See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/276272858

Study of Black Core, �ceramic tile's defect, �by a multi-technique

approach

Conference Paper · August 2014

CITATION READS

1 1,333

3 authors, including:

Giorgia Ferrari Cecilia Baraldi

Università degli Studi di Modena e Reggio Emilia Università degli Studi di Modena e Reggio Emilia
8 PUBLICATIONS   7 CITATIONS    46 PUBLICATIONS   777 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Nanosponges View project

Qualitative characterization of emissions from firing of digital ceramic inks View project

All content following this page was uploaded by Giorgia Ferrari on 14 May 2015.

The user has requested enhancement of the downloaded file.

 University of Modena
and Reggio Emilia

Study of Black Core,

ceramic tile's defect,
by a multi-technique
approach

Ferrari G. , Baraldi C ., Zannini P.

XXIV International Conference on Raman Spectroscopy – 10-15 August 2014 – Jena (Germany)
 Study of Black Core, ceramic tile’s defect, by a multi-technique approach

Overview
1. What is “Black Core” defect?
1.1. Technological evolution
1.2. Black Core appearance
1.3. Causes of formation
2. Aims of the research
3. Analytical techniques
3.1. Raman Spectroscopy for Fe Oxides
3.2. Raman Mapping
4. Results
4.1. Raman punctual analysis
4.2. Raman Mapping analysis
5. Conclusions

XXIV International Conference on Raman Spectroscopy – 10-15 August 2014 – Jena (Germany)
 Study of Black Core, ceramic tile’s defect, by a multi-technique approach

1. What is the “Black Core” defect?

1.1. Technological evolution

Production technology in constant evolution

Changes in forming, decoration and firing processes

Organic additives Faster firing

addition processes

Higher probability of technological and esthetical defects

XXIV International Conference on Raman Spectroscopy – 10-15 August 2014 – Jena (Germany)
 Study of Black Core, ceramic tile’s defect, by a multi-technique approach

1. What is the “Black Core” defect?

1.2. Black Core appearance

A darker area inside the tile

Swellings and bubbles

XXIV International Conference on Raman Spectroscopy – 10-15 August 2014 – Jena (Germany)
 Study of Black Core, ceramic tile’s defect, by a multi-technique approach

1. What is the “Black Core” defect?

1.3. Causes of formation

Hypotheses on its nature and causes of formation:

 High Carbon and Iron minerals content

Fe2O3 Fe3O4 or FeO

 Extra-fine
granulometry

Low permeability to gases

 Too high forming

pressures

XXIV International Conference on Raman Spectroscopy – 10-15 August 2014 – Jena (Germany)
 Study of Black Core, ceramic tile’s defect, by a multi-technique approach

2. Aims of the research

 Identification of reduced species

Fe Oxides (Magnetite and/or Wϋstite)

Fe3O4 FeO

 Deeper understanding of reactions

 Technological parameters influence on Black
Core formation

Technological solutions to minimize/remove

the Black Core defect
XXIV International Conference on Raman Spectroscopy – 10-15 August 2014 – Jena (Germany)
 Study of Black Core, ceramic tile’s defect, by a multi-technique approach

3. Analytical Techniques
Red outer area
White intermediate area
Black Core area

a. XRF (chromophore elements)

No significant difference in elements content

b. XRPD (crystalline byproducts)

No trace of new crystalline phases in Black Core
c. SEM-EDS (morphological data)
Higher porosity of Black Core than healthy ceramic body
d. FTIR (residual organic compounds?)
No trace of residual organic compounds
e. Mössbauer Spectroscopy (oxidation state of Fe)
Too low quantity of Fe Oxides inside ceramic body
XXIV International Conference on Raman Spectroscopy – 10-15 August 2014 – Jena (Germany)
 Study of Black Core, ceramic tile’s defect, by a multi-technique approach

3. Analytical Techniques
3.1. Raman Spectroscopy for Fe Oxides

Fe(II) Oxides
(Magnetite and/or Wϋstite)
Fe3O4 FeO

675 cm-1

650 cm-1

Top: Magnetite (Fe3O4) Top: Hematite (α-Fe2O3)

Bottom: Wϋstite (FeO) Bottom: Maghemite (γ-Fe2O3)

References:
D. L. A. de Faria,S. Venaüncio Silva and M. T. de Oliveira, Journal of Raman Spectroscopy, vol. 28, 873-878 (1997)
R. J. Thibeau, C. W. Brown and R. H. Heidersbach, Appl. Spectrosc . 32, 532 (1978)

XXIV International Conference on Raman Spectroscopy – 10-15 August 2014 – Jena (Germany)
 Study of Black Core, ceramic tile’s defect, by a multi-technique approach

3. Analytical Techniques
3.2. Raman Mapping

Selected mapping area Sequence of spectra

Peaks under
investigation

LabSpec v5.0 software

False-colour image Punctual spectrum

XXIV International Conference on Raman Spectroscopy – 10-15 August 2014 – Jena (Germany)
 Study of Black Core, ceramic tile’s defect, by a multi-technique approach

4. Results
4.1. Raman punctual analysis

Fe Oxides
in Outer and
Intermediate areas:
Hematite (Fe2O3)
Magnetite (Fe3O4)

Red outer area Intermediate area

Magnetite standard

Hematite standard

XXIV International Conference on Raman Spectroscopy – 10-15 August 2014 – Jena (Germany)
 Study of Black Core, ceramic tile’s defect, by a multi-technique approach

4. Results
4.1. Raman punctual analysis

Fe Oxides in Black Core area:Wϋstite (FeO)

-350

-300

-250

-200

-150

-100

-50
Y (µm)

50

100

150

200

250

300
40 µm
350

-400 -200 0 200 400

X (µm )

XXIV International Conference on Raman Spectroscopy – 10-15 August 2014 – Jena (Germany)
 Study of Black Core, ceramic tile’s defect, by a multi-technique approach

4. Results
4.2. Raman Mapping analysis

Outer and Intermediate areas maps: no Wϋstite

Outer area

150 x 100 μm
20 x 20 points

600 x 550 μm
20 x 20 points
Intermediate area

XXIV International Conference on Raman Spectroscopy – 10-15 August 2014 – Jena (Germany)
 Study of Black Core, ceramic tile’s defect, by a multi-technique approach

4. Results
4.2. Raman Mapping analysis

Black Core

450 x 450 μm
10 x 10 points

Peak around 650 cm-1 = Wϋstite (FeO)

XXIV International Conference on Raman Spectroscopy – 10-15 August 2014 – Jena (Germany)
 Study of Black Core, ceramic tile’s defect, by a multi-technique approach

5. Conclusions

 Different Iron Oxides in Black Core

(Wϋstite) and healthy ceramic body
(Hematite and Magnetite)

 Hypotheses on Black Core formation

processes are confirmed once more

 Raman mapping is a good method for a

better understanding of Black Core nature

 Deeper studies are necessary to reveal

Black Core composition and formation
processes
XXIV International Conference on Raman Spectroscopy – 10-15 August 2014 – Jena (Germany)
 University of Modena
and Reggio Emilia

Thank you for

your attention

XXIV International Conference on Raman Spectroscopy – 10-15 August 2014 – Jena (Germany)
View publication stats