selection of suitable titanium dioxide grades for paints and coatings, plastics, decor paper...

Selection of Suitable Titanium Dioxide Grades for Paints and Coatings, Plastics, Decor Paper Applications.

Andriy Gonchar, Director, RD Titan Group, TOVwww.innovativetio2.com [email protected]

Classification of TiO2 Rutile Grades Depending on Their Properties and End-use

Lakokraska UA · 6th Annual Ukrainian Paints & Coatings Conference · Ukraine · Irpin· 11 February 2016

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1. The Problem of Selecting Appropriate Types of Titanium Dioxide Grades for a

Particular Application.• TiO2 and Ti-based products manufacturing plants in the world:

>100• Titanium dioxide grades and Ti-based materials (including color

pigments-titanates) for various applications: > 1100

• A titanium dioxide consumer faces a choice:

Which type of TiO2 or Ti-based products has to be chosen depending on the end-use?

Selection Algorithm

Function

Pigmentation

UV Protection

Catalysis

PhotocatalysisIR Scattering

Chemical Reactions

Reinforcement

If you select “Pigmentation”,

then…

Selection Algorithm

Color of Pigment

White

Gray

Beige

GreenYellow

Brown

Orange

If you select “Pigmentation”,

then…

If the color of the pigment is “White”,

then…

Selection Algorithm

Lattice type

Rutile

Anatase

If the color of the pigment is “White”,

then…

If lattice type is “rutile”,

then…

Selection Algorithm

General Application

Paint & Coatings

Plastics

Décor Paper for Laminates

Other (Paper, Ceramics,

Electroceramics, Vitreous

Enamels, Glass etc.)

Food, Pharma, Cosmetics

If lattice type is “rutile”,

then…

Method of Production (relevant to

~10% of application

areas)

Chloride

Sulphate

Hydrochloride (future-

oriented, not commercialized

at present).

If application area is “Paint&Coatings”,

then…

Selection Algorithm If application area is “Paint&Coatings”,

then…

At this stage a decision should be made on the choice of the appropriate pigment, at the same time solving other tasks and

striking a compromise between different pigment properties which are often conflicting – see the details in Section 4.

Selection Algorithm

Function

Pigmentation

UV Protecti

on

Catalysis

PhotocatalysisIR Scattering

Chemical Reactions

Reinforcement

Color of Pigment

White

Gray

Beige

GreenYellow

Brown

Orange

Lattice Type

Rutile

Anatase

Main Application Area

Paint & Coatings

Plastics

Décor Paper for

Laminates

Other (Paper, Ceramics,

Electroceramics, Vitreous

Enamels, Glass etc.)

Food, Pharma,

Cosmetics

Method of Production

(relevant to ~10% of application

areas)

Chloride

Sulphate

Hydrochloride (future-oriented,

not commercialized

at present).

2. Classification of TiO2 Rutile Grades Depending on Their Properties and End-use.

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 TypeTiO2 for Food,

Pharma, Cosmetics

E171 Rutile Type

3. RD Titan Group ‘s TiO2 Classification by Type via Examples of Some Grades Manufactured by the World's Top 5 Producers of Titanium Dioxide and Technologies (for Three Main Application Areas).

TiO2 Grade Type Grades Manufactured by the World's Top 5 TiO2 Producers

RD Titan Group Production Technology

Typical TiO2 Content (%)

Inorganic Surface

Treatment

Type According to

ISO 591-1:2000

Type According to ASTM D 476-

00 P&C Type 1 RCL-9 (by Cristal) RC-30 94-96 Al R2 II

P&C Type 2 Tioxide TR88 (by Huntsman) RC-44 92-94 Al, Si R2 II, III

P&C Type 3 Kronos 2044 (by Kronos) RC-80 80-86 Al, Si R3 III

P&C Type 4 Sachtleben RDI-S (by Huntsman)

RC-31 94-96 Al R2 II

P&C Type 5 Tronox CR-828 (by Tronox) RC-54 92-95 Al, Zr, (sometimes

+Si)

R2 II, V

P&C Type 6 (Subtype A)

TiPure R-960 (by Chemours [DuPont])

- 89-91 Al, Si R2/R3 II, IV


TiPure R-706 (by Chemours [DuPont])

RC-74 92-93 Al, Si R2 II, IV

3. RD Titan Group ‘s TiO2 Classification by Type via Examples of Some Grades Manufactured by the World's Top 5 Producers of Titanium Dioxide and Technologies (for Three Main Application Areas).



