CN104788021A - Enamel glaze and product obtained by using enamel glaze - Google Patents
Enamel glaze and product obtained by using enamel glaze Download PDFInfo
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- CN104788021A CN104788021A CN201510110805.6A CN201510110805A CN104788021A CN 104788021 A CN104788021 A CN 104788021A CN 201510110805 A CN201510110805 A CN 201510110805A CN 104788021 A CN104788021 A CN 104788021A
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- steel plate
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Abstract
An enamel glaze comprises a base material and reinforcing particles, the base material comprises one or more of silica, zirconia, alumina, calcium oxide, nickel oxide and titanium dioxide, and the reinforcing particles comprise zirconia particles. A sheet sprayed with the enamel glaze can be widely used in various strict high temperature environments, such as fields of gas turbine systems, engine systems, aircraft heat exchanger apparatuses, spaceflight and aviation heat exchangers, and turbine assemblies.
Description
Technical field
The application relates to a kind of vitreous enamel, a kind of steel plate, a kind of turbine assembly, a kind of gas turbine engine systems, a kind of engine system, a kind of heat exchanger unit.
Background technology
Glassed Steel is a kind of being coagulated in matrix steel plate by melting by unorganic glass material and matrix material together with steel plate mortise.The glaze of surface of steel plate is usually used in preventing steel plate from getting rusty, and makes steel plate can not in Surface Creation zone of oxidation when being heated, simultaneously for preventing the corrosion of steel plate.Wherein fish scaling resistance is the important indicator weighing Glassed Steel enamel property.In order to improve the fish scaling resistance of steel plate, the quality improving steel plate interior tissue and raising steel plate is very important.Prevent squama quick-fried, must containing enough inclusiones, hole or precipitate in steel.Inclusion is conducive to improving fish scaling resistance, and reason is to there is tiny holes around inclusion, and these tiny holes play a part to catch hydrogen, become hydrogen trap.But inclusion can damage forming property and the mechanical property of steel plate, the impact of the inclusion of dissimilar inclusion and different size distribution is also not quite similar, and therefore, the characteristic for inclusion will be allowed a choice.
For the problems referred to above, applicant carries out a series of research thus develops multiple new steel grade, but, for different steel grade, the vitreous enamel being covered in surface is also different, for the environment of high temperature strong corrosion, applicant provides a kind of vitreous enamel for using on Glassed Steel surface, can ensure that sheet material has good resistance to elevated temperatures, solve the problem of currently available products Glassed Steel resistance to elevated temperatures deficiency.
Summary of the invention
The application provides a kind of vitreous enamel, and it is made up of base-material and reinforcing particle.Wherein base-material is adopted as the LMP material in high-melting-point substances replacement routine techniques is to improve the high-temperature stability of finished product glaze layer.
Wherein base-material comprises one or more in silicon-dioxide, zirconium white, aluminium sesquioxide, calcium oxide, nickel oxide and titanium dioxide.Wherein reinforcing particle comprises zirconia particles.
The preferred version of the application is: vitreous enamel is made up of base-material and reinforcing particle, base-material is made up of silicon-dioxide 50-70wt%, zirconium white 10-20wt%, aluminium sesquioxide 5-10wt%, calcium oxide 5-10wt%, nickel oxide 1-5wt%, titanium dioxide 1-5wt%, and above-mentioned each composition mass fraction sum is 100wt%.Reinforcing particle is zirconia particles, and reinforcing particle consumption is the 10-20wt% of base-material weight part.
Further preferred version is: base-material is made up of silicon-dioxide 60-70wt%, zirconium white 15-20wt%, aluminium sesquioxide 5-7wt%, calcium oxide 8-10wt%, nickel oxide 1-2wt%, titanium dioxide 1-2wt%, and above-mentioned each composition mass fraction sum is 100wt%.
The 10-15wt% of the further preferred version of reinforcing particle to be its consumption be base-material weight part.
And for the selection of zirconia particles, the zirconium white preferably selected is nano particle, and the overall dimension scope of nanoparticle size is no more than 500nm, wherein particle size range accounts for 10-20% at the particle of 100-500nm, particle size range accounts for 30-70% at the particle of 50-100nm, particle size range accounts for 10-20% at the particle of 20-50nm, and the particle sum of three kinds of particle size range is 100%.
