Technical Information

Automotive Glass

High Chemical Durability Excellent Non-stick Performance Innovative Solutions for Windshield Application Fine Line Silver Paste Systems Ferro: enhancing life through superior materials performance Headquartered in Mayfield Heights, Ohio, USA, Ferro Corporation is a world leading producer of Performance Materials, with operations in 20 countries across Europe, Asia and the Americas.

We apply core technologies in organic and Meeting the needs of the Color World calls for inorganic chemistry to develop leading market great foresight, flexibility and innovation … positions in a diverse range of industries. • Our global presence is a strong competitive Our mission is “to achieve market leadership advantage. Technical, marketing and management through a customer-focused and highly creative personnel are in continuous contact with customers organisation committed to delivering top quality in every major region. Multinational customers can products and outstanding services to customers be assured of standard products and consistent worldwide”. quality wherever they have operations.

Our materials are used to add value to, and to • We co-ordinate our R&D activities globally and improve the performance of products in a variety use our international talent to ensure that product of end markets including building and renova- specifications and performance are designed tion, home appliances, cookware, giftware and to satisfy the specific requirements demanded by tableware, transportation, household furnishings, regional markets. leisure, electronics and industrial products. • Ferro views the world-wide concern for the en- We are among the world’s leading suppliers of vironment as an opportunity to develop improved ceramic glazes and colors, glass decoration, products and also to participate in chemical indus- speciality glasses and porcelain enamel coatings. try effor ts to address public concern. Environmen- We pioneered the development of forehearth tal concerns are a major driving force behind the color technology for coloring of glass. evolution of our lead- and cadmium-free technology and our low VOC decoration systems. Our global commitment to quality, reliability, innovation and personal customer care is founded on • The markets we cover are extremely service over 80 years of experience in serving the changing intensive. Ferro has established regional color needs of industry, from our international network matching, blending/pasting and technical support of manufacturing plants and service centres. Our facilities, to provide the level of service demanded commitment to quality management has been by our customers in all time zones. recognised with the award of ISO9001 accredita- tion to all of our global manufacturing and research Think of us as High Performance Partners facilities. to manufacturers around the world …

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Technical Information AUT04

Performance Colors & Glass Automotive Glass Enamels

Introduction

Ferro can draw on decades of experience in the The different products are grouped by production and application of ceramic colors, application: media and silver pastes. Automotive glass enamels for: To secure our high share of the market into the future, our research and development in • laminated safety glass recent years has focussed on extending our sag bending and press bending surface range of high performance products. No. 2 printings

Our objective is not only to satisfy current • tempered safety glass customer needs but to market products that side and rear windows sunroofs already meet future standards for environmental compatibility and technological challenges. An excellent example was the In the last few years, we have successfully introduction of the New Generation introduced innovative and environmentally Windshield enamels 2012. These enamels pass compatible screen-printing media for use with the high chemical durability requirements automotive glass, and this brochure features a which are actually requested by more and selection of these products. more carmakers. This brochure presents a representative With this brochure, we want to give an selection of products for specific applications. overview of our wide range of automotive glass For optimum selection of paste systems for enamels for the coating of tempered and your individual requirements, our customer laminated safety glass. service teams will be pleased to advise.

Edition 09/2016

Europe: Ferro GmbH Gutleutstrasse 215 D-60327 Frankfurt am Main Germany Telephone +49 (0) 69 271 16 - 0 Telefax +49 (0) 69 271 16 - 321

Asia: Ferro Japan KK, 21 Kasuminosato Ami-Machi, Inashiki-Gun Ibaraki Pref. 300-0315 Telephone +81-29-889-2144 Telefax +81-29-889-2490

Americas: Ferro Corporation 251, West Wylie Avenue, Washington, PA 15301, USA Telephone +1-724-207-2300 Telefax +1-724-207-2301

We can offer package solutions tailored to your specific needs. Benefit from our experience and our global presence. We are your partner – WORLDWIDE. page 3 / 14

General Information

Composition of Ceramic Automotive Glass Enamels

Ceramic automotive glass colors are glass percent. The color powder is a ground ceramic enamels that fire on to the glass during the vitrifiable color composed of glass frits, stain bending process above 560 °C, forming a glassy and any additives required. inorganic layer. For screen printing, these As shown in the table below, the components consist of an inorganic component, the color of the color powder largely determine the powder and an organic component, the properties of the fired color. medium. The content of the color powder in a screen printing paste varies between 75 and 86 wt.

