CN101734858A - Lead and cadmium-free glass composite for coating porcelain glaze and enamel on and decorating glass or glass ceramics - Google Patents
Lead and cadmium-free glass composite for coating porcelain glaze and enamel on and decorating glass or glass ceramics Download PDFInfo
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- CN101734858A CN101734858A CN200810174455A CN200810174455A CN101734858A CN 101734858 A CN101734858 A CN 101734858A CN 200810174455 A CN200810174455 A CN 200810174455A CN 200810174455 A CN200810174455 A CN 200810174455A CN 101734858 A CN101734858 A CN 101734858A
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Abstract
The invention relates to lead and cadmium-free glass composite for coating porcelain glaze and enamel on and decorating glass or glass ceramics. Particularly, the invention relates to lead and cadmium-free glass for coating porcelain glaze and enamel on and decorating glass or glass ceramics, which takes high-quartz mixed crystal and/or keatite mixed crystal as a main crystal phase after crystallization, has low-heat expansion which is less than 2X10-6 at the temperature of between 20 and 700 DEG C, and comprises the following components in percentage by weight: 0 to 5 percent of LiO2, 0 to 5 percent of Na2O, 0 to 2 percent of K2O, 1 to 1 percent of sigma Li2O+Na2O+K2O, 0 to 3 percent of MgO, 0 to 4 percent of CaO, 0 to 4 percent of SrO, 0 to 4 percent of BaO, 0 to 4 percent of ZnO, 15 to 27 percent of B2O3, 10 to 20 percent of Al2O3, 43 to 58 percent of SiO2, 0 to 3 percent of TiO2, 0 to 4 percent of ZrO2, 0 to 2 percent of Sb2O3, 0 to 3 percent of F which is used for replacing oxygen, and at most 30 percent of dye which is stabilized at the sintering temperature.
Description
Technical field
The present invention relates to glass or glass-ceramic are coated with glass composition with enamel, enamel and the not leaded and cadmium decorated, it contains high quartzy (Hochquarz) mixed crystal and/or keatite (Keatit-mischkristalle) mixed crystal as principal crystalline phase after crystallization, also relate to the method that is used to make the glass-ceramic that is equipped with this glass composition.
Background technology
Conventional glass-ceramic contains high quartzy mixed crystal and/or keatite mixed crystal as principal crystalline phase, and it is responsible for low thermal expansivity.Different with grain-size according to crystalline phase, these glass-ceramic can be transparent, translucent or opaque form existence.Come to be undertaken painted according to required application difference by colored oxide.The laboratory equipment that these main application fields with glass-ceramic of low-thermal-expansion are heatproof degree alternations, cooking utensil (Kochgeschirre) but, fireproof glass, fireplace viewing window and particularly hot-plate, for example cooking surface
The decorative coat material is classified as " enamel (Glasur) " or " enamel (Email) " usually.Enamel is formed by clarification or through painted glass (glass substance (Glasflu β)) usually, and enamel is the coating material that contains opaque coloured material (for example pigment).Can use colored mineral compound as pigment.Pigment must not be corroded by glass substance or only be corroded a little usually.
Enamel and enamel also are used for applying and the ornamenting glass-ceramic.The big area coating is generally used for protecting, covering or is used to realize required outward appearance.Decoration is used for mark (Beschriftung), is used to realize required design or bears a certain technical functionality, for example under the situation of display window (Display-Fenstern) or sign cooking area.
Enamel or enamel is at the temperature of the softening temperature that is lower than object to be coated fired (einbrennen), wherein each the glass composition fusion of enamel or enamelled and with the body surface stable bond.Firing temperature is usually less than the softening temperature of object to be coated, thereby uncontrollable distortion can not occur.Fire the volatilization that also is used for organic additive (for example conduct is in order to apply enamel or enamelled suspension agent).
Applying thermal expansivity is about 4 * 10
-6Under the glass-ceramic of/K or bigger scope or the situation of glass, can seek enamel or enamel with matched coefficient of thermal expansion.Wherein be described upholstery cover according to what prior art strove realizing
Have the thermal expansivity lower slightly than object to be coated.To guarantee thus to produce stress under compression (Druckspannung) in the cooling after firing of enamel or enamel, and the performance of base material not brought adverse influence, particularly reduced intensity thus.Under the situation of coefficient of thermal expansion mismatch, between upholstery cover and base material, produce stress during cooling, produce minute crack or crackle thus, it may extend in base material.The stress that causes owing to mismatch makes the adhesivity variation.Under bigger mismatch situation, upholstery cover may be immediately or passage in time during use and peeling off from base material.
