In this paper, a series of colloidal polymers with various Tg, composition, and sphere size were synthesized by surfactant-free emulsion polymerization and dispersion polymerization methods and then blended with colloidal silica particles to obtain polymer/silica nanocomposite latexes. When these nanocomposite latexes were forced dry at high temperature (e.g., 110℃) for 2h, a three-dimensional ordered porous structure was directly obtained. Neither complex processes nor removal of any templates like in a templating method is needed. These ordered pores should form from the top surface and then propagate layer by layer from the top surface to substrate.

Zirconia (ZrO2) nanocrystals, synthesized from zirconium(IV) isopropoxide isopropanol complex and benzyl alcohol, were dispersed and functionalized in organic solvents using three kinds of bifunctional silane coupling agents (SCAs), 3-glycidoxypropyltrimethoxysilane (GPTMS), 3-aminopropyltriethoxysilane (APTES), and 3-isocyanatopropyltriethoxysilane (IPTES). Completely transparent ZrO2 dispersions were achieved in tetrahydrofuran (THF) with all three SCAs, in pyridine and toluene with APTES and IPTES, and in N,N-dimethylformamide with IPTES. Dynamic laser scattering (DLS) measurements and high-resolution transmission electron microscopical (HRTEM) observation indicated that the ZrO2 nanocrystals are dispersed on a primary particle size level. Fourier transform infrared spectroscopy, solid-state 13C-and 29Si NMR spectroscopy, and thermogravimetric analysis demonstrated that all three SCAs are chemically attached to the surface of the ZrO2 nanoparticles, however, in different bonding modes. Except for GPTMS/ ZrO2/THF dispersion and IPTES/ZrO2/pyridine dispersion, all other transparent dispersions have poor long-term stability. The increasing polarity, due to high amount of APTES attached and high hydrolysis and condensation degree of the bonded APTES, and the aggregation, due to interparticle coupling via the bonded triethoxysilyl group, are the causes of the poor long-term stability for the ZrO2 dispersions with APTES and IPTES, respectively. Nevertheless, the APTES-functionalized ZrO2 precipitates can be deagglomerated in water to get a stable and transparent aqueous ZrO2 dispersion via addition of a little hydrochloric acid.

Transparent zirconia (ZrO2) nanocrystal dispersions in butyl acetate (BAc) or tetrahydrofuran (THF) were prepared by functionalizing zirconia nanocrystals, synthesized from a solvothermal reaction of zirconium (IV) isopropoxide isopropyl alcohol complex in benzyl alcohol, with 3-methacryloxypropyltrimethoxysilane (MPS), and were embedded into UV-curable polyurethane (PU) coatings. It was found that the ZrO2 concentration was the dominating factor influencing the transparency of the ZrO2 dispersion, while the molar ratio of MPS to ZrO2 was rather efficient in adjusting the amount of MPS attached. Phase separation of the ZrO2 nanocrystals in polyurethane coatings was observed, and was strongly related to the MPS-modified ZrO2 (MPS-ZrO2) content and the amount of MPS chemically bonded. The phase separation of the PU/ZrO2 nanocomposite coatings appeared more seriously for higher MPS-ZrO2 content and higher amounts of MPS attached; thus the transparency of the nanocomposite coatings was lower. However, completely transparent PU/ZrO2 nanocomposite coatings could be still achieved even with a ZrO2 content up to 7.5 wt.-% using a ZrO2/BAc dispersion. Improvements in pendulum hardness, microhardness and scratch resistance of the polyurethane coatings via addition of MPS-ZrO2 were demonstrated, but were not remarkable because of the low cross-linking efficiency of the MPS-ZrO2 nanoparticles resulting from the poor compatibility of the MPS-ZrO2 nanoparticles with the pure PU oligomers.

Waterborne adhesives are extremely environment-friendly but unfortunately deficient in mechanical properties. In this article, nanosilica, stemming from tetraethyl orthosilicate (TEOS), silica sol, and/or fumed silica powder, was employed to reinforce the waterborne silylated polyether adhesives. Effects of TEOS content, silica sol content, and the type and content of fumed silica on the shear strength of the adhesive were investigated using a scanning electronic microscope and an electronic instron tester and the strengthening mechanisms of different silica source were discussed. All the shear strengths of silylated polyether adhesives first increased and then decreased as TEOS content, silica sol content or fumed silica content increased. Colloidal silica particles was less efficient than fumed silica particles for reinforcing the polyether adhesive but can increase the shear strength of hydrophobic fumed silica embedded adhesive. Comparing the adhesives with the hydrophilic fumed silica (HS-5) or the extremely hydrophobic fumed silica (TS-720), the adhesive with moderate hydrophobic fumed silica (TS-610) had the highest shear strength. The maximal shear strength of 2.5 MPa was achieved when TEOS, silica sol, and fumed silica were combined. It seemed that TEOS, silica sol, and fumed silica played crosslinking (with polyether chain), dispersing (for fumed silica), and reinforcing roles on waterborne adhesive, respectively. This reinforcing mechanism opened a new way to fabricate waterborne adhesives (or coatings) with high performances.

This paper presents a novel and facile method for the fabrication of nanocomposite films with ordered porous surface structures. In this approach, a water-borne poly(styrene-co-butyl acrylate-co-acrylic acid)/silica nanocomposite dispersion was synthesized in situ by surfactant-free emulsion polymerization by using 3-allyloxy-2-hydroxy-1-propanesulfonate as a polymerizable surfactant. When this dispersion was dried to form a film at a certain temperature, an ordered porous structure could be directly obtained on the surface of the nanocomposite film. SEM, TEM, and AFM were employed to observe the morphology, and XPS and particle analyzer were used to analyze the surface composition of the ordered porous nanocomposite film and the particle size, respectively.