Component Chemical composition Function

glass frit glass flux with Bi, B, Zn, Si oxides as forms the matrix of the enamel, strength, 60 – 85 % the main components chem. resistance, melt-on behaviour; firing range

stain oxides with Cu, Co, Fe, Ni, Mn, Cr color shade and light transmission 15 – 40 %

additives oxides, sulphides, metal compounds, antistick effect, 0 – 15 % silicates silver-non-bleed-through

The medium used determines the drying The following table shows the differences mechanism after screen printing. A between the chemical compositions and the differentiation is made between infrared drying / curing mechanism of the two systems. drying (IR) and ultraviolet curing (UV) systems.

Type Chemical composition Drying / Curing

IR oils and organic resins in physical drying by evaporation of the solvents, combination with solvents recommended glass temp. 80 – 150 °C

UV monomers and acrylate compounds photoinduced cross-linking by UV radiation; no evaporation of solvents, no heat required

The medium has a crucial influence on the been printed on the glass. The medium is also screen printing properties of the paste and the partly responsible for the storage stability of adhesion of the dried enamels after they have the paste.

page 4 / 14

Selected Requirements for Modern Automotive Glass Enamels

Associated with the development of While around 30 years ago, it was sufficient for automotive glass from simple protection of the glass enamel to be “simply black”, today driver and passengers against wind and rain to there is a growing demand for multifunctional multifunctional glass used as a stability automotive glass enamels. In the following, the component in the body of the vehicle, the higher requirements for ceramic screen requirements of the glass and car printing are briefly explained: manufacturers for ceramic screen printing have steadily increased.

a) Heavy metal free composition b) Antistick properties

New legislation on environment protection, The further development of glass bending safety at work and the labelling of packaging technology from sag to press bending has for transport and handling in Europe were enabled the production of glass panels with leading to complete prohibition on the use of increasingly complex curvature and faster lead, cadmium, hexavalent chromium etc. firing cycles (see schematic).

Today, nearly all of our customers expect enamels to be free of toxic heavy metals. New types of glass panels are decorated almost exclusively with heavy metal free automotive glass enamels. Zn, Bi or Zn/Bi systems are used.

sag bending (gravity) press bending

In press bending processes, the ceramic automotive glass enamel printed on the top surface of the glass comes into contact with the press ram during the forming process. page 5 / 14

In this process, the melted enamel must d) High opacity withstand the pressure applied. The enamel coating should not be damaged and no traces There is a tendency that automotive and glass of enamel should be left on the press cloth. The manufacturers more and more specify visible enamel should not stick to the press ram, as light transmission values of below 0.1 % for the otherwise the softened glass deforms when printed glass. The optical density of the enamel the press ram is lifted away. The resulting depends primarily on the thickness and density deviations in shape are not tolerable. These of the fired layer. antistick properties can be achieved by varying the product composition accordingly: Ensuring reproducible values is not just down to the color paste supplier (e.g. with an Either highly viscous systems with high surface appropriate pasting ratio, rheology, special tension, additive systems or reactive and high loading media), but is also partly the crystallising systems are used. The antistick responsibility of the glass manufacturer as the effects differ depending on the system. Ferro printed layer thickness (wet film thickness) – supplies automotive glass enamels from all and ultimately the thickness of the three systems. fired layer – is largely influenced by the printing viscosity, screen mesh, screen coating and the machine settings. c) Silver-non-bleed-through

Car rear windows are generally printed with e) Chemical resistance / hydrolytic heat conductors from conductive silver pastes, resistance which are fired together with the ceramic color. The standards for chemical resistance vary very widely around the world. The approval tests During firing, the silver ions (Ag+) migrate from range from three minute exposure to the overprinted silver layer through the not hydrochloric acid (3 % HCl) at room completely molten ceramic color to the surface temperature to a 140 hour sulphuric acid of the float glass. This migration is the result of attack at 80°C. Depending on the region and ionic exchange processes, promoted by the nature of application, very different capillary forces of the porous automotive glass specifications are issued. In the last two years enamel. requirement on chemical resistance grew enormously. In 2008 the The reduction of the silver ions by the sulphuric acid test at 80°C became standard for polyvalent tin in the surface of the float glass tempered glasses and recently also for leads to the formation of colloidal silver laminated complexes, which tint the glass a yellowish glasses. brown color: Ferro can supply enamels to meet those 2 Ag+ + Sn2+ ==> 2 Ag0 + Sn4+ specific requirements.

