WO1995009132A1

WO1995009132A1 - Lead-free glaze or enamel for use on ceramic bodies

Info

Publication number: WO1995009132A1
Application number: PCT/US1994/010511
Authority: WO
Inventors: Emilio D. Spinosa; Kevin J. Davies
Original assignee: Ferro Corporation
Priority date: 1993-09-29
Filing date: 1994-09-19
Publication date: 1995-04-06
Also published as: EP0721431A4; EP0721431A1; AU7798394A; US5447891A

Abstract

The invention concerns a lead-free glaze or enamel for use on ceramic bodies such as bone china. In one embodiment the glaze or enamel includes a hard glass frit which comprises by weight percent from about 45 % to about 70 % SiO2, from about 4 % to about 15 % B2O3, from about 4 % to about 17 % Al2O3, from about 1 % to about 9 % Na2O, from about 1 % to about 9 % K2O, from about .2 % to about 5 % Li2O, from about .4 % to about 12 % CaO, from about .1 % to about 7 % ZrO2, up to about 3 % ZnO, up to about 2 % WO3, up to about 2 % Bi2O3, and up to about 2 % MoO3.

Description

Title: LEAD-FREE GLAZE OR ENAMEL FOR USE ON CERAMIC BODIES

Field of the Invention

This invention relates to a lead-free glaze or enamel. More particularly, the invention concerns a lead-free glaze or enamel for use on ceramic bodies used to produce articles such as chinaware or dinnerware.

Background of the Invention Lead containing glazes and enamels for use on ceramic bodies are well-known in the ceramic art. Such glazes and enamels generally comprise a vehicle and one or more glass frits. A glaze is typically thought of as a clear coating, whereas an enamel is a glaze which contains a pigment or similar particles in suspension. Such glazes and enamels are applied to the surfaces of a green, partially, or fully fired ceramic body in the form of a paste. After application of the glaze or enamel to the surface of the ceramic body by silk screening or other conventional techniques, the coated ceramic body is fired to cure the ceramic body, bond the glaze or enamel to the surface of the ceramic body, and volatilize the vehicle. In the past, the use of lead oxide in these compositions served to lower the fusing point of the frit and to render an acid/alkali resistant finish. Recent efforts have been made at retaining the low fusion temperature of these glazes and enamels and the acid/alkali durability of the coating, but with the removal of the lead oxide.

Summary of the Invention The present invention concerns a lead-free composition for use in forming a coating on ceramic bodies and a method of using the same. The lead-free composition comprises a hard glass frit, a flux frit, and a clay. A vehicle is generally included to facilitate the application of the composition. The hard frit comprises by weight percent from about 45% to about 70% Si0₂, from about 4% to about 15% B₂0₃, from about 4% to about 17% A1₂0₃, from about 1% to about 9% Na₂0, from about 1% to about 9% K₂0, from about .2% to about 5% Li₂0, from about .4% to about 12% CaO, from about .1% to about 7% Zr0₂, up to about 3% ZnO, up to about 2% 0₃, up to about 2% Bi₂0₃, and up to about 2% Mo0₃.

The flux frit comprises in weight percent from about 40% to about 52% Si0₂, from about 17% to about 26% B₂0₃, from about 2% to about 10% A1₂0₃, from about 6% to about 14% Na₂0, from about .5% to about 3% K₂0, up to about 3% MgO and from about 8% to about 17% CaO.

Various commercially available clays may be used in conjunction with the present invention. Preferably, the clay comprises from about 40% to about 55% Si0₂, from about 20% to about 45% A1₂0₃, up to about 5% Na₂0, up to about 5% K₂0, up to about 5% MgO and up to about 5% CaO.

The solids portion of the glaze or enamel comprises in weight percent from about 70% to about 95% hard frit, from about 2% to about 10% flux frit, and from about 4% to about 18% clay.

These and other aspects of the invention will become clear to those of ordinary skill in the art upon the reading and understanding of the specification.

Detailed Description of the Invention This invention concerns lead-free and cadmium-free glazes and glass enamels which possess excellent resistance to both alkali and acid environments and moderate firing or maturation temperatures. The glazes and enamels also display good gloss, and a coefficient of thermal expansion that is compatible with a china ceramic body.

