阅读说明：本技术 一种用于熔炼铝锂合金坩埚的涂料及其制备和涂覆方法 (Coating for smelting aluminum-lithium alloy crucible and preparation and coating methods thereof ) 是由 刘晓光 马天豪 郝智藩 王俊升 李斌 孙加林 薛文东 于 2021-08-16 设计创作，主要内容包括：一种用于熔炼铝锂合金的坩埚的涂料及其制备和涂覆方法。涂料成分为粘结剂占40-90wt％,骨料占10-60wt％。所述粘结剂中含磷酸二氢铝10-50wt％,碳和B-(2)O-(3)混合粉体共3-5wt％,缓蚀剂0.5-3wt％,固化剂0.5-3wt％,填料0.5-5wt％等,分散剂0.1-2wt％,余量为水。骨料为六方氮化硼BN,颗粒度为500-800目；涂料制备方法为：先将聚乙烯醇60mol％和硼酸40mol％,按照溶胶凝胶法制得聚乙烯醇硼酸酯凝胶,并在空气条件下于400-600℃裂解,得到碳和B-(2)O-(3)粉体；然后将其与磷酸二氢铝、缓蚀剂、固化剂、分散剂和填料一并与水混合,得到以磷酸二氢铝(浓度为10-50wt％)为主的混浊液；最后将其该混浊液与BN粉末球磨22-26h,得到磷酸二氢铝结合的BN涂料。本发明涂料分散性和流动性好,易涂覆,与基底附着力强,高温化学结构稳定,抗热震性优异。(A coating for a crucible for smelting aluminum lithium alloy and a preparation and coating method thereof. The coating comprises 40-90 wt% of binder and 10-60 wt% of aggregate. 10-50 wt% of aluminum dihydrogen phosphate, carbon and B in the binder 2 O 3 