NL194123C - Glass composition, free of lead and cadmium, for glazing, enamelling and decorating and its application. Method for glazing, enamelling and decorating a support material with a glass composition free of lead and cadmium. - Google Patents

Glass composition, free of lead and cadmium, for glazing, enamelling and decorating and its application. Method for glazing, enamelling and decorating a support material with a glass composition free of lead and cadmium. Download PDF

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Publication number
NL194123C
NL194123C NL9202217A NL9202217A NL194123C NL 194123 C NL194123 C NL 194123C NL 9202217 A NL9202217 A NL 9202217A NL 9202217 A NL9202217 A NL 9202217A NL 194123 C NL194123 C NL 194123C
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Netherlands
Prior art keywords
glass
glass composition
compositions
cadmium
lead
Prior art date
Application number
NL9202217A
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Dutch (nl)
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NL9202217A (en
NL194123B (en
Inventor
Werner Dr Kiefer
Erich Dr Rodek
Friedrich Dr Siebers
Original Assignee
Schott Glaswerke
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Publication date
Priority to DE4201286 priority Critical
Priority to DE19924201286 priority patent/DE4201286C2/en
Application filed by Schott Glaswerke filed Critical Schott Glaswerke
Publication of NL9202217A publication Critical patent/NL9202217A/en
Publication of NL194123B publication Critical patent/NL194123B/en
Application granted granted Critical
Publication of NL194123C publication Critical patent/NL194123C/en

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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02Frit compositions, i.e. in a powdered or comminuted form

