The effect of annealing on the self-organized morphology and component gradient distribution of films prepared from bimodal latexes blend containing 1:1 silicon-containing acrylate copolymer/silicon-free acrylate copolymer blend was studied using attenuated total reflectance–Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscopy with X-ray energy-dispersive (SEM-EDX) spectrometry, and atomic force microscopy (AFM). The distribution of silicon through the whole thickness of the film as a function of annealing was investigated using confocal Raman spectroscopy (CRS). AFM results show that poly(methyl methacrylate-co-n-butyl acrylate) latex fuses to form a continuous film at 25 °C. The wettability of the acrylate components and the heterogeneous composition of poly(3-[tris(trimethylsilyloxy)silyl] propyl methacrylate-co-methyl methacrylate) result in a graded block film. ATR-FTIR and SEM-EDX measurements reveal silicon-containing components segregate at the film–air interface upon annealing. CRS further shows that the nonlinear model gradient distribution of silicon is obtained, where the content of silicon component is enhanced and it gradually varies in the bulk. When the annealing temperature increases to 120 and 180 °C, blend latexes films demonstrate varying topography and phase images, indicating phase separation is induced by annealing. Furthermore, CRS implies that the destruction of the gradient structure is attributed to the phase separation of the two blend components.

In this work, a functional gradient polymeric material derived from silicon-containing acrylate blend emulsion film is prepared in two steps. Firstly, 3-[tris(trimethylsilyloxy)silyl] propyl methacrylate (TRIS)-modified acrylate latex is prepared using multiple emulsifiers by the two-stage semicontinuous emulsion copolymerization method. Next, blend latexes composed of TRIS-containing and TRIS-free acrylate latexes are obtained. Detailed studies on the effects of the film-formation temperature and the glass transition temperature (Tg) differences on the compositional gradient film are conducted. Surface energy analysis shows that silicon elements enriched at the film-air (F-A) interface and Tg differences facilitate the fabrication of silicon gradient in emulsion blend films. Scanning electron microscopy-energy dispersive X-ray further reveals that the concentration of silicon components varies in a gradient-like manner along the overall transaction of the film when the film-formation temperature is 55 °C. However, excessive temperature creates the formation of a segmental gradient distribution of silicon in the emulsion blend films.