Up to now, still have problems when the low thermal expansion glass pottery of decorating with enamel or enamel based on high quartzy (Hochquarz) or keatite mixed crystal, described glass-ceramic is to prepare by the suitable initial glass of thermal treatment (so-called potteryization).Such glass-ceramic is characterised in that in 20-700 ℃ of temperature range less than 2 * 10
-6The thermal expansion of/K.Consider the softening temperature and the thermotolerance of this glass-ceramic, described decoration carries out in the temperature that is lower than 1200 ℃ usually.Under described glass-ceramic situation, enamel or enamelled are fired preferably and are implemented during the pottery process, also are about to upholstery cover and are applied to living glass
Last and fired during potteryization.For this glass-ceramic, still can not provide the upholstery cover that to produce economically so far with matched coefficients of thermal expansion with low thermal coefficient of expansion.People seek to solve this mismatch problems with different approaches, to avoid described major defect occurring when realizing desired properties.
The stress that is produced in the time of for example can being reduced in coefficient of thermal expansion mismatch by the upholstery cover that applies low bed thickness.But this means that color effects (Farbwirkung) (opacifying power (Deckkraft), color sensation) and protection effect also can be subjected to remarkable restriction.
So far, usually contain lead and also contain cadmium sometimes in order to cover and/or decorate employed enamel of the glass-ceramic with low thermal coefficient of expansion and enamel.Except the very favorable effect aspect the reduction firing temperature, use lead and cadmium also to make it possible to realize adhering to good upholstery cover, even thermal expansivity is 5 * 10
-6/ K up in addition 10 * 10
-6The size of/K.Do not bring infringement ground to allow that the reason of the mismatch between upholstery cover and the glass-ceramic base material is the plasticity of leaded flux.Also help through the intensity of the glass-ceramic of decoration and the chemoresistance of bronsted lowry acids and bases bronsted lowry a little less than giving the relative good opposing of glass substance (Glasflu β) by additive plumbous and that cadmium is formed, for example in family or industry, be used as those that exist in those or the food of sanitising agent with enamel.
Has these favourable character although contain lead finish, because the disadvantageous toxicology character enamel and the enamel now of plumbous and cadmium does not allow to contain these elements again.Therefore, proposed various approach in the literature and had the glass-ceramic of low-thermal-expansion under the situation of the compound that does not use leaded or cadmium, to apply.
In German DE 4241411A1, attempt to be chemically by being added on that inert, optics are inactive, the inorganic, elastic material solves the mismatch problems between glass-ceramic base material and the ornament layer.Such additive for example is made up of mica sheet, and it gives upholstery cover certain plasticity.Can realize firm and attrition resistant upholstery cover by this additive.Shortcoming is this upholstery cover preparation complexity and does not always desirably influence the color harmony reflection of coating.
Be used for thermal expansion is lower than 5.0 * 10 by known not leaded and glass composition cadmium of German DE 4201286C2
-6The glass of/K and glass-ceramic are coated with enamel and enamelled purposes.Described composition contains Li
2O 0-12 weight %, MgO 0-10 weight %, CaO 3-18 weight %, B
2O
35-25 weight %, Al
2O
33-18 weight %, Na
2O 3-18 weight %, K
2O 3-18 weight %, BaO 0-12 weight %, SiO
225-55 weight %, TiO
20-5 weight % and ZrO
20-＜3 weight %.High relatively alkali and alkaline earth content (K particularly here
2O and CaO) make it possible to realize having the upholstery cover of excellent adhesion.High alkali and alkaline earth content are unfavorable for to the antacid chemical resistance with through the intensity of ambetti pottery.
