CN108298819B - High-temperature porcelain glaze for high-chromium white cast iron - Google Patents
High-temperature porcelain glaze for high-chromium white cast iron Download PDFInfo
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- CN108298819B CN108298819B CN201810128246.5A CN201810128246A CN108298819B CN 108298819 B CN108298819 B CN 108298819B CN 201810128246 A CN201810128246 A CN 201810128246A CN 108298819 B CN108298819 B CN 108298819B
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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
- 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
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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
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Abstract
Hair brushThe high-temperature porcelain glaze for the high-chromium white cast iron is characterized by comprising the following components in percentage by weight: al (Al)2O315‑35％，SiO211.5‑45％，ZrO23‑16％，CoO 1‑4％，TiO22.5‑13.5％，Cr2O31.5‑7.9％，Fe2O30.5‑12％，CaO 3‑6％，Li2O1‑15％，K2O 3‑8％，MgO 2.5‑9.3％，P2O53 to 18 percent. The high-temperature porcelain glaze can be directly coated on the surface of high-chromium white cast iron, is sintered at the temperature of 1250 ℃ plus 1300 ℃ and is naturally cooled, a hard and bright porcelain surface is formed on the surface of the high-chromium white cast iron, has excellent high-temperature corrosion resistance and oxidation resistance, is firmly bonded with the high-chromium white cast iron after being quenched and suddenly heated in a chain furnace at the temperature of 1050 plus 1200 ℃, has no stripping and oxidation phenomena, can be widely used in various severe high-temperature environments or sulfur-containing high-temperature environments, and can also be used in high-temperature wear-resistant environments.
Description
Technical Field
The invention relates to the field of enamel, in particular to a high-temperature enamel for high-chromium white cast iron.
Background
The high-chromium white cast iron is a heat-resistant wear-resistant material with excellent performance, wherein Cr2O3The content is 11.3-30%, the use temperature is 720 ℃ and 950 ℃, and the high-temperature wear-resistant material is widely used in modern industry. With the development of industrial technology, the temperature of modern sintering furnaces has been increased to 1050-. The working limit of the high-chromium white cast iron at 950 ℃ is exceeded, the problems of accelerated oxidation corrosion rate and shortened service life appear, and particularly, the high-temperature corrosion of the high-chromium white cast iron is more serious under the condition of containing sulfur in furnace gas. In order to solve the problems, a refractory coating is often used and coated on the surface of the high-chromium white cast iron so as to achieve the purpose of high-temperature oxidation resistance, but the coating is not firmly bonded with a substrate and is easy to peel off, and the enamel on the high-chromium white cast iron is easy to generate pinholes and bubbles and cannot protect the substrate.
Therefore, aiming at the problems, the invention provides the high-temperature porcelain glaze for the high-chromium white cast iron, solves the problems of oxidation resistance and wear resistance in the high-temperature work of the high-chromium white cast iron, and is well combined with the porcelain glaze to avoid the occurrence of pinholes and bubbles.
Disclosure of Invention
The invention aims to provide a high-temperature porcelain glaze for high-chromium white cast iron, which solves the problems in the prior art, so that the high-temperature porcelain glaze has excellent high-temperature corrosion resistance and oxidation resistance, and is firmly bonded with the high-chromium white cast iron without stripping and oxidation phenomena.
In order to achieve the purpose, the invention provides the following scheme:
the inventionThe high-temperature porcelain glaze for the high-chromium white cast iron is characterized by comprising the following components in parts by weight: the high-temperature porcelain glaze comprises the following components in percentage by weight: al (Al)2O315-35％，SiO211.5-45％，ZrO23-16％，CoO 1-4％，TiO22.5-13.5％，Cr2O31.5-7.9％，Fe2O30.5-12％，CaO 3-6％，Li2O 1-15％，K2O 3-8％，MgO2.5-9.3％，P2O53-18％。
Preferably, the high-temperature porcelain glaze for the high-chromium white cast iron comprises the following raw materials in percentage by mass: al (Al)2O39.3-21.3%, feldspar 20-31%, quartz 4-7%, ZrO23-16％，CoO 1-4％，TiO22.0-10.5％，Cr2O31.5-7.9％，Fe2O30.5-12%, dolomite 5-15%, Suzhou soil 3-10%, L iCO32.5-37％，Al(H2PO4)35-25% of cordierite microcrystalline ceramic and 3.5-30% of cordierite microcrystalline ceramic.
