The Next Generation of TiO2 Pigments

The Next Generation of
TiO2 Pigments
as a result of overcoming the antagonism of pigment properties:
high hiding power, better dispersibility, extraordinary durability.
Head of R&D and QA of
RD Titan Group Innovative TiO2
Director of
RD Titan Group, TOV
TiO2 World Summit 2016
4th - 6th October 2016, Cleveland, OHIO
http://www.pigmentmarkets.com/tio2

Titanium Dioxide is an Almost Perfect White Pigment
• The highest refraction index among known transparent materials;
• Whiteness is almost close to 100%;
• Low color tone;
• Wide occurrence of titanium raw materials in nature;
• Availability of well-proven and well-optimized titanium dioxide
production technologies (Sulfate and Chloride Processes), as well as
the prospect of the new technology commercialization
(Hydrochloride-Organic Extraction Process);
• Relative cheapness.
Alternatives to replace titanium dioxide as a white pigment are not
expected in the next few decades

• TiO2 crystal absorbs UV
radiation.
• As a result of UV absorption
some chemical reactions
leading to a number of
negative phenomena are
initiated.
ALMOST perfect as there is one substantial defect:
photocatalytic activity of TiO2.
Flow chart of photochemical
reactions in TiO2 crystal (anatase)*
*This figure is taken from Semiconductor/biomolecular composites for solar energy
applications. Chuanhao Li, Feng Wang and Jimmy C. Yu Energy Environ. Sci., 2011,4, 100-113

• For systems open to atmospheric oxygen and water exposure, such as
various coatings or plastics - destruction of polymer film molecules and
as a consequence:
• Loss of gloss;
• Chalking.
• For systems closed to atmospheric oxygen and water exposure, such as
laminate paper - transition of some titanium dioxide lattice atoms from
Ti4+ to Ti3+ and consequently:
• Irreversible laminate graying.
After-effects of TiO2 photocatalytic activity.

Ways to Eliminate Negative Effects of TiO2
Photocatalytic Activity
• Coating the surface of titanium dioxide particles with dense dielectric layer
to prevent the charge transfer from TiO2 surface to the binder molecule:
• SiO2;
• Phosphates of some metals.
• Coating the surface of titanium dioxide particles with materials, providing
the capture of TiO2 photocatalytic activity products (●OH, ●O2
-, ●O2H
radicals) and their subsequent mutual annihilation:
• Metal oxides/hydroxides, e.g., Zr;
• Phosphates of some metals.
• Doping of TiO2 lattice with atoms of other elements to create traps for
excitons (migrating electron-hole pairs within the crystal) with a view to
reduce the number of excitons reaching the surface of titanium dioxide
particles.
• Introducing inhibitors to pigments to prevent the formation of Ti3+.

Initial Gloss
• Resistance to
Photocatalytic
Activity
• UV screening
• Hiding Power
• Blue
undertone
(CBU)
Antagonism of Pigment Properties
Resistance to
Photocatalytic
Activity
• Initial Gloss
• UV screening
• Hiding Power
• Blue
undertone
(CBU)
UV screening
• Resistance to
Photocatalytic
Activity
• Blue
undertone
(CBU)
• Hiding Power
• Initial Gloss

Classification of Rutile TiO2
*
TiO2 for
Paint &
Coatings
P&C Type 1
P&C Type 2
P&C Type 3
P&C Type 4P&C Type 5
P&C Type 6
(Subtype
A)
P&C Type 6
(Subtype B)
TiO2 for
Plastics
Plastic
Type 1
Plastic
Type 2
Plastic
Type 3
TiO2 for
Décor
Paper
DP
Type 1
TiO2 for other
applications (Paper,
Ceramics,
Electroceramics,
Vitreous Enamels,
Glass etc.)
Uncoated
Rutile
Type
TiO2 for Food,
Pharma,
Cosmetics
E171
Rutile
Type
Durable grades
* Hereinafter is the classification of titanium dioxide grades by type as it is accepted in the RD Titan Group Innovative TiO2 publication “Comprehensive Dossier of the World's
Titanium Dioxide Grades and TiO2 Manufacturers. Year 2016” - http://innovativetio2.com/dossier/