US-PS 5326728 claimed a kind of lead-less glasses materials (Fritte), it contains SiO
235-50 weight %, B
2O
323-30 weight %, Al
2O
310-22 weight %, Li
2O 1-3 weight %, Na
2O0-3 weight %, K
2O 2-5 weight %, CaO 1-5 weight %, TiO
20-2 weight % and ZrO
20-5 weight %, wherein Li
2O+Na
2O+K
2The O sum is less than 8 weight %, and the CaO+MgO+ZnO+BaO+SrO sum is less than 7 weight %.Under the situation of said composition, need to add K equally
2Even O and CaO are to realize the enough adhesions in the mismatch situation.Yet said composition still often can not satisfy at acid resistance and the high request through proposing aspect the intensity of ambetti pottery.
Summary of the invention
Therefore, task of the present invention is to be provided for glass or glass-ceramic are coated with glass composition with enamel, enamel or the not leaded and cadmium decorated, and it contains high quartzy mixed crystal or keatite mixed crystal as principal crystalline phase, and has less than 2 * 10
-6The low-thermal-expansion of/K, said composition satisfy all above-mentioned requirements.Especially, described glass composition should be in low processing with relative wide temperature range without a doubt, such enamel or enamel is provided in addition, and it demonstrates with regard to adhesion strength, the chemoresistance to bronsted lowry acids and bases bronsted lowry, gloss, wear resistance, the extraordinary performance in resistant spot (Fleckunempfindlichkeit) aspect for industry and family field use.In addition, the glass-ceramic of decorating with this glass composition should have high strength.
Task of the present invention solves by the described glass composition of claim 1.
Show that with regard to adhesion strength, chemoresistance and intensity, composition of the present invention has reached the performance that contains PbO and CdO glass composition.In addition, with regard to lower to regard to the stain susceptibility of dirt itself in addition have advantage.In glass composition of the present invention, will be in order to the component that reduces viscosity (for example alkali (Alkali), B
2O
3And optional alkaline earth (Erdalkali), ZnO and F) combine with the oxide compound that participates in the structure glass network with relative narrow limit value, described oxide compound is SiO particularly
2, Al
2O
3, randomly have a spot of TiO
2, ZrO
2, La
2O
3, SnO
2, Bi
2O
3Or P
2O
5
Alkali Li
2O, Na
2O and K
2The summation of O should be 1-10 weight %.In order to reach required sintering temperature and low, must add alkali.Except reducing the viscosity effect, alkali also is responsible for the gloss of the ornament layer that applied to a great extent.Higher alkali content makes the acid resistance variation of institute's applied layer.Higher alkali content also brings negative impact to the intensity of coated glass-ceramic.Li
2O content and Na
2O content all is limited in 5 weight %.K
2O content allows for 2 weight % at most.K
2O is favourable for the adhesion strength of the ornament layer that is applied, but relatively poor for the effect that reduces viscosity.Higher K
2O content has very special adverse influence to the intensity of decorated glass-ceramic.Preferably, Li
2O content is 1-4 weight %, Na
2O content is 0-3 weight %, and alkali content is 2-7 weight %.
B
2O
3Content is 15-27 weight %.For the stabilization glass melt to avoid the unacceptable glass that takes off, need B
2O
3Additive.B
2O
3Reduced the viscosity of glass and made it possible to and fired in the temperature that reduces.In addition, B
2O
3Help gloss.At the higher B that is higher than 27 weight %
2O
3Under the content situation, the acid resistance variation of coating.The lower aq that is lower than 15 weight % causes the viscosity performance deficiency.B by 15-23 weight %
2O
3The glass composition of content has obtained particularly advantageous performance.
SiO
2And Al
2O
3It is the main component of glass of the present invention.SiO
2As network former stability, chemoresistance and intensity are responsible for.SiO
2Content is 43-58 weight %.Higher SiO
2Content is disadvantageous, because it plays the effect of rising viscosity and stops the smooth flow of coating when firing.When being lower than 43 weight %, the acid resistance of glass composition is low excessively.Preferably, described SiO
2Content is 48-57 weight %.SiO
2Help intensity through the ambetti pottery.Al
2O
3Content is 10-20 weight %.Al
2O
3Promote the stability of glass and the wear resistance and the intensity of the glass-ceramic of improvement through decorating.Yet the content that is higher than 20 weight % can not have been improved viscosity with allowing and made the gloss variation.Different therewith is to be lower than the intensity level deficiency of the content of 10 weight %.Al with 14-19 weight %
2O
3The glass composition of content obtains particularly advantageous performance.
