comunicaÇÃo tÉcnicaworkshop de rmn aplicada a biofísica molecular e tecnologia e 2ª. escola de...

COMUNICAÇÃO TÉCNICA ______________________________________________________________________________________________________________________________________________________________________________________________________

Nº 172629

Structural determination of materials by solid state NMR: using technique in practice Claudia Maria Guimarães de Souza S. Greiser Eduardo Garcia Valdecir Angelo Quarcioni CH. Jäger

Slides apresentado no 1.Workshop de RMN Aplicada a Biofísica Molecular e Tecnologia e 2. Escola de Bofísica Molecular, 2014.

A série “Comunicação Técnica” compreende trabalhos elaborados por técnicos do IPT, apresentados em eventos, publicados em revistas especializadas ou quando seu conteúdo apresentar relevância pública. ___________________________________________________________________________________________________

Instituto de Pesquisas Tecnológicas do Estado de São Paulo S/A - IPT

Av. Prof. Almeida Prado, 532 | Cidade Universitária ou Caixa Postal 0141 | CEP 01064-970

São Paulo | SP | Brasil | CEP 05508-901 Tel 11 3767 4374/4000 | Fax 11 3767-4099

www.ipt.br

“Structural determination of materials by solid state NMR – using technique in practice” C. M. G. de Souza1, S. Greiser2, E. Garcia1, V. A. Quarcioni1, Ch. Jäger2

1- IPT, São Paulo/Brazil 2- BAM, Berlin/Germany

1º. Workshop de RMN aplicada a biofísica molecular e tecnologia e 2ª. Escola de biofísica molecular, S. J. do Rio Preto September 1-5, 2014


Portland cement industry

is undergoing major changes.

contribution to climate change and the environment - environmentally friendly and economical alternative for its production

need to make the final product

more durable

more resistant

buildings with slender structures, cheaper maintenance, and durable.


Portland cement

In Brazil for decades has been using partial additions replacement.

The some additives in the Brazilian market:

CPII-E: cement with granulated blast furnace slag (6% - 34%)

CPII-F: cement with limestone filler (6% - 10%)

CPII-Z: cement with pozzolan (6%-14%)

CPIII: with higher granulated blast furnace slag (35% - 70%)

CPIV: with higher pozzolan (15%-50%)


Supplementary cementing materials (SCMs)

contribute to the properties of hardened concrete through hydraulic or pozzolanic activity.

Typical examples: fly ashes, slag cement (ground, granulated blast-furnace slag), and silica fume.

are often added to concrete to:

make concrete mixtures more economical,

reduce permeability,

increase strength, or

influence other concrete properties.


Supplementary Cementing Materials (SCM)

Pozzolans

Natural

Volcanic

glasses

Volcanic ash

Pome Stone

Pumice

Volcanic

Tuff

zeolites

Siliceous

Opal

Diatomaceous Earth

Artificial

Calcined Materials

Calcined Clay

Calcined Xisto

Calcined Bauxite

Rice husk ash

Sugarcane bagasse ash

Straw sugarcane ash

Industrial residues

Fly ash;

Activated silica;

Slags


Reaction of cement - hydration

Portland Cement

(Alite) 2[3CaO•SiO2]

(Belite) 2[2CaO•SiO2]

Water

H2O

=

Calcium Silicate Hydrate

(C-S-H ) (Cimenticious)

3CaO•2SiO2•4H2O

3CaO•2SiO2•4H2O

Calcium Hydroxide

Ca(OH)2

+

+

(RAMANCHANDRAN et al, 2002)

Pozzolan

Metakaolin

Ca(OH)2 and H2O

6Ca(OH)2 + 9H2O

5Ca(OH)2 + 3H2O

3Ca(OH)2 + 6H2O

CnASmHx

C4AH13 (tetracalcium aluminate hydrate)

C3AH6 (tricalcium aluminate hydrate)

C2ASH8 (dicalcium silicoaluminate hydrate)

C-S-H

2 C-S-H

2 C-S-H

C-S-H

+

+

=

(MURAT, 1983)

Pozzolanic reactivity


Pozzolanic Material

calcined clays: e.g. kaolinite clay.

Amapá

Amazonas (2 mines)

Bahia (5 mines)

Goiás (6 mines)

Minas Gerais (16 mines)

Pará (4 mines)

Paraíba

Paraná

Rio Grande do Norte (4 mines)

http://www.mindat.org/min-2156.html#themap


Metakaolin

Calcined clay - Metakaolin (Pozzolanic Material)

In Natura

Commercial

Calcin. 500°C

Calcin. 550°C

Calcin. 600°C

Calcin. 650°C

Calcin. 700°C

Calcin. 750°C

Calcin. 800°C

Calcin. 850°C

Metakaolin = calcined product of

the mineral kaolinite

clay.