As used in this specification and the claims below the terms "lead-free" and "cadmium-free" mean no intentional addition of cadmium or lead, and less than .005% by weight lead or cadmium, respectively.

The glazes and enamels of the present invention are especially adapted for use on green ceramic bodies such as those used to produce chinaware or dinnerware, or fine bone china. The glazes and enamels of the present invention are especially well suited for use on fine bone china. Bone china may be produced utilizing various compositions to form the ceramic body. However, bone china is a ceramic ware which is generally formed by firing a composition comprising about 47% calcined bone, about 27% china clay, and about 30% china stone. The maturation temperature of the glazes and enamels of the present invention are well below the temperature at which a china ceramic body thermally deforms. Specifically, the glazes and enamels of the present invention may be fired between about 1000°C to about 1200°C using conventional furnaces or kilns.

The glaze or enamel compositions of the present invention comprise a hard glass frit, a flux glass frit, and a clay. The glass frits of the present invention can be melted in conventional refractory crucibles at 1400-1600°C with little attack on the crucibles. The glass melt may be handled by any suitable conventional means though typically it is quenched by steel rolls into flake or frit, using techniques well-known to those skilled in the art.

The enamels and glazes of the present invention include a hard glass frit having the following compositions:

Preferred More Preferred

Component Ranαe (Wt.%) Ran e (Wt.%) Ranσe (Wt.%)

Si0₂ 45-70 50-65 52-63

B₂0₃ 4-15 5-14 6-13

A1₂0₃ 4-17 5-16 6-15

Na₂0 1-9 1.5-8 2-7

K₂0 1-9 1.5-8 1.75-7.5

Li₂0 .2-5 .3-4 .4-3.5

CaO 4-12 5-11 5.5-10

Zr0₂ .1-7 .1-6.0 .1-5.5

The hard glass frit contains some Zr0₂ to enhance alkali durability, but preferably the Zr0₂ level is not so high so as to induce crystallization, which manifests itself as a dull or f°ggy coating. To avoid undesirable color develc—ent, the hard glass frit preferably includes a maximum of 3-< r>y weight ZnO, preferably a maximum of 2.5% by weight ZnO, and more preferably a maximum of 2% by weight ZnO. To decrease the surface tension of the glaze or glass enamel, the hard glass frit contains a maximum of 2% by weight, and preferably a maximum of 1% by weight, of each of tungsten oxide (W0₃) , bismuth oxide (Bi₂0₃) , and molybdenum oxide(Mo0₃) . More preferably, the hard glass frit contains substantially no tungsten oxide, bismuth oxide, or molybdenum oxide.

The enamels and glazes of the present invention include a flux frit having the following compositions:

Component Ranσe (Wt%) Preferred Rancre (Wt%)

Si0₂ 40-52 42-49

B₂0₃ 17-26 18-24

A1₂0₃ 2-10 3-9

Na₂0 6-14 7-13

K₂0 .5-3 .7-1.8

MgO 0-3 0-2

CaO 8-17 9-16

Any number of commercially available clays may be used to produce the enamels and glazes of the present invention. Such clays include the following compositions:

Component Range (Wt%) Preferred Range (Wt%) Si0₂ 40-55 42-52

A1₂0₃ 20-45 32-42

Na₂0 0-5 0-3

K₂0 0-5 0-3

MgO 0-5 0-3 CaO 0-5 0-3

The portions of hard frit, flux frit, and clay utilized in enamels or glazes of the present invention are as follows:

Component Range (Wt%) Preferred Rancre (Wt%)

Hard frit 70-95 75-90 Flux frit 2-10 3-8

Clay 4-18 5-15 The hard frit, flux frit, and clay define or form the "solids portion" of the glaze or enamel. In addition to the "solids portion, " it would be appreciated that the glaze or enamel may_/ include other additives such as vehicles, flocculants, deflocculants, binders, wetting agents, antifoaming agents, dyes, and pigments.