The application also provides a kind of preparation method of enamel, and detailed process is as follows: 1) proportioning is on request prepared burden, and then carries out melt.Melting technology is constant-speed heating, and heat-up rate is 10-50 DEG C/minute, and when being warming up to 1500-1700 DEG C, preferably 1550 DEG C, be then incubated 1-2 hour, cold water is quenched and obtained vitreous enamel base-material; 2) the vitreous enamel base-material ball milling obtained is obtained micro mist, then mix with zirconia particles, be dispersion agent with ethanol, stir to obtain suspension; 3) use mesohigh spraying coating process that gained suspension is sprayed on plate surface, obtain stock, then through 950-1100 DEG C of sintering 5-20 hour, naturally cooling obtains finished product.
Wherein step 2) be less than 10 μm to being milled to particle diameter during base-material ball milling.
And for the sheet material that vitreous enamel is used, preferably use counterenamel plate, and its sheet material Chemical Composition is: C:0.02-0.05%, N:0.012-0.015%, S:0.01-0.05%, P :≤0.045%, Si :≤0.04%, W≤0.025%, Mn:0.05-1.3%, Al:0.01-0.05%, Ti:0.01-0.05%, RE:0.05-0.2%, surplus is Fe and inevitable impurity, is all weight percentage above.
Wherein RE refers to rare earth metal, and can be used alone lanthanoid metal in this application, also can be used alone metallic cerium, also can use the mishmetal be made up of with 1:1 lanthanoid metal and metallic cerium.
The mechanical property of above-mentioned sheet material is: yield strength is 350-480MPa, and tensile strength is 300-500MPa, and unit elongation is 25-50%, and the cupping degree of depth is more than or equal to 6mm.
By in process of production to the accurate control of W content in sheet material, and make the relation between its content and all the other elements can obtain the optimal performance of sheet material, wherein relational expression can illustrate with following formula: W=(C+0.98N+0.5S)/2-Ti.And inevitably there is error due to the measurement of constituent content each in actual production process, therefore the limit of error of above formula controls to be allow within ± 1%, and those skilled in the art can understand the reasonableness that error exists.And for the point of theory of above-mentioned arithmetic expression, the ratio can inferring between element W and each element can reach its space as the site of trapping hydrogen, thus make it have the state that height catches Hydrogen Energy power, thus be easy to react with hydrogen and absorbed.Scheme listed by above formula is the most preferred technique scheme of the application's hot-rolled steel sheet.
Further, by hot rolling, roll rear rapid cooling, the step of batching to prepare above-mentioned sheet material.
Wherein hot rolling start rolling temperature is 1100-1300 DEG C, and finishing temperature is 800-900 DEG C, and accumulative draught is 50%-90%.
Wherein roll rear rapid cooling and adopt cooling fast, such as section cooling, speed of cooling is 25-40 DEG C/s, and coiling temperature is 600-650 DEG C, and final sheet metal thickness is 15-25mm.
In addition, the processing parameter for hot rolling is specific as follows: first stage hot-rolled temperature is 1200 ± 50 DEG C, and draught is 15-25%; Subordinate phase hot-rolled temperature is 1100 ± 50 DEG C, and draught is 10-20%; Phase III hot-rolled temperature is 1000 ± 30 DEG C, and draught is 10-20%, and fourth stage hot-rolled temperature is 850 ± 10 DEG C, and draught is 5-15%; Accumulative draught controls within 50-90% interval range.In addition, the sheet material draught of above-mentioned every one-phase is all calculate based on original blank sheet metal thickness.
Obtained vitreous enamel is sprayed on above-mentioned steel plate, and adopt 900 DEG C of heat erosions experiment to test matrix, sheet material produces without overburden, vitreous enamel and sheet material associativity good, after the test of high-temperature fusion salt hot corrosion, sample is without weightlessness, and sample weightening finish is at 0.24-0.27mg/cm
2between.
The application also provides a kind of turbine assembly using above-mentioned steel plate.
The application also provides a kind of gas turbine engine systems using above-mentioned steel plate.
The application also provides a kind of engine system using above-mentioned steel plate.