E. Garcia Estudo de investigação de caulim para pozolana com avaliação de técnicas selecionadas de caracterização.

(Master degree Dissertation ), IPT, São Paulo, Brazil, 2013, 264p.

51.77% SiO2, 29.45% Al2O3; 2.22% Fe2O3; 2.87% K2O; 1.38% TiO2;

Fire Loss 10.58% and other lesser extent.

Metakaolin* = commercial sample.

http://en.wikipedia.org/wiki/calcination

http://en.wikipedia.org/wiki/Kaolinite


Metakaolin

calcined product of the clay mineral kaolinite. The particle size of metakaolin is smaller than cement particles, but not as fine as silica fume.

Calcined kaolin is transformed to an amorphous phase - metakaolin. (activated and metastable)

Metakaolin can then react with cement and lime.

Kaolinite = a layered silicate mineral with a distance of 7,13 Å between the layer of SiO2 and Al2O3

Calcined = the water contained between the layers is evaporated and turned to amorphous phase.

D. Bézard, http://www.metakaolin.info/quality-criteria/chapelle-test/index.html


Characterization

BET & Blaine – pore size measurements

Chapelle test (pozzolanic reactivity)

27Al and 29Si MAS-NMR

XRD – crystalline phase evolution


Chapelle Test : NF P18.513 (2012)

NBR 15,895 (2012) (similar test applied in France)

The pozzolanic reactivity - Chapelle test using 1:1 and 1:2 metakaolin/CaO ratio (16h test at 90 ± 5oC).

Circulating water

Condenser column

2 holes drilled cap

Thermometer

Erlenmeyer

Magnetic bar

Stirrer

Distilled water without CO2

CaO

Metakaolin

Drawing assembly

Pozzolanic Reactivity

The results are expressed in mg Ca(OH)2 fixed by

metakaolin


Chapelle Test

Comparative evaluation

Pozzolan : calcium oxide 1:1(RAVERDY,1980)

Pozzolan : calcium oxide 1:2 (NBR 15,895: 2012 and NF P18,513:2012)


Characterization






BET and Blaine

Sample Blaine (cm²/g) BET (cm²/g)

in natura 19.550 166.200

Calcined at 550°C 17.701 161.100

Calcined at 600°C 17.160 175.000

Calcined at 650°C 17.020 161.800

Calcined at 700°C 17.170 165.200

Calcined at 750°C 16.850 171.100

Calcined at 800°C 16.360 170.700

Blaine - shows spherical particles with the same dimensions. BET - shows large internal structural changes from 600ºC


Characterization






XRD

Mu

Ka

Q

Mu - Muscovite Ka - Kaolinite Q - Quartz

The results showed: Decreasing of crystalline phases (Ka, Q and Mu) with

increasing the calcined temperature Improvement of amorphous phase to a high amount in

700ºC calcined sample


Characterization






29Si MAS NMR

(29Si), ppm

Engelhardt, G.; Michel, D. High-Resolution Solid-

State NMR of Silicates and Zeolites (1987)

Natural kaolinite clay

Commercial metakaolin

700oC calcined metakaolin


29Si MAS NMR

29Si MAS-NMR spectra of calcined samples at different temperatures.

Evolution of Si Qn sites with temperature

(29Si), ppm


Reagidas MAS


Reagidas mas


Reagidas cpmas


29Si CP-MAS NMR

(29Si), ppm

(29Si), ppm

Kaolinite clay in natura

Metakaolin (commercial sample)

(29Si), ppm

Metakaolin (calcined at 700oC)

27Al MAS NMR

/ ppm

0 10 20 30 40 50 60 70 80 90 100 - 10 110 120

aluminates

aluminosilicates

aluminates

aluminosilicates

aluminates

aluminosilicates

aluminosilicates

3 - f

old

co

ord

.

4 - f

old

co

ord

ina

ted

5 - fo

ld

co

ord

ina

ted

6

- fo

ld

co

ord

ina

ted

- 20


27Al MAS NMR

27Al MAS-NMR spectra of calcined samples in different temperatures.

Evolution of Al(V) sites with

temperature


27Al MAS NMR

Evolution of Al coordination with

temperature


Comparatative Pozzolanic Reactivity

Calcined samples

The higher amount of Al(V) = a higher reactivity.

