阅读说明：本技术 一种耐高温、耐磨、耐强冲击的防腐微晶釉的制备方法 (Preparation method of high-temperature-resistant, wear-resistant and strong-impact-resistant anticorrosive microcrystalline glaze ) 是由 陈鸿美 张倩 余亭月 于 2021-08-23 设计创作，主要内容包括：本发明涉及一种耐高温、耐磨、耐强冲击的防腐微晶釉的制备方法,制备方法的具体步骤为：首先熔制出面釉和底釉,面釉和底釉熔块(片)分别经过粉碎后加入球磨机,并在球磨机内加入规定比例的磨加物一起球磨；球磨机研磨成规定细度粉末后,通过真空输送系统后进入打包机包装入袋,面釉和底釉打包包装后,进入自动喷搪工艺,釉料喷搪完成后进入搪烧工艺,最终会得到防腐微晶釉。此配方、工艺制得的釉料具有超高的抗机械冲击、抗热应力及温差急变性能优,且耐磨性能优,同时耐酸侵蚀性、耐碱侵蚀性优良,适用于反应介质温度高、或反应介质为固液混合有固体颗粒磨损的搪玻璃设备、搅拌配件。(The invention relates to a preparation method of high-temperature-resistant, wear-resistant and strong-impact-resistant anticorrosive microcrystalline glaze, which comprises the following specific steps: firstly, melting out surface glaze and ground glaze, respectively crushing the surface glaze and ground glaze frits (sheets), adding the crushed materials into a ball mill, and adding grinding materials in a specified proportion into the ball mill for ball milling; grinding the mixture into powder with specified fineness by a ball mill, then packaging the powder in a bag by a packaging machine after passing through a vacuum conveying system, packaging and packaging the overglaze and the ground glaze, then performing an automatic enameling process, and performing an enameling firing process after the enameling of the glaze is finished to finally obtain the anticorrosive microcrystalline glaze. The glaze prepared by the formula and the process has the advantages of ultrahigh mechanical impact resistance, excellent thermal stress resistance and temperature difference rapid change performance, excellent wear resistance, excellent acid erosion resistance and alkali erosion resistance, and is suitable for glass lining equipment and stirring accessories with high reaction medium temperature or solid-liquid mixed solid particles for abrasion.)

1. A preparation method of high-temperature-resistant, wear-resistant and strong-impact-resistant anticorrosive microcrystalline glaze is characterized by comprising the following steps: the preparation method comprises the following specific steps:

1) firstly, melting out surface glaze and ground glaze;

2) respectively crushing the surface glaze and the bottom glaze block by a crusher, adding the crushed surface glaze and the ground glaze block into a ball mill, and adding grinding materials in a specified proportion into the ball mill for ball milling;

3) grinding the powder into powder with specified fineness by a ball mill, and then feeding the powder into a packaging machine for packaging into bags through a vacuum conveying system;

4) after the cover glaze and the bottom glaze are packaged, an automatic enamel spraying process is carried out, wherein the automatic enamel spraying process comprises the following steps:

firstly, spraying base glaze twice, wherein the total thickness of the porcelain layer is less than or equal to 0.3 mm;

secondly, 5-time surface glaze spraying is carried out, the layering thickness of 1-3-time glaze layers is 0.15-0.25 mm, and the layering thickness of 4-5-time glaze layers is 0.10-0.15 mm;

thirdly, the thickness of the finished product total ceramic layer is 1.2-1.5 mm;

5) after the glaze is enameled, entering an enameling firing process, wherein the enameling firing process adopts a curve firing process, and the firing process comprises the following specific steps:

firstly, primary ground glaze: when the temperature of the furnace rises to 910-920 ℃, the product enters the furnace, the furnace door is closed, when the temperature rises to 920 ℃ again, and the product is discharged after 2-6 minutes;

secondly, base glaze twice: keeping the temperature at 550-600 ℃ for 30 minutes, then heating and controlling the heating rate to 900-910 ℃ for sintering;

surface glaze: firing temperature of the overglaze is 820-840 ℃;

crystallization treatment process: and (3) using a enameling furnace with an intelligent instrument, heating the product to 300 ℃, feeding the product into the furnace, heating the product to 700-720 ℃ for 2 hours, keeping the temperature for 30 minutes, cutting off a power supply, cooling the product to room temperature, discharging the product out of the furnace, and finally obtaining the anticorrosive microcrystalline glaze.

