Materials research and surface

functionalization

at

Section of Chemistry

Department of Biotechnology, Chemistry, Environmental Engineering

Aalborg University

Yuanzheng Yue

AAU Matchmaking og NanoLab arrangement 9. december 2010

Glass group

Academic staff:

Yuanzheng Yue (Professor) → different subjects

Vittorio Boffa (Assi. Professor) → membrane

Technician:

Lisbeth Wybrandt → assist allLisbeth Wybrandt → assist all

PhD students:

Martin Jensen → stone wool process

Qiuju Zheng → glass forming ability

Mette Moesgaard → cement CO2 reduction

Morten M. Smedskjær → functional surface

Xiaoju Guo → glass relaxation

Tommy Madsen (res. assistant) → surface modification

Research areas• Structure, dynamics, relaxation and properties of glasses

• Glass for energy conversion

• Functional surfaces of glasses and other materials

• Glass and glass fiber technology

• Metallic glasses

• Heterogeneity of glass-forming liquids• Heterogeneity of glass-forming liquids

• Glass formation and glass transition

• Theoretical prediction of materials properties

• Nano-materials and nanoporous ceramic materials

• Crystallization and phase transition

• CO2 reduction in cement production

• Mesoporous materials and membrane

• Rheology of melts

Area I

Surface modification on glass and

glass fibers

In collaboration with

Rockwool International A/SRockwool International A/S

and

Ferro GmbH

It protects people and

environment and save energy.

due to its high temperature

stability and remarkable

insulation effect

Rock Wool’s role

insulation effect

Despite its HT stability, it

cannot sustain a temperature

above 1000 ºCT ~ 1000 ºC

So we did something to increase the HT stability!

O2

Surface Oxidation front

Oxidized partUnoxidized

part

Fe2+ + h●→ Fe3+

h●

Mg2+, Ca2+

MgO

layer

O2-

Cooper et al., Geoch. Cosmoch. Acta (1996)

Heat-treatment around Tg

Oxidation of Fe2+ to Fe3+

Inward diffusion of h•

Yue et al., J. Am. Ceram. Soc. (2009)

Outward diffusion of Mg2+

MgO on surface

Increases of HT stability

Inward diffusion of h

Treated at 600ºC

for 0.5 h in air

Stand1050 ºC in Ar

Without heat-

treatment

H2

Surface Reduction front

Reduced Unreduced

Ax+→A(x-1)+ + h●

h●

Me+, Me2+

e-

H2O

Silica-rich layer

O2-

Smedskjaer, et al., Chem. Mater. (2009)

Heat-treatment around Tg

Reduction of Fe3+ to Fe2+

Outword diffusion of h•

Smedskjaer, et al., Chem. Mater. (2009)

Smedskjaer and Yue, J. Non-Cryst. Solids (2009)

Inward diffusion of Mg2+

SiO2 rich layer on surface

Improvement of properties

Heat-treatment

atmosphere

Hv

[GPa]

c(Na+)acid

[mg/L]

c(Mg2+)alkali

[mg/L]

Untreated 8.9 ± 0.2 8.7 2.4

H2/N2 (1/99) 9.9 ± 0.3 1.9 1.3

Higher hardness and chemical durability, optical properties …..(ideal solar cell substrate?)

Recent: Quantum cutting

Area II

Prediction of mechanical properties

Strengthening glass and glass fibers

In collaboration with

Corning IncorporateCorning Incorporate

Rockwool International A/S

PPG Industries Inc.

Pennsylvania State University

A piece of a special flat glass

Prediction of Glass Hardness and Tg by Constraint Theory

2.4 2.6 2.8 3.0 3.2 3.40

2

4

6

8

10

12 Experiment (P = 98 mN)

Model (P = 98 mN)

Experiment (P = 0.25 N)

Model (P = 0.25 N)

HV (

GP

a)

(a)

0 10 20 30 404

6

8

10

12

Experiment (P = 98 mN)

Model (P = 98 mN)

Experiment (P = 0.25 N)

Model (P = 0.25 N)

HV (

GP

a)

(b)

2.4 2.6 2.8 3.0 3.2 3.4

Atomic constraints

0 10 20 30 40

[Na2O] (mol%)