Changes in Al(V) sites - related to the reactivity (NMR x Chapelle tests).


Conclusions

All techniques high of pozzolanic reactions for calcined samples (600oC to 750oC)

The evolution in the calcination temperature produces larger particles.

The pozzolanic reactivity (Chapelle test: NBR 15.985) pozzolan/CaO = 1:2 ratio was more appropriate than the 1:1 ratio.

The actual Chapelle tests better reactivity for 650oC to 750oC calcined samples - tendency of higher reactivity at 700oC.

29Si and 27Al MAS-NMR structural modification of the samples from crystalline to amorphous phases with increasing temperature of calcination.

Change silicon and aluminum coordination sites related to the reactivity of the samples: the higher amount of Al(V) showed a higher reactivity of the calcined samples.

Samples

Silica-rich residue (waste water treatment of chlorosilane production)

ICP-OES measurement with 3.23% loss of ignition:

Solid sodium aluminate

(Sigma Aldrich, 50-56% Al2O3 and 40-45% Na2O)

Blended with mass ratio of 4:3

De-ionized water with water-to-solid ratio of 0.60

Cured for 1, 3 and 7 days (80°C, 98% rel. humidity)

Degree of reaction of the silicia residue ~51%

SiO2/Al

2O

3 = 1.8

[1] G. J. G. Gluth, C. Lehmann, K. Rübner, H.-C. Kühne: Geopolymerization of a silica residue from waste

treatment of chlorosilane production Materials and Structures, ISSN 1359-5997, 2012.

SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O TiO2 SO3 Cl¯

89.32 3.71 0.47 1.99 0.18 0.01 0.05 0.05 0.22 0.86

29Si-MAS-NMR

Single Pulse excitation Cross Polarisation experiment (using hydroxen for excitation)

Q2

Q3

Q4

O¯

Si O Si O Si

O¯ Si

O

Si O Si O Si

O¯

Si

O

Si O Si O Si

O

Si

29Si

1H

Q2

Q3

Q4

1H-MAS-NMR

Single Pulse excitation

Echo experiment

Water

bridging Si(OH)Al hydroxyl groups

of zeolites of faujasite type [4]

Non-framework

hydroxyaluminium

species (AlOH) [3]

Si(OH)Al hydroxyl groups of the zeolite framework [2]

[2] Engelhardt G. High-resolution solid-state NMR of silicates and

zeolites. Chichester [West Sussex]; New York: Wiley; 1987. 485 p.

[3] Lohse U, Löffler E, Hunger M, Stöckner J, Patzelová V. Zeolites. 1987;7(1):11–13.

[4] Freude D, Hunger M, Pfeifer H, Schwieger W. Chemical Physics Letters. 1986;128(1):62–66.

27Al{1H} REDOR

1. Experiment

2. Experiment (---)

27Al

1H IIIIIII IIIIIII

Aluminium-nuclei

with spatial

proximity

to Hydroxen

[5] Gullion T, Schaefer J: Journal of Magnetic Resonance. 1989; 81(1):196-200

27Al

27Al{1H} REDOR

τ = 0.08 ms

τ = 0.56 ms

τ = 5.04 ms

I: Amorphous phase

(~66ppm)

II: Zeolite Na-A

(~58ppm)[6]

III: Faujasite

(~61ppm)[7]

IIIIIII IIIIIII

27Al

1H

[6] Engelhardt G, Fahlke B, Mägi M, Lippmaa E. Zeolites. 1985;5(1):49–52.

[7] Fyfe CA, Gobbi GC, Hartman JS, Klinowski J, Thomas JM. Journal of Physical Chemistry. 1982;86(8):1247–1250.

27Al{29Si} REDOR

- τ = 0.64 ms

- τ = 2.00 ms

Lineshift caused by the two crystalline phases

Despite of 36,864 accumulations,

no AlO6 resonance with Al-O-Si connections is obvious

IIIIIII IIIIIII 29Si

27Al

Conclusions

Various lines in overlapped resonances can be resolved

using 1H-29Si-Cross Polarisation, 1H-rotor synchronized

echo, 27Al{1H} and 27Al{29Si} REDOR experiments

Amorphous AlO4 and AlO6 coordinated sites were found

in a one-part geopolymer (SiO2/Al

2O

3 = 1.8)

Q2, Q3 and Q4 areas were found

Zeolite Na-A and Faujasite

Thank you for your attention!


Thank You!

Danke!

Obrigada!

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