Preparation of Polymer/Clay Hybrid Encapsulation for Barrier Applications Controlled by Hansen Solubility Parameters
Total Page:16
File Type:pdf, Size:1020Kb
Preparation of polymer/clay hybrid encapsulation for barrier applications controlled by Hansen Solubility Parameters by Michael Huth A thesis submitted in fulfillment of the requirements for the degree of Doctor of Philosophy in Physics Approved Dissertation Committee Prof. Dr. Veit Wagner Jacobs University Bremen Prof. Dr. J¨urgenFritz Jacobs University Bremen Dr. Odo Wunnicke Evonik Industrie AG Date of Defense: 12.07.2018 Physics & Earth Sciences ii Statutory Declaration Family Name, Given/First Name Huth, Michael Matriculation number 20331540 What kind of thesis are you submitting: Bachelor-, Master- or PhD-Thesis PhD-Thesis English: Declaration of Authorship I hereby declare that the thesis submitted was created and written solely by myself without any external support. Any sources, direct or indirect, are marked as such. I am aware of the fact that the contents of the thesis in digital form may be revised with regard to usage of unauthorized aid as well as whether the whole or parts of it may be identified as plagiarism. I do agree my work to be entered into a database for it to be compared with existing sources, where it will remain in order to enable further comparisons with future theses. This does not grant any rights of reproduction and usage, however. The Thesis has been written independently and has not been submitted at any other university for the conferral of a PhD degree; neither has the thesis been previously published in full. German: Erkl¨arungder Autorenschaft (Urheberschaft) Ich erkl¨arehiermit, dass die vorliegende Arbeit ohne fremde Hilfe ausschließlich von mir erstellt und geschrieben worden ist. Jedwede verwendeten Quellen, direkter oder indirekter Art, sind als solche kenntlich gemacht worden. Mir ist die Tatsache bewusst, dass der Inhalt der Thesis in digitaler Form gepr¨uftwerden kann im Hinblick darauf, ob es sich ganz oder in Teilen um ein Plagiat handelt. Ich bin damit einverstanden, dass meine Arbeit in einer Datenbank eingegeben werden kann, um mit bereits bestehenden Quellen verglichen zu werden und dort auch verbleibt, um mit zuk¨unftigenArbeiten verglichen werden zu k¨onnen.Dies berechtigt jedoch nicht zur Verwendung oder Vervielf¨altigung. Diese Arbeit wurde in der vorliegenden Form weder einer anderen Pr¨ufungsbeh¨ordevorgelegt noch wurde das Gesamtdokument bisher ver¨offentlicht. Date, Signature iii F¨urmeinen Großvater, Adolf Erich Albert Moll “It is a myth that the success of science in our time is mainly due to the huge amounts of money that have been spent on big machines. What really makes science grow is new ideas, including false ideas.” -Karl Raimund Popper, ’The Porcupine: A Pilgrimage to Popper’, The New Yorker (1 Apr 2002) iv Acknowledgment This thesis is part of a cooperated research project between Evonik Industries AG and Jacobs University, Bremen. I am grateful to Evonik Industries AG for funding this research project. This project has given me the opportunity to work multiple working groups and locations in Germany and Taiwan, as well as help me grow with and grow on it. I would like to express my sincere gratitude to Prof. Veit Wagner for constructive discussions, his valuable guidance, and advice. I am grateful for this opportunity to work on this very interesting, multi-continental and multidisciplinary topic. I would like to thank for the huge amount of freedom and trust which you have granted me during my work in Bremen and Taiwan. Firstly, I am sincerely grateful for Prof. J¨urgenFritz and Dr. Odo Wunnicke for kindly agreeing to be members of my dissertation committee. I also would like to thank you, Odo, for your guidance and commitment during my time in your working group in Creavis. Secondly, I would like to extend my gratitude towards Dr. J¨urgen Steiger who initiated this whole opportunity for me in the Evonik CLE in Hsinchu. I would like to express my appreciation to Dr. Jackie Chen for his outstanding work as my supervisor in Evonik CLE. Furthermore, I would like to thank all of my colleagues at Jacobs University and Evonik CLE for their kind support, discussions, and encouragement. As such colleagues, I thank Dr. Vladislav Jovanov, Arne M¨uller,Jonas K¨ohling,Talha Nisar, Xiaoling Zeng, Maike Wirtz, Simon Riechmann, Bj¨orn Gensicke and Xavier Bergamini. Particularly Dr. Torsten Balster for his maintenance of the lab and his job as safety advisor in Prof. Wagner’s workgroup, Bremen. I would like to thank Dr. Tom Wu, for his lab management in Evonik CLE and connections to the laboratories in Industrial Technology Research Institute of Taiwan (ITRI), Hsinchu. Last but not least, I would like to thank Ute Helmboldt-Caesar at the University of Bremen for the unconditional assistance