Classification of Rutile TiO2
*
* Hereinafter is the classification of titanium dioxide grades by type as it is accepted in the RD Titan Group Innovative TiO2 publication “Comprehensive Dossier of the World's
Titanium Dioxide Grades and TiO2 Manufacturers. Year 2016” - http://innovativetio2.com/dossier/
TiO2 Grade
Type
Typical TiO2
Content (%)
Inorganic
Surface
Treatment
Applications
P&C Type 1 94-96 Al Electrodeposition paints*, Automotive (Primers), Can
Coatings, Coil Coatings,
Water-borne and Solvent-borne Industrial and
Decorative Coatings, Wood Paints
P&C Type 2 92-94 Al, Si Water-borne and Solvent-borne Industrial and
Decorative Coatings
P&C Type 3 80-86 Al, Si Highly pigmented emulsion paints, Exterior and
interior trade sales paints, Paper filler and coating
applications, Wallpaper coatings, Flat flexographic
inks
P&C Type 4 94-96 Al Printing Inks, Can Coatings, Coil Coatings,
Wood Paints, Water-born or solvent-born coatings
with very high gloss
P&C Type 5 92-95 Al, Zr,
(sometimes
+Si)
Automotive finishes and Refinishes,
Coil Coatings, Powder coatings, Marine Coatings,
Water-born or solvent-born coatings
P&C Type 6
(Subtype A)
89-91 Al, Si Exterior Coatings, Automotive Finishes and
Refinishes, Coil Coatings, Powder Coatings, Marine
Coatings, Aerospace Coatings
P&C Type 6
(Subtype B)
92-93 Al, Si Exterior Coatings, Automotive Finishes and
Refinishes, Coil Coatings, Powder Coatings, Marine
Coatings, Aerospace Coatings
Durable grades
TiO2 Grade
Type
Typical
TiO2
Content (%)
Inorganic
Surface
Treatment
Applications
Plastic Type
1
97-98 Al
(+hydrophobi
c surface
treatment)
Polyolefin Masterbatch, Flexible PVC (interior),
High Temperature Cast Films, Thin Films, PVC-
plastisols
Plastic Type
2
95-96 Al
(+hydrophobi
c surface
treatment)
Polyolefin Masterbatch, Polyethylene,
Polypropylene, PVC (Interior), PVC (Exterior,
Chalking), PVC Pipe, ABS, Polycarbonate,
Polystyrene, Polyamide
Plastic Type
3
91-93 Al, Si or
sometimes Zr
(+hydrophobi
c surface
treatment)
PVC and polyolefines (Exterior, Nonchalking),
Agricultural Films, Outdoor Furniture, PVC-
Windows sections
DP Type 1 87-90 Al, P
compounds
High and Low Pressure Laminate, Printing Inks
for Décor Paper, Melamine moulding powders

Durable TiO2 Timeline
Benefits
One of the first technologies to improve the durability of titanium dioxide in modern
practice (since the mid-1960s) was to coat titanium dioxide particles with dense dielectric
layer, in particular, dense SiO2
(P&C Type 6 [Subtype A]*)
Drawbacks
• Significant decrease
of pigment
photocatalytic
activity;
• Superior durability
when using binders
having middle and
high resistance to
UV.
• Deterioration of
dispersibility;
• Initial gloss reduction;
• Low efficiency when using
binders having low resistance
to UV;
• Hiding power reduction (in
comparison to P & C Type 1);
• Tendency to yellow
undertone (CBU).