The enamels or glazes are made according to the following technique. The glass frits (hard frit and flux frit) , in flake or granular form, and clay are ball-milled with water to an average particle size of about 5 to about 6 microns as measured on a Microtrac at the 50% level. The resulting slip, which comprises generally about 35% water, is screen printed, hand printed, sprayed, brushed, or otherwise applied on the ceramic body by methods known in the art, and then fired using conventional firing techniques. Of course, it will be appreciated that the amount of water utilized in the slip can be varied to best accommodate the application technique being utilized. Also, instead of water, other conventional vehicles may be employed. Firing times greatly depend on such factors as the previous firing history of the ceramic body, furnace conditions, and the size of the charge or load placed in the furnace. However, generally, the coated ceramic bodies are fired for a period of 4 to 12 hours.

Subsequent to firing, the "solids portion" of the glaze or enamel yields a coating composition comprising by weight from about 50% to about 66% Si0₂, from about 6% to about 12% B₂0₃, from about 10% to about 15% A1₂0₃, from about .25% to about 2.5% Li₂0, from about 2.5% to about 7% Na₂0, from about 2.5% to about 6.5% K₂0, from about 7% to about 9% CaO, and up to 4% Zr0₂. As with the hard glass frit, preferably the coating includes some Zr0₂; and a maximum of 3% by weight ZnO, preferably a maximum of 2.5% by weight ZnO, and more preferably a maximum of 2% by weight ZnO. Similarly, the coating contains a maximum of 2% by weight, and preferably a maximum of 1% by weight of each of W0₃, Bi₂0₃, and Mo0₃. More preferably, the coating contains substantially no W0₃, Bi₂0₃, and Mo0₃.

The glazes and enamels of the present invention exhibit excellent alkaline durability. Alkaline durability may be determined in various manners. One known method is to immerse pieces of ceramic that have been coated and fired with the glaze or enamel in a heated, stirred, alkaline, dishwasher detergent solution (e.g., a group 4 detergent such as British Calgonite) . The detergent solution is prepared by creating a .5% by weight concentration of Calgonite using deionized or distilled water. After the 32 hours of exposure, the samples are removed from the solution, dried, and then rubbed with a metal object such as a silver spoon. The following evaluation scale is utilized to evaluate the marked glass or enamel:

Definition Visual Appearance Feel "Drag" of Spoon

No marking No mark No

Very slightly marked Mark removed when rubbed No with dry cloth Slightly marked Mark removed with rubbed No with damp cloth

Marked Mark remains when rubbed No with damp cloth

Looks like a light pencil Mark remains when rubbed Yes line on paper with damp cloth

Glazes or enamels made in accordance with the principles of the present invention exhibit "No marking" or a "Very slightly marked" condition after 32 hours of exposure to the detergent solution.

By way of illustration and not by any limitation, the following examples will describe specific compositions within the scope of the present invention. Unless otherwise indicated, all parts and percentages are by weight, and all temperatures are in degrees Centigrade (°C) .

Example 1 ,::

A glaze composition is produced utilizing a hard glass frit indicated in Table I as Formulation A, a flux glass frit as indicated in Table II, and a clay as indicated in Table

III. The glass frits and clay are prepared as a slip by ball milling the glass frits and clay in- water until a particle size of about 3 microns- to about 4..microns, as determined by a Microtrac at a 50%„ level, is achieved. The slip comprises about 35% water. The slip is then applied by spraying to 6" conventional bone china bisque fired plates and then fired at

1100°C using a conventional 8 hour glost kiln cycle.

Example 2 A second glaze composition is prepared by using Formula

B in Table I, the flux -frit of Table II, and the clay of Table III, and by following the steps set forth in Example 1.

Example 3 A third glaze composition is prepared by using Formula C in Table I, the flux frit of Table II, and the clay of Table III, and by following the steps set forth in Example 1. Example 4 A fourth glaze composition is prepared by using Formula D in Table I, the flux frit of Table II, and the clay of Table III, and by following the steps set forth in Example 1.

Table I

Composition of Hard Frit - g, o bv Weiαht

Component Formula A* Formula B* Formula C*

Formula D*

Si0₂ 55.39 60.92 55.75 63.

B₂0₃ 11.65 11.81 11.75 6.3

A1₂0₃ 12.30 7.97 12.42 12.

