CN1058947C - Energy-accumulated luminous enamel glaze material and preparing process and products thereof - Google Patents

Energy-accumulated luminous enamel glaze material and preparing process and products thereof Download PDF

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Publication number
CN1058947C
CN1058947C CN98110267A CN98110267A CN1058947C CN 1058947 C CN1058947 C CN 1058947C CN 98110267 A CN98110267 A CN 98110267A CN 98110267 A CN98110267 A CN 98110267A CN 1058947 C CN1058947 C CN 1058947C
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CN
China
Prior art keywords
glaze
enamel
luminous
luminescent
energy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
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CN98110267A
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Chinese (zh)
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CN1198413A (en
Inventor
张玉军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lunbo Luminous Material Co., Ltd., Shandong
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LUNBO COMMERCIAL AND INDUSTRIAL GROUP Co Ltd SHANDONG PROV
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Priority to CN98110267A priority Critical patent/CN1058947C/en
Publication of CN1198413A publication Critical patent/CN1198413A/en
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Publication of CN1058947C publication Critical patent/CN1058947C/en
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Classifications

    • 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
    • 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

Abstract

The present invention relates to the technical field of inorganic non-metal materials (silicate), particularly to an enamel luminous glaze material, preparation technology thereof and a product of the enamel luminous glaze material. The enamel luminous glaze material comprises a luminous material, a parent glaze material and an additive agent, wherein the luminous material has the composition formula of MO. nAl2O3: Eu<+2>, and the glaze material additive agent is one of clay soil, carboxymethyl cellulose and xanthan gum or is the mixture of all the elements. All the components comprise (parts by weight) 20 to 45 of luminous powder, 45 to 100 of parent glaze and 0.2 to 3 of the additive agent. The luminous enamel product of the present invention has the advantages of white bright surfaces or no semi-matt, no light, zero radioactive harm and long luminous afterglow time (about 24 hours).