Benefits
Due to the shortcomings of P&C Type 6 (Subtype A), in the 1980s some efforts were made to develop the
type of pigments that would have sufficiently high durability and no drawbacks of P&C Type 6 (Subtype
A). As a result of this work pigments surface-treated with a layer of zirconium oxides / hydroxides and
other treatment chemicals were developed (P&C Type 5*)
Drawbacks
• High durability when using
binders having middle and
high resistance to UV;
• High durability when using
binders having low
resistance to UV;
• High initial gloss;
• Neutral or blue undertone
(CBU);
• High hiding power.
• Failure to reach the
level of Superior
Durability (in
comparison to Type 6
[Subtype A]).

Benefits
In the 1990s, a number of Western companies developed technologies of uniform coating with dense SiO2, due to which
they managed to reduce the amount of silica used for surface treatment (3-3,5% vs 4,5-7% ) in comparison to P & C Type 6
(Subtype A) and to increase the TiO2 content (92,5-93% vs 88-91%), as well as to improve dispersibility and initial gloss
(P&C Type 6 [Subtype B]*)
Drawbacks
• Superior durability when
using binders having middle
and high resistance to UV;
• High efficiency when using
binders having low
resistance to UV;
• High initial gloss;
• Neutral or blue undertone
(CBU);
• High hiding power.
• Slightly inferior to the
level of durability in
comparison to
pigments of Type 6
[Subtype A] with 5-7%
level of SiO2
treatment;
• Slightly inferior to the
hiding power of P&C
Type 1 pigments.

Benefits
The development of titanium dioxide grades for Décor Paper (Laminates) was a
separate direction, the type of modern grades emerged in 1990s-2000s.s
(DP Type 1*)
Drawbacks
• High Lightfastness
(Blue Wool Scale
≥6 according to
DIN EN 13329, DIN
54004);
• High brightness;
• Neutral undertone
(CBU);
• Good opacity.
• Inferior to the opacity
of P&C Type 1
pigments;
• Some grades can have
excessive yellow
undertone.

Benefits
Super Durable Grades for Plastic application were developed in the 1990s using
dense SiO2 coating technologies (and in some cases using a Zr coating or a
combination of Zr, Si) (Plastic Type 3*)
Drawbacks
• Superior durability in
plastics;
• Excellent
compatibility with
non-polar resins due
to hydrophobic
surface treatment.
• Hiding power is lower
than that of Plastic
Types 1, 2;
• Low Lacing
Resistance;
• Yellow undertone
(CBU);
• UV Screening is lower
than that of Plastic
Types 1, 2.

What improvements should be expected in the next generation titanium
dioxide grades for the following applications?
The Next Generation of TiO2 Pigments
• Paint and Coatings;
• Plastics;
• Décor Paper.
The next few slides will give the answers to these questions
Due to what can these results be achieved?

Paint and Coatings: P&C Next Generation TiO2 Type
Durability Increase
Creation of
100% insulating
layer on the
surface of TiO2
UV screening
increase
Increase in
resistance to
photocatalytic
activity
Doping of
TiO2 crystal
lattice
Technologies of
most uniform
distribution of a
coating layer on
TiO2 surface Technologies to
eliminate coating
imperfections
(cracks, bald spots
etc.)
Securing the
optimal size and
maximum
dispersion of
pigment
Technologies to
produce pigment
with maximum blue
undertone and
maximum hiding
power
Surface treatment
technologies while
maintaining the
maximum
dispersion of
pigment
Maximum
decrease in
photocatalytic
activity while
maintaining the
optical properties
Initial Gloss Increase
Using
technologies to
provide Free
Radical
Scavenger Effect
Reaching maximum
blue undertone
(CBU)
Hiding Power
Increase
Increasing the relative
light refraction index
at the interface
between the phases
TiO2-medium around
the pigment particle
Use of additional
materials for UV-
absorption /
scattering
Changes in key
pigment properties

Paint and Coatings: P&C Next Generation TiO2 Type
• New level of
Durability: +10÷15%;
• Increased Hiding
Power: +5÷10%;
• Superior Initial Gloss:
similar to P&C Type 1;
• Strong blue
undertone (CBU):
similar to P&C Type 1
or even P&C Type 4;
• Equilibrium of
properties;
• Greater versatility.