Description

* 1 194123
Method for glazing, enamelling and decorating a support material with a glass composition free of lead and cadmium
The invention relates to a method for glazing, enamelling and decorating a carrier material, in which a lead and cadmium-free glass composition containing at least Li 2 O, CaO, B 2 O 3, Al 2 O 3, Na 2 O, K 2 O, and SiO 2 is used.
Such a method is known from Chemical Abstracts, Vol. 110, No. 6, 100422X (1989), p. 329. According to this document, a lead-free glass composition consisting of 25 wt% SiO 2, 19 wt% Na 2, 5 wt% K 2 O, 9 wt% Al 2 O 3, 33 wt% B 2 O 3, 3 wt% CaO and 5 wt% U 2 O as a glaze applied to an iron plate. Iron, however, has a coefficient of thermal expansion of more than 5.0 x 10 / K.
Therefore, this Chemical Abstract describes applying a glaze to a support material with a coefficient of thermal expansion of more than 5.0 x 10 / K, such as borosilicate glasses as well as glass-ceramic objects.
According to the present invention it has now been found that certain specific glass compositions are very suitable for glazing objects with a coefficient of thermal expansion of less than 5.0 x 10 / K, such as borosilicate glasses as well as glass ceramic objects.
The invention therefore relates to a method of the type described above, characterized in that the carrier material has a coefficient of thermal expansion of less than 5.0 10 / K and the glass composition from the components: 20 U20 0-12 wt.%
CaO 3-18 wt% B203 5-25 wt%
Al2 O3 3-18 wt%
Na20 3-18 wt% 25 KgO 3-18 wt%
SiO 2 25-55% by weight, and optionally also the components
MgO 0-10 wt%
BaO 0-12 wt% 30 TiO2 0-5 wt%
ZrO 2 contains 0- <3 wt% and up to 30 wt% of a stoving temperature resistant pigment
In the method according to the present invention glass compositions are used which are free of lead, cadmium and other toxicologically objectionable components, which meet high requirements, so that in particular in a wide and relatively low temperature range, they can be processed without any problems and, moreover, glazes resp. Enamels provide very good properties for adhesion strength, thermal resistance, resistance to temperature change, resistance to abrasion and noticeable wear behavior, 40 stain sensitivity to contamination, and resistance to wear for technical and domestic use. chemical resistance to acids and bases.
Furthermore, the method according to the invention has proven to be particularly suitable for the glaze and / or glaze. enamel decoration of borosilicate glasses and in particular of glass-ceramic objects with low heat expansion on the basis of β-eukryptite or h-quartz mixed crystals, which are manufactured from a suitable starting glass by heat treatment, so-called ceramicization. Such glass ceramic 45 objects are distinguished by a heat expansion of 0 ± 1χ10 · ® / Κ in the temperature range between 20 and 700 ° C.
The following is noted with regard to the further prior art.
East German patent specification 257,355 describes a glass layer which itself consists of a bottom layer and a top layer with different compositions. This glass layer is applied to thermocouples 50 of sintered corundum, steatite or platinum.
These latter materials, however, have coefficients of thermal expansion of 7x10 / e / K, 6-9x1 / 2 / K and 9χ10 / Κ / respectievelijk, respectively. Moreover, the glass compositions used according to this patent - i.e. for the top or bottom layer - differ from the glass compositions used according to the present application.
55 European patent application 0,018,559 describes a glass composition which is applied to an iron oxide-containing support material. However, this support material has a coefficient of thermal expansion that is higher than Sx10 / K. Also, the glass composition used is again different from the 194123 2 glass composition used according to the present application.
Austrian Patent 324,925 discloses a method of glazing ceramic materials using such a glass composition for glazing that the resulting glazing layer has a coefficient of thermal expansion of less than 10 × 10 / K.
However, this literature teaches that the amount of Al2O3 is essential for obtaining a sufficiently low heat expansion: with Al2O3 amounts below 17% by weight, the heat expansion of the enamel layer would become too high and therefore unsuitable for ceramics with also low to glaze expansion coefficients.
According to a preferred embodiment, the glass compositions used according to the present application have transition temperatures of 300-510 ° C, softening temperatures of 400-610 ° C and processing temperatures of 430-840 ° C.
Furthermore, the glazes formed from the glass compositions used according to the application have, according to a preferred embodiment, thermal expansion coefficients of 9.20 to 16.40 x 10 "/ K.
A glass composition used in the method according to the application according to a preferred embodiment consists of the components: U20 4-10 wt.%
MgO 0-8 wt%
CaO 5-15 wt% 20 B203 10-20 wt%
Al2 O3 5-15 wt%
NagO 5-15 wt% K20 5-15 wt%
BaO 0-10 wt% 25 SiO 2 30-50 wt%
TiO2 0-5 wt%
Zr02 0- <3 wt%
The process of the application is particularly suitable for use in glazing, enamelling and decorating glass objects with low heat expansion, and in particular in borosilicate glass or glass ceramic objects.
According to a preferred embodiment, the carrier material therefore consists of borosilicate glasses or glass ceramic objects.
An important area of application of such glasses, respectively. glass ceramic objects are temperature-resistant laboratory equipment, cooking vessels or, in particular, heatable plates, such as, for example, hobs.
Glazes are low-melting glasses, which protect, improve and / or modify the physical or chemical surface properties, embedding, for example in electronics, or only for decorating and decorating a wide variety of objects from glass, 40 glass ceramic, ceramic or porcelain.
Glazes usually consist of a transparent or translucent glass composition, which are applied to the article according to known techniques, such as, for example, screen printing or application with a brush in finely divided form, of a paste. The finely ground glass powder is often referred to as frit.
Enamels are enamels containing coloring constituents such as pigments, the portion of pigment in the enamel being up to 30% by weight.
Pigments are usually enamel-resistant oxides which, depending on their selection, produce the desired color impression.
The glaze or enamel are fired at temperatures below the softening point of the molded article to be treated, the glaze composition or glaze used, respectively. the enamel melts and stably binds to the surface of the molded article.
Burning also serves to volatilize organic carrier materials, which are auxiliary agents for applying the glaze or. the enamel can be applied.