The bleed through of the silver busbars can be avoided by preventing diffusion of the silver ions and reducing them again within the enamel layer. Ferro supplies automotive glass enamels based on a patented process to achieve exactly this effect. page 6 / 14

In the following section of the product information, the chemical resistance of the enamels is evaluated based on the following nomenclature:

Test method: The sample is exposed during 5 min at room temperature with 3 % hydrochloric acid

Classification: Grade 1 - no attack Grade 2 - iridescent surface or just noticeable loss of gloss Grade 3 - obvious matting without strong effect on color respective surface changes Grade 4 - strongly affected color respective surface changes, not scratch resistant Grade 5 - glass enamel disappeared, the glass substrate is free or partly free

On request, we can provide you with details on the performance of our various enamels in other test conditions, e.g. the sulphuric acid test at 80°C.

The Future

The requirements for automotive glass Finally we expect that the chemical resistance enamels will continue to increase in will remain as one of the key requirement future. Bending of the automotive glass around the world. As a manufacturer of panels will become increasingly complex, ceramic colors, Ferro will in future be such that higher press forces during confronted by greater challenges requiring the elaboration of new solutions. We will face shaping can be expected. Additionally these challenges. As your partner – the firing cycles become faster, WORLDWIDE. combined with lower temperatures to further increase the optical quality of the bent glass.

The standard for the opacity of the screen printed enamel will rise further, to improve the long-term UV protection of the adhesive – especially for primerless glueing application.

page 7 / 14

Automotive Glass Enamels for Laminated Glass

Heavy metal free enamels for Sag Bending

The main requirements are a wide firing range, We offer three product families for the gloss, good opacity and maximum blackness of standard application of sag bending process the color shade. The firing range is generally (surface No. 4). between 570°C and 650°C (laboratory values). The requirements for chemical resistance vary from low to very high.

Product Frit system Color Firing range Remarks No. (laboratory values) 14 305 Bi-Si-B-Alkali black 560 – 640 °C excellent chemical resistance – semi-matt 4 – 8 min passes 72 hrs Toyota test, very good opacity, uniform gloss in the whole firing range, wet fire possible, low melting 14 304 Bi-Si-B-Alkali black, 555 – 630°C excellent chemical resistance – glossy 4 – 8 min passes 72 hrs Toyota test; very good opacity wide firing range, wet fire possible lower melting 14 303 Bi-Si-B-Alkali black, 565 – 640°C excellent chemical resistance – glossy 4 – 8 min passes 72 hrs Toyota test; very good opacity, wide firing range, wet fire possible higher melting 14 300 Bi-Si-B-Alkali black, 560 – 630°C good chemical resistance glossy 4 – 8 min very good opacity wet fire possible lower melting 14 279 Bi-Si-B-Alkali black, 570 – 640°C good chemical resistance glossy 4 – 8 min very good opacity wet fire possible higher melting 14 301 Zn-based black, 570 – 640°C good chemical resistance Bi-System semi-matt 4 – 8 min good opacity wide firing range wet fire possible

The new enamels 14 303 and 14 304 provide an The high bismuth containing enamels 14 279 excellent chemical durability and pass 72 hrs and 14 300 fulfil highest requirements with Toyota test (lab conditions). In addition, the regard to chemical resistance, color shade, 14 305 provides a uniform gloss in the whole opacity and firing range. firing range. This allows a very uniform appearance of the fired enamel on the 14 301 is reduced in bismuth content and offers windshields even when larger temperature best value for all standard applications. gradients occur. page 8 / 14

Heavy Metal Free Enamels for Press Bending

Press bending became more and more common For some applications the enamels have to pass in the production of LSG in Europe in the past up to 72 hrs in the sulphuric acid test at 80°C. two years. Particularly important requirements The firing range is usually between 580°C and are very good breaking strength, fast maturing 620°C (laboratory values). and good antistick properties.

Product No. Frit system Color Firing range Remarks (laboratory values) 14 310 Bi-Zn-System black, matt 580 – 620 °C passes > 8 hrs Toyota test wet fire 6 min possible 14 316 Bi-System black, matt 570 – 640 °C passes > 72 hrs Toyota test 6 min wide firing range, wet fire possible lower melting 14 315 Bi-System black, matt 580 – 640 °C passes > 72 hrs Toyota test 6 min wide firing range, wet fire possible higher melting

Surface No. 2 Enamels for Pre-Firing

These enamels are applied to surface 2 They require a carefully co-ordinated color (sometimes surface 3) of the laminate to powder-organic-system and special adaptation optically hide antenna, heat conducting and to the specific pre-firing and bending processes. sensor connections in the increasingly complex composition of laminated glasses.

