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WO2022041785A1 - 一种不锈钢搪瓷板的底釉釉料及其制备方法和应用 - Google Patents

一种不锈钢搪瓷板的底釉釉料及其制备方法和应用 Download PDF

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Publication number
WO2022041785A1
WO2022041785A1 PCT/CN2021/087687 CN2021087687W WO2022041785A1 WO 2022041785 A1 WO2022041785 A1 WO 2022041785A1 CN 2021087687 W CN2021087687 W CN 2021087687W WO 2022041785 A1 WO2022041785 A1 WO 2022041785A1
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Prior art keywords
glaze
stainless steel
temperature
enamel
time
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PCT/CN2021/087687
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English (en)
French (fr)
Inventor
邢翰学
曹益亭
傅昂挺
张军
黄新亮
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浙江开尔新材料股份有限公司
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Publication of WO2022041785A1 publication Critical patent/WO2022041785A1/zh

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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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
    • C23D5/00—Coating with enamels or vitreous layers
    • C23D5/02—Coating with enamels or vitreous layers by wet methods
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/19—Iron or steel

Definitions

  • the invention relates to the field of enamel material preparation, in particular to a bottom glaze glaze of a stainless steel enamel plate and a preparation method and application thereof.
  • Enamel plate refers to a composite material in which inorganic vitreous materials are condensed on the base steel plate by melting and firmly combined with the steel plate. Enamel coating on the surface of the steel plate can prevent the steel plate from rusting, so that the steel plate will not form an oxide layer on the surface when it is heated and can resist the erosion of various liquids. Enamel products have excellent properties such as high hardness, high temperature resistance, wear resistance, insulation, safety and non-toxicity, and easy washing and cleaning, and the enamel layer can also give the products a beautiful appearance. Inner and outer walls, decorative wall panels for tunnels, sterile operating room walls, pedestrian underpass wall panels and heat exchangers, etc.
  • the enamel plate is generally made of low carbon steel plate, but once the edge and corner of the low carbon steel enamel plate explodes, the bottom plate exposed to the external environment will be rusted. Furthermore, when it is used as an outer curtain wall, due to the The larger perforation rate pursued by the exterior curtain wall decoration will also cause the problem of plate deformation.
  • These problems have been the main reasons for limiting the application of mild steel enamel panels in exterior curtain wall decoration.
  • stainless steel has the properties of corrosion resistance, high strength, steel deformation is not easy to break, and environmental protection, and stainless steel has good ductility and toughness, suitable for harsh environments (humidity, acid and alkali and other indoor and outdoor environments) use. Therefore, replacing low carbon steel with stainless steel base material will be able to solve some problems existing in the current exterior curtain wall decoration.
  • the present invention achieves the goals of good enamel adhesion and high quality of the porcelain surface by improving the formulation and preparation process of the enamel layer bottom glaze glaze.
  • a base glaze for a stainless steel enamel plate comprising the following components: in terms of mass percentage, including the following components: SiO 2 30-38%; B 2 O 3 15-19%; Al 2 O 3 6-10%; TiO2 1-2 %; BaO 1-4%; Na2O 14-19%; K2O 5-10 %; MgO 0.1-0.6%; P2O5 2-4 %; ZnO 0.2-0.8%; Cr2O3 0.1-0.3%; CuO 0.4-0.8%; CoO 0.3-0.9%; NiO 0.7-1.2% and MnO2 0.8-1.3%.
  • bottom glaze There are two types of stainless steel enamel glaze: bottom glaze and top glaze.
  • the bottom glaze needs to be combined with stainless steel. How to make the bottom glaze and stainless steel achieve high adhesion is the technical difficulty of stainless steel enamel plates.
  • SiO 2 is the main component and is the main glass network forming body.
  • Increasing the content of SiO 2 in the range of 30-38% can improve the mechanical strength and hardness of the glaze, as well as the gloss, chemical stability and thermal stability of the glaze.
  • the B 2 O 3 in the glaze provided by the present invention is not only a solvent for the enamel but also a network former of the enamel, which can promote the formation of a glass phase at a low temperature stage.
  • the increase of B 2 O 3 content will increase the mechanical strength and abrasion resistance of the enamel.
  • B 2 O 3 has a good fluxing effect, which can reduce the softening temperature, viscosity, surface tension and expansion coefficient of the enamel, which is beneficial to the melting of metal oxides and the formation of adhesion.
  • Al 2 O 3 in the glaze provided by the present invention is an intermediate oxide, which can not only combine with silicon dioxide, but also combine with alkaline oxides. It can not only improve the vitrification ability of the enamel, but also inhibit the crystallization, and can significantly improve the elasticity, hardness and chemical stability of the glaze, and improve the resistance to chemical corrosion.
