DOCSLIB.ORG

Leeds Thesis Template

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Leeds Thesis Template Use of Confinement and Additives to Control Inorganic Crystallization Yunwei Wang Submitted in accordance with the requirements for the degree of Doctor of Philosophy The University of Leeds Faculty of Mathematics and Physical Sciences School of Chemistry March, 2014 - ii - The candidate confirms that the work submitted is his/her own, except where work which has formed part of jointly-authored publications has been included. The contribution of the candidate and the other authors to this work has been explicitly indicated below. The candidate confirms that appropriate credit has been given within the thesis where reference has been made to the work of others. Chapter 3: is based on the paper “A new precipitation pathway for calcium sulfate dihydrate (gypsum) viaamorphous and hemihydrate intermediates Yun-Wei Wang, Yi-Yeoun Kim, Hugo K. Christenson and Fiona C. Meldrum, Chem. Commun., 2012,48, 504-506”. All the experimental work done is attributable to me, under the supervision of Prof. Fiona Meldrum, except the cryo-TEM and Titration work which was done at Eindhoven University. Chapter 4: is based on the paper “Additives stabilize calcium sulfate hemihydrate (bassanite) in solution, Yun-Wei Wang and Fiona C. Meldrum , J. Mater. Chem., 2012,22, 22055-22062”. Chapter 5: is based on the paper “Confinement Leads to Control over Calcium Sulfate Polymorph, Yun-Wei Wang, Hugo K. Christenson and Fiona C. Meldrum , Advanced Functional Materials, Article first published online: 3 JUN 2013”. Chapter 7: is based on the paper “In Situ Study of the Precipitation and Crystallization of Amorphous Calcium Carbonate (ACC), Yun-Wei Wang, Yi- Yeoun Kim, Chris J. Stephens, Hugo K. Christenson and Fiona C. Meldrum, J. Mater. Chem., 2012,22, 22055-22062”. This copy has been supplied on the understanding that it is copyright material and that no quotation from the thesis may be published without proper acknowledgement. - iii - Acknowledgements I would never have been able to finish my thesis without the guidance of my supervisor, group members, help from friends, and support from my family. I would like to express my deepest gratitude to my supervisor, Prof. Fiona Meldrum, for her excellent guidance, caring, patience, and providing me with an excellent atmosphere for doing research. I want to thank you to give me opportunity to study in Leeds and for all the help you gave me during my PhD, especially patiently and careful correcting my bad writing! In addition, I would like to thank all the people from my group. I would like to thank Dr. Yi Yeoun Kim. Thank you for all your help to give the best suggestions during my whole PhD study. And many thanks to Dr Alex Kulak, the good homemade food, snacks and wines. It would have been a lonely lab without him. Furthermore I want to thank my favourite team neighbors, Dr Bram Cantaert and Mr. Johannes Ihli, to chitchat with and start annoying. I also want to thank Anna Schenk and Ciara Mc Nally, the most sweet and pretty girls in our group, and always bring their nice cakes! And of course also Dr. Lukmaan Bawazar, Dr.Bartosz Marzec, Dr.Tony Gong, Dr David Green, Dr. Harvey He, Miss Marie France, Mr. Phillip Lee and Mr William Marchant for their help and interesting talks about all kinds of different subjects. Furthermore I would like to thank the people from Physics, Dr. Hugo Christenson, Dr. Chris Stephens and Mr. James Campbell. My research and papers would not have been possible without their help! I also want to thank all the people from the University of Eindhoven, especially Dr. Nico Sommerdijk for his advice and giving me the opportunity to use Cryo-TEM and Titration. Of course also special thanks to Dr.Paul Bomans, Mr. Vladimir Dmitrović and Miss Juliet Li. - iv - Finally, I would like to thank my parents. They were always supporting me and encouraging me with their best wishes. - v - Abstract This thesis describes the investigation of the three minerals, calcium sulfate, calcium phosphate and calcium carbonate under two bio-inspired methods, additives and confinement. The first experiment in Chapter 3 investigated the precipitation pathway of calcium sulfate above and under the solubility levels. Two metastable phases were obtained at ambient condition, hemihydrate and amorphous calcium sulfate (ACS), that first revealed hemihydrate can be found in room temperature and the existence of ACS. The transformation of ACS to the most stable phase, gypsum via hemihydrate was also proved under the titration and Cryo-TEM at undersaturated solution. Chapter 4 deals with the investigation of calcium sulfate grown in the presence of additives. These additives which have the profound inhibition effect provide another evidence of the existence of hemihydrate and ACS in the ambient conditions. Neglected before in literature, the morphology change of gypsum and hemihydrate also provide an aggregation-based transformation from hemihydrate to gypsum. Similar results were obtained growing calcium carbonate in confinement allowing formation of amorphous calcium carbonate. The results in Chapter 5 also demonstrated that confinement plays a significant role in the formation not only of the amorphous phase, but also the metastable phase, hemihydrate. Results were obtained in the absence and presence of the additives that lead to stabilize hemihydrate and ACS for more than 24 hours. Precipitation of calcium phosphate in confinement in the absence and presence of the additives used the same method as mentioned in the previous chapter. Similar results were obtained and again demonstrated that confinement and additives play a more significant role in bone formation. The last chapter investigated the crystallization pathway of calcium carbonate under UV-Vis at 2-10 mM concentration solutions with/without additives. The in-situ experiment in Chapter 7 provides a simple method to investigate the influence of concentrations of calcium carbonate solution and additives. Amorphous calcium carbonate nanoparticles were formed at early stage which transformed to stable calcite with time. - vi - Table of Contents Acknowledgements........................................................................................ iii Abstract ......................................................................................................... v Table of Contents .......................................................................................... vi List of Tables ................................................................................................ xi List of Figures .............................................................................................. xii Chapter 1 Introduction .................................................................................. 1 1.1 Biomineralization: Life and Crystals .................................................... 2 1.2 Crystallization Concepts ..................................................................... 4 1.2.1 Amorphous Phase and Crystals ................................................. 4 1.2.2 Classical Crystallization ........................................................... 5 1.2.2.1 Nucleation .................................................................... 6 1.2.2.2 Crystal Growth ............................................................. 8 1.2.3 Non-Classical Crystallization .................................................. 10 1.2.3.1 Oriented Attachment ................................................... 10 1.2.3.2 Mesocrystal formation ................................................. 12 1.3 Biological control of crystallization .................................................... 12 1.3.1 Magnesium and Proteins Control Crystal Formation .................. 13 1.3.1.1 Magnesium ions .......................................................... 13 1.3.1.2 Proteins ..................................................................... 14 1.3.2 Control of Biomineral growth in Confined volumes .................. 14 1.3.2.1 Intracellular Vesicles ................................................... 15 1.3.2.2 Cellular assemblies ..................................................... 16 1.3.2.3 Macromolecular frameworks ........................................ 18 1.4. Synthetic Control of Crystal Growth .................................................. 19 1.4.1 Additives control of Crystal Growth ........................................ 19 1.4.1. 1 Simple Ionic Additives ............................................... 22 1.4.1.2 Low Molecular Mass Organic Additives ....................... 22 1.4.1.3 Polymer additives ....................................................... 22 1.4.2 Synthesis in confined reaction spaces ....................................... 23 1.4.2.1. Synthetic Vesicles ...................................................... 24 1.4.2.2. Polymer sponges ........................................................ 24 1.4.2.3. Droplet Arrays ........................................................... 25 - vii - 1.4.2.4. Track-etch membranes ................................................ 26 1.5.2.5. Crossed-cylinders ....................................................... 27 Chapter 2 Experimental Methods ................................................................. 29 2.1 Experimental Preparation .................................................................. 30 2.2 Crystallization .................................................................................. 31 2.2.1 General procedure.................................................................
Load more

Recommended publications
  • Fiona Meldrum to Lead MRS Bulletin Editorial Board
    SOCIETY NEWS Fiona Meldrum to lead MRS Bulletin Editorial Board www.mrs.org/bulletin RS Bulletin recently celebrated its University of London in M 40th anniversary. What started 1998. In 2003, Meldrum as an eight-page newsletter in 1975 has moved to the School of transformed into a widely recognized Chemistry, University of and highly respected publication in ma- Bristol where she remained terials research that serves as a valuable until she joined the benefi t to more than 16,000 members of University of Leeds in 2009. the Materials Research Society. “It’s certainly a great Fiona Meldrum, chair of inorganic privilege to be taking over chemistry at the University of Leeds, has as chair of the editorial accepted the position of chair of the MRS board, and I hope to be able Bulletin Editorial Board. She follows Paul to support the Bulletin team Drzaic, who has served in this role for and all of our volunteers to more than 10 years and was recently ensure that the Bulletin main- Paul Drzaic and Fiona Meldrum elected to the MRS Board of Directors. tains its status as the fl agship “I am quite confident that Fiona will MRS publication,” said Meldrum. “The Webinars, all while maintaining the bring perspective, insight, and energy last few years have seen a range of new quality and prestige of the MRS Bulletin to the position, and successfully lead the innovations, such as the introduction of theme articles. The MRS Bulletin contin- Bulletin into its next phase,” said Drzaic. MRS Bulletin Webinars, and I look forward ues to provide a major benefi t for MRS Meldrum has been an active member to helping the team to continue to develop members, and the greater scientifi c/engi- of MRS for many years, including serving the journal—both in print and online— neering community,” said Drzaic.
