ANFFECC / CERAMICOLOR / EPSOM / V d M i

Ceramic Decorating Materials

Aspects of Product Stewardship

Introduction

Disclaimer
The information and recommendations contained in this publication are not intended to relieve the reader of responsibility for complying with laws applicable to the reader's enterprise and place of business. Each reader should verify independently the information contained in this guide and should consider such information in the context of the use to which it proposes to put the products referred to in this publication, including their use in conjunction with other products. The information and recommendations contained in this publication summarize the publishing associations' best knowledge of these products as at the date of publication. This information has been obtained from sources believed to be reliable and is believed by the publishing associations to be accurate. The publishing associations assume no obligation for updating or amending this publication for any reason, including where new or contrary information concerning the safe handling of ceramic colours and glaze systems becomes available or where there are changes to the laws and regulations of any jurisdiction affecting the subject matter of this publication. If clarification or further information is required regarding the safe handling of the products referred to in this publication, the reader should contact the relevant manufacturer or his selling agents. The responsibility for products manufactured and sold by the manufacturers of ceramic colours and glaze systems is subject to that manufacturer's standard terms and conditions of sale. A copy of the standard terms and conditions of sale may be obtained on request from the individual company in question. The authors of this publication, the publishing associations, the members of the publishing associations and their respective directors, officers, employees and agents make no warranty, expressed or implied, concerning this publication or the accuracy of the information contained herein and, subject to any law to the contrary, will not be liable (including the negligence) for any loss, damage, injury or claim suffered or incurred as a result of the use of this publication or any reliance by readers on the information contained herein.

Acknowledgements
This publication is based on the "Safe Handling of Pigments" (European Edition) published in 1995 by ETAD, BCMA, VdMi and EPSOM.

Introduction

Copyright 1998: ANFFECC, CERAMICOLOR, EPSOM, VdMi (see last page for further information on these publishing associations). No reproduction of this document or any part thereof, or any transmission in any form or by any means of this document or any part thereof is permitted without the expressed permission of the publishing associations. All requests for reproduction should be addressed to one of these publishing associations at the addresses listed on the last page. Reproduction of short excerpts and citations will normally be permitted with prior request. Editorial changes or chapter length excerpts for private commercial purposes will not be approved for publication.
Layout: Dr. Michael Zillgitt, D60385 Frankfurt/M., Germany Printed by: Neumann Druck, D69126 Heidelberg, Germany

Contents

Contents
1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 2 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3 3.1 3.2 3.3 3.4 3.5 4 4.1 4.2 4.3 5 5.1 5.2 5.3 5.4 5.5 General Information ....................................................................................................... 6 Health Effects / Toxicology .............................................................................................. 6 Physical Hazards ............................................................................................................... 8 Hazard Communication ..................................................................................................... 9 Industrial Hygiene Considerations .................................................................................. 11 Environmental Concerns ................................................................................................. 12 Transportation and Storage ............................................................................................. 15 Consumer Protection ....................................................................................................... 16 Definitions ...................................................................................................................... 17 Inorganic Raw Materials ................................................................................................. 17 Frits ................................................................................................................................. 20 Glazes and Composti ....................................................................................................... 21 Ceramic Stains ................................................................................................................ 22 Ceramic Colours .............................................................................................................. 23 Glass Enamels ................................................................................................................. 24 Precious Metal Preparations and Lustres ........................................................................ 24 Organic Additives (media, covercoats, solvents) ........................................................... 25 Decals Ceramic Transfers ............................................................................................ 26 Toxicological Aspects .................................................................................................... 28 Frits ................................................................................................................................. 28 Ceramic Stains ................................................................................................................ 31 Precious Metal Preparations and Lustres ........................................................................ 50 Inorganic Raw Materials ................................................................................................. 52 Organic Additives ........................................................................................................... 57 Preparations .................................................................................................................. 60 Chemical Aspects ............................................................................................................ 60 Physical Aspects of Special Forms of Delivery .............................................................. 61 Decals Ceramic Transfers ............................................................................................ 65 Annexes .......................................................................................................................... 67 Selected R- and S-phrases ............................................................................................... 67 EU Waste Catalogue ....................................................................................................... 68 Symbols used in Labelling .............................................................................................. 68 Glossary ........................................................................................................................... 70 Index ................................................................................................................................ 74

1 General Information

1 General Information
The intention of this publication is to report on safe handling and hazards related to the use of products supplied by the manufacturers of ceramic colours and glaze systems. It is our intention to make this publication available in various languages such as French, German, Italian and Spanish. The manufacturers of ceramic colours and glaze systems encourage the users of this publication to use it as a general reference guide to safe handling of products used for ceramic decoration (stains, frits, glazes, ceramic colours, precious metal preparations and lustres) and some of the regulations which affect their use. The publication consists of four basic parts: general information, definitions, toxicological aspects of special products and preparations thereof, and product group specific information. More detailed information about a specific product must be obtained from the suppliers' safety data sheets (SDS) and other safe handling literature.

1.1 Health Effects / Toxicology

Acute Toxicity
The acute toxicity describes all general short-term toxic effects to humans and animals, excluding reproductive, genotoxic, carcinogenic or local effects (4). Therefore general toxicity (acute toxicity) may include nonspecific effects, such as decreases in body-weight gain, specific target organ toxicity, neurotoxicity and immunotoxicity. Acute toxicity is measured by determining the LD50 value. The LD50 is the amount of material (usually expressed for oral route as dosage in mg of chemical / kg body weight of the test animal) administered once by a given route (oral, dermal, etc.) that would be expected to kill 50 % of a group of experimental animals, usually rats. A large LD50 value (for example, 5000 mg/kg, equivalent to an average person swallowing 350 g) represents a low degree of acute toxicity. Throughout this brochure LD50 values are cited, where applicable, as > 5000 mg/kg even if higher values are specified in the literature. The EU Dangerous Substances Directive ("Chemical Law") defines three acute toxicity classes (rat, oral) for a material (1, 2): LD50 25 mg/kg: very toxic 25 200 mg/kg: toxic LD50 LD50 200 2000 mg/kg: harmful

Irritation
Irritant substances are non-corrosive substances which through immediate, prolongued or repeated contact with the tissue under consideration (skin, eye or mucuous membrane / respiratory tract) may cause inflammation (4). Depending on the degree and reversibility of damage at the point of exposure, substances are classified as nonirritants, irritants, or corrosive.

Corrosivity
Corrosive substances are those which may destroy living tissue with which they come into contact (4).

1.1 Health Effects / Toxicology

Toxicity after Repeated Application

Subchronic toxicity studies involve the repeated application of a test substance to animals, for a period of 28 days. A subchronic study covers a period of 90 days. Under the EU Chemicals Law substances, which cause serious damage on repeated application or prolonged exposure, are required to be labelled with R 48 (Danger of serious damage to health by prolonged exposure).

Sensitizing
Sensitizing may be caused by certain chemicals due to their interaction with the human immune system. Although many allergens do commonly occur in nature, not every individual person is responding with the same sensitivity. A number of synthetic chemicals are known as sensitizing agents. Therefore it is necessary to reduce skin contact with such chemicals to a minimum. Also inhalation of allergenic substances can give rise to corporal overreaction. Due to the restricted knowledge on the allergenic potential of many chemicals those persons with a known disposition against certain chemicals (Nickel alloys, perfumes) are advised for special care due to the high risk of cross-allergic reaction and further sensibilization against other chemicals.

Mutagenicity
A chemical capable of altering the genetic material (genes, chromosomes) in a living cell is a mutagen. A variety of methods is available to test for mutagenicity. Most important as a pre-screening test is the Ames test, which is a bacterial test allowing fast performance under internationally standardized conditions and requiring limited expense. Other tests for mutagenicity can involve cell cultures (e.g. the HGPRT or the cytogenetic-in vitro assays) or live animals (the micronucleus or the cytogenetic-in vivo test). These tests are often used to screen for the mutagenic potential of a chemical and to draw inferences about its carcinogenic potential. Definite conclusions regarding a potential cancer hazard cannot be drawn from the outcome of a single mutagenicity test.

Teratogenicity
Teratogenicity is the ability of a substance to influence an organism so that malformations of the developing embryo or fetus can occur.

Chronic Toxicity
Chronic toxicity describes all long-term health effects to humans and animals as a result of exposure to a substance. Delayed effects are also considered chronic effects. The intent of chronic toxicity testing in animals is to check the possible tumorigenic potential of a chemical. Carcinogens are substances which induce cancer or increase its incidence when they are inhaled or ingested or if they penetrate the skin. The Carcinogens are subdivided into two subgroups according to the presumed mechanism of action, that is, "genotoxic" and "non-genotoxic" mechanisms (4). Genotoxic carcinogens are defined in (4) as those substances which "induce cancer as a consequence of the direct interaction of the substance, or an active metabolite, with the DNA".

1 General Information For further information, the reader is referred to the literature (4, 5). Adverse health effects by inhalable substances must be regarded as a potential problem. Even when certain organic or inorganic particles are described as inert, any dusting material may cause lung damage. Therefore users should follow the recommended safety precautions (wearing dust masks, closed systems etc.). Due to the complexity of the health effect area the reader is referred to available textbooks for further information (4, 5). In general, ceramic stains are of very low toxicity, whereas especially lead containing products are harmful. Products based on organic compounds should be regarded as potentially harmful.

References
(1) Council Directive 67/548/EEC (June 27, 1967) on the approximation of laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances, and subsequent amendments (O.J. L196, 16.8.67). (2) Council Directive 92/32/EEC (April 30, 1992) amending for the seventh time Directive 67/548/EEC on the approximation of the laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances (O.J. L154, 5.6.92). (3) OECD Guidelines for Testing of Chemicals No. 404 and 405. (4) Technical Guidance Documents in Support of Commission Directive 93/67/ EEC on Risk Assessment for New Notified Substances and Commission Regulation (EC) No. 1488/94 on Risk Assessment for Existing Substances. Luxembourg: Office for Official Publications of the EC, 1996, ISBN 92-827-8011-2. (5) Marquardt H., Schfer, S. G. (Eds.); "Lehrbuch der Toxikologie"; BI-Wissenschaftsverlag, Mannheim, 1994.

1.2 Physical Hazards

Dust
In general, ceramic colours and glazes do not cause physical hazards in the most common forms of delivery. Nevertheless, attention should be paid to the sharp edges of broken or milled frit particles. As many of the products are finely divided powders, effective aspiration and filter systems must be properly installed to ensure the safe handling of dusting products.

Flammability
Liquid or pasteous preparations often may contain organic solvents, which can be ignited easily. The ignition can be initiated by electrostatic discharge as well as by open flames in the vicinity of the ceramic furnaces. Frits and glazes are not flammable and do not give rise to combustion.

Electrostatic Discharge
All insulating substances may accumulate static electric charge which can give rise to sparks and induce fire. This may occur during all transfer or processing operations. Particular care must be taken with solvents, liquid metal-organic preparations and finely divided powders such as ceramic colours, glazes, and stains. Accordingly any equipment for the handling of those substances should routinely be "grounded" to remove the possibility of such hazard (1).

1.3 Hazard Communication

Combustion Products
During the firing process in ceramic kilns organic materials start decomposing and burning already at relatively low temperatures (200 C). Depending on the type of chemicals used during the decoration process, the fumes may contain hazardous substances (2). Some constituents of products for ceramic decoration may generate volatile metal oxides. It should be noted that the generation of any combustion product strongly depends on the firing conditions used. In any case good ventilation and exhaustion should prevent the worker from coming into contact with dangerous combustion products.

References
(1) Gloor, M. "Electrostatic Hazards in Powder Handling"; Research Studies Press, Letchworth, Herts. UK., 1988. (2) Schmidt, W.; "Analyse und thermische Zersetzung von Dekor-Abziehbildern fr Porzellan"; Dissertation Universitt Saarbrcken, 1987.

1.3 Hazard Communication

General Information
In order to protect the workforce, general public and environment from hazards associated with chemicals, the European Directives 67/548/EEC ("the Dangerous Substances Directive") (1) and 88/379/EEC (the "Dangerous Preparations Directive") (2) together with all amendments and adaptations place certain obligations upon suppliers of chemicals. In particular, the supplier must identify hazards associated with any chemicals supplied; communicate safety advice to the user; package products suitably for safe usage; consider storage and transport related risks.

Classification
Under the European Directives, the supplier of a chemical substance or preparation has the duty to identify hazards associated with his products. This may be done in one of two ways, a) by using the pre-determined classification derived for a substance by the EU Technical Progress Committee and listed in Annex 1 to the "Dangerous Substances Directive" or b) where a substance is not listed, by self-classification based on criteria defined in Annex VI of the directive 67/548/EEC, using all available information. As a consequence, a product may not require classification or may be classified in one or more categories of danger covering physicochemical, toxic and environmental effects.

Labelling
Once a product has been classified and assigned to a category of danger, there is a requirement that all containers are labelled to indicate these dangers. For all dangerous chemicals, certain aspects of the label are obligatory.

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1 General Information Suppliers must ensure that the container is correctly labelled with the following information: The name, address and telephone number of the supplier within the European Union responsible for placing the product on the market. The chemical name (or the trade name plus the name of the dangerous components in the case of preparations) as given in Annex I to the Dangerous Substances Directive or, where the chemicals do not appear in the Annex I as a single item, an internationally recognised designation, preferably the name as used in the EINECS. The category or categories of danger together with the corresponding symbols. Risk phrases which relate to the classification (note that although these phrases are styled risk phrases, in fact they describe the intrinsic hazard of the material). Safety phrases which advise on correct use. The EEC number for single substance dangerous products (4). The word "EEC label" if the substance appears in Annex 1 of the Dangerous Substances Directive. There are also requirements relating to the size of the label and these are determined by the capacity of the package.

Safety Data Sheets (SDS)

Safety data sheets must be provided for all dangerous substances by the supplier to the recipient with or before first supply and irrespective of the mode of supply (3). Should further significant information arise, the supplier is also obliged to revise the SDS and supply this update to all those who received the product within the last 12 months. Responsible suppliers provide SDS for all products. The information supplied in the SDS must be sufficient for the user to ascertain how best to protect persons coming into contact with the dangerous chemical and to protect the environment. According to Commission Directive 91/155 EEC (3) the required information must be given under sixteen specific headings covering identification of the chemical product and its supplier; composition information; hazard identification; first aid measures; handling and storage; exposure control and personal protection; physical and chemical properties; stability and reactivity; toxicological information; ecotoxicological information; disposal; transport requirements; regulatory information and any other information which might facilitate safe use of the product. As with the label in the EU, the safety data sheet must be offered in the recipients' own language.

References
(1) Council Directive 67/548/EEC (June 27, 1967) on the approximation of laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances, and subsequent amendments (O.J. L196, 16.8.67). (2) Council Directive 88/379/EEC (June 7, 1988) on the approximation of the laws, regulations and administrative provisions of the Member States relating to the classification, packaging and labelling of dangerous preparations (O.J. L187, 16.7.88), and subsequent amendments. (3) Commission Directive 91/155/EEC (March 5, 1991) defining and laying down the detailed arrangements for the system of specific information relating to dangerous preparations in implementation of Article 10 of Directive 88/379/EEC (O.J. L76, 22.3.91).

1.4 Industrial Hygiene Considerations

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(4) Commission Directive 93/112/EEC (Dec. 10, 1993) amending Commission Directive 91/155/EEC defining and laying down the detailed arrangements for the system of specific information relating to dangerous preparations in implementation of Article 10 of Directive 88/379/EEC.

1.4 Industrial Hygiene Considerations

Industrial hygiene is integrated in the safety and health protection program. In this program, workplace risk levels are determined within a framework of methodical evaluation of working conditions and processes; suitable measures are then taken to avoid risks for the life and health of employees, and in any case to reduce remaining risks to the lowest possible level (14). A risk may result from physical, chemical or biological effects, the design, selection and use of working material (materials, machines, instruments and systems), equipment installation in working areas and individual workplaces, layout of working and production methods, working processes and insufficient employee qualification and instructions. Measures to optimize industrial hygiene must take into account state-of-the-art technology, industrial medicine and hygiene and a solid basis of industrial medical experience. The objective is to properly correlate technology, working conditions, organization of work and environmental influence at the workplace. The measures have to be documented. Control and efficacy have to be monitored constantly by means of suitable control methods. Participation of employees at all company levels has to be an integrated part of the program. Technical measures always have priority over organizational and personal measures. Direct contact to hazardous substances has to be minimized to the lowest level possible. Special risks for employees such as pregnant women and youths require high levels of protection. Areas dedicated to the processing of hazardous chemicals must be effectively separated from adjacent production areas. If necessary, effective exhaust systems have to be installed. Suitable working material has to be used, in particular mechanical equipment for heavy loads. Organizational measures include the engineering of safety work and production methods; employee training programs have to be developed, installed and implemented. To ensure the safety and protection of the employees, the pathways to the emergency exits and the emergency exits themselves must be kept free of obstructions. Safety equipment must be subject of maintenance measures and checked for its functionality in regular intervals. If technical and organizational measures are insufficient, personal safety equipment must be used. Personal safety equipment is widely used in the production and processing of ceramic colours. The equipment is selected according to the type of hazard involved. A dust mask must be used for working procedures involving dust. Effective respirators have to be used in case of dust containing dangerous chemical substances, such as lead and cadmium. The personal safety equipment may include: Protective shoes, Protective goggles, Ear protection, Respirators, Dust masks

12 Protective gloves, Protective clothing. Skin protection,

1 General Information

Personal safety equipment has to be selected, based on the information given in the safety data sheets of the suppliers; it is advantageous to involve the employees in the selection of the personal safety equipment. Good personal hygiene and clean working methods are important in the production and processing of ceramic colours. Eating, drinking, smoking and the use of cosmetics must be avoided at the workplace. Employees should wash their hands before engaging in any of these activities. Suitable rooms for dressing, washing and breaks must be provided. Beverages and cigarettes must not be kept at the workplace. Work clothing must be stored separately from street clothes. Workplaces must be cleaned at regular intervals and kept clean. The employees have to be instructed about the risks involved in handling hazardous substances and the rules of good personal hygiene at work. Instructions to the employees must be given in such a way that the content of the instructions is easily understood.

References
(1) Council Directive 89/654/EEC (November 30, 1989) concerning the minimum safety and health requirements for the workplace (first individual directive within the meaning of Article 16(1) of Directive 89/391/EEC) (O.J. L393, 30.12.89). (2) Council Directive 89/391/EEC (June 12, 1989) on the introduction of measures to encourage improvements in the safety and health of workers at work (O.J. L183, 29.6.89). (3) Council Directive 89/655/EEC (November 30, 1989) concerning the minimum safety and health requirements for the use of work equipment by workers at work (second individual Directive within the meaning of Article 16(1) of Directive 89/391/EEC) (O.J. L393, 30.12.89). (4) Council Directive 89/656/EEC (November 30, 1989) on the minimum health and safety requirements for the use by workers of personal protective equipment at the workplace (third individual directive within the meaning of Article 16(1) of Directive 89/391/EEC) (O.J. L393, 30.12.89).

1.5 Environmental Concerns

Waste and Waste Disposal
The EU Directive 91/156/EEC to which is referred to the other Community Legislation on waste, states in Article 1a that a waste is defined as "any substance or object in the categories set out in Annex I which the holder discards or intends or is required to discard". The definition of waste is independent of its qualitative or commercial value, possible market, geographical purpose or the waste destination. In the EU-states it is necessary to give evidence that the waste cannot be recycled according to the packaging directive and to obtain permission for the deposit of the waste according to the local laws. Examples of typical waste are: contaminated products, spill cleanups, waste treatment plant sludge, retained laboratory samples, used packaging materials, equipment wash downs, etc.

1.5 Environmental Concerns

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According to present regulations in the EU, the treatment, storage, disposal and transboundary shipment of waste is regulated in the whole EU (15). Only, if the avoidance and the recycling of waste is not possible, is it allowed to deposit the waste. Disposal of waste water treatment sludge depends on the composition of the sludge and of the sludge eluate. The permissible composition and physical conditions for each type of disposal are regulated by the national and state waste departments. The classification of any waste depends on its composition, physical condition, and the substances present in the eluted water. Depending on these properties and the local regulations for waste it is possible to get permission for one type of disposal facility or waste combustion. As a guideline an extract from the European Waste Catalogue is given in Section 5.2. If the information in the safety data sheets is not sufficient, or there are problems, the product suppliers should be contacted for specific questions about the disposal or secondary use.

Source Emission
Source emissions should be considered during both the manufacturing and handling of any chemical and the production of end products that use those products as raw materials. Potential emissions mainly include hydrocarbon vapours from lustres, precious metal preparations and pasted colours manufacturing processes. Dust particles from dry colour and glaze manufacturing and processing have also to be considered. Gases and fumes liberated by the firing process must also be taken into account. Source emissions should be controlled by the best available control technologies for particular containment or process and must be approved by the supervising department. If the chemicals used or the process make it necessary, the responsible department may also have to control the plant. In all types of plant the exposure of the workers to dust, gas and vapours must be less than the permitted limits. Compliance will also be monitored by the supervising department.