  • the TiO2 in the glaze provided by the present invention is to increase the opacity, acid resistance and luster of the enamel. Due to the good opacity, the enamel only needs to be coated with a thin layer, so this porcelain layer has high thermal stability, impact resistance and flexural strength, and has good chemical stability; at the same time, TiO 2 improves the luster of the enamel. , make the surface of enamel products more smooth and delicate.
  • BaO in the glaze provided by the invention is a fluxing agent, barium has the largest ionic radius among alkali metals, the strongest alkalinity is also the best fluxing effect among alkali metal oxidations, and can also improve the anti-organic resistance of the glaze. Acid corrosion ability.
  • K 2 O and Na 2 O in the glaze provided by the invention are strong fluxes of the glaze, which can significantly reduce the melting temperature and high temperature viscosity of the glaze, increase the refractive index of the glaze, and thereby improve the gloss of the glaze.
  • K 2 O and Na 2 O have low melting points. During the melting process of enamel, they are prone to chemical reaction with SiO 2 , and the reaction will release a lot of heat, thereby reducing the external heating temperature and reducing the viscosity at high temperature.
  • MgO is also a fluxing agent of the glaze, which can not only reduce the melt viscosity, but also reduce the expansion coefficient of the glaze, reduce the cracking of the glaze surface, and improve the quality of the porcelain surface.
  • the P 2 O 5 in the glaze provided by the invention can increase the opacity of the glaze, increase the reflection coefficient of the porcelain layer, and cooperate with titanium dioxide to jointly improve the chemical stability of the glaze.
  • the ZnO in the glaze provided by the invention can play a good fluxing effect in a large range, reduce the expansion coefficient of the glaze, and improve the gloss.
  • the mass fraction of zinc oxide is selected to be 0.2-0.8%.
  • the Cr 2 O 3 in the glaze provided by the invention can improve the chemical stability and high temperature resistance performance of the enamel, and at the same time can also be beneficial to the formation of the stainless steel enamel adhesion in the invention.
  • CuO, CoO, NiO and MnO 2 in the glaze provided by the present invention are adhesives, and the four adhesives have an interaction relationship, and their interaction can react with iron, so that the enamel penetrates into the surface layer of the steel plate and promotes the enamel glaze Infiltrating the stainless steel surface at high temperature promotes the dissolution of iron and iron oxide, and controls the oxidation conditions of the interface, which is conducive to the formation of a more uniform bubble structure in the porcelain layer and a good adhesion between the bottom glaze and the stainless steel.
  • the bottom glaze of the above-mentioned stainless steel enamel plate in terms of mass percentage, includes the following components: SiO 2 36.39%; B 2 O 3 17.87%; Al 2 O 3 7.06%; TiO 2 1.15%; BaO 2.79% ; Na 2 O 17.59%; K 2 O 9.96%; MgO 0.18%; P 2 O 5 2.95%; ZnO 0.57%; Cr 2 O 3 0.15% ; %.
  • the invention also discloses a method for preparing the base glaze of the above-mentioned stainless steel enamel plate, comprising the following steps: (1) mixing the components according to the proportion;
  • the enamel frit is turned into a ball mill and ground to form a glaze.
  • the melting temperature is 1000-1200° C.
  • the enamel frit is ground and passed through a 70-90 mesh sieve.
  • a stainless steel enamel plate comprising a stainless steel substrate, a bottom glaze and a top glaze; the bottom glaze and the top glaze are sequentially attached to the stainless steel substrate; and the raw material of the bottom glaze is any one of claims 1-2 The bottom glaze glaze.
  • the surface glaze formula in the present invention has no particularity, and the general surface glaze formula can realize enamel coating.
  • the components of the surface glaze are: SiO 2 : 30%-50%, B 2 O 3 : 15%-25%, Al 2 O 3 : 5%-10%, CaO: 3%-5% %, TiO 2 : 15% to 18%, BaO: 7% to 10%, Na 2 O: 10% to 16%, K 2 O: 3% to 5%, MgO: 0.5% to 0.8%, P 2 O 5 : 2% to 4%, ZnO: 2% to 5%.
  • the thickness of the bottom glaze is controlled at 90-140um; the thickness of the top glaze is controlled at 80-120um.
  • the thickness of the porcelain layer has a great influence on the porcelain surface and the adhesion.
  • the thickness of the bottom glaze is between 90-140um to obtain a better porcelain surface and a better adhesion level.
  • the problem of chromatic aberration if the thickness of the surface glaze exceeds 120um, it is easy to have insufficient surface uniformity, and the problem of chromatic aberration will also occur.
  • the firing temperature of the bottom glaze is 800-840°C, and the firing time is 4 minutes; the firing temperature of the top glaze is 800-840°C, and the firing time is 4-5 minutes.
