Fine-tuned order-order phase transitions in giant surfactants via interfacial engineering
Wenpeng Shan,
Wei Zhang,
Mingjun Huang,
Yuyang Ji,
Ruimeng Zhang,
Rui Zhang,
Zebin Su,
Hao Liu,
Xueyan Feng,
Dong Guo,
Jiahao Huang,
Tong Liu,
Tao Li,
Jialin Mao,
Chrys Wesdemiotis,
An-Chang Shi,
Stephen Z.D. Cheng
Affiliations
Wenpeng Shan
Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, OH 44325-3909, USA
Wei Zhang
Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, OH 44325-3909, USA; Corresponding authors.
Mingjun Huang
South China Advanced Institute for Soft Matter Science and Technology, School of Molecular Science and Engineering, South China University of Technology, Guangzhou 510640, China
Yuyang Ji
Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, OH 44325-3909, USA
Ruimeng Zhang
Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, OH 44325-3909, USA
Rui Zhang
South China Advanced Institute for Soft Matter Science and Technology, School of Molecular Science and Engineering, South China University of Technology, Guangzhou 510640, China
Zebin Su
Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, OH 44325-3909, USA
Hao Liu
Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, OH 44325-3909, USA
Xueyan Feng
Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, OH 44325-3909, USA
Dong Guo
Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, OH 44325-3909, USA
Jiahao Huang
Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, OH 44325-3909, USA
Tong Liu
Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, OH 44325-3909, USA
Tao Li
X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439, USA; Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA
Jialin Mao
Department of Chemistry, The University of Akron, Akron, OH 44325, USA
Chrys Wesdemiotis
Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, OH 44325-3909, USA; Department of Chemistry, The University of Akron, Akron, OH 44325, USA
An-Chang Shi
Department of Physics and Astronomy, McMaster University, Hamilton, Ontario L8S 4M1, Canada; Corresponding authors.
Stephen Z.D. Cheng
Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, OH 44325-3909, USA; South China Advanced Institute for Soft Matter Science and Technology, School of Molecular Science and Engineering, South China University of Technology, Guangzhou 510640, China; Corresponding author at: Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, OH 44325-3909, USA.
Thermotropic order-order phase transitions (OOTs) in block copolymers are not commonly observed in the strong segregation region. Phase separation of giant surfactants composed of hydrophilic molecular nanoparticles (MNPs) as heads and hydrophobic flexible polymer chains as tails occurs generally in the strong segregation region. By introducing a rigid molecular segment at the junction point of the giant surfactants, the interface between the MNPs and polymer tails could be delicately manipulated, resulting in the occurrence of thermotropic OOTs that are sensitively dependent on the properties of those junction segments. For samples with hydrophilic junction segments, no thermal-induced OOT has been observed. However, for samples with hydrophobic junction segments, complicated thermotropic OOTs between as many as four different ordered phases in a single giant surfactant system, from lamellae (LAM) to hexagonally perforated layer structure (HPL), double gyroids (DG), and finally to hexagonally packed cylinders (HEX), have been observed with increasing temperature. These results demonstrated that interfacial engineering could be used to regulate the self-assemble behavior of macromolecules at the nanometer scales.
