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 20164th - 6th October 2016, Cleveland, OHIO

http://www.pigmentmarkets.com/tio2

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 PropertiesResistance 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/

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

TypicalTiO2 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


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


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

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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 TypeDurability 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 TypeDurability Increase



UV screening increase

Increase in resistance to

photocatalytic activity


lattice





etc.)



pigment







Maximum decrease in



Lacing Resistance Increase

Using technologies to

provide Free Radical

Scavenger Effect


(CBU)

Hiding Power Increase






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.

Hiding

Dispersibility

Lacing Resistance

Resistance to the Photocatalytic Ativity

Blue undertone (in CBU)

UV screening

0

100

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 TypeLightfastness

Increase



UV screening Increase

Greying Resistance Increase


lattice





etc.)



pigment







Maximum decrease in



Brightness Increase, Yellowness ReductionUsing

technologies to inhibit the

recovery of Ti4 + to Ti3 +


(CBU)

Opacity Increase






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 Super Durable Grade, P&C Type 6 (Subtype B)

Produced according to RD Titan Group Innovative TiO2

proprietary technology

3 F 17 Super Durable Grade, P&C Type 6 (Subtype B)

Grade produced by Manufacturer ‘F’ belonging to Top-5 global TiO2 producers

4 G 26 Medium-High Durable Grade, P&C Type 2

Grade produced by Manufacturer ‘G’ belonging to Top-5 global TiO2 producers

5 H 54 Medium Durable Grade, P&C Type 2

Grade produced by Manufacturer ‘H’ belonging to Top-5 global TiO2 producers

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 !

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Technology

The Next Generation of TiO2 Pigments