In order to ensure sufficient and long-term adhesion of the enamel or enamel after firing and subsequent application in practice, in particular, according to the theoretical considerations hitherto prevailing, the thermal expansion coefficients of the object to be decorated and that of the enamel whether the enamel is carefully coordinated.
* 3 194123
So far, problems have been encountered with the glaze resp. enamel decoration of borosilicate glasses and in particular of glass-ceramic objects with low heat expansion based on β-eukryptite or h-quartz mixed crystals, which are produced by a suitable starting glass by heat treatment, so-called ceramicization. Such glass ceramic objects are distinguished by a thermal expansion of Otlx 10 / K in the temperature range between 20 and 700 ° C.
Taking into account the thermal resistance of these types of glass, the decoration with glaze resp. enamel at temperatures below 1000 ° C.
With the glass ceramic, the burn-in of the glaze resp. the enamel is preferably carried out simultaneously, so-called direct burn-in, together with the ceramicization process.
The glazes and enamels used hitherto for the coating and / or for the decoration of glasses with low coefficients of thermal expansion and glass-ceramic objects usually still contain lead and often even cadmium.
The reason for the application of lead and cadmium in glazes is their positive effect on the melting properties, a marked reduction in the melting temperature with simultaneously optimal viscosity behavior of the glaze, respectively. the enamel.
In addition, these glazes show resp. Enamels, after direct firing, have excellent adhesion resistance to the support material and are sufficiently resistant to long-term application times in practice.
This is all the more surprising since, contrary to the theoretical requirement of approximately equal coefficients of thermal expansion between support material and glaze, respectively. enamel these lead and cadmium containing glass compositions have high heat expansions from δχΙΟ ^ / Κ to even 10x10 "/ K.
The reason why these high heat-expanding glass compositions adhere sufficiently to carrier materials, which have virtually no heat expansion, such as, for example, glass ceramic, is, in so far as this phenomenon has been understood heretofore, also attributed to the additives of lead and optionally cadmium.
However, unfavorable toxicological effects of these substances on humans and the environment have meanwhile led to a partial or total prohibition of such lead or cadmium compounds in decor coatings.
. Glazes and enamels can be prepared with the glass compositions according to the invention, which meet the high requirements of practice without the use of toxic or environmentally relevant materials.
It has been found that these compositions according to the invention also possess all desirable properties without additives of lead, cadmium, zinc, tin and fluorine compounds.
It is presumed that the CaO content which is clearly above the prior art in connection with the choice according to the invention and the amount of the other components used leads to an intensive and positive interaction between the carrier glass and the glaze, respectively. the enamel during burn-in leads, and thereby to a tension-free and tightly adhering connection for a sufficiently long time in the practical application.
With the glass composition according to the invention, excellent bonding strengths of the glazes formed therefrom were found after burning, after quenching tests and during a long operation at 670 ° C. Even at greater enamel coating thicknesses, for example up to 9 µm, there were no jumps or flaking tendencies of the carrier glass; and that also with an extreme load of temperature changes over a fairly long period of time. The thermal resistance of the compositions is good and shows practically no color change even after 75 hours at 670 ° C.
With good resistance to chemicals, acids and alkalis, the glass compositions according to the invention have a high gloss, low wear and practically no conspicuous wear against wear during both grid and all-over application.
Glazes according to the composition of the invention can also be mixed with pigments up to 30% by weight at any time without problems and then used for the preparation of colored coatings 50 and / or decors. The pigments used here are conventional oxidic materials which are resistant to the glass composition at the burn-in temperature.
However, the glaze can also be colored per se, for example by the targeted addition of coloring oxides.
The composition of the glazing glass is first homogeneously melted, and a glass powder having a grain size of <10 µm, preferably 1-3 µm, is then produced from the forming glass 55 by grinding, in particular wet grinding.
This powder is then adapted with a standard screen printing oil, for example on the basis of fir oil, and applied according to generally known techniques, for example by screen printing, using a print image or brush.
After firing on a glass with low heat expansion or a glass-ceramic object, glaze layers are obtained, the thickness of which is between 2 and 9 µm. Despite the very large differences in the heat expansion between glaze and / or glaze, these layers have enamel and the carrier glass have excellent adhesion and resistance to temperature changes.
In a preferred embodiment, Li20 of the order of 4-10% by weight is added to the glass composition according to the invention and the content of CaO is increased.
Both measures clearly improve the meltability of the glass composition, completely overcompensating the increased content of CaO, the deteriorating chemical resistance due to the addition of LiO2.
Further embodiments, which are preferred, also contain, for example, according to the later application purpose, for example 8-10 wt.% BaO and / or, for example, 6-10 wt.% MgO.
Depending on the use of the glass composition, the addition to the optional oxides proves advantageous, with higher U20 content generally resulting in a reduction in the firing temperature.
BaO can serve as a substitute for CaO up to a certain level, but usually causes an increase in the burn-in temperature and heat expansion.
Additives of TiO2 improve acid resistance, while ZrO2 can further improve alkali resistance.
The invention is illustrated by the following examples.
Table A contains the composition of Examples I-XVII of the glazes of the invention in weight percent on an oxide basis:
25 TABLE A
Nr. I II III IV V VI
Li20 10.0 4.0 10.0 4.0 4.0 4.0 30 B203 10.0 20.0 12.0 10.0 10.0 10.0
Naj, 0 5.0 15.0 5.0 5.0 15.0 5.0
MgO 0.0 0.0 8.0 6.0 0.0 8.0
Al2 O3 5.0 5.0 15.0 15.0 15.0 5.0
SiO 2 50.0 30.0 30.0 30.0 46.0 48.0 35 KjjO 5.0 15.0 5.0 15.0 5.0 15.0
CaO 5.0 11.0 15.0 5.0 5.0 5.0
BaO 10.0 0.0 0.0 10.0 0.0 0.0
40 No. Skin VIII IX X XI XII
U20 4.0 10.0 4.0 10.0 10.0 10.0 B203 10.0 20.0 20.0 20.0 20.0 10.0
Na20 15.0 15.0 5.0 5.0 5.0 5.0 45 MgO 8.0 8.0 0.0 0.0 8.0 0.0
Al2 O3 5.0 7.0 5.0 15.0 5.0 15.0
SiO 2 30.0 30.0 46.0 30.0 32.0 30.0
KjO 5.0 5.0 5.0 5.0 15.0 15.0
CaO 13.0 5.0 15.0 5.0 5.0 15.0 50 BaO 10.0 0.0 0.0 10.0 0.0 0.0

