{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/105874"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/105874","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Chemical amplification in self-stiffening materials","abstract":"Self-healing and self-stiffening materials represent bio-inspired materials which can recover and even improve their properties after a damage event ideally without human intervention. These materials are able to utilize a neutral or even harmful environmental stimulus generated in the damage event but very often require the stimulus to be above a threshold level to enable effective property recovery, which may not be always fulfilled especially in the early stage of a damage that leads to stimulus release. In this dissertation, an easily generalizable strategy was proposed to deal with the situation where an above-threshold stimulus is not available: a common self-healing or self-stiffening material can be endowed with the capability of chemical amplification to amplify the initially dilute or localized stimulus. Decoupling these two reactions largely simplifies requirements of synthesizing specific and sometimes complex functionality for sensitive response and allows for myriad combinations of reactions. In Chapter 2, an organic acid amplifier was first used to amplify a below-threshold acid trigger to constructive reactions of functional polymers. The low reactivity and stability of acid amplifier stimulated me to utilize base amplifiers as alternatives which show much better reactivity-stability balance than acid amplifiers. After monitoring of base amplification kinetics in solutions in the absence and presence of functional molecules in Chapter 3, the ability of using base amplification to amplify a dilute or localized base trigger to productive macroscopic material property changes was confirmed in Chapter 4. Base amplification allows for temporal control of gelation of a catechol-bearing polymer solution. A prototype self-stiffening material that is sensitive to a localized base trigger was constructed by incorporating base amplifier and FeCl3 into a catechol-containing polymeric matrix. Systematic studies were also conducted to clarify the effects of base amplifier and FeCl3 contents, shedding a light on designing a self-stiffening material with excellent stiffening performance. In Chapter 5, the feasibility of utilizing base amplification to accelerate base transport was explored in solid and organogel materials by tuning both reaction and diffusion components. Although a constant-velocity wave propagation (x∝t) was not achieved in current systems, a conceptual phase diagram was proposed and may serve as a guide for future research on the propagating chemical wave together with computation input. Chapter 6 pointed out challenges of transforming the prototype self-stiffening material to a practical one and proposed plausible solutions. Other promising applications of base amplifiers were also discussed for future work in this area.","abstract_html":"Self-healing and self-stiffening materials represent bio-inspired materials which can recover and even improve their properties after a damage event ideally without human intervention. These materials are able to utilize a neutral or even harmful environmental stimulus generated in the damage event but very often require the stimulus to be above a threshold level to enable effective property recovery, which may not be always fulfilled especially in the early stage of a damage that leads to stimulus release. In this dissertation, an easily generalizable strategy was proposed to deal with the situation where an above-threshold stimulus is not available: a common self-healing or self-stiffening material can be endowed with the capability of chemical amplification to amplify the initially dilute or localized stimulus. Decoupling these two reactions largely simplifies requirements of synthesizing specific and sometimes complex functionality for sensitive response and allows for myriad combinations of reactions. In Chapter 2, an organic acid amplifier was first used to amplify a below-threshold acid trigger to constructive reactions of functional polymers. The low reactivity and stability of acid amplifier stimulated me to utilize base amplifiers as alternatives which show much better reactivity-stability balance than acid amplifiers. After monitoring of base amplification kinetics in solutions in the absence and presence of functional molecules in Chapter 3, the ability of using base amplification to amplify a dilute or localized base trigger to productive macroscopic material property changes was confirmed in Chapter 4. Base amplification allows for temporal control of gelation of a catechol-bearing polymer solution. A prototype self-stiffening material that is sensitive to a localized base trigger was constructed by incorporating base amplifier and FeCl3 into a catechol-containing polymeric matrix. Systematic studies were also conducted to clarify the effects of base amplifier and FeCl3 contents, shedding a light on designing a self-stiffening material with excellent stiffening performance. In Chapter 5, the feasibility of utilizing base amplification to accelerate base transport was explored in solid and organogel materials by tuning both reaction and diffusion components. Although a constant-velocity wave propagation (x∝t) was not achieved in current systems, a conceptual phase diagram was proposed and may serve as a guide for future research on the propagating chemical wave together with computation input. Chapter 6 pointed out challenges of transforming the prototype self-stiffening material to a practical one and proposed plausible solutions. Other promising applications of base amplifiers were also discussed for future work in this area.","abstract_has_math":false,"creators":["Lai, Shuqi"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Materials Science & Engr","degree_department":null,"school":null,"contributors":["Braun, Paul V","Moore, Jeffrey S","Sottos, Nancy R","Evans, Christopher M"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2019,"date_issued":"2019-11-26T20:58:32Z","date_published":"2019-11-26T20:58:32Z","updated_at":"2026-07-22T22:24:45Z","subjects":["Chemical amplification","sol-gel transition","rheology","self-stiffening"],"languages":["en"],"rights":["Copyright 2019 Shuqi Lai"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/105874","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Braun, Paul V","Moore, Jeffrey S","Sottos, Nancy R","Evans, Christopher M"]},{"key":"dc:creator","label":"Author","values":["Lai, Shuqi"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2019-11-26T20:58:32Z","2021-11-27T10:15:20Z","2019-06-26","2019-08"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Materials