In-situ observation of spatial organization of natural rubber latex particles and exploring the relationship between particle size and mechanical properties of natural rubber

Natural rubber (NR), an important source of elastomeric material, has superior comprehensive properties compared to synthetic high cis-1, 4-polyisoprene, which are attributed to its peculiar architecture. However, it is a challenge to identify the precise structure of NR, especially the structure of NR particles, as there are no direct characterization methods to perform in-situ investigation of structure of NR particles at an intact state. In this study, we used cryogenic transmission electron microscopy (cryo-TEM) to directly explore the morphology of NR particles existing in the latex without drying or chemical fixation. Then, the spatial organization of proteins and phospholipids on the surface of NR particles was visualized by stochastic optical reconstruction microscopy (STORM). The results show that NR particles are spherical particles with an average particle size of 88 ± 15 nm, and the exterior of NR particles is a mixed monolayer of proteins and phospholipids (ca. 4.6 ± 0.77 nm in thickness). Thus, a more complete model for the Hevea brasiliensis rubber particles was proposed. Moreover, we explicated the relationship between the particle size of NR particles, molecular characteristics, and mechanical properties of NR. The Mn and Mw of small rubber particles (SRPs) with a particle size of 106 nm are (1.56 ± 0.06) × 106 g/mol and (2.21 ± 0.07) × 106 g/mol respectively, which are much larger than those of the large rubber particles (LRPs) with a particle size of 628 nm (Mn: (0.41 ± 0.05) × 10 6 g/mol; Mw: (1.63 ± 0.10) × 106 g/mol). After vulcanization, the SRPs have better mechanical properties. Compared with LRPs, SRPs exhibit a 4.3-fold increase in tensile strength (from 5.7 to 24.6 MPa) and a 3.5-fold increase in toughness (from 12.9 to 44.9 kJ/m2). This work not only provides rational design for the new biomimetic synthetic rubber with unique hierarchical structures and excellent properties, but also offers a new possibility for tuning the mechanical properties of NR by preparation of LRPs/SRPs blend of various ratios.