Typical TiO2 Content

(%)

Inorganic Surface Treatment

Type According to

ISO 591-1:2000

Type According to ASTM D 476-

00 Plastic Type 1 Tioxide R-FC5 (by Huntsman) RP-12 and RP-13 97-98 Al (+hydrophobic

surface treatment)

R1 II

Plastic Type 2 Tiona 90 (by Cristal) RP-32 and RP-33 95-96 Al (+hydrophobic surface

treatment)

R2 II

Plastic Type 3 Kronos 2222 (by Kronos) RP-72 and RP-73 91-93 Al, Si (+hydrophobic

surface treatment)

R2 II, IV

DP Type 1 TiPure R-796+ (by Chemours [DuPont])

RL-96 87-90 Al compounds R3 IV

4. Solution to the Problem of the Appropriate Titanium Dioxide Grade Choice for a Particular

Application (Through the Example of ‘Paints&Coatings’ Area).

Criterion: PVC

(Pigment Volume Concentration)

≥ Critical PVC

P&C Type 3 (highly

recommended)P&C Type 2

(can be used)

≤ Critical PVC

P&C Type 1

P&C Type 2

P&C Type 4

P&C Type 5

P&C Type 6 (Subtypes A, B)



Criterion: Weather Resistance (Durability)

Moderate

P&C Type 1P&C Type 2

P&C Type 3 P&C Type 4

High

P&C Type 5P&C Type 2 (can

be used partially)

Extremely High

P&C Type 6 (Subtype A}

P&C Type 6 (Subtype B}



Criterion: Gloss of the Coating

Low

P&C Type 3

P&C Type 2

Moderate

P&C Type 2


High

P&C Type 1

P&C Type 2

P&C Type 5


Extremely High

P&C Type 4



Acid-Base Properties of the Surface

Selection of Wetting and Dispersing Agents

Acid surface

Dispersing Agent:Good - with base functional groups

Satisfactory – with mixed (acid and base) functional groups

P&C Type 3 P&C Type 6 (Subtype A)

Neutral surface

Dispersing Agent:Good - with mixed (acid and base) functional groups

Satisfactory – both with acid and base functional groups

P&C Type 2 P&C Type 5 P&C Type 6 (Subtypes A, B)

Base surface

Dispersing Agent:Good – with acid functional groups

Satisfactory - with mixed (acid and base) functional groups

P&C Type 1 P&C Type 4 P&C Type 5



Criterion: Carbon Black

Undertone (CBU)

Yellow Undertone

P&C Type 2

P&C Type 3


Neutral Undertone

P&C Type 1

P&C Type 2

P&C Type 5

P&C Type 6 (Subtype A, B)

Blue Undertone

P&C Type 1

P&C Type 4

P&C Type 5


Very Blue Undertone

P&C Type 4

5. Formal Classification of TiO2 Grades by a Particular Type and Full Correspondence Issues

• The given classification of titanium dioxide grades is the result of TiO2 market development under the influence of the world’s top 5 producers and their main customers over the last 50 years. • Generally, other TiO2-producers tend to reproduce the products

offered by Top 5, which either leads to:• Full correspondence with the quality level of the world’s top 5 producers’

grades;• Partial correspondence with the quality level of the world’s top 5 producers’

grades;• Or lack of correspondence with the quality level of the world’s top 5

producers’ grades.


• It is not fairly easy for a TiO2 consumer to assess prima facie the degree of correspondence of the products, manufactured by companies other than Top 5, with the world standards.• Technical Data Sheets (TDS) provided by these producers can contain the descriptions of

products which are very similar to products of the world’s top 5 producers, but in fact the key parameters of those products are not corresponding;

• When selecting a new titanium dioxide grade for a particular formulation or production technology one should take into account the following:• High amounts of SiO2 in the test titanium dioxide grade do not guarantee high and extremely high

weatherability;• Use of Zr compounds in the test titanium dioxide grade does not guarantee that one can obtain a product

with high weatherability;• If the test titanium dioxide grade is chemically similar to P&C Type 1 and P&C Type 4, this does not guarantee

that the grade has superior dispersibility and can be used in the production of high gloss coatings;• If one uses the same chemical compounds for the surface treatment (as are typically used by the world’s top

5 companies) to produce DP Type 1 grades, this does not guarantee that the grade has a high light fastness to be used in the production of decor paper.


