In situ functionalization of cellular aluminosilicates

In situ functionalization of cellular

aluminosilicates

Nuno Vitorino

Aveiro Institute of Materials CICECO-DEMaC

University of Aveiro

Materials Science Research & Development Center

Polytechnic Institute of Viana do Castelo

N.Vitorino, In situ functionalization of cellular aluminosilicates, ECERS2015

Ou

tlin

e

1. Introduction

2. Ceramic emulsions preparation

3. Ceramic emulsions processing - Extrusion

4. Cellular ceramics functionalization

5. Conclusions and actual guidelines


1. Introduction

Filtration

Micro

filtration

Ultra

filtration

Nano

filtration

Reverse

osmosis

Absorption

Diesel

filters

Catalysis

suports

Enzymes

immobilization

Ion

exchange

Sensors/

Electrods

Refratories

Bioceramics

-12 -9 -6 -3 0Log (Cavity size / m)

i) Infiltration

ii) Gel casting

iii) Coating

iv) Emulsification

Typical preparation routes:


1. Introduction

• To propose a new method to process large scale

cellular ceramics;

• To promote bulk modification of the cellular monoliths

by hydrothermal route

Objectives:


2. Ceramic emulsions preparation

Slurry

(50%V/V)

Emulsification

1000 rpm, 10 min, 500 cP

Drying

72h, room temperature

Sintering

1200 ºC, 2 h dwell

Melted Paraffin

(M.P.60ºC)

Surfactant

(LAS)

Collagen

(Oxoid)

C. Freitas, N. Vitorino, J.C.C. Abrantes, J.R. Frade, JECS, 35 (2015),971-979


3. Extrusion of ceramic emulsions

N. Vitorino, C. Freitas, M.J. Ribeiro, J.C.C. Abrantes, J.R. Frade, Appl. Clay Sci. 101 (2014) 315

• Plastic behavior ~ ceramic pastes

• The samples with less humidity

have ability to support higher

stress without rupture, but the

plastic deformation range is

shorter

0

0.01

0.02

0.03

0.04

0 15 30 45 60

Str

ess

/ M

Pa

% Deformation

20.1% Water

21.6% Water

23.1% Water



Similar microstructural features with and without extrusion

N. Vitorino, C. Freitas, M.J. Ribeiro, J.C.C. Abrantes, J.R. Frade, Appl. Clay Sci. 105–106 (2015) 60–65

2 h 1200 ºC



sc

sf

→

1

1.2

1.4

1.6

1.8

2

2.2

4

8

12

16

20

1050 1150 1250 1350

Darc

y c

on

stan

t, a

x10

4 /

cm s

-1

Mec

han

ical

stre

ngth

, s

/ M

Pa

Temperature / ºC

• Mechanical strength (sc & sf)

increases with firing temperature,

by consolidation and formation of

mullite.

• Permeability decreases with firing

temperatures due to the reduction

of cell size.

C. Freitas; N. Vitorino; M. Ribeiro; J. Abrantes; J. Frade; Appl. Clay Sci., 109–110 (2015) 15–21



Hydrothermal

reactorSintered kaolin

disks

• 3-5 mm thick;

• F ~ 1 cm;• 190 ºC

• 150 ºC

• 5 h

• 20 hVsolution/Vreactor=40%

NaOH

• 3 M

N. Vitorino, A. Kovalevsky, J. Abrantes, J. Frade, JECS, 35 (2015) 3119–3125



Without functionalization

Mullite

Quartz

• “Clean” cell surface • Typical sintered kaolin mineralogical phases



Sodalite

Quartz

Mullite

150ºC

5 h

150 ºC

20 h



SodaliteCancrinite

Nephelinte

190 ºC

5 h


5. Conclusions and actual guidelines

• Extrusion of ceramic emulsions is suitable to process porous cellular

bodies with constant cross section;

• Sodalite microstructural features are strongly dependent on the

hydrothermal treatment;

• Higher hydrothermal temperatures favours cancrinite zeolite phase

synthesis;

• Hydrothermal treatment of kaolin cellular ceramic is a versatile

method to obtain zeolite monolithic bodies for catalysis, filtration, &

other applications.


CICECO-Aveiro Institute of Materials (Ref. FCT UID/CTM/50011/2013, PTDC/CTM-ENE/2073/2012 and

PEst-C/CTM/LA0011/2013), financed by national funds through theFCT/MEC and when applicable co-financed

by FEDER under the PT2020 Partnership Agreement. PosDoc Grant SFRH/BPD/99367/2013.

Thank you for

your attention !


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In situ functionalization of cellular aluminosilicates