The application also provides a kind of heat exchanger unit using above-mentioned steel plate.
The beneficial effect of the application: the base-material that (1) enamel uses all is made up of high-melting-point substances, thus improves the high-temperature stability of enamel layer, makes glaze layer can play good provide protection to sheet material under High Temperature Hot-corrosion Behaviorof environment; (2) glaze layer preparation technology is simple, and long service life, has a good application prospect; (3) adopt the zirconium white reinforcing particle of small particle size can increase glaze layer solidity to corrosion further, and decrease sintering time relative to use corundum material, decrease energy consumption; (4) steel plate spraying enamel has good surface property, compact structure, without obvious microdefect.
The Glassed Steel of what the method obtained be covered with glaze layer can be used for the hot environment of various harshness, such as gas turbine engine systems, engine system, aircraft heat exchanger unit, space flight, aviation heat exchanger, the fields such as turbine assembly.
Embodiment
(1) prepare hot-rolled steel sheet: in following table, embodiment 1-6 is the hot-rolled steel sheet of example, comparative example 7-9 is the hot-rolled steel sheet not adding tungsten and rare earth element.
Table 1 hot rolled plate component list (unit: wt%).
| Embodiment | C | N | S | P | Si | W | Mn | Al | Ti | La | Ce |
| 1 | 0.05 | 0.015 | 0.05 | 0.05 | 0.04 | 0.02 | 1.5 | 0.05 | 0.025 | 0.06 | — |
| 2 | 0.02 | 0.015 | 0.04 | 0.02 | 0.04 | 0.0074 | 1.5 | 0.04 | 0.02 | 0.16 | — |
| 3 | 0.03 | 0.015 | 0.05 | 0.02 | 0.02 | 0.025 | 0.05 | 0.01 | 0.01 | 0.1 | 0.1 |
| 4 | 0.04 | 0.012 | 0.05 | 0.02 | 0.03 | 0.013 | 1.0 | 0.04 | 0.025 | — | 0.12 |
| 5 | 0.05 | 0.015 | 0.05 | 0.05 | 0.01 | 0.015 | 1.5 | 0.05 | 0.025 | 0.05 | 0.14 |
| 6 | 0.05 | 0.015 | 0.05 | 0.05 | 0.04 | 0.024 | 1.5 | 0.05 | 0.025 | 0.13 | 0.03 |
| Comparative example | C | N | S | P | Si | W | Mn | Al | Ti | La | Ce |
| 7 | 0.05 | 0.015 | 0.05 | 0.05 | 0.04 | — | 1.5 | 0.05 | 0.05 | — | — |
| 8 | 0.02 | 0.015 | 0.04 | 0.02 | 0.04 | — | 1.5 | 0.04 | 0.04 | — | — |
| 9 | 0.04 | 0.012 | 0.05 | 0.02 | 0.03 | — | 1 | 0.04 | 0.05 | — | — |
(2) impose enamel to the surface of steel plate of embodiment 1-6 and comparative example 7-9, operation steps is as follows.
1. prepare base-material.Raw material is: silicon-dioxide 50-70wt%, zirconium white 10-20wt%, aluminium sesquioxide 5-10wt%, calcium oxide 5-10wt%, nickel oxide 1-5wt%, titanium dioxide 1-5wt% form, and above-mentioned each composition mass fraction sum is 100wt%.Melting technology is constant-speed heating, and heat-up rate is 10-50 DEG C, and at 1500-1700 DEG C of temperature range inside holding 1-2 hour, cold water is quenched and obtained glaze base.
2. add reinforcing particle.The glaze base ball milling obtained is obtained micro mist; then mix with zirconia particles; take ethanol as dispersion agent; stir to obtain suspension, wherein zirconium white is nano particle, and the overall dimension scope of nanoparticle size is no more than 500nm; wherein particle size range accounts for 10-20% at the particle of 100-500nm; particle size range accounts for 30-70% at the particle of 50-100nm, and particle size range accounts for 10-20% at the particle of 20-50nm, and the particle sum of three kinds of particle size range is 100%.