    [Show full text]
  • Bio-Inspired Crystallization of Oxide Compounds Within Inorganic Matrices
    BIO-INSPIRED CRYSTALLIZATION OF OXIDE COMPOUNDS WITHIN INORGANIC MATRICES A Dissertation Presented to the Faculty of the Graduate School of Cornell University In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy by Emily Asenath Smith May 2015 © 2015 Emily Asenath Smith BIO-INSPIRED CRYSTALLIZATION OF OXIDE COMPOUNDS WITHIN INORGANIC MATRICES Emily Asenath Smith, Ph. D. Cornell University 2015 The energy crisis facing our planet requires solutions that take an interdisciplinary approach to the improvement of existing energy systems as well as the development of new energy sources. Moreover, the composition of the materials is important: thermally- and chemically-stable materials based on abundant, non-toxic elements are needed to support the sustainability of both the technology and our environment. Biological organisms present multiple examples of hierarchical structures that are optimized for a given function. In particular, biomineralized materials: (i) display crystallographic control across length scales; (ii) are often organic-inorganic composites due to the occlusion of components from the associated organic growth matrix; (iii) and exhibit tailored mechanical properties that are unique to their function. Of great importance to the development of advanced energy materials is the observation that biomineral architectures are built from crystallographically-defined structural elements with interfaces that span multiple length scales. Synthetically, the translation of biological mineralization strategies to oxide compounds is hindered by the low melting temperatures of biopolymer hydrogels that compose extracellular matrices. In order to successfully crystallize oxide compounds using a (bio-inspired) matrix-mediated approach, I had to identify and develop a hydrogel system with thermal stability and chemical compatibility to the growth conditions needed for the oxide.
    [Show full text]
  • Controlled Crystallisation of Calcium Phosphate and Calcium Carbonate Via Bio-Inspired Approaches: Additives and Confinement
    Controlled crystallisation of calcium phosphate and calcium carbonate via bio-inspired approaches: additives and confinement Bram Cantaert Submitted in accordance with the requirements for the degree of Doctor of Philosophy The University of Leeds Faculty of Mathematics and Physical Sciences School of Chemistry May, 2013 The candidate confirms that the work submitted is his/her own, except where work which has formed part of jointly-authored publications has been included. The contribution of the candidate and the other authors to this work has been explicitly indicated below. The candidate confirms that appropriate credit has been given within the thesis where reference has been made to the work of others. “Chapter 4: Concerning Positively Charged Additives and their Effect on Crystallization” is based on the paper “Think Positive: Phase Separation Enables a Positively Charged Additive to Induce Dramatic Changes in Calcium Carbonate Morphology. Bram Cantaert , Yi-Yeoun Kim , Henning Ludwig , Fabio Nudelman ,Nico A. J. M. Sommerdijk , and Fiona C. Meldrum Adv. Func. Mater 22(5), 907-9015”. All the experimental work done is attributable to me, under the supervision of Prof. Fiona Meldrum, except the cryo-TEM work which was done at Eindhoven University by Dr. Fabio Nudelman in cooperation with me. This copy has been supplied on the understanding that it is copyright material and that no quotation from the thesis may be published without proper acknowledgement. © 2013 The University of Leeds and Bram Cantaert i Acknowledgements Could I have done this PhD by myself? Of course not. There would never have been a PhD for Bram if there hadn’t been this lovely woman from Bristol four years ago called Fiona Meldrum.
    [Show full text]
  • Droplet-Based Microfluidics for the Study of Caco3 Crystallisation
    Imperial College London Department of Chemistry Droplet-Based Microfluidics for the Study of CaCO3 Crystallisation Alexandra Yashina June 2012 A thesis submitted in partial fulfillment of the requirement for the degree of Doctor of Philosophy Declaration of Originality Except where specific reference is made, the material contained in this thesis is the result of my own work and has not been submitted in any form for another degree or diploma at this or other university. Alexandra Yashina 2 Abstract Research into the crystallisation of calcium carbonate traverses many disciplines, including chemistry, physics, biology and materials science. Control over the polymorph, hierarchical assembly, orientation, size and shape has been the focus of significant interest in developing new applications. Current synthetic techniques offer limited control over the crystallisation process and often require high temperatures and/or pressures and the use of organic additives and functionalised templates. Microfluidic systems offer superior control over reaction conditions when compared to traditional macroscale methods and hence provide an alternative approach for the synthesis of particles. Not surprisingly, the literature includes hundreds of papers reporting the microfluidic synthesis of nanomaterials. The control provided by microfluidics allows the arrest of a reaction at any particular time, which is hugely advantageous when studying the nucleation and crystallisation of such particles. Moreover, since most biochemical reactions occur in aqueous media, droplet-based microfluidic devices are excellent tools for the miniaturisation of reaction volumes and the simulation of natural or synthetic processes. In the first part of this thesis, custom built droplet-based microfluidic systems are applied to the study of the precipitation of calcium carbonate under highly controlled conditions.
