CN1128114C - Enamel ground-coat using nanometer Al2O3 powder as adherence promotor and its preparation method - Google Patents

Enamel ground-coat using nanometer Al2O3 powder as adherence promotor and its preparation method Download PDF

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Publication number
CN1128114C
CN1128114C CN 01117289 CN01117289A CN1128114C CN 1128114 C CN1128114 C CN 1128114C CN 01117289 CN01117289 CN 01117289 CN 01117289 A CN01117289 A CN 01117289A CN 1128114 C CN1128114 C CN 1128114C
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ground
coat enamel
powder
enamel
weight percent
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CN1321617A (en
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凌国平
郦剑
黄磊
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The present invention relates to a base enamel utilizing nanometer Al2O3 powder as an adhesive agent and a preparation method thereof. Antimony oxide-molybdenum oxide or nickel oxide base enamel prepared according to a certain proportion is smelted in a crucible, is pulverized, and is mixed with mill additions, and slurry is prepared through ball milling; nanometer Al2O3 powder is dispersed in a water solution to prepare into 10 to 25 wt% emulsion, and 0.5 to 2.5 wt % emulsion is added to the base enamel slurry. The preparation method utilizes the size effect of the nanometer Al2O3 powder, the nanometer Al2O3 powder is added to the base enamel utilizing antimony oxide-molybdenum oxide or nickel oxide as an adhesive agent, the adherence of the base enamel utilizing antimony oxide-molybdenum oxide or nickel oxide as an adhesive agent is equivalent to that of the cobalt oxide base enamel, and thus, the cobalt oxide base enamel can be replaced, and the cost is lowered.