3. vitreous enamel is sprayed on the steel plate of sample 1-9.Use mesohigh spraying coating process that gained suspension is sprayed on plate surface, obtain stock, then through 950-1100 DEG C of sintering 5-20 hour, naturally cooling obtains finished product.
4. Experimental comparison.900 DEG C of high-temperature fusion brine corrosion test (75wt%Na are carried out to gained glazing Glassed Steel
2sO
4+ 25% NaCl), the thermal etching time is respectively 30 hours, 50 hours and 100 hours, and the sample thermal etching rear surface coating of embodiment 1-6 is without obscission, and sample weightening finish is at 0.24-0.27mg/cm
2between.And the sample thermal etching rear surface coating of comparative example 7-9 produces hickie, with finger wipe surfaces generating portion peeling phenomenon.
Claims (7)
1. a vitreous enamel, is made up of base-material and reinforcing particle, base-material comprise in silicon-dioxide, zirconium white, aluminium sesquioxide, calcium oxide, nickel oxide and titanium dioxide one or more, wherein reinforcing particle comprises zirconia particles.
2. the preparation method of a vitreous enamel according to claim 1, it comprises the steps: 1) proportioning on request prepares burden, then melt is carried out, melting technology is constant-speed heating, heat-up rate is 10-50 DEG C/minute, be warming up to 1500-1700 DEG C, be then incubated 1-2 hour, cold water is quenched and is obtained vitreous enamel base-material; 2) the vitreous enamel base-material ball milling obtained is obtained micro mist, then mix with zirconia particles, be dispersion agent with ethanol, stir to obtain suspension; 3) use mesohigh spraying coating process that gained suspension is sprayed on plate surface, obtain stock, then through 950-1100 DEG C of sintering 5-20 hour, naturally cooling obtains finished product.
3. a surface spraying is had the right the steel plate of the vitreous enamel described in requirement 1.
4. a turbine assembly, comprises steel plate as claimed in claim 3.
5. a gas turbine engine systems, comprises steel plate as claimed in claim 3.
6. an engine system, comprises steel plate as claimed in claim 3.
7. a heat exchanger unit, comprises steel plate as claimed in claim 3.
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| CN201510110805.6A CN104788021B (en) | 2015-03-14 | 2015-03-14 | A kind of vitreous enamel and obtained product |
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| CN201510110805.6A CN104788021B (en) | 2015-03-14 | 2015-03-14 | A kind of vitreous enamel and obtained product |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409138A (en) * | 2018-04-11 | 2018-08-17 | 东北大学 | The enamel coating and its preparation process of a kind of resistance to sulfuric acid, salt acid dew piont corrosion |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1681742A (en) * | 2002-07-08 | 2005-10-12 | Aos控股公司 | Water-resistant porcelain enamel coatings and method of manufacturing same |
| CN101130451A (en) * | 2007-08-06 | 2008-02-27 | 江阴硅普搪瓷有限公司 | Milling of energy-saving type glassed steel overglaze added with ultra-fine zro* powder body as fortifier |
| 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 |
-
2015
- 2015-03-14 CN CN201510110805.6A patent/CN104788021B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1681742A (en) * | 2002-07-08 | 2005-10-12 | Aos控股公司 | Water-resistant porcelain enamel coatings and method of manufacturing same |
| CN101130451A (en) * | 2007-08-06 | 2008-02-27 | 江阴硅普搪瓷有限公司 | Milling of energy-saving type glassed steel overglaze added with ultra-fine zro* powder body as fortifier |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409138A (en) * | 2018-04-11 | 2018-08-17 | 东北大学 | The enamel coating and its preparation process of a kind of resistance to sulfuric acid, salt acid dew piont corrosion |
| CN108409138B (en) * | 2018-04-11 | 2020-09-25 | 东北大学 | Sulfuric acid and hydrochloric acid dew point corrosion resistant enamel coating and preparation process thereof |
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Effective date of registration: 20190425 Address after: 038300 Industrial Structure Adjustment Project Base of Huairen County, Shuozhou City, Shanxi Province Patentee after: Huairen Bihua Ceramic Industry Service Co., Ltd. Address before: 362000 Mei Ren Village, purple mountain town, Huian County, Quanzhou, Fujian Patentee before: Huian Xintong Technology Development Co Ltd |
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