  • the stainless steel substrate is austenitic stainless steel, and the content of some chemical elements in it is as follows: carbon ⁇ 0.030%, silicon ⁇ 1.00%, manganese ⁇ 2.00%, phosphorus ⁇ 0.035%, sulfur ⁇ 0.030%, nickel 8.00- 20.00%, chromium 18.00-20.00%.
  • the commonly used stainless steel is austenitic stainless steel, so the present invention focuses on the enamelling on austenitic stainless steel.
  • the bottom glaze glaze provided by the present invention has the best enamel coating effect on the austenitic stainless steel with the above chemical element content.
  • the invention also discloses the preparation method of the above-mentioned stainless steel enamel plate, comprising the following steps:
  • S1 stainless steel substrate preparation stainless steel plate is obtained after laser nitrogen cutting, corner bending, laser welding, grinding and surface treatment;
  • S2 glaze spraying glaze spraying by wet spraying process
  • the bottom glaze firing temperature is 800-840 °C, and the firing time is 4 minutes; the surface glaze firing temperature is 800-840 °C, and the firing time is 4-5 minutes.
  • the invention uses laser cutting to complete the cutting of the stainless steel plate, which can ensure the accuracy of the cutting size and facilitate the installation of the plate; and nitrogen cutting is used to protect the cutting surface from being oxidized, reduce the probability of the knife edge bursting, and the laser automatically cuts, reducing labor operation, to maximize the production capacity, the used stainless steel laser cutting process is consistent with the existing process, and the present invention will not describe it in detail. Corner bending is formed according to the existing production process. Due to the special material of stainless steel, the deformation of manual welding is large, and the process test is changed to laser welding. Since the oxidation of the laser welding seam is less, the welding seam can be slightly polished. In addition, the present invention achieves the purpose of good enamel adhesion and high quality of the enamel surface at a firing temperature of 800° C. at a low temperature.
  • the thickness of the stainless steel plate during laser welding in S1 is 1.5mm, the welding power is 800W, the welding speed is 0.8m/min, and the focal length is the positive focus point.
  • the welding parameters of the normal production steel plate are the welding power of 2400W, the welding speed of 1m/min, and the focal length of the positive focus point.
  • the present invention reduces the power to reduce the amount of deformation, and then reduces the welding speed by reducing the welding speed. In order to achieve the effect of full welding seam, but the power is too low, the plate cannot be fully welded, and the laser light output is unstable.
  • the welding effect of stainless steel plate is the best under the above parameters.
  • the surface treatment in the S1 is specifically:
  • the first course degreasing, sodium carbonate concentration: 8-10%, temperature: 60-70 °C, time: 7-8min;
  • Second pass degreasing, sodium carbonate concentration: 8-10%, temperature: 60-70°C, time: 7-8min;
  • the third course hot water rinse, temperature: 50-60 °C, time: 3-4min;
  • the fourth course rinse with cold water, normal temperature, time: 2-3min;
  • the fifth step drying, temperature: 300-350 °C, time: 8-10min.
  • the method to increase the adhesion of stainless steel in the industry is surface sandblasting, which forms a certain roughness on the surface of the stainless steel plate, but the sandblasting of the large plate is difficult for the site, equipment and uniformity.
  • the invention adopts the chemical immersion method to treat the surface of the stainless steel, which has the advantages of small treatment difficulty and good effect.
  • the present invention obtains a smooth and delicate porcelain surface through the overall ratio of the above-mentioned components, using titanium dioxide and phosphorus pentoxide with good turbidity, and cooperates with CuO, CoO, NiO, MnO 2 to promote adhesion, and then combine with
  • the bottom glaze of the stainless steel enamel plate provided by the present invention has the characteristics of high adhesion, high weather resistance and high corrosion resistance;
  • the stainless steel enamel plate prepared by using the glaze provided by the present invention at a relatively low firing temperature has good adhesion, and the obtained enamel porcelain surface is smooth and delicate;
  • Table 1 List of mass fractions (%) of each component in Examples 1-3
  • a preparation method of bottom glaze glaze of stainless steel enamel plate comprising the following steps:
  • Examples 4-6 were prepared by using the glaze formulations of Examples 1-3 respectively.
  • a preparation method of a stainless steel enamel plate comprising the following steps:
  • S1 stainless steel substrate preparation 304 stainless steel plate is obtained after laser nitrogen cutting, corner bending, laser welding, grinding and surface treatment;
  • the thickness of the stainless steel plate is 1.5mm, the welding power is 800W, the welding speed is 0.8m/min, and the focal length is the positive focus point;
  • the surface treatment is as follows:
  • the first course degreasing, concentration: 8%, temperature: 70°C, time: 8min;
  • Second pass degreasing, concentration: 8%, temperature: 70°C, time: 8min;
  • the third course hot water rinse, temperature: 50-60 °C, time: 3min;
  • the fourth course rinse with cold water, normal temperature, time: 2min;
  • the fifth step drying, temperature: 300°C, time: 8min;
  • S2 glaze spraying use the base glaze glaze of Example 4 to carry out glaze spraying by wet spraying process; the base glaze thickness is controlled at 90-140um; the top glaze thickness is controlled at 80-120um;
  • Examples 7-9 all adopt the above-mentioned preparation method, the difference is that the firing temperature of the bottom glaze is 800°C, 820°C and 840°C, respectively.
