Application of IGC for Characterisation of TIO2 Pigments. Thomas Koch Colone, June

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1 Application of IGC for Characterisation of TIO2 Pigments Thomas Koch Colone, June

2 Content - KRONOS - Pigments and Applications - IGC and TIO2 - Examples - Conclusions 2 Dr. Th. Koch, Colone June 20, 2017

3 KRONOS Locations KRONOS INTERNATIONAL, Inc. 3 Dr. Th. Koch, Colone June 20, 2017

Production: 560 000 t Development of TiO 2

4 KRONOS KRONOS INTERNATIONAL, Inc. Inventor of Titanium Dioxide Pigment (1916) Producer of Titanium Dioxide (TiO 2 ) Pigment + Special Products Yearly Production: t Development of TiO 2 -Photokatalysts since 2003 Leverkusen 4 Dr. Th. Koch, Colone June 20, 2017

5 TiO 2 Application TiO 2 daily life luxury good 2015 consumption per year and head Germany 5 kg China 500 g Bangladesch 50 g yearly market volume: t usage almost everywhere in daily life Leverkusen Werk Leverkusen 5 Dr. Th. Koch, Colone June 20, 2017

6 TiO 2 Application TiO 2 daily life luxury good 2015 consumption per year and head Germany 5 kg China 500 g Bangladesch 50 g yearly market volume: t usage almost everywhere in daily life Leverkusen Werk Leverkusen 6 Dr. Th. Koch, Colone June 20, 2017

7 IGC and TiO2 Sources of Data - IGC SMS KRONOS Research Services - 40 C experiment temperature id/fc - IGC SMS KRONOS Research Services C experiment temperature id - IGC Adscientis Adscientis Labs C experiment temperature - id - 30 C experiment temperature - fc 7 Dr. Th. Koch, Colone June 20, 2017

8 Open Questions Source SMS Manual?? Is surface water able support or to hinder measurement of pigment properties???? Temperature influence on adsorption properties of TiO 2?? 8 Dr. Th. Koch, Colone June 20, 2017

9 IGC and TiO2 Source SMS Manual 9 Dr. Th. Koch, Colone June 20, 2017

10 IGC and TiO2 - Agglomeration (Aggregation) Source SMS Manual 10 Dr. Th. Koch, Colone June 20, 2017

11 IGC and TiO2 - Agglomeration (Aggregation) - Water Contact Angle (Hydrophilicity) Source SMS Manual 11 Dr. Th. Koch, Colone June 20, 2017

12 IGC and TiO2 - Agglomeration (Aggregation) - Water Contact Angle (Hydrophilicity) - Surface Energy and Processinduced Disorder Source SMS Manual 12 Dr. Th. Koch, Colone June 20, 2017

13 IGC and TiO2 - Agglomeration (Aggregation) - Water Contact Angle (Hydrophilicity) - Process-Induced Disorder - Particle Adhesion Source SMS Manual 13 Dr. Th. Koch, Colone June 20, 2017

14 IGC and TiO2 KRONOS produces metric tons per year = 9 % of world market volume! Left: Ore = Black Part Right: Pigment = White Part Ilmenite? Rutile 14 Gloss, Gloss-Haze, Tinting Strength, Hiding Power, Stability, Brightness, Powder, Flowability, Matrix Adoption, Dispersibility, Dr. Th. Koch, Colone June 20, 2017?

IGC and TiO2 Microscopic Structure => Macroscopic Properties

Example for Optical Properties: Optical Properties Substrate Coatings

$film adoption of refraction index = antireflection coating local$

15 IGC and TiO2 Microscopic Structure => Macroscopic Properties Dispersitivity, Powder Flowability Stability Customer Matrix Adoption Example for Optical Properties: Optical Properties Substrate Coatings Brightness Stability Colour 15 Dr. Th. Koch, Colone June 20, 2017 Creation: 20 nm thick, nanopourous polymer film adoption of refraction index = antireflection coating local mechanical compression => holes vanish watermark!

16 Examples Comparison K2220 and K2220 without Organics finite KII RS K2220 wthout Organics, BET 9,4 m²/g K2220 with 0,15% Organics, BET ),) m²/g γs t γs t γs d γs d γs ab γs ab γs d γs t γs d Finite SMS γs t γs ab γs ab 16 Dr. Th. Koch, Colone June 20, 2017

17 Examples Al2O3 Content of Base Material Sample Series - I Dispersive Surface Energy vs. Al 2 O 3 - Content Dispersive Surface Energy [mj/m²] I mj/m² I mj/m² I mj/m² I mj/m² I mj/m² I mj/m² Al 2 O 3 - Content [%] R² = R² = Sample Series - I Regression Line - 1 Regression Line - 2 Finite Concentration KII RS - Plot of the dispersive surface energies versus the Al 2 O 3 - contents of the particles - Al 2 O 3 concentration on Particle surface seams to be proportional to the core content - In addition, two regression lines are shown. - (black) includes all samples - (blue) excludes sample I 6 (reason: different oxygen concentration) - The values are analyzed by LC-SEA according to Schultz with a surface coverage of 0.1 at the peak parameter Ø Peak Max/Com. 17 Dr. Th. Koch, Colone June 20, 2017

Examples Al2O3 Content of Base Material 75 γ s d [mj/m²] - Al 2 O 3 [%] 70 65 60 55 50 45 40 0.5 0.88 1.21 1.22 1.63 1.

