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Title: Segregation of mass at the periphery of N -isopropylacrylamide-co-acrylic-acid microgels at high temperatures

Journal Article · · Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics
 [1];  [2];  [1];  [3];  [4];  [1];  [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Shinsegae International, Seoul (South Korea)
  4. Hanyang Univ., Gyeonggi (South Korea)

Here, we investigate poly(N-isopropylacrylamide) (pNIPAM) microgels randomly copolymerized with large mol % of protonated acrylic acid (AAc), finding that above the lower critical solution temperature the presence of the acid strongly disrupts pNIPAM's collapse, leading to unexpected new behavior at high temperatures. We see a dramatic increase in the ratio between the radius of gyration and the hydrodynamic radius above the theoretical value for homogeneous spheres, and a corresponding increase of the network length scale, which we attribute to the presence of a heterogeneous polymer distribution that forms due to frustration of pNIPAM's coil-to-globule transition by the AAc. Finally, we analyze this phenomenon using a Debye-Bueche-like scattering contribution as opposed to the Lorentzian term often used, interpreting the results in terms of mass segregation at the particle periphery.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-00OR22725; 50603-DNI7
OSTI ID:
1265870
Alternate ID(s):
OSTI ID: 1222430
Journal Information:
Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics, Vol. 92, Issue 3; ISSN 1539-3755
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

References (16)

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Surface grafting of thermoresponsive microgel nanoparticles journal January 2011
Effect of Cross-Link Density on the Internal Structure of Poly( N -isopropylacrylamide) Microgels journal September 2001
Small-angle neutron scattering study of structural changes in temperature sensitive microgel colloids journal April 2004
Responsive core-shell microgels: Synthesis, characterization, and possible applications journal May 2013
Suppression of Multiple Scattering by Photon Cross-correlation Techniques journal September 1991
On the Structure of Poly( N -isopropylacrylamide) Microgel Particles journal May 2004
Temperature-sensitive poly(N-Isopropyl-Acrylamide) microgel particles: A light scattering study journal November 2008
The diffusion coefficient of a swollen microgel particle journal May 2003
Colloidal nature of star polymer dilute and semidilute solutions journal May 1991
Scattering by an Inhomogeneous Solid journal June 1949
Structural properties of thermoresponsive poly( N -isopropylacrylamide)-poly(ethyleneglycol) microgels journal June 2012
UV Resonance Raman Determination of Molecular Mechanism of Poly( N -isopropylacrylamide) Volume Phase Transition journal April 2009
Microcalorimetric Investigation on the Lower Critical Solution Temperature Behavior of N -Isopropycrylamide- c o -Acrylic Acid Copolymer in Aqueous Solution journal June 2006
Structural modifications in the swelling of inhomogeneous microgels by light and neutron scattering journal November 2002
Investigation on the structure of temperature-responsive N-isopropylacrylamide microgels containing a new hydrophobic crosslinker journal March 2015

Cited By (2)

Synthesis of smart dual-responsive microgels: correlation between applied surfactants and obtained particle morphology journal January 2019
Tuning the Swelling Properties of Smart Multiresponsive Core-Shell Microgels by Copolymerization journal July 2019

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