Description

A kind of energy-accumulating luminous frit for porcelain enamel and preparation technology and goods
The present invention relates to ceramic (silicate) field, particularly a kind of enamel luminescent glaze and preparation technology and its goods.
In tourist attractions, places such as road, river course, hazardous area, protective belt, forbidden zone, forest need sign at night, prompting or caution, if adopt lighting system, can't realize because the region is big.If adopt that energy-accumulating luminous enamelware is marked, label etc., absorb energy owing to solar radiation daytime, will bring great convenience as light source night.
Japan's publication (spy opens clear 51-93923) and Chinese patent (application number 88105798.3, publication number CN104213) have been introduced the luminescent enamel goods respectively.These two patents all adopted zinc-cadmium sulfide (Cu)～ZnS.Cu or (Zn.Cd) S.Cu} fluorescent material be luminescent material, match suitable basic glaze and make the luminescent enamel goods.The shortcoming of this fluorescent article is that fluorescent lifetime is short, and the luminescent material that some of them contain rare earth elements can produce radiological hazard, is unfavorable for producing and practical.
The objective of the invention is to overcome the deficiencies in the prior art, enamel luminescent glaze preparation technology that a kind of weathering resistance and chemical stability are good, luminous intensity is high, time of persistence is long and products thereof is provided.
The objective of the invention is to realize in the following manner:
Enamel luminescent glaze of the present invention is made up of luminescent material, basic glaze and glaze feed additives three parts.Luminescent material is for having MOnAl 2O 3: Eu + 2The luminescent powder of structural formula, M=Sr in the formula, Mg, Ba, Ca can be one or more, n=1～3.The glaze feed additives is selected from the miscellany of one of clay, carboxymethyl cellulose (CMC), xanthan gum or its arbitrary proportion.Each several part consists of (weight part): luminescent powder 20～45, parent glaze 45～100, additive 0.2～3.
The preferred europkium-activated strontium aluminate base (SrOnAl of above-mentioned luminescent material 2O 3: Eu + 2) overlength afterglow luminescent powder, n=1～3.
Europkium-activated strontium aluminate base (SrOnAl 2O 3: Eu + 2) overlength afterglow luminescent powder has the luminous intensity height, stable performance, characteristics such as the noctilucence time is long, and is "dead" are the ideal luminescent material.
The present invention does not have strict restriction to above-mentioned parent glaze, and the general known parent glaze in this area all can use, as long as it does not have side effect with luminescent powder.From optimized angle, preferably select the parent glaze (weight part) of following composition for use:
CaO 0～5 CaF 2 0～8
K 2O 1～10 Na 2O 6～15
ZnO 0～3 PbO 0～0.6
P 2O 5 0～5 SrO 0～35
SiO 2 10～70 Al 2O 3 5～15
MgO 0～6 BaO 0～20
B 2O 3 6～32 Li 2O 0～6
The step of preparation process of above-mentioned luminescent glaze is:
1. form batching by above-mentioned parent glaze earlier, mix, found shrend at 1000～1350 ℃.
2. parent glaze frit and luminescent powder and glaze feed additives are mixed in proportion ball milling together, preparation glaze slip.
The goods of luminescent enamel goods of the present invention use above-mentioned glaze to obtain with any known method.Also available following method:
Above-mentioned glaze slip is coated on above the common enamel white cover-coat enamel, and baking is 1～3 minute under 780～820 ℃ temperature, get final product the luminescent enamel goods.
In the preparation of luminescent enamel goods of the present invention, can on luminescent glaze, apply the very thin transparent of one deck again.
Luminescent enamel goods of the present invention, its surface white light or semi-matt, unglazed, or be with yellowish green tone slightly; Performance meets country's " noncontact food enamelware standard (QB/T 1855-93) "."dead" harm, about 24 hours of luminous time of persistence.Luminous time of persistence is with can be visual to being as the criterion in the darkroom.
The present invention selects the JY-III type fluorescent material relative brightness tester of photoelectron institute of China Measures Institute production for use to the relative brightness of luminescent enamel glaze and the test of twilight sunset, and this instrument is recommended by GB/T14633-93.The relative brightness value: I = VI 0 V 0 &times; 100 %
I is the sample relative brightness, I 0Be sample brightness, V is the corresponding photovoltage value of sample, V 0Be the corresponding photovoltage value of sample.
Twilight sunset test: after sample reaches the brightness maximum value, close light source, calculate its prima facies to brightness value by the photovoltage value.Close light source then, write down twilight sunset relative brightness value subsequently in required time, make sample and time curve at last.Close light source I=27% after a minute, I=16% after 5 minutes.
Below in conjunction with embodiment the present invention is elaborated.
Embodiment 1. luminous enamel glaze materials
The preferred europkium-activated strontium aluminate base (SrOnAl of luminescent material 2O 3: Eu + 2) overlength afterglow luminescent powder, 25 weight parts, n=2.
Totally 100 parts of luminescent enamel parent glazes, prepare burden by following composition (weight part):
CaO 0.1 CaF 2 1.2
K 2O 4.5 Na 2O 13.8
ZnO 0.1 PbO 0.1
P 2O 5 0.3 SrO 8.5
SiO 2 53.5 Al 2O 3?6.5
MgO 0.5 BaO 0.2
B 2O 3?10.5 Li 2O 0.2
The glaze feed additives is xanthan gum 0.2 weight part.
The preparation technology of 2. 1 kinds of luminous enamel glaze materials of embodiment such as embodiment 1 described luminous enamel glaze material, its step of preparation process is:
1. earlier with above-mentioned parent glaze each component batching weighing, mix, totally 100 parts, found shrend at 1300 ℃ by part.
2. with 0.2 part of 25 parts of above-mentioned parent glaze frit and strontium aluminate luminescent powders and glaze feed additives xanthan gum, mix by weight, ball milling together, fineness is: median size＜60 μ m, preparation glaze slip.Glaze slip proportion 1.6～1.7.
3. 1 kinds of luminescent enamel goods of embodiment.
The glaze that makes as the preparation technology of embodiment 1 described glaze and embodiment 2 described luminous enamel glaze materials.Glaze is granted on the cover-coat enamel, form light-emitting area or form pattern with colored glaze, baking is 1.5 minutes under 800 ℃ temperature, obtains to have the enamelware of illumination effect.Its surface white light is with yellowish green tone slightly; Performance meets country's " noncontact food enamelware standard (QB/T 1855-93) "."dead" harm, about 24 hours of luminous time of persistence.
Embodiment 4. luminous enamel glaze materials
Luminescent material selects europkium-activated strontium aluminate base (SrOnAl 2O 3: Eu + 2) overlength afterglow luminescent powder, 22 weight parts, n=2.5.
Totally 80 parts of luminescent enamel parent glazes, prepare burden by following composition (weight part):
CaO 0.1 CaF 2 1
K 2O 2.5 Na 2O 9
ZnO 0.1 PbO 0
P 2O 5 0.3 SrO 9.5
SiO 2 44.5 Al 2O 3 5.6
MgO 0.5 BaO 0.2
B 2O 3 6.5 Li 2O 0.2
The glaze feed additives is carboxymethyl cellulose (CMC) 0.3 weight part.
Embodiment 5. luminous enamel glaze materials
Luminescent material selects BaOnAl 2O 3: Eu + 2) overlength afterglow luminescent powder, 30 weight parts, n=2.
Totally 80 parts of luminescent enamel parent glazes, prepare burden by following composition (weight part):
CaO 0.1 CaF 2 1
K 2O 2.5 Na 2O 11
ZnO 0.1 PbO 0.1
P 2O 5 0.3 SrO 0.2
SiO 2 44.5 Al 2O 3 5.5
MgO O.5 BaO 7.5
B 2O 3 6.5 Li 2O 0.2
The glaze feed additives is clay 3% weight part.
Embodiment 6. luminous enamel glaze materials
Luminescent material selects CaOnAl 2O 3: Eu + 2) overlength afterglow luminescent powder, 30 weight parts, n=2.5.
Totally 100 parts of luminescent enamel parent glazes, prepare burden by following composition (weight part):
CaO 0.5 CaF 2 1
K 2O 5 Na 2O 12
ZnO 1 PbO 0.6
P 2O 5 3 SrO 11
SiO 2 50 Al 2O 3?8.5
MgO 0.5 BaO 0.2
B 2O 3?6.5 Li 2O 0.2
The glaze feed additives is xanthan gum 0.2 weight part.