Auxilliary viscosity is reduced of alkaline earth additive helps out.Gloss and adhesion strength also improve.Allow the CaO of the MgO of maximum 3 weight %, maximum 4 weight % and SrO and the BaO of maximum each 4 weight % as additive.If surpass the given upper limit, acid resistance and intensity are with unallowed mode variation so.In a preferred form, the summation of alkaline earth is 1-9 weight %.
In order to improve viscosity behavior and abradability, described glass composition can contain the ZnO of maximum 4 weight %.Yet too high ZnO content causes the intensity variation.
Be no more than the Sb of 2 weight %
2O
3Additive allows that it promotes the adhesion strength of upholstery cover.Higher content is not desirable and cause the acid resistance variation on toxicology.
In order to improve acid resistance, described glass can also contain the TiO of 0-3 weight %
2Higher TiO
2The stability of content harm glass.ZrO
2Can be to be no more than 4 weight %, the amount that preferably is no more than 3 weight % is present in the glass.ZrO
2Additive promotes the intensity to the chemoresistance of alkali and the glass-ceramic through decorating.Higher content causes the wear resistance variation and endangers the stability that glass is taken off in the glass opposing.
In addition, glass can contain fluoride additive with the degree that is no more than 3 weight %, preferably is no more than 2 weight %.Fluoride additive has reduced viscosity and has reduced firing temperature thus.Fluorion has been replaced the oxygen anion of respective amount in the glass structure.Yet higher content makes the acid resistance variation of glass.As other additive, can contain Bi in the glass
2O
3, La
2O
3, SnO
2And P
2O
5The maximum of each oxide compound should not surpass 3 weight %.But if use multiple such oxide compound together, so described oxide content sum should not surpass 5 weight %.SnO
2Additive has improved chemoresistance, but causes viscosity to increase.La
2O
3, Bi
2O
3And P
2O
5Improved melting, but glass stability and chemoresistance are taken off in the harm of higher content.
The glass powder of the glass of composition of the present invention can mix without a doubt being no more than the pigment of 30% pigment content, thereby is used to prepare coloured coating, enamel and/or decoration.Can use in the firing temperature conventional inorganic materials basicly stable as pigment with respect to glass composition.But the coloring oxide that is dissolved in glass by interpolation itself on purpose also can change the color of enamel.
Glass of the present invention is at first through even fusion and form glass thus and by grinding preparation intermediate value (mittler) granularity less than 10 μ m, preferably less than the glass powder of 5 μ m.Then, set out, randomly after adding corresponding pigments, it is coated on the glass-ceramic to be decorated by the glass powder of preparation like this.In coating, use for example dip-coating of known technological method, spraying, silk screen printing etc. usually.Described processing is carried out adding under conventional organic additive and/or the suitable suspension agent condition.For example when silk screen printing, this powder is mixed with silk screen printing oil, described lotion is directly applying or is applying according to transfer printing (Abziehbildverfahren) (indirect screen printing) in the silk screen printing then through three roller rubber mixing machine (Dreiwalzenstuhl) homogenizes.Alternatively, allow under heat effect to silk screen printing mixture heat plasticity auxiliary agent.Fire the back and on glass-ceramic to be decorated, obtain the layer that thickness is generally 2-9 μ m.Glass-ceramic to be coated preferably exists with the glass initial state.Firing preferably of enamel or enamel layer carried out in the pottery process.The composition of glass-ceramic to be coated and potteryization process prescription are at document for example among the EP 220333B1.As principal crystalline phase, pottery does not divide not in the temperature range of 800-950 ℃ and 900-1200 ℃ and carries out according to the high quartzy still keatite of hope.In order to reach enough crystalline densities, the temperature at 650-800 ℃ is carried out to nuclear process before potteryization usually.When the compositing range that provides from above selects transition temperature, softening temperature and processing temperature to be significantly higher than those glass of so far prior art, obtain particularly advantageous performance through the coated glass pottery by glass preparation according to the present invention.For example transition temperature (Tg) is 450-650 ℃, is in particular 490-590 ℃, softening temperature (E
w) be 600-850 ℃, be in particular 640-800 ℃, processing temperature (V
A) be 880-1150 ℃, be in particular 900-1120 ℃.At 20-300 ℃ thermalexpansioncoefficient is 3.5-7 * 10
-6/ K is preferably 4-6 * 10
-6/ K.High relatively Tg, E
w, V
ATemperature plays particularly advantageous effect for the thermotolerance of upholstery cover.For example do not demonstrate the perceptible colour-change of naked eyes basically after 75 hours at 670 ℃.
