CN108409146A - A kind of no zirconium sapphirine crystalline opaque glaze and its manufacturing method - Google Patents
A kind of no zirconium sapphirine crystalline opaque glaze and its manufacturing method Download PDFInfo
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- CN108409146A CN108409146A CN201810544981.4A CN201810544981A CN108409146A CN 108409146 A CN108409146 A CN 108409146A CN 201810544981 A CN201810544981 A CN 201810544981A CN 108409146 A CN108409146 A CN 108409146A
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- Prior art keywords
- glaze
- sapphirine
- zirconium
- opaque glaze
- crystalline
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
Abstract
The invention discloses a kind of no zirconium sapphirine crystalline opaque glaze and its manufacturing methods.The mass percent of the component and each component without zirconium sapphirine crystalline opaque glaze is：Na2O：1~3%；K2O：2~3%；Al2O3：25~28%；MgO：8~10%；B2O3：5~7%；Li2O：0~1%；CaO：0~1%；P2O5：0~1%；Surplus is SiO2.The present invention replaces ZrSiO with sapphirine4Opaque glaze is prepared as opacifiers.Gained of the invention without zirconium sapphirine crystalline opaque glaze, glaze glossiness is high, hardness is high, wearability is good, resistance to acid and alkali is good and anti-scratch.In addition, compared to ZrSiO4Opaque glaze, the present invention are free of zircon sand, are free of any radioactive element, and of low cost, environmentally friendly and milky white effect is good, and production technology is just the same with zirconium system milkiness fritted glaze, reduces production cost.
Description
Technical field
The present invention relates to ceramic glaze fields, and in particular to a kind of no zirconium sapphirine crystalline opaque glaze and its manufacturer
Method.
Background technology
In order to cover color and defect, the source for expanding raw material of green body, there is good decoration function and covering power
Strong opaque glaze is widely used in ceramic surface and ground-coat enamel.The common opaque glaze of construction sanitary ceramic has oxidation tin system at present
Opaque glaze, titanium oxide system opaque glaze and zircon system opaque glaze.Tin oxide system opaque glaze, opaque effect is good but price is high
It is expensive, it is of high cost；Titanium oxide is easily precipitated with anatase from melt in high temperature firing, and glaze is made to change colour；Zircon system milkiness
In glaze, ZrSiO4It is current most popular opacifiers, has many advantages, such as high refractive index, high rigidity and is not influenced by atmosphere,
Make glaze layer that there is good opaque effect, and the mechanical property of glaze layer can be improved.But China's zirconium resource is poorer, in recent years silicon
Sour zirconium cost of material quickly goes up, and zircon and radioactive element thorium, uranium association, and thorium, uranium are difficult to remove in post-production
It goes, it is harmful to the health of people.In addition, in ZrSiO4In opaque glaze, the ZrSiO of high level is only added4（10~15wt%）, and
ZrSiO4Granularity it is very thin（<1μm）In the case of, just there is preferable opaque effect.But ZrSiO4（Mohs' hardness 7.5）Hardness
Greatly, superfine powder preparation process complex and expensive, ball milling cost can increase with the reduction of particle.Therefore, development cost it is cheap,
Environmental protection, the good no zirconium opaque glaze of opaque effect have great importance.Sapphirine crystalline opaque glaze, glaze layer precipitate crystal for
Mg2Al4SiO10Sapphirine, crystallite dimension is suitable, strong to the scattering process of visible light, both reaches common zirconium white frit glaze
Whiteness, and glossiness, hardness, wearability, resistance to acid and alkali and the mar-resistance of glaze can be improved, reduce production cost.
Invention content
The object of the present invention is to provide a kind of no zirconium sapphirine crystalline opaque glaze, Mg is precipitated in glaze layer2Al4SiO10It is false blue precious
Stone crystal, dispersion effect is strong, and opaque effect is good, improves the glossiness of glaze, hardness, wearability, resistance to acid and alkali and anti-scratch
Property, reduce production cost.
