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Studies of Hydrogels and Concentrated Aqueous Ionic Solutions by Optical Kerr Effect
Studies of Hydrogels and Concentrated Aqueous Ionic Solutions by Optical Kerr Effect
Studies of Hydrogels and Concentrated Aqueous Ionic Solutions by Optical Kerr Effect

상세정보

자료유형  
 학위논문 서양
최종처리일시  
20260202104745
ISBN  
9798290651484
DDC  
541.33
저자명  
Van Wyck, Stephen Jedidiah.
서명/저자  
Studies of Hydrogels and Concentrated Aqueous Ionic Solutions by Optical Kerr Effect
발행사항  
[Sl] : Stanford University, 2023
발행사항  
Ann Arbor : ProQuest Dissertations & Theses, 2023
형태사항  
154 p
주기사항  
Source: Dissertations Abstracts International, Volume: 87-01, Section: B.
주기사항  
Advisor: Fayer, Michael.
학위논문주기  
Thesis (Ph.D.)--Stanford University, 2023.
초록/해제  
요약A comprehensive understanding of water and its properties is vital for many Earth processes, ranging from the vast scales of climate and geology to the molecular impact on life. It is essential to have a deep knowledge of water to address critical issues such as climate change, energy, and medicine. This research is specifically focused on two main questions: how water impacts polymer structure and how salt affects water properties.Optical heterodyne-detected optical Kerr effect (OHD-OKE) technique was employed to study the dynamics of the aqueous systems. This technique involves using a polarized pump pulse to align molecules with the electric field, creating temporary birefringence. A probe pulse measures birefringence, which has timing adjusted using a mechanical delay stage, allowing for tracking of the dynamics. OHD-OKE measures the time derivative of the polarizability-polarizability correlation function, detecting only molecules with anisotropic polarizability. This technique is applicable to a wide range of condensed phase materials without relying on resonance or molecular probes.The ultrafast dynamics of acrylamide monomers (AAm), polyacrylamide (PAAm), and polyacrylamide hydrogels (PAAm-HG) in water were investigated using OHD-OKE. Previous measurements showed identical water dynamics for AAm, PAAm, and PAAm-HG at the same acrylamide concentration and uniformly slowed with increasing concentration. In contrast, data from OHD-OKE show that AAm's dynamics occur on distinctly different timescales compared to PAAm and PAAm-HG. In this study, the systems' dynamics slowed with increasing concentration. AAm samples exhibited tetra-exponential decays, mostly following Debye-Stokes-Einstein behavior except at the highest concentration. Low PAAm concentrations displayed a single power law decay, while high PAAm concentrations and all PAAm-HG concentrations exhibited two power laws. PAAm and PAAm-HG displayed nearly identical dynamics at high concentrations, indicating similar chain-chain interactions.The dynamics of concentrated lithium chloride and lithium bromide aqueous solutions were also studied at moderate to high concentrations. There were insufficient water molecules to solvate the ions at the highest concentrations. The dynamics were observed using OHD-OKE experiments, which can capture dynamics across various timescales and signal amplitudes. While pure water decayed biexponentially, LiCl/LiBrwater decays were tetra-exponential at all concentrations. The faster two decays originated from water dynamics, while the slower two decays reflected ion-water network dynamics. The fastest decay was the same as pure water at all concentrations. The second-fastest decay matched pure water at lower concentrations but was slower with increasing concentrations. The slower dynamic, the third- and fourth-time constants, arose from ion-water complexes and an extended ion-water network at the highest concentrations. Comparisons with simulations enabled the assignment of dynamics to specific ion-water structures. The concentration-dependent bulk viscosity and ion-water network dynamics were directly correlated, providing an atomistic-level understanding of viscosity.
일반주제명  
Aqueous solutions
일반주제명  
Receivers & amplifiers
일반주제명  
Polymers
일반주제명  
Chloride
일반주제명  
Electrolytes
일반주제명  
Physical chemistry
일반주제명  
Viscosity
일반주제명  
Hydrogen bonds
일반주제명  
Fourier transforms
일반주제명  
Lasers
일반주제명  
Nuclear magnetic resonance--NMR
일반주제명  
Electric fields
일반주제명  
Water
일반주제명  
Salt
일반주제명  
Lithium
일반주제명  
Hydrogels
기타저자  
Stanford University.
기본자료저록  
Dissertations Abstracts International. 87-01B.
전자적 위치 및 접속  
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MARC

