and not LPE ones, another photodetector fabricated with one of the MoS2 grades used in this thesis is presented to highlight the excellent photoresponse of this material. A method of producing thin nanosheets with-out stabilizers by pre-processing the MoS2 grades withs and papers is introduced. With this method, nanosheets with a lateral size of around 200nm and a concentration around 0.14 g L−1 - that is half the concentration at the same processing conditions in solvent n-methyl pyrrolidone (NMP) - are discussed. Inkjet printing as a deposition method is discussed together with the requirements for the 2D inks. Printed organic electronics using the conductive polymer PEDOT:PSS are compared to those using commercially-available graphene ink, with a focus on printing on paper substrates. In order to bring the thesis into perspective from materials to device fabrication, I study the suitability of inkjet paper substrates for printed electronics, by extensively characterizing the chemical and physical properties of their ink-receiving layers (IRLs) and their impact on the electronic properties of the conductive printed lines.
|
|
| 4. |
- Halvarsson, Sören, 1956-
(författare)
-
Manufacture of straw MDF and fibreboards
- 2010
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The purpose of this thesis was to develop an economical, sustainable, and environmentally friendly straw Medium Density Fibreboard (MDF) process, capable of full-scale manufacturing and to produce MDF of requested quality. The investigated straw was based on wheat (Triticum aestivum L.) and rice (Oryzae sativa L.). In this thesis three different methods were taken for manufacture of straw MDF; (A) wheat-straw fibre was blowline blended with melamine-modified urea-formaldehyde (MUF), (B) rice-straw fibre was mixed with methylene diphenyl diisocyanate (MDI) in a resin drum-blender, and (C) wheat-straw fibre was activated in the blowline by the addition of Fenton’s reagent (H2O2/Fe2+) for production of non-resin MDF panels. The MUF/wheat straw MDF panels were approved according to the requirements of the EN standard for MDF (EN 622-5, 2006). The MDI/rice-straw MDF panels were approved according to requirements of the standard for MDF of the American National Standard Institute (ANSI A208.2-2002). The non-resin wheat-straw panels showed mediocre MDF panel properties and were not approved according to the requirements in the MDF standard. The dry process for wood-based MDF was modified for production of straw MDF. The straw MDF process was divided into seven main process steps. 1. Size-reduction (hammer-milling) and screening of straw 2. Wetting and heating of straw 3. Defibration 4. Resination of straw fibre 5. Mat forming 6. Pre-pressing 7. Hot-pressing The primary results were that the straw MDF process was capable of providing satisfactory straw MDF panels based on different types of straw species and adhesives. Moreover, the straw MDF process was performed in pilot-plant scale and demonstrated as a suitable method for producing straw MDF from straw bales to finished straw MDF panels. In the environmental perspective the agricultural straw-waste is a suitable source for producing MDF to avoid open field burning and to capture carbon dioxide (CO2), the biological sink for extended time into MDF panels, instead of converting straw directly into bio energy or applying straw fibre a few times as recycled paper. Additionally, the straw MDF panels can be recycled or converted to energy after utilization. A relationship between water retention value (WRV) of resinated straw fibres, the thickness swelling of corresponding straw MDF panels, and the amount of applied adhesive was determined. WRV of the straw fibre increased and the TS of straw MDF declined as a function of the resin content. The empirical models developed were of acceptable significance and the R2 values were 0.69 (WRV) and 0.75 (TS), respectively. Reduced thickness swelling of MDF as the resin content is increased is well-known. The increase of WRV as a function of added polymers is not completely established within the science of fibre swelling. Fortunately, more fundamental research can be initiated and likely a simple method for prediction of thickness swelling of MDF by analysis of the dried and resinated MDF fibres is possible.