Claims (5)

    5 U20 4.0 10.0 10.0 9.4 6.4 B203 20.0 10.0 11.3 10.0 10.0 Na20 5.0 15.0 6.8 5.0 7.6 MgO 6.0 0.0 0.0 0.0 3.3 Al203 5.0 5.0 12.8 11.4 7.6 10 SiO2 30.0 30.0 49.1 41.7 45.1 K20 5 .0 15.0 5.0 5.0 5.0 CaO 15.0 5.0 5.0 15.0 5.0 BaO 10.0 10.0 0.0 2.5 10.0 15 Table B shows for the compositions I-XVII from table A the transition temperature (Tg) in ° C, the softening temperature (EW) in ° C, the processing temperature (VA) in ° C, as well as the coefficients of thermal expansion (CTE) between 20 and 300 ° C in 10 / K. 20 TABLE B No. Tg EW VA CTE I 454 567 690 10.18 25.ii 374 469 596 14.49 III 433 533 840 11.41 IV 382 495 830 12.38 V 444 557 750 11.50 VI 447 568 756 10.98 30 VII 374 490 700 13.62 VIII 365 447 597 13.65 IX 511 610 765 9.20 X 422 513 639 10.83 XI 378 456 630 13.13 35 XII 385 515 755 12.60 XIII 466 567 689 10.51 XIV 300 400 430 16.40 XV 435 537 780 11.02 XVI 432 531 750 11.48 40 XVII 436 543 705 11.14 Examples of the presently preferred examples of the invention are the compositions I, XI , XV, XVI and XVII, with transition temperatures in the range of 380 to 450 ° C, 45 softening temperatures in the range of 460-570 ° C, processing temperatures of 630-780 ° C and heat expansion coefficients from 10.18 to 13.13x1 O ^ / K. These compositions also exhibit very good bonding strengths, a high thermal and chemical resistance and excellent utilization properties in the course of tests carried out according to conventional and known standard methods, as well as in long-term tests. 50
  1. A method of glazing, enamelling and decorating a support material using a lead and 55 cadmium-free glass composition containing at least Li 2 O, CaO, B 2 O 3, Al 2 O 3, Na 2 O, 10 O, and SiO 2, characterized in that: that the support material has a coefficient of thermal expansion of less than 5.0 10 K and the glass composition of the components: 194 123 6 U 2 O 0-12 wt% CaO 3-18 wt% B 2 O 3 5-25 wt%
    5 Al 2 O 3 3-18 wt.% NagO 3-18 wt.% K 2 O 3-18 wt.% SiO 2 25-55 wt.%, And optionally also the components 10 MgO 0-10 wt.% BaO 0-12 wt. % TiO 2 0-5 wt% ZrO 2 0- <3 wt% and contains up to 30 wt% of a stoving temperature resistant pigment.
  2. Method according to claim 1, characterized in that the glass compositions have transition temperatures of 300-510 ° C, softening temperatures of 400-610 ° C and processing temperatures of 430-840 ° C.
  3. Method according to claim 1 or 2, characterized in that the glazes formed from the glass compositions have coefficients of thermal expansion of 9.20 to 16.40 x 10 / K.
  4. Method according to one or more of the preceding claims, characterized in that the glass composition consists of the components: Li 2 O 4-10 wt.% MgO 0-8 wt.% CaO 5-15 wt.%
    25 B203 10-20 wt% Al203 5-15 wt% NagO 5-15 wt% KgO 5-15 wt% BaO 0-10 wt%
    30 SiO 2 30-50 wt% TiO 2 0-5 wt% ZrO 2 0- <3 wt% exists.
  5. Method according to one or more of the preceding claims, characterized in that the support material 35 consists of borosilicate glasses or glass ceramic objects.
NL9202217A 1992-01-20 1992-12-21 Glass composition, free of lead and cadmium, for glazing, enamelling and decorating and its application. Method for glazing, enamelling and decorating a support material with a glass composition free of lead and cadmium. NL194123C (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE4201286 1992-01-20
DE19924201286 DE4201286C2 (en) 1992-01-20 1992-01-20 Use of lead and cadmium-free glass compositions for glazing, enameling and decorating and their composition

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NL9202217A NL9202217A (en) 1993-08-16
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NL194123C true NL194123C (en) 2001-07-03

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JP (1) JPH05270860A (en)
DE (1) DE4201286C2 (en)
FR (1) FR2686333B1 (en)
GB (1) GB2263478B (en)
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JPH05270860A (en) 1993-10-19
GB2263478B (en) 1995-06-07
FR2686333A1 (en) 1993-07-23
FR2686333B1 (en) 1995-02-17
GB9300476D0 (en) 1993-03-03
DE4201286C2 (en) 1994-11-24
NL9202217A (en) 1993-08-16
GB2263478A (en) 1993-07-28
NL194123B (en) 2001-03-01
DE4201286A1 (en) 1993-07-22

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