Preferably, the Al is2O3And ZrO2The powder has a particle size of 0.06mm, and contains 15-40% of 50-200 μm superfine powder particles.
Preferably, the cordierite microcrystalline ceramic material is prepared from the following raw materials in percentage by mass: SiO 2248-53％，Al2O321-25％，MgO 15-18％，TiO29.5-11.5％，P2O50.5-5％。
Preferably, the Al (H)2PO4)3The preparation method comprises the following steps: adding 85% industrial phosphoric acid into water, stirring to obtain 60% aqueous solution, adding Al (OH)3Heating to 70-80 deg.C, reacting for 30-60min until the solution is clear, and generating Al (H)2PO4)3；
The preparation method of the cordierite microcrystalline ceramic material comprises the following steps: accurately weighing the raw material formula according to claim 4 by using a balance, mixing, putting into a high-temperature furnace in an oxidizing atmosphere, heating to 1600 ℃ at a speed of 6-8 ℃/min for melting, preserving heat for 3-6h, naturally cooling to 1240 ℃ after fully dissolving, preserving heat for 8h, performing crystallization treatment, and cooling to room temperature to obtain the cordierite microcrystalline ceramic material.
Preferably, the Al (H)2PO4)3In the preparation of (3), the Al (OH)3The weight ratio of the phosphoric acid solution to the phosphoric acid aqueous solution is 1: 6.7.
The research shows that the reason why the grey cast iron can be well combined with the porcelain glaze is as follows: the C in the grey cast iron is infiltrated and exists in ferrite, so the section is grey, and the C in the grey cast iron structure can react with Si in the enamel to form Si-C bonds, thereby being beneficial to the combination of the enamel and the cast iron. On the other hand, white cast iron has another alloy composition, so that C is rarely infiltrated into ferrite, and most of C exists in the iron structure in the form of carbide, so that the cross section of the white cast iron is silvery white. The carbide in the high-chromium white cast iron is easy to decompose at the temperature of 950 ℃ and 1050 ℃ and releases CO and CO2The gas breaks through the porcelain layer, causing bubbles and pinholes in the porcelain face. And the sulfur in the cast iron is a harmful substance, is dissolved in cementite to block the graphitization process of carbon, and is easy to deposit and separate out sulfide on the surface of the cast iron, so that micro cracks, small holes, bubbles and the like are generated on the surface of the cast iron.
Thus, the present invention is based on the use of high temperatures and added TiO2The destructiveness of C in the high-chromium white cast iron structure to the enamel is eliminated, for example, the C removing treatment temperature of the high-chromium white cast iron is 950-2The effect can form hard-to-decompose TiC to eliminate the damage of C in high-chromium white cast iron to enamel.
The grey cast iron is coated with the enamel glaze, the temperature is kept above 750 ℃ for 30-60 minutes to carry out the de-C treatment, and then the enamel glaze is coated, while the high-chromium white cast iron is composed of other alloys and has higher S, P, C content in the structure, and the coated enamel glaze is easy to generate pinholes and bubbles. Therefore, the invention omits the de-C process before the cast iron glaze coating, and avoids the occurrence of phenomena of pinholes, bubbles and the like of the coated porcelain glaze.
The invention adds Al (H)2PO4)3The pearlite (P) in the high-chromium white cast iron is decomposed, the P exists in the high-chromium white cast iron as binary alloy, ternary alloy or multicomponent alloy and is a eutectic body combining the P and other elements, and the P can promote the surface of the high-chromium white cast iron to generate liquid phase at 950-1050 ℃ to increase the mutual dissolution combination of the enamel and the base material.
