Nov 11, 2014 - 1,5. 2,0 γs d [mJ/m2]. Coverage [mg/m2]. REDICOTE. SMAX. DINORAM. Reference data of used silica (T30). S. BET. : 300 m2 γs d : 83 mJ/m2.
Performance Characterization of Road-Building Stones by inverse Gas and Liquid Chromatography Dr. Ralf Dümpelmann, Inoly2x Ltd. Dr. Eric Brendle, Adscien2s S.A.
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Content • • • • • •
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The Problem Introduction of Adscientis & Inolytix The Approach Results by Inverse Gas Chromatography (IGC) Results by Inverse Liquid Chromatography (ILC) Conclusions
The Problem
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Compatibility? • Wetting between stones and asphalt emulsion • Treatment by surfactants
Poor we'ng
• Surface properties of stone? • Effect of surfactants? 11/11/2014
Good we'ng
Introduction • Adscientis S.A.: expert laboratory for inverse gas and liquid chromatography (IGC, ILC) – Dr. Eric Brendle, 15 years successful business in iGC
• Inolytix Ltd.: connecting spezialized analytical labs, especially for surfaces, to the chemical industry – Dr. Ralf Dümpelmann, 20 years experience in R&D – Inolytix founded Feb. 2014 with passion
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Inolytix: portfolio of analytical methods
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The Approach 1. Characterization of stones – Surface energy, heterogenity
2. Characterization of tensides – Impregnated on silica
3. Effect of tensides on stones – By IGC
4. Principles of ILC and results 5. Conclusions
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Road building stones • Study: Diorite as road building material – – – –
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Specific surface: 2 m2/g (sieved) Dispersive Surface energy, γsd : 140 mJ/m2 Strong specific acidic and basic interactions Heterogeneous surface energy as measured by iGC
Surface heterogenity • Measured by inverse Gas Chromatorgaphy at Finite Concentrations Sites [µmole/(kJ/mole)]
0.40 0.35
TEA à 40°C DPA à 40°C HA à 40°C
2,2 m2/g
0.30 0.25
1,6 m2/g
0.20
2,7 m2/g
0.15 0.10 0.05
Energie [kJ/mole]
0.00 10
15
20
25
30
35
40
45
50
• Limited accessibility by triethylamine (TEA) vs. Dipropylamine (DPA) and linear hexylamine (HA) 11/11/2014
The Surfactants •
Characterization of surfactant properties independent of the stones • Principle: impregnation in silica – Different loadings – Use of IGC Surfactants • Redicoate EN1009
H3C
– Tallow ampho-polycarboxy glycinate – Amphoteric
•
•
DINORAM S – Linear N-alkyl propylene diamine
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CH3
CH2 CH2 CH2
SMAX 4000 – Copolymer styrene-malein-imide (4/1) – Strongly branched
N
O
*
CH2 CH
C 4 H
N
O C H
n
*
Surfactants decrease dispersive surface energy (measured on silica carrier) 90
γ sd [mJ/m2]
REDICOTE SMAX DINORAM
80
70
Reference data of used silica (T30) SBET : 300 m2 γsd : 83 mJ/m2 Average surface roughness Acidic surface
60
50
40
30 Coverage [mg/m2]
20
0,0
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0,5
1,0
1,5
2,0
Surface acidity and basicity estimation • Use of probe’s acceptor number AN and donor number DN (Gutmann) to obtain Ka and Kb values of sample.
δ+ CHCl3 Ether
Basic probe
AN=3.9 DN=19.2 8
δ-
CH3-CH2-O-CH2-CH3 δ+
δ+
Cl
δ-
Cl
Ether
6 5 dioxane
3
0
acetone CH3-NO2
Example: Crystalline cellulose
Ethyl acetate
€
Methyl acetate CH3-CN
Ethanol Methanol CHCl3
0 11/11/2014
−ΔH asp DN = .K A + K B AN AN
THF
4
1
δ-
δ-
∆Hasp/NA
7
2
Acidic probe AN=25.1 DN=0.0
Cl
1
DN/AN 2
3
4
5
6
Ka and Kb values by inverse gas chromatography (measured on silica carrier) 1.20
Ka
1.00
Acidic sites are covered, especially by Dinoram (linear diamine)
REDICOTE SMAX DINORAM
0.80
0.80
REDICOTE SMAX DINORAM
Kb
0.60
0.60
0.40
0.40
0.20
Taux [mg/m2]
0.00 0.0
0.5
1.0
1.5
2.0
Taux [mg/m2]
0.20 0.0
0.5
1.0
1.5
• Influence of surfactants on acidic (Ka) and basic (Kb) properties and can well be determined by inverse gas chromatography 11/11/2014
2.0
Surfactants on Diorite by inverse Gas Chromatography
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Surface Energy of Surfactants on Diorite • •
Higher than on silica! SMAX little decreased
γsd [mJ/m2]
160
REDICOTE SMAX DINORAM
140
120 100
ð Surface only partly covered
80
60 40
∼ 30 on silica
20
Coverage [mg/m2]
0 0
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0,2
0,4
0,6
0,8
1
1,2
1,4
IM
1,60
Morphology Index
1,40 REDICOTE
1,20
SMAX DINORAM
1,00
Size exclusion
• Solubility effects by DINORAM (linear amine) • Size exlusion effects by REDICOTE and SMAX (branched molecules)
Solubility effects
(Nano-)Morphology of surfactants on diorite by iGC
0,80
0,60 0,40
0,20 Coverage [mg/m2]
0,00
0
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0,2
0,4
0,6
0,8
1
1,2
1,4
Surfactants on Diorite by inverse LIQUID Chromatography
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Inverse Liquid Chromatography • Principle: as in inverse gas chromatography BUT surfactants can be used in liquid flow – C0 = surfactant concentration
ð Adsorption, desorption, irreversible adsorption
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Kinetics of inverse Liquid Chromatography • Integration curve provides adsorbed quantity and desorption behavior
0.45
DINORAM REDICOTE SMAX
Qads [mg/m2]
0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 Concentration [g/l]
0.00 0.0
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0.1
0.2
0.3
0.4
0.5
0.6
0.7
• DINORAM adsorbed most • Very little SMAX adsorbs
Qantités adsorbées [mg/m2]
Quantitative results of ILC: adsorbed surfactants 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00 DINORAM
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Redicote
SMAX PH 5
SMAX PH 3
a
b
Qads maximale [mg/m2]
DINORAM S
21,2
50,9
0,42
SMAX à pH 3
0,22
19,2
0,011
SMAX à pH 5
0,27
19,9
0,014
Redicote
1,62
9,9
0,16
Conclusions • Results of inverse GAS and LIQUID chromatography are complementary – Very good coverage: DINORAM (linear diamine) – Average: REDICOTE (amphoteric) – Poor: SMAX (branched polymer)
• Diorite has heterogeneous surface – Linear molecule covers best – Brached polymers worst ð size exclusion
• Surfactants adsorb differently – Quantification and effect by iGC and iLC
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THANK YOU FOR YOUR ATTENTION! Use
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