CN1321617A - 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
CN1321617A
CN1321617A CN 01117289 CN01117289A CN1321617A CN 1321617 A CN1321617 A CN 1321617A CN 01117289 CN01117289 CN 01117289 CN 01117289 A CN01117289 A CN 01117289A CN 1321617 A CN1321617 A CN 1321617A
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Prior art keywords
powder
ground
enamel
coat enamel
nanometer
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CN 01117289
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Chinese (zh)
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CN1128114C (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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Priority to CN 01117289 priority Critical patent/CN1128114C/en
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Abstract

The present invention relates to a base enamel utilizing nanometer Al2O3 powder body as adherence promotor and its preparation method. It includes the following steps: melting the antimony oxide-molybdenum oxide or nickel oxide base enamel formed according to a certain mixing proportion by using a crucible for melting, then pulverizing, mixing with additive to implement ball grinding to obtain slurry; dispersing nanometer Al2O3 powder body in aqueous solution to make them form emulsion whose weight percentage is 10-25%, then adding (by wt%) 0.5-2.5% of the above-mentioned emulsion to the base enamel slurry so as to obtain the invented base enamel. It can be substituted for cobalt oxide base enamel, and can reduce cost.

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 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 proportioning (weight percent):
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) mill addition proportioning (weight percent):
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 all the other
3) nanometer Al 2O 3The milk sap of powder (weight percent):
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-the molybdenum oxide ground-coat enamel mixes in proportion, found with crucible in box-type furnace, glass melting temperature is 1190～1250 ℃, and melting time is to pulverize after 2 hours;
2) ground-coat enamel after will pulverizing carries out ball milling with the mill addition that is mixed in proportion and makes 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 by weight percentage with it.
Scheme 2:
1. utilize nanometer Al 2O 3The base enamel that powder is made adhesive agent comprises:
1) nickel oxide ground-coat enamel proportioning (weight percent):
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) mill addition proportioning (weight percent):
Clay 3.0～6.0%
Na 3BO 3 0.2～1.2％
NaOH 0.1～0.8％
Water 50%
Ground-coat enamel all the other
3) nanometer Al 2O 3The milk sap of powder (weight percent):
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) the nickel oxide ground-coat enamel is mixed in proportion after, in box-type furnace, found with crucible, glass melting temperature is 1190～1250 ℃, melting time is to pulverize after 2 hours;
2) ground-coat enamel after will pulverizing carries out ball milling with the mill addition that is mixed in proportion and makes 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 by weight percentage with it.
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 proportioning (weight percent):
Na 2O 5.09％
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) mill addition proportioning (weight percent):
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 all the other
3) nanometer Al 2O 3The milk sap of powder (weight percent):
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-the molybdenum oxide ground-coat enamel 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) ground-coat enamel after will pulverizing carries out ball milling with the mill addition that is mixed in proportion and makes 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 proportioning (weight percent):
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) mill addition proportioning (weight percent):
Clay 6.0%
Na 3BO 3 0.5％
NaOH 0.5％
Water 50%
Ground-coat enamel all the other
3) nanometer Al 2O 3The milk sap of powder (weight percent):
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) the nickel oxide ground-coat enamel 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) ground-coat enamel after will pulverizing carries out ball milling with the mill addition that is mixed in proportion and makes 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 proportioning (weight percent):
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) mill addition proportioning (weight percent):
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 all the other
3) nanometer Al 2O 3The milk sap of powder (weight percent):
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-the molybdenum oxide ground-coat enamel mixes in proportion, found with crucible in box-type furnace, glass melting temperature is 1190～1250 ℃, and melting time is to pulverize after 2 hours;
2) ground-coat enamel after will pulverizing carries out ball milling with the mill addition that is mixed in proportion and makes 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 by weight percentage with it.
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 proportioning (weight percent):
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) mill addition proportioning (weight percent):
Clay 3.0～6.0%
Na 3BO 3 0.2～1.2％
NaOH 0.1～0.8％
Water 50%
Ground-coat enamel all the other
3) nanometer Al 2O 3The milk sap of powder (weight percent):
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) the nickel oxide ground-coat enamel is mixed in proportion after, in box-type furnace, found with crucible, glass melting temperature is 1190～1250 ℃, melting time is to pulverize after 2 hours;
2) ground-coat enamel after will pulverizing carries out ball milling with the mill addition that is mixed in proportion and makes 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 by weight percentage with it.
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

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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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CN1321617A true CN1321617A (en) 2001-11-14
CN1128114C CN1128114C (en) 2003-11-19

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN102391018A (en) * 2011-08-10 2012-03-28 刘冬青 Method for making archaistic semimatte thin glaze for Ru porcelain
CN102391017A (en) * 2011-08-09 2012-03-28 武汉钢铁(集团)公司 High-temperature infrared radiation glaze and preparation method thereof
CN102408196A (en) * 2010-09-21 2012-04-11 湖南立发釉彩科技有限公司 Fish-scaling-resistant enamel glaze for hot-rolled steel plates
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
CN106810073A (en) * 2015-11-30 2017-06-09 青岛海尔新能源电器有限公司 Enamel powdered frit and enamel internal container of water-heater
CN113233921A (en) * 2021-05-18 2021-08-10 广东宏海陶瓷实业发展有限公司 Preparation method of mold texture ceramic tile and ceramic tile

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN102408196A (en) * 2010-09-21 2012-04-11 湖南立发釉彩科技有限公司 Fish-scaling-resistant enamel glaze for hot-rolled steel plates
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
CN102391017A (en) * 2011-08-09 2012-03-28 武汉钢铁(集团)公司 High-temperature infrared radiation glaze and preparation method thereof
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
CN102391018A (en) * 2011-08-10 2012-03-28 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
CN106810073A (en) * 2015-11-30 2017-06-09 青岛海尔新能源电器有限公司 Enamel powdered frit and enamel internal container of water-heater
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
CN113233921A (en) * 2021-05-18 2021-08-10 广东宏海陶瓷实业发展有限公司 Preparation method of mold texture ceramic tile and ceramic tile
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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