Water Pollution
Water pollution must be avoided when storing, handling or disposing products containing water-polluting substances. Any substance or preparation which is classified as environmental dangerous, carcinogenic, teratogenic, mutagenic or toxic and which has a certain bioaccummulation potential should be considered as water-polluting. As a guideline, the German catalogue of water-hazardous substances can be used. This catalogue establishes 4 water-hazard classes: Class 0: Generally not water-hazardous; Class 1: Weakly water-hazardous; Class 2: Water-hazardous; Class 3: Strongly water-hazardous. Depending on the water-hazard class, the layout of storage areas and areas with processing equipment must be carefully planned to ensure an acceptable safety for the environment, also in case of an accident.

Accidental Spills
Spills of any substance are regarded as waste and should therefore not pollute the environment. Manufacturers as well as users should be familiar with the reporting

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1 General Information requirements of their authorities. Spills and clean-up residues should be contained and cleaned up in accordance with the SDS and applicable regulations.

Responsible Care
The manufacturers of materials for ceramic decoration in Europe fully support the initiative "Responsible Care" of the European Chemical Industry Council (CEFIC). Our industry played an active part in developing and implementing guidelines, activities, recommendations and voluntary self restrictions for environmental protection. At company level, Responsible Care is a commitment to continuous improvement of performances in health, safety and environmental protection (6). In fulfilling such a commitment companies are helped by the specific programme, guidelines and codes of conduct developed by their national chemical industry association. In any case, they would have in place suitable management systems fixing, among others, the responsibilities for environmental and safety issues as well as the corresponding audit procedures. Even in an early stage of research and development environmental protection and safety aspects are considered. This is called "Environmental Protection integrated into Innovation". Safe transport of chemical products and raw materials, especially of hazardous materials, is of special importance to the chemical industry. Safety in transport of chemicals covers two different aspects: the prevention of accidents, mainly focused on a thorough selection, information and training of safe carriers; the limitation of the consequences of accidents when they occur. Both aspects are dealt with by the CEFIC ICE-Programme (International Chemical Environment). The emergency response part of the programme is developing a network for assistance using the same principle as the German TUIS system (Transport Accident Information and Assistance System). Product Stewardship, which can be described as Responsible Care applied to products (7), includes the development and use of safety data sheets. The chemical industry plays a decisive part in the program by investigating the ecological properties of existing substances. In accordance with Quality Assurance Guidelines the producers of ceramic colours and glaze systems are implementing a total quality management system.

References
(1) Council Directive 91/156/EEC amending Directive 75/442/EEC on waste (O.J. L78, 26.3.91). (2) Commission Decision 94/3/EEC (December 20, 1993) establishing a list of wastes pursuant to Article 1(a) of Council Directive 75/442/EEC on waste (O.J. L5, 7.1.94). (3) Council Directive 91/689/EEC (December 12, 1991) on hazardous waste (O.J. L377, 31.12.91). (4) Council Decision 94/904/EC (December 22, 1994) establishing a list of hazardous waste pursuant to Article 1(4) of Council Directive 91/689/EEC on hazardous waste (O.J. L356, 31.12.94).

1.6 Transportation and Storage

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(5) Council Directive 84/631/EEC (December 6, 1984) on the supervision and control within the EU of the transfrontier shipment of hazardous waste (O.J. L326, 13.12.84), and subsequent amendments. (6) Responsible Care: a chemical industry commitment to improve performance in health, safety and the environment. CEFIC, 1993. (7) Product stewardship: Responsible care applied to products Guiding principles. CEFIC, 1994.

1.6 Transportation and Storage

Within Europe there are a number of special organisations which regulate the transport of goods by the various modes of transport. Dangerous goods have to be classified, labelled and packaged according to these regulations and it is the responsibility of the manufacturer to decide if his product is "dangerous". In order to provide some uniformity regarding the regulations for the classification (and corresponding labelling and packaging), the United Nations set up, in 1953, a committee of experts on the Transport of Dangerous Goods. This committee provides recommendations for all modes of transport and it is expected that governments, intergovernmental organisations and other international organisations will take cognisance of these when revising their regulations. Sea and air transport are controlled internationally by the International Maritime Organisation (IMO), International Civil Aviation Organisation (ICAO) and International Air Transport Association (IATA). The European countries, together with some North African States, are controlled under the International Regulations concerning the Carriage of Dangerous Goods by Rail (RID), while road transport is covered by the European Agreement Concerning the International Carriage of Dangerous Goods by Road (ADR). "Dangerous" in the meaning of transport regulations means "flammable", "highly flammable", "toxic" and so on. If materials for ceramic glazing and decoration are classified as "dangerous", employers (both the manufacturer and the freight company) have specific responsibilities to train and certify those who load or handle those products during their transportation. All goods have to be declared as "dangerous" or "non-dangerous" on the appropriate transport papers. Additionally for transport by road, documentation must also be handed over to the driver to take with him the so-called Transport Emergency Card, which outlines the steps to be taken in the case of an incident involving the dangerous goods. These instructions must be provided in the language of all the countries that are passed through as well as in the language of the driver. Emergency phone numbers are also given for contact in the case of an emergency. The safety data sheet gives information on the physico-chemical properties of any material for ceramic decoration as well as those properties which are of importance in the case of fire and for the protection of man and the environment and can thus be used for the determination of the necessary storage conditions. The transport regulations are regularly updated, therefore manufacturers, distributors, and users need to be aware of the current regulations.

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1 General Information

References
(1) Recommendations on the Transport of Dangerous Goods, published by United Nations, New York (updated yearly). (2) Dangerous Goods Regulations, published by International Air Transport Association, Montreal - Geneva (27. Amendment 94, IMDG Code). (3) International Maritime Dangerous Goods Code, published by International Maritime Organisation, London (updated yearly). (4) European Agreement concerning the international carriage of dangerous goods by road, published by the United Nations (12. ADR Amendment, 20.12.94). (5) Convention concerning International Carriage by Rail (COTIF), Appendix B. Uniform Rules concerning the Contract for International Carriage of Goods by Rail (CIM), Annex 1: Regulations concerning the International Carriage of Dangerous Goods by Rail (RID), published by the Central Office for International Transport by Rail, Bern (updated regularly).

1.7 Consumer Protection

Consumer products which have been fabricated with products supplied by our industry must fulfill certain legal requirements with respect to the release of cadmium and lead into foodstuff. The producers of those ceramic products are urged to obey existing legislation (1). Various standards describe the determination of leachability and release of cadmium and lead (ISO 7086, ISO 4531, ISO 6486, DIN 51031, DIN 51032, ASTM D 4236-94, FDA 7117.06, FDA 7117.07). A summary of existing legislation, test methods and limit values for the release of harmful substances from everyday foodstuff articles, made from ceramics, glass, or enamel is given in (2). The producers and suppliers of ceramic colours and glaze systems are not liable for any damage, injury or danger caused by the improper use of their products, if they have been properly labelled and advised.

References
(1) Council directive 89/109 EEC on the approximation of the laws of the Member States related to materials and articles intended to come into direct contact with foodstuffs of December 21, 1988. (2) Herrmann, H. J.; Keramische Zeitschrift 45 (5) 267273 (1993) and 45 (6) 331336 (1993).

2.1 Inorganic Raw Materials

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2 Definitions
The definitions used in this publication do not intend to be exhaustive nor do they contain terminology of a highly scientific nature. The manual is aimed at giving the reader an exact understanding of "what is what" by using everyday words in the intent of avoiding misinterpretations and giving appropriate instructions as to the handling of products and the risks connected with this, if any. A definition of what is meant by frits, fluxes, glazes, compostos, stains, oxides, ceramic colours, glass enamels, precious metal preparations, lustres, additives and raw materials is also given. All products are used in the glazing, colouring and decorating processes as well as in the firing of ceramic material. With different but suitable compositions they can also be used for the decoration of glass and coating of metal (in the latter case the glazes are usually called porcelain enamels).

2.1 Inorganic Raw Materials

Besides the specific synthetic products such as frits and pigments for the ceramic industry (dinnerware, tiles, sanitaryware, roof tiles, etc.) there is a very important complementary number of inorganic raw materials and minerals that enter into the composition of ceramic glazes, decorating colours, enamels, etc. Alumina Al2O3 exists in various types. From a chemical point of view all of them are the same aluminium oxide, distinguished by the crystal system. Since it is an amphoteric substance and has the capacity to combine with both the silica and the basic oxides, it is the most effective stabilizer in glass systems. Alumina is used to increase the viscosity of glazes, decreasing their trend to devitrify, increasing the maturation interval and their mechanical resistance, decreasing the dilatation coefficient and improving the opacity. The addition of high amounts of alumina results in matte glazes. Ammonium Metavanadate NH4VO3 is added to the frit to introduce vanadium. Vanadium ions, present in the molten glaze, reduce the surface tension and act as an efficient deflocculant of the glaze. Vanadium ions reduce the viscosity during melting. Anatase TiO2 is a crystal phase of titanium dioxide. It is added to frits and glazes to obtain the opacifying effects of the titanium dioxide. Barium Carbonate BaCO3 is added to frits to introduce barium oxide, which is an effective flux which increases the brilliance (but doesn't reach the level obtained with the lead oxide) and improves the mechanical resistance compared to alkaline earth frits. Calcium Carbonate CaCO3 is added to frits and glazes to introduce calcium oxide, which is a flux at high temperatures, increases the mechanical resistance and devitrifies easily.

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2 Definitions Cerium Oxide CeO2 is added to glazes due to its great opacifying power. It is soluble in the vitreous phase but it has a small solution velocity; CeO2 has to be introduced as an additive. Chromium(III) Oxide Cr2O3 is added to the frit to get the typical chrome green, chrome red and chrome yellow colours. Under reducing and oxidizing conditions, chromium(III) oxide is a stable pigment, generally giving green colour. It is not a flux, but rather makes glazes difficultly fusible and highly viscous and opaque. In glazes rich in lead and fired at low temperatures (max. 1040 C) the formation of lead chromates can give red, orange or yellow colours. High amounts of Al2O3, SiO2 and other basic oxides (but also more than 4 % of Cr2O3) alters the chrome red colours, which are destroyed at high temperatures. Clays are naturally occurring minerals, which are always mixtures of various silicates, for example K11.5 Al4 Si76.5 Al11.5 O20 (OH)4, kaolinite 2 SiO2 Al2O3 2 H2O, vermiculite (Mg, Ca)0.7 (Mg, Fe+3, Al)6 (Al, Si)8 O20 (OH)4 8 H2O, biotite K(Mg,Fe)3 Al Si3 O10 (OH,F)2, chlorite (Mg,Al,Fe)12 (Si,Al)8 O20 (OH)16 and other minerals as calcite CaCO3, dolomite CaMg(CO3)2, quartz SiO2, limonite and hematite Fe2O3. Clays are added to frits and glazes to introduce silica and alumina. Clays may contain free crystalline silica. Cobalt Oxides CoO, Co3O4 are added to the frit to get blue colours in bodies and glazes. It is added in small quantities and the colour does not alter in a wide range of temperatures and firing conditions, as long as the atmosphere is oxidizing. Colemanite CaB3O4(OH)3 . H2O is a boron containing mineral, which is added to frits as a source of boron oxide, which lowers the melting point of the frit. Colemanite has a low melting point and is soluble in hydrochloric acid. Copper Oxides CuO, Cu2O are added to frits and glazes to get, under oxidizing conditions, turquoise to green colours, and, under reducing conditions, red and purple colours. Corundum Al2O3 is a form of alumina, used for hardening the glaze surfaces. Dolomite CaMg(CO3)2 is a natural mineral, consisting of a homogeneous mixture of calcium and magnesium carbonate. Feldspars XY4O8 are a group of minerals. In the general formula given above represent: X generally Na+, K+ or Ca2+; Y almost always Al3+ and Si4+, although sometimes partially substituted by Fe3+. Feldspars are added to the frit as a source of SiO2, Al2O3 and alkaline elements. Feldspars may contain free crystalline silica. Fluorspar CaF2 is a mineral which is used as a flux and as an opacifier. Iron Oxides Fe2O3, FeO, Fe3O4 with different compositions are added to frits and glazes to get red, brown or yellow colours.

2.1 Inorganic Raw Materials

19

Kaoline 2 SiO2 Al2O3 2 H2O is a white clay mainly composed of kaolinite mineral. It is used to introduce alumina and silica. Kaoline may contain free crystalline silica. Lithium Carbonate Li2CO3 is added to the frit to introduce lithium oxide, which increases the resistance to the acids. Lithium also contributes to the high resistance to abrasion of the glazes. Magnesium Carbonate MgCO3 is added to the frit to increase the viscosity of the melt. Magnesium carbonate may give rise to colour changes in the glaze. Manganese Oxide MnO2 is added to frits and glazes to get red, yellow, brown, purple or black colours in bodies and glazes. Nepheline Na3KAl4Si4O16 is a feldspar. It is added to the frit as a source of sodium and potassium. Nickel Oxides NiO and Ni2O3 are added to the frit to introduce nickel oxide. Blue, green, grey, brown and yellow colours can be obtained, depending on the glaze composition. Olivine (Mg,Fe)2SiO4 is a silicate in the nesosilicate group; it is a source of MgO. Petalite LiAlSi4O10 is a feldspar. It is added to the frit as a source of lithium. Quartz SiO2 is the most frequent form of crystalline silica. Natural quartz can be accompanied by other crystalline silica phases, as tridymite and cristobalite with identical chemical formula. Quartz is added to the frit as a lattice former; it penetrates in the amorphous structure, doesn't devitrify and contributes to the increase of the viscosity of the frit. Respirable quartz is of mayor health concern. Rutile TiO2 is a crystal phase of titanium dioxide and is added to frits as an opacifier. Spodumene LiAlSi2O6 is a mineral of the group of piroxenes. It is added to the frit as a source of lithium. Spodumene may contain free crystalline silica. Strontium carbonate SrCO3 is added to frits and glazes to partially substitute barium and to reduce the viscosity. Strontium carbonate is soluble in acids. Talcum Mg3Si4O10(OH)2 is a phyllosilicate of the mica group. It is a source of MgO. Tin Dioxide SnO2 is added to the frit as an opacifier. In the glaze it decreases the dilatation coefficient and increases the elasticity and the resistance to acid and alkali. Tungsten Oxide WO3 is added to the frit to get yellow or blue colours. Ulexite CaNa(B5O6(OH)6) . 5 H2O is a boron containing mineral, which is added to frits and glazes as a source of boron oxide, which lowers the melting point of the frit. Ulexite has a low solubility in hot water.

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2 Definitions Vanadium Pentoxide V2O5 is an effective flux and decreases the surface tension of the fused glazes, facilitating the wetting of the support. In lead glazes it is used as a crystalliser, since it easily forms crystalline lead vanadates. It is (due to its high price) rarely used as an oxidant colourant to get green, yellowish green or reddish brown colours. Wollastonite CaSiO3 is an inosilicate in piroxenoides group. It is added to the frit substituting calcium carbonate and quartz in the corresponding proportions. It is a matting agent for low temperatures. The effect is very strong in glazes at fast firing conditions in which the complete reaction is only obtained with wollastonite. Zinc oxide ZnO is added to frits and glazes for various reasons. In glasses with a high content of alumina, zinc oxide acts as a flux. a) At low percentage additions, ZnO increases the brightness of the glazes and colours, except green and blue colours; mixed with alumina it improves the opacity and the glaze whiteness, whenever it has a low percentage of CaO and in absence of B2O3. Generally, ZnO decreases the expansion coefficient. b) At high percentage additions, ZnO devitrifies the vitreous mass imparting to the glaze surface a characteristic matted appearance. c) With percentages even higher: it crystallises, forming zinc silicate crystals. Glasses that are very rich in ZnO are strongly attacked by acids. Zircon ZrSiO4 is a naturally occurring zirconium silicate. It is added to frits and glazes due to its opacifying effect. Zirconia ZrO2 is naturally occurring as baddeleyite. It is added to frits and glazes due to its opacifying effect. Most of the above mentioned raw materials are naturally occurring or enriched by means of industrial processes (washing, leaching, flotation, separation) or, alternatively, may also be the result of synthesis and chemical and thermal processes. Each of the above mentioned raw materials make up a large part of glazes and colour preparations. The safety data sheets (SDS) of these preparations have very clear descriptions with regard to their characteristics, handling and possible risks involved and toxicity, if any.

2.2 Frits
Frit is a mixture of inorganic chemical substances produced by rapidly quenching a molten, complex combination of materials, confining the chemical substances thus manufactured as nonmigratory components of glassy solid flakes or granules. This category includes all of the chemical substances specified below when they are intentionally used in the production of frits. The primary members of this category are oxides of some or all of the elements listed below. Fluorides of these elements may also be added. Aluminum, antimony, arsenic, barium, bismuth, boron, cadmium, calcium, cerium, chromium, cobalt, copper, gold, iron, lanthanum, lead, lithium, magnesium, manga-

2.3 Glazes and Composti

21

nese, molybdenum, neodymium, nickel, niobium, phosphorus, potassium, silicon, silver, sodium, strontium, tin, titanium, tungsten, vanadium, zinc and zirconium. Frits are described with CAS No. 65997-18-4 and with the EINECS No. 266-047-6. Raw materials may be natural or synthetic products such as oxides, silicates, carbonates, alumino silicates, borates etc. Most of the elements such as alkali, earth alkali, zinc, boron, silicon, titanium, lead, tin, cadmium, antimony, selenium, zirconium and transition elements may be present in the compositions. Citation of lead, cadmium, antimony and selenium has been performed according to the fact that they are considered toxic, harmful or dangerous in Council Directive 67/548/EEC and concordant legislation. Usually frits are fully vitrified but occasionally they may also contain crystalline phases. Frits should be totally homogeneous but it may occur that some unsmelted materials appear. Frits allow the use of chemical compounds which cannot be used as they are because of their solubility and toxicity. Frits represent the stable form of elements needed for glaze preparation. Frits are particularly advantageous in glaze preparation and during the firing process because their elements are already homogeneously combined. Frits do not undergo any loss on ignition (water, CO2, organics) for they have already reacted with each other. Frits are usually water quenched (cooled directly when falling into cold water) in the form of "grains" or air cooled after being squeezed between rollers (roller quenched) in the form of "flakes". Frits are usually the main components of ceramic glazes, composti, glass enamels and porcelain enamels. This type of classification ist not only helpful in risk-assessment at the working-place, but helps also in defining ways of disposal.

2.2.1 Fluxes
In some countries special low melting frits (usually fired between 500 and 900 C) are called fluxes. Fluxes usually contain a high percentage of alkali, boron and/or lead in different combinations and percentages and are used to lower the melting temperature of glazes for any type of firing but especially for decoration and third fire. Fluxes are also used to protect decorated surfaces from chemical and mechanical attacks.

2.3 Glazes and Composti

There are several names that are used for compounded glazes: composto, incomposto, mixed glazes. The complete composition of a glaze is usually made up of one or more frits and several raw materials with the addition of pigments, salts, deflocculants, etc., when required. This is prepared by weighing the components individually and collecting them in a container (hopper, big bag, bag, drum). The complete composition takes the name of compounded glaze or composto. The components may already be finely milled and may be very unhomogeneous and have very differentiated grain size distribution. All the components making the composition may be mixed together thoroughly or may simply be put together in the container in bulk form or very roughly blended.

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2 Definitions Compounded glazes are ready to be milled, usually in ball mills, with the addition of water and some additives (salt, CMC, deflocculants, etc.) and the resulting slip is usually called "glaze". Occasionally, the medium is not water. Occasionally, glazes can be dry milled and used both in a water suspension and/or dry for special dry applications.

Crushed Frits (graniglia, granilla)

The same frits that are usually used in a very fine milled form can also be used in grain form. In this case they are called crushed frits or graniglia (Italy), granilla (Spain), etc. Frit grains or frit flakes need to be crushed or broken, usually with roller breakers, and reduced to a specific size. Their grain classification between a set of sieves is needed. Usually crushed frits have grain size distribution between 0.1 and 1.2 mm but narrower ranges are used. Fine dust, impurities, unsmelted grains are not acceptable. Crushed frits can be made up of a single frit or of a mixture of several frits, they can be transparent, opaque, coloured and colour coated.

Granulated glazes (granulati, granulados, pelletized glazes)

A glaze (made using a formulation of different components, frits and raw materials) already powdered in fine milled form, treated with suitable binders inside special equipment (called "granulators") changes into agglomerates or granulates. The result is a homogeneous aggregation of particles in the form of round grains whose diameter can vary from 0.2 to 2.5 mm. Grains are dried and classified in specific grain size ranges. Occasionally, the process may involve calcination or sintering of the powders and in this case granulated glazes are better known as pelletized glazes. Granulated glazes are used dry with dry application equipment and have the advantage of being more adjustable in composition than the equivalent crushed frits. They can be used singly or mixed together with other granulates of different compositions, behaviour and colour.

2.4 Ceramic Stains

Ceramic stains or pigments are particulate inorganic solids that can be coloured, black and white, physically and chemically stable and unaffected by the vehicle or substrate in which they are incorporated. Due to their extremely low solubility (in water as well as in acids and alkalis) their bioavailability and toxicity are very low. They pose very little threat to the environment. Ceramic stains retain a crystal or particulate structure throughout the colouration process. Most of the stains are produced by calcining at high temperatures mixtures of very fine, inorganic powders such as carbonates, silicates, oxides, etc. of coloured metal compounds, uncoloured compounds and mineralizing agents. This way new stable crystalline structures are formed. The structure of these pigments and ceramic stains are well defined and are identified with specific EINECS and CAS numbers.

