______________________________________________________________________________ ______________________________________________________________________________ Production, Surface Modification and Functionalization of Reference Particles Mainz 29./30.09.2011 Katja Mader , Hendrik Mainka Content 1)P d i Ti i 1.)Production Titanium Dioxide 2.) Surface Glass Beads Modification and Functionalization 10/4/2011 2
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Production, Surface Modification and Functionalization of Reference Particles
Mainz 29./30.09.2011 Katja Mader, Hendrik Mainka
Content
1 ) P d i Ti i1.) Production Titanium Dioxide
2.) Surface Glass BeadsModification andFunctionalization
10/4/2011 2
1.) Production of Titanium dioxide
04.10.20113
Production of Titanium Dioxide
Reaction Scheme
Isopropanol
OHHC4OHTiOH4HOCTi 7342473 1. Step: Hydrolysis
Titanium tetra isopropoxide Titanium hydroxide
OH2TiOOHTi 224 2. Step:Polycondensation
Titanium dioxide
10/4/20114
Task
Titanium dioxide
porous particles non porous particlesporous particles (agglomerated)
non porous particles(non agglomerated)
chemical conversion of tetraalkyl orthotitanate
aqueous phase alcoholic phase with a base/acid
10/4/20115
/
Porous TiO2 particles
Alcoholic phase: Isopropanol Base: ammonium hydroxide solution (25 %)Base: ammonium hydroxide solution (25 %) Temperature: 20 °C 100 ml batch Stabilizer: SDS (1 g > 100 ml)( g )
50 mlIsopropanol
Ammonium hydroxide fraction 0 66 M
< 160 µmp p+ Ammonium hydroxide
fraction 0.66 Mwater fraction(reactant = 0.5 M) [1]
µ
50 ml50 mlIsopropanol +0.2 M tetraalkylorthotitanate +
1 mm
< 500 µm
10/4/20116
orthotitanate +SDS
[1] N.I. Ivanova, D.S. Rudelev, B.D. Summ und A.A. Chalykh,„Synthesis of Barium Sulfate Nanoparticles in Water‐in‐OilMicroemulsion Systems”, Colloid Journal, vol. 63, pp. 714–717,2001
Porous TiO2 particles
100
Comparison of TiO2 particles in an alcoholic phase
80
90
100Q₃ [%
]
60
70
tibution Q
d50,3,dry= 6.4 µmd50,3,wet= 12.2 µm
30
40
50
e Size Disrt
10
20
30
Particle
Dry
Wet
0
0,01 0,1 1 10 100 1000 10000
ParticleSize d [µm]
10/4/20117
Particle Size d [µm]
Non Porous TiO2 particles
Aqueous phase Base: ammonium hydroxide solution (25 %)Base: ammonium hydroxide solution (25 %) Temperature: 20 °C 300 ml batch Stabilizer: SDS (0.5 g > 300 ml)( g )
150 mlIsopropanol+ < 100 µmIsopropanol+
0.2 M tetraalkylorthotitanate+ Ammonium
< 100 µm
hydroxide
150 mlWater +
1 mm
500
10/4/20118
SDS < 500 µm
Non Porous TiO2 particles
100
Comparison of TiO2 particles in an aqueous phase
80
90
100Q₃ [%
]
60
70
tibution Q
d50,3,wet= 18.6 µm
30
40
50
Size Disrt d50,3,dry= 24.6 µm
10
20
30
Particle
Dry
Wet
0
10
0,01 0,1 1 10 100 1000 10000
P ti l Si d [ ]Particle Size d [µm]
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Scale Up ‐Miniplant
3 L b t h (170 TAOT)3 L batch (170 g TAOT)Production: 56 g
10/4/201110
Summary Titanium Dioxide
First tests in alcoholic and aqueous phaseq p Average diameter (alcoholic phase, dry): d50,3 = 6.4 µm Average diameter (aqueous phase, dry): d50,3 = 24.6 µm
Polydisperse particles Polydisperse particles Stabilizer influences the particle size Scale up in Miniplant
Next steps:
Monodisperse Characterization of the particles (X‐ray analysis)
10/4/201111
2.) Surface Modification and Functionalization of Glass BeadsFunctionalization of Glass Beads
10/4/201112
Task
Surface Modification
Hydrophilic HydrophobicHydrophilic Hydrophobic
Silanization
Characterization10/4/2011
13
Characterization
Hydrophilic Glass Beads
Surface has to be free of contaminations Glass particles were purified by using chemical cleaning
A id
Alkaline
Acid
Chemical
Alkaline
SolventCleaning Solvent
ElectroElectro
Emulsion10/4/2011
14
Emulsion
Hydrophilic Glass Beads
Surface has to be free of contaminations Glass particles were purified by using chemical cleaning
Oxidation of organic molecules at the surface Activated surface of the glass particles – many reactive Si‐OH groups
10/4/201115
Hydrophilic Glass Beads
Surface has to be free of contaminations Glass particles were purified by using chemical cleaning