Science & Engr"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemical amplification","sol-gel transition","rheology","self-stiffening"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2019 Shuqi Lai"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/105874"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Self-healing and self-stiffening materials represent bio-inspired materials which can recover and even improve their properties after a damage event ideally without human intervention. These materials are able to utilize a neutral or even harmful environmental stimulus generated in the damage event but very often require the stimulus to be above a threshold level to enable effective property recovery, which may not be always fulfilled especially in the early stage of a damage that leads to stimulus release. In this dissertation, an easily generalizable strategy was proposed to deal with the situation where an above-threshold stimulus is not available: a common self-healing or self-stiffening material can be endowed with the capability of chemical amplification to amplify the initially dilute or localized stimulus. Decoupling these two reactions largely simplifies requirements of synthesizing specific and sometimes complex functionality for sensitive response and allows for myriad combinations of reactions. In Chapter 2, an organic acid amplifier was first used to amplify a below-threshold acid trigger to constructive reactions of functional polymers. The low reactivity and stability of acid amplifier stimulated me to utilize base amplifiers as alternatives which show much better reactivity-stability balance than acid amplifiers. After monitoring of base amplification kinetics in solutions in the absence and presence of functional molecules in Chapter 3, the ability of using base amplification to amplify a dilute or localized base trigger to productive macroscopic material property changes was confirmed in Chapter 4. Base amplification allows for temporal control of gelation of a catechol-bearing polymer solution. A prototype self-stiffening material that is sensitive to a localized base trigger was constructed by incorporating base amplifier and FeCl3 into a catechol-containing polymeric matrix. Systematic studies were also conducted to clarify the effects of base amplifier and FeCl3 contents, shedding a light on designing a self-stiffening material with excellent stiffening performance. In Chapter 5, the feasibility of utilizing base amplification to accelerate base transport was explored in solid and organogel materials by tuning both reaction and diffusion components. Although a constant-velocity wave propagation (x∝t) was not achieved in current systems, a conceptual phase diagram was proposed and may serve as a guide for future research on the propagating chemical wave together with computation input. Chapter 6 pointed out challenges of transforming the prototype self-stiffening material to a practical one and proposed plausible solutions. Other promising applications of base amplifiers were also discussed for future work in this area.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2021-08-01","The student, Shuqi Lai, accepted the attached license on 2019-06-24 at 21:23.","The student, Shuqi Lai, submitted this Dissertation for approval on 2019-06-24 at 21:37.","This Dissertation was approved for publication on 2019-06-26 at 11:45.","DSpace SAF Submission Ingestion Package generated from Vireo submission #14075 on 2019-11-26 at 14:00:23","Made available in DSpace on 2019-11-26T20:58:32Z (GMT). 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These materials are able to utilize a neutral or even harmful environmental stimulus generated in the damage event but very often require the stimulus to be above a threshold level to enable effective property recovery, which may not be always fulfilled especially in the early stage of a damage that leads to stimulus release. In this dissertation, an easily generalizable strategy was proposed to deal with the situation where an above-threshold stimulus is not available: a common self-healing or self-stiffening material can be endowed with the capability of chemical amplification to amplify the initially dilute or localized stimulus. Decoupling these two reactions largely simplifies requirements of synthesizing specific and sometimes complex functionality for sensitive response and allows for myriad combinations of reactions. In Chapter 2, an organic acid amplifier was first used to amplify a below-threshold acid trigger to constructive reactions of functional polymers. The low reactivity and stability of acid amplifier stimulated me to utilize base amplifiers as alternatives which show much better reactivity-stability balance than acid amplifiers. After monitoring of base amplification kinetics in solutions in the absence and presence of functional molecules in Chapter 3, the ability of using base amplification to amplify a dilute or localized base trigger to productive macroscopic material property changes was confirmed in Chapter 4. Base amplification allows for temporal control of gelation of a catechol-bearing polymer solution. A prototype self-stiffening material that is sensitive to a localized base trigger was constructed by incorporating base amplifier and FeCl3 into a catechol-containing polymeric matrix. Systematic studies were also conducted to clarify the effects of base amplifier and FeCl3 contents, shedding a light on designing a self-stiffening material with excellent stiffening performance. In Chapter 5, the feasibility of utilizing base amplification to accelerate base transport was explored in solid and organogel materials by tuning both reaction and diffusion components. Although a constant-velocity wave propagation (x∝t) was not achieved in current systems, a conceptual phase diagram was proposed and may serve as a guide for future research on the propagating chemical wave together with computation input. Chapter 6 pointed out challenges of transforming the prototype self-stiffening material to a practical one and proposed plausible solutions. Other promising applications of base amplifiers were also discussed for future work in this area.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2021-08-01","The student, Shuqi Lai, accepted the attached license on 2019-06-24 at 21:23.","The student, Shuqi Lai, submitted this Dissertation for approval on 2019-06-24 at 21:37.","This Dissertation was approved for publication on 2019-06-26 at 11:45.","DSpace SAF Submission Ingestion Package generated from Vireo submission #14075 on 2019-11-26 at 14:00:23","Made available in DSpace on 2019-11-26T20:58:32Z (GMT). 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