    [Show full text]
  • Fiona Meldrum to Lead MRS Bulletin Editorial Board
    SOCIETY NEWS Fiona Meldrum to lead MRS Bulletin Editorial Board www.mrs.org/bulletin RS Bulletin recently celebrated its University of London in M 40th anniversary. What started 1998. In 2003, Meldrum as an eight-page newsletter in 1975 has moved to the School of transformed into a widely recognized Chemistry, University of and highly respected publication in ma- Bristol where she remained terials research that serves as a valuable until she joined the benefi t to more than 16,000 members of University of Leeds in 2009. the Materials Research Society. “It’s certainly a great Fiona Meldrum, chair of inorganic privilege to be taking over chemistry at the University of Leeds, has as chair of the editorial accepted the position of chair of the MRS board, and I hope to be able Bulletin Editorial Board. She follows Paul to support the Bulletin team Drzaic, who has served in this role for and all of our volunteers to more than 10 years and was recently ensure that the Bulletin main- Paul Drzaic and Fiona Meldrum elected to the MRS Board of Directors. tains its status as the fl agship “I am quite confident that Fiona will MRS publication,” said Meldrum. “The Webinars, all while maintaining the bring perspective, insight, and energy last few years have seen a range of new quality and prestige of the MRS Bulletin to the position, and successfully lead the innovations, such as the introduction of theme articles. The MRS Bulletin contin- Bulletin into its next phase,” said Drzaic. MRS Bulletin Webinars, and I look forward ues to provide a major benefi t for MRS Meldrum has been an active member to helping the team to continue to develop members, and the greater scientifi c/engi- of MRS for many years, including serving the journal—both in print and online— neering community,” said Drzaic.
    [Show full text]
  • University of Florida Thesis Or Dissertation
    MAGNETOELECTRIC COMPOSITE NANOMATERIALS FOR THE STIMULATION OF NEURONAL PROLIFERATION AND DIFFERENTIATION By AMANDA MAE UHL A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2019 © 2019 Amanda Mae Uhl To my Dad ACKNOWLEDGMENTS Firstly, I would like to thank my family for constantly encouraging me to learn and to follow my dreams. I would like to thank both of my parents for instilling in me a sense of perseverance that can only come from facing hardship. To my father (may he rest in peace), for constantly being there and for teaching me that math, science and building things with your own two hands can be both fun and extremely rewarding. And to my mother, for being an inspiration to be both kind and patient. To my little sister, Julie, for being a built in best friend and support system. I would like to thank the teachers I have had who encouraged me to follow my passion for math, science, and engineering. Without them, I would not have had the courage to pursue a bachelor’s degree in engineering. I would also like to thank my undergraduate research advisor, Dr. Lara Estroff, for taking me under her wing and enabling me to discover my passion for research. Without her generosity and advice I would never have considered pursuing a Ph.D. I would also like to thank my friends Moniek and Stephanie who grounded me throughout my undergraduate studies and have greatly influenced the person I am today.
    [Show full text]
  • Invited Speakers Include: Symposium Organizers
    Symposium BI01: Incorporating Sustainability into Materials Science Education, Training and Public Outreach Materials science is central to the sustainable development of new products and processes, from applications spanning clean energy technologies to water purification, to industrial-scale processes that are energy-efficient and benign to the environment and human health. The COVID-19 pandemic has emphasised the importance of materials science and how it scaffolds humanity. Meeting the challenges of sustainable development will require a materials science workforce that is well-educated and trained in the principles of sustainability and how they interface with the broader context of related scientific fields, industrial-scale up, socioeconomics, and policy. Since sustainable technologies must ultimately be adopted by the public to be successful, public perception and outreach are also critical components to enabling a sustainable future. Many of the 17 United Nations Sustainable Development Goals (UN SDGs), which originated at the United Nations Conference on Sustainable Development in 2012, intersect with the field of materials science. The UN SDGs also inform and underpin the research funding landscape, and represent an opportunity for companies, NGO’s and university researchers and educators to contribute to sustainable development. This symposium will bring together materials researchers and educators, industry and sustainability leaders, and science communications and outreach specialists. They will share and explore innovative
    [Show full text]