Control of crystallization by polymer additives

Download statistics - Document (COUNTER):

Gindele, Maxim Benjamin: Control of crystallization by polymer additives. Hannover : Gottfried Wilhelm Leibniz Universität, Diss., 2023, VI, 210 S., DOI: https://doi.org/10.15488/13946

Selected time period:

year: 
month: 

Sum total of downloads: 152




Thumbnail
Abstract: 
Understanding how crystallization processes are controlled by polymer additives is relevant for a vastly diverse number of fields, for example in biomineralization, where the morphology of minerals is controlled by proteins or in scale inhibition strategies in industrial plants, in which macromolecules are added to prevent the precipitation of minerals. While numerous investigations have focused on elucidating additive-controlled crystallization, a detailed understanding of the underlying mechanisms is still desired. Herein, based on calcium carbonate as a mineral system, a comprehensive study on the manifold effects of selected polycarboxylate additives on the distinct species along the crystallization pathway is presented. Poly(glutamic acid) and poly(aspartic acid) are chosen as additives, as these polyaminoacids resemble biomineralization-associated peptides, as well as poly(acrylic acid), a commercially used scale inhibitor. Using potentiometric titrations, it is shown that even the basic interaction of polycarboxylates with calcium ions is more complex than commonly assumed. Quantitative determination of the Langmuir parameters of the binding process reveals that higher order effects and contributions arising from the whole polymer chain play a significant role, while the chemistry of the monomer unit constituting the polymer plays a subordinate role. The results put a question mark on whether the binding processes can be accurately described using solely the Langmuir binding model that assumes non-interacting binding sites. The investigation of the following stages of the crystallization pathway reveals that the polymer additives show the largest effect in the stabilization of liquid-like mineral precursors. A key step of this inhibition is the additive-driven binding of bicarbonates. Quantitative evaluation of ion association in the prenucleation regime reveals that more than 20% of bicarbonate species are bound in mineral precursors at pH 9.8, which can also be detected in isolated solid amorphous intermediates. Surprisingly, the protons introduced by bicarbonates are highly mobile, causing the formation of amorphous mineral ion conductors, which opens up possibilities for novel applications of mineral materials. The importance of liquid-like precursors for the mineral formation pathway is still highly debated in the community, and they are often ignored in the explanation of crystal formation. Using a refined gas diffusion method, it is demonstrated that liquid-like precursors show sufficient kinetic stability to be detected, both in presence of polymers and in additive-free systems. Observing the time dependent formation and transformation of the precursors shows that they play an important role in the early stages of crystallization and must be generally considered for the interpretation of gas diffusion experiments. Regarding the technological application of liquid-like minerals, a new and easily scalable synthesis method is presented, which solves existing limitations of the available synthesis methods. The “scalable controlled synthesis and utilization of liquid-like precursors for technological applications” (SCULPT) method effectively allows the isolation of the precursor on a gram scale and to access to the full potential of these mineral precursors for material synthesis. Implementing the gained insights into the current picture of nonclassical mineral formation, which was subject of many advancements in recent years, an updated view on additive-controlled mineralization is presented. The discoveries presented in this work are beneficial for the scientific and industrially-related communities far beyond the field of nucleation and crystallization mechanisms, such as materials chemistry, and improve the understanding of the mechanisms underlying biomineralization and mineral formation in general.
License of this version: CC BY 3.0 DE
Document Type: DoctoralThesis
Publishing status: publishedVersion
Issue Date: 2023
Appears in Collections:Naturwissenschaftliche Fakultät
Dissertationen

distribution of downloads over the selected time period:

downloads by country:

pos. country downloads
total perc.
1 image of flag of Germany Germany 107 70.39%
2 image of flag of United States United States 18 11.84%
3 image of flag of China China 4 2.63%
4 image of flag of Netherlands Netherlands 2 1.32%
5 image of flag of Monaco Monaco 2 1.32%
6 image of flag of Japan Japan 2 1.32%
7 image of flag of Israel Israel 2 1.32%
8 image of flag of United Kingdom United Kingdom 2 1.32%
9 image of flag of Spain Spain 2 1.32%
10 image of flag of United Arab Emirates United Arab Emirates 2 1.32%
    other countries 9 5.92%

Further download figures and rankings:


Hinweis

Zur Erhebung der Downloadstatistiken kommen entsprechend dem „COUNTER Code of Practice for e-Resources“ international anerkannte Regeln und Normen zur Anwendung. COUNTER ist eine internationale Non-Profit-Organisation, in der Bibliotheksverbände, Datenbankanbieter und Verlage gemeinsam an Standards zur Erhebung, Speicherung und Verarbeitung von Nutzungsdaten elektronischer Ressourcen arbeiten, welche so Objektivität und Vergleichbarkeit gewährleisten sollen. Es werden hierbei ausschließlich Zugriffe auf die entsprechenden Volltexte ausgewertet, keine Aufrufe der Website an sich.

Search the repository


Browse