|
|
| 5. |
- Svanedal, Ida, 1979-
(författare)
-
Fundamental Characterization and Technical Aspects of a Chelating Surfactant
- 2014
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The purpose of this study was to investigate the fundamental characteristics of a chelating surfactant in terms of solution behaviour, chelation of divalent metal ions, and interaction in mixtures with different foaming agents and divalent metal ion, as well as examining its prospects in some practical applications. Chelating surfactants are functional molecules, with both surface active and chelating properties, which are water soluble and therefore suitable for chelation in many aqueous environments. The dual functionality offers the possibility to recover the chelating surfactant as well as the metals.The DTPA (diethylenetriaminepentaacetic acid)-based chelating surfactant 4-C12-DTPA (2-dodecyldiethylenetriaminepentaacetic acid) was synthesized at Mid Sweden University. In the absence of metal ions, all eight donor atoms in the headgroup of 4-C12-DTPA are titrating and the headgroup charge can be tuned from +3 to -5 by altering the pH. The solution properties, studied by surface tension measurements and NMR diffusometry, were consequently found strongly pH dependent. pH measurements of chelating surfactant solutions as a function of concentration was used to extract information regarding the interaction between surfactants in the aggregation process.Small differences in the conditional stability constants (log K) between coordination complexes of DTPA and 4-C12-DTPA, determined by competition measurements utilizing electrospray ionization mass spectrometry (ESI-MS), indicated that the hydrocarbon tail only affected the chelating ability of the headgroup to a limited extent. This was further confirmed in hydrogen peroxide bleaching of thermomechanical pulp (TMP) treated with 4-C12-DTPA.Interaction parameters for mixed systems of 4-C12-DTPA and different foaming agents were calculated following the approach of Rubingh’s regular solution theory. The mixtures were also examined with addition of divalent metal ions in equimolar ratio to the chelating surfactant. Strong correlation was found between the interaction parameter and the phase transfer efficiency of Ni2+ ions during flotations. Furthermore, a significant difference in log K between different metal complexes with 4-C12-DTPA enabled selective recovery of the metal ion with the highest log K.The findings in this study contribute to the understanding of the fundamental characteristics of chelating surfactants, which can be further utilized in practical applications.
|
|
| 6. |
- Yang, Jiayi
(författare)
-
Utilization of cellulosic biomass towards sustainable chemicals and novel biomaterials
- 2020
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- It is predicted by the United Nations that by year 2030 the world will need at least 50 percent more food, 45 percent more energy and 30 percent more water. The emissions of carbon dioxide from combustion of fossil fuels and waste are also increasing. At the same time, the demand for natural resources has never been higher and the planet is under unprecedented stress. This increasing awareness and concerns also drive and accelerate the research to facilitate switching the fossil-dependent economy to biobased economy. In this premise, forest industry plays a significant role, from leading the sustainable development to providing more materials to meeting the expanding demand. Moreover, the forest industry is a crucial part of the solution to global warming. The utilization of forest product has a long history, and the efforts of converting the biomass into value-added products or innovative applications have never been more stimulated than now. This thesis presents some examples of the exploration of lignocellulosic biomass based on the fractionation of lipophilic extractives and utilization of non-derivatized cellulose in novel materials.In the first part of thesis, the biorefinery of thermo-mechanical pulping (TMP) process water for lipophilic extractives was investigated as a way to extract the dissolved and colloidal substance (DCS). It was found that induced air flotation (IAF) combined with the foaming agent dodecyl trimethylammonium chloride (DoTAC) can efficiently remove the unwanted lipophilic extractives (Paper I) and retain valuable hemicelluloses (Paper II) in the TMP process water. By applying 80 ppm of DoTAC at a pH of 3.5 and 50 °C with induced air flotation, 94% of the lipophilic extractives were refined from the process water. The efficient biorefining of lipophilic extractives not only enabled the purification of TMP process water, but also facilitate the selective harvesting of hemicelluloses with very low impurities.In the second part of the work, non-derivatized cellulose (sulfite pulp) dissolved in LiOH/urea was used as substrate to fabricate spherical nanocomposite particles (Paper III), pH-responsive nanocomposite films (Paper IV) and crosslinked cellulose hydrogel (Paper V), respectively. The cellulose-chitosan nanocomposite particles were prepared in three different ways: instantly by dripping alkaline cellulose solution into dissolved chitosan in diluted acetic acid, and by mixing and emulsifying the biopolymer solutions to a water-in-oil emulsion, with or without addition of a crosslinking agent. Spherical cellulose-chitosan nanocomposite particles in the size from millimeter to micrometers were successfully prepared. It was demonstrated that some properties of the spherical particles, for example, morphology and size distribution, could be tuned by choosing between the different routes of preparation. In a different application of LiOH/urea dissolved cellulose, in the form of cellulose-chitosan nanocomposite films with pH-responsive swelling, were shown in the thesis. The nanocomposite film with 75% chitosan content exhibited maximum swelling ratio of 1500% and weight loss of chitosan of 55 wt% after 12 hours at pH 3. The utilization of the non-derivatized cellulose continued with cross-linking the macromolecules with methylenebisacrylamide (MBA) to form a robust hydrogel with superior water absorption properties. The cellulose hydrogel cured at 60 °C for 30 minutes, with a [MBA]/[glucose] molar ratio of 1.05, exhibited the highest water swelling capacity absorbing ca. 220 g H2O/g dry weight. This innovative procedure based on the direct dissolution of unmodified cellulose in LiOH/urea followed by MBA cross-linking provides a simple and fast approach to prepare chemically cross-linked cellulose hydrogels of high molecular weight with superior water uptake capacity.
|
|