Description

Utilize nanometer Al 2O 3Powder is made the base enamel and the preparation method of adhesive agent
The present invention relates to the preparation method of vitreous enamel, is a kind of nanometer Al that utilizes 2O 3Powder is made the base enamel and the preparation method of adhesive agent.
Enamel is these two kinds of matrix materials that different materials organically is combined into one under hot conditions of metal and glass glaze, it have concurrently intensity, extensibility and the glass of steel acid-alkali-corrosive-resisting, be difficult for polluted product, easy advantages such as cleaning, be widely used in chemical industry, agricultural chemicals, medicine, dyestuff, control in the industries such as gold, food.But,, do not have adherence between them because metal and glass are two kinds of distinct materials.Have adhesion property between the two for making, must in glass glaze, add by " adhesive agent ".General adhesive agent have three kinds at present: weisspiessglanz-molybdenum oxide, nickel oxide, cobalt oxide.Wherein the cobalt oxide effect is best but cost an arm and a leg; Weisspiessglanz-molybdenum oxide is the most cheap but effect is relatively poor; Nickel oxide is then placed in the middle.
It is generally acknowledged that the adhesion property of antimony molybdenum enamel is owing to the galvanic corrosion of weisspiessglanz to steel surface produces.Antimony, iron mixed crystal strengthen adherence with the dendritic crystal form; Molybdenum oxide then plays a driving role to adherence because of reducing smelt surface tension.The appropriate combination of weisspiessglanz-molybdenum oxide could obtain good adherence.The adherence mechanism of nickel oxide, cobalt oxide is: the ferric oxide dissolving that iron surface formed when the enamel that contains nickel oxide or cobalt oxide easily made high temperature burn till, and with newborn iron-based body generation redox reaction, iron-based is produced corrosion entirely, cobalt, nickel are restored simultaneously, make its surface irregularity, and then improve adhesion property.
Purpose of the present invention provides a kind ofly adds nano-powder in weisspiessglanz-molybdenum oxide or the nickel oxide ground-coat enamel slip to, improve ground-coat enamel and metallic substance adhesion property utilize nanometer Al 2O 3Powder is made the base enamel and the preparation method of adhesive agent.
In order to achieve the above object, the present invention takes following measures:
Scheme 1:
1. utilize nanometer Al 2O 3The base enamel that powder is made adhesive agent comprises:
1) weisspiessglanz-molybdenum oxide ground-coat enamel batching proportioning (accounting for the weight percent of ground-coat enamel batching):
Na 2O 15.0～17.0％
B 2O 3 12.0～15.0％
K 2O 4.0～4.8％
Al 2O 3 4.8～5.0％
SiO 2 46.0～52.0％
CaF 2 8.4～9.8％
MnO 2 2.0～2.4％
Sb 2O 3 0.8～1.0％
BaO 0.5～0.9％
MoO 3 0.5～0.9％
2) ground-coat enamel slip proportioning (accounting for the weight percent of ground-coat enamel slip):
Clay 3.0～6.0%
Sb 2O 3 0.2～1.5％
BaMoO 3 0.3～1.5％
Na 3BO 3 0.2～1.2％
NaNO 2 0.1～0.8％
Water 50%
Ground-coat enamel is prepared burden all the other
3) ground-coat enamel proportioning (accounting for the weight percent of ground-coat enamel):
Nanometer Al 2O 3The milk sap 0.5～2.5% of powder
The ground-coat enamel slip all the other
4) nanometer Al 2O 3The milk sap proportioning of powder (accounting for the weight percent of this milk sap):
Particle diameter is the Al of 10～20nm 2O 3Powder 10～25%
Water all the other
2. nanometer Al 2O 3Powder is that the base enamel preparation method of adhesive agent is:
1) with after weisspiessglanz-molybdenum oxide ground-coat enamel batching mixes in proportion, found with crucible in box-type furnace, glass melting temperature is 1190～1250 ℃, and melting time is 2 hours, and pulverize the back;
2) batching of the ground-coat enamel after will pulverizing is carried out ball milling with other batchings that are mixed in proportion and is made the ground-coat enamel slip, ball milling after 20 hours aging 1～2 day;
3) with particle diameter be the Al of 10～20nm 2O 3Powder is dispersed in the aqueous solution, make weight percent and be 10～25% milk sap, is 0.5～2.5% to add the ground-coat enamel slip with it by the ground-coat enamel weight percent.
Scheme 2:
1. utilize nanometer Al 2O 3The base enamel that powder is made adhesive agent comprises:
1) nickel oxide ground-coat enamel batching proportioning (accounting for the weight percent of ground-coat enamel batching):
Na 2O 14.0～16.0％
B 2O 3 11.0～13.0％
K 2O 2.0～5.0％
Al 2O 3 3.0～6.0％
SiO 2 42.0～51.0％
CaF 2 8.0～10.0％
NiO 1.0～2.0％
MnO 2 2.0～2.5％
NaSiF 4 3.0～4.2％
Fe 2O 3 0～2.0％
2) ground-coat enamel slip proportioning (accounting for the weight percent of ground-coat enamel slip):
Clay 3.0～6.0%
Na 3BO 3 0.2～1.2％
NaOH 0.1～0.8％
Water 50%
Ground-coat enamel is prepared burden all the other
3) ground-coat enamel proportioning (accounting for the weight percent of ground-coat enamel):
Nanometer Al 2O 3The milk sap 0.5～2.5% of powder
The ground-coat enamel slip all the other
4) nanometer Al 2O 3The milk sap proportioning of powder (accounting for the weight percent of this milk sap):
Particle diameter is the Al of 10～20nm 2O 3Powder 10～25%
Water all the other
2. nanometer Al 2O 3Powder be the base enamel preparation method of agent be:
1) nickel oxide ground-coat enamel batching is mixed in proportion after, in box-type furnace, found with crucible, glass melting temperature is 1190～1250 ℃, melting time is 2 hours, pulverize the back;
