國立高雄大學圖資館 |

Improving the world one monomer at a time: In silico and on silica investigations of polymerization reactions and polymers /

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Improving the world one monomer at a time: In silico and on silica investigations of polymerization reactions and polymers /Annemieke Irene van Dam-Engelbert.
作者:	van Dam-Engelbert, Annemieke Irene,
面頁冊數:	1 electronic resource (201 pages)
附註:	Source: Dissertations Abstracts International, Volume: 85-12, Section: B.
附註:	Advisors: Zuilhof, Han; Smulders, Maarten.
Contained By:	Dissertations Abstracts International85-12B.
標題:	Polymers.
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=31472664
ISBN:	9798382828930

Improving the world one monomer at a time: In silico and on silica investigations of polymerization reactions and polymers /
van Dam-Engelbert, Annemieke Irene,

Improving the world one monomer at a time: In silico and on silica investigations of polymerization reactions and polymers /Annemieke Irene van Dam-Engelbert. - 1 electronic resource (201 pages)

Source: Dissertations Abstracts International, Volume: 85-12, Section: B.

Surface modification is often used to enhance or adapt surface properties. In printing industries, heavily fluorinated materials are often applied as antifouling coating to prevent polymeric fouling of printhead nozzles. Such heavily fluorinated materials are toxic and will soon be prohibited in the European Union. A less toxic alternative is thus desired. Moreover, the durability of such a coating could be improved by rendering these coatings self-healing. In chapter 1 of this thesis, the current status of the field is explored. A general overview of grafting techniques for coatings is provided, and various polymerization techniques are discussed with a focus on polymer brushes. More specifically, antifouling and self-healing coatings are discussed. On the topic of bulk polymers, we touch upon dynamic covalent chemistry, SuFEx polymerization, and natural polymers such as lignin. A brief summary of the history of DFT and its current use, is provided as well. In chapter 2 of this thesis, the self-healing and antifouling properties of a range of partially fluorinated polymer brushes are reported. Eleven methacrylates are selected with linear side chains with varying degree of fluorination. After synthesis of six of the methacrylates, polymer brushes of all monomers are made by surface-initiated atom transfer radical polymerization (SI-ATRP). Characterization of the coatings is done with static contact angle measurements, ellipsometry, AFM and XPS, and the antifouling property of each coating is evaluated with confocal fluorescence microscopy. As expected, the polymer brushes with fully fluorinated side chains, be it short, medium or long, show excellent antifouling ability. With a decrease in the degree of fluorination, the antifouling capability decreases as well. Remarkably, the non-fluorinated side chains perform significantly better than their singly fluorinated counterparts. A correlation between the antifouling ability and the minimal surface tension of the polymer brushes is established. Furthermore, the self-healing ability is determined by repeated exposure to pH 3 solutions and a 120 °C atmosphere. Under these conditions, all coatings are found to be fully self-healing. Additionally, no damage is observed in the self-healing experiments of the longest non-fluorinated brushes. To investigate the remarkable performance of the longest non-fluorinated side chain, we test a range of fluorine-free polymer brushes in the work described in chapter 3. Synthesis, polymerization, characterization and self-healing performance testing is similar to the work described in chapter 2. Polymer brushes with linear side chains of seven or less carbons display reversible damage, while polymer brushes with linear side chains of nine or more carbons are unharmed by repeated pH 3 exposure. We propose that longer side chains can pack tightly, preventing H3O + reaching the ester bonds in the backbone of the polymer chain. Shorter chains cannot pack tightly enough, therefore acidic hydrolysis of the backbone will occur. To further support this hypothesis, we observe that coatings derived from polymers with branched side chains show reversible damage. Overall, the work in this chapter provides a promising basis for how fluorine-free coatings could still be made antifouling and/or self-healing.