2.5 Ceramic Colours

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Various oxides can also react to complex, stable forms that are not mixtures but are new compounds. These pigments are also called Complex Inorganic Colour Pigments (CIC Pigments). In brief, the major families of ceramic stains are based on different crystal structures such as: Rutile: for stains based on mixed oxides of Ti, Cr, Mn, V, Sb, Ni, Nb, W in which heavy metal oxides are incorporated in the form of Complex Inorganic Colours.

Spinels: considering the model of the spinel structure (MgAl2O4) and partially replacing the ions with Co, Ni, Zn, Fe, Cu, Mn, Cr, Ti, Sn (these have different oxidation levels) in different percentages the spinel crystal structure is maintained and new stable crystalline Complex Inorganic Colours are obtained. Zircon: in which Fe, V, Pr and Cd(S,Se) or other elements enter the crystal of the zircon silicate. In a similar way, other pigments are based on the structures of: Baddeleyite, Cassiterite, Corundum, Garnet, Sphene, Olivine, Phenacite, Periclase, etc. In addition to these CIC Pigments pure single oxides, such as Fe2O3, Cr2O3, TiO2, can be used and a group of sulphides based on Cd, Zn, Se has to be mentioned.

2.5 Ceramic Colours

Ceramics colours are preparations of frits (fluxes), ceramic stains and various inorganic raw materials. The mixture of those is milled to obtain a finely divided powder. Frequently the finely milled mixture is calcined again to its softening point and then milled again. In any case ceramic colours are marketed with a defined grain size distribution to achieve reproducible decoration effects. Depending on the decoration technology and on the specific requirements to the decorated and fired end product three different types of ceramic colours are offered: Onglaze colours are applied on the fired glaze of the ceramic support (tableware, tiles) and then the ceramic products are fired again at temperatures between 700 and 950 C, depending on the firing cycle. Onglaze colours are part of the surface of the decorated product. Inglaze colours sink into the glaze during the firing process. In porcelain production the firing temperatures are normally between 1150 and 1400 C, depending on the properties of the body and the firing conditions. Inglaze colours are very resistant to chemical attack and are dishwasher-proof. Underglaze colours are usually covered by a glaze. This technology is widely used on bone china and earthenware. The firing temperatures are between 1000 and 1250 C. The resulting decoration is dishwasher-proof. Ceramic colours are normally delivered in a powderous form. In order to be able to apply those powders on a ceramic support, those powders are mixed with liquid organic substances in order to adhere the ceramic colours to the substrate. During firing those organic substances burn off and the ceramic colours melt and react with the ceramic surface. In some cases ceramic colours are already mixed with an organic medium by the supplier to facilitate handling at the users.

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2 Definitions For decoration of unglazed vitrified stone ware (gres porcellanato) a new family of ceramic colours has been developed recently. Those ceramic colours consist of organic chelate transition metal ions which are normally dissolved in their application medium prior to application.

2.6 Glass Enamels

Glass enamels are preparations of frits (fluxes) and ceramic stains and other raw materials. This mixture is finely ground and in some cases calcined to its softening point and milled again. Glass enamels are normally delivered as powderous materials or in some cases in pasted form. Glass enamels are used to decorate flat glass and hollow glass articles like car windshields, architectural glass, bottles, vases and flacons. For application the powder is mixed with a decoration aid to adhere the glass enamel powder to the surface of the glass article. During firing the decoration aid burns off and the glass enamel melts onto the surface and forms an integrated part of the glass. The possible firing temperatures are limited by the composition of the glass to be decorated. Generally speaking, glass can be decorated at temperatures not exceeding the respective softening temperature. Therefore the firing temperatures of glass colours are adapted to the type of glass and range from 500 C to 800 C. Various types of glass colours are offered: Low melting glass colours, firing range 500 580 C. Glass colours for container glass, firing range 580 630 C. Glass colours for borosilicate glass, firing range 580 650 C. Glass colours for flat glass (car windows), firing range 550 800 C.

2.7 Precious Metal Preparations and Lustres

Lustre preparations are lacquer-like preparations composed of precious metal based metal organic compounds combined with resins as film formers. Fired onto glass, earthenware or porcelain, they produce very thin, intensely coloured layers with thicknesses of the same order as the wavelength of visible light. Interference and luminous reflectance produce shimmering, iridescent colour effects. They are characterized according to colour shade, precious metal content and the type of effect, e.g. craquelling, marbling, running or "halo" lustres. Bright metal preparations are lacquer-like mixtures consisting of precious metal containing organic compounds, combined with other organo-metallic fluxes to promote adhesion and resins to achieve film formation. Given a smooth substrate, after firing a highly reflective metallic film is formed. Depending on the combination of precious metals various fired colours are produced, e.g. bright gold (reddishyellow), bright citron gold (greenish-yellow, Au/Ag alloy) as well as bright platinum (white gold coloured, Au/Pt alloy) or a less expensive bright palladium (white gold coloured, Au/Pd alloy). Matte preparations are lacquer-like preparations consisting of precious metal containing organic compounds, combined with organo-metallic fluxes and resins, containing a small amount of a matting agent. Fired onto smooth substrates, they produce a satin surface which looks similar to a polished burnishing preparation but without the need of further processing or handling.

2.8 Organic Additives (media, covercoats, solvents)

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Burnish metal preparations contain precious metal or precious metal compounds and adhesives in solid, finely dispersed form in liquid resins as film formers. After firing, dull, non-glossy metallic layers are formed, which must be compacted by polishing with glass fibre brushes, sand or other materials to produce a satin finish. Similar to bright preparations, the fired colour is dependent on the composition of precious metals, e.g. burnish gold, burnish palladium and burnish platinum. Burnish silver is mainly used for the decoration of giftware and contains only silver as a precious metal. Since silver is known to react with sulphur compounds forming silver sulphide, this type of decoration may tarnish in the course of time. Tarnishing may be prevented by coating the fired decoration with a suitable varnish. Dusting preparations are used on the basis of gold flakes (gold leaf parings) and precipitated powder gold. They are used for the manufacture of high quality transfers or decals and produce a rich, durable metallic film, without the need of polishing or burnishing. Again a distinction is made between dusting gold, dusting white gold and dusting silver. As regards tarnishing the same applies to dusting silver as to burnishing silver.

2.8 Organic Additives (media, covercoats, solvents)

Ceramic decoration (glazing of the bisquit as well as the decoration with colours, pictures, a.s.o.) needs inorganic powders (coarse frits, glazes, ceramic colours, a.s.o) to be dispersed in a liquid and to be fixed onto the body, which has to be decorated. To achieve this, a huge family of chemically very different organic binders is available. The decorating technology (spraying, dipping, banding, screen printing, thermoplastic transfer, UV-curing, a.s.o.) determines the choice of the organic system. After application and eventually drying, the enamel has to be sintered or molten onto the body. During this step all organic material has to burn off. Media based on organic solvents usually contain poly(meth)acrylates or alkyd resins. They are choosen depending on their solubility, wetting behaviour, rheological properties, film formation, burning behaviour, a.s.o. Organic additives for ceramic and glass decoration are called oils or media. They can be based on different solvents: water, water soluble glycols and glycol ethers, paraffines, esters, aromatic solvents or terpenes from natural sources. Usually mixtures of solvents with different polarity and drying velocity are used. Water soluble systems are particularly common in glazing of tiles. Solvent based compositions are used for direct decoration of porcelain, earthen-ware and glass (often IR-drying is needed) as well as for the production of decals (so called indirect decoration). Soluble salts (penetrating salts). Recently a new category of colouring substances is entering the market. These substances are conventionally called "soluble salts" or "penetrating salts" and are made by using organometallic compounds. They are usually complex salts of transition metals with carboxylic acids. They are sold as aqueous solutions with some specific additives. Organic binders are choosen depending on the solvent system. Normally they are polymeric materials from natural or, more frequently, from synthetic sources. Water based and water soluble media contain mostly polyglycols, polycarbonic acids and

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2 Definitions cellulose derivates alone or as a mixture. Polymer lattices dispersed in water / glycol are another possibility. Plasticizers are often used too. In these cases different phthalates or polymeric materials are used. In addition to these compounds, also many organic additives common to the ink and paint industry are used: silicon containing or silicon free defoamers, dispersing agents, slip and rheology control agents, a.s.o. Covercoats are needed for the production of decals. They are used for high quality decoration of glass, porcelain and earthen-ware as well as for third-fire decoration of tiles. Covercoats are polymer-softener-solutions, which produce flexible, stretchy films after drying. Their chemical basis is similar to solvent containing oils. Filmforming and burning behaviour are the most important properties of these products. UV-curing and thermoplastic systems are different from traditional oils, since they do not need any solvent. UV-media contain monomers and oligomers (mostly acrylates) as reactive components, so that the binders are polymerized on the object to be decorated by irradiation with UV-light. Polymeric binders and plasticizers can be used as additives. Thermoplastic media are based on waxes (fatty alcohols, polyglycols, poly(meth)acrylates, a.s.o.), which are choosen depending on their melting range. Precious metal preparations are used for metallic glossy or matte decorations as well as for special effects obtained through the use of burnishing gold. In these cases we encounter organo-metallic compounds of Au, Ag, Pd, Pt, Rh, a.s.o. Synthetic sulfur containing polymeric compositions are used. In most cases very complicated mixtures of natural and synthetic derivatives are needed. Solvents, binders and plasticizers are chemically similar to other traditional systems.

2.9 Decals Ceramic Transfers

General Information
Ceramic printing is the manufacture of printed products using ceramic colours. Coated stable heavy duty papers are used as the print carrier. The process is mainly screen printing but offset and gravure printing is also used. The images are created by varying the printing carrier, printing method, ink deposit and application technique. A typical example: Carrier: Stable heavy duty paper with the print surface coated with water soluble gum Printing process: Screen printing Inking: a) Ceramic colour b) Printing medium based on methacrylic resin c) Covercoat based on methacrylic resin Application: Manually or automatically Organic substances are used as a printing medium for pasting the ceramic colour to act as a binding agent and also to give a film for the application of the transfer.

2.9 Decals Ceramic Transfers A typical medium consists of: 20 35 % thermoplastic resin, for example methacrylic resin; 5 25 % plasticizer, for example dioctylphthalat; 50 70 % solvent, for example diacetonalcohol and solvent naphtha.

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The covercoat differs from the medium only in the type of solvent and quantitity of plasticizer used. Principally no toxic materials are used for the majority of the printing media and covercoats produced. If toxic materials are used, they are only used in very low concentrations. This also applies to organo-halogenic compounds. In most countries, there is no need for safety data sheets, for example Germany (according to German Chemical Law, 3, Section 5); nevertheless some suppliers of ceramic prints offer some safety data sheets or handling advices.

Reference
(1) Pfaff, P. "Dekorfarben fr Porzellan, Anwendungen fr Schiebebilder." Vortrag im Symposium "Dekorfarben in der Keramik", 13. und 14. Dezember 1994, Bayreuth.

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3 Toxicological Aspects

3 Toxicological Aspects
3.1 Frits
3.1.1 General Remarks
Frits, as a result of the melting of inorganic raw materials, are glasses with a much lower solubility than the batch ingredients. This means, that also the acute toxic effects decrease in comparison to the ingredients. Acute Toxicity Rat feeding studies have shown, that frits and fluxes have generally low acute toxicity. Even in frits with a high lead, cadmium or barium content were found LD50 values greater than 2000 mg/kg. Also the acute inhalative toxicity in high lead-containing frits is low. Typical values of LC50 (rat) are greater than 5 mg / l / 4 h. Chronic Toxicity Some frits may contain lead and cadmium in the silicate matrix. Long-term studies of inorganic lead compounds showed neurotoxic effects. In hydrochloric acid at stomach-acid concentration, soluble lead could be formed and may result in lead accumulation in the organism. The result of a high lead intake includes inactivation of enzymes and disturbances in the synthesis of haemoglobin. In addition, lead compounds are considered to be embryotoxic (EU-classification: category 1). Frits containing 0.5 % ore more lead must be labelled with the skull-andcrossbones symbol and the R-phrase 61 ("May cause harm to the unborn child"). At higher blood-levels (> 500 g/l) there is a possible risk of impairments of the fertility of man and woman (EU-classification: category 3). Therefore R-phrase 62 ("Possible risk of impaired fertility") is necessary if the lead content exceeds 5 %. If cadmium is present in frits, small quantities may dissolve in dilute hydrochloric acid at stomach-concentration. Prolonged intake of soluble cadmium may cause chronic toxic effects by accumulating especially in the kidneys. Due to these effects, cadmium frits must be classified as harmful and labelled with the R-phrases 20/21/22 and S 22, if the cadmium content is 0.1 % or higher. Merely as an orientation, Table 3.1 shows TLV values for generic compounds of lead, cadmium, antimony and selenium. Due to the insolubility of the frit, values for corresponding frits are supposed to be higher. Table 3.1: TLV values of components of frits
Substance Inorganic lead (calculated as Pb) Soluble compounds of cadmium (as Cd) Antimony and compounds (as Sb) Selenium compounds (as Se) TLV (TWA), mg/m3 0.15 0.05 0.5 0.2 TLV (STEL)

3.1 Frits

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3.1.2 Detailed Description of Frit Systems

Since 1993, lead compounds have to be labelled as "toxic" but they are classified as "harmful". In addition the EU has classified all lead compounds as category 1, toxic to reproduction (embryotoxic). Lead compounds and preparations containing 0.5 % of lead must be labelled with the skull-and-crossbones symbol and the phrase R-6l: "May cause harm to the unborn child". The reason for this classification was the positive outcome of studies on embryotoxicity caused by high lead exposure during pregnancy. In various countries differing regulatory requirements apply to the employment of female workers in production areas. In 1994 the EU has classified all lead compounds additionally as toxic to the reproduction (fertility), category 3, due to the possible impairments of the fertility of man and woman. This leads to the labelling with the R-phrase 62: "Possible risk of impaired fertility". Moreover, the Council Directive 94/60/EEC limits the use to professional users of substances presenting among other things toxic effects to reproduction, categories 1 and 2, labelling with R-phrases 61, 62. Acute Toxicity Frits are not considered to be acutely toxic. Rat feeding studies showed LD50 values greater than 2000 mg/kg. Only cadmium compounds as present in frits are considered to be toxic. In the unlikely case of oral intake and possible lesions in the digestive system medical attention is required. Some frits may produce alkaline solutions by reaction with water, which can result in damage of the connective tissue directly in contact with. Chronic Toxicity Some frits contain lead in a soluble and bioavailable form. By ingestion lead could be acculmulated in the organisms. The results of high lead intake include inactivation of enzymes and disturbances in the synthesis of haemoglobin. Prolonged intake of soluble cadmium may cause chronic toxic effects by accumulating especially in the kidneys. Also prolonged intake of soluble antimony and selenium causes chronic toxic effects by accumulation. Antimony is accumulated especially in the liver, and selenium is accumulated especially in the kidneys. Physical Hazards Normally frits are delivered in large grain sizes where the only hazard exists in cuts of the skin. Therefore anti-cut gloves and safety glasses are required during handling. Environmental Concerns The release of frits containing hydrosoluble lead, cadmium, antimony or selenium must be effectively prevented, according to EU Directive 76/464/EC. All water which has come into contact with these types of frits (also fire extinguishing water) has to be treated in a suitable industrial waste water treatment plant. Therefore, those frits must be stocked in areas, which are fully paved, equipped with suitable water collecting systems and fully protected from outside weather conditions. In case of leakage or spillage into the environment the zone of spillage should be mechanically cleaned immediately. Solid wastes must be taken to a controlled dump according to the laws of the respective state. Waters of washing should be treated in an industrial waste water treatment plant.

30

3 Toxicological Aspects In some states, there are limits for the absolute concentration of lead in the air at the working place of 0.15 mg lead / m3. The EU Directive 91/338/EC allows the use of cadmium in ceramic products, establishing a limit of 0.01 % soluble cadmium by weight.

Labelling and Transport Regulations In general, frits are not subject to labelling and to transport regulations. Only lead containing frits are classified as "harmful" and have to be labelled with "T" and R 61, 62, 20/22, 33 and S 53-45. Frits containing cadmium are subject to labelling requirements (Xn) and R 20, 21, 22. In certain cases special requirements for transport regulations may apply. Advice for Safe Handling Due to the glassy nature of frits special care has to be taken to avoid cuts. Therefore anti-cut gloves and safety glasses should be used. The presence of dust in some forms of delivery requires protective masks. Storage, load and discharge in exteriors as well as in interiors must be performed in such a way to avoid any contamination of the area. In case of the formation of dust, it should be immediately removed by properly installed aspiration and filter systems. When lead frits are handled, attention must be paid to information on the special hazards and to the safety advice in the safety data sheets. Very important is the observance of the safety phrases: When using, do not eat, drink, smoke. Especially smokers are endangered: The lead frit is carried from dirty fingers to the cigarette. Lead will get from the lungs directly up to 80 % in the circulation of the blood. Occupational hygiene and safety measures must be observed when cadmium frits are used. Exposure to cadmium can be determined by measurement of workplace concentrations (0.015 mg/m3) and by examination of the cadmium levels in blood and urine. In Germany, the following maximum biological tolerance levels (BAT) are allowed at the workplaces: 15 g Cd / l urine and 1.5 g Cd / 100 ml blood. Occupational hygiene and safety measures must be observed when antimony frits are used. Exposure to antimony can be determined by measurement of workplace concentration, which is limited to 0.5 mg/m3. If an exposition and taking up of lead frit cannot be surely excluded at the workplace, the workplace concentrations have to be measured. The EU Directive 82/605/EEC specifies maximum lead concentrations: at the workplace blood lead levels (2) urine delta-amino-levulinic acid values Some national limits are as follows (1): MAK value lead BAT value lead (blood) lead (blood women < 45 years) delta-amino-levulinic acid (urine, Davis method) (women < 45 years) 0.1 mg/m3 70 g/100 ml 30 g/100 ml 15 mg/l 6 mg/l 0.15 mg/m3 70 g/100 ml 20 mg/g creatinine

If the MAK value cannot be surely observed at short-term dusty activities, a dust mask must be worn during this time.

3.2 Ceramic Stains

31

No special measures are necessary for the protection against fire and explosion. Eventually fire debris and contaminated extinguishing water have to be disposed of in accordance with local regulations. References (1) MAK- und BAT-Werte-Liste, Deutsche Forschungsgemeinschaft, VCH. (2) Council Directive 98/24/EC on the protection of workers against dangerous substances (O.J. L 131/1, 5.5.98).

3.2 Ceramic Stains

Ceramic stains can be subdivided in complex inorganic colour pigments, single metal oxide pigments and cadmium pigments.

General Information
Ceramic stains are inorganic materials, which usually contain one or more of the transition metals often in combination with other elements. Therefore all ceramic stains contain heavy metal constituents except for titanium dioxide. It is therefore necessary to have some basic information about heavy metals and stains containing heavy metals. What is a heavy metal? The technical literature describes them as metals with a density of greater than 4.5 g/ml. By this definition, most of the chemical elements are heavy metals. Are all heavy metals toxic and dangerous to the environment? As is apparent from the definition, the term "heavy metals" only gives an idea of the density of the metal, and says nothing about its toxicity or behaviour in the environment. Heavy metals are a natural constituent of our environment. Considerable amounts occur naturally in the rock and soil, for example barium 650 mg/kg, chromium 83 mg/kg, manganese 1000 mg/kg, nickel 58 mg/kg, zinc 83 mg/kg and iron about 5 % (1). The environment is not free from heavy metals. Traces also occur, for example, in petroleum, coal and wood. As a result of absorption from the soil by plants, they are present in our food. During the course of evolution, life forms have developed in an environment with a natural content of heavy metals and these have been included in the build-up of organisms. Many heavy metals are vital trace elements, without which human and animal life would not be possible. The trace elements essential to life include the following heavy metals: Iron, zinc, manganese, copper, chromium, molybdenum and cobalt. Other elements regarded as beneficial are nickel, vanadium, arsenic, selenium and tin. A radical demand for the absence of heavy metals in all spheres of life is thus absurd due to their ubiquity and biological necessity. As with all other substances, heavy metals can be regarded as harmful to the human being and the environment when specific concentrations are exceeded. The range depends on the heavy metal and on the form in which it is present. A number of heavy metals are so firmly bound in the pigment that they are soluble neither in the soil nor in the organism; i.e. they are not bioavailable (2). Just how beneficial or toxic one and the same heavy metal can be is illustrated by the chromium compounds. The simple question of whether chromium compounds are hazardous or not cannot be answered with a yes or no. Chromium is vital to organisms. Chromium deficiency has been shown in animal experiments to result in diabe-

32

3 Toxicological Aspects tes, arteriosclerosis and growth disturbances. Commercial chromium compounds contain trivalent or hexavalent chromium, which differ very greatly in their effects. Hexavalent chromium compounds (chromates) have a strong tendency to change into trivalent chromium compounds while giving up oxygen. They therefore have a strong oxidizing action and a toxic effect on biological materials. For humans and animals as well as for plants they are more than 1000 times more toxic than trivalent chromium compounds (3). Hexavalent chromium compounds such as lead chromates are suspected of being carcinogenic. In chromium oxide green, chromium titanium yellow, chromium iron oxide brown and some cobalt blue pigments, chromium is present solely in trivalent form. The pigments are mainly insoluble in water, alkaline medium and mineral acids. If they are inadvertently ingested, the human body is not capable of dissolving significant amounts of chromium. In the case of chromium titanium yellow, the same is true for antimony. In such cases we say that the heavy metals are not bioavailable. As pigments are calcined products, they do not liberate heavy metals when burned in a waste incinerator (2). In this form, the heavy metals are practically inert and constitute no hazard to human beings or the environment.