Na₂0 4.86 6.38 2.81 4.2

K₂0 4.25 2.29 4.28 2.7

Li₂0 2.46 1.42 2.48 2.7

CaO 7.68 7.85 7.74 7.2

Zr0₂ 1.09 1.10 2.44 0

*substanti ally no ZnO, Bi₂0 >₃ , W0₃ , Mθ0₃ Table II

Composition of Flux Frit

Component g. by_ Weiαht

Si0₂ 46 .42

B₂0₃ 21 .49

A1₂0₃ 6. 79

Na₂0 10 .44 κ₂o 1. 12

MgO 0

CaO 13 .64 Table III Composition of Clay Component % by Weiαht

Si0₂ 47.50 A1₂0₃ 37.0

Na₂0 .08

K₂0 1.18

MgO .3

CaO .06 While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification.

Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims

In The Claims :

1. A lead-free composition for use in forming a coating on ceramic bodies comprising a hard glass frit, said hard glass frit comprising by weight percent from about 45% to about 70% Si0₂, from about 4% to about 15% B₂0₃, from about 4% to about 17% A1₂0₃, from about 1% to about 9% Na₂0, from about 1% to about 9% K₂0, from about .2% to about 5% Li₂0, from about .4% to about 12% CaO, from about .1% to about 7% Zr0₂, up to about 3% ZnO, up to about 2% W0₃, up to about 2% Bi₂0₃, and up to about 2% Mo0₃.

2. A lead-free composition as set forth in claim 1 wherein said hard glass frit comprises in weight percent from about 50% to about 65% weight percent Si0₂, from about 5% to about 14% B₂0₃, from about 5% to about 16% A1₂0₃, from about 1.5% to about 8% Na₂0, from about 1.5% to about 8% K₂0, from about .2% to about 5% Li₂0, from about 4% to about 12% CaO, from about .1% to about 6% Zr0₂, up to about 2.5% ZnO, up to about 1% W0₃, up to about 1% Bi₂0₃, and up to about 1% Mo0₃.

3. A lead-free composition as set forth in claim 2 wherein said hard glass frit comprises in weight percent up to about 2.0% ZnO, substantially no W0₃, substantially no Bi₂0₃, and substantially no Mo0₃.

4. A lead-free composition as set forth in claim 1 wherein said hard glass frit comprises in weight percent from about 52% to about 63% Si0₂, from about 6% to about 13% B₂0₃, from about 6% to about 15% A1₂0₃, from about 2% to about 7% Na₂0, from about 1.75% to about 7.5% K₂0, from about .4% to about 3.5% Li₂0, from about 5.5% to about 10% CaO, from about 1% to about 5.5% Zr0₂, up to about 2.0% ZnO, substantially no W0₃, substantially no Bi₂0₃, and substantially no Mo0₃.

5. A lead-free composition as set forth in claim 1 including a flux frit, said flux frit comprising in weight percent from about 40 to about 52% Si0₂, from about 17% to about 26% B₂0₃, from about 2% to about 10% A1₂0₃, from about 6% to about 14% Na₂0, from about .5% to about 3% K₂0, up to 3% MgO, and from about 8% to about 17% CaO.

6. A lead-free composition as set forth in claim 1 including a flux frit, said flux frit comprising in weight percent from about 42% to about 49% Si0₂, from about 18% to about 24% B₂0₃, from about 3% to about 9% A1₂0₃, from about 7% to about 13% Na₂0, from about .7% to about 1.8% K₂0, up to 2% MgO, and from about 9% to about 16% CaO.

7. A lead-free composition as set forth in claim 5 including a clay, said clay comprising in weight percent from about 40% to about 55% Si0₂, from about 20% to about 45% A1₂0₃, up to 5% each of Na₂0, K₂0, MgO and CaO.

8. A lead-free composition as set forth in claim 5 including a clay, said clay comprising in weight percent from about 42% to about 52% Si0₂, from about 32% to about 42% A1₂0₃, and up to 3% each of Na₂0, K₂0, MgO and CaO.

