Titanium Dioxide in
Masterbatch
Revy Saerang (4005330)
December 9, 2011
Advanced Analytical Chemistry
Buzzword: Masterbatch
What is it?
• Color-pigmented material for plastic industry
– Packaging (Food, beverage, cosmetic), computer hardware,
automotive parts, etc. Use to insert colors and impart special
properties to plastic products.
– 1-2 % contribution in cost of production but master batch
drives the quality, durability of the plastic product.1
1Clariant
Corp. Masterbatches Profile. 2011
<//www.clariant.com/C125766B004CDFBC/vwWebPagesByID/04872E207B80A989C12568CE003E269A> (accessed on
November 29, 2011)
Background
• Titanium Dioxide in Masterbatch Industry
– Inorganic nanoparticle.
– It is used extensively in masterbatch production
as a white pigment, opacifier for colored
systems and UV stability agent3.
– a central ingredient to imparting clean, bright
whites, or fine tuning the shades of color for the
right eye appeal2.
2 Dupont
Titanium Dioxide Ri-104 Brochure. Dupont Corp.
www2.dupont.com/Titanium_Technologies/en_US/products/104/R104_Intro_Brochure.pdf Accesed on (Nov 29, 2011)
3Fisher, J. and Egerton, T.A.2001. Titanium Compounds, Inorganic. Kirk-Othmer Encyclopedia of Chemical Technology
Problem
Reformulation of masterbatch production when
the batch production does not meet the right
appeal or specification and this affects cost of
manufacturing, production schedule,
customers’ satisfaction.
Hypothesis
The actual content and the particle size of titanium
dioxide in masterbatch formulation has a significant
effect in non-homogeneity of mixing of masterbatch
formulation and to cause to reduce optimized pigment
coloration
Possible Analytical Methods
Analytical
Methods
Advantages
Disadvantages
Size Exclusion
Chromatography
Good separation of large
and small molecule, good
sensitivity, Cheap
It is normally combined with
other characteristics (acidity,
charge), limited number of
bands
ICP-MS
Easy sample introduction,
quick analysis, low
detection limit, accurate,
capable of trace at part per
trillion level
Expensive, interferences
from plasma gas, matrix
effects
X-ray
Fluorescence
Spectrometry5
High precision, determine
major element, detect
several thousands atoms
Low cost, space limitation on
sample, high scattering, low
detecting intensities
5 Potts, P.J and Webb.P.C. X-ray Fluorescence Spectrometry [Online]. In: G.E.M Hall (Editor). Geoananalysis. J.
Geochem. Explor., 44:251-296
Sample Preparation4
• Collect sample powder and dilute with nitric acid to give
required acid concentration and add distilled water to
adjust volume.
• Add 0.01% (m/v) of PVA (Poly Vinyl Alcohol) as a
dispersion agent and stabilizer
• In a beaker, use magnetic stirrer and stir for 10 minutes
to ensure homogenization before it is nebulized.
• Use an ultrasonicator and shake the flask vigorously for
around 30 minutes prior to analysis
4Guoqiang
X, Bin H, Zucheng J and Chuqing. A comparison of slurry sampling electrothermal
vaporization and slurry nebulization inductively coupled plasma mass spectrometry for the direct
determination of trace impurities in titanium dioxide powder. Journal of Mass Spectrometry.
2006:41B:1378-1385
ICP-MS
(Inductively-Coupled Plasma with Mass
Spectrometry)
Temperature of
plasma at the order
of 10,000 K
Fine droplets
of mist
Slurry
nebulized
sample
• Fine mist is extracted using high
velocity Argon (14-18 L/min)12
• Atomization and ionization
process at ICP torch
• Couple with MS, ions are passed
at vacuum condition
• Through mass filter, ions
separate at specific m/z ratio.
• A detector receives an ion
signal proportional to the
concentration
10 Inductively Coupled Plasma Mass Spectrometry. Advanced Technologies Department. [Online].2011
<http://eetd.lbl.gov/aet/inductively.html> Accessed on Dec 7, 2011
Agilant 7500a
ICP-MS7
• Dynamic Range>1000 ppm
• Wide range of detection
limit
• Extreme Sensitivity > 500
Mcps/ppm
Specifications
• Price: $64,0008
ICP Source: 27.12 Mhz (max.1600 W)
Mass analyzer: Quadrapole
Detector: Electron multipier
Pressure: Vacuum system
Mass range: 2-260 amu
8 Agilant Technologies. Agilant 7500a ICP-MS brochure.<http://www.chem.agilent.com/Library/brochures/5968-8813E.pdf> Accessed on
Dec 3, 2011.