Product No. Frit system Color Remarks 14 331 Bi-Zn-System black, matt wide firing range 560 – 610°C silver-hiding possible lower melting 14 330 Bi-Zn-System Black, matt wide firing range 570 – 620°C silver-hiding possible higher melting 14 316 Bi-System black, matt 570-640°C passes > 72 hrs Toyota test wide firing range, wet fire possible higher melting

Please contact our technical service to select We can offer tailor- made products to existing the best product for your process. product lines.

page 9 / 14

Automotive Glass Enamels for Tempered Glass

Heavy Metal Free Enamels for Side Windows

The requirements for these enamels include good silver-hiding properties for specific good opacity, maximum blackness of the color applications (e.g. antennas and alarm circuits). shade and a wide firing range as well as

Product Frit system Color Firing range Remarks No. (laboratory value) 14 624 No Bi black, matt 660°C Non-Bismuth System Si-Zn-B-Ti 3,5 – 4,5 min passes > 72 hrs Toyota test intermixable with 14 633 14 633 Low Bi black, matt 660°C Low-Bismuth System Si-Zn-B-Ti 4 – 5 min passes > 72 hrs Toyota test (Bi) intermixable with 14 624 14 242 Si-Bi-Zn-B- high 660°C chem. resistance 3 Alkali blackness 3,5 – 4 min intermixable with 14 233 semi-matt 14 233 Si-Bi-Zn-B- high 660°C chem. resistance 3 Alkali blackness 4 – 4,5 min intermixable with 14 242 semi-matt 14 251 Si-Bi-Ti-B- black, 660°C chem. resistance 1 - 2 Zn-Alkali semi-matt 3,5 – 4,5 min intermixable with 14 252 14 252 Si-Bi-Ti-B- black, 660°C chem. resistance 1 - 2 Zn-Alkali semi-matt 4 – 5 min intermixable with 14 251

Automotive Glass Enamels for Sunroofs

Ferro offers different heavy metal free enamels customer service team who will recommend for this specific application. Please contact our the best products for your requirements. page 10 / 14

Heavy Metal Free Enamels for Rear Windows

The requirements for automotive glass enamels current specifications of the automakers and used on rear windows increased constantly glass producers. In automotive glass fabrication over the last few years – especially with regard processes, the new enamel series provides to antistick, busbar hiding, chemical durability performance at faster cycle times and lower and opacity. The Ferro “New Generation” firing temperatures. Antistick System fulfils and even surpasses the

The Ferro “New Generation” Antistick Systems:

Product No. Temperature range Firing range Remarks for application (laboratory values)

14 500 very low – low 650°C / 3,0 - 4,0 min

The “14 500 family” 14 501 very low – medium 660°C / 3,0 - 4,0 min Frit system: Si-Bi-Ti-B-Zn-Alkali

excellent antistick and busbar hiding, 14 502 low – high 660°C / 3,5 - 4,5 min excellent chemical durability, very good color shade, very good opacity, very wide firing range 14 503 medium – high 660°C / 4,0 - 5,0 min intermixable system

14 509 very low – medium 660°C / 3,0 - 4,0 min The “14 510 family” designed for Outside Pressbend Furnaces

Frit system: Si-Bi-Ti-B-Zn-Alkali 14 510 low – high 660°C / 3,5 - 4,5 min

less crystallizing, deep black color shade, excellent chemical durability, excellent 14 511 medium – high 660°C / 4,0 - 5,0 min busbar hiding, very good opacity, very wide firing range

intermixable system page 11 / 14

Ferro always works to improve and optimize provides a larger working range than the 14 500 existing product lines, even when they reach family and passes up to 144 hours Toyota test. benchmark status. The latest development for application on deep bend tempered glasses

The Ferro “New Generation” Antistick System:

Product No. Temperature range Firing range Remarks for application (laboratory values)

14 530 very low – medium 650 – 710 °C The “14 530 family”

3 min Frit system: Si-Bi-Ti-B-Zn-Alkali

14 531 low – medium high 660 – 720 °C excellent antistick, deep black color shade, excellent busbar hiding range, very good 3 min opacity, very wide firing range, excellent chemical durability (passes up to 144 hrs 14 532 medium – high 675 – 730 °C Toyota test) 3 min intermixable system

Automotive Glass Enamels with less than 5 % of Bismuth

Ferro has developed enamels for tempered requirements to chemical durability, firing and glasses which contain maximum up to 5 wt-% of busbar hiding range. Bismuth in the paste and still fulfils highest

Product No. Frit system Color Firing range Remarks (laboratory values)