Claims (5)

1. an energy-accumulating luminous vitreous enamel comprises luminescent material, basic glaze and additive, it is characterized in that; The luminescent material composition formula is MOnAl 2O 3: Eu + 2, wherein, M represents Sr, Mg, Ba, one or more in the Ca element, n=1～3; The glaze feed additives is selected from the miscellany of one of clay, carboxymethyl cellulose, xanthan gum or its arbitrary proportion; Each several part consists of (weight part): luminescent powder 20～45, parent glaze 45～100, additive 0.2～3.
2. energy-accumulating luminous frit for porcelain enamel according to claim 1 is characterized in that, the luminescent material composition formula is SrOnAl 2O 3: Eu + 2, n=1～3.
3. energy-accumulating luminous frit for porcelain enamel according to claim 1 is characterized in that, basic glaze (weight part) is:
SiO 2 10～70 Al 2O 3 5～15
CaO 0～5 CaF 2 0～8
K 2O 1～10 Na 2O 6～15
ZnO 0～3 PbO 0～0.6
P 2O 5?0～5 SrO 0～35
MgO 0～6 BaO 0～20
B 2O 3?6～32 Li 2O 0～6
One kind prepare claim 12 or the processing step of described energy-accumulating luminous frit for porcelain enamel be:
(1),, founds shrend at 1000-1350 ℃ by a part mixing with above-mentioned parent glaze each component batching weighing;
(2) above-mentioned parent glaze frit and luminescent powder and glaze feed additives are mixed in proportion ball milling together, preparation glaze slip.
5. the goods of claim 1 glaze is characterized in that, described glaze slip is coated on above the common enamel white cover-coat enamel, and baking is 1～3 minute under 780～820 ℃ temperature, get final product the luminescent enamel goods.
CN98110267A 1998-06-05 1998-06-05 Energy-accumulated luminous enamel glaze material and preparing process and products thereof Expired - Fee Related CN1058947C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN98110267A CN1058947C (en) 1998-06-05 1998-06-05 Energy-accumulated luminous enamel glaze material and preparing process and products thereof

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Application Number Priority Date Filing Date Title
CN98110267A CN1058947C (en) 1998-06-05 1998-06-05 Energy-accumulated luminous enamel glaze material and preparing process and products thereof

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CN1058947C true CN1058947C (en) 2000-11-29

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Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1308254C (en) * 2003-10-20 2007-04-04 梁锋 High temperature luminous glazing and its production process and application in luminous glazed tile
CN103058521A (en) * 2012-12-27 2013-04-24 龙门协成新材料有限公司 Vitreous enamel material
CN105272365A (en) * 2015-11-24 2016-01-27 武汉广益交通科技股份有限公司 Energy-accumulating luminous glazed tile, glazing technology and glazing equipment
CN107032617A (en) * 2017-04-06 2017-08-11 佛山欧神诺陶瓷股份有限公司 A kind of ceramic cover-coat enamel with illumination effect and its preparation method and application
CN109206013B (en) * 2018-09-17 2021-05-18 泉州市陶瓷科学技术研究所 Long-afterglow ceramic with non-cracking glaze and manufacturing process thereof
CN109808404B (en) * 2019-03-22 2021-04-27 黄淮学院 Ceramic mural decoration process applied to environmental art design

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1042137A (en) * 1988-10-28 1990-05-16 长沙搪瓷厂 Luminescent enamel

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1042137A (en) * 1988-10-28 1990-05-16 长沙搪瓷厂 Luminescent enamel

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Owner name: LUNBO LUMINESCENT MATERIAL CO., LTD, SANDONG

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