2) batching of the ground-coat enamel after will pulverizing is carried out ball milling with other batchings that are mixed in proportion and is made the ground-coat enamel slip, ball milling after 20 hours aging 1～2 day;
3) with particle diameter be the Al of 10～20nm 2O 3Powder is dispersed in the aqueous solution, make weight percent and be 10～25% milk sap, is 0.5～2.5% to add the ground-coat enamel slip with it by the ground-coat enamel weight percent.
The present invention compares with general enamel adhesive agent, and the present invention utilizes nanometer Al 2O 3The dimensional effect of powder is by adding nanometer Al in the base enamel that with weisspiessglanz-molybdenum oxide with the nickel oxide is adhesive agent 2O 3Powder, the dendritic crystal between fining metal and the vitreous enamel in the zone of transition, and it is mild that the concentration gradient of elements such as zone of transition iron is changed makes the adhesion property of above-mentioned two kinds of ground-coat enamels and ground-coat enamel that cobalt oxide is adhesive agent suitable.Thereby alternative cobalt oxide ground-coat enamel reduces high quality enamelled cost.Enlarge enamelled firing temperature and firing time scope simultaneously.
Be embodiments of the invention below.
Embodiment 1:
1. utilize nanometer Al 2O 3The base enamel that powder is made adhesive agent comprises:
1) weisspiessglanz-molybdenum oxide ground-coat enamel batching proportioning (accounting for the weight percent of ground-coat enamel batching):
Na 2O 15.09％
B 2O 3 13.01％
K 2O 4.5％
Al 2O 3 4.9％
SiO 2 49.07％
CaF 2 8.51％
MnO 2 2.32％
Sb 2O 3 0.89％
BaO 0.89％
MoO 3 0.82％
2) ground-coat enamel slip proportioning (accounting for the weight percent of ground-coat enamel slip):
Clay 4.0%
Sb 2O 3 1.0％
BaMoO 3 0.9％
Na 3BO 3 0.7％
NaNO 2 0.4％
Water 50%
Ground-coat enamel is prepared burden all the other
3) ground-coat enamel proportioning (accounting for the weight percent of ground-coat enamel):
Nanometer Al 2O 3The milk sap 1.0% of powder
The ground-coat enamel slip all the other
4) nanometer Al 2O 3The milk sap proportioning of powder (accounting for the weight percent of this milk sap):
Particle diameter is the Al of 10～20nm 2O 3Powder 25%
Water all the other
2. nanometer Al 2O 3Powder is that the base enamel preparation method of adhesive agent is:
1) with after weisspiessglanz-molybdenum oxide ground-coat enamel batching mixes in proportion, found with crucible in box-type furnace, glass melting temperature is 1190～1210 ℃, and melting time is 2 hours, the check of reeling off raw silk from cocoons, and reeling off raw silk from cocoons is can pulverize after 1～2 joint/rice;
2) batching of the ground-coat enamel after will pulverizing is carried out ball milling with other batchings that are mixed in proportion and is made the ground-coat enamel slip, and ball milling 20 hours, alligatoring degree are 0.5～1.0g/100ml, spends behind 150 mesh sieves aging 1～2 day;
3) with particle diameter be the Al of 10～20nm 2O 3Powder is dispersed in the aqueous solution, makes weight percent and be 25% milk sap.
Before the application of slip, add the ground-coat enamel slurry with mechanical stirring, addition 1.0%, adopting body material is enamel steel plate special SPCC, thick 0.5mm, the application of slip after degreasing, pickling, bake out temperature is 160 ℃, burns till 840 ℃, the time is 2 minutes.
Embodiment 2:
1. utilize nanometer Al 2O 3The base enamel that powder is made adhesive agent comprises:
1) nickel oxide ground-coat enamel batching proportioning (accounting for the weight percent of ground-coat enamel batching):
Na 2O 14.42％
B 2O 3 12.89％
K 2O 4.46％
Al 2O 3 4.86％
SiO 2 45.94％
CaF 2 8.43％
NiO 1.89％
MnO 2 2.26％
NaSiF 4 3.65％
Fe 2O 3 1.2％
2) ground-coat enamel slip proportioning (accounting for the weight percent of ground-coat enamel slip):
Clay 6.0%
Na 3BO 3 0.5％
NaOH 0.5％
Water 50%
Ground-coat enamel is prepared burden all the other
3) ground-coat enamel proportioning (accounting for the weight percent of ground-coat enamel):
Nanometer Al 2O 3The milk sap 1.5% of powder
The ground-coat enamel slip all the other
4) nanometer Al 2O 3The milk sap proportioning of powder (accounting for the weight percent of this milk sap):
Particle diameter is the Al of 10～20nm 2O 3Powder 25%
Water all the other
2. nanometer Al 2O 3The preparation method that powder is made the adhesive agent base enamel is:
1) nickel oxide ground-coat enamel batching is mixed in proportion after, in box-type furnace, found with crucible, glass melting temperature is 1230～1250 ℃, melting time is 2 hours, the check of reeling off raw silk from cocoons, reeling off raw silk from cocoons is can pulverize after 0～1 joint/rice;
2) batching of the ground-coat enamel after will pulverizing is carried out ball milling with other batchings that are mixed in proportion and is made the ground-coat enamel slip, and ball milling 20 hours, alligatoring degree are 0.5～1.0g/100ml, spends behind 150 mesh sieves aging 1～2 day;
3) with particle diameter be the Al of 10～20nm 2O 3Powder is dispersed in the aqueous solution, makes weight percent and be 25% milk sap.
Before the application of slip, add the ground-coat enamel slurry with mechanical stirring, addition 1.5%, adopting body material is enamel steel plate special SPCC, thick 0.5mm, the application of slip after degreasing, pickling, bake out temperature is 160 ℃, and firing temperature is 880 ℃, and the time is 2 minutes and 20 seconds.

