Multifunctional coatings that adhere to chemically distinct substrates are vital in many industries, including automotive, aerospace, shipbuilding, construction, petrochemical, biomedical, and pharmaceutical. We design well-defined, nearly monodisperse microgels that integrate hydrophobic dopamine methacrylamide monomers and hydrophilic zwitterionic monomers. The dopamine functionalities operate as both intraparticle cross-linkers and interfacial binders, respectively providing mechanical strength of the coatings and their strong adhesion to different substrates. In tandem, the zwitterionic moieties enable surface hydration to empower antifouling and antifogging properties. Drop-casting of microgel suspensions in ambient as well as humid environments facilitates rapid film formation and tunable roughness through regulation of cross-linking density and deposition conditions.
Fundamental understanding of rigid particle indentation into soft elastic substrates has been elusive for decades. In conventional heterogeneous and multicomponent systems, the ill-defined interplay between elastic and capillary forces has confounded explanation of the crossover region between the classical wetting and adhesion regimes. Herein, we study the indentation behavior of micrometer-sized silica particles on supersoft, solvent-free PDMS elastomers with brush-like network strands. By varying the side chain grafting density and the crosslinking density of the networks, we control their elastic modulus from ∼1 to 100 kPa without adding solvent. This isostructurally regulated balance between elastic and capillary forces allows for accurate mapping of the entire range of particle− substrate interactions by measuring indentation depth as a function of substrate stiffness and particle radius. A generalized theoretical model, accounting for the collaborative contribution of both forces to the system free energy, demonstrates excellent quantitative agreement with our experimental results as well as with results of computer simulation for particles in contact with soft surfaces.
Knowledge of the
work of adhesion and surface tension directs the
design of new materials for coatings, adhesives, and lubricants. We
develop an approach to determine both properties from analysis of
equilibrium indentations of rigid particles in contact with soft polymeric
materials. In accord with coarse-grained molecular dynamics simulations,
the indentation depth is described by the crossover expression combining
together the adhesion and wetting models, which takes into account
both the elastic energy of the contact and full surface free energy
change outside and inside the contact area. The crossover expression
is applied to obtain the work of adhesion and substrate surface tension
for polystyrene (PS), carboxyl-modified polystyrene (PS-COOH), and
poly(methyl methacrylate) (PMMA) particles in contact with poly(dimethylsiloxane)
(PDMS) networks made of brush-like and linear chains. This analysis
results in the work of adhesion W = 48.0 ± 2.9
mN/m for PS/PDMS, W = 268.4 ± 27.0 mN/m for
PS-COOH/PDMS, and W = 56.2 ± 2.4 mN/m for PMMA/PDMS
and the surface tension of the PDMS substrate to be γs = 23.6 ± 2.1 mN/m.
This paper describes the synthesis, swelling behavior, and applications of well-defined narrowly dispersed zwitterionic (ZW) microgels prepared by dispersion polymerization in aqueous media. Microgel stability was achieved through precise control of the dispersant composition, timely addition of a cross-linker after the nucleation stage, and the utilization of ionic initiators. Dispersion polymerization allowed for incorporation of both hydrophilic and hydrophobic comonomers, including acrylamide (AAm) and dopamine methacrylamide (Dopa-MA). The broad variety of compositions created many opportunities for practical applications such as encapsulation of mineral acids and synthesis of metal nanoparticles. The swelling behavior of ZW-co-AAm microgels in 6 M HCl was particularly interesting: whereas ZW moieties remained stable in contact with the strong acid, the amide groups underwent hydrolysis to carboxylic acid, resulting in microgel contraction and acid release. Zw-co-Dopa-MA microgels were employed as particulate microreactors, where the ZW moieties played a role of an osmotic pump delivering Ag ions to the DOPA moieties for conversion to silver nanoparticles uniformly dispersed inside the microgel particles.
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