Coupling HAADF-STEM Tomography and Image Reconstruction for the Precise Characterization of Particle Morphology of Composite Polymer Latexes

The performance of waterborne polymer–polymer composite materials strongly depends on the particle morphology, but the precise quantitative characterization of complex morphologies is a long-standing problem. In this work, high angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) has been used to obtain a 3D quantitative characterization of the morphology of polymer–polymer particles. The potential of this technique was demonstrated in the study of the effect of process variables (Tg of the seed, type of initiator, and instantaneous conversion of the monomer) on particle morphology during the semicontinuous emulsion copolymerization of styrene and butyl acrylate on methyl methacrylate-rich seeds. This analysis unveiled new mechanisms of morphology development.

[1]  Johannes M. M. Faust,et al.  Dynamic optimization of a two-stage emulsion polymerization to obtain desired particle morphologies , 2019, Chemical Engineering Journal.

[2]  J. Asua,et al.  Experimental validation of a mathematical model for the evolution of the particle morphology of waterborne polymer-polymer hybrids: Paving the way to the design and implementation of optimal polymerization strategies , 2019, Chemical Engineering Journal.

[3]  J. Asua,et al.  Role of Grafting on Particle and Film Morphology and Film Properties of Zero VOC Polyurethane/Poly(meth)acrylate Hybrid Dispersions , 2018, Macromolecular Materials and Engineering.

[4]  D. Sundberg,et al.  Multi-lobed composite polymer nanoparticles prepared by conventional emulsion polymerization , 2017 .

[5]  T. Epicier,et al.  HAADF‐STEM characterization and simulation of nanoparticle distributions in an inhomogeneous matrix , 2017, Journal of microscopy.

[6]  J. Leiza,et al.  Morphology of Composite Polymer Latexes: An Update on Synthesis and Applications, Modeling, and Characterization , 2017 .

[7]  José M. Asua,et al.  A new approach for mathematical modeling of the dynamic development of particle morphology , 2016 .

[8]  Bin Wang,et al.  An efficient strategy for preparation of polymeric Janus particles with controllable morphologies and emulsifiabilities , 2016 .

[9]  J. Asua,et al.  Knowledge-Based Production of Waterborne Hybrid Polymer Materials , 2016 .

[10]  Osama Alaidi,et al.  Electron Tomography: A Three‐Dimensional Analytic Tool for Hard and Soft Materials Research , 2015, Advanced materials.

[11]  T. Guraya,et al.  Film forming hybrid acrylic/ZnO latexes with excellent UV absorption capacity , 2015 .

[12]  J. Asua.  Challenges for industrialization of miniemulsion polymerization , 2014 .

[13]  D Wolf,et al.  Weighted simultaneous iterative reconstruction technique for single-axis tomography. , 2014, Ultramicroscopy.

[14]  X. Ge,et al.  Morphological control of multihollow polymer latex particles through a controlled phase separation in the seeded emulsion polymerization. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[15]  T. Guraya,et al.  High‐Solids‐Content Hybrid Acrylic/CeO2 Latexes with Encapsulated Morphology Assessed by 3D‐TEM , 2013 .

[16]  John G. Tsavalas,et al.  Quantitative measurements of the extent of phase separation during and after polymerization in polymer composites using DSC , 2013 .

[17]  M. Paulis,et al.  UV screening clear coats based on encapsulated CeO2 hybrid latexes , 2013 .

[18]  Christopher Tollan,et al.  Determination of the coalescence temperature of latexes by environmental scanning electron microscopy. , 2012, ACS applied materials & interfaces.

[19]  P. Midgley,et al.  Morphological study of nanoparticle-polymer solar cells using high-angle annular dark-field electron tomography. , 2011, Nano letters.

[20]  Chengyou Kan,et al.  Influences of MAA on the porous morphology of P(St-MAA) latex particles produced by batch soap-free emulsion polymerization followed by stepwise alkali/acid post-treatment. , 2010, Journal of colloid and interface science.

[21]  Ray F. Egerton,et al.  Advances in the Transmission Electron Microscopy of Polymers , 2010 .

[22]  J. Asua,et al.  Morphology of Three-Phase PS/PBA Composite Latex Particles Containing in Situ Produced Block Copolymers , 2010 .

[23]  J. Loos,et al.  Imaging polymer systems with high-angle annular dark field scanning transmission electron microscopy (HAADF−STEM) , 2009 .