The object of the invention is achieved by the following technical programs.
A kind of no zirconium sapphirine crystalline opaque glaze, is grouped as by each group of following weight fraction：Na2O：1%~3%；K2O：
2%~3%；Al2O3：25%~28%；MgO：7%~10%；；B2O3：5%~8%；Li2O：0~1%；CaO：0~1%；
P2O5：0~1%；Surplus is SiO2。
Preferably, the no zirconium sapphirine crystalline opaque glaze is grouped as by each group of following weight fraction：Na2O：
1.84%；
K2O：2.76%；Al2O3：27.62%；MgO：8.21%；B2O3：6.14%；Li2O：0.25%；CaO：0.28%；
P2O5：0.47%；SiO2：52.43%.
A kind of manufacturing method of above-described no zirconium sapphirine crystalline opaque glaze, includes the following steps：
(1) potassium feldspar, albite, talcum, silica flour, boric acid, phosphorus pentoxide and bauxite are mixed, is passed through after ball milling
Melted, water quenching is crossed, frit powder is obtained after ball milling；
(2) water for ball milling is added into frit powder, obtains the suitable glaze slip of consistency；
(3) glaze slip is sieved；
(4) plus water adjusts glaze pulp density；
(5) glaze spraying, firing.
Preferably, step（1）The raw material after evenly mixing, 1450 DEG C ~ 1500 DEG C melted 40min ~ 60min, then water
Quenching, ball milling obtain frit powder.
Preferably, step（2）The kaolin for adding frit powder weight 3% ~ 6%, frit powder weight are needed when the ball milling
0.2% ~ 0.5% carboxymethyl cellulose.
Preferably, step（2）The material when ball milling:Ball:Water=1:2:1.1.
Preferably, step（3）The mesh screen is 200 ~ 250 mesh screens.
Preferably, step（3）Tailing over less than 0.15wt% when the sieving.
Preferably, step（4）The adjusting glaze pulp density is 1.5 ~ 1.6g/cm3。
Preferably, step（5）The system of the firing is 1200 DEG C ~ 1210 DEG C heat preservation 8min ~ 10min, and heating rate is
10~20 DEG C/min.
The manufacturing process flow of the no zirconium sapphirine crystalline opaque glaze is as follows：
Raw material detection → dispensing → uniformly mixing → is starched in 1450 DEG C ~ 1500 DEG C heat preservation → water quenching → ball milling → sievings → enamel frit makeing
→ glazing → firing → finished product.
The present invention replaces ZrSiO with sapphirine4Opaque glaze is prepared as opacifiers.Sapphirine width (~
250nm) suitable with visible wavelength range, length is 1~2 μm, generates strong scattering so that sapphirine microcrystalline glaze has both
ZrSiO4The opaque effect of opaque glaze, and hardness, wearability, resistance to acid and alkali and the mar-resistance of glaze are improved simultaneously.Due to
Sapphirine is compared to ZrSiO4With smaller size, thus has higher glossiness.
Compared with prior art, the invention has the advantages that：
The present invention without zirconium sapphirine crystalline opaque glaze, glaze glossiness is high, hardness is high, wearability is good, resistance to acid and alkali is good
With it is anti-scratch, be free of zircon sand, be free of any radioactive element, of low cost and milky white effect is good, production technology and zirconium system breast
Turbid fritted glaze is just the same, can reduce production cost.
Description of the drawings
Fig. 1 is that treated with 5wt%HF solution corrosions 30s for the glaze without zirconium sapphirine crystalline opaque glaze of embodiment 1
Scanning electron microscope (SEM) photograph.
Specific implementation mode
The specific implementation of the present invention is further described with reference to specific embodiment, but embodiments of the present invention
It is without being limited thereto.