Plastics: Plastic Next Generation TiO2 Type
Durability Increase
Creation of
100% insulating
layer on the
surface of TiO2
UV screening
increase
Increase in
resistance to
photocatalytic
activity
Doping of
TiO2 crystal
lattice
Technologies of
most uniform
distribution of a
coating layer on
eliminate coating
imperfections
(cracks, bald spots
etc.)
Securing the
optimal size and
maximum
dispersion of
pigment
Technologies to
produce pigment
with maximum blue
undertone and
maximum hiding
power
Surface treatment
technologies while
maintaining the
maximum
dispersion of
pigment
Maximum
decrease in
photocatalytic
activity while
maintaining the
optical properties
Lacing Resistance
Increase
Using
technologies to
provide Free
Radical
Scavenger Effect
Reaching maximum
blue undertone
(CBU)
Hiding Power
Increase
at the interface
between the phases
TiO2-medium around
Use of additional
materials for UV-
absorption /
scattering
Changes in key
pigment properties
Special
technologies of
post-processing
and
hydrophobization

Plastics: Plastic Next Generation TiO2 Type
• New level of Durability:
+10÷15%;
• Increased Hiding
Power: +10÷15%;
• High level of Lacing
Resistance: similar to
Plastic Type 1;
• Strong blue undertone
(CBU): similar to Plastic
Type 2;
• Equilibrium of
properties;
• Greater versatility;
• Hydrophobicity, high
compatibility with non-
polar resins melts.
0
20
40
60
80
100
Hiding
Dispersibility
Lacing Resistance
Resistance to the
Photocatalytic Ativity
Blue undertone (in
CBU)
UV screening
Comparison of different TiO2 Rutile Types (%)
Plastic Type 1
Plastic Type 2
Plastic Type 3
Plastic Next
Generation TiO2
Type

Décor Paper: DP Next Generation TiO2 Type
Lightfastness
Increase
Creation of
100% insulating
layer on the
surface of TiO2
UV screening
Increase
Greying
Resistance
Increase
Doping of
TiO2 crystal
lattice
Technologies of
most uniform
distribution of a
coating layer on
eliminate coating
imperfections
(cracks, bald spots
etc.)
Securing the
optimal size and
maximum
dispersion of
pigment
Technologies to
produce pigment
with maximum blue
undertone and
maximum hiding
power
Surface treatment
technologies while
maintaining the
maximum
dispersion of
pigment
Maximum
decrease in
photocatalytic
activity while
maintaining the
optical properties
Brightness Increase,
Yellowness
ReductionUsing
technologies to
inhibit the
recovery of Ti4 +
to Ti3 +
Reaching maximum
blue undertone
(CBU)
Opacity Increase
at the interface
between the phases
TiO2-medium around
Use of additional
materials for UV-
absorption /
scattering
Changes in key
pigment properties
Surface treatment and
post-processing
technologies that
provide higher
brightness and
reduced yellowness

Décor Paper: DP Next Generation TiO2 Type
• New level of
Lightfastness: 8 (blue
wool scale) after
double exposure (DIN
EN 13329, DIN 54004);
• Increased Opacity:
+10÷15%;
• Increased brightness,
reduced yellowness
(for sulphate grades):
ΔL*=+1÷5%, Δb*=-
10÷15% ;
• Blue undertone (CBU):
similar to P&C Type 1
• Equilibrium of
properties