  • Example 7-9 The base glaze in Example 7-9 was changed to the base glaze glaze prepared in Example 5, and the rest was the same as that of Example 7-9.
  • Example 4-6 The bottom glaze in Example 4-6 was changed to the bottom glaze glaze prepared in Example 6 and fired, and the rest were the same as those in Example 7-9.
  • the stainless steel enamel glaze is obtained according to the components and mass fractions of Example 1 to Example 3. After firing at different temperatures, the porcelain surfaces fired by the glaze formula of Example 1 are all smooth and delicate. , the lowest temperature required to form a level 1 bond. Therefore, the base glaze glaze formula of Example 1 is the best formula, and the obtained stainless steel enamel glaze has good porcelain surface quality while ensuring good adhesion.
  • the spraying thickness of the bottom glaze was modified to 90-120um and 120-140um respectively, and the rest were the same as those in Example 7.
  • the spraying thickness of the bottom glaze was modified to 30-50um, 50-70um, 70-90um, and 140-160um respectively, and the rest were the same as those in Example 7.
  • the thickness of the underglaze porcelain layer has a great influence on the porcelain surface and the adhesion.
  • the porcelain layer thickness between 90-140um can obtain better porcelain surface and better adhesion.
  • the 304 stainless steel plate was welded by laser welding, and the welding power and welding speed were changed.
  • the welding effect is shown in Table 4.
  • Table 4 Stainless steel welding process test record table: using laser welding process.

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Abstract

一种不锈钢搪瓷板的底釉釉料，按质量百分比计，包括以下组分：SiO 230-38％；B 2O 315-19％；Al 2O 36-10％；TiO 21-2％；BaO 1-4％；Na 2O 14-19％；K 2O 5-10％；MgO 0.1-0.6％；P 2O 52-4％；ZnO 0.2-0.8％；Cr 2O 30.1-0.3％；CuO 0.4-0.8％；CoO 0.3-0.9％；NiO 0.7-1.2％和MnO 20.8-1.3％。该釉料在较低的烧成温度下制备的不锈钢搪瓷板密着性好，且获得的搪瓷瓷面光滑细腻。

Description

一种不锈钢搪瓷板的底釉釉料及其制备方法和应用 技术领域
本发明涉及搪瓷材料制备领域，具体的说涉及一种不锈钢搪瓷板的底釉釉料及其制备方法和应用。