According to the invention, the cordierite microcrystalline ceramic material is added, so that a microcrystalline structure is formed on the ceramic surface, and the strength, hardness and cold and hot shock properties of the fired ceramic layer are enhanced.
The high-temperature enamel for the high-chromium white cast iron has the advantages that the base material does not need surface treatment, the enamel can be directly coated, the surface treatment process is simplified, and the high-temperature enamel for the high-chromium white cast iron is a bottomless enamel porcelain material and only needs to be coated once.
The high-temperature porcelain glaze for the high-chromium white cast iron is prepared by directly adding water into raw materials and grinding the raw materials to form dispersion liquid, simplifies the complicated process of raw material melting, water quenching and pulp grinding, and can save energy by over 60 percent.
The high-temperature porcelain glaze for the high-chromium white cast iron has Al (H) in the process of sintering with the base material2PO4)3Polymerization and decomposition occur during heating, and the decomposition products can be mixed with SiO in the high-temperature porcelain glaze2、Al2O3And (3) reacting, wherein phosphorus and aluminum in the high-temperature porcelain glaze diffuse into the substrate and can react with an oxide film on the surface of the substrate to form a transition layer of a connection structure, so that a good connection effect is achieved.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will be described in further detail with reference to specific embodiments in order to make the above objects, features and advantages more apparent and understandable.
The raw materials used in the following examples were commercially available materials and were obtained by procurement.
Example 1
(1) Raw materials
Preparation of Al (H)2PO4)3The raw materials are as follows: 85% strength technical phosphoric acid and Al (OH)3；
The prepared cordierite microcrystalline ceramic material comprises the following raw materials in percentage by mass: SiO 2249％，Al2O322％，MgO17％，TiO210.5％，P2O51.5％。
(2)Al(H2PO4)3Preparation of cordierite microcrystalline porcelain
Al(H2PO4)3The preparation method comprises the following steps: adding 85% industrial phosphoric acid into 41.7% (by weight of phosphoric acid) water, stirring to obtain 60% aqueous solution, adding Al (OH)3，Al(OH)3Heating to 70-80 deg.C at a weight ratio of 1:6.7 with phosphoric acid water solution, reacting for 30-60min until the solution is clear, and generating Al (H)2PO4)3。
The preparation of the cordierite microcrystalline ceramic material comprises the following steps: accurately weighing a raw material formula contained in the prepared cordierite microcrystalline ceramic material by using a balance, mixing, placing in a high-temperature furnace in an oxidizing atmosphere, heating to 1600 ℃ at a speed of 6-8 ℃/min for melting, preserving heat for 3-6h, after full dissolution, naturally cooling to 1240 ℃, preserving heat for 8h, carrying out crystallization treatment, and cooling to room temperature to obtain the cordierite microcrystalline ceramic material.
Example 2
(1) Raw materials
The high-temperature porcelain glaze comprises the following raw materials in percentage by mass: al (Al)2O312%, feldspar 25%, quartz 4%, ZrO25％，CoO 1％，TiO24％，Cr2O33％，Fe2O35%, dolomite 7%, Suzhou soil 6%, L iCO313％，Al(H2PO4)35 percent of cordierite microcrystalline porcelain and 10 percent of cordierite microcrystalline porcelain. Al (Al)2O3And ZrO2The powder of (4) has a particle size of 0.06mm and contains 20% of 80 μm ultrafine particles.
(2) Preparation of high-temperature porcelain glaze for high-chromium white cast iron
Accurately weighing the raw material formula for preparing the high-temperature porcelain glaze by using a balance, adding 45% (by total mass of the raw materials) of water, mixing, grinding into dispersion, sieving by using a 80-mesh sieve, wherein the residue on the sieve is less than 1.5%, and the density of the obtained dispersion is 1.65g/m L.