English

ISBN: 9798382828930Subjects--Topical Terms:

188330
Polymers.

Improving the world one monomer at a time: In silico and on silica investigations of polymerization reactions and polymers /
LDR:04772nmm a22003973i 4500 001 676357
005 20250420214350.5
006 m o d
007 cr|nu||||||||
008 250901s2024 miu||||||m |||||||eng d
020 $a 9798382828930
035 $a (MiAaPQD)AAI31472664
035 $a (MiAaPQD)Wageningen629804
035 $a AAI31472664
040 $a MiAaPQD $b eng $c MiAaPQD $e rda
100 1 $a van Dam-Engelbert, Annemieke Irene, $e author. $3 990153
245 1 0 $a Improving the world one monomer at a time: In silico and on silica investigations of polymerization reactions and polymers / $c Annemieke Irene van Dam-Engelbert.
264 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 2024
300 $a 1 electronic resource (201 pages)
336 $a text $b txt $2 rdacontent
337 $a computer $b c $2 rdamedia
338 $a online resource $b cr $2 rdacarrier
500 $a Source: Dissertations Abstracts International, Volume: 85-12, Section: B.
500 $a Advisors: Zuilhof, Han; Smulders, Maarten.
502 $b Ph.D. $c Wageningen University and Research $d 2024.
520 $a Surface modification is often used to enhance or adapt surface properties. In printing industries, heavily fluorinated materials are often applied as antifouling coating to prevent polymeric fouling of printhead nozzles. Such heavily fluorinated materials are toxic and will soon be prohibited in the European Union. A less toxic alternative is thus desired. Moreover, the durability of such a coating could be improved by rendering these coatings self-healing. In chapter 1 of this thesis, the current status of the field is explored. A general overview of grafting techniques for coatings is provided, and various polymerization techniques are discussed with a focus on polymer brushes. More specifically, antifouling and self-healing coatings are discussed. On the topic of bulk polymers, we touch upon dynamic covalent chemistry, SuFEx polymerization, and natural polymers such as lignin. A brief summary of the history of DFT and its current use, is provided as well. In chapter 2 of this thesis, the self-healing and antifouling properties of a range of partially fluorinated polymer brushes are reported. Eleven methacrylates are selected with linear side chains with varying degree of fluorination. After synthesis of six of the methacrylates, polymer brushes of all monomers are made by surface-initiated atom transfer radical polymerization (SI-ATRP). Characterization of the coatings is done with static contact angle measurements, ellipsometry, AFM and XPS, and the antifouling property of each coating is evaluated with confocal fluorescence microscopy. As expected, the polymer brushes with fully fluorinated side chains, be it short, medium or long, show excellent antifouling ability. With a decrease in the degree of fluorination, the antifouling capability decreases as well. Remarkably, the non-fluorinated side chains perform significantly better than their singly fluorinated counterparts. A correlation between the antifouling ability and the minimal surface tension of the polymer brushes is established. Furthermore, the self-healing ability is determined by repeated exposure to pH 3 solutions and a 120 °C atmosphere. Under these conditions, all coatings are found to be fully self-healing. Additionally, no damage is observed in the self-healing experiments of the longest non-fluorinated brushes. To investigate the remarkable performance of the longest non-fluorinated side chain, we test a range of fluorine-free polymer brushes in the work described in chapter 3. Synthesis, polymerization, characterization and self-healing performance testing is similar to the work described in chapter 2. Polymer brushes with linear side chains of seven or less carbons display reversible damage, while polymer brushes with linear side chains of nine or more carbons are unharmed by repeated pH 3 exposure. We propose that longer side chains can pack tightly, preventing H3O + reaching the ester bonds in the backbone of the polymer chain. Shorter chains cannot pack tightly enough, therefore acidic hydrolysis of the backbone will occur. To further support this hypothesis, we observe that coatings derived from polymers with branched side chains show reversible damage. Overall, the work in this chapter provides a promising basis for how fluorine-free coatings could still be made antifouling and/or self-healing.
546 $a English
590 $a School code: 2157
650 4 $a Polymers. $3 188330
650 4 $a Hydrocarbons. $3 224671
650 4 $a Recycling. $3 990154
650 4 $a Perfluorocarbons. $3 990155
650 4 $a Fluorine. $3 208579
650 4 $a Polymerization. $3 190507
650 4 $a Chemical bonds. $3 194338
650 4 $a Fluorides. $3 646937
650 4 $a Materials science. $3 221779
650 4 $a Polymer chemistry. $3 708579
650 4 $a Organic chemistry. $3 708640
690 $a 0490
690 $a 0495
690 $a 0794
710 2 $a Wageningen University and Research. $3 915573
720 1 $a Zuilhof, Han $e degree supervisor.
720 1 $a Smulders, Maarten $e degree supervisor.
773 0 $t Dissertations Abstracts International $g 85-12B.
790 $a 2157
791 $a Ph.D.
792 $a 2024
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=31472664