18 Examples Al2O3 Content of Base Material 75 γ s d [mj/m²] - Al 2 O 3 [%] SMS Software 40 C Adscientis Software 100 C Finite KII RS - Plot of the dispersive surface energies versus the Al 2 O 3 - contents of the particles - Al 2 O 3 concentration on Particle surface seams to be proportional to the core content - the 100 C measurement shows stronger slope 18 Dr. Th. Koch, Colone June 20, 2017

Examples Comparison K2360 and K2230 VSSA (BET): K2230 5,7 m³/g, K2360 14,6 m³/g 30 25 20 K2230 K2360 Free Surface Energy: Code G a (CH 2 ) [kj/mol] γ s d [mj/m 2 ] r 2 G a [kj/mol] 15 10 5 0 5 K2230

19 Examples Comparison K2360 and K2230 VSSA (BET): K2230 5,7 m³/g, K ,6 m³/g K2230 K2360 Free Surface Energy: Code G a (CH 2 ) [kj/mol] γ s d [mj/m 2 ] r 2 G a [kj/mol] K ± ± K ± ± Carbon number or Χ T Molecular Roughness: K2230 K2360 Code 2,2-DiMeHexane Cyclooctane K ± ± 0.04 K ± ± 0.01 G a [kj/mol] isooctane cyclooctane Carbon number or Χ T K2230 is significantly less acidic (e.g. Et.-Acetat, Esther) Much more adsorption on K2360 (BET method) 70.0 K2230 isopropanol 60.0 K2360 Isopropanol Q ads [µmol/g] K2230 Eth. Acet. K2360 Eth. Acet. K2230 n-c 8 K2360 n-c P/Po Infinite Adscientis 19 Dr. Th. Koch, Colone June 20, 2017

20 Examples Comparison K2360 and K2230 K2230 lower surface energy 3D probe-grafting interactions diminished acidic character K2360 higher surface energy nanorough (molecular surface roughness) strong surface polarity Infinite Adscientis 20 Dr. Th. Koch, Colone June 20, 2017

21 Examples Comparison K2360 and K2230 Normalized to 1 µmol Topological heterogeneity (n-octane) Equivalent for K2230 and K2360 Site Number [µmol/(kj/mol)] n-octane 30 C K2230 K Adsorption Energy [kj/mol] Chemical heterogeneity (Etyl Acetate) Strong for K2360 Reduced for K2230 Site Number [µmol/(kj/mol)] Ethyl Acetate 30 C K2230 K Adsorption Energy [kj/mol] Chemical heterogeneity (Isopropanol) Strong for K2360 Reduced for K2230 Finite Adscientis Site Number [µmol/(kj/mol)] Isopropanol 40 C K2230 K2360 Adsorption Energy [kj/mol] 21 Dr. Th. Koch, Colone June 20, 2017

22 Examples Comparison K2360 and K2230 The probes mainly see the remaining free surface The organic treatment applied to K2230: reduce the interactive surface area (-90%) strong adsorption sites remains at the surface beyond the organic layer IGC-ID and IGC-FC results are consistent and complementary Finite Adscientis 22 Dr. Th. Koch, Colone June 20, 2017

23 Examples Processability of K aggregates in application - small not dispersable aggregates - worse processability - bad dispersion properties Squalan Oil Number [ml/g] γ sd ka kb ka/kb * K , ,1 68 K2900_def1 54,4 30,97 65,17 48 K2900_def2 48,53 33,13 57,23 58 IGC Comparison K K2900 K2900_def1 K2900_def2 70 Squalan Torque [mnm] γsd ka kb ka/kb * K2900 K2900_def1 K2900_def2 K2900 K2900_def1 K2900_def2 Finte KII RS Brabender Abs KII RS 23 Dr. Th. Koch, Colone June 20, 2017

Examples Processability of K2900 - aggregates in application - small not dispersable aggregates - worse processability - bad dispersion properties Squalan Oil Number [ml/g] γ sd ka kb ka/kb * 100 40

24 Examples Processability of K aggregates in application - small not dispersable aggregates - worse processability - bad dispersion properties Squalan Oil Number [ml/g] γ sd ka kb ka/kb * K , ,1 68 K2900_def1 54,4 30,97 65,17 48 K2900_def2 48,53 33,13 57,23 58 IGC Comparison K K2900 K2900_def1 K2900_def2 70 Squalan Torque [mnm] change of polarity γsd ka kb ka/kb * K2900 K2900_def1 K2900_def2 K2900 K2900_def1 K2900_def2 Infinite KII RS Brabender Abs KII RS 24 Dr. Th. Koch, Colone June 20, 2017

25 Conclusions Application of IGC for TiO 2 : - Averaging over many particles => statistical product information - sensitive for small changes of surface properties => fine tuning for application - classification of TiO 2 Pigments => tuning for application - detection of production variations => quality control, complaint management - molecular surface roughness => tuning on molecular level 25 Dr. Th. Koch, Colone June 20, 2017

26 Thanks To: Ralf Duempelmann Eric Brendle Robert Kohler Sven Böhm Tamara Rochow Manuel Weckbecker 26 Dr. Th. Koch, Colone June 20, 2017

New ways to characterize 'hard' and 'soft' surface properties by IGC-ID. Eric BRENDLE

New ways to characterize 'hard' and 'soft' surface properties by IGC-ID Eric BRENDLE Content IGC at Infinite Dilution Principle and Assumptions Real surfaces and accessibility Morphology index (IM) and