• Even if the tests of pilot samples have yielded positive results, it is unknown whether industrial batches will have the same quality level or not and what the quality variability from batch to batch will be; • Some quality assessment tests take a long time, for example, light

fastness or weather resistance tests (accelerated testing will take several months, and research in the natural environment can take a few years).

6. Classification of Rutile Titanium Dioxide Grades Produced by Ukrainian Companies According to the

Following Application Areas: Paints&Coatings, Plastics, Décor Paper.TiO2 Grade Type Grades Manufactured by the

World's Top 5 TiO2 Producers RD Titan Group

Production TechnologySumykhimprom JSC Ukrainian Chemical

Products PJSC (former Crimea Titan PJSC)

P&C Type 1 RCL-9 (by Cristal) RC-30 SumTitan R-2071 TiOx-270, TiOx-271

P&C Type 2 Tioxide TR88 (by Huntsman) RC-44 SumTitan R-202, SumTitan R-203, SumTitan R-204,

SumTitan R-206, SumTitan R-2041, SumTitan R-2061

TiOx-220, TiOx-230

P&C Type 3 Kronos 2044 (by Kronos) RC-80 No Grades No Grades

P&C Type 4 Sachtleben RDI-S (by Huntsman) RC-31 No Grades No Grades

P&C Type 5 Tronox CR-828 (by Tronox) RC-54 SumTitan R-208 TiOx-280

P&C Type 6 (Subtype A) TiPure R-960 (by Chemours [DuPont])

- No Grades No Grades

P&C Type 6 (Subtype B) TiPure R-706 (by Chemours [DuPont])

RC-74 No Grades No Grades

6. Classification of Rutile Titanium Dioxide Grades Produced by Ukrainian Companies According to the

Following Application Areas: Paints&Coatings, Plastics, Décor Paper.



Sumykhimprom JSC Ukrainian Chemical Products PJSC (former

Crimea Titan PJSC)Plastic Type 1 Tioxide R-FC5 (by Huntsman) RP-12 and RP-13 No Grades No Grades

Plastic Type 2 Tiona 90 (by Cristal) RP-32 and RP-33 No Grades No Grades

Plastic Type 3 Kronos 2222 (by Kronos) RP-72 and RP-73 No Grades No Grades

DP Type 1 TiPure R-796+ (by Chemours [DuPont])

RL-96 No Grades No Grades

7.1 China’s TiO2 Industry: a Brief Introduction

• The increase in TiO2 production over the last 20 years• 1995: The effective capacity of 130’000 tons / year (mainly anatase)

• 3,8% of world consumption• Sulphate plants only

• 2014: The effective capacity of 2’750’000 tons / year (rutile, anatase)• 47,8% of world consumption

• Sulphate plants;• 4 chloride plants (total capacity - ~240’000 tons / year )

• Yunnan Xinli Non-Ferrous Metals Co., Ltd.• Jinzhou Titanium Industry Co., Ltd.• Luohe City Xingmao Titanium Industry Co., Ltd.• Henan Billions Chemical Co., Ltd.

• 46 companies in China• Own 56 plants for the production of TiO2

• Produce about 350 TiO2 grades

7.1 China’s TiO2 Industry: a Brief Introduction

• Well-known Chinese companies:

• Henan Billions Chemical Co., Ltd. and Sichuan Lomon Titanium Co., Ltd. Alliance.

• Pangang Titanium Industry Co., Ltd.

• Anhui Annada Titanium Industry Co., Ltd.

• Shandong Doguide Group Co., Ltd.

• Jinan Yuxing Chemical Co (Bluestar Group).