Some current achievements of RD Titan Group Innovative TiO2 in
development of the Next Generation TiO2 Types
Picture shows the results of
uncoated TiO2 Calciner
Discharge exposure to UV in the
so-called ‘lead test’, based on
the reduction of metal lead from
oxides, hydroxides or salts in the
process of photocatalysis. The
more photochemically active the
sample, the greater amount of
metallic lead is formed, the
greyer the sample becomes.
Sample 1 is an experimental
sample of Project RC-8828
Calciner Discharge. According to
the measurement results
photocatalytic activity of Sample
1 is reduced by 5-6 times
compared to other samples.
Durability increase by doping TiO2 lattice
1 – Calciner Discharge with
reduced photocatalytic
activity, Project RC-8828 of RD
Titan Group Innovative TiO2. 2
- Calciner Discharge No.1, a
European manufacturer ‘А’. 3 -
Calciner Discharge No.2, a
European manufacturer ‘А’. 4 -
Calciner Discharge, a Chinese
manufacturer ‘B’, belonging to
Top-15 Chinese TiO2
Manufacturers. 5 - Calciner
Discharge, a Chinese
manufacturer ‘С’, belonging to
Top-5 Chinese TiO2
Manufacturers. 6 - Calciner
Discharge, a European
manufacturer ‘D’.

Some current achievements of RD Titan Group Innovative TiO2 in
development of the Next Generation TiO2 Types
Table shows the results of the ‘acid
test’ - the procedure of titanium
dioxide dissolution in the
concentrated sulfuric acid at a
temperature of 175°C to evaluate
the completeness of titanium
dioxide coating with a SiO2 layer
(silica is not dissolved in hot sulfuric
acid, as opposed to titanium
dioxide). The more uniform and
dense the SiO2 layer coating
titanium dioxide particles, the less is
the degree of pigment dissolution
during the test.
At the moment, we have achieved
more than twice the better effect
for Project RC-8828 in comparison
with one of the best P&C Type 6
(Subtype B) representatives – Grade
‘E’
Durability increase by creation of insulating layer on the surface of TiO2
# Grade Acid solubility, % TiO2 Type Notes
1 E 11
Super Durable Grade,
P&C Type 6 (Subtype B)
Grade produced by
Manufacturer ‘E’ belonging to
Top-5 global TiO2 producers
2 RC-74 11
Produced according to RD Titan
Group Innovative TiO2
proprietary technology
3 F 17
Grade produced by
Manufacturer ‘F’ belonging to
4 G 26
Medium-High Durable
Grade, P&C Type 2
Grade produced by
Manufacturer ‘G’ belonging to
5 H 54
Medium Durable Grade,
P&C Type 2
Grade produced by
Manufacturer ‘H’ belonging to
6 Uncoated rutile J 59
Low-medium Durable
Uncoated Rutile
Sample provided by a European
manufacturer ‘J’
7
Prototype from
Project RC-8828
5
Super+ Durable Grade of
the Next Generation
TiO2
Pilot sample produced
according to RD Titan Group
Innovative TiO2 proprietary
technology for Project RC-8828

Market Advantages and Net Cost of Next Generation TiO2
Types
• Improvement of quality characteristics of
materials that use Next Generation TiO2 Types
• Reducing the amount of titanium dioxide used in
formulations
• Versatility of titanium dioxide, expansion of areas
where the same grade can be used for different
applications, which previously required different
types of grades
• Development of new directions in which titanium
dioxide use has previously been limited due to its
insufficient Durability
• Expenditures for R&D
• Costs for additional production
equipment
• Additional costs for energy and auxiliary
materials
• Increase in the production process
stages
Negative factors affecting cost
supplement:
Positive factors affecting the increase in
customer value:
The balance between the benefits of new application properties and the price is the key factor in
the development of Next Generation TiO2 Types and their subsequent market appearance.
Rough estimate:
Economy +5÷15%
Rough estimate:
Cost development +5÷20%

Time Frame for the Emergence of Next Generation TiO2 Types
Leading global manufacturers of TiO2:
~2017-2025 yrs.
Other TiO2 manufacturers :
~2025-2035 yrs.

THANKS FOR YOUR ATTENTION !
www.innovativetio2.com
info@innovativetio2.com

The Next Generation of TiO2 Pigments

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