9 Agilant Technology. Agilant 7500a ICP-MS pricing.<http://conquerscientific.com/product/agilent-7500a-inductively-coupled-plasma-massspectrometer-icpms-with-chiller-als-and-computer> accessed on Dec 3, 2011
Results
• The bar chart show how the particle size of
titanium dioxide affect the relative signal
intensity4 (intensity a content of titanium dioxide)
• Scattering efficiency decreases rapidly as particle
size varies (Figures with masterbatch with
different particle size)6
6 Fisher,
Particle size
12B/R=Blue/Red
reflectence
values
J. and Egerton, T. A. 2001. Titanium Compounds, Inorganic. Kirk-Othmer Encyclopedia of Chemical Technology
12 DuPont Ti-Pure titanium dioxide. DuPontTM<http://www2.dupont.com/Titanium_Technologies/en_US/tech_info/literature/Coatings/CO_B_H_65969_Coatings_Brochure.pdf> accessed Dec 8, 2011
Alternative
Technique
• X-Ray Fluorescence
Spectrometry
 Low cost (~$4000)
 Rapid analysis
 Convenient for solid
sample: disk sample11
 Precise, comparably
sensitive
 More complex detection
and calibration method
11X-Ray
Fluorescence Spectroscopy Unit. Network of Research Supporting Laboratories <http://www.uoi.gr/services/labnet/net-web/XRF_en.pdf> accessed on Dec 7, 2011
Conclusion
• Slurry Nebulization-Inductively Coupled Plasma-Mass
spectrometry (SN-ICP-MS) can be used to quantify the
actual content of Titanium Dioxide and recognize the
particle size effect.
• Particle size of titanium dioxide and the actual content of
titanium dioxide in one formulation of masterbatch
production is significantly important in determining the
right shade of color appeal due to its photocatalytic effect,
scattering efficiency, and other optical properties.
References
1.
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12.
Clariant Corp. Masterbatches Profile. 2011
<//www.clariant.com/C125766B004CDFBC/vwWebPagesByID/04872E207B80A989C12568CE003E269A> (accessed on
November 29, 2011)
Dupont. DupontTM Ti-Pure R-104 titanium dioxide.
<www2.dupont.com/Titanium_Technologies/en_US/products/104/R104_Intro_Brochure.pdf > Accesed on (Nov 29, 2011)
Fisher, J. and Egerton, T.A.2001. Titanium Compounds, Inorganic. Kirk-Othmer Encyclopedia of Chemical Technology
Guoqiang X, Bin H, Zucheng J and Chuqing. A comparison of slurry sampling electrothermal vaporization and slurry nebulization
inductively coupled plasma mass spectrometry for the direct determination of trace impurities in titanium dioxide powder. Journal
of Mass Spectrometry. 2006:41B:1378-1385
Potts, P.J and Webb.P.C. X-ray Fluorescence Spectrometry [Online]. In: G.E.M Hall (Editor). Geoananalysis. J. Geochem.
Explor., 44:251-296
Fisher, J. and Egerton, T. A. 2001. Titanium Compounds, Inorganic. Kirk-Othmer Encyclopedia of Chemical Technology
Skoog, D.; Holler, F.; Crouch, S. Principles of Instrumental Analysis, 6th ed
8Agilant Technologies. Agilant 7500a ICP-MS brochure.<http://www.chem.agilent.com/Library/brochures/5968-8813E.pdf>
Accessed on Dec 3, 2011
Agilant Technology. Agilant 7500a ICP-MS pricing.<http://conquerscientific.com/product/agilent-7500a-inductively-coupledplasma-mass-spectrometer-icpms-with-chiller-als-and-computer> accessed on Dec 3, 2011
Inductively Coupled Plasma Mass Spectrometry. Advanced Technologies Department. [Online].2011
<http://eetd.lbl.gov/aet/inductively.html> Accessed on Dec 7, 2011
X-Ray Fluorescence Spectroscopy Unit. Network of Research Supporting Laboratories <http://www.uoi.gr/services/lab-net/netweb/XRF_en.pdf> accessed on Dec 7, 2011
DuPont Ti-Pure titanium dioxide. DuPontTM .2011
<http://www2.dupont.com/Titanium_Technologies/en_US/tech_info/literature/Coatings/CO_B_H_65969_Coatings_Brochure.pdf>
accessed Dec 8, 2011