14 624 Zn-B-Ti-Si black, matt 670 – 710 °C passes > 72 hrs Toyota test 3 min intermixable with 14 633 14 633 Zn-B-Ti-Si black, matt 680 – 720 °C passes > 72 hrs Toyota test (Bi) 3 min intermixable with 14 624 page 12 / 14

Media

The automotive glass enamels described can be percent) are empirical values and depend to a supplied as infrared drying or ultraviolet curing large extent on the properties of the color pastes (except for the special enamels for powder used. surface No. 2 printing). The solid concentrations specified for the We specially recommend the use of the ready-to-print pastes (=SC, specified in wt- following media for screen printing:

Screen Printing Media IR - Oil Based

Data/Media 80 1018 80 007F C80-1631 C80-1623

Flash point / °C 75 95 75 77

Density / 23 °C 0,93 0,94 0,99 0,88

Viscosity / mPa*s 270 100 230 120 at 23 °C and D = 200 1/s

Solid content of lead free pastes 78 – 81 80 – 85 80-85 81 – 86

Thinner 80 063 80 007F C80 1631 C80-1623

Cleaner 80 452 80 452 80 452 80 452

Due to optimum selection of solvents with slow properties. All three media are highly evaporation rates, medium 80 007F guarantees compatible with Ferro conductive silver pastes. long lasting on the screen. The universal screen printing medium 80 1018 With medium 80 007F and C80-1623, and features a medium drying rate and favourable C80-1631 particularly high loading of the firing behaviour. It allows high loading of the enamel pastes are possible. This allows enamel paste (good opacity) and is highly extremely good opacity and improved busbar compatible with Ferro conductive silver pastes. hiding by keeping very good printing Multilayer printing is possible. page 13 / 14

Screen Printing Media IR – Water-Soluble

Data/Media 80 1026 80 8003 C80-1565

Flash point / °C > 100 > 100 > 100

Density / 23°C 0,97 1,01 1,01

Viscosity / mPa*s 340 210 220 at 23°C and D = 200 1/s

Solid content of lead free pastes 77 – 80 77 – 80 77 – 80

Thinner 80 868 80 868 80 868 80 890

Cleaner Water Water Water

These media feature water soluble solvents The slow drying medium C80-1565 and the which facilitate both the use of the products faster drying 80 8003 are also compatible with and cleaning of the application tools. Ferro conductive silver pastes (oil and water based) and therefore especially suitable for side They are intermixable without any problem. and rear windows. page 14 / 14

Screen Printing Media UV

Data/Media 80 8004 80 8015 80 887/80 1708

Flash point / °C > 100 > 100 > 100

Density / 23°C 1,06 1,06 1,08

Viscosity / mPa*s 220 235 150 at 23°C and D = 200 1/s

Solid content lead free pastes 77 – 80 77 – 81 77 – 80

Reactivity High medium medium

Thinner C80-1709 80 8016 C80-1709

Cleaner 80 452 80 452 80 452

UV enamels cure after printing as the result of a frequently applied blend of media 80 1708 and photo-initiated cross linking reaction. No 80 887 are highly suitable for overprinting with solvents are released in this process. Costly Ferro conductive silver pastes. In addition heating and cooling of the glass are not medium 80 8004 shows low sensitivity to necessary. humidity while 80 8015 shows excellent burn- 80 8004, the new 80 8015, as well as the out.

If you have any questions or require advice regarding the use of our products, please consult our customer service team.

FERRO GmbH I Gutleutstrasse 215 I D-60039 Frankfurt/Main Germany P +49 6927116.0 F +049 6927116.321 E [email protected] W ferro.com AUT04 09, 2016

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Limitation of Warranty and Liability Safety&Handling

Ferro believes that the information contained in this document is accurate at the Please refer our Material Safety time of its publication. Ferro makes no warranty with respect to the information Data Sheet for safe handling and contained in this document. The information in this document is not a product use of our products, prior to use. specification, either in whole or in part. Your use of the information contained in this document and your purchase and use of this Ferro product are at your sole discretion. Downstream users are responsible for determination of the suitability of this product and for testing in specific applications. Nothing in this document shall be construed as a license for use that infringes upon any property rights of any third party. Please refer to the Safety Data Sheet (SDS) for safe use, handling and disposal information. All sales by Ferro to you are subject to Ferro’s Terms and Conditions of Sale, as amended from time to time and available at www.ferro.com. In the event this document conflicts with Ferro’s Terms and Conditions of Sale, Ferro’s Terms and Conditions of Sale shall control. Performance Colors & Glass

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