2. The preparation method of the high-temperature-resistant, wear-resistant and high-impact-resistant anticorrosive microcrystalline glaze according to claim 1, characterized in that: in the step 1), the overglaze porcelain layer base material comprises the following components in percentage by weight:

SiO₂ 60～62；

Al₂O₃ 5～8；

TiO₂ 8～10；

K₂O 5～7；

Li₂O 10～12；

Na₂O 6～7；

MoO₃ 2～3；

BaO 3～4；

Na₂SiF₆ 0.5～1.5；

the base material of the ground glaze porcelain layer comprises the following components in percentage by weight:

SiO₂ 50～52；

Al₂O₃ 0～1.0；

TiO₂ 2～5；

B₂O₃ 14～16；

Li₂O 2～3；

Na₂O 11～13；

CaF₂ 8～10；

CoO 1～1.5；

MnO 2～2.5。

3. the preparation method of the high-temperature-resistant, wear-resistant and high-impact-resistant anticorrosive microcrystalline glaze according to claim 1, characterized in that: in the step 2), the mass parts of ground materials of the overglaze are as follows:

a glaze 100;

0.2-0.4% of sodium nitrite;

0.5-1% of an emulsion;

0.2 to 0.5 of cellulose;

0-0.1% of preservative;

40-50 parts of water;

the ground material of the ground glaze comprises the following components in parts by mass:

a glaze 100;

14-18 parts of quartz sand;

5-10 parts of zirconia fiber;

0.3-0.5 of magnesium carbonate;

0.3-0.5% of borax pentahydrate;

0.5-1% of lithium carbonate;

0.2-0.4% of sodium nitrite;

0.2 to 0.5 of cellulose;

1-2 parts of nickel protoxide;

0.3-0.5 of cobalt oxide;

0-1% of soda ash.

Technical Field

The invention relates to a preparation method of high-temperature-resistant, wear-resistant and strong-impact-resistant anticorrosive microcrystalline glaze.

Background

The silicate system glass-lined glaze has SiO as main skeleton₂The internal structure of the enamel glass glaze contains silicon-oxygen tetrahedronSiO₄Firm skeletons formed by interconnection are relatively complete. Generally, a true crystal has a complete and regular appearance and a complete and regular internal arrangement, and a crystalline substance generally has a melting point, but there is no uniform arrangement of particles inside the amorphous body, and the temperature required for breaking the structure of each part is different, so there is no certain melting point, which is an important characteristic different from a crystalline substance.

The enamel glass is an amorphous object, similar to glass, wherein original crystals which are remained and do not participate in the reaction and a small amount of crystals are separated out in the melt cold quenching process, the crystals are only embedded in the glass phase, and microcracks exist in the glass phase, which is the characteristic of the material. The surface of the conventional glass-lined glaze is in a smooth glass state after being sintered, and if hard particles are repeatedly rubbed on the surface of an enamel surface, the surface of the glass-lined layer of equipment is abraded, so that the good corrosion resistance is lost. And the glass-lined glaze softens first and then gradually becomes a viscous liquid when heated.

Disclosure of Invention

The invention aims to overcome the defects and provides a preparation method of high-temperature-resistant, wear-resistant and strong-impact-resistant anticorrosive microcrystalline glaze, and the glaze prepared by the formula and the process has the advantages of ultrahigh mechanical impact resistance, excellent thermal stress resistance and temperature difference rapid change performance, excellent wear resistance, excellent acid erosion resistance and alkali erosion resistance, and is suitable for glass lining equipment and stirring accessories with high reaction medium temperature or solid-liquid mixed solid particle abrasion as a reaction medium.