Example 3
(1) Raw materials
The high-temperature porcelain glaze comprises the following raw materials in percentage by mass: al (Al)2O39.5 percent of feldspar, 20 percent of feldspar, 5 percent of quartz and ZrO26％，CoO 2％，TiO23％，Cr2O32％，Fe2O34%, 8% of dolomite, 6% of Suzhou soil and L iCO%311％，Al(H2PO4)311 percent of cordierite microcrystalline porcelain and 12.5 percent of cordierite microcrystalline porcelain. Al (Al)2O3And ZrO2The powder of (4) has a particle size of 0.06mm and contains 25% of ultrafine particles of 100 μm.
(2) Preparation of high-temperature porcelain glaze for high-chromium white cast iron
Accurately weighing the raw material formula for preparing the high-temperature porcelain glaze by using a balance, adding 65% (by total mass of the raw materials) of water, mixing, grinding into dispersion, sieving by using a 80-mesh sieve, wherein the residue on the sieve is less than 1.5%, and the density of the obtained dispersion is 1.60g/m L.
Example 4
(1) Raw materials
The high-temperature porcelain glaze comprises the following raw materials in percentage by mass: al (Al)2O321 percent of feldspar, 21 percent of quartz, 4 percent of ZrO25％，CoO 1％，TiO22％，Cr2O31.5％，Fe2O33.5%, dolomite 7%, Suzhou soil 5%, L iCO38.5％，Al(H2PO4)39 percent of cordierite microcrystalline porcelain and 11.5 percent of cordierite microcrystalline porcelain. Al (Al)2O3And ZrO2The powder of (2) has a particle size of 0.06mm, and contains 30% of 150 μm ultrafine powderAnd (4) granulating.
(2) Preparation of high-temperature porcelain glaze for high-chromium white cast iron
Accurately weighing the raw material formula for preparing the high-temperature porcelain glaze by using a balance, adding 45% (by total mass of the raw materials) of water, mixing, grinding into dispersion, sieving by using a 80-mesh sieve, wherein the residue on the sieve is less than 1.5%, and the density of the obtained dispersion is 1.65g/m L.
Example 5
Component detection of high temperature enamel
The high-temperature porcelain glaze prepared in the embodiment 2-4 comprises the following components in percentage by weight after being detected: al (Al)2O315-35％，SiO211.5-45％，ZrO23-16％，CoO 1-4％，TiO22.5-13.5％，Cr2O31.5-7.9％，Fe2O30.5-12％，CaO 3-6％，Li2O 1-15％，K2O 3-8％，MgO 2.5-9.3％，P2O53-18％。
Example 6
(1) Coating and firing of high-temperature porcelain glaze
The dispersions prepared in examples 2-4 were respectively directly sprayed or dip-coated on high-chromium white cast iron without surface treatment, fired at 1250-.
(2) Performance testing
The coated and sintered high-chromium white cast iron is subjected to a suspension test in a furnace at the temperature of 1000-1100 ℃ for 6 months, and after being taken out, the high-chromium white cast iron has no corrosion and oxidation phenomena, which shows that the high-temperature porcelain glaze has excellent high-temperature corrosion resistance and oxidation resistance. Then, the bonding firmness of the enamel and the base material is tested by quenching and rapid heating in a chain furnace at 1050-.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (5)
1. A high-temperature porcelain glaze for high-chromium white cast iron is characterized in that: the high-temperature porcelain glaze comprises the following components in percentage by weight: al (Al)2O315-35％，SiO211.5-45％，ZrO23-16％，CoO 1-4％，TiO22.5-13.5％，Cr2O31.5-7.9％，Fe2O30.5-12％，CaO 3-6％，Li2O 1-15％，K2O 3-8％，MgO 2.5-9.3％，P2O53-18％；
The high-temperature porcelain glaze comprises the following raw materials in percentage by mass: al (Al)2O39.3-21.3%, feldspar 20-31%, quartz 4-7%, ZrO23-16％，CoO 1-4％，TiO22.0-10.5％，Cr2O31.5-7.9％，Fe2O30.5-12%, dolomite 5-15%, Suzhou soil 3-10%, L iCO32.5-37％，Al(H2PO4)35-25% of cordierite microcrystalline ceramic and 3.5-30% of cordierite microcrystalline ceramic.