[24]  C. A. Rezende,et al.  Molecular mapping by low-energy-loss energy-filtered transmission electron microscopy imaging. , 2009, Analytical chemistry.

[25]  J. Asua,et al.  Evolution of the morphology of HIPS particles , 2009 .

[26]  Shinzo Kohjiya,et al.  Visualization of nanostructure of soft matter by 3D-TEM : Nanoparticles in a natural rubber matrix , 2008 .

[27]  M. Libera,et al.  Dose-limited spectroscopic imaging of soft materials by low-loss EELS in the scanning transmission electron microscope. , 2008, Micron.

[28]  R. Vaia,et al.  Morphology of Layered Silicate− (NanoClay−) Polymer Nanocomposites by Electron Tomography and Small-Angle X-ray Scattering , 2008 .

[29]  D. Sundberg,et al.  Core-shell and other multiphase latex particles—confirming their morphologies and relating those to synthesis variables , 2008 .

[30]  J. Asua,et al.  Morphology control in polystyrene/poly(methyl methacrylate) composite latex particles , 2007 .

[31]  H. Kawaguchi,et al.  Impact of initiators in preparing magnetic polymer particles by miniemulsion polymerization. , 2007, Colloids and surfaces. B, Biointerfaces.

[32]  D. Sundberg,et al.  Nonequilibrium morphology development in seeded emulsion polymerization. V. The effect of crosslinking agent , 2006 .

[33]  D. Sundberg,et al.  Nonequilibrium morphology development in seeded emulsion polymerization. IV. Influence of chain transfer agent , 2006 .

[34]  Shinzo Kohjiya,et al.  Three-Dimensional Morphology of Carbon Black in NR Vulcanizates as Revealed by 3D-Tem and Dielectric Measurements , 2006 .

[35]  Victoria M. Bryg,et al.  Staining Polymers for Microscopical Examination , 2006 .

[36]  W. Ming,et al.  Clay Platelets Encapsulated Inside Latex Particles , 2006 .

[37]  M. Libera,et al.  Diffuse polymer interfaces in lobed nanoemulsions preserved in aqueous media. , 2006, Journal of the American Chemical Society.

[38]  K. Nagayama,et al.  Application of phase contrast transmission microscopic methods to polymer materials , 2005 .

[39]  S. Horiuchi,et al.  Nanoscale Analysis of Polymer Interfaces by Energy-Filtering Transmission Electron Microscopy , 2005 .

[40]  D. Sundberg,et al.  A round robin study for the characterization of latex particle morphology: multiple analytical techniques to probe specific structural features , 2005 .

[41]  D. Sundberg,et al.  Nonequilibrium particle morphology development in seeded emulsion polymerization. III. Effect of initiator end groups , 2004 .

[42]  O. Karlsson,et al.  Nonequilibrium particle morphology development in seeded emulsion polymerization. II. Influence of seed polymer Tg , 2003 .

[43]  Brian F. G. Johnson,et al.  Z-Contrast tomography: a technique inthree-dimensional nanostructural analysis based on Rutherfordscattering , 2001 .

[44]  K. Yase,et al.  Analysis of an interface between an immiscible polymer pair by electron spectroscopic imaging , 1999 .

[45]  K. Yase,et al.  Energy-Filtering Transmission Electron Microscopy for the Characterization of Polymer Blend Morphologies , 1997 .

[46]  Y. Durant,et al.  Thermodynamic and Kinetic Aspects for Particle Morphology Control , 1997 .

[47]  G. Wegner,et al.  Electrically conducting polymers: preparation and investigation of oxidized poly(acetylene) by EFTEM , 1996 .

[48]  J. Asua,et al.  Development of Particle Morphology in Emulsion Polymerization. 3. Cluster Nucleation and Dynamics in Polymerizing Systems , 1996 .

[49]  M. El-Aasser,et al.  Development of morphology in latex particles: The interplay between thermodynamic and kinetic parameters , 1993 .

[50]  M. El-Aasser,et al.  Effect of interfacial phenomena on the development of particle morphology in a polymer latex system , 1991 .

[51]  B. Kronberg,et al.  Morphology development of polymeric microparticles in aqueous dispersions. I. Thermodynamic considerations , 1990 .

[52]  Christian Colliex,et al.  Spectrum-image: The next step in EELS digital acquisition and processing , 1989 .

[53]  A. Yamada,et al.  Estimation of morphology of composite polymer emulsion particles by the soap titration method , 1980 .