背景技术
搪瓷板，是指一种将无机玻璃质材料通过熔融凝于基体钢板并与钢板牢固结合在一起的复合材料。在钢板表面进行瓷釉涂搪可以防止钢板生锈，使钢板在受热时不至于在表面形成氧化层并且能抵抗各种液体的侵蚀。搪瓷制品具有硬度高、耐高温、耐磨、绝缘、安全无毒和易于洗涤洁净等优良性能，并且瓷釉层还可以赋予制品美丽的外表，因此，被广泛用于地铁车站用装饰墙板、建筑内外墙、隧道用装饰墙板、无菌手术室墙面、人行地下通道墙板和换热器等领域。
目前，搪瓷板一般是选用低碳钢钢板，但是低碳钢搪瓷板一旦出现边角爆瓷，就会使暴露在外环境中的底板出现锈蚀问题，再者，将其用作外幕墙时，由于外幕墙装饰追求的较大穿孔率也会引起板块变形问题。这些问题一直是限制低碳钢搪瓷板在外幕墙装饰的应用中的主要原因。而不锈钢相比一般的低碳钢板具有耐腐蚀、高强度、钢材变形不易破裂和环保的性能，且不锈钢具有良好的延展性和韧性，适用于恶劣环境(湿、酸碱等户内外环境)下使用。所以用不锈钢基材替代低碳钢将能够顺利的解决目前外幕墙装饰上存在的一些问题，但是不锈钢搪瓷板存在底釉与不锈钢结合不牢固、搪瓷层易脱落的问题。
因此，如何提供一种底釉与不锈钢结合牢固、且具有优异化学性能的不锈钢搪瓷板是本领域亟需解决的技术问题。
发明内容
鉴于上述问题，本发明通过搪瓷层底釉釉料配方和制备工艺的改进实现了搪瓷密着好，且瓷面质量高的目的。
为了实现上述目的，本发明采用如下技术方案：
一种不锈钢搪瓷板的底釉釉料，按质量百分比计，包括以下组分：按质量百分比计，包括以下组分：SiO 2 30-38％；B 2O 3 15-19％；Al 2O 3 6-10％；TiO 2 1-2％；BaO 1-4％；Na 2O 14-19％；K 2O 5-10％；MgO 0.1-0.6％；P 2O 5 2-4％；ZnO 0.2-0.8％；Cr 2O 3 0.1-0.3％；CuO 0.4-0.8％；CoO 0.3-0.9％；NiO 0.7-1.2％和MnO 2 0.8-1.3％。
不锈钢搪瓷釉料分两种：底釉釉料和面釉釉料，其中底釉是需要与不锈钢进行结合的，如何使底釉与不锈钢能够实现高附着是不锈钢搪瓷板的技术难点。
本发明提供的釉料中SiO 2是主要成分，是主要的玻璃网络形成体，釉料中SiO 2的量越高，烧成温度也越高。在SiO 2的含量在30-38％的范围内提高可以提高釉料的机械强度和硬度，也能够提高釉面的光泽度、化学稳定性和热稳定性。
本发明提供的釉料中的B 2O 3不仅是瓷釉的溶剂亦是瓷釉的网络形成体，会在低温阶段促进玻璃相的形成。B 2O 3含量增加会使瓷釉的机械强度增大，抗磨性提高。B 2O 3有很好的助熔作用，能降低瓷釉的软化温度、粘度、表面张力及膨胀系数，利于熔解金属氧化物，有助于密着的形成。
本发明提供的釉料中的Al 2O 3是中间体氧化物，不仅能与二氧化硅结合，也能与碱性氧化物结合。不仅能够提高瓷釉的玻璃化能力，也能够抑制析晶，能够显著提高釉料的弹性、硬度和化学稳定性，提高抗化学腐蚀能力。
本发明提供的釉料中的TiO 2是增加瓷釉的乳浊作用，耐酸性和光泽。由于乳浊性好，瓷釉只需薄薄的涂布一层，因而这种瓷层具有高的热稳定性和 耐冲击以及抗折强度，具有良好的化学稳定性；同时TiO 2提高瓷釉的光泽，使搪瓷制品的表面更加光滑细腻。
本发明提供的釉料中的BaO是一种助熔剂，钡在碱金属中离子半径最大，碱性最强也是碱金属氧化中中助熔效果最佳的一个，也能够提高釉面的抗有机酸腐蚀能力。
本发明提供的釉料中的K 2O和Na 2O为釉料的强助熔剂，能显著的降低釉的熔融温度和高温粘度，增大釉的折射率，从而提高釉面的光泽度。K 2O和Na 2O熔点较低，在瓷釉熔制的过程中，容易与SiO 2发生化学反应，反应会放出大量的热量，从而降低外界的加热温度，并且在高温下能降低粘度。
本发明中MgO也是釉料的一种助熔剂，不仅能够降低熔体粘度，还可以降低釉的膨胀系数，减少釉面龟裂，提高瓷面品质。
本发明提供的釉料中的P 2O 5能增加瓷釉的乳浊作用，增加瓷层的反射系数，配合二氧化钛，共同提高釉料的化学稳定性。
本发明提供的釉料中的ZnO能在较大范围内起到良好的助熔作用，降低釉料的膨胀系数，提高光泽度。但是使用过量会使釉料析晶导致釉面失去通透性，因此选择选择氧化锌的质量分数在0.2-0.8％。
本发明提供的釉料中的Cr 2O 3能提高瓷釉的化学稳定性和耐高温性能，同时也能有利于本发明中不锈钢瓷釉密着的形成。
本发明提供的釉料中的CuO、CoO、NiO、MnO 2为密着剂，四种密着剂存在互相作用的关系，它们的互相作用能够与铁发生反应，从而让瓷釉渗透到钢板表层，促进瓷釉在高温下浸润不锈钢表面，促进铁与氧化铁的溶解，控制界面的氧化条件，有利于瓷层形成较为均匀的气泡结构，对底釉与不锈钢形成良好的密着。
