**3. Experimental results**

SPM images of the surface structure of the synthesized composites with shungit unmodified and modified by organosilanes [9] are shown in **Figures 1**–**4**.

### **Figure 1.**

*SPM image of distribution in the rubber of original schungit. Scan 8.14 × 8.14 μm2 . Left—topography; and right—phase contrast.*

**43**

**Figure 4.**

*Left—topography; and right—phase contrast.*

**Figure 2.**

**Figure 3.**

*10.9 μm2*

*right—phase contrast.*

*Scanning Probe Microscopy of Elastomers with Mineral Fillers*

*SPM image of distribution in the rubber of milled nanoshungit. Scan 4.16 × 4.16 μm2*

*SPM image of distribution in the rubber of milled nanoshungit, modified by organosilane Glymo. Scan 10.9 ×* 

*SPM image of distribution in the rubber of milled nanoshungit, modified by organosilane thiol. Scan 10.9 × 10.9 μm2*

*. Left—topography; and right—phase contrast.*

*. Left—topography; and* 

*.* 

*DOI: http://dx.doi.org/10.5772/intechopen.84554*

*Scanning Probe Microscopy of Elastomers with Mineral Fillers DOI: http://dx.doi.org/10.5772/intechopen.84554*

### **Figure 2.**

*Renewable and Sustainable Composites*

11 Diatomite (nano)

13 Neosyl 120 (nano)

**Table 5.**

(Germany). Kinetics of vulcanization was investigated by analyzer RPA 2000 (Alpha Technologies, England). The mixture optimum curing was determined from obtained graphs. The composition of the synthesized elastomeric materials Ш-940–Ш-948 with taurit, diatomit, and Neosyl-120 fillers is presented in **Table 5**. The study of the obtained samples of composites was carried out on an easyScan scanning probe microscope (Nanosurf, Switzerland), which operated in contact or semicontact modes in air at room temperature [7]. The modulation of force or phase contrast was also used to obtain the material contrasts of the composites under study. The processing of the obtained SPM images was carried out using the computer program SPIP (Image Metrology, Denmark). Scanning electron microscopy (SEM) images of the original Neosyl-120 powders were obtained using the electron microscope Jeol JSM-6510LV. Studies of physico-mechanical properties of the composites with these micro- and nanofillers were conducted on a universal tensile testing machine UTS-10 (Zwick Roell, Germany) and tensile testing machine with a pendulum force meter RMI-60 (ZIM, Tochmashpribor, Russia). The five repetitions for each type in tensile tests were done, and the mean values in the figures are presented. Dimensions of the samples of double-sided composite blades (type 1)

*The composition of the studied rubber mixtures Ш-940–Ш-948 (weight percentage).*

**No Ingredients** Ш**-940** Ш**-941** Ш**-942** Ш**-943** Ш**-944** Ш**-945** Ш**-946** Ш**-947** Ш**-948**

12 Neosyl 120 0 0 0 0 0 0 0 65 0

0 0 0 0 0 0 65 0 0

0 0 0 0 0 0 0 0 65

SPM images of the surface structure of the synthesized composites with shungit

*. Left—topography; and* 

unmodified and modified by organosilanes [9] are shown in **Figures 1**–**4**.

*SPM image of distribution in the rubber of original schungit. Scan 8.14 × 8.14 μm2*

correspond to the drawing and the table of reference [8].

**3. Experimental results**

**42**

**Figure 1.**

*right—phase contrast.*

*SPM image of distribution in the rubber of milled nanoshungit. Scan 4.16 × 4.16 μm2 . Left—topography; and right—phase contrast.*

### **Figure 3.**

*SPM image of distribution in the rubber of milled nanoshungit, modified by organosilane Glymo. Scan 10.9 × 10.9 μm2 . Left—topography; and right—phase contrast.*

### **Figure 4.**

*SPM image of distribution in the rubber of milled nanoshungit, modified by organosilane thiol. Scan 10.9 × 10.9 μm2 . Left—topography; and right—phase contrast.*

### **Figure 5.**

*The graphs of conventional strain-strength properties of studied composites with shungite. Engineering strain (%) are plotted in abscissa and engineering stress (MPa) in ordinates.*

#### **Figure 6.**

*SPM images of the surface structure of rubber composites with (a) taurit (microstructural), scan 1.99 × 1.99 μm<sup>2</sup> , and (b) taurit (nanostructured), scan 3.65 × 3.65 μm2 . Topography on the left, and material contrast on the right.*

**45**

**Figure 8.**

*SEM images of the original "Neosyl-120."*

**Figure 7.**

*2.94 × 2.94 μm2*

*material contrast on the right.*

*Scanning Probe Microscopy of Elastomers with Mineral Fillers*

*SPM images of the surface structure of rubber composites with (a) diatomite (microstructural), scan* 

*. Topography on the left, and* 

*, and (b) diatomite (nanostructured), scan 3.61 × 3.61 μm2*

*DOI: http://dx.doi.org/10.5772/intechopen.84554*

*Scanning Probe Microscopy of Elastomers with Mineral Fillers DOI: http://dx.doi.org/10.5772/intechopen.84554*

**Figure 7.**

*Renewable and Sustainable Composites*

*The graphs of conventional strain-strength properties of studied composites with shungite. Engineering strain* 

*SPM images of the surface structure of rubber composites with (a) taurit (microstructural), scan 1.99 × 1.99 μm<sup>2</sup>*

*. Topography on the left, and material contrast on* 

*(%) are plotted in abscissa and engineering stress (MPa) in ordinates.*

**Figure 5.**

**44**

**Figure 6.**

*the right.*

*and (b) taurit (nanostructured), scan 3.65 × 3.65 μm2*

*SPM images of the surface structure of rubber composites with (a) diatomite (microstructural), scan 2.94 × 2.94 μm2 , and (b) diatomite (nanostructured), scan 3.61 × 3.61 μm2 . Topography on the left, and material contrast on the right.*

**Figure 8.** *SEM images of the original "Neosyl-120."*

*,* 

**Figure 9.** *TEM images of grounded Neosyl-120.*

### **Figure 10.**

*The graphs of conventional strain-strength properties of studied composites with taurit, diatomite, and Neosyl-120. Engineering strain (%) are plotted in abscissa and engineering stress (MPa) in ordinates.*

The graphs of conventional strain-strength properties of these elastomer composites with shungite [9]—are shown in **Figure 5**. These curves are typical ones for each type, corresponding to mean values from five repetitions for tests. Designations SHIKNI and SHIKNM in **Figure 5** mean rubber is filled by original and milled nanoshungit, respectively, and others by nanoshungit, modified by proper organosilanes.

SPM images of the surface structure of the synthesized composites with taurit and diatomit are shown in **Figures 6(a, b)** and **7(a, b)**.

Scanning electron microscopy images of the original Neosyl-120 powder are presented in **Figure 8**. From the data obtained, it is clear that the particle size varies from submicrosized to large, with a size of the order of several hundred micrometers, with the second prevailing. Particles Neosyl-120 have a rough, sometimes porous, and layered structure, which implies a large value of its specific

**47**

*Scanning Probe Microscopy of Elastomers with Mineral Fillers*

surface. However, the large value of the specific surface in this case cannot provide a high interaction area of the filler particles with the elastomeric matrix due to its

Transmission electron microscopy has been used to obtain images of grounded Neosyl-120 particles in high resolution (**Figure 9**). Particle size has a wide distribution and amounts to tens and hundreds of nanometers. The particle morphology is

The physico-mechanical characteristics of the SBR-30ARK styrene-butadiene rubber-based vulcanizates, filled with taurit, diatomit, and Neosyl-120 of varying

Surface topography SPM images and the phase contrast of the composite material allowed to directly visualize the distribution of the fillers in the matrix rubber

Analysis of **Figure 1** revealed the uneven distribution of original micro shungite filler in the rubber matrix. Predominant size of the shungite aggregates remains in the micron region. The distribution of aggregates and agglomerates of milled nanoshungit in the rubber (**Figure 2**) is considerably more homogeneous with a primary particle size of the filler already in the nanometer range. **Figure 3** shows that the use of organosilane Glymo as nanoshungit chemical modifier significantly improves the uniform distribution of the agglomerates and the aggregates in the matrix rubber. The aggregates and agglomerates of nanoshungit modified by organosilane Thiol (**Figure 4**) are distributed more uniformly at the rubber matrix

Analyses of the experimental data allow deducing certain conclusions. Modification of nanoshungit filler by organosilanes significantly improves the quality of rubber compounds. Using the Thiol organosilane, we obtained the highest tensile strength at 5 MPa more than rubber filled with nanoshungit without modification, with the extension not reaching 300%, which shows good mechanical properties of the vulcanizate. Organosilane Glymo sulfur-free showed an increase in rubber tensile strength, but its elongation was over 300%. The use of Si 264 as nanoshungit modifier also showed an increase in elastomer strength about 3 MPa relative to composites filled by nanoshungit without modification. This shows that the modification has been successfully completed. The sample with TESPT showed

Due to using force modulation or phase-contrast modes, separate aggregates and agglomerates of taurit or diatomit in sizes from 100 nm to 1 μm in the elastomeric matrix are visualized by SPM. The form of these aggregates and agglomerates in **Figures 6** and **7** is characterized by a sharp anisotropy of shape and an isolated heterogeneity of the filler particle structure. The images obtained show that in samples with microdispersed taurit or diatomit, the filler forms large inclusions with a size of several micrometers. When grinding the filler, a much more uniform distribution of nanostructured aggregates in the elastomeric matrix is observed. The results of experiments demonstrate also that the dispersity of the filler has a significant effect on tensile behavior of composites. Materials with microdispersed fillers have much lower tensile strength than samples with nanodispersed fillers. When grinding taurit to the nanodispersed phase, the strength of the vulcanizates increased from 3 to 12 MPa, and diatomit from 5 to 13 MPa, respectively. Grinding of particles of the Neosyl-120 products allows increasing the level of interaction of the filler with the elastomeric matrix, which leads to a noticeable improvement in the elastic-strength

degree of dispersion (Ш-940–Ш-948), are presented in **Figure 10**.

*DOI: http://dx.doi.org/10.5772/intechopen.84554*

high structurality.

close to spherical.

**4. Discussion of the results**

SBR-30ARK (**Figures 1**–**4**).

even in comparison with modification by Glymo.

increased elastic-strength properties up to 30%.

*Scanning Probe Microscopy of Elastomers with Mineral Fillers DOI: http://dx.doi.org/10.5772/intechopen.84554*

surface. However, the large value of the specific surface in this case cannot provide a high interaction area of the filler particles with the elastomeric matrix due to its high structurality.

Transmission electron microscopy has been used to obtain images of grounded Neosyl-120 particles in high resolution (**Figure 9**). Particle size has a wide distribution and amounts to tens and hundreds of nanometers. The particle morphology is close to spherical.

The physico-mechanical characteristics of the SBR-30ARK styrene-butadiene rubber-based vulcanizates, filled with taurit, diatomit, and Neosyl-120 of varying degree of dispersion (Ш-940–Ш-948), are presented in **Figure 10**.