7.2 China’s TiO2 Industry: Statistics on Manufactured Rutile Titanium Dioxide Types for the Following Applications: Paints&Coatings, Plastics,

Décor Paper.Representation of Different TiO2 Types by World’s Top 5 Companies

Representation of Different TiO2 Types by 33 Chinese Companies Producing Rutile TiO2 (Sulphate Route)

Representation of Different TiO2 Types by 4 Chinese Companies Producing Rutile TiO2 (Chloride Route)


Décor Paper.Proportion of Various Types of TiO2 Rutile Grades by World’s Top 5 Companies

Proportion of Various Types of TiO2 Rutile Grades by Chinese Companies (Sulphate Route)

Proportion of Various Types of TiO2 Rutile Grades by Chinese Companies (Chloride Route)


Décor Paper.So what will a potential titanium dioxide consumer from Europe or North America find out, if

he decides to replace the titanium dioxide produced by world’s top 5 companies which he uses with a comparable product from China?

Everything will depend on the application for which the consumer looks for a product.• If it is a production that requires universal grades without special requirements, the variety would be rather wide. • If it is, for example, a company producing Décor Paper for laminates, the choice will be reduced to only 6-7 grades by 4-5 TiO2 companies. • If it is a company searching for high weather resistant grades for marine and aerospace applications or the like, the choice will be from 4-6 grades by 4-6 companies.• If it is a manufacturer of PVC window profiles, then he will have to choose from 5-7 grades by 5-7 producers.• If it is a manufacturer of ink (Printing Inks), he will choose from 1-2 grades, one of which is a TR-52 (manufactured by Huntsman for Henan Billions).• If it is a manufacturer of electrodepositable paints, he will choose from 5-7 grades by 5-6 producers.• If it is a manufacturer of highly filled grades, he will have to choose from 2-3 grades by 2-3 manufacturers.• If it is a manufacturer of thin high-polymer films, then he will have to choose from 6-7 grades by 6-7 companies.• If it is a manufacturer of engineering plastics, he will have to choose from 8-9 grades by 8-9 companies.


Décor Paper.But if it is a manufacturer of automotive enamels, looking for a superfine grade with high weather resistance, he will face plenty of offers: he will have to select a suitable grade from 50 or more offers by more than 25 companies. But the real problem would be that in spite of the abundance of offers, not all but just a few products with their similarity in chemical composition to P & C Type 5 grades manufactured by world’s Top 5 TiO2 producers, will have important properties required for this type, namely, the required level of dispersibility, initial gloss and weatherability.

The same problem may be faced by companies from all of the above examples. It may happen that not all grades (if at least one) out of those 5-6 titanium dioxide grades, which formally (we mean a Chinese TiO2 manufacturer’s declaration on the applicability and chemical composition similar to the same products by world’s top 5 TiO2 manufacturers etc.) fit the desired type, will actually have the required properties for a particular application.

But for a Ukrainian producer oriented toward paints in "standard" and "economy" class segments there is a variety of different suitable products manufactured in China.

Thank You for Your Attention

www.innovativetio2.com [email protected]

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Release of“Comprehensive Dossier of the World's Titanium Dioxide

Grades and TiO2 Manufacturers. Year 2016”

• Brief information on the companies-manufacturers in titanium dioxide world, from the world's top 5 companies to small manufacturers from China and India (115+ companies).

• Principles of rutile titanium dioxide grades classification.

• The classification of all TiO2 and Ti-based grades produced in the world according to their application:

- 13 Types of Rutile grades,- 4 Types of Anatase Grades,- Several types of nano-TiO2 grades,- Type of Non-spherical TiO2 grades,- 3 Types of Electro-Conductive TiO2 grades,- 6 Types of Reactive Ti-based grades,- 9 Types of colored TiO2 grades

• Approximately 1100+ TiO2 and Ti-based Grades of different types

• TDS’s for most Rutile, Anatase, Nano, Colored, and other TiO2 grades.

• SDS’s/MSDS’s for most Rutile Anatase, Nano, Colored, and other TiO2 grades

• Information on the availability of REACH registration.

• Additional information materials on the products and technologies of various companies.

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• Several videos of some Companies, Products, Application Practices, Technology Descriptions etc.

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The electronic version of the Dossier will be available from March 14, 2016

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Release of“Comprehensive Dossier of the World's Titanium Dioxide

Grades and TiO2 Manufacturers. Year 2016”


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