Embodiment 1
The present embodiment is grouped as without zirconium sapphirine crystalline opaque glaze by the group of following weight fraction：Na2O：1.84%；K2O：
2.76%；Al2O3：27.62%；MgO：8.21%；B2O3：6.14%；Li2O：0.25%；CaO：0.28%；P2O5：0.47%；SiO2：
52.43%。
Calculate raw materials used formula according to formula rate as above, select in the present embodiment 25.88 parts by weight potassium feldspars,
6.96 parts by weight albites, 24.17 parts by weight talcums, 9.19 part by weight of boric acid, 0.47 parts by weight phosphorus pentoxide and 33.32 weights
Amount part bauxite is raw material, passes through ball milling after evenly mixing, 60min is kept the temperature at 1480 DEG C, frit is obtained after quenching, then ball
Mill obtains frit powder.By 100g frits powder, 5g kaolin, 0.25g carboxymethyl celluloses and 110ml water for ball milling, 200 mesh are crossed
Mesh screen, tails over 0.1g, and when glazing adds water that glaze pulp density is made to be adjusted to 1.55g/cm3, glaze spraying is warming up to 1200 DEG C of guarantors with 10 DEG C/min
Warm 10min obtains no zirconium sapphirine crystalline opaque glaze.
Vickers hardness without zirconium sapphirine crystalline opaque glaze obtained by the present embodiment is 7.5GPa, L* 95.62, a* be-
0.61, b* 0.36, glossiness 85GU.
Scanning of the glaze without zirconium sapphirine crystalline opaque glaze of the present embodiment after 5 parts by weight HF solution corrosions 30s
Electron microscope is as shown in Figure 1.
Embodiment 2
The present embodiment is grouped as without zirconium sapphirine crystalline opaque glaze by the group of following weight fraction：Na2O：1.87%；K2O：
2.79%；Al2O3：27.90%；MgO：8.27%；B2O3：6.20%；Li2O：0.18%；CaO：0.32%；P2O5：0.50%；SiO2：
51.97%。
Calculate raw materials used formula according to formula rate as above, select in the present embodiment 26.81 parts by weight potassium feldspars,
6.91 parts by weight albites, 21.84 parts by weight talcums, 0.92 parts by weight silica flour, 10.17 part by weight of boric acid, 0.50 parts by weight
Phosphorus pentoxide and 32.85 parts by weight bauxites are raw material, pass through ball milling after evenly mixing, keep the temperature 60min at 1480 DEG C, quench
Frit is obtained after cold, then ball milling obtains frit powder.By 100g frits powder, 5g kaolin, 0.25g carboxymethyl celluloses and
110ml water for ball milling crosses 200 mesh mesh screens, tails over 0.1g, and when glazing adds water that glaze pulp density is made to be adjusted to 1.55g/cm3, glaze spraying, with 15
DEG C/min be warming up to 1200 DEG C heat preservation 10min, obtain no zirconium sapphirine crystalline opaque glaze.
Vickers hardness without zirconium sapphirine crystalline opaque glaze obtained by the present embodiment is 8.7GPa, L* 95.57, a* be-
0.47, b* 0.20, glossiness 86GU.
Scanning of the glaze without zirconium sapphirine crystalline opaque glaze of the present embodiment after 5 parts by weight HF solution corrosions 30s
Electron microscope is referring to Fig. 1.
Embodiment 3
The present embodiment is grouped as without zirconium sapphirine crystalline opaque glaze by the group of following weight fraction：Na2O：1.00%；K2O：
3.00%；Al2O3：28.00%；MgO：8.00%；B2O3：5.00%；CaO：1.00%；SiO2：54.00%.
Calculate raw materials used formula according to formula rate as above, select in the present embodiment 22.27 parts by weight potassium feldspars,
0.29 parts by weight albite, 20.96 parts by weight talcums, 11.20 parts by weight silica flours, 8.16 part by weight of boric acid and 20.96 weight
Part bauxite is raw material, passes through ball milling after evenly mixing, 60min is kept the temperature at 1480 DEG C, frit is obtained after quenching, then ball milling
Obtain frit powder.By 100g frits powder, 5g kaolin, 0.25g carboxymethyl celluloses and 110ml water for ball milling, 200 mesh nets are crossed
Sieve, tails over 0.1g, and when glazing adds water that glaze pulp density is made to be adjusted to 1.55g/cm3, glaze spraying is warming up to 1200 DEG C of guarantors with 10 DEG C/min
Warm 10min obtains no zirconium sapphirine crystalline opaque glaze.