during important sample preparations. I am sincerely grateful for all the support, encouragement and time during these three years of work with friends in both Germany and Taiwan: Isabel Fr¨uhauf,Kay Petzold, Janna Mattern, Danny Humburg, Markus Voight, Anne Wollenberg, Anton Hoffmann, Brian Stamper and Dmitry v Sherstoboev. To Arne Reinsdorf, Laura Donath, Arne and Nina M¨uller,and the whole Hsinchu climbing community, thanks for the climbing trips around the world. Finally, I would like to express my deep gratitude for the support from my dear family and the love and help from my girlfriend, Annie Yujung Li. vi Abstract Barrier materials play important roles in modern food packaging or as a protection of electronics/ metals against water permeation. There are often a combination of permeable and impermeable materials and can be divided into inorganic coatings, multilayer structures or nanocomposites. Impermeable layered materials can play an important role in such composites. Studies have shown that layer materials can have a high impact on nanocomposite-based barrier applications, described by the tortuous path model. This model describes the enhancement of a barrier by increasing the diffusion path of permeant molecules. In nanocomposites, such an increase in the diffusion path is due to the introduced impermeable particles. The increase in diffusion path is influenced by the volume fraction and the geometry of the particles. For such an approach, layer materials have a very advantageous geometry. Belonging to this group of materials, graphene, layered silica, and molybdenum disulfide (MoS2) can be used to reduces water permeation. Layer silicates, such as organophilic fluoromica, are of particular interest due to their optical transparency. But also candidates which absorb light, such as graphene or MoS2, can be of benefit for barrier applications and can in addition change optical performance into the desired direction. Nevertheless, for a high impact, complete delamination (exfoliation) is needed for each particle into separate layers. Furthermore, the particle distribution should be uniformly distributed in the matrix. Exfoliation needs to be energetically favorable, which means that interface interactions must be precisely adjusted between filler and matrix. An energetically favorable system offers high processability, reproducibility and a wide process window for the preparation of such composites. Surface energies evaluation offers a way to identify such favorable systems. Unfortunately, those components are known for just a small number of materials. This lack of information can be avoided by describing surface energies via Hansen solubility parameters (HSP). Those parameters are known for more than 1200 materials like solvents, polymers, and optical absorbing materials, such as graphene or MoS2. I, therefore, have investigated whether it is possible to determine HSP of organophilic fluoromica. For that, I have centrifugated dispersions of fluoromicas and afterward estimate the concentration of filler in solvents by gravimetric analysis. The preparation method, results, and conclusion have shown that experimental determinate HSP are more accurate than those calculated theoretically, using group-contribution approach. Such precise HSP values are important for the prediction of dispersion interactions of those fluoromicas with dispersants and polymers. With the help of Flory-Huggins vii theory, I have shown that HSP are related to the energy costs of exfoliation and are controlling the dispersion quality of fluoromicas. I have shown that experimentally determined HSP can help by the exfoliation of organophilic fluoromica (Somasif mica). Furthermore, I have observed that different modifications of fluoromica, associated with HSP changes and Flory-Huggins (F-H) parameter q have a clear influence on the morphology and delamination of the Somasif mica in chloroform. With reducing q the delamination state improves noticeably. The methods, results, and conclusion have shown that in the case of a high F-H parameter (q > 0.15), aggregated and unstable fluoromica dispersions are obtained. Whereas in the case of F-H parameters near zero, exfoliated and stable fluoromica dispersions are achieved. After evaluating the HSP of organophilic fluoromicas, I have investigated whether such values have an impact on the performance of barrier applications. First, an inorganic coatings/ multilayer structures are prepared from solution processing. The prediction is that dispersants with different HSP values influence the coating quality of an organophilic fluoromica (Somasif MAE). For that MAE samples are dispersed in two different dispersants and cast on a polyurethane acylate to form inorganic coatings and multilayer stacks. The methods, results, and conclusion have shown that in the case of a dispersant with similar