Smedskjaer, Mauro, Yue, PRL 2010

0 10 20 30 40 500

10

20

30

40

50(a)

100

90

80

70

60

>5

>6

>7

>8

>8

>7

>6

>5

CaO

(mol %

)

B 2O 3

(mol

%)

Na2O (mol %)

4.5

5.05.56.0

6.57.07.5

8.08.5

Hv (GPa)

50

0 10 20 30 40 500

10

20

30

40

50(b)

>560

>610

>660

>560

>610>660

>710

>760

>810

70

100

80

60

90

CaO

(mol %

)B 2O 3

(mol

%)

Na2O (mol %)

510

560

610

660

710

760

810

860

910

Tg (K)50

>860

Useful for designing new materials!

Heat-treatment around Tg

Reduction of Fe3+ to Fe2+

Outword diffusion of h•

Inward diffusion of Mg2+

SiO2 rich layer on surface

Hardening of glass

Outword diffusion of h

2000

3000

4000

interval 1

Wool fibers

Continuous fibers

b Basaltic compositions

Tensile

str

en

gth

σo (

MP

a) a E-glass compositions

Continuous fibers

Origin of the high tensile strength of glass fibers (a PhD project supported by RI)

0 20 40 60 800 20 40 60 800

1000

Bulk glass

Wool fibers interval 2

Bulk glass

Wool fibers

Tensile

str

en

gth

Axial stress σax (MPa)

Lund and Yue, J. Am. Ceram. Soc. (2010)

Increasing the drawing stress enhances the structural anisotropy, and hence, the strength of glass fibers!

Area III

Rheology and homogeneity of high

temperature melts

In collaboration with

Rockwool International A/SRockwool International A/S

Corning Incorporated

Rheology is important for geology and industry!

HawaiiRockwool process

Rockwool projects: Viscous behaviour, relaxation, glass forming ability and fiber spininability; Quantification of melt homogeneity….

A new model has been established, which is superior to any existing ones containing 3 parameters in terms of both the accuracy of describing the viscosity-temperature relation of glass-forming liquids and the physical meaning.

logη = logη∞ +B

Texp

C

T

8

10

12 SiO2 Window glass Corning aluminosilicate Basalt Anorthite

Oxide and molecular liquids

T T

Mauro, Yue, Ellison, Gupta, Allan, PNAS, (2009)

0.0 0.2 0.4 0.6 0.8 1.0

-4

-2

0

2

4

6

8 Anorthite Glycerol Propylene carbonate Triphenylethe O-terphenyl 4Ca(NO3)2-6KNO3

log

η (

Pa s

)

Tg/T (K/K)

fragility

( )

−

−

−−+=

∞

∞∞ 11log12

explog12loglogT

Tm

T

T gg

ηηηη

Area IV

Nanoporous materials

In collaboration with In collaboration with

Shandong Institute of Light Industry

Formation of the mesoporous TiO2 using yeast as template

Remarkable photocatalytic performances of the derived TiO2!

W. He et al. J. Colloid and Interface Sci. (2010)

Nanoporous membranes for gas separation: A silica nanosol is prepared by hydrolysis and condensation of tetraethyl orthosilicate

(TEOS) in aqueous ethanol.

Silica membranes with pores smaller than 5 Å are obtained by coating this nanosol

on top of asymmetric supports.

These membranes can be used, for

instance, to recover pure H2 from gaseous mixtures.

Ultrathin nanoporous films for microfluidic devices:

gaseous mixtures.

1-2 nm large pores can be obtained by adding to the silica sol an organic template, which is removed during

calcination.

Microfluidic devices were fabricated

by depositing a layer of this material on microsieves with ∼ 1 µm large perforations.