Vickers hardness without zirconium sapphirine crystalline opaque glaze obtained by the present embodiment is 8.5GPa, L* 95.58, a* be-
0.46, b* 0.31, glossiness 84GU.
Scanning of the glaze without zirconium sapphirine crystalline opaque glaze of the present embodiment after 5 parts by weight HF solution corrosions 30s
Electron microscope is referring to Fig. 1.
Embodiment 4
The present embodiment is grouped as without zirconium sapphirine crystalline opaque glaze by the group of following weight fraction：Na2O：3.00%；K2O：
2.00%；Al2O3：25.00%；MgO：10.00%；B2O3：7.00%；Li2O：1%；SiO2：52.00%.
Calculate raw materials used formula according to formula rate as above, select in the present embodiment 18.21 parts by weight potassium feldspars,
17.82 parts by weight albites, 25.89 parts by weight talcums, 11.16 part by weight of boric acid and 26.92 parts by weight bauxites are raw material,
By ball milling after even mixing, 60min is kept the temperature at 1480 DEG C, frit is obtained after quenching, then ball milling obtains frit powder.It will
100g frits powder, 5g kaolin, 0.25g carboxymethyl celluloses and 110ml water for ball milling cross 200 mesh mesh screens, tail over 0.1g, apply
Add water that glaze pulp density is made to be adjusted to 1.55g/cm when glaze3, glaze spraying, with 20 DEG C/min be warming up to 1200 DEG C heat preservation 10min, obtain no zirconium
Sapphirine crystalline opaque glaze.
Vickers hardness without zirconium sapphirine crystalline opaque glaze obtained by the present embodiment is 8.5GPa, L* 95.59, a* be-
0.41, b* 0.34, glossiness 88GU.
Scanning of the glaze without zirconium sapphirine crystalline opaque glaze of the present embodiment after 5 parts by weight HF solution corrosions 30s
Electron microscope is referring to Fig. 1.Obviously, the above embodiment of the present invention is only to clearly illustrate example of the present invention, and simultaneously
Non- is the restriction to embodiments of the present invention.For those of ordinary skill in the art, on the basis of above description
On can also make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.
All any modification, equivalent and improvement made by all within the spirits and principles of the present invention etc. should be included in power of the present invention
Within the protection domain that profit requires.
Claims (10)
1. a kind of no zirconium sapphirine crystalline opaque glaze, which is characterized in that the component without zirconium sapphirine crystalline opaque glaze and
The mass percent of each component is：
Na2O：1~3%；
K2O：2~3%；
Al2O3：25~28%；
MgO：8~10%；
B2O3：5~7%；
Li2O：0~1%；
CaO：0~1%；
P2O5：0~1%；
Surplus is SiO2。
2. a kind of no zirconium sapphirine crystalline opaque glaze as described in claim 1, which is characterized in that this is micro- without zirconium sapphirine
The component of brilliant opaque glaze and the mass percent of each component are：
Na2O：1.84%；
K2O：2.76%；
Al2O3：27.62%；
MgO：8.21%；
B2O3：6.14%；
Li2O：0.25%；
CaO：0.28%；
P2O5：0.47%；
SiO2：52.43%.
3. a kind of method of no zirconium sapphirine crystalline opaque glaze of manufacturing claims 1-2 any one of them, which is characterized in that
Include the following steps：
(1) potassium feldspar, albite, talcum, silica flour, boric acid, phosphorus pentoxide and bauxite are mixed, is passed through after ball milling
Melted, water quenching is crossed, frit powder is obtained after ball milling；
(2) to step（1）Water for ball milling is added in gained frit powder, obtains glaze slip；
(3) by step（2）Gained glaze slip is sieved；
(4) plus water adjusts glaze pulp density；
(5) glaze spraying, firing, obtains no zirconium sapphirine crystalline opaque glaze.