The purpose of the invention is realized as follows:

a preparation method of high-temperature-resistant, wear-resistant and strong-impact-resistant anticorrosive microcrystalline glaze comprises the following specific steps:

1) firstly, melting out surface glaze and ground glaze;

2) adding a grinding material into the ball mill when the surface glaze and the bottom glaze are respectively ball-milled by the ball mill;

3) after the ball mill finishes crushing, the crushed materials pass through a vacuum conveying system and then enter a packaging machine to be packaged into bags;

4) respectively mixing and ball-milling the surface glaze and the bottom glaze into powder, packaging, and then entering an automatic enamel spraying process, wherein the automatic enamel spraying process comprises the following steps:

firstly, spraying base glaze twice, wherein the total thickness of the porcelain layer is less than or equal to 0.3 mm;

secondly, 5-time surface glaze spraying is carried out, the layering thickness of 1-3-time glaze layers is 0.15-0.25 mm, and the layering thickness of 4-5-time glaze layers is 0.10-0.15 mm;

thirdly, the thickness of the finished product total ceramic layer is 1.2-1.5 mm;

5) after the glaze is enameled, entering an enameling firing process, wherein the enameling firing process adopts a curve firing process, and the firing process comprises the following specific steps:

firstly, primary ground glaze: when the temperature of the furnace rises to 910-920 ℃, the product enters the furnace, the furnace door is closed, and when the temperature rises to 920 ℃ again, the product is discharged after 2-6 minutes;

secondly, base glaze twice: keeping the temperature at 550-600 ℃ for 30 minutes, then heating and controlling the heating rate to 900-910 ℃ for sintering;

surface glaze: firing temperature of the overglaze is 820-840 ℃;

crystallization treatment process: and (3) using a enameling furnace with an intelligent instrument, heating the product to 300 ℃, feeding the product into the furnace, heating the product to 700-720 ℃ for 2 hours, keeping the temperature for 30 minutes, cutting off a power supply, cooling the product to room temperature, discharging the product out of the furnace, and finally obtaining the anticorrosive microcrystalline glaze.

Preferably, in the step 1), the overglaze porcelain layer base material comprises the following components in percentage by weight:

SiO₂ 60～62；

Al₂O₃ 5～8；

TiO₂ 8～10；

K₂O 5～7；

Li₂O 10～12；

Na₂O 6～7；

MoO₃ 2～3；

BaO 3～4；

Na₂SiF₆ 0.5～1.5；

the base material of the ground glaze porcelain layer comprises the following components in percentage by weight:

SiO₂ 50～52；

Al₂O₃ 0～1.0；

TiO₂ 2～5；

B₂O₃ 14～16；

Li₂O 2～3；

Na₂O 11～13；

CaF₂ 8～10；

CoO 1～1.5；

MnO 2～2.5。

preferably, in the step 2), the ground glaze comprises the following components in parts by mass:

a glaze 100;

0.2-0.4% of sodium nitrite;

0.5-1% of an emulsion;

0.2 to 0.5 of cellulose;

0-0.1% of preservative;

40-50 parts of water;

the ground material of the ground glaze comprises the following components in parts by mass:

a glaze 100;

14-18 parts of quartz sand;

5-10 parts of zirconia fiber;

0.3-0.5 of magnesium carbonate;

0.3-0.5% of borax pentahydrate;

0.5-1% of lithium carbonate;

0.2-0.4% of sodium nitrite;

0.2 to 0.5 of cellulose;

1-2 parts of nickel protoxide;

0.3-0.5 of cobalt oxide;

0-1% of soda ash.

The preparation method of the high-temperature-resistant, wear-resistant and strong-impact-resistant anticorrosive microcrystalline glaze has the following advantages:

the silicate physical and chemical knowledge tells us that the crystallization of silicate melt is realized by two stages of nucleation and crystallization, and the two stages are divided into homogeneous nucleation and heterogeneous nucleation and homogeneous crystallization and heterogeneous crystallization, wherein the homogeneous nucleation and crystallization are mainly generated in a uniform glass medium, namely crystal nuclei can be separated out under certain conditions without an additive and grow into crystals, but the heterogeneous nucleation and crystallization are different, the additive, namely a nucleating agent, is introduced to induce new crystal nuclei to be attached on the crystal nuclei to generate and develop crystals, and the enamel glass glaze becomes microcrystalline glaze, and belongs to the category of the heterogeneous nucleation and crystallization.