优选的，上述不锈钢搪瓷板的底釉釉料，按质量百分比计，包括以下组分：SiO 2 36.39％；B 2O 3 17.87％；Al 2O 3 7.06％；TiO 2 1.15％；BaO 2.79％；Na 2O  17.59％；K 2O 9.96％；MgO 0.18％；P 2O 5 2.95％；ZnO 0.57％；Cr 2O 3 0.15％；CuO 0.57％；CoO 0.57％；NiO 1.05％和MnO 2 1.15％。
本发明还公开了上述不锈钢搪瓷板的底釉釉料的制备方法，包括以下步骤：(1)将各组分按照比例混合；
(2)将混合物放入高温炉中熔融；
(3)熔平后放入水中急冷，形成瓷釉熔块；
(4)将瓷釉熔块翻入球磨机中研磨形成釉料。
优选的，所述步骤(2)中熔融温度为1000-1200℃，所述瓷釉熔块研磨后过70-90目筛。
一种不锈钢搪瓷板，包括不锈钢基板、底釉和面釉；所述底釉和所述面釉依次附着在所述不锈钢基板上；且所述底釉的原料为权利要求1-2任一项所述的底釉釉料。
本发明中的面釉配方无特殊性，一般面釉配方均可实现涂搪。例如：按重量份计，面釉组分为：SiO 2：30％～50％，B 2O 3：15％～25％，Al 2O 3：5％～10％，CaO：3％～5％，TiO 2：15％～18％，BaO：7％～10％，Na 2O：10％～16％，K 2O：3％～5％，MgO：0.5％～0.8％，P 2O 5：2％～4％，ZnO：2％～5％。
优选的，所述S2釉料喷涂时底釉厚度控制在90-140um；面釉厚度控制在80-120um。
瓷层厚度对瓷面和密着有较大影响，底釉厚度在90-140um之间可以获得较好的瓷面与较好的密着等级，面釉厚度低于80um易出现无法遮盖底釉，产生色差的问题；面釉厚度超过120um，易出现表面均匀性不够，也会产生色差的问题。
优选的，所述底釉烧成温度800-840℃，烧成时间4min；所述面釉烧成温度800-840℃，烧成时间4-5min。
优选的，所述不锈钢基板为奥氏体不锈钢，且其中的部分化学元素含量 如下：碳﹤0.030％，硅﹤1.00％，锰﹤2.00％，磷﹤0.035％，硫﹤0.030％，镍8.00-20.00％，铬18.00-20.00％。
由于不锈钢种类较多，有铁素体不锈钢、奥氏体不锈钢、奥氏体-铁素体双相不锈钢、马氏体不锈钢。而我们常用的不锈钢是奥氏体不锈钢，所以本发明重点研究的是在奥体不锈钢上的涂搪。本发明提供的底釉釉料在上述化学元素含量下的奥氏体不锈钢上涂搪的效果最佳。
本发明还公开了上述不锈钢搪瓷板的制备方法，包括以下步骤：
S1不锈钢基板准备：不锈钢板材经过激光氮气切割、边角折弯、激光焊接、打磨和表面处理后得到不锈钢基板；
S2釉料喷涂：采用湿法喷涂工艺进行釉料喷涂；
S3烘干：烘干温度150-200℃，时间10-15min；
S4烧成：底釉烧成温度800-840℃，烧成时间4min；面釉烧成温度800-840℃，烧成时间4-5min。
本发明采用激光切割完成对不锈钢板的切割，能够保证切割尺寸的精度，便于板块的安装；且选用氮气切割，保护切割面防止被氧化，减少刀口爆瓷的概率，激光自动切割，减少人工作业，实现产能的最大化，使用的不锈钢激光切割工艺与现有工艺是一致的，本发明不再具体描述。边角折弯按照现有的生产工艺折弯成型。由于不锈钢材质的特殊，人工焊接变形量较大，通过工艺试验改成激光焊接，由于激光焊接焊缝氧化较少，轻微抛光焊缝即可。并且本发明实现了在低温800℃的烧成温度下搪瓷密着好，瓷面质量高的目的。
优选的，S1中所述激光焊接时不锈钢板的厚度为1.5mm，焊接功率为800W，焊接速度为0.8m/min，焦距为正对焦点。
正常生产钢板的焊接参数为焊接功率2400W，焊接速度为1m/min，焦距为正对焦点，但焊接奥氏体不锈钢时不锈钢变形严重，本发明将功率降低使 变形量减少，然后通过降低焊接速度来达到焊缝饱满的效果，但功率过低板块焊不透，且激光器出光不稳定。上述参数下不锈钢板的焊接效果最好。
优选的，所述S1中表面处理具体为：
第一道：脱脂，碳酸钠浓度：8-10％，温度：60-70℃，时间：7-8min；
第二道：脱脂，碳酸钠浓度：8-10％，温度：60-70℃，时间：7-8min；
第三道：热水冲洗，温度：50-60℃，时间：3-4min；
第四道：冷水冲洗，常温，时间：2-3min；
第五道：烘干，温度：300-350℃，时间：8-10min。
现在行业内增加不锈钢密着的方法是表面喷砂处理，在不锈钢板表面形成一定的粗糙度，但大板喷砂对场地、设备、均匀性难度较大。本发明采用化学浸泡的方式对不锈钢表面处理，处理难度小、效果好。
与现有技术相比，本发明的有益效果为：
1、本发明通过上述各组分的整体配比，利用二氧化钛和五氧化二磷具有好的乳浊度得到光滑细腻的瓷面，配合CuO、CoO、NiO、MnO 2的促进密着作用，再与其他组分配合，使本发明提供的不锈钢搪瓷板底釉釉料具备高附着、高耐候、高耐腐的特性；
