Inorganic and Hybrid

Organic-Inorganic Materials

for Energy Saving

LABORATORIO DI SINTESI DI MATERIALI

INORGANICI

Massimiliano D’Arienzo

Barbara Di Credico

Roberto Scotti

2 0 n m2 0 n m 2 0 n m 2 0 0 n m

1 0 n m

5 0 n m 2 0 0 n m

5 n m0 . 2 µ m 2 0 n m

0 . 2 µ m

2 0 n m

2

Argomenti di tesi

Oxide nanomaterials forphotocatalytic applications and gas sensing

Role of the Structure, Size and Morphology in

Upgrading the Functional Properties and

the Technological applications of Oxide Materials

New nanofillers forrubber reinforcement in tires

In collaboration withPirelli Tyre

Polymeric hybrid materials with dielectric properties

Struttura della tesi

• Functional

properties

• Electronic and magnetic properties

Synthesis ofthe material

Structural & Morphological

characterization

Functionalcharacterization

Oxide nanomaterials forPhotocatalytic application

and sensing

Synthesis

Solvothermal synthesis

Sol-gel synthesis

Characterizations Functional properties& Applications

XRD diffraction, SEM & TEM microscopySurface area

Shape-controlled TiO2

NOx abatement in air

Organic pollutant in water

5

New nanofillers for rubber reinforcement in tires Characterizations Applications

XRD diffraction, SEM and TEM microscopy

In-situ and ex-situsynthesis (sol-gel, hydrothermal)

Stress-strain measurementsViscoelastic properties

Resistenza al rotolamento

Aderenza sul bagnatoResistenza all’abrasione

Aderenza sul bagnato

HD-Silica

Carbon Black

Rolling resistance

Abrasion resistance Wet gripAbrasion resistance

IMMOBILIZED RUBBER

NS-SilSepS9

•Synthesis of shape controlled silica NPs as filler for rubber reinforcement

•Anysotropic filler for rubber reinforcement (Phyllosilicates)

Synthesis

Aim: high-performance rubber composites

•Synthesis of ZnO decorated silica NPs as activator for rubber vulcanization

2 0 n m 5 n m5 0 n m

100 nm100 nm

a) b) c)

d) e) f)

5 n m

d =0.26 nm

S8

curing additives

+

heating

ZnO

SiO2

rubber

•Silica based nanofiller-latex composites for green tyres compounds

Layered silicates in latex natural rubber

TEM

7

Polymeric hybrid materials with dielectric properties

Advanced “molecular” fillers for rubber reinforcement

Nanocomposites enclosing PSQs with controlled cage-like or ladder-like structure and reactivefunctionalities (thiol or methacryl groups), which enable to modulate both the dielectric and thereinforcement properties of the composites

POSS/ladder-like nanounits with tailored structure and highly

reactive functional groups (-SH or methacryl)

0,0 0,2 0,4 0,6 0,8 1,0

0

5

10

15

20

25

30

35

40

0 10 20 30

0,0000

0,0005

0,0010

0,0015

0,0020

0,0025

0,0030

Pore

volu

me / (

cm

3g

-1nm

-1)

Pore diameter / nm

Vo

lum

e a

dso

rbe

d S

TP

(cm

3 g

-1)

Relative pressure (P/P0)

Determination of the specific surface area (BET)

Pore size distribution (BJH)

Thermal decomposition and

weight loss

Other characterization techniques available

TGA-MSNitrogen Physisorption

9

Proprietà elettroniche e magnetiche: Spettroscopia ESR

Vo

O2-

Vo Vo + e-

2 O2 + VO + e- 2 O2

-

SnO2

3250 3300 3350 3400 3450 3500 3550

R=100%

A=52% R=48%

A=39% R=61%

A=80% R=20%

H(Gauss)

A=100%

gain x 10

TiO2 + h → e-CB + h+

VB

Ti4+ + e-CB → Ti3+

O2- + h+VB → O-

TiO2

Ti3+

O- • The type, abundance and

stability of the paramagnetic

centers are relatable to

photocatalytic efficacy and to

the sensing properties

Info about catalytic and

sensing mechanisms