The enamel layer is not an amorphous substance with various properties but an inorganic silicate crystal material with a similar metal internal structure, so that the stress value can be continuously weakened and the stress propagation direction can be changed under the action of external force (due to the fact that the crystal material has various properties), and the destructive effect of stress is reduced.

The addition of crystal nucleus agent greatly reduces the work required by crystal nucleus formation, so that the nucleation can be implemented at lower temp., the type and quantity of crystal are determined, and the chemical composition of glass-lined glaze (including crystal nucleus agent) and the temp. and time system for controlling nucleation and crystallization are controlled.

Detailed Description

The invention relates to a preparation method of high-temperature-resistant, wear-resistant and strong-impact-resistant anticorrosive microcrystalline glaze.

The preparation method of the high-temperature-resistant, wear-resistant and strong-impact-resistant anticorrosive microcrystalline glaze comprises the following steps:

1) firstly, a surface glaze and a bottom glaze need to be melted, wherein the surface glaze and the bottom glaze are two raw materials with different components.

Wherein, the glass lining overglaze is composed of a complex silicate system [ SiO ]₂-R₂O₃-R₂O-RO-F ], the overglaze porcelain layer base stock comprises the following components in percentage by weight:

SiO₂ 60～62；

Al₂O₃ 5～8；

TiO₂ 8～10；

K₂O 5～7；

Li₂O 10～12；

Na₂O 6～7；

MoO₃ 2～3；

BaO 3～4；

Na₂SiF₆ 0.5～1.5；

wherein Li₂O: it is not only a strong fluxing agent in glaze, which can endow glass enamel with a series of valuable physical and chemical properties, but also can be used as a typical crystal nucleus promoter for manufacturing microcrystalline glaze to precipitate spodumene and eucryptite in the glaze.

TiO₂: as a strong opacifier, the titanium dioxide has extremely high covering power, the thermal stability is excellent in nuclear chemical stability, the mechanical strength is high, and titanium oxide crystals are precipitated in the sintering process.

Na₂SiF₆ : as an auxiliary agent, oxide crystals are precipitated during sintering, and meanwhile, the emulsion is taken into consideration, and the emulsion is also a lubricant for process operation.

MoO₃: the product can reduce the surface tension of melt, enhance adhesion, and assist crystal precipitation and opacification.

Al₂O₃: the additive is introduced as an auxiliary agent to coordinate the physical and chemical properties of the glaze, so that the glass is not easy to reach the homogeneous formation degree, and the thermal stability, the chemical stability and the wear resistance are improved.

BaO: the introduction of the glaze improves the fluidity and the luster of glaze melt and improves the tensile strength and the bending strength of the glaze.

SiO₂The skeleton as the body agent of glass lining glaze.

Na₂O: introduced as an adjuvant.

K₂O: introduced as an adjuvant.

The base material of the ground glaze porcelain layer comprises the following components in percentage by weight:

SiO₂ 50～52；

Al₂O₃ 0～1.0；

TiO₂ 2～5；

B₂O₃ 14～16；

Li₂O 2～3；

Na₂O 11～13；

CaF₂ 8～10；

CoO 1～1.5；

MnO 2～2.5；

the ground glaze formula is characterized in that: the sintering range is wide, and the method can be used for 900-; the adherence performance is good; the thermal shock resistance is excellent, and the temperature difference resistance is higher than 600 ℃; the expansion coefficient is large; has excellent anti-scaling effect.

2) Respectively pulverizing the overglaze clinker (sheet) and the ground glaze clinker (sheet) by a pulverizer, respectively adding into a ball mill for grinding to form powder, and adding the ground material into the ball mill when the overglaze and the ground glaze are ball-milled by the ball mill.

Wherein the ground substance of the overglaze comprises the following components in parts by mass:

a glaze 100;

0.2-0.4% of sodium nitrite;

0.5-1% of an emulsion;

0.2 to 0.5 of cellulose;

0-0.1% of preservative;

40-50 parts of water;

the formula of the overglaze mill is adopted to eliminate clay, an imported nano organic suspending agent is used, and the wet milling process is adopted in a ball milling mode, so that the uniformity of the glaze slip is improved.