Claims (4)

1. utilize nanometer Al 2O 3Powder is made the base enamel of adhesive agent, it is characterized in that it comprises:
1) weisspiessglanz-molybdenum oxide ground-coat enamel batching proportioning accounts for the weight percent that ground-coat enamel is prepared burden:
Na 2O 15.0～17.0％
B 2O 3 12.0～15.0％
K 2O 4.0～4.8％
Al 2O 3 4.8～5.0％
SiO 2 46.0～52.0％
CaF 2 8.4～9.8％
MnO 2 2.0～2.4％
Sb 2O 3 0.8～1.0％
BaO 0.5～0.9％
MoO 3 0.5～0.9％
2) ground-coat enamel slip proportioning accounts for the weight percent of ground-coat enamel slip:
Clay 3.0～6.0%
Sb 2O 3 0.2～1.5％
BaMoO 3 0.3～1.5％
Na 3BO 3 0.2～1.2％
NaNO 2 0.1～0.8％
Water 50%
Ground-coat enamel is prepared burden all the other
3) ground-coat enamel proportioning accounts for the weight percent of ground-coat enamel:
Nanometer Al 2O 3The milk sap 0.5～2.5% of powder
The ground-coat enamel slip all the other
4) nanometer Al 2O 3The milk sap proportioning of powder accounts for the weight percent of this milk sap:
Particle diameter is the Al of 10～20nm 2O 3Powder 10～25%
Water all the other
2. the nanometer Al that utilizes according to claim 1 2O 3Powder is made the base enamel preparation method of adhesive agent, it is characterized in that:
1) with after weisspiessglanz-molybdenum oxide ground-coat enamel batching mixes in proportion, found with crucible in box-type furnace, glass melting temperature is 1190～1250 ℃, and melting time is 2 hours, and pulverize the back;
2) batching of the ground-coat enamel after will pulverizing is carried out ball milling with other batchings that are mixed in proportion and is made the ground-coat enamel slip, ball milling after 20 hours aging 1～2 day;
3) with particle diameter be the Al of 10～20 nanometers 2O 3Powder is dispersed in the aqueous solution, make weight ratio and be 10～25% milk sap, is 0.5～2.5% to add the ground-coat enamel slip with it by the ground-coat enamel weight percent.
3. utilize nanometer Al 2O 3Powder is made the base enamel of adhesive agent, it is characterized in that it comprises:
1) nickel oxide ground-coat enamel batching proportioning accounts for the weight percent that ground-coat enamel is prepared burden:
Na 2O 14.0～16.0％
B 2O 3 11.0～13.0％
K 2O 2.0～5.0％
Al 2O 3 3.0～6.0％
SiO 2 42.0～51.0％
CaF 2 8.0～10.0％
NiO 1.0～2.0％
MnO 2 2.0～2.5％
NaSiF 4 3.0～4.2％
Fe 2O 3 0～2.0％
2) ground-coat enamel slip proportioning accounts for the weight percent of ground-coat enamel slip:
Clay 3.0～6.0%
Na 3BO 3 0.2～1.2％
NaOH 0.1～0.8％
Water 50%
Ground-coat enamel is prepared burden all the other
3) ground-coat enamel proportioning accounts for the weight percent of ground-coat enamel:
Nanometer Al 2O 3The milk sap 0.5～2.5% of powder
The ground-coat enamel slip all the other
4) nanometer Al 2O 3The milk sap proportioning of powder accounts for the weight percent of this milk sap:
Particle diameter is the Al of 10～20nm 2O 3Powder 10～25%
Water all the other
4. the nanometer Al that utilizes according to claim 3 2O 3Powder is made the base enamel preparation method of adhesive agent, it is characterized in that:
1) nickel oxide ground-coat enamel batching is mixed in proportion after, in box-type furnace, found with crucible, glass melting temperature is 1190～1250 ℃, melting time is 2 hours, pulverize the back;
2) batching of the ground-coat enamel after will pulverizing is carried out ball milling with other batchings that are mixed in proportion and is made the ground-coat enamel slip, ball milling after 20 hours aging 1～2 day;
3) with particle diameter be the Al of 10～20 nanometers 2O 3Powder is dispersed in the aqueous solution, make weight percent and be 10～25% milk sap, is 0.5～2.5% to add the ground-coat enamel slip with it by the ground-coat enamel weight percent.
CN 01117289 2001-04-28 2001-04-28 Enamel ground-coat using nanometer Al2O3 powder as adherence promotor and its preparation method Expired - Fee Related CN1128114C (en)

