4. Preparation of the Stimuli-Responsive ZnS/PNIPAM Hollow Spheres
1.3 Introduction of stimuli response polymer
1.3.2 PH responsive polymers
A pH-responsive conformation with solubility changes is common behavior in biopolymers. The pH-responsive polymers consist of ionizable pendants that can accept and donate protons in response to the environmental change in pH. As the environmental pH changes, the degree of ionization in a polymer bearing weakly ionizable groups is dramatically altered at a specific pH that is called pKa. This rapid change in net charge of pendant groups causes an alternation of the hydrodynamic volume of the polymer chains. The transition from collapsed state to expanded state is
explained by the osmotic pressure exerted by mobile counterions neutralizing the network charges [88]. The polymers containing ionizable groups in their backbone form polyelectrolytes in the aqueous system. There are two types of pH-responsive polyelectrolytes; weak polyacids and weak polybases. The representative acidic pendant group of weak polyacids is the carboxylic group. Weak polyacids such as poly(acrylic acid) (PAAc) accept protons at low pH and release protons at neutral and high pH. [89]
The same group also prepared diblock copolymers that formed two types of
micelles in aqueous solution depending on pH.[90–92] These resulting states were
described as ‘schizophrenic’ since by changing external pH, temperature or ionic
strength the more hydrophilic block could be transformed to a hydrophobic state in
order to form the core of a micelle. By altering pH again, the second block became
hydrophobic, effectively switching the micelle. The key to this behaviour was in
choosing the correct polymer block components (Figure 1-33): the use of
poly(4-vinylbenzoic acid) (pKa =7.1) as one block and
poly(2-N-(morpholino)ethylmethacrylate) (pKa of the conjugate acid = 4.9) ensured
that precipitation did not occur during pH variation across the isoelectric point.
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Figure 1-1. Structure of 2:1 layered silicates.
Figure 1-2. Scheme of effect of cationic exchange on interlayer spacing.
Figure 1-3. Chemical structures of the surfactants used to prepare the modified clays. [15]
Figure 1-4. (a) Chemical structure of organic clay 10A, in which HT is hydrogenated tallow with ~65% C18, ~30% C16, and ~5% C14. (b) Chemical structure of organic
clay VB16. [21]
Figure 1-5. Schematic representation of various methods used to prepare polymer-layered-silicate nanocomposites. [30]
Figure 1-6. Preparation of polytetrahydrofuran/montmorillonite clay nanocomposites by in situ cationic ring opening polymerization. [32]
Figure 1-7. (a) Azide-functionalized montmorillonite clay and its “Click” reactions with propargyl methacrylate and (b) Alkyne-functionalized olytetrahydrofuran. [32]
Figure 1-8. The synthesis of the photoiniferter procgress. [36]
Figure 1-9. The concept of in situ living polymerization from the silicateanchored photoiniferter. [36]
Figure 1-10. The preparation of block copolymers by sequential addition of monomers. [36]
Figure 1-11. Schematically illustration of three different types of thermodynamically achievable polymer/layered silicate nanocomposites.
Figure 1-12. TGA curves for polystyrene, PS, and the nanocomposites. [37]
Figure 1-13. Peak heat release rates for polystyrene and the three nanocomposites.
[37]
Figure 1-14. PS and PS/clay nanocomposites after dimension stability test. Clay loading
Figure 1-15. Formation of tortuous path in PLS nanocomposites.
Figure 1-16. Relative gas permeability versus clay loading for polymer/clay nanocomposites per the model be Nielsen. The different curves represent aspect ratios
of 50, 100, 150, and 200 for series 1–4 respectively.
Figure 1-17. Storage modulus of (a) pure PS, (b) PS/MMT-1, (c) PS/MMT-2 and (d)
PS/MMT-3.
Figure 1-18. Tanδ values of (a) pure PS, (b) PS/MMT-1, (c) PS/MMT-2 and (d) PS/MMT-3.
Figure 1-19. (a) Tensile strengths, (b) Young’s modulus and (c) elongations at break of PS/MMT nanocomposites. [49]
Figure 1-20. Schematic illustration of formation of hydrogen bonds in N6/MMT nanocomposite.
Figure 1-21. Effect of clay content on tensile modulus in case of N6/OMLS nanocomposites prepared via melt extrusion. [50]
Figure 1-22. Schematic illustration of the density of states in metal and semiconductor clusters. [53]
Figure 1-23. Idealized density of states for one band of a semiconductor structure of 3, 2, 1, and “0” dimensions. (In the 3d case the energy levels are continuous, while in the
“0d” or molecular limit the levels are discrete) [56]
(a) The Zinc-blend Structure (Cubic ZnS or β-ZnS)
(b) The Wurtzite Structure (Hexagonal ZnS or α-ZnS)
Figure 1-24. Structures of the ZnS crystals (a) cubic phase and (b) hexagonal phase.
Figure 1-25. Quantum confinement effect of the electrons and the photons.
Figure 1-26. Configuration coordiance diagrams of the phosphor.
Figure 1-27. Energy transformation diagram of the excitation energy.
Figure 1-28. Progress of the relaxation.
Figure 1-29. Diagram of the Stokes shift.
Figure 1-30. Influence of the different coupling effect on width of the emission peaks.
Figure 1-31. Potential stimuli and responses of synthetic polymers.
Figure 1-32. Schematic of ‘smart’ polymer response with temperature.
Figure 1-33. Control of micellar states dependent on pH.