The ground material of the ground glaze comprises the following components in parts by mass:

a glaze 100;

14-18 parts of quartz sand;

5-10 parts of zirconia fiber;

0.3-0.5 of magnesium carbonate;

0.3-0.5% of borax pentahydrate;

0.5-1% of lithium carbonate;

0.2-0.4% of sodium nitrite;

0.2 to 0.5 of cellulose;

1-2 parts of nickel protoxide;

0.3-0.5 of cobalt oxide;

0-1% of soda ash;

the ground material of the ground glaze is added with zirconium oxide (ZrO)₂) The fiber obviously improves the toughness of the porcelain layer and the thermal shock resistance of the ground glaze, and the addition of magnesium carbonate in the ground addition can adjust the performance of the glaze slip and generate micro bubbles in the ground glaze layer, thereby increasing the elasticity of the ground glaze layer. The nickel protoxide and the cobalt oxide can increase the adherence of the ground coat and have excellent anti-scaling effect.

3) And after the ball mill finishes crushing, sending the crushed material into a packaging machine for packaging.

4) After the surface glaze and the bottom glaze are mixed into powder and packaged, an automatic enamel spraying process is carried out, the labor intensity of workers can be reduced by the automatic enamel spraying process, the thickness uniformity of an enamel layer is improved, and the automatic enamel spraying process comprises the following steps:

firstly, spraying base glaze twice, wherein the total thickness of the porcelain layer is less than or equal to 0.3 mm;

secondly, 5-time surface glaze spraying is carried out, the layering thickness of 1-3-time glaze layers is 0.15-0.25 mm, and the layering thickness of 4-5-time glaze layers is 0.10-0.15 mm;

thirdly, the thickness of the finished product total ceramic layer is 1.2-1.5 mm;

5) after the glaze is sprayed with enamel, the glaze enters an enamel firing process, and the enamel firing process adopts a curve firing process and has the characteristics of good glaze compactness, good enamel surface glossiness and good flatness.

The firing process comprises the following specific steps:

firstly, primary ground glaze: when the temperature of the furnace rises to 910-920 ℃, the product enters the furnace, and the furnace door is closed. And when the temperature is increased to 920 ℃ again and the red heat of each part of the product is basically consistent and kept for 2-6 minutes, discharging the product out of the furnace.

Secondly, base glaze twice: in order to eliminate the defects of the fire-blocking part generated in the process of firing the cold spray product, the secondary ground coat needs to be fired in a curve mode. Keeping the temperature at 550-600 ℃ for 30 minutes, then heating and controlling the heating rate to 900-910 ℃ for sintering.

Surface glaze: sintering in a curve mode, wherein the sintering temperature of the overglaze is 820-840 ℃.

Crystallization treatment process: the method comprises the steps of using a enameling furnace with an intelligent instrument, heating products to 300 ℃ in the furnace for 2 hours, heating the products to 700-720 ℃, keeping the temperature for 30 minutes, cutting off a power supply, cooling the products to room temperature, discharging the products, and finally obtaining the anticorrosive microcrystalline glaze with different properties by adopting different crystallization treatment temperatures, wherein the following table 1 shows.

Table 1 is a summary table of experimental data of the crystallization treatment process

After the microcrystalline glaze is subjected to crystallization treatment by the special process, the strength, the wear resistance, the temperature difference shock resistance and the pressure resistance of the porcelain layer can be improved. The acid corrosion resistance is less than or equal to 0.85 g/square meter; the temperature difference and acute denaturation resistance is not less than 380 ℃; the mechanical impact resistance is not less than 500X 10-3J.

The enamel layer is not an amorphous substance with various properties but an inorganic silicate crystal material with a similar metal internal structure, so that the stress value can be continuously weakened and the stress propagation direction can be changed under the action of external force (due to the fact that the crystal material has various properties), the stress destruction is reduced, and the temperature difference rapid change resistance, the mechanical impact resistance and the abrasion resistance of the enamel layer are finally improved.