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CN 01117289 CN1128114C (en) 2001-04-28 2001-04-28 Enamel ground-coat using nanometer Al2O3 powder as adherence promotor and its preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 01117289 CN1128114C (en) 2001-04-28 2001-04-28 Enamel ground-coat using nanometer Al2O3 powder as adherence promotor and its preparation method

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CN1128114C true CN1128114C (en) 2003-11-19

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Families Citing this family (8)

* Cited by examiner, † Cited by third party
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CN1314610C (en) * 2003-01-22 2007-05-09 王强 Method for producing blackboard and whiteboard made from enamel in super strength, and glaze of enamel
CN102408196B (en) * 2010-09-21 2015-01-21 湖南立发釉彩科技有限公司 Fish-scaling-resistant enamel glaze for hot-rolled steel plates
CN102391017B (en) * 2011-08-09 2013-07-31 武汉钢铁(集团)公司 High-temperature infrared radiation glaze and preparation method thereof
CN102391018B (en) * 2011-08-10 2013-06-26 刘冬青 Method for making archaistic semimatte thin glaze for Ru porcelain
WO2013139257A1 (en) * 2012-03-19 2013-09-26 东莞市海格瑞化工有限公司 Burn-free colored glaze material
CN104529162A (en) * 2014-12-12 2015-04-22 常熟市永达化工设备厂 Efficient glass lining agitator
CN106810073B (en) * 2015-11-30 2019-11-05 青岛海尔新能源电器有限公司 Enamel powdered frit and enamel internal container of water-heater
CN113233921B (en) * 2021-05-18 2022-11-29 广东宏海陶瓷实业发展有限公司 Preparation method of mold texture ceramic tile and ceramic tile

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