Area V Glass Particles as an Active and CO2

Reducing Component in Future Cement

Supported by the Danish Advanced Technology FoundationTechnology Foundation

In collaboration with Aalborg Portland, GEUS,

and iNano

Ph.D. defense of Mette MoesgaardAt 12:30, Friday, December 10, 2010 Aalborg UniversitySohngaardsholmsvej 57, 9000 AalborgAuditorium F108

Promising results

1.0

1.1

1.2

1.3

σ) re

l (-)

Fly ash

CLS9N

CLS9N fine

CLS9N fiber

Inert filler

/str

ength

) re

l

0.0 0.2 0.4 0.6 0.8 1.0

0.8

0.9

1.0

(mC

O2/σ

)

P/(P+L)

More than 20% CO2 reduction for a comparable strength!

glass/(glass+lime)

(mC

O2/s

trength

)

Supramolecular Chemistry Group

Asc. Prof. Kim Lambertsen Larsen

Asc. Prof. Donghong Yu

Asc. Prof. Laurent Duroux (2010-2013)

Ass. Prof. Thorbjørn Terndrup Nielsen (2010-2013)

Lab. Tech. Anne Flensborg

Ph.d.-student Peter Andreas Lund Jacobsen (-2010)

Ph.d.-student Mladen Stojanov (-2011)

Ph.d.-student Harsha Vardan Reddy Burri (-2011)

Ph.d.-student Lars Wagner Städe (-2012)

Vid. Ass/ Ph.d.-student Lasse Bo Lumholdt Riisager (-2013)

Vid. Ass/ Ph.d.-student Lars Damgaard Løjkner (-2013)

Organic synthesis

Polymers Photovoltaic polymers (DY)Molecular imprinted polymers (DY)

Cyclodextrin polymers (TTN)

Cyclodextrin derivatives Functionalized CD´s (TTN)Amphiphilic CD´s (LDL)

Surface modification PP-Nonwoven (LDL)Bone implants (PALJ)

Stationary phases (LWS, LD)

Biosensors/Biocompat. interfaces (LD,

TTN)Protein interaction with CD mod.

Surfaces (LD)

Self assembly

Cyclodextrin Technology Channel type CD crystals (KLL)

Drug delivery Formulation of small molecule actives

(MS)Formulation of proteins (LD, KLL)

Formulation of RNA/DNA (TTN)

Polymeric drug delivery systems Polymeric drug delivery systems (TTN, KLL)

Protein display Dock´n´flash (LWS, LD)

Polymers Photovoltaics (DY)

Formulation (cyclodextrin technology)

Project: Use of cyclodextrins in medical chewing gum (Mladen Stojanov)

Cyclodextrin

Release

Bioavailability

Stability

Drug Ingredients(Sweetners, Flavours,

gumbase and many more)

StabilityTaste masking

Interactions

Interactions

Project: Cyclodextrin modified bioresorbable implants (Peter AL Jacobsen)

• Grafting of cyclodextrin to hydroxyapatite

• Development of grafting and analysis techniques

• Drug release properties• Structuring of protein layer

Surface modification

B1

A14

B16

Monomeric Insulin pH 7.5

B1

A14

B16

Monomeric Insulin pH 7.5

Surface modification

Project: Protein purification using CD´s (Lars Wagner Städe)

B25

B26

B16

B24

A19

B25

B26

B16

B24

A19

Surface modification

Project: Dock´n´flash (Laurent Duroux)

Dock a CD on pBpa

p-benzoyl-L-phenylalanine(pBpa)

+

Flash with UVA

Covalent bond formation

Polymers

Project: Novel cyclodextrin polymers (Thorbjørn Terndrup Nielsen)

Gene therapy

Drug delivery to

OH19

OHHO

ClO

Cl

O On

N

HO

Drug delivery to

the eye

OH

OHOO

O

On

O

O

OO

O

O O

OH

O

nO

R

O O

O

O

O

O

O

O

O

O

OO

O

O RO

O

O

R

O

O

n

n

n

n

B1

A14

B25

B26

B16

B24

A19

B1

A14

B25

B26

B16

B24

A19

Formulation of

proteins

Polymers

Project: Synthetic antibody-like receptors from molecular imprinted inorganic/organic hybrids (Harsha Vardan Reddy Burri)

•Assay study: Covalent imprinting and covalent rebinding

•Peptide/Oligo-peptides imprinting

•Molecular imprinted hybridsFTP

Photovoltaic polymers

Project: Organic-based photovoltaic cells with morphology control (Lasse)

Efficiency

Processing Stability

Thank you for your attention!Thank you for your attention!