9. A lead-free composition as set forth in claim 7 wherein said composition includes a solids portion, said solids portion comprising in weight percent from about 70% to about 95% said hard frit, from about 2% to about 10% said flux frit, and from about 4% to about 18% said clay.

10. A lead-free composition as set forth in claim 7 wherein said composition includes a solids portion, said solids portion comprising in weight percent from about 75% to about 90% said hard frit, from about 3% to about 8% said flux frit, and from about 5% to about 15% said clay.

11. A method of producing a coated ceramic body comprising the steps of:

I. providing a coating composition comprising a vehicle, a clay and a hard glass frit, said hard glass frit comprising by weight percent from about 45% to about 70% Si0₂, from about 4% to about 15% B₂0₃, from about 4% to about 17% A1₂0₃, from about 1% to about 9%

Na₂0, from about 1% to about 9% K₂0, from about 2% to about 5% Li₂0, from about 4% to about 12% CaO, from about .1% to about 5% Zr0₂, up to about 3% ZnO, up to about 2% W0₃, up to about 2% Bi₂0₃, and up to about 2% Mθ0₃;

II. providing a ceramic body having an outer surface;

III. applying such coating composition to such outer surface of such ceramic body; and IV. firing such coated ceramic body of said step

III.

12. A method of producing a coated ceramic body as set forth in claim 11 wherein such coating composition includes a flux frit, and such coating composition comprises from about 2% to about 10% by weight such flux frit, from about 70% to about 95% by weight such hard glass frit, and from about 4% to about 18% by weight such clay.

13. A method of producing a coated ceramic body as set forth in claim 13 wherein such flux frit comprises in weight percent from about 40-52% Si0₂, from about 17% to about 26% B₂0₃, from about 2% to about 10% A1₂0₃, from about 6% to about 14% Na₂0, from about .5% to about 3% K₂0, up to 3% MgO, and from about 8% to about 17% CaO.

14. A method of producing a coated ceramic body as set forth in claim 12 wherein such flux frit comprises in weight percent from about 42% to about 49% Si0₂, from about 18% to about 24% B₂0₃, from about 3% to about 9% A1₂0₃, from about 7% to about 13% Na₂0, from about .7% to about 1.8% K₂0, up to 2% MgO, and from about 9% to about 16% CaO.

15. A method of producing a coated ceramic body as set forth in claim 11 wherein such clay comprises in weight percent from about 40% to about 55% Si0₂, from about 20% to about 45% A1₂0₃, and up to 5% each of Na₂0, K₂0, MgO and CaO.

16. A method of producing a coated ceramic body as set forth in claim 11 wherein such clay comprises in weight percent from about 42% to about 52% Si0₂, from about 32% to about 42% A1₂0₃, and up to 3% each of Na₂0, K₂0, MgO and CaO.

17. A method of producing a coated ceramic body as set forth in claim 11 wherein such hard glass frit comprises in weight percent from about 50% to about 65% weight percent Si0₂, from about 5% to about 14% B₂0₃, from about 5% to about 16% A1₂0₃, from about 1.5% to about 8% Na₂0, from about 1.5% to about 8% K₂0, from about .2% to about 5% Li₂0, from about 4% to about 12% CaO, from about .1% to about 6% Zr0₂, up to about 2.5% ZnO, up to about 1% W0₃, up to about 1% Bi₂0₃, and up to about 1% Mo0₃.

18. A method of producing a coated ceramic body as set forth in claim 11 wherein such ceramic body comprises bone china.

19. A coated ceramic body comprising a ceramic body having a coating, said coating having been formed by firing a composition comprising a hard frit, a flux frit, and a clay, said coating comprising in weight percent from about 50% to about 66% Si0₂, from about 6% to about 12% B₂0₃, from about 10% to about 15% A1₂0₃, from about .25% to about 2.5% Li₂0, from about 2.5% to about 7% Na₂0, from about 2.5% to about 6.5% K₂0, from about 7% to about 9% CaO, up to about 4% Zr0₂, up to about 2% ZnO, and substantially no W0₃, Bi₂0₃ and Mo0₃.

20. A coated ceramic body as set forth in claim 19 wherein said ceramic body comprises bone china.