 008260126s2023        us                              c    eng  d
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■00520260202104745
■006m          o    d                
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■020    ▼a9798290651484
■035    ▼a(MiAaPQ)AAI32149743
■035    ▼a(MiAaPQ)Stanfordxc632jn4938
■040    ▼aMiAaPQ▼cMiAaPQ
■0820  ▼a541.33
■1001  ▼aVan  Wyck,  Stephen  Jedidiah.
■24510▼aStudies  of  Hydrogels  and  Concentrated  Aqueous  Ionic  Solutions  by  Optical  Kerr  Effect
■260    ▼a[Sl]▼bStanford  University▼c2023
■260  1▼aAnn  Arbor▼bProQuest  Dissertations  &  Theses▼c2023
■300    ▼a154  p
■500    ▼aSource:  Dissertations  Abstracts  International,  Volume:  87-01,  Section:  B.
■500    ▼aAdvisor:  Fayer,  Michael.
■5021  ▼aThesis  (Ph.D.)--Stanford  University,  2023.
■520    ▼aA  comprehensive  understanding  of  water  and  its  properties  is  vital  for  many  Earth  processes,  ranging  from  the  vast  scales  of  climate  and  geology  to  the  molecular  impact  on  life.  It  is  essential  to  have  a  deep  knowledge  of  water  to  address  critical  issues  such  as  climate  change,  energy,  and  medicine.  This  research  is  specifically  focused  on  two  main  questions:  how  water  impacts  polymer  structure  and  how  salt  affects  water  properties.Optical  heterodyne-detected  optical  Kerr  effect  (OHD-OKE)  technique  was  employed  to  study  the  dynamics  of  the  aqueous  systems.  This  technique  involves  using  a  polarized  pump  pulse  to  align  molecules  with  the  electric  field,  creating  temporary  birefringence.  A  probe  pulse  measures  birefringence,  which  has  timing  adjusted  using  a  mechanical  delay  stage,  allowing  for  tracking  of  the  dynamics.  OHD-OKE  measures  the  time  derivative  of  the  polarizability-polarizability  correlation  function,  detecting  only  molecules  with  anisotropic  polarizability.  This  technique  is  applicable  to  a  wide  range  of  condensed  phase  materials  without  relying  on  resonance  or  molecular  probes.The  ultrafast  dynamics  of  acrylamide  monomers  (AAm),  polyacrylamide  (PAAm),  and  polyacrylamide  hydrogels  (PAAm-HG)  in  water  were  investigated  using  OHD-OKE.  Previous  measurements  showed  identical  water  dynamics  for  AAm,  PAAm,  and  PAAm-HG  at  the  same  acrylamide  concentration  and  uniformly  slowed  with  increasing  concentration.  In  contrast,  data  from  OHD-OKE  show  that  AAm's  dynamics  occur  on  distinctly  different  timescales  compared  to  PAAm  and  PAAm-HG.  In  this  study,  the  systems'  dynamics  slowed  with  increasing  concentration.  AAm  samples  exhibited  tetra-exponential  decays,  mostly  following  Debye-Stokes-Einstein  behavior  except  at  the  highest  concentration.  Low  PAAm  concentrations  displayed  a  single  power  law  decay,  while  high  PAAm  concentrations  and  all  PAAm-HG  concentrations  exhibited  two  power  laws.  PAAm  and  PAAm-HG  displayed  nearly  identical  dynamics  at  high  concentrations,  indicating  similar  chain-chain  interactions.The  dynamics  of  concentrated  lithium  chloride  and  lithium  bromide  aqueous  solutions  were  also  studied  at  moderate  to  high  concentrations.  There  were  insufficient  water  molecules  to  solvate  the  ions  at  the  highest  concentrations.  The  dynamics  were  observed  using  OHD-OKE  experiments,  which  can  capture  dynamics  across  various  timescales  and  signal  amplitudes.  While  pure  water  decayed  biexponentially,  LiCl/LiBrwater  decays  were  tetra-exponential  at  all  concentrations.  The  faster  two  decays  originated  from  water  dynamics,  while  the  slower  two  decays  reflected  ion-water  network  dynamics.  The  fastest  decay  was  the  same  as  pure  water  at  all  concentrations.  The  second-fastest  decay  matched  pure  water  at  lower  concentrations  but  was  slower  with  increasing  concentrations.  The  slower  dynamic,  the  third-  and  fourth-time  constants,  arose  from  ion-water  complexes  and  an  extended  ion-water  network  at  the  highest  concentrations.  Comparisons  with  simulations  enabled  the  assignment  of  dynamics  to  specific  ion-water  structures.  The  concentration-dependent  bulk  viscosity  and  ion-water  network  dynamics  were  directly  correlated,  providing  an  atomistic-level  understanding  of  viscosity.
■590    ▼aSchool  code:  0212.
■650  4▼aAqueous  solutions
■650  4▼aReceivers  &  amplifiers
■650  4▼aPolymers
■650  4▼aChloride
■650  4▼aElectrolytes
■650  4▼aPhysical  chemistry
■650  4▼aViscosity
■650  4▼aHydrogen  bonds
■650  4▼aFourier  transforms
■650  4▼aLasers
■650  4▼aNuclear  magnetic  resonance--NMR
■650  4▼aElectric  fields
■650  4▼aWater
■650  4▼aSalt
■650  4▼aLithium
■650  4▼aHydrogels
■690    ▼a0494
■71020▼aStanford  University.
■7730  ▼tDissertations  Abstracts  International▼g87-01B.
■790    ▼a0212
■791    ▼aPh.D.
■792    ▼a2023
■793    ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17358740▼nKERIS▼z이  자료의  원문은  한국교육학술정보원에서  제공합니다.

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