Oxidation of organic molecules at the surface Activated surface of the glass particles – many reactive Si‐OH groups
Si‐OH groups are very reactive – basis for water repellencyg p y p y Contact angle is less than 15°
10/4/201116
Hydrophilic Glass Beads
Surface has to be free of contaminations Glass particles were purified by using chemical cleaning
A id
Alkaline
Acid
Chemical
Alkaline
SolventCleaning Solvent
ElectroElectro
Emulsion10/4/2011
17
Emulsion
Hydrophilic Glass Beads
Materials• Spheriglass 5000 (d50,3=10.7 µm) with about 72 % SiO2
• Caro‘s acid (sulfuric acid+hydrogen peroxide [3:1])
10/4/201118
Hydrophilic Glass Beads
9/23/201119
Hydrophobic Glass Beads
Water repellence of glass beads by using silanization Interaction between the activated surface and silane coupling agentsInteraction between the activated surface and silane coupling agents
10/4/201120
Hydrophobic Glass Beads
Water repellence of glass beads by using silanization Interaction between the activated surface and silane coupling agentsInteraction between the activated surface and silane coupling agents
Contact angle is more than 90°
10/4/201121
Hydrophobic Glass Beads
Three surface silanization reactions were tested Difference between the reactions: leaving group
Reaction 1: R1
C2H5O
2Reaction 2: R
2 HO
Reaction 3: R3
Cl
10/4/201122
Hydrophobic Glass Beads
Three surface silanization reactions were tested Difference between the reactions: leaving group
As hydrophobic residue following functional groups of atoms are used
10/4/201123
methyl radical phenyl radical
Hydrophobic Glass Beads
Three surface silanization reactions were tested Difference between the reactions: leaving group
As hydrophobic residue following functional groups of atoms are used
The following silanes were combined with the hydrophobic residue
Silanes
• Trimethylethoxysilane
• Triphenylsilanol
• ChlorodimethylphenylsilaneChlorodimethylphenylsilane
• (3,3,3‐Trifluoropropyl)‐trimethoxysilane
• Chlorotriphenylsilanep y
• 1H,1H,2H,2HPerfluorooctyl‐trimethoxysilane
10/4/201124
Hydrophobic Glass Beads
FTIR Glass BeadsFTIR Glass Beads
Characterization
Fourier TransformInfrared Spectrometermeasurements withmeasurements withthe methyl groupshydrophobized glassparticle s rfaceparticle surface
10/4/201125
Hydrophobic Glass Beads
Other planned characterization methods are:
Solid state NMR Solid‐state NMR(Nuclear Magnetic Resonance Spectroscopy)
Water vapour isotherms( d ti )(adsorption)
10/4/201126
Hydrophobic Glass Beads
Chlorodimethylphenyl silane modified glass
1H,1H,2H,2H Perfluorooctyltrimethoxysilane modified glassglass modified glass
Hydrophobic Hydrophobic &
10/4/201127
y p y pLipophobic
Hydrophobic Glass Beads
Behaviour of 1H,1H,2H,2H Perfluorooctyltrimethoxysilane hydrophobic glass surface
04.10.201128
Hydrophobic Glass Beads
Behaviour of 1H,1H,2H,2H Perfluorooctyltrimethoxysilane hydrophobic glass surface
04.10.201129
Summary Glass Beads
Production of hydrophilic glass particles by using Caro’s acid
H drophobic s rfaces reali ed b sing silani ation Hydrophobic surfaces – realized by using silanization
(chemical bonding of a silane compound to a surface)
Test of 7 different silanes Test of 7 different silanes
Preparation of hydrophobic and lipophobic surfaces
04.10.201130
Thank you for your attention!
Contact: Dipl ‐Ing Katja MaderContact: Dipl. Ing. Katja Mader
Otto‐von‐Guericke‐University MagdeburgInstitute of Process EngineeringInstitute of Process EngineeringMechanical Process EngineeringUniversitätsplatz 2D‐39106 Magdeburgg g
Phone: +49 (0) 391 67 11866
Email: [email protected]
04.10.2011 31
Rate of Yield
Laboratory approach (100 ml):
Input tetraalkyl orthotitanate (mass percentage titanium ≙ 20,9 %): 5,68 g ≙ 0,2 M
Input water:
0,9 g ≙ 0,5 MMaximum yield:Maximum yield:
1,99 g (measured: 1,75 g ~ 88 %)
Miniplant approach (3000 ml):Miniplant approach (3000 ml):
Input tetraalkyl orthotitanate :
170,4 g ≙ 0,2 MInput water:
2000 g ≙ excessMaximum yield:
10/4/2011 32
Maximum yield:
59,638 g (measured: 56,6 g ~ 94,9 %)
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