2. High temperature enamel for high chromium white cast iron according to claim 1, characterized in that: the Al is2O3And ZrO2The powder has a particle size of 0.06mm, and contains 15-40% of 50-200 μm superfine powder particles.
3. High temperature enamel for high chromium white cast iron according to claim 1, characterized in that: the cordierite microcrystalline ceramic material is prepared from the following raw materials in percentage by mass: SiO 2248-53％，Al2O321-25％，MgO 15-18％，TiO29.5-11.5％，P2O50.5-5％。
4. High temperature enamel for high chromium white cast iron according to claim 3, characterized in that: the Al (H)2PO4)3The preparation method comprises the following steps: adding 85% industrial phosphoric acid into water, stirring uniformly to obtain the concentrationIs 60% aqueous solution, then Al (OH) is added3Heating to 70-80 deg.C, reacting for 30-60min until the solution is clear, and generating Al (H)2PO4)3；
The preparation method of the cordierite microcrystalline ceramic material comprises the following steps: accurately weighing the raw material formula according to claim 3 by using a balance, mixing, putting into a high-temperature furnace in an oxidizing atmosphere, heating to 1600 ℃ at a speed of 6-8 ℃/min for melting, preserving heat for 3-6h, naturally cooling to 1240 ℃ after fully dissolving, preserving heat for 8h, performing crystallization treatment, and cooling to room temperature to obtain the cordierite microcrystalline ceramic material.
5. High temperature enamel for high chromium white cast iron according to claim 4, characterized in that: the Al (H)2PO4)3In the preparation of (3), the Al (OH)3The weight ratio of the phosphoric acid solution to the phosphoric acid aqueous solution is 1: 6.7.
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Citations (7)
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| JPS598639A (en) * | 1982-07-05 | 1984-01-17 | Matsushita Electric Ind Co Ltd | Enamel coating layer and preparation thereof |
| JPH01138152A (en) * | 1987-11-20 | 1989-05-31 | Ngk Insulators Ltd | Production of porcelain enamel product |
| CN1037933A (en) * | 1988-04-28 | 1989-12-13 | 日本钢管株式会社 | The method and apparatus of preparation silicon single-crystal |
| CN1169967A (en) * | 1996-07-08 | 1998-01-14 | 山东新华医药集团有限责任公司 | Low temperature firing acid-alkali resistant enamel and preparation thereof |
| CN101961203A (en) * | 2009-07-21 | 2011-02-02 | 深圳市金凯科技有限公司 | Environmental-friendly heat-resistant microcrystal color ceramic container and manufacturing method thereof |
| CN102167513A (en) * | 2010-12-26 | 2011-08-31 | 湖南省无机色釉料工程技术研究中心有限公司 | Preparation technology of phosphosilicate enamel |
| 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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2018
- 2018-02-08 CN CN201810128246.5A patent/CN108298819B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS598639A (en) * | 1982-07-05 | 1984-01-17 | Matsushita Electric Ind Co Ltd | Enamel coating layer and preparation thereof |
| JPH01138152A (en) * | 1987-11-20 | 1989-05-31 | Ngk Insulators Ltd | Production of porcelain enamel product |
| CN1037933A (en) * | 1988-04-28 | 1989-12-13 | 日本钢管株式会社 | The method and apparatus of preparation silicon single-crystal |
| CN1169967A (en) * | 1996-07-08 | 1998-01-14 | 山东新华医药集团有限责任公司 | Low temperature firing acid-alkali resistant enamel and preparation thereof |
| CN101961203A (en) * | 2009-07-21 | 2011-02-02 | 深圳市金凯科技有限公司 | Environmental-friendly heat-resistant microcrystal color ceramic container and manufacturing method thereof |
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| 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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