Use glass of the present invention on the glass-ceramic base material, to produce upholstery cover, its aspect gloss and the wear resistance corresponding to so far the glass that contains PbO and CdO.With regard to thermotolerance and resistant spot, glass of the present invention even surpass the glass contain PbO and CdO.A special advantage of glass of the present invention is the adhesivity that it is excellent, even it also is so that the thermal expansion between upholstery cover and glass-ceramic base material differs under the very large situation, and extraordinary thermotolerance and the high strength through the glass-ceramic of coating brought thus.Even until also not peeling off during at jump in temperature under the big upholstery cover bed thickness situation of 9 μ m, wherein tolerate the big difference between upholstery cover and the glass-ceramic from glass-ceramic for example.Good adhesivity like this (wherein is accompanied by extreme temperature alternating) in actual use and is kept for a long time.Chemoresistance the and particularly tolerance of acid is better than so far lead-free composition.Under thick decoration design conditions, significantly be better than so far lead-free composition especially with the intensity of the glass-ceramic of vitreous coating of the present invention.
Embodiment
The present invention further illustrates by following embodiment.
Table 1 comprises that 22 are formed the embodiment and the measurement of correlation parameters (described measuring parameter sign viscosity) of (weight %) about glass, transition temperature (Tg, ℃) for example, softening temperature (E
w, ℃), processing temperature (V
A, ℃) and the thermalexpansioncoefficient between 200-300 ℃ (10
-6/ K) and density (g/cm
3).Embodiment 21 and 22 is in outside the compositing range of the present invention and is implemented in the lump to be used to contrast purpose.
Glass according to embodiment 1-22 is ground into the powder that median particle is 1-3 μ m.Thus obtained powder mixes with pigment according to table 2 and is incorporated in interpolation based on rosinol
The silk screen printing oil condition under be processed into silk screen printing cream.Recording viscosity through the Brookfield viscometer is 1-5Pas.The gained lotion is printed onto (according to the EP220333B 1) initial on glass that can change glass-ceramic into.The silk screen printing of being implemented had both comprised that different decoration designs also comprised the sample of pure flat printing.Wherein use the silk screen of mesh width as 150T.Described coating is being fired in finishing stove or the laboratory stove continuously.In glass-ceramic, implement the potteryization of initial glass as accounting for leading crystalline phase thus with quartzy mixed crystal of height (experiment numbers 1-22) or keatite mixed crystal (experiment numbers 23-27).The top temperature of firing is listed in table 2.Fire and potteryization after, described coating has the bed thickness of about 4 μ m.Measured performance is listed in table 2.Adhesion strength is decorated on the sample at pure flat and is tested.Wherein fired ornament layer and transparent adhesive tape film band (
Typ 104, Beiersdorf company) bonding.Described band is torn then suddenly through wiping the jail.Be with and make an appraisal according to there being how many coating particless to adhere to this then.Wherein implication is as follows: 0=does not find the particle of adhering, and the particle of a small amount of adhesion of 1=is not serious for reality is used, the adhesion particle of 2=a greater number, and the 3=ornament layer becomes face to tear off.
Acid resistance is assessed with regard to the perceptible color change of vision according to similar scheme, and wherein implication is as follows: 0=does not have perceptible corrosion, the corrosion that 1=is very little, and not serious, 2=significantly corrodes, and 3=corrodes substantially with the 4=ornament layer and changes fully.Acetate with 4% was boiling temperature test 4 hours.This testing method is brought relative intensive corrosion, to obtain at the evaluation that has the practical application of acid proof peak demand.
Intensity is tested on the sample through decorating, and it has the size of 100 * 100mm and has 50 * 50mm square of pure flat printing of central authorities.Bending strength is measured according to dicyclo method (Doppelringmethode) (DIN 52300, the 5 parts).Use at least 12 samples to measure its bending strength for each coating.In table 2, provide mean value.