References (1) Fiedler H. J.; Rssler, H. J. "Spurenelemente in der Umwelt"; Enke Verlag, Stuttgart, 1988. (2) Endri, H.; Haid, M. Kunststoffe schwermetallfrei einfrben? Kunststoffe 1992, 82, 771776. (3) Merian, E. "Metalle in der Umwelt"; VCH, Weinheim, 1994.

3.2.1 Complex Inorganic Colour (CIC) Pigments

The term "complex inorganic colour pigment" denotes an inorganic pigment as a homogenous chemical phase, replacing the formerly used term "mixed-phase metal oxide pigment", which arouses the false impression that it is a mixture. In the stable lattice e.g. of a rutile or a spinel different metal cations are replaced. In comparison to the primary oxides the electron movability is normally increased, which is shown in colour and tone. Whether the new term "complex inorganic colour pigments" will contribute to a more clearly definition, is questionable. The significance of these pigments is their outstanding light fastness and resistance to temperature, chemicals and weathering. They are chemically and thermally very stable pigments. The following complex inorganic colour pigments are categorized according to their crystal structure. Each product may encompass a range in concentration of its constituent oxides, or put the other way, some variability in stoichiometry and the presence of minor or dopant elements in the host crystal lattice.

3.2.1.1 Rutile
Common Name Nickel antimony titanium yellow Nickel niobium titanium yellow Nickel tungsten titanium yellow Chromium antimony titanium yellow Chromium niobium titanium yellow Chromium tungsten titanium yellow Formula (Ti,Ni,Sb)O2 (Ti,Ni,Nb)O2 (Ti,Ni,W)O2 (Ti,Cr,Sb)O2 (Ti,Cr,Nb)O2 (Ti,Cr,W)O2 EINECS No. 232-353-3 271-892-9 273-686-4 269-052-1 271-891-3 269-054-5 CAS No. 8007-18-9 68611-43-8 69011-05-8 68186-90-3 68611-42-7 68186-92-5

3.2 Ceramic Stains Manganese antimony titanium brown Vanadium antimony titanium gray Antimony titanium orange/yellow (Ti,Mn,Sb)O2 (Ti,V,Sb)O2 (Ti,Sb)O2 270-185-2 269-062-6 305-908-3

33 68412-38-4 68187-00-8 95193-93-4

These are rutile pigments on the basis of titanium dioxide. The rutile lattice of titanium dioxide absorbs nickel oxide, chromium(III) oxide, manganese oxide or vanadium(III) oxide as colouring components and antimony(V) oxide, niobium oxide or tungsten oxide to maintain an average cation valency of four. Incorporation of these oxides in the inorganic complex colour pigment results in the loss of their chemical identity and consequently of their original chemical, physical and physiological properties (1). Therefore these rutile pigments cannot be described as e.g. nickel, chromium or antimony compounds. For these reasons they are not considered to fall under the generic hazard classifications of e. g. "Nickel and its compounds, if not listed oherwise" in IARC Monographs and various other listings of hazardous substances. All these pigments are produced by a calcining process at temperatures above 1000 C. They are chemically and thermally very stable pigments. They are used in enamel, floor tiles (body colouring), tiles, tableware and ceramic colours with chromium antimony titanium yellow as main component. Acute Toxicity Negligible acute toxicity is shown by these products. Oral LD50 values for rats are typically > 5000 mg/kg. Tests have shown that these pigments do not cause irritation to the skin or the mucous membranes. Chronic Toxicity These inorganic pigments contain one or more heavy metals, the oxides of which may cause toxic effects. However, these heavy metals in the inorganic complex pigments behave as different compounds, even if the respective oxides are used as raw material for pigment production. Toxicological investigation with nickel and chromium antimony titanium yellow have shown that, even at high dosage rates (up to 1 % in animal feeds), these pigments are neither toxic nor biologically available (24). Although the presence of nickel sometimes triggers allergies, it was reported that workers exposed to these pigments for many years have not shown any allergic reactions (1). Some rutiles contain 10 to 12 % antimony firmly bonded in the lattice. On account of their chemical and toxic behaviour these pigments can not be regarded as antimony compounds which are labelled as hazardous substance. Physical Hazards None known at this time. Environmental Concerns These pigments are insoluble in acids and alkalis and in general practically inert materials heavy metals. Because they do not contain leachable heavy metals, they do not contribute to any ecological or toxicological problems by other heavy metal compounds. Due to their insolubility in water they can be removed mechanically from waste water by purification plants. They do not add dissolved heavy metal to sewage water or landfill leachate. When articles coloured with these pigments are burned in incinerators, the pigments are recovered in their insoluble form (1).

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3 Toxicological Aspects

Labelling and Transport Regulations The mentioned products are not subject to labelling and to transport regulations. Advice for Safe Handling The usual precautions for the handling and processing of chemicals must be observed. In the different countries there are for certain metals workplace control parameters for fine dust. When large quantities are decanted without local exhaust ventilation usually dust masks have to be worn. No special measures are necessary for the protection against fire and explosion. Eventually fire debris and contaminated extinguishing water have to be disposed of in accordance with local regulations. References (1) Endri, H. "Aktuelle anorganische Bunt-Pigmente", Vincentz, Hannover, 1997. (2) Bomhard, E. et al. Subchronic oral toxicity and analytical studies on Nickel Rutile Yellow and Chrome Rutile Yellow with rats. Toxicol. Lett. 1982, 14, 189194. (3) Hara, S. et al. Pharmacological Studies of Titanium Yellow with regards to its Toxicity. Tokyo Ika Daika Zasshi 1963, 21, 111132. (4) Toxikologisch-arbeitsmedizinische Begrndung von MAK-Werten, DFG, VCH, 1983.

3.2.1.2 Spinels
Common Name Cobalt blue Cobalt nickel zinc titanite green Cobalt zinc alumina blue Zinc iron chromite brown Copper chromite black Manganese ferrite black Chrome iron manganese zinc brown Iron cobalt chromite black Iron titanium black Cobalt tin blue Iron chromite brown Nickel ferrite brown Cobalt chromite blue Cobalt chromite green Iron cobalt black Zinc ferrite brown Zinc chrome alumina pink Chrome iron manganese brown Chrome iron nickel black Chrome manganese zinc brown Formula CoAl2O4 (Co,Ni,Zn)2TiO4 Co,Zn(Al)2O4 Zn(Fe,Cr)O4 CuCr2O4 (Fe,Mn)(Fe,Mn)2O4 (Zn,Fe,Mn)(Fe,Cr,Mn)O4 (Co,Fe)(Fe,Cr)2O4 Fe2TiO4 Co2SnO4 Fe(Fe,Cr)2O4 NiFe2O4 Co(Al,Cr)2O4 CoCr2O4 (Fe,Co)Fe2O4 (Zn,Fe)Fe2O4 Zn(Al,Cr)2O4 (Fe,Mn)(Fe,Cr,Mn)O4 (Ni,Fe)(Cr,Fe)2O4 (Zn,Mn)Cr2O4 EINECS No. CAS No. 1345-16-0 269-047-4 269-049-5 269-050-0 269-053-7 269-056-3 269-058-4 269-060-5 269-064-7 269-066-8 269-069-4 269-071-5 269-072-0 269-101-7 269-102-2 269-103-8 269-230-9 271-411-2 275-738-1 275-985-5 310-193-6 68186-85-6 68186-87-8 68186-88-9 68186-91-4 68186-94-7 68186-96-9 68186-97-0 68187-02-0 68187-05-3 68187-09-7 68187-10-0 68187-11-1 68187-49-5 68187-50-8 68187-51-9 68201-65-0 68555-06-6 71631-15-7 71750-83-9

Colour pigments with spinel structure represent the largest and also most multifarious group of ceramic colours. Numerous metal oxides can be combined with each other.

3.2 Ceramic Stains

35

Acute Toxicity During the examination of representative products the following was found out: Oral LD50 values for rats are typically > 5000 mg/kg. Tests have shown that these pigments do not cause irritation to the skin or the mucous membranes. Because of the chemically similarity of the products it can be assumed that all spinels do not show acute toxicity. Chronic Toxicity These inorganic pigments contain one or more heavy metals, the oxides of which may cause toxic effects. However, these heavy metals in the inorganic complex pigments behave as different compounds, even if the respective oxides are used as raw material for pigment production. The heavy metals are so firmly bonded in the spinel lattice that they do not have a relevant solubility as condition for a bioavailability. This was confirmed by solubility tests with hydrochloric acid in the same concentration as stomach acid. Some zinc iron pigments show a higher zinc solubility maybe because of the presence of zinc. As ZnO shows no chronic toxicity, it is not expected for these products to show a chronic toxicity. Although the presence of nickel and cobalt sometimes triggers allergies, it was reported that workers exposed to these pigments for many years have not shown any allergic reactions (1). In the chromium containing spinels the chromium is trivalent. In dependence on the manufacturing process some of these products can contain traces of hexavalent chromium on the pigment surface in ppm-range, but far away from the EU-labelling limit of 0.1 %. Physical Hazards None known at this time. Environmental Concerns These pigments are insoluble in acids and alkalis with the exception of zinc and iron and in general practically inert materials heavy metals. Because they do not contain leachable heavy metals, they do not contribute to any ecological or toxicological problems by other heavy metal compounds. Due to their insolubility in water they can be removed mechanically from waste water by purification plants. They do not add dissolved heavy metal to sewage water or landfill leachate. When articles coloured with these pigments are burned in incinerators, the pigments are recovered in their insoluble form (1). Labelling and Transport Regulations The mentioned products are not subject to labelling and to transport regulations. Advice for Safe Handling The usual precautions for the handling and processing of chemicals must be observed. In the different countries there are for certain metals workplace control parameters for fine dust. When large quantities are handled without local exhaust ventilation usually dust masks have to be worn. No special measures are necessary for the protection against fire and explosion. Eventually fire debris and contaminated extinguishing water have to be disposed of in accordance with local regulations. Reference (1) Endri, H. "Aktuelle anorganische Bunt-Pigmente", Vincentz, Hannover, 1997.

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3 Toxicological Aspects

3.2.1.3 Baddeleyite Cassiterite Corundum Zircon Garnet Sphene

Common Name Baddeleyite Zirconium vanadium yellow Cassiterite Tin vanadium yellow Tin chromium orchid Tin antimony gray Corundum Manganese alumina pink Chrome alumina pink Zircon Zirconium vanadium blue Zirconium praseodymium yellow Zirconium iron pink Zirconium silicon grey Garnet Victoria Green Sphene Chrome tin pink Formula (Zr,V)O2 (Sn,V)O2 (Sn,Cr)O2 (Sn,Sb)O2 (Al,Mn)2O3 (Al,Cr)2O3 (Zr,V)SiO4 (Zr,Pr)SiO4 (Zr,Fe)SiO4 n. a. 3CaO:Cr2O3:3SiO2 CaO:SnO2:SiO2:Cr2O3 EINECS No. CAS No. 269-063-1 269-055-8 269-104-3 269-105-9 269-061-0 269-083-0 269-057-9 269-075-7 270-210-7 305-902-9 271-385-2 269-073-6 68187-01-9 68186-93-6 68187-53-1 68187-54-2 68186-99-2 68187-27-9 68186-95-8 68187-15-5 68412-79-3 95193-95-6 68553-01-5 68187-12-2

The baddeleyite lattice of ZrO2 incorporates pentavalent vanadium to produce the zirconium vanadium yellow. The corundum lattice of Al2O3 incorporates manganese or chromium(III), whereby different and very stable pink colouring matter is produced. Owing to the incorporation of specific transition metal ions in the ZrSiO4-lattice zirconium colouring matter is produced, that is distinguished by high temperature stability and chemical resistance. By the incorporation of different metals in the tin dioxide lattice different very stable cassiterite colouring matter is produced. The application fields of these stains are tiles, tableware, sanitary and decoration colours. Acute Toxicity During the examination of representative products the following was found: Oral LD50 values for rats are typically > 5000 mg/kg. Tests have shown that these pigments do not cause irritation to the skin or the mucous membranes. Because of the chemically similarity of the products it can be assumed that all these products do not show acute toxicity. Chronic Toxicity These inorganic pigments contain one or more heavy metals, the oxides of which may cause toxic effects. However, these heavy metals in the inorganic complex pigments behave as different compounds, even if the respective oxides are used as raw material for pigment production.

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37

The heavy metals are so firmly bound in the lattice that they do not have a relevant solubility as condition for a bioavailability. This was confirmed by solubility tests with hydrochloric acid in the same concentration as stomach acid. The chromiumcontaining products contain trivalent chromium. Physical Hazards None known at this time. Environmental Concerns These pigments are insoluble in acids and alkalis and in general practically inert materials. Because they do not contain leachable heavy metals, they do not contribute to any ecological or toxicological problems by other heavy metal compounds. Due to their insolubility in water they can be removed mechanically from waste water by purification plants. They do not add dissolved heavy metal to sewage water or landfill leachate. When articles coloured with these pigments are burnt in incinerators, the pigments are recovered in their insoluble form. Labelling and Transport Regulations The mentioned products are not subject to labelling and to transport regulations with the exception of some modified products, which additionally may contain lead oxide. Advice for Safe Handling The usual precautions for the handling and processing of chemicals must be observed. In the different countries there are for certain metals workplace control parameters for fine dust. When large quantities are decanted without local exhaust ventilation usually dust masks have to be worn. No special measures are necessary for the protection against fire and explosion. Eventually fire debris and contaminated extinguishing water have to be disposed of in accordance with local regulations.

3.2.1.4 Inclusion Pigments

Common Name Cadmium sulfide inclusion pigment Cadmium sulfoselenide inclusion pigment Formula CdS in (ZrSiO4) Cd(S,Se) in ZrSiO4 EINECS No. 310-077-5 277-135-9 310-077-5 CAS No 102184-95-2 72-968-34-4 102184-95-2 72-828-62-7

Starting from the idea to combine thermal stability of zirconium silicate and high brilliance of cadmium pigments in yellow, orange or red colour shades the cadmium sulfide and sulfoselenide inclusion pigments have been developed in the 1970ies. Firing stability up to 1350 C is achieved by coating the crystals of Cd(S,Se) during their formation with zirconium silicate, ZrSiO4. Thus a novel class of pigments evolved comprising a shielded chromophor compound via a both thermally and chemically inert matrix (1). Inclusion pigments reduce the amount of cadmium necessary to achieve an intense red shade by a factor of ten to twenty compared to traditional cadmium glazes. Application fields of those pigments range from glazes used in general ceramics to e. g. screen printing glazes for tile manufacturing, sanitary production to decoration colours used for tableware.

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3 Toxicological Aspects

Acute Toxicity Both zirconium silicate (capsula) and cadmium pigment (colouring agent) have no acute toxic effects (oral LD50, rat > 5000 mg/kg). They also do not have any adverse effects on skin and mucous membranes. Release of cadmium from fired inclusion pigment glazes based on EN 1388 results in values of less than 0.02 mg/dm2. Chronic Toxicity See section 3.2.3. Physical Hazards None known at this time. Environmental Concerns Inclusion pigments are insoluble, even in strong acids. Pigments and pigmented articles are considered to be safe for landfill disposal. Cadmium and its compounds have been classified as List 1 substances in EU Directive 76/464/EEC relating to pollution of the aquatic environment and EU member states are required to take special measures to control all discharges of cadmium pigments. The European Directive 91/338/EEC restricts the use of cadmium pigments in certain polymers. The use in artists' colours and ceramic products is permitted. The restriction of coated media does not refer to preparations which are intended for ceramic use. Labelling and Transport Regulations Inclusion pigments are not subject to labelling and to transport regulations. Advice for Safe Handling Strong mechanical impact on the cadmium inclusion pigments or on products made thereof may cause cracking of the surrounding shell of zirconium silicate and facilitates chemical attack of the sulfoselenide. Once destroyed, inclusion pigments behave toxicologically as cadmium pigments (see section 3.2.3). Therefore it is essential, that milling of cadmium inclusion pigments has to be avoided. The pigment must not be added till 90 % of the glazes milling time has passed. Even better is the use of stains in an already dispersible form which can easily be added to the glaze by stirring. References (1) Cadmium hinter Gittern. Einschlupigmente: Neue Zirkonsilikatfarbkrper. Cerdec, 1997. (2) M. Novotny: Inorganic Pigments in: Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed., John Wiley and Sons, 1996.

3.2.1.5 Pyrochlore
Common Name Lead antimonate yellow Formula Pb2Sb2O7 EINECS No. 269-105-9 CAS No. 68187-54-2

Whereas the other complex inorganic colour pigments obtain their colour by the structure (valency states, co-ordination, surroundings), the lead antimony compound itself is the chromophor. Known as "Naples yellow" it counts to the oldest colouring matter. It is used for enamel, glazes and ceramic colours (glass and porcelain onglaze).

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39

Acute Toxicity The LD50 values of rat feeding studies are > 5000 mg/kg. In terms of primary skin irritation (rabbit) and primary mucous membrane irritation (rabbits' eyes) the pigments are non-irritating. Chronic Toxicity Lead antimonate contains lead and antimony, both metals are of chronic hazard concern. Lead antimonate pigments are lead compounds of low solubility. In hydrochloric acid, at stomach-acid concentrations, soluble lead could be formed and may result in lead accumulation in the organism. The results of a high lead intake include inactivation of enzymes and disturbances in the synthesis of haemoglobin. Therefore the EU has classified all lead compounds as harmful (R 20/22, 33). In addition, the EU has classified all lead compounds as category 1, toxic to reproduction (embryotoxic). Lead compounds and preparations containing 0.5 % of lead must be labelled with the skull-and-cross bones symbol and the phrase R-61: "May cause harm to the unborn child". The reason for this classification was the positive outcome of studies on embryotoxicity caused by high lead exposure during pregnancy. In various countries differing regulatory requirements apply to the employment of female workers in production areas. In 1994 the EU has classified all lead compounds additionally as toxic to the reproduction (fertility) category 3 due to the possible impairments of the fertility of man and woman. This leads to the labelling with the R-phrase 62: "Possible risk of impaired fertility". However, in a literature study it was stated that only at blood lead levels above 500 g/litre a possible fertility impairment is expected (2). Physical Hazards None known at this time. Environmental Concerns Lead antimonate pigments contain high quantities of lead and antimony. Their release into the environment must be prevented. Lead antimonate pigments are insoluble in water. They may be virtually separated mechanically in purification plants. They may dissolve in waste water containing acids and must then be eliminated by chemical flocculation / precipitation. Waste containing lead antimonate that cannot be recycled must be disposed of as a special waste in accordance with local regulations. Uncontaminated packaging can be treated as domestic refuse. Contaminated empties should be disposed of in the same manner as the content. Labelling and Transport Regulations Lead antimonate pigments are classified as harmful substances. They must be labelled with T and R 61, 62, 20/22 and 33. Additionally they are classified as dangerous substances referring transportation with the acid soluble lead content of above 5 %. Advice for Safe Handling When lead antimonate pigments or lead antimonate-containing preparations are handled, attention must be paid to information on the special hazards and to the safety advise in the safety data sheets. Very important is the observance of the safety phrase: No eating, drinking, smoking or snuff-taking at the place of work. Especially smokers are endangered. The lead antimonate, which is carried from dirty fingers to the ciga-

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3 Toxicological Aspects rette, decomposes in the cigarette heat. Lead will be volatile and will get from the lungs directly up to 80 % in the circulation of the blood. If an exposition and taking up of lead antimonate cannot be surely excluded at the work place, the workplace control concentrations have to be measured. The EU Directive 82/605/EEC specifies maximum lead concentrations. If the MAK value cannot be surely observed at short-termed dusty activities, a dust mask must be worn during this time.

No special measures are necessary for the protection against fire and explosion. Eventually fire debris and contaminated extinguishing water have to be disposed of in accordance with local regulations. References (1) MAK- und BAT-Werte-Liste, Deutsche Forschungsgemeinschaft, VCH. (2) Literature study: Compilation and evaluation of data on the reproductive toxicity of lead. Unpublished, 1993.

3.2.1.6 Olivine Phenacite Periclase

Common Name Zirconium titanium oxide Olivine Cobalt silicate blue Phenacite Cobalt zinc silicate blue Periclase Cobalt nickel gray Formula (Zr,Ti)O2 EINECS No. 25193-95-6 25046-44-9 269-093-5 CAS No. 306-909-9 306-832-0 68187-40-6 68412-74-8 68186-89-0

Co2SiO4

(Co,Zn)2SiO4 270-208-6 (Co,Ni)O 269-051-6

The stains are mainly used in tile manufacturing and for the preparation of ceramic colours. Acute Toxicity In cobalt silicate blue an oral LD50 values for rats of 1600 mg/kg was found. For cobalt silicate blue and cobalt zinc silicate blue show the same high acid soluble cobalt content, both products have to be classified as harmful substances. Additional tests have shown that these pigments do not cause irritation to the skin or the mucous membranes. Less information is available for cobalt nickel gray. It shows only a low acid soluble cobalt content. Chronic Toxicity There are no studies available on chronic toxicity. It this known that some cobalt containing substances are suspicious for sensibilisation properties. Physical Hazards None known at this time. Environmental Concerns Due to their insolubility in water they can be removed mechanically from waste water by purification plants. They do not add dissolved heavy metal to sewage water or landfill leachate. When articles coloured with these pigments are burned in incinerators, the pigments are recovered in their insoluble form.