2、使用本发明提供的釉料在较低的烧成温度下制备的不锈钢搪瓷板密着性好，且获得的搪瓷瓷面光滑细腻；
3、通过对制备方法的改进，进一步提高了不锈钢搪瓷板的密着性，解决了低碳钢搪瓷板碰撞后瓷层脱落，内部钢板没有搪瓷层保护，发生锈蚀的问题。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发 明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1-3
一种不锈钢搪瓷板的底釉釉料，具体组分含量见表1。
表1：实施例1-3各组分的质量分数列表(％)
组分 实施例1 实施例2 实施例3
SiO 2 36.39 36.39 38
B 2O 3 17.87 17.87 19
Al 2O 3 7.06 7.06 7.06
TiO 2 1.15 1.15 1.15
BaO 2.79 2.79 2.79
Na 2O 17.59 17.59 14.85
K 2O 9.96 9.96 9.96
MgO 0.18 0.18 0.18
P 2O 5 2.95 2.95 2.95
ZnO 0.57 0.57 0.57
Cr 2O 3 0.15 0.15 0.15
CuO 0.57 0.66 0.57
CoO 0.57 0.57 0.57
NiO 1.05 1.05 1.05
MnO 2 1.15 1.06 1.15
实施例4-6
一种不锈钢搪瓷板的底釉釉料的制备方法，包括以下步骤：
(1)将各组分按照比例混合；
(2)将混合物放入高温炉中，在1000-1200℃下熔融；
(3)熔平后放入水中急冷，形成瓷釉熔块；
(4)将瓷釉熔块翻入球磨机中研磨过70-90目筛形成釉料。
实施例4-6分别采用实施例1-3的釉料配方进行制备。
实施例7-9
一种不锈钢搪瓷板的制备方法，包括以下步骤：
S1不锈钢基板准备：304不锈钢板材经过激光氮气切割、边角折弯、激光焊接、打磨和表面处理后得到不锈钢基板；
激光焊接时不锈钢板的厚度为1.5mm，焊接功率为800W，焊接速度为0.8m/min，焦距为正对焦点；
表面处理具体为：
第一道：脱脂，浓度：8％，温度：70℃，时间：8min；
第二道：脱脂，浓度：8％，温度：70℃，时间：8min；
第三道：热水冲洗，温度：50-60℃，时间：3min；
第四道：冷水冲洗，常温，时间：2min；
第五道：烘干，温度：300℃，时间：8min；
S2釉料喷涂：使用实施例4的底釉釉料采用湿法喷涂工艺进行釉料喷涂；底釉厚度控制在90-140um；面釉厚度控制在80-120um；
S3烘干：烘干温度160℃，时间12min；
S4烧成：底釉烧成烧成时间4min；面釉烧成温度820℃，烧成时间4min。
实施例7-9均采用上述制备方法，不同的是底釉烧成温度分别为800℃、820℃和840℃。
实施例10-12
将实施例7-9中的底釉改成由实施例5制备的底釉釉料烧制，其余与实施例7-9相同。
对比例13-15
将实施例4-6中的底釉改成由实施例6制备的底釉釉料烧制，其余与实施 例7-9相同。
将实施例7-15制成的不锈钢搪瓷板分别用密着仪测试密着。将密着测试结果以及瓷面质量记录在表2中。
表2：实施例4-12制成的不锈钢搪瓷板的各项测试结果
项目 烧成工艺 密着等级 瓷面质量
实施例7 800℃；4.0min 1级 光滑细腻
实施例8 820℃；4.0min 1级 光滑细腻
实施例9 840℃；4.0min 1级 光滑细腻
实施例10 800℃；4.0min 3级 光滑细腻
实施例11 820℃；4.0min 3级 光滑细腻
实施例12 840℃；4.0min 1级 瓷面发沸、有针孔
实施例13 800℃；4.0min 3级 光滑细腻
实施例14 820℃；4.0min 1级 光滑细腻
实施例15 840℃；4.0min 1级 瓷面发沸、有针孔
结合表1和表2可知，按照实施例1至实施例3的组分和质量分数获得不锈钢搪瓷釉料经过不同温度的烧成后，实施例1的釉料配方烧成的瓷面均光滑细腻，形成1级密着所需的温度最低。因此，实施例1的底釉釉料配方是最佳配方，获得的不锈钢搪瓷釉料在保证了良好的密着情况下，同时具有良好的瓷面质量。
实施例16-17
将底釉喷涂厚度分别修改为90-120um、120-140um，其余同实施例7。
对比例1-4
将底釉喷涂厚度分别修改为30-50um、50-70um、70-90um、140-160um，其余同实施例7。
将实施例16-17和对比例1-4制成的不锈钢搪瓷板分别用密着仪测试密 着。将密着测试结果以及瓷面质量记录在表3中。
表3：实施例4、13和对比例1-4制成的不锈钢搪瓷板的各项测试结果