Measured value shows, adhesion strength that composition of the present invention not only provided but also the acid resistance that provides and relative high bending strength (＞30MPa).Utilize Comparative composition to fail to realize this combination.Described performance is near the enamel and the enamel that contain PbO and/or CdO.In addition, said composition has the resistant spot and the thermotolerance of remarkable improvement with respect to enamel that contains PbO and/or CdO and enamel.Gloss, wear resistance, show equally that to the resistance of alkalis with according to the cleaning behavior of routine and known standard method glass composition of the present invention is suitable for substituting the glass that contains PbO and CdO in the mode of excellence.
Claims (8)
1. be used for glass or glass-ceramic are coated with glass with enamel, enamel and the not leaded and cadmium decorated, it contains high quartzy mixed crystal and/or keatite mixed crystal as principal crystalline phase after crystallization, and has between 20-700 ℃ and be lower than 2 * 10
-6Low-thermal-expansion, it is characterized in that following composition (weight %):
Li
2O 0-5
Na
2O 0-5
K
2O 0-2
∑Li
2O+Na
2O+K
2O 1-10
MgO 0-3
CaO 0-4
SrO 0-4
BaO 0-4
ZnO 0-4
B
2O
3 15-27
Al
2O
3 10-20
SiO
2 43-58
TiO
2 0-3
ZrO
2 0-4
Sb
2O
3 0-2
F 0-3
In order to replacement oxygen, and
Contain 30 weight % at the most in the stable pigment of firing temperature.
2. the glass of claim 1 is characterized in that following composition (weight %):
Li
2O 1-4
Na
2O 0-3
K
2O 0-2
∑Li
2O+Na
2O+K
2O 2-7
MgO 0-3
CaO 0-3
SrO 0-4
BaO 0-3
∑MgO+CaO+SrO+BaO 1-9
ZnO 0-3
B
2O
3 15-23
Al
2O
3 14-19
SiO
2 48-57
TiO
2 0-3
ZrO
2 0-3
Sb
2O
3 0-1
F 0-2, in order to replacement oxygen, and
Contain 30 weight % at the most in the stable pigment of firing temperature.
3. claim 1 or 2 glass composition is characterized in that the oxide compound Bi of 3 weight % at the most
2O
3, La
2O
3, SnO
2, P
2O
5One of, the summation of wherein said oxide compound is less than 5 weight %.
4. the glass composition of at least one of claim 1-3 is characterized in that
∑ Li
2O+Na
2O+K
2O+F 2-7 weight %
∑ MgO+CaO+SrO+BaO 1-7 weight %
∑ Al
2O
3+ SiO
2+ TiO
2+ ZrO
2+ SnO
2+ La
2O
3+ Bi
2O
3+ P
2O
564-75 weight %.
5. the glass composition of at least one of claim 1-4 is characterized in that transition temperature is 450-650 ℃, is in particular 490-590 ℃, softening temperature is 600-850 ℃, particularly 640-800 ℃, processing temperature is 880-1150 ℃, is in particular 900-1120 ℃ and thermalexpansioncoefficient
20/300Be 3.5-7 * 10
-6/ K, particularly 4-6 * 10
-6/ K.
6. the glass composition of at least one of claim 1-5 is characterized in that described glass has the median particle less than 10 μ m, especially less than 5 μ m.
7. the glass composition of at least one of claim 1-6 is characterized in that, bed thickness is in particular 2-7 μ m firing the back less than 9 μ m.
8. be used to prepare utilization and be coated with method with enamel, enamel and the glass-ceramic of being decorated according to the glass composition of at least one of aforementioned claim, it is characterized in that fire and glass to the pottery process of glass-ceramic of enamel layer, enamel layer or ornament layer are implemented together.
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|---|---|---|---|
| CN200810174455A CN101734858A (en) | 2008-11-07 | 2008-11-07 | Lead and cadmium-free glass composite for coating porcelain glaze and enamel on and decorating glass or glass ceramics |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810174455A CN101734858A (en) | 2008-11-07 | 2008-11-07 | Lead and cadmium-free glass composite for coating porcelain glaze and enamel on and decorating glass or glass ceramics |
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|---|---|
| CN101734858A true CN101734858A (en) | 2010-06-16 |
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|---|---|---|---|
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