3.2 Ceramic Stains

41

Labelling and Transport Regulations Cobalt and cobalt zinc silicate blue have to be labelled with Xn and R 20/22. These products are not subject to transport regulations. Advice for Safe Handling Due to the acid solubility of the cobalt in these pigments, an oral or inhalative intake has to be avoided when handling or processing. As a precaution contact with skin has to be avoided too. In the different countries there are for certain metals workplace control parameters for fine dust. When large quantities are decanted without local exhaust ventilation usually dust masks have to be worn. No special measures are necessary for the protection against fire and explosion. Eventually fire debris and contaminated extinguishing water have to be disposed of in accordance with local regulations.

3.2.2 Colouring Oxides

3.2.2.1 Iron oxide
Common Name Iron brown Formula Fe2O3 EINECS No. 215-278-0 CAS No. 1317-63-1

Iron oxides are mainly used for brown glazes, and also the famous "Meissen red" is based on iron oxide. Acute Toxicity Rat feeding studies have shown these pigments to have low toxicity. The oral LD50, rat, is > 5000 mg/kg. Iron oxides are neither sensitizing nor do they irritate the skin. In the presence of extremely high dust concentrations, mechanical effects may cause irritation of the mucous membranes of the eye (1). A large number of toxicological tests have revealed no indication of iron oxides causing damage to the human organism. Whereas natural iron oxide pigments may contain crystalline silica, the content of such substances in synthetic iron oxides is usually below the level of detection by diffused radiation testing. Chronic Toxicity Since 1992, iron oxides have been included in the yellow pages of Germany's MAK list. As large amounts of iron oxides are handled world-wide in the form of iron ores, epidemiological studies on carcinogenicity have been carried out (2, 3). To date, there are no recorded cases of illness specifically caused by the handling of iron oxides. Recent inhalation studies in rats prompted that other substances which have always been considered to be inert may also cause lung tumours in the form of ultra fine dust (4). Physical Hazards None known at this time. Environmental Concerns Iron oxides are natural constituents of virtually every type of natural stone and soil. Because of their insolubility under natural conditions, they are carried as a suspension with clay minerals in rivers. Even higher concentrations do not harm aquatic flora and fauna. The LC50 values are therefore greater than 5000 mg/l (1).

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3 Toxicological Aspects

Labelling and Transport Regulations Iron oxide pigments are not subject to labelling and to transport regulations. Advice for Safe Handling The usual precautions for the handling and processing of chemicals must be observed. In the different countries there are for certain metals workplace control parameters for fine dust. When large quantities are decanted without local exhaust ventilation usually dust masks have to be worn. No special measures are necessary for the protection against fire and explosion. Eventually fire debris and contaminated extinguishing water have to be disposed of in accordance with local regulations. References (1) EUCLID Data Sheets: Fe2O3 (13.1.93), FeOOH (25.9.92), Fe3O4 (5.8.92). (2) Steinhoff, D.; Mohr, U.; Hahnemann, S. Carcinogenesis studies with iron oxides. Exp. Pathol. 1991, 43, 189194. (3) Stockinger, H. E. A review of world literature finds iron oxides noncarcinogenic. Am. Ind. Hyg. Ass. J. Pathol. 1986, 45, 127133. (4) Heinrich, U. et al. Comparative longterm animal inhalation studies using various particulate matter: objectives, experimental design and preliminary results. Exp. Pathol. 1989, 37, 2731.

3.2.2.2 Chromium oxide

Common Name Chromium green hematite Formula Cr2O3 EINECS No. 272-713-7 CAS No. 68909-79-5

The chromium(III) oxide, which forms the basis of chromium oxide pigments, crystallises in a corundum lattice, therefore it has a correspondingly high thermal stability (up to 1000 C). Chromium oxide green pigments contain only trivalent chrome. Under natural conditions, there is no reason to expect the release of chromium ions from chromium oxide green pigments. Even under highly acidic conditions (pH 1 2), only a few ppm of chromium(III) will be released. Oxidation to chromium(VI) is possible if chromium(III) oxide is treated thermally under alkaline conditions. Chromium oxide pigments yield a fairly dark olive-green shade. Their main use in ceramics is as body stain and green stain for ceramic colours. Acute Toxicity The oral LD50 value in rats is > 5000 mg/kg. Chromium(III) oxide is neither sensitizing nor does it irritate the skin. In the presence of extremely high dust concentrations, mechanical effects may cause irritation of the mucous membranes of the eye. In the evaluation of the toxicity of chromium, a distinction must be drawn between trivalent and hexavalent chromium compounds. Chronic Toxicity Toxic effects have not been detected in rats receiving up to 5 % of the pigment in their feed (1) nor in medical studies performed in chemical plants producing chromium(III) oxide (2). In practice, this means that chromium(III) oxide pigments can be regarded as inhalable fine dust with a MAK value of 4 mg/m3. The use of freeflowing, non-dusting pigments significantly improves occupational hygiene conditions.

3.2 Ceramic Stains Physical Hazards None known at this time.

43

Environmental Concerns Trivalent chromium is a widely occurring natural substance. Concentrations up to 200 mg/kg have been found in soil. Even higher concentrations do not harm aquatic flora and fauna. The LC50 values are greater than 5000 mg/l (3). If pigments containing chromium(III) enter the soil or water, no negative effects on living organisms or contamination of the ground water will be expected. Labelling and Transport Regulations Chromium oxide pigments are not subject to labelling and to transport regulations. Advice for Safe Handling The usual precautions for the handling and processing of chemicals must be observed. In the different countries there are for certain metals workplace control parameters for fine dust. When large quantities are handled without local exhaust ventilation usually dust masks have to be worn. No special measures are necessary for the protection against fire and explosion. Eventually fire debris and contaminated extinguishing water have to be disposed of in accordance with local regulations. References (1) Ivankovic, S.; Preussmann, R. Food Cosmet. Toxicol. 1975, 13, 347351. (2) Korallus, U.; Ehrlicher, H.; Wstefeld, E. Dreiwertige Chromverbindungen Ergebnisse einer arbeitsmedizinischen Untersuchung. Arbeitsmedizin Sozialmedizin Prventivmedizin 1974, 3, 51. (3) EUCLID Data Sheet, Chromium Oxide.

3.2.2.3 Cobalt oxides

Common Name Tricobalt tetroxide Cobalt monoxide Formula Co3O4 CoO EINECS No. 215-157-2 215-154-6 CAS No. 1308-06-1 1307-96-6

Cobalt oxides are mainly used for colouring all types of ceramics and in the glass industry. Only small amounts form a deep reddish blue. In practice, normally Co3O4 or a combination of Co3O4 and CoO is used. Acute Toxicity For CoO an oral LD50 value for rats of 202 mg/kg was found. Co3O4 has no acute oral toxicity (LD50 > 5000 mg/kg) but the acute inhalative toxicity LC50 (24 h) for rats is 4,8 mg/l. Inhalation and skin contact may cause irritation of skin and respiratory tract. If swallowed in large amounts, cobalt oxides may damage blood, heart, thyroid gland and pancreas. Chronic Toxicity In some countries, cobalt oxides and certain cobalt compounds are considered to be carcinogenic. Long-term inhalation of cobalt oxides may cause severe disease of the respiratory tract. Physical Hazards None known at this time.

44

3 Toxicological Aspects

Environmental Concerns Depending of the processing parameters of the manufacturer, cobalt oxides may be dangerous to the environment. If bioavailable forms of cobalt oxide are used, release in the environment must be effectively prevented. Labelling and transport regulations According to the EU regulations, cobalt oxide CoO has to be labelled as harmful (Xn) with the R-phrases 22 and 43. Cobalt oxides are normally not subject to transport regulations. Advice for Safe Handling Due to the irritant and sensitizing effects, an inhalative intake has to he avoided when handling or processing. A dust exhaustion system should be installed to reduce the workplace concentration to the limit of 0.1 mg/m3 (MAK, Germany). If technical measures are not sufficient to reduce dust to this level, fine dust respirators must be used. To avoid skin irritation, protective cloves and clothes should be used. Reference (1) RTECS: Register of Toxic Effects of Chemical Substances, NIOSH, edition 1997. Sax's Dangerous Properties of Industrial Materials (8th edition), Richard J. Lewis Sr.

3.2.2.4 Copper oxide

Common Name Copper(I) oxide Formula Cu2O EINECS No. 215-27-07 CAS No. 1317-39-1

Red Copper(I) oxide, also called cuprous oxide, is synthetically produced in high purity. It crystallizes in the cubic structure and has a correspondingly high thermal stability (above 1200 C). Copper oxide dissolves easily in liquid glasses and produces, depending on the alkali content of the glass, greenish to bluish shades. Antique Persian tiles are an excellent example for colour effects obtained with Copper oxides. Acute Toxicity Copper is an essential element for warm-blooded species, and the uptake and excretion of bioavailable Cu(II) ions are controlled by special regulative enzyme systems in the body. For rats an LD50 value of 470 mg/kg was found. Therefore copper(I) oxide is classified as harmful. Chronic Toxicity Chronic effects have not yet been recorded. Physical Hazards None known at this time. Environmental Concerns Copper(I) oxide is practically insoluble in water, but it is soluble in mineral acids and excess ammonia. For certain marine species Cu(II) ions are toxic at low levels and Cu(II) ions also act as fungicides. In Germany Cu(I) oxide is classified as "weakly water-hazardous" (water hazard class 1 ).Therefore any spillage into the environment has to be avoided.

3.2 Ceramic Stains

45

Labelling and Transport Regulations Copper(I) oxide has to be labelled with Xn, R 22 and is not subject to transport regulations. Advice for Safe Handling The usual precautions for handling and processing of chemicals have to be observed. There may exist certain limitations of the dust level at the work place, which in Germany should not exceed 1 mg/m3. No special measures are necessary for the protection against fire and explosion. Eventually contaminated extinguishing water has to be disposed of in accordance with local regulations.

3.2.2.5 Nickel oxides

Common Name Nickel monoxide Nickel dioxide Formula NiO NiO2 EINECS No. 215-215-7 234-823-3 CAS No. 1313-99-1 12035-36-8

Nickel oxides are compounds which are used for the manufacture of stains and for certain glazes in artistic ceramics. For nickel containing stains see sections 3.2.1.1, 3.2.1.4 and 3.2.1.5. Acute Toxicity Nickel oxides are sensitizing substances, but are not considered to be acutely toxic. Chronic Toxicity Nickel monoxide causes cancer and is classified in class III A 1. Increased cancer risk was found for lung and sino-nasal cancers. Physical Hazards None known at this time. Environmental Concerns Nickel oxides should not enter the environment, neither air, water or land. In Germany a TRK-value of 0.5 mg Ni/m3 is valid. Labelling and Transport Regulations Nickel oxide containing products have to be classified as carcinogenic, Cat. 1, and have to be labelled, whenever the free NiO-content exceeds 0.1 %, as toxic, with T and R 49, S 53-45. If the free NiO-content exceeds 1 %, R 49-43 is required. Nickel oxides and nickel salts with the exception of nickel nitrate / nitrite (oxidizers) and nickel cyanide (toxic) are not subject to transport regulations. Advice for Safe Handling Due to the carcinogenicity and the sensitizing effects of nickel and its low soluble compounds, an inhalative intake has to be avoided when handling or processing. A dust exhaustion system must be used to reduce the workplace concentration to the lowest possible level. Fine dust respirators must be used to prevent inhalative intake.

3.2.2.6 Manganese dioxide

Common Name Manganese dioxide Formula MnO2 EINECS No. 215-202-6 CAS No. 1313-13-9

Manganese dioxide is commonly used for the production of stains (see sections 3.2.1.2 and 3.2.1.3) and for various coloured glazes in artistic ceramics and tile production.

46 Acute Toxicity Manganese dioxide is not acutely toxic.

3 Toxicological Aspects

Chronic Toxicity Prolonged intake leeds to accumulation in the body causing neurotic symptoms similar to Parkinson disease. Physical Hazards None known at this time. Environmental Concerns Manganese dioxide should not enter the environment. It is considered as "weakly water-hazardous". Labelling and Transport Regulations Manganese dioxide has to be labelled as harmful at concentrations higher than 25 % (Xn with R 20/22) and is not subject to transport regulations. Advice for Safe Handling Occupational hygiene and safety measures have to be observed to avoid especially inhalative intake of manganese dioxide. A dust exhaust system should be installed to reduce the workplace concentration to the limit of 0,5 mg/m3 (MAK). If the technical measures are not sufficient to reduce dust to this level, fine dust respirators must be used.

3.2.2.7 Pearlescent Pigments

Common Name Pearlescent Pigment / Mica Formula K2Al6Si6O20(OH)4 EINECS No. 310-127-6 CAS No. 12001-26-2

Mica-based pearlescent pigments (pearlescent pigments) are generally mixtures where colour effect is achieved through the layering of mica flakes with one or more metal oxides, e.g. TiO2, Fe2O3 or other component pigments. Except for a few mixtures, pearlescent pigments are inorganic substances. They are used to obtain pearl iridescent, or metallic effects, and in transparent colour formulations to obtain brilliant twotone flops. Pearlescent pigments are mainly used for the production of decorating colours to achieve lustre-like or metallic effects. Acute Toxicity All acute toxicity tests performed to date indicate oral LD50 > 5000 mg/kg (1). Three different studies on the acute inhalation toxicity of special pearlescent pigments provided LC50 values of 4.6 mg/l 14.9 mg/l, > 14.9 mg/l and 10.1 mg/l (1). Pearlescent pigments do not show any irritating or sensitizing effects on the skin or mucous membranes (1). Evaluation of potential impact to human health resulting from normal occupational exposure to pearlescent pigments revealed no adverse effects (2). Chronic Toxicity Chronic health effects have not been identified yet (3). Physical Hazards None known at this time (4).

3.2 Ceramic Stains

47

Environmental Concerns The stability and inertness of pearlescent pigments result in negligible availability of the metal ions they contain to the environment. Mica-based pigments are inorganic, stable compounds which do not decompose and therefore are practically inert. Labelling and Transport Regulations Pearlescent pigments are not subject to labelling and transport regulations. Advice for Safe Handling The usual precautions for the handling and processing of chemicals must be observed. In the different countries there are for certain metals workplace control parameters for fine dust. When large quantities are handled without local exhaust ventilation usually dust masks have to be worn. No special measures are necessary for the protection against fire and explosion. Eventually fire debris and contaminated extinguishing water have to be disposed of in accordance with local regulations. References (1) Eberstein, M. V.; Heusener, A.; Jacobs, M. E.Merck Institute of Toxicology, Darmstadt, Germany, 22 Reports, 1970 1991. (2) Bruch, J. "Expert report on Health and Hazards caused by Pearl Lustre Pigments", Occupational Medicine and Toxicology, Institute of Hygiene and Occupational Medicine, University Clinic Essen, Germany, 1990. (3) Bernhard, B. K. et al. Toxicology and carcinogenesis studies of dietary titan dioxide-coated mica in male and female Fischer 344 rats. J. Toxicol. Environ. Health 1989, 28, 415426. (4) Patty's Industrial Hygiene and Toxicology, Third Edition. Clayton, G. E., Clayton, F. E., Eds.; John Wiley & Sons, New York, 1981, pp. 30243025.

3.2.3 Cadmium Pigments

Common Name Cadmium zinc sulphide, yellow Cadmium sulfoselenide, orange Cadmium sulfoselenide, red Formula (Cd,Zn)S Cd (S,Se) Cd (S,Se) EINECS No. 232-466-8 235-758-3 261-218-1 CAS No. 8048-07-5 12656-57-4 58339-34-7

All cadmium pigments are based on cadmium sulphide and exist in a highly stable hexagonal crystal form. Inclusion of zinc yields greenish yellow pigments and inclusion of selenium changes the shades to orange, red and bordeaux. Cadmium pigments are temperature sensitive. Therefore, although they can be used in glass colours, in porcelain enamels, and in low-temperature glazes fired up to ca. 900 C, they cannot be used in higher temperature applications. Acute Toxicity Cadmium pigments have no acute toxic effects (oral LD50, rat > 5000 mg/kg). The pigments do not have any adverse effects on skin and mucous membranes. No mortality was observed in an inhalation study in which rats inhaled cadmium pigment at 100 mg/m3 (as Cd) for two hours. Similarly negative mortality rates were reported for rats exposed continuously to an airborne pigment concentration of 1 mg/m3 (as Cd) for one month.

48

3 Toxicological Aspects

Chronic Toxicity Cadmium pigments are compounds with a low solubility, but small quantities of cadmium dissolve in dilute hydrochloric acid (at a concentration equivalent to stomach concentration). Long-term oral intake of cadmium pigments leads to accumulation in the human body, especially in the kidneys. On inhalation of subchronic amounts of cadmium pigments, a small proportion of cadmium is bioavailable (1). Toxicity of cadmium pigments is nonetheless very much lower (by several orders of magnitude) than that of other cadmium compounds. Long-term animal feeding studies with various cadmium compounds showed no carcinogenic potential. However, inhalation studies with rats, mice, and hamsters showed a significant increase of lung cancer in rats for each of four used cadmium compounds, including cadmium sulphide (2). The results for mice were inconclusive and no carcinogenicity in hamsters was observed (3). Subsequent investigations (4) showed that the aerosol generation technique of cadmium sulphide exposed the rats to other forms of cadmium. The original findings of the rat study can be entirely explained by the inadvertent exposure to non-pigmentary forms of cadmium (5). Despite these findings the European Commission has classified cadmium sulphide as a category 3 carcinogen. However, cadmium pigments have not been thus classified and are specifically excluded from the hazard labelling requirements of the EU's "Dangerous Substances Directive" (67/548/EEC) as adapted to technical progress. Physical Hazards None known at this time. Environmental Concerns Cadmium pigments are nearly insoluble in dilute acids. The insolubility is further enhanced when the pigments are incorporated in ceramics. Pigments and pigmented articles are considered to be safe for landfill disposal. Cadmium and its compounds have been classified as List 1 substances in EU Directive 76/464/EEC relating to pollution of the aquatic environment, and EU member states are required to take special measures to control all discharges of cadmium, including cadmium pigments. The European Directive 91/338/EEC restricts the use of cadmium pigments only in certain polymers, depending on the purpose of use and in coating media. The use in artists' colours and ceramic products is permitted. The restriction of the use of cadmium pigments for coatings does not apply to preparations which are intended for ceramic use. Labelling and Transport Regulations Cadmium pigments are officially not subject to labelling and to transport regulations. Some pigment manufacturers are labelling cadmium pigments as cadmium compounds with Xn and R 20/21/22. to refer to the possible risks and the small but existing bioavailability when handling cadmium pigments. Advice for Safe Handling Occupational hygiene and safety measures must be observed when cadmium pigments are used. Exposure to cadmium can be determined by measurement of workplace concentrations (0.01 mg/m3) and by examination of the cadmium levels in blood and urine. In Germany, the following maximum biological tolerance levels (BAT) are allowed at the workplaces: 15 g Cd/l urine and 1.5 g Cd/100 ml blood.

3.2 Ceramic Stains

49

To reduce the risk of inhalation, cadmium pigments are also supplied as low-dust powders and fine granules. No special measures are necessary for the protection against fire and explosion. Eventually fire debris and contaminated extinguishing water have to be disposed of in accordance with local regulations. References (1) Klimisch, H.-J. Lung deposition, lung clearance and renal accumulation of inhaled cadmium chloride and cadmium sulphide in rats. Toxicology 1993, 84, 103124. (2) Oldiges, H.; Hochrainer, D.; Glaser, M. Long-term inhalation study with Wistar rats and four cadmium compounds. Toxicol. Environ. Chem. 1988, 19, 217222. (3) Heinrich, U. et. al. Investigation of the carcinogenic effects of various cadmium compounds after inhalation exposure in hamsters and mice. Exp. Pathol. 1989, 37, 253. (4) Gagliardi, G. B.; Ulciny, L.J. "Photodecomposition of Dilute Cadmium Sulphide Slurries", presented at the XXIVth RETEC, October 1990, Charlotte, NC, USA. (5) Ulciny, L.J. "What is the evidence for the Carcinogenicity of Cadmium Sulphide Pigments?", presented at the 7th International Cadmium Conference, April 1992, New Orleans, LA, USA.

3.2.4 Gold purple

Common Name Gold purple Formula n. a. EINECS No. 215-710-2 CAS No. 1345-24-0

Traditional gold purple is produced by the reaction of tin(II) chloride and gold chloride. The tin chloride is oxidised to stannic acid and the gold chloride is reduced to metallic gold forming a colloidal precipitation onto the stannic acid. The so-called "Cassius purple" is only stable as a slurry and must be used immediately as pigment in glass- and ceramic-colours. By applicating a fritting process, the purple colours become totally stable. Nowadays there are some other ways to get a stable gold purple. Purple stains containing high amounts of gold are offered now. Due to their high thermal stability, they are used to colour porcelain enamels rose, frequently in sanitary ware decoration. Acute and Chronic Toxicity Because of the composition of metallic gold and tin dioxide, it can be assumed that gold purples do not show acute and chronic toxicity. Physical Hazards None known at this time. Environmental Concerns These pigments are insoluble in acids and alkalis. As they do not contain leachable metal ions they do not contribute to any ecological or toxicological problems due to other heavy metal compounds. Due to their insolubility in water they can be removed mechanically from waste water by purification plants. They do not add dissolved metal ions to sewage water or landfill leachate. When articles coloured with these pigments are burned in incinerators, the pigments are recovered in their insoluble form.