4. a kind of manufacturing method of no zirconium sapphirine crystalline opaque glaze as claimed in claim 3, which is characterized in that step
(1) the melted temperature is 1450 DEG C~1500 DEG C.
5. a kind of manufacturing method of no zirconium sapphirine crystalline opaque glaze as claimed in claim 3, which is characterized in that step
(1) the melted time is 40min~60min.
6. a kind of manufacturing method of no zirconium sapphirine crystalline opaque glaze as claimed in claim 3, which is characterized in that step
(2) add the kaolin of frit powder weight 4%~6%, the carboxymethyl cellulose of frit powder weight 0.2%~0.5% when the ball milling
Element.
7. a kind of manufacturing method of no zirconium sapphirine crystalline opaque glaze as claimed in claim 3, which is characterized in that step
(2) the material when ball milling, ball, water weight ratio be 1:2:1.1.
8. a kind of manufacturing method of no zirconium sapphirine crystalline opaque glaze as claimed in claim 3, which is characterized in that step
(3) mesh screen used in is 200~250 mesh mesh screens；Tailing over less than 0.15wt% when the sieving.
9. a kind of manufacturing method of no zirconium sapphirine crystalline opaque glaze as claimed in claim 3, which is characterized in that step
(4) the adjusting glaze pulp density is 1.5 ~ 1.6g/cm3。
10. a kind of manufacturing method of no zirconium sapphirine crystalline opaque glaze as claimed in claim 3, which is characterized in that step
(5) system of the firing is 1200 DEG C ~ 1210 DEG C heat preservation 8min ~ 10min, and heating rate is 10~20 DEG C/min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810544981.4A CN108409146B (en) | 2018-05-31 | 2018-05-31 | Zirconium-free sapphirine microcrystal opaque glaze and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810544981.4A CN108409146B (en) | 2018-05-31 | 2018-05-31 | Zirconium-free sapphirine microcrystal opaque glaze and manufacturing method thereof |
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| CN108409146A true CN108409146A (en) | 2018-08-17 |
| CN108409146B CN108409146B (en) | 2021-01-19 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113955942A (en) * | 2021-12-22 | 2022-01-21 | 广东简一(集团)陶瓷有限公司 | High-hardness glaze and preparation method thereof |
| CN114656151A (en) * | 2022-05-26 | 2022-06-24 | 佛山市东鹏陶瓷发展有限公司 | Polished tile wear-resistant glaze and preparation method thereof |
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| CN107082566A (en) * | 2017-03-31 | 2017-08-22 | 华南理工大学 | Single-phase cordierite transparent wear glaze and preparation method thereof |
| CN107129150A (en) * | 2017-06-27 | 2017-09-05 | 佛山市大千色釉料有限公司 | A kind of high abrasion glaze for glazed tile and preparation method thereof |
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| CN107082566A (en) * | 2017-03-31 | 2017-08-22 | 华南理工大学 | Single-phase cordierite transparent wear glaze and preparation method thereof |
| CN107129150A (en) * | 2017-06-27 | 2017-09-05 | 佛山市大千色釉料有限公司 | A kind of high abrasion glaze for glazed tile and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113955942A (en) * | 2021-12-22 | 2022-01-21 | 广东简一(集团)陶瓷有限公司 | High-hardness glaze and preparation method thereof |
| CN113955942B (en) * | 2021-12-22 | 2022-03-15 | 广东简一(集团)陶瓷有限公司 | High-hardness glaze and preparation method thereof |
| CN114656151A (en) * | 2022-05-26 | 2022-06-24 | 佛山市东鹏陶瓷发展有限公司 | Polished tile wear-resistant glaze and preparation method thereof |
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| CN108409146B (en) | 2021-01-19 |
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