Figure PCTCN2021087687-appb-000001
从表3可以看出，底釉瓷层厚度对瓷面和密着有较大影响，瓷层厚度在90-140um之间可以获得较好的瓷面与较好的密着。
不同焊接工艺的研究
采用激光焊接对304不锈钢板进行焊接，改变焊接功率和焊接速度，焊接效果如表4所示。
表4：不锈钢焊接工艺试验记录表：采用激光焊接工艺。
Figure PCTCN2021087687-appb-000002
Figure PCTCN2021087687-appb-000003
从表4中可以看出，本发明限定的焊接参数下不锈钢板的焊接效果最好。
以上对本发明所提供的技术方案进行了详细介绍，本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想；同时，对于本领域的一般技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本发明的限制。

Claims (10)

  1. 一种不锈钢搪瓷板的底釉釉料，其特征在于，按质量百分比计，包括以下组分：
    SiO 230-38％；B 2O 315-19％；Al 2O 36-10％；TiO 21-2％；BaO 1-4％；Na 2O 14-19％；K 2O 5-10％；MgO 0.1-0.6％；P 2O 52-4％；ZnO 0.2-0.8％；Cr 2O 30.1-0.3％；CuO 0.4-0.8％；CoO 0.3-0.9％；NiO 0.7-1.2％和MnO 20.8-1.3％。
  2. 根据权利要求1所述的一种不锈钢搪瓷板的底釉釉料，其特征在于，按质量百分比计，包括以下组分：
    SiO 236.39％；B 2O 317.87％；Al 2O 37.06％；TiO 21.15％；BaO 2.79％；Na 2O 17.59％；K 2O 9.96％；MgO 0.18％；P 2O 52.95％；ZnO 0.57％；Cr 2O 30.15％；CuO 0.57％；CoO 0.57％；NiO 1.05％和MnO 21.15％。
  3. 根据权利要求1或2所述的一种不锈钢搪瓷板的底釉釉料的制备方法，其特征在于，包括以下步骤：
    (1)将各组分按照比例混合；
    (2)将混合物放入高温炉中熔融；
    (3)熔平后放入水中急冷，形成瓷釉熔块；
    (4)将瓷釉熔块翻入球磨机中研磨形成釉料。
  4. 一种不锈钢搪瓷板，其特征在于，包括：不锈钢基板、底釉和面釉；
    其中，所述底釉和所述面釉依次附着在所述不锈钢基板上；且所述底釉的原料为权利要求1-2任一项所述的底釉釉料。
  5. 根据权利要求4所述的一种不锈钢搪瓷板，其特征在于，所述底釉厚度为90-140um；所述面釉厚度为80-120um。
  6. 根据权利要求4所述的一种不锈钢搪瓷板，其特征在于，所述底釉烧成温度800-840℃，烧成时间4min；所述面釉烧成温度800-840℃，烧成时间4-5min。
  7. 根据权利要求4所述的一种不锈钢搪瓷板，其特征在于，所述不锈钢基板为奥氏体不锈钢，且其中的部分化学元素含量如下：碳﹤0.030％，硅﹤1.00％， 锰﹤2.00％，磷﹤0.035％，硫﹤0.030％，镍8.00-20.00％，铬18.00-20.00％。
  8. 根据权利要求4-7所述的一种不锈钢搪瓷板的制备方法，其特征在于，包括以下步骤：
    S1不锈钢基板准备：不锈钢板材经过激光氮气切割、边角折弯、激光焊接、打磨和表面处理后得到不锈钢基板；
    S2釉料喷涂：采用湿法喷涂工艺进行釉料喷涂；
    S3烘干：烘干温度150-200℃，时间10-15min；
    S4烧成：底釉烧成温度800-840℃，烧成时间4min；面釉烧成温度800-840℃，烧成时间4-5min。
  9. 根据权利要求8所述的一种不锈钢搪瓷板的制备方法，其特征在于，S1中所述激光焊接时不锈钢板的厚度为1.5mm，焊接功率为800W，焊接速度为0.8m/min，焦距为正对焦点。
  10. 根据权利要求8所述的一种不锈钢搪瓷板的制备方法，其特征在于，所述S1中表面处理具体为：
    第一道：脱脂，碳酸钠浓度：8-10％，温度：60-70℃，时间：7-8min；
    第二道：脱脂，碳酸钠浓度：8-10％，温度：60-70℃，时间：7-8min；
    第三道：热水冲洗，温度：50-60℃，时间：3-4min；
    第四道：冷水冲洗，常温，时间：2-3min；
    第五道：烘干，温度：300-350℃，时间：8-10min。
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