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3 Toxicological Aspects

Advice for Safe Handling The usual precautions for the handling and processing of chemicals must be observed. In the different countries there are for certain metals workplace control parameters for fine dust. When large quantities are handled without local exhaust ventilation usually dust masks have to be worn. No special measures are necessary for the protection against fire and explosion. Eventually fire debris and contaminated extinguishing water have to be disposed of in accordance with local regulations.

3.3 Precious Metal Preparations and Lustres

Precious metal preparations and lustres are complex mixtures of up to 40 components with different chemical and toxicological properties. Their toxic and ecological effects vary from product to product, and only a summary of the generally observed hazards can be given. For more details, please refer to the individual safety data sheet of the respective product. Storage Storage of precious metal preparations and lustres must comply with the requirements of chemical-, safety- and environmental-legislation. In general, the following hazards may be present and may cause limitations in storage:

Certain products are highly flammable or flammable and/or may form flammable and/or hazardous vapours. They should be stored in a cool, well-ventilated place in containers tightly closed. Products containing solvents with ether-groups may form explosive peroxides after prolonged storage, especially in presence of air. Certain products are water-hazardous because of their content of environmentally dangerous substances. Toxic and very toxic products must be stored under lock and key or in a way, that only skilled persons have access to them. Those products must be kept away from food, drink and animal feeding stuffs.

Depending of the product's hazards and the quantity to be stored, there may be restrictions in the layout of the containment. Internal and external safety measure may apply. Transport All goods have to be classified and declared as "dangerous" or "non-dangerous" on the appropriate transport papers complying the ADR/RID, IMO and ICAO/IATA regulations. In general, precious metal preparations and lustres are classified as follows:

"Non-dangerous", if transport of the product includes no special hazard. Class 3, if the product is highly flammable (flash point less then 23 C) or flammable (flash point 23 62 C). If the viscosity exceeds special limits, the products do not require labelling in class 3, if they are shipped in containers of 450 l max. Class 6.1, if short-term toxicity exceeds certain limits (e.g. oral toxicity LD50 less than 500 mg/kg for liquids). Class 8, if the product contains corrosive substances.

3.3 Precious Metal Preparations and Lustres

51

Class 9, if the product contains more than 25 % of environmental hazardous substances and no substances of any other classification are present.

On Sea Transport, certain products must be classified as "Marine Pollutant" because of their content of marine polluting substances as described in the GESAMP-List. Labelling The main hazard information is given in form of a hazard symbol. Precious metal preparations and lustres are labelled, if they are classified as dangerous, with one or more of the following symbols:

"F+", if the product is extremely flammable (flash point < 0 C). "F", if the product is highly flammable (flash point 0 < 21 C). No symbol, but risk-phrase "flammable", if the flash point is 21 55 C. "T+" or "T", if the product is very toxic or toxic. "Xn" or "Xi", if the product is harmful or irritant. "C", if the product is corrosive.

Although the classification "Toxic to the environment" (Symbol "N") is not (yet) in use for preparations, it is recommended to comply with the corresponding rules for pure substances, if environmentally dangerous substances are present. See also Annex 5.1 For further risk- and safety-information on the label, refer to the risk-phrases, which describe the intrinsic hazard of the material, or to the safety-phrases, which advise on the correct use. Disposal In the European Waste Catalogue, precious metal preparations and lustres are listed as waste-no. 080101 (paints containing halogenated solvents), 080102 (paints not containing halogenated solvents), 080103 (paints, water based). Waste with waste no. 080101 and 080102 may generally be considered as hazardous. For disposal, liquid products are normally treated by incineration. Compliance with national regulations has to be ensured. In case of doubt the local authorities should be consulted. Precious metals may be recycled in accordance with the regulations issued by local or national authorities. Advice for Safe Handling The following hazards should be taken into account by the user:

Certain products may be highly flammable or flammable. In these cases, explosion protective equipment must be used. Open fire, hot surfaces and sparks (e. g. electrical discharges) must be eliminated. In case of fire, the combustion of precious metal preparations and lustres can produce hazardous gases such as oxides of carbon, nitrogen and in cases of chlorine- and sulphur-containing ingredients hydrochloric acid, chlorine, phosgene, sulphur dioxide or metal oxides. Products may also be harmful, toxic or very toxic. They may contain ingredients with concentration limits in the air regulated by national rules (MAK-, ILO-List). Some products may contain components like glycol ethers, glycol ether acetates or special phthalates, which are classified as (possibly) toxic for human reproduction

52

3 Toxicological Aspects or (possibly) embryotoxic (EC-category RE1, RE2, RE3, RF2, RF3). Also carcinogenic substances like methylene chloride (EC-category C3) may be present. In these cases, compliance with employment limitations for youths, pregnant women and nursing mothers have to be ensured.

3.4 Inorganic Raw Materials

Many of the inorganic additives which are used in our products are not subject to labelling or of special health and environmental concerns. Those substances are listed in table 3.2, and in case there are critical by-products or admixtures those critical components are mentioned in the right column of the table. Table 3.2: Substances without major concerns
Substance Alumina Anatase Calcium Carbonate Cerium Dioxide Chromium(III) Oxide Clays Colemanite Corundum Dolomite Feldspars Fluorspar Iron Oxides Kaoline Lithium Carbonate Magnesium Carbonate Nepheline Olivine Petalite Quartz, Crystalline Silica Rutile Spodumene Strontium Carbonate Talcum Tin Dioxide Tungsten Oxide Ulexite Wollastonite Zinc Oxide Zircon, Zirconium Silicate Zirconia Remarks see also section 3.2.1.3 see also section 3.4.1

see also section 3.2.2.2 see also Crystalline Silica (section 3.4.2) see also section 3.2.1.3 see also Crystalline Silica (section 3.4.2) see also section 3.2.2.1 see also Crystalline Silica (section 3.4.2)

see section 3.4.2 see also section 3.4.1 see also Crystalline Silica (section 3.4.2) see also Crystalline Silica (section 3.4.2) see also section 3.2.1.3

see also section 3.4.3 see also sections 3.2.1.3 and 3.4.4 see also section 3.2.1.3

3.4 Inorganic Raw Materials

53

The table 3.3 lists substances with a certain hazard potential during their use. This does not mean that there exists the same hazard in the final product, where they are used for. The reader is asked to consult the SDS and to enter in contact with the supplier if there are any doubts. Table 3.3: Substances with specific labelling requirements
Substance Ammonium Metavanadate Barium Carbonate Cobalt Oxides Copper Monoxide Manganese Dioxide Nickel Oxides Vanadium Pentoxide see also section 3.2.2.3 see also section 3.2.2.4 see also section 3.2.2.6 see also section 3.2.2.5 Remarks Labelling Requirements T+, R 20, 25, 36/37, S 7/8, 22, 25 Xn, R 22, S 24/25 Xn, R 22, 43, S 24/37 Xn, R 22, S 22 Xn, R 20/22, S 25 T, R 49/43, S 53-45 Xn, R 20, S 22

3.4.1 Titanium Dioxide

Common Name Titanium dioxide Formula TiO2 EINECS No. 236-675-5 CAS No. 13463-67-7

Titanium dioxide occurs in nature in the modifications rutile, anatase, and brookite. Rutile and anatase are produced industrially as the most important pigments in terms of quantities (1). Titanium dioxide is of outstanding importance as a white pigment because of its scattering properties, chemical stability, biological inertness and lack of toxicity. Acute Toxicity The pigments are not considered to be toxic: Oral LD50 values, rats, >5000 mg/kg, inhalation LC50 values, rats, > 6.82 mg / l / 24 h (2). Skin contact causes no irritation. A slight irritation of the eyes and respiratory tract by mechanical abrasion is possible (2). Chronic Toxicity Investigations on animals which have been fed titanium dioxide over a long period give no indication of titanium uptake (2). No chronic effects have been reported during many years of manufacturing and using titanium dioxide. Due to its excellent physiological compatibility titanium dioxide of appropriate purity is approved in the United States and the European Union as colourant for food, cosmetics and pharmaceutical products. Physical Hazards None known at this time. Environmental Concerns Although different manufacturing processes for titanium dioxide pigments are subject to critical environmental discussions, no adverse environmental effects are known to result from the use of titanium dioxide pigments. These pigments show no toxicity to

54

3 Toxicological Aspects aquatic organisms (2). They are insoluble and in the environment practically inert materials.

Labelling and Transport Regulations Titanium dioxide products are not subject to labelling and to transport regulations. Advice for Safe Handling The usual precautions for the handling and processing of chemicals must be observed. When large quantities are decanted without local exhaust ventilation usually dust masks have to be worn. No special measures are necessary for the protection against fire and explosion. Eventually fire debris and contaminated extinguishing water have to be disposed of in accordance with local regulations. References (1) Rmpps Chemie-Lexikon. "Titandioxid", 9. Auflage; Georg Thieme Verlag, Stuttgart, New York, 1992. (2) EUCLID Data Sheet, Titanium dioxide.

3.4.2 Crystalline Silica

Common Name Silica, Quartz Formula SiO2 EINECS No. 238-878-4 CAS No. 14808-60-7

Crystalline silica occurs naturally as quartz, cristobalite and tridymite. All three crystalline forms are of health concern, whenever they are in a resiprable form. Acute Toxicity Acute effects have not been reported. Chronic Toxicity Silicosis: Silicosis is an illness produced by the infiltration of silica powder in the respiratory system; it develops in workers who are exposed to high concentrations of fine particles of crystalline silica powder, normally quartz, during many years. Most countries have a TLV (TWA) value for quartz of 0.1 mg/m3 for the inhalable fraction. IARC concluded that "crystalline silica inhaled in the form of quartz or cristobalite from occupational sources is carcinogenic to humans" (2). Physical Hazards None known at this time. Environmental Concerns None known at this time, as silica forms the major part (approx. 75 %) of the earth's crust. Nevertheless disposal in the air of fine crystalline silica must be avoided. Labelling and Transport Regulations Crystalline silica, i.e. quartz, is not subject to labelling and transport regulations. Bulk loads must be covered to avoid disposal in the air. Advice for Safe Handling The usual precautions for the handling and processing of chemicals must be observed. When large quantities are suspended in the air and there is no appropriate local exhaust ventilation usually dust masks have to be worn.

3.4 Inorganic Raw Materials

55

No special measures are necessary for the protection against fire and explosion. Any fire debris and contaminated extinguishing water have to be disposed of in accordance with local regulations. References (1) IOM Report TM-97-09: Epidemiological evidence on the carcinogenicity of silica: Factors in scientific judgement (1997). (2) IARC Monograph, vol. 68, 1997.

3.4.3 Zinc Oxide

Common Name Zinc White, Zinc Oxide Formula ZnO EINECS No. 215-222-5 CAS No. 1314-13-2

Zinc oxide is a fine white powder, which is amphoteric; it reacts with organic and inorganic acids, and also dissolves in alkalis to form zincates (1). In ceramic applications, ZnO is widely used for white and matte glazes in the form of frits or as an additive to glazes. Various grades in terms of purity and grain size are in use. Acute Toxicity An acute LD50 value of >5000 mg/kg body weight applies to the high-purity grades and even to the lead-containing zinc oxides (2). Chronic Toxicity Zinc is an essential element for human beings, animals, and plants. If large quantities of zinc oxides are accidentally ingested, fever, nausea, and irritation of the respiratory tract occur after several hours. These symptoms rapidly disappear without any longterm consequences. Some non-pigmentary zinc oxide grades may contain up to 5 % Pb and must therefore be handled with care to avoid intoxication by dust inhalation or by digestion. Such mixtures or products are hazardous, and due to their lead content must be labelled with "T" (skull and crossbones), if the lead content exceeds 0.5 %. Lead concentration in the air has to be monitored in case of high lead-containing zinc oxides to make sure it is safely kept below 0.15 mg/m3 lead in air (see also section 3.1.2). Physical Hazards None known at this time. Environmental Concerns Although zinc is a vital aspect for mammalian cell growth, even low concentrations can be lethal to aquatic life. Excessive supplies inhibit growth and photosynthesis, and result in death. Pigments containing zinc in a chemically-bound form (i.e. zinc oxide, zinc sulphide, zinc phosphate, zinc carbonate) do not release zinc ions in hazardous quantities. Even bioaccumulation after accidental spillage and dissolution cannot result in hazardous or toxic levels for mammals including human beings. On the other hand, hazardous properties for some aquatic life species render water protection a necessity, by measures mentioned here. A general limit for waste water discharges is 1 5 mg/l Zn, dictated by fish toxicity. Zinc ions must be eliminated by chemical precipitation or precipitation with flocculation. The solubility of zinc hydroxide is lowest near pH 8.

56

3 Toxicological Aspects

Labelling and Transport Regulations Zinc oxides with lead contents exceeding 0.5 % have to be labelled as toxic, "T" (see also section 3.1.2.2). Zinc oxides are not subject to transport regulations. Advice for Safe Handling The usual precautions for the handling and processing of chemicals must be observed. When large quantities are suspended in the air and there is no appropriate local exhaust ventilation usually dust masks have to be worn. No special measures are necessary for the protection against fire and explosion. Any fire debris and contaminated extinguishing water have to be disposed of in accordance with local regulations. If possible, zinc containing waste material should be recycled and not disposed of by combustion or landfill. References (1) Definitions: ISO 275; RAL 844: C 2, C 3 1974; ISO-DP 9238 1992. (2) HEDSET 1314132, Zinc oxide, 1994.

3.4.4 Zirconium Silicate

Common Name Zircon Formula ZrSiO4 EINECS No. 239-019-6 CAS No. 14940-68-2

Zirconium silicate (Zircon) is a naturally occurring mineral, which is obtained as a byproduct of rutile mining. It is separated by physical means from sand deposits, which mainly consist of quartz, rutile, monazite and zircon. Due to its genesis, zircon also contains trace amounts of radioactive substances, mainly -radiators. But legally, zirconium silicate is not considered as a radioactive material and does not fall under the regulations considering the handling and processing of radioactive materials (1). Zircon is commercialized in its natural grain size distribution or finely milled as zircon flour and micronized zircon. Acute Toxicity None known at this time. Chronic Toxicity None known at this time. Physical Hazards The low natural radioactivity is not considered as harmful (2). Environmental Concerns None known at this time. Zircon is naturally present in many rocks (granite). Nevertheless, uncontrolled disposal into the environment should be avoided. Labelling and Transport Regulations Zirconium silicate is not subject to labelling and transport regulations. Advice for Safe Handling The usual precautions for the handling and processing of chemicals must be observed. When large quantities are suspended in the air and there is no appropriate local exhaust ventilation usually dust masks have to be worn.

3.5 Organic Additives

57

No special measures are necessary for the protection against fire and explosion. Any fire debris and contaminated extinguishing water have to be disposed of in accordance with local regulations. References (1) Council Directive 96/29/Euratom (May 13, 1996) on the determination of basic safety standards for the protection of health of staff and population against the dangers by ionizing radiation (O.J. L 159, 29.6.96). (2) Strahlenschutzkommission des Bundesministeriums fr Umwelt, Naturschutz und Reaktorsicherheit, Heft 10, (1997): Strahlenexposition an Arbeitspltzen durch natrliche Radionuklide.

3.5 Organic Additives

This chapter gives a survey of main groups of organic additives, which are applied by the ceramic industry to adapt products to special needs. Each group covers many different substances and it is impossible to name them all. For further details, the reader is asked to refer to the SDS supplied.

3.5.1 Solvents
Aromatic hydrocarbons Hazard profile: Normally used as a mixture of C7 C10 hydrocarbons which are considered to be harmful. If a possible benzene-content exceeds 0.1 %, products must be labelled with "T". Most of these mixtures are dangereous for the aquatic environement. The flash point of these products varies between 23 C and 80 C depending on their composition. Examples for labelling: Xn (harmful), R 10 (flammable), F (highly flammable) Classification for transport: Class 3 or 9, depending on flash point Hydrocarbons with low content of aromates Hazard profile: Depending of their content of aromates, some of these products are irritant to skin or even harmful. The flash point depends on the composition and may vary between 20 C and more than 100 C. Products with low flash point strictly require the elimination of open fire, hot surfaces and sparks (e.g. electric discharges) during handling. Examples for labelling: Xi (irritant), Xn (harmful), R 10 (flammable), F (highly flammable), F+ (extremely flammable) Classification for transport: Class 3 or none, depending on flash point Hydrotreated aromatic hydrocarbons (tetraline) Hazard profile: Tetraline is a colourless liquid, which is irritant to the eyes and the skin. Tetraline is toxic to the aquatic environment and may form explosive peroxides after prolonged storage. Its flash point is 71 C. Examples for labelling: Xi (irritant), N (dangerous to the environment) Classification for transport: Class 9 Alcoholes and ketones (propanoles, butanoles, butanones and diacetone alcohol) Hazard profile: These solvents are substances with normally low toxicity, but diacetone alcohol is irritant to eyes, skin and respiratory tract. Their low flash points

58

3 Toxicological Aspects strictly require eliminating open fire, hot surfaces and sparks (e.g. electric discharges) during handling. Examples for labelling: Xi (irritant), Xn (harmful), R 10 (flammable), F (highly flammable), F+ (extremely flammable) Classification for transport: Class 3

Terpenes (turpentine oil and etheric oils) Hazard profile: Turpentine oil and many etheric oils are irritant or in the case of turpentine oil even sensitizing. Depending on the type of substance, the flash points vary between 23 C and up to 100 C (e.g. turpentine oil 38 C). Examples for labelling: Xn (harmful), Xi (irritant), R 10 (flammable) Classification for transport: Class 3 or none, depending on the flash point

3.5.2 Softeners
Phthalates (dibutyl phthalate, ethyl hexyl phthalate) Hazard profile: These phthalates are products of low acute toxicity, but there is a possible risk of impaired fertility. Some phthalates are considered to be toxic to the aquatic environment. Examples for labelling: Xn (harmful), N (dangerous to the environment) Classification for transport: Class 9 Dioles Hazard profile: Most of the dioles used are hazardous substances with a flash point > 61 C. Examples for labelling: Xn (harmful) Classification for transport: None Glycolic ethers and ether acetates Hazard profile: Glycolic ethers and ether acetates are substances with boiling points exceeding 150 C and flash points >22 C. Some members of this group are not toxic, but others may impair fertility and may cause damage to the unborn child. Examples for labelling: T (toxic), Xn (harmful), R 10 (flammable) Classification for transport: Class 3 or none, depending on the flash point

3.5.3 Liquifiers
Lecithines Salts of polycarboxylic acids Hazard profile: No hazards are known at this time. If these substances are dissolved in an organic solvent, the dangerous properties of the mixture result of the solvent used. Examples for labelling: No labelling required (pure substances) Classification for transport: None (pure substances)

3.5 Organic Additives

59

3.5.4 Suspending agents

Cellulose ethers Hazard profile: No hazards are known at this time. If these substances are dissolved in an organic solvent, the dangerous properties of the mixture result of the solvent used. Examples for labelling: No labelling required (pure substance) Classification for transport: None (pure substance)

3.5.5 Fixatives
Cellulose ethers Acrylic resins Hazard profile: No hazards are known at this time. If these substances are dissolved in an organic solvent, the dangerous properties of the mixture result of the solvent used. Examples for labelling: No labelling required (pure substance) Classification for transport: None (pure substance)

3.5.6 Defoamers
Silicones Hazard profile: No hazards are known at this time. If these substances are dissolved in an organic solvent, the dangerous properties of the mixture result of the solvent used. Examples for labelling: No labelling required (pure substance) Classification for transport: None (pure substance)

3.5.7 Preservatives
Amides Isothiazolones Hazard profile: Preservatives are solids or solutions of solids which may be toxic, harmful or sensitizing. They are strong water-hazardous substances. Examples for labelling: T (toxic), Xn (harmful), Xn (irritant) Classification for transport: Class 6.1 or none

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4 Preparations

4 Preparations
4.1 Chemical Aspects
4.1.1 Chemical Aspects of Glazes
Glazes are preparations of frits, inorganic pigments and raw materials in varying amounts, where glass composition and pigment type are adapted to the special needs of the glaze. This may be firing range, coefficient of thermal expansion, transparency, type of surface and naturally the colour. Whenever possible, non-toxic components are used to obtain products which do not affect persons and the environment coming into contact with glazed surfaces. Frit systems Glazes normally contain finely milled frits, as described in sections 2.2 and 2.3. Content and composition vary largely for traditional glazes and glazes for artistic ceramics. Colouring systems All types of pigments and colouring oxides as mentioned in section 3.2 are used. The content depends on the pigment type and desired colour shade. White glazes may contain milled zirconium silicate or other opacifiers. Raw materials For glazes, colouring oxides and other inorganic and / or organic raw materials are used to obtain the desired surface effects. Stability Glaze powders There are no chemical reactions between glass and pigments at usual storage temperature, if containers are tightly closed and no humidity can enter. The shelf life of glaze powders under these conditions is practically unlimited. Fired glazes Fired glazes and colours are highly resistent to chemical and mechanical action, heat and light. For dinnerware, cadmium- and lead-free glazes are available. If the user prefers cadmium- and lead-containing glazes, also glazes with low cadmium- and lead-release values (method: ISO 6486, acetic acid solution 4 %) are available.

4.1.2

Chemical Aspects of Decorating Colours

The chemical composition of decorating colours comprises a varying amount of frit (flux) and a specific amount of stains and sometimes supplementary materials. Depending on the application temperature of the decorating colours and the substrate the amount of frit (flux) and stains has to be adjusted. Typical raw materials for frits and fluxes are compounds, mainly oxides of silicon, boron, aluminum, zircon, sodium, potassium, calcium, magnesium and optionally lead and cadmium. Raw materials for decorating colours have to be of high chemical purity. Lead and cadmium containing decorating colours may release lead and / or cadmium in acidic or alkaline solutions. Food contact can be simulated with acetic acid (ISO

4.2 Physical Aspects of Special Forms of Delivery

61

6486), a method which is accepted worldwide. But in various countries there are different limits for lead and cadmium release. Stability Colour powders There are no chemical reactions between glass and pigments at usual storage temperature, if containers are tightly closed and no humidity can enter. The shelf life of colour powders under this condition is practically unlimited. Colours dispersed in organic binder systems Chemical stability of this form of delivery depends on the stability of the organic components of the composition. The following chemical reactions may occur in case the shelf life is expired: IR-drying systems are in general uncritical and do generally not suffer chemical reactions. For UV- and other reactive systems a pre-reaction due to long storage time or high temperatures might occur. In this case the paste viscosity is increased and lumps of polymerised material might occur in the paste. Thermoplastic systems are in general uncritical. However in special cases a reaction between parts of the thermoplastic resin and metal ions in the colour might occur. Such an effect will influence the rheology and printing behaviour of the molten product. Even if no chemical reactions are observed, shelf life is limited by physical effects like sedimentation of the inorganic material or evaporation of solvents during storage of the products. Based on the experience and laboratory testing, the minimum shelf life is as follows: IR systems: 6 months; UV systems: 4 months; Thermoplastic systems: 12 months.

4.2 Physical Aspects of Special Forms of Delivery

Apart from the chemical properties of the materials, there are certain hazards and precautions to be taken which are specifically related to the physical form in which the material is delivered.

4.2.1. Powders
Many materials used in the ceramic industry are supplied in powder form. Acute and Chronic Toxicity Fine powders easily lead to the formation of dust clouds during handling, which can increase the local concentration in the air and spread (hazardous) materials over larger areas away from the original source. Inside the plant this may lead to concentrations over the TLV for the employees handling the material and may result in uncontrolled exposure of larger groups of workers to a certain material. Whether the effect is acute or chronical is caused by the chemical nature of the products. Generally these risks have to be minimized by handling powderous material only at workplaces where adequate dust ventilation is present.

62

4 Preparations Fine particles in dust clouds may be inhaled. Some materials in the ceramic industry exhibit specific hazards on inhalation generally chronic effects. These hazards are especially present when the material is present in fine particles, where the extent to which they enter into the respiratory system is inversely proportional to the particle size. This relation is defined in EN 481, "Workplace Atmospheres. Size fraction definitions for measurement of airborne particles". For some substances, like asbestos, the hazardous effects are determined by the physical form of the individual particles (in this case fine, long fibres) and not by the chemistry of the substance as such. Investigations have been done on the potential hazards of very fine powders, which enter deeply into the lung. Some fine dusts have been found to have adverse effects on health. But investigations have also shown that this is not the case in general for substances in finely powdered form. Fine powders have a large specific surface. Many interactions between a (hazardous) substance and its environment be it man or nature occur at the surface of the material. Bioavailability of harmful components in a compound may increase in such a way that the threshold between harmless and hazardous is exceeded. This may be valid for acute as well as for chronic toxicity.

Physical Hazards Finely dispersed organic materials in the air involve the risk of dust explosions; although ceramic materials generally are of inorganic nature, care must be taken in case of organic additives or auxiliary materials. Environmental Concerns Outside the plant, e.g. in case of spills of powderous material due to failure of the containment, may lead to an impact to large areas in the environment. Therefore handling preferably should take place on smooth floors where cleaning is easily possible. Also the properties of such fine powders in leaching tests, which are part of the evaluation of waste materials, may differ from the bulk material in such a way that it leads to classification in a higher waste hazard category (cf. national laws and regulations as well as EU Directives 91/689/EC and 94/904/EC and their revisions). When fine particles enter into the waste water stream, the higher leachability depending on pH may cause concentrations in the waste water which exceed permitted limits (dependant on the local regulations). Generally it is possible to separate particles from the waste water by simple flocculation with the aid of flocculants, and subsequent sedimentation and / or filtration. By keeping the pH in the process between 8 and 8.5 leachability for e. g. lead and zinc mostly can be kept low enough to meet water emission standards.

4.2.2 Grainy Materials

In the ceramic industry, materials in grain form are used in different applications. They have coarser particle sizes than powders. Grains give rise to less dust formation on handling, and are more free-flowing (important in automatic dosing equipment) than powdered materials.

4.2 Physical Aspects of Special Forms of Delivery

63

Grainy materials can be of two different origins: a) granulates formed by agglomerating fine ceramic powders with a suitable binding material (see section 4.2.2.1); b) crushed frits formed by crushing or coarse milling of ceramic frits (see section 4.2.2.2).

4.2.2.1 Granulates by Agglomeration

Acute and Chronic Toxicity Due to the larger size of the agglomerates formation of dust when handling these materials is limited, and largely dependant on the amount of fine particles still present in the granulate after manufacturing. Another factor is the hardness of the granules which determines how many fines are formed during transportation and handling of the granulates. In general the handling of these granulates is less hazardous than that of the "in composto" powders because of the lower concentration of airborne dust. The properties of this dust are similar to the properties of the constituting powder(s). The binders are often water based. Under the influence of water the granulate may disintegrate into the constituting powder particles, exposing the original surface and exhibiting the same properties as the same quantity of original powder. In this case, the hazards of the granulate with respect to the bioavailability of the constituents are identical to those of the powdered material. Physical Hazards The fact that the material is more free-flowing can also be a physical hazard as spillage from (big) bags in stacks may lead to mechanical instability and even collapse of the stack, which is a hazard to workers in the transportation or storage area. Environmental Concerns The fact that the material is more free-flowing can also be a disadvantage or even an environmental hazard: damaged packaging (e.g. during transportation) will lose relatively large quantities of material which may spread into the environment. As stated above, the binders are often water based and the granulate may desintegrate into the constituting powder particles under the influence of water. In that case, the leaching properties for classification in waste categories and the handling in waste water systems are identical to powderous material (see above).

4.2.2.2 Crushed Frits (Graniglie, Granilla)

Acute and Chronic Toxicity Depending on the coarse grain size distribution on delivery, this kind of material limits the formation of dust during handling. However, because of the much smaller specific surface area compared to a powdered material the properties with regard to the bioavailability are between those of the bulk original pieces and the fine powder. Physical Hazards The fact that the material is more free-flowing can also be a physical hazard as spillage from (big) bags in stacks may lead to mechanical instability and even collapse of the stack which is a hazard to workers in the transportation or storage area.

64

4 Preparations

Environmental Concerns Because of the much smaller specific surface compared to a powdered material the properties with regard to leachability are in between those of the bulk original pieces and the fine powder. In waste water systems coarse fractions are generally easily separated by sedimentation.

4.2.3 Paste
In the ceramic industry materials in paste form are used for decoration. This paste consists of a fine ceramic powder with a binder dispersed in water or in an organic medium. After application the binder hardens to give stability to the decorated product for further handling. During subsequent firing of the product the organic binder is burnt off. Acute Toxicity Some organic media contain irritant or harmful substances (see section 3.5). During application ventilation is required to minimize the concentration of volatiles in the air to acceptable levels. The paste application process gives in no stage rise to the formation of dust, as the powder particles are bound firmly with the organic binder in each phase of the process. Chronic Toxicity Some organic media contain harmful substances which cause chronic effects (see section 3.5). As many solvents are hazardous and long term exposure to organic solvents is known to bear a risk for damage to the brain and nerve system, attention should be paid that also cleaning activities should be carried out with adequate ventilation and / or personal protection with masks suitable for absorbing organic vapours (active coal). Physical Hazards The paste can burn due to the presence of organic components and, depending on its nature and concentration, it may be classified as flammable. Attention has to be paid also to solvents which are used for cleaning equipment which has been used for the application of ceramic decoration pastes. As many solvents are flammable these should be handled under adequate ventilation. Environmental Concerns Cleaning waste and paste residues have to be treated according to local regulations, generally as special or hazardous waste.

4.2.4 Slips
Ceramic materials are often processed and to some extent also supplied in slip form. A slip is a suspension of the fine ceramic powders in water with a relatively low viscosity compared to the paste materials. There are often small quantities of natural binder present, which may be inorganic (e.g. clay minerals) or organic (e.g. cellulose compounds). These binders contribute in part to mechanical stability of the material after drying. Acute and Chronic Toxicity Due to its nature the slip as such does not lead to dust formation. Also after drying the binder prevents the formation of airborne particles. Only in case of mechanical work

4.3 Decals Ceramic Transfers

65

on the dried slip dust may be formed, for which the same considerations apply as for powderous material. Environmental Concerns In handling and storage of the slip, usually in containers, adequate care should be taken to prevent spillage. Damage of a container may lead to spillage of the total content of the container at the loading / storage area. To prevent soil contamination it may be recommendable (dependant on the chemical nature of the slip) that this area has a sealed floor, in which the slip is contained and from which the clean-up of spillage is relatively easy. Waste water can be treated in the same way as in the case waste water is contaminated with dry powder (see above). Waste classification of dried slips is similar to that for powder materials.

4.3 Decals Ceramic Transfers

Acute Toxicity 1) Storage Storage of ceramic transfers may lead to the emission of organic substances (smell). In the case of methacrylic transfers this could be mainly hydrocarbons from C10 to C15, but there are no reported cases of harmful concentrations being reached. 2) Application a) Waterslide transfer: Sometimes, water soluble substances like Ethyllactate are used in the steep water and cause skin irritation. b) Waterslide transfer and PVB transfer: Using fixatifs or sloshes, there can be evaporation of solvents, and corresponding exposure limits have to be considered. c) Automatic decoration: Using wax-coated base paper can cause vapours of wax components, for example polyethylene glycol. Corresponding exposure limits have to be considered. 3) Firing At approximately 200 C the organic material volatilize, releasing organic substances, the toxic potential of which is not known. Due to the variety of base materials and firing conditions a general recommendation cannot been made. Typical example: Firing of waterslide transfer pictures with methacrylic resins may reveal monomeric acrylates. Exposure limits: Germany: MAK 50 ppm or 210 mg/m3 USA: ACGIH 410 mg/m3 OSHA 410 mg/m3 4) Labelling If ceramic prints are ingested, for example by children, a reaction of stomach acid with lead containing substances may cause complications. Therefore, in the USA (since 1996) there has to be an individual labelling of ceramic prints for consumers, fulfilling the CPSC (Consumer Product Safety Commission) or ASTM D-4236-94 (ASTM = American Society of Testing Materials) or LHAMA (Labelling of Hazar-

66

4 Preparations dous Art Materials Act) or FHSA (Federal Hazardous Substances Act). There is no need for labelling for commercial users. According to German chemical law 3, section 5, ceramic prints do not have to be labelled.

Chronic Toxicity None known at this time. Physical Hazards Transfer pictures are flammable, depending on the support they are printed on, generally paper. Environmental Concerns 1) Printing base a) Waterslide transfer and other transfer: Mostly recyclable as paper or carton. (EU Waste Catalogue 150101) b) Automatic decoration with wax-coated paper: According to local authorities and local laws, it can be recycled landfilled or separate waste. 2) Ceramic prints Most of the ceramic prints contain lead and are therefore treated similar to ceramic colours. In Germany they have to be disposed as separate waste. (EU Waste Catalogue 200112) They have to be disposed under the following criteria: a) contents of harmful substances in the ceramic colour; b) contents of harmful substances in the printing media; c) contents of harmful substances in the covercoat; d) contents of harmful substances in the printing base. 3) Interleafing paper (EU Waste Catalogue 150101 for "wax coated paper", 150102 for "polyethylene foil"). Reference (1) Schmidt, W. "Analyse und thermische Zersetzung von Dekor-Abziehbildern fr Porzellan"; Dissertation Universitt Saarbrcken, 1987.

5.1 Selected R- and S-phrases

67

5 Annexes
5.1 Selected R- and S-phrases
R 20 R 20/22 R 20/21/22 R 21 R 22 R 25 R 33 R 36 R 37 R 38 R 40 R 43 R 49 R 61 R 62 S7 S8 S 22 S 24 S 24/25 S 25 S 37 S 45 S 53 Harmful by inhalation Harmful by inhalation and if swallowed Harmful by inhalation, in contact with skin and if swallowed Harmful in contact with skin Harmful if swallowed Toxic if swallowed Danger of cumulative effects Irritating to eyes Irritating to respiratory system Irritating to skin Possible risks of irreversible effects May cause sensitation by skin contact May cause cancer by inhalation May cause harm to the unborn child Possible risk of impaired fertility Keep container tightly closed Keep container dry Do not breathe dust Avoid contact with skin Avoid contact with skin and eyes Avoid contact with eyes Wear suitable gloves In case of accident or if you feel unwell, seek medical advice immediately (show the label where possible) Avoid exposure Obtain special instructions before use

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5 Annexes

5.2 EU Waste Catalogue

060401 080101 080102 080103 150101 150102 170202 200112 Metal oxides (pigments, unsoluble stains, iron oxides, chromium oxide) Old paints containing halogenated solvents Old paints not containing halogenated solvents Waste of paints, water based Paper, cardboard (wax coated paper) Plastics (polyethylene foil) Glass Paints, printing inks, adhesives and resins (ceramic prints)

5.3 Symbols used in Labelling

According to the Dangerous Substances and Dangerous Preparations Directives, special Symbols have to be used for the labelling of dangerous substances and preparations. These symbols have to be printed in black on orange ground. This brochure provides in the table on the next page these symbols and the respective meanings in all official languages used within the European Union. To facilitate the identification of a certain language, the same key country identification system is being used as for automotive vehicles.

5.3 Symbols used in Labelling Xn

D: Gesundheitsschdlich DK: Sundhedsskadelig E: Nocivo F: Nocif GB: Harmful GR: I: Nocivo NL: Schadelijk P: Nocivo S: Hlsoskadlig SF: Haitallinen D: Giftig DK: Giftig E: Txico F: Toxique GB: Toxic GR: I: Tossico NL: Vergiftig P: Txico S: Giftig SF: Myrkyllinen D: tzend DK: tsende E: Corrosivo F: Corrosif GB: Corrosive GR: I: Corrosivo NL: Bijtend P: Corrosivo S: Frtande SF: Syvyttv

69 Xi
D: Reizend DK Lokalirriterende E: Irritante F: Irritant GB: Irritant GR: I: Irritante NL: Irriterend P: Irritante S: Irriterande SF: rsyttv D: Sehr giftig DK: Meget giftig E: Muy txico F: Trs toxique GB: Very toxic GR: I: Molto tossico NL: Zeer vergiftig P: Muito txico S: Mycket giftig SF: Erittin myrkyllinen D: Umweltgefhrlich DK: Miljfarlig E: Peligroso para el medio ambiente F: Dangereux pour l'environnement GB: Dangerous for the environment GR: I: Pericoloso per l'ambiente NL: Milieugevaarlijk P: Perigoso para o ambiente S: Miljfarlig SF: Ympristlle vaarallinen D: Brandfrdernd DK: Brandnrende E: Comburente F: Comburant GB: Oxidizing GR: I: Comburente NL: Oxyderend P: Comburente S: Oxiderande SF: Hapettava D: Hochentzndlich DK: Yderst brandfarlig E: Extremadamente inflamable F: Extrmement inflammable GB: Extremely flammable GR: I: Estremamente infiammabile NL: Zeer licht ontvlambaar P: Extremamente inflamvel S: Ytterst brandfarlig SF: Erittin helposti syttyv

T+

D: Explosionsgefhrlich DK: Eksplosiv E: Explosivo F: Explosif GB: Explosive GR: I: Esplosivo NL: Ontplofbaar P: Explosivo S: Explosiv SF: Rjhtv D: Leichtentzndlich DK: Meget brandfarlig E: Fcilmente inflamable F: Facilement inflammable GB: Highly flammable GR: I: Facilmente infiammabile NL: Licht ontvlambaar P: Facilmente inflamvel S: Mycket brandfarlig SF: Helposti syttyv

F+

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5 Annexes

5.4 Glossary
This glossary includes terms commonly used in safety data sheets and in publications concerning health and the environment. Accumulation Successive additions of a substance to a target organism, or organ, or to a part of the environment, resulting in an increasing amount or concentration of the substance in the organism, organ, or environment American Conference of Governmental Industrial Hygienists (see also MAK for Germany) A sludge produced in sewage works by continually recirculating sewage through aeration tanks; activated sludge contains large numbers of micro-organisms and is therefore very efficient at biodegradation Describes all short-term health effects to humans and animals Taking place in the presence of oxygen; requiring the presence of oxygen A pre-screening in vitro test for gene mutation, carried out with bacteria (Salmonella) Taking place in the absence of oxygen; not requiring the presence of oxygen American Society for testing Materials Able to utilize carbon dioxide for nutrition Biologische Arbeitsstoff-Toleranz Progressive increase in the amount of a substance in an organism or a part of an organism which occurs because the rate of intake exceeds the organism's ability to remove the substance from the body Extent to which a substance to which a body is exposed (by ingestion, inhalation, injection or skin contact) reaches the systemic circulation, and the rate at which this occurs Community of mutually compatible living organisms formed in response to specific environmental influences Process leading to a higher concentration of a substance in an organism than in environmental media to which it is exposed The capacity of a substance to be broken down by the biological action of living organisms Biochemical oxygen demand; the amount of oxygen required for the biodegradation of an organic chemical or waste water; BOD measurements are used to assess the extent to which an organic substance is biodegradable by comparing it with e.g. the COD Substance which induces cancer or increases its incidence A term indicating relationship to the heart and blood vessels

ACGIH Activated sludge

Acute toxicity Aerobic Ames test Anaerobic ASTM Autotrophic BAT Bioaccumulation

Bioavailability

Biocenosis Bioconcentration Biodegradability BOD

Carcinogen Cardiovascular

5.4 Glossary CAS Number Chronic toxicity COD The Chemical Abstract Service registry number Describes all long-term health effects to humans and animals Chemical oxygen demand; the amount of oxygen required for the chemical oxidation e.g. by chromic acid of an organic chemical into carbon dioxide and water under standardized conditions Causing visible destruction or irreversible alteration by chemical action at the site of contact A population of bacteria propagated under laboratory conditions

71

Corrosive Cultures Decals Decomposition DOC EC50 Ecotoxicity EEC EINECS EUCLID Excretion Exhaustion, Degree of Explosive Limit Harmful Hazard Heterotrophic HGPRT Test IARC IC50

Ceramic colours printed on a carrier, mainly paper, from which they can be transferred to a (glass or ceramic) substrate Breakdown of a material or substance Dissolved organic carbon, normally analysed after filtration or centrifugation of an aqueous suspension Effect concentration 50; the concentration of a substance required to have an effect on 50 % of the organisms exposed to it The toxic hazard posed by a substance to biological species (plants and animals) or ecosystems European Economic Community, now called EC (European Community) European Inventory of Existing Commercial Substances European Chemical Information Database The process of expelling waste, e.g. faeces, urine from a living being The proportion of the total dye charged which is taken up by the substrate The concentration of a flammable gas, vapour, or dust at which explosion can occur upon ignition in a confined area A technical term used to classify dangerous substances as layed down in Directive 67/548/EEC, Article 2 An inherent property of a substance, which may make it capable of causing adverse effects Description of organisms which require organic carbon for their nutrition The hypoxanthine guanine phosphoribosyltransferase test is an in vitro gene mutation test conducted in mammalian cells. International Agency for Research on Cancer (WHO) Inhibitory concentration 50; the concentration of a substance required to inhibit the growth rate or other function of organisms exposed to it by 50 % International Labour Organization, Geneva Experiment with cells or tissues conducted outside of a living organism

ILO In vitro test

72 In vivo test Inhibition Intratracheal instillation Irritant LC50 LD50 LHAMA MAK value Study performed on a living organism

5 Annexes

The slowing down of such biological processes as respiration, plant growth (e.g. by toxic effects) Dosing of the test material through a tube into the upper respiratory tract A material which causes reversible redness and / or swelling at the site of contact Lethal concentration 50; the concentration of a substance required to kill 50 % of the organisms exposed to it Lethal dose 50; a dose of a material that kills 50 % of a group of animals exposed to it Labelling of Hazardous Art Materials Act, USA Maximale Arbeitsplatzkonzentration (maximum occupational exposure concentration) is the highest permissible air concentration which is considered safe for prolonged exposure. The MAK values are set by the German Senate Commission for examination of harmful occupational substances. Degradation product produced in the organism by a biochemical reaction Microscopically small living beings, bacteria, plants or animals The ability to move from one environmental compartment to another A substance or agent capable of altering the genetic material in a living cell A material that affects the nerve cells and may produce emotional or behavioural abnormalities No observed effect concentration, i.e. the highest concentration at which no effect has been observed The Organisation for Economic Cooperation and Development Description of a surface water containing little nutritive material Occupational Safety and Health Administration (USA) Permissible Exposure Limit The oxygen consumption of aerobic micro-organisms. Often used as an indirect measure of either toxicity to a bacterial culture (inhibition of respiration activity) or biodegradability (promotion of respiration activity) Possibility that a harmful event arising from exposure to a substance may occur under specific conditions Safety Data Sheet Toxic effects occurring as a result of the repeated exposure to a chemical The effect of a material on an organ or system

Metabolite Microorganisms Mobility Mutagen Neurotoxin NOEC OECD Oligotrophic OSHA PEL Respiration Activity

Risk SDS Subchronic Toxicity Target Organ Effect

5.4 Glossary Teratogen TLV TOC Toxicity, acute Toxicity, chronic Toxicity, subchronic TWA VOC WHO A material which has the capability of causing malformations in the offspring as a result of exposure to the pregnant female Threshold Limit Value Total Organic Carbon: the amount of bound organic carbon Describes all short-term health effects to humans and animals Describes all long-term health effects to humans and animals Toxic effects occurring as a result of the repeated exposure to a chemical Time Weighted Average Volatile Organic Chemical World Health Organization

73

74

5 Annexes

5.5 Index
A Accumulation ......................................... 5.4 ACGIH .................................................... 5.4 Acrylic resins ....................................... 3.5.5 Activated sludge ..................................... 5.4 Additives, inorganic ............................... 3.4 Additives, organic .......................... 2.8, 3.5 Adhesives ............................................... 5.2 ADR ........................................................ 1.6 Aerobic ................................................... 5.4 Agglomeration ..................................... 4.2.2 Alcoholes ............................................. 3.5.1 Alumina .......................................... 2.1, 3.4 Ames test ................................................ 5.4 Amides ................................................. 3.5.7 Ammonium metavanadate .............. 2.1, 3.4 Anaerobic ............................................... 5.4 Anatase ................................ 2.1, 3.4, 3.4.1 Antimonate pigments ........................ 3.2.1.5 Antimony ................................................ 3.1 Antimony titanium orange/yellow .... 3.2.1.1 Aromatic hydrocarbons ....................... 3.5.1 ASTM ..................................................... 5.4 Autotrophic ............................................. 5.4 B Baddeleyite ....................................... 3.2.1.3 Barium carbonate ........................... 2.1, 3.4 BAT ........................................................ 5.4 Benzene ............................................... 3.5.1 Binders ......................................... 2.8, 4.1.2 Bioaccumulation ..................................... 5.4 Bioavailability ........................................ 5.4 Biocenosis .............................................. 5.4 Bioconcentration .................................... 5.4 Biodegradability ..................................... 5.4 BOD ........................................................ 5.4 Bright metal preparations ........................ 2.7 Brookite ............................................... 3.4.1 Burnish metal preparations ..................... 2.7 Butanoles ............................................. 3.5.1 Butanones ............................................ 3.5.1 C Cadmium ...................................... 3.1, 4.1.1 Cadmium pigments ...................... 3.2, 3.2.3 Cadmium, inclusion pigments .......... 3.2.1.4 Calcium carbonate .......................... 2.1, 3.4 Carcinogenicity ............................... 1.1, 5.4 Cardboard ............................................... 5.2 Cardiovascular ........................................ 5.4 CAS number ................................... 2.4, 5.4 Cassiterite ......................................... 3.2.1.3 Cassius purple ...................................... 3.2.4 CEFIC ..................................................... 1.5 Cellulose ethers ......................... 3.5.4, 3.5.5 Ceramic colours ...................................... 2.5 Ceramic decoration ................................. 2.8 Ceramic glazes ........................................ 2.2 Ceramic prints ......................... 2.9, 4.3, 5.2 Ceramic stains ................. 2.4, 2.5, 2.6, 3.2 Ceramic transfers ............................ 2.9, 4.3 Cerium oxides ................................. 2.1, 3.4 Chemical Law ......................................... 1.1 Chrome alumina pink ........................ 3.2.1.3 Chrome iron manganese brown ........ 3.2.1.2 Chrome iron manganese zinc brown . 3.2.1.2 Chrome iron nickel black .................. 3.2.1.2 Chrome manganese zinc brown ........ 3.2.1.2 Chrome tin pink ................................ 3.2.1.3 Chromium antimony titanium yellow 3.2.1.1 Chromium green hematite ................. 3.2.2.2 Chromium niobium titanium yellow . 3.2.1.1 Chromium oxides .............. 2.1, 3.4, 3.2.2.2 Chromium tungsten titanium yellow 3.2.1.1 CIC pigments ............................... 3.2, 3.2.1 Clays ............................................... 2.1, 3.4 Cobalt blue ........................................ 3.2.1.2 Cobalt chromite blue ......................... 3.2.1.2 Cobalt chromite green ....................... 3.2.1.2 Cobalt nickel gray ............................. 3.2.1.6 Cobalt nickel zinc titanite green ....... 3.2.1.2 Cobalt oxides .................... 2.1, 3.2.2.3, 3.4 Cobalt silicate blue ........................... 3.2.1.6

5.5 Index Cobalt tin blue .................................. 3.2.1.2 Cobalt zinc alumina blue .................. 3.2.1.2 Cobalt zinc silicate blue ................... 3.2.1.6 COD ........................................................ 5.4 Colemanite ...................................... 2.1, 3.4 Colour powders ................................... 4.1.2 Colouring oxides ................................. 3.2.2 Colouring systems ............................... 4.1.1 Colours, ceramic ..................................... 2.5 Colours, decorating ............................. 4.1.2 Colours, glass ......................................... 2.6 Combustion products .............................. 1.2 Complex inorganic colour pigments (CIC pigments) ....................... 3.2, 3.2.1 Composti .............................. 2.2, 2.3, 4.2.2 Consumer protection .............................. 1,7 Copper chromite black ..................... 3.2.1.2 Copper oxides ................... 2.1, 3.2.2.4, 3.4 Corrosivity ...................................... 1.1, 5.4 Corundum ......................... 2.1, 3.2.1.3, 3.4 Covercoats ...................................... 2.8, 2.9 Crushed frits ................................ 2.3, 4.2.2 Crystalline Silica ......................... 3.4, 3.4.2 Cultures .................................................. 5.4 Cuprous oxide ................................... 3.2.2.4 D Dangerous Preparations Directive .......... 1.3 Dangerous Substances Directive .... 1.1, 1.3 Decals ..................................... 2.9, 4.3, 5.4 Decomposition ........................................ 5.4 Decoration ........................... 2.8, 4.1.2, 4.3 Defoamers ............................................ 3.5.6 Delivery, forms of .................................. 4.2 Diacetone alcohol ................................ 3.5.1 Dibutyl phthalate ................................. 3.5.2 Dioles ................................................... 3.5.2 Discharge, electrostatic .......................... 1.2 DOC ........................................................ 5.4 Dolomite ......................................... 2.1, 3.4 Dust ........................................................ 1.2 Dusting preparations ............................... 2.7 E EC50 ........................................................ 5.4 Ecotoxicity .............................................. 5.4

75 EEC ......................................................... 5.4 EINECS ........................................... 2.4, 5.4 Electrostatic discharge ............................ 1.2 Enamels, glass ......................................... 2.6 Environmental concerns .......................... 1.5 Etheric oils ........................................... 3.5.1 Ethers ...................................................... 3.5 Ethyl hexyl phthalate ........................... 3.5.2 EU Waste Catalogue ....................... 3.3, 5.2 EUCLID .................................................. 5.4 Excretion ................................................. 5.4 Exhaustion .............................................. 5.4 Explosive limit ........................................ 5.4 F Feldspars ......................................... 2.1, 3.4 Fired glazes .......................................... 4.1.1 Firing temperatures ................................. 2.6 Fixatives ............................................... 3.5.5 Flakes ...................................................... 2.2 Flammability ........................................... 1.2 Fluorspar ......................................... 2.1, 3.4 Fluxes ............................... 2.2, 2.5, 2.6, 3.1 Frits .......................... 2.2, 2.3, 2.5, 2.6, 3.1 Frits, crushed ................................ 2.3, 4.2.2 Frit systems .......................................... 4.1.1 G Garnet ............................................... 3.2.1.3 Genotoxicity ........................................... 1.1 Glass ....................................................... 5.2 Glass colours ........................................... 2.6 Glass decoration ...................................... 2.8 Glass enamels ......................................... 2.6 Glazes .............................................. 2.2, 2.3 Glazes, fired ......................................... 4.1.1 Glazes, pelletized .................................... 2.3 Glazes, powders ................................... 4.1.1 Glycolic ethers ..................................... 3.5.2 Gold purple .......................................... 3.2.4 Grains ...................................................... 2.2 Grainy materials ................................... 4.2.2 Graniglia ...................................... 2.3, 4.2.2 Granilla ........................................ 2.3, 4.2.2 Granulados .............................................. 2.3 Granulates .................................... 2.3, 4.2.2

76 H Halogenated solvents ...................... 3.3, 5.2 Harmful ................................................... 5.4 Hazard ..................................... 1.2, 1.3, 5.4 Health ............................................. 1.4, 1.5 Heavy metals .......................................... 3.2 Hematite ........................................... 3.2.2.2 Heterotrophic .......................................... 5.4 HGPRT test ............................................ 5.4 Hydrocarbons ...................................... 3.5.1 Hydro-solubility ..................................... 2.2 Hygiene ................................................... 1.4 I IARC ....................................................... 5.4 IATA ....................................................... 1.6 IC50 ......................................................... 5.4 ICAO ...................................................... 1.6 ICE-Program ........................................... 1.5 ILO ......................................................... 5.4 IMO ........................................................ 1.6 In vitro test .............................................. 5.4 In vivo test .............................................. 5.4 Inclusion pigments ............................ 3.2.1.4 Industrial hygiene ................................... 1.4 Inglaze colours ........................................ 2.5 Inorganic additives ................................. 3.4 Inorganic raw materials .................. 2.1, 3.4 Instillation, intratracheal ......................... 5.4 Interleafing paper ................................... 4.3 Intratracheal instillation .......................... 5.4 Iron brown ........................................ 3.2.2.1 Iron chromite brown ......................... 3.2.1.2 Iron cobalt black ............................... 3.2.1.2 Iron cobalt chromite black ................ 3.2.1.2 Iron oxides ........................ 2.1, 3.2.2.1, 3.4 Iron titanium black ........................... 3.2.1.2 Irritation .......................................... 1.1, 5.4 Isothiazolones ...................................... 3.5.7 K Kaoline ........................................... 2.1, 3.4 Ketones ................................................ 3.5.1 L Labelling ................................................. 1.3 Labelling symbols .................................. 4.3

5 Annexes LC50 ........................................................ 5.4 LD50 ................................................ 1.1, 5.4 Lead ............................................. 3.1, 4.1.1 Lead antimonate yellow .................... 3.2.1.5 Lecithines ............................................. 3.5.3 LHAMA .................................................. 5.4 Liquifiers .............................................. 3.5.3 Lithium carbonate ........................... 2.1, 3.4 Lustres ............................................. 2.7, 3.3 M Magnesium carbonate ..................... 2.1, 3.4 MAK value ............................................. 5.4 Manganese alumina pink .................. 3.2.1.3 Manganese antimony titanium brown 3.2.1.1 Manganese ferrite black .................... 3.2.1.2 Manganese oxides ............. 2.1, 3.2.2.6, 3.4 Matte preparations .................................. 2.7 Media ...................................................... 2.8 Metabolite ............................................... 5.4 Metal oxide pigments ............................. 3.2 Metal preparations .................. 2.7, 2.8, 3.3 Metals, heavy .......................................... 3.2 Mica .................................................. 3.2.2.7 Microorganisms ...................................... 5.4 Minerals .................................................. 2.1 Mobility .................................................. 5.4 Mutagenicity ................................... 1.1, 5.4 N Naples yellow ................................... 3.2.1.5 Nepheline ........................................ 2.1, 3.4 Neurotoxin .............................................. 5.4 Nickel antimony titanium yellow ..... 3.2.1.1 Nickel ferrite brown .......................... 3.2.1.2 Nickel niobium titanium yellow ....... 3.2.1.1 Nickel oxides .................... 2.1, 3.2.2.5, 3.4 Nickel tungsten titanium yellow ....... 3.2.1.1 NOEC ...................................................... 5.4 O OECD ...................................................... 5.4 Oils ....................................................... 3.5.1 Oligotrophic ............................................ 5.4 Olivine .............................. 2.1, 3.2.1.6, 3.4 Onglaze colours ...................................... 2.5 Organic additives ............................ 2.8, 3.5

5.5 Index Organic binders ...................................... 2.8 OSHA ..................................................... 5.4 Oxides .......................................... 3.2.2, 5.2 P Paints .............................................. 3.3, 5.2 Paper ............................................... 4.3, 5.2 Paste ..................................................... 4.2.3 Pearlescent pigments ........................ 3.2.2.7 Pelletized glazes ..................................... 2.3 Penetrating salts ...................................... 2.8 Periclase ............................................ 3.2.1.6 Personal safety equipment ...................... 1.4 Petalite ............................................ 2.1, 3.4 Phenacite .......................................... 3.2.1.6 Phthalates ............................................. 3.5.2 Physical hazards ..................................... 1.2 Pigments ......................................... 2.4, 5.2 Pigments, antimony .......................... 3.2.1.5 Pigments, cadmium ....... 3.2, 3.2.1.4, 3.2.3 Pigments, CIC .............................. 3.2, 3.2.1 Pigments, inclusion .......................... 3.2.1.4 Pigments, metal ...................................... 3.2 Pigments, pearlescent ....................... 3.2.2.7 Pigments, Rutile ............................... 3.2.1.1 Pigments, Spinel ............................... 3.2.1.2 Plasticizers .............................................. 2.8 Plastics .................................................... 5.2 Polycarboxylates ................................. 3.5.3 Polyethylene ........................................... 5.2 Powders .................................... 4.1.1, 4.2.1 Powders, colour ................................... 4.1.2 Precious metal preparations ... 2.7, 2.8, 3.3 Preparations ............................................ 4.1 Preservatives ........................................ 3.5.7 Printing base ........................................... 4.3 Printing inks ........................................... 5.2 Printing, ceramic .................... 2.9, 4.3, 5.2 Product Stewardship ............................... 1.5 Propanoles ........................................... 3.5.1 Protective equipment .............................. 1.4 Purple ................................................... 3.2.4 PVB transfer ........................................... 4.3 Pyrochlore ........................................ 3.2.1.5

77 Q Quality Assurance Guidelines ................ 1.5 Quartz ................................... 2.1, 3.4, 3.4.2 R Radioactivity ........................................ 3.4.4 Raw materials ........................... 4.1.1, 4.1.2 Raw materials, inorganic ................ 2.1, 3.4 Resins ........................................... 3.5.5, 5.2 Respiration activity ................................. 5.4 Responsible Care .................................... 1.5 RID .......................................................... 1.6 Risk ......................................................... 5.4 R-phrases (risk phrases) .................. 1.3, 5.1 Rutile ............................ 2.1, 2.4, 3.4, 3.4.1 Rutile, pigments ................................ 3.2.1.1 S Safety ...................................................... 1.5 Safety Data Sheet, SDS .................. 1.3, 5.4 Safety phrases (S-phrases) ...................... 1.3 Safety protection program ...................... 1.4 Salts, soluble ........................................... 2.8 SDS, Safety Data Sheed .................. 1.3, 5.4 Selenide .................................. 3.2.1.4, 3.2.3 Selenium ................................................. 3.1 Sensitizing ............................................... 1.1 Silica ............................................ 3.4, 3.4.2 Silicones ............................................... 3.5.6 Silicosis ................................................ 3.4.2 Slips ..................................................... 4.2.4 Sludge ..................................................... 5.4 Softeners .............................................. 3.5.2 Softening temperatures ........................... 2.6 Solvents ........................................ 2.8, 3.5.1 Solvents, halogenated ..................... 3.3, 5.2 Source emission ...................................... 1.5 Sphene ............................................... 3.2.1.3 S-phrases (safety phrases) ....................... 5.1 Spills ....................................................... 1.5 Spinels ..................................................... 2.4 Spinels, pigments .............................. 3.2.1.2 Spodumene ...................................... 2.1, 3.4 Stains ....................................................... 5.2 Stains, ceramic ................ 2.4, 2.5, 2.6, 3.2

78 Storage .................................................... 1.6 Strontium carbonate ....................... 2.1, 3.4 Sulfo-selenide ........................ 3.2.1.4, 3.2.3 Suspending agents ............................... 3.5.4 Symbols for labelling ............................. 4.3 T Talcum ............................................ 2.1, 3.4 Target Organ Effect ................................ 5.4 Teratogenicity ................................. 1.1, 5.4 Terpenes .............................................. 3.5.1 Tetraline .............................................. 3.5.1 Thermoplastic media .............................. 2.8 Tin antimony gray ............................ 3.2.1.3 Tin chromium orchid ........................ 3.2.1.3 Tin dioxide ..................................... 2.1, 3.4 Tin vanadium yellow ........................ 3.2.1.3 Titanium dioxide ................... 3.2.1.1, 3.4.1 TLV ........................................................ 5.4 TOC ........................................................ 5.4 Toxicity .......................................... 1.1, 5.4 Transfers, ceramic .......................... 2.9, 4.3 Transportation ........................................ 1.6 Tricobalt tetroxide ............................ 3.2.2.3 Tungsten oxide ............................... 2.1, 3.4 Turpentine oil ...................................... 3.5.1 TWA ....................................................... 5.4 U Ulexite ............................................ 2.1, 3.4 Underglaze colours ................................. 2.5 UV-curing systems ................................. 2.8

5 Annexes V Vanadates ........................................ 2.1, 3.4 Vanadium antimony titanium gray ... 3.2.1.1 Vanadium pentoxide ....................... 2.1, 3.4 Victoria Green .................................. 3.2.1.3 VOC ........................................................ 5.4 W Waste ....................................................... 1.5 Waste Catalogue, European ............ 3.3, 5.2 Water based paints .................................. 3.3 Water-hazard classes .............................. 1.5 Waterslide transfer .................................. 4.3 Wax coated paper ................................... 5.2 WHO ....................................................... 5.4 Wollastonite .................................... 2.1, 3.4 Z Zinc chrome alumina pink ................ 3.2.1.2 Zinc ferrite brown ............................. 3.2.1.2 Zinc iron chromite brown ................. 3.2.1.2 Zinc oxide .................................... 2.1, 3.4.3 Zinc sulphide ....................................... 3.2.3 Zinc white ............................................ 3.4.3 Zircon ............. 2.1, 2.4, 3.2.1.3, 3.4, 3.4.4 Zirconia ........................................... 2.1, 3.4 Zirconium iron pink .......................... 3.2.1.3 Zirconium praseodymium yellow ..... 3.2.1.3 Zirconium silicate .................. 3.2.1.4, 3.4.4 Zirconium silicon grey ...................... 3.2.1.3 Zirconium vanadium blue ................. 3.2.1.3 Zirconium vanadium yellow ............. 3.2.1.3

Asociacion Nacional de Fabricantes de Fritas, Esmaltes y Colores Ceramicos (ANFFECC) Association of the Spanish manufacturers of frits, glazes and ceramic pigments. Address: Caballeros 55, E12001 Castelln, Espana Tel.: + 34 - (9)64 - 22 49 75 Fax: + 34 - (9)64 - 22 02 82 E-mail: breva@ctac.es

CERAMICOLOR Association of the Italian manufacturers of ceramic glazes, metal oxides and inorganic pigments. Ceramicolor comprises the manufactures of glazes or frits for the ceramic industry or in application on metal supports, dyes, metal oxides (lead, lithium, aluminium, tin and antimony oxides) and inorganic pigments (titanium oxides, iron oxides and hydroxides, chromium, manganese, cobalt and copper oxides and cadmium sulfo-selenides). Address: Ceramicolor Federchimica, Via Accademia 33, I20131 Milano, Italia Tel.: + 39 - 2 - 26 810 - 304 / - 307 Fax: + 39 - 2 - 26 810 - 461 E-mail: ceramicolor@federchimica.it

Syndicat des Fabricants dEmaux, Pigments, Sels et Oxydes Mtalliques (EPSOM) Association of the French manufacturers of enamels, pigments, salts and metallic oxides who produce porcelain enamels, ceramic glazes, inorganic colours for glass industry, inorganic pigments, some organic pigments, precious metals and inorganic pastes for decoration, conductive pastes for automotive industry, various metallic salts and oxides for the chemical industry, the housing and the health sectors. Address: EPSOM, F92909 Paris-La Dfense, Cedex, France Tel: + 33 - 1 - 46 - 53 11 95 Fax: + 33 - 1 - 46 - 53 11 98 E-mail: sicos@dial.oleane.com

Verband der Mineralfarbenindustrie (VdMi) Association of the German manufacturers of inorganic pigments, printing inks and printing ink additives, carbon black, white reinforcing fillers, chemicals for enamel, glass and ceramics, artists and school colours, food colorants. Address: VdMi, Karlstrasse 21, D60329 Frankfurt / M., Germany Tel: + 49 - 69 - 2556 - 1351 Fax: + 49 - 69 - 25 30 87 E-mail: hashash@vdmi.vci.de