Transcript Hybrid SiO2@POSS nanofiller: a promising reinforcing system for

Electronic Supplementary Material (ESI) for Materials Chemistry Frontiers.
This journal is © the Partner Organisations 2017
Supporting Information:
Hybrid SiO2@POSS nanofiller: a promising reinforcing
system for rubber nanocomposites
Massimiliano D’Arienzo*a, Matteo Redaellia, Emanuela Calloneb, Lucia Conzattic, Barbara Di
Credicoa, Sandra Dirèb, Luca Gianninid, Stefano Polizzie, Ilaria Schizzid, Roberto Scottia, Luciano
Tadiellod and Franca Morazzonia
a Dept.
of Materials Science, INSTM, University of Milano-Bicocca, Via R. Cozzi, 55, 20125 Milano,
Italy. Fax: +39-02-64485400 Tel: +39-02-64485023 *E-mail: [email protected]
b “K.
Müller” Magnetic Resonance Lab., Dept. of Industrial Engineering, University of Trento, Via
Sommarive, 9, 38123 Trento, Italy
c Istituto
per lo Studio delle Macromolecole, ISMAC, CNR, Via De Marini 6, 16149 Genova, Italy
d
Pirelli Tyre SpA, Viale Sarca, 222, 20126 Milano, Italy
e
Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari Venezia and Centro di
Microscopia Elettronica “G. Stevanato” Via Torino 155/b, 30172 Venezia-Mestre (Italy)
KEYWORDS: rubber nanocomposites, hybrid materials, POSS, nanofillers
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a)
b)
100
100
60
2940 cm-1
80
Trasmittance (%)
Trasmittance (%)
80
3446 cm-1
1720 cm-1
40
1383
cm-1
20
60
40
20
1630 cm-1
0
4000
1715 cm-1
0
1090 cm-1
3500
3000
2500
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1500
1000
1320
cm-1 1290
cm-1
500
Wavenumber (cm-1)
4000
3500
3000
1165
cm-1
2500
2000
1500
1000
500
Wavenumber (cm-1)
Figure S1. FT-IR spectra of: a) pristine ZnO (black line) and ZnO functionalized with TMMS (ZnOTMMS, red line); b) ZnO-TMMS (red line) and ZnO@POSS-10 (blue line).
Pristine ZnO (Fig. S1a, black line) showed broad absorption bands at 3380 cm-1 and 1550 cm-1 assigned
to the stretching and bending vibration modes of water most likely adsorbed by H-bonding to OH groups
on the surface of ZnO nanoparticles. The other band at 1383 cm-1 in the ZnO sample was considered an
impurity. After reacting ZnO with TMMS, the spectrum (Fig. S1a, red line) revealed the characteristic
absorption bands of the silane. In detail, the weak band at 2940 cm-1 was assigned to the stretching of
C−H vibration, while those at 1725 and at 1085 cm-1 were associated to the vibration of C=O and Si–
O–C bonds of TMMS (i).
In Figure S1b the spectra of ZnO-TMMS (red line) and ZnO@POSS-10 (blue line) are compared.
ZnO@POSS-10 NPs show the bands at 2950 and 2890 cm-1 attributable to the C−H stretching vibrations
of methyl and methylene groups of POSS terminations. The vibrations typical of methacryloxy groups
(ν C=O, ν C=C, ν −C−CO−O−) and the Si–O–C stretching increase in intensity if compared to those
observed in ZnO-TMMS (see inset Fig. S1b).
(i) C. G. Allen, D. J. Baker, J. M. Albin, H. E. Oertli, D. T. Gillaspie, D. C. Olson, T. E. Furtak, R. T.
Collins Langmuir 2008, 24, 13393–13398
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100
Weight loss (%)
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0
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900 1000
Temperature (°C)
Figure S2. TGA curves of pristine SiO2 Rhodia (black line), SiO2-TMMS (blue line) and SiO2@POSS10 (red line) nanoparticles.
Volume adsorbed STP (cm3 g-1)
350
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0
0.0
0.2
0.4
0.6
0.8
1.0
Relative pressure (p/p0)
Figure S3. Adsorption/desorption isotherms at liquid nitrogen temperature for pristine SiO2 Rhodia
NPs. The curve corresponds to a type IV isotherm with capillary condensation in the mesopores.
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SBR/SiO2@POSS-10
SBR/SiO2+POSS-10
SBR/SiO2+POSS-0
SBR/SiO2@POSS-0
Loss Modulus (kPa)
240
200
160
120
80
0
20
40
60
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100
Strain %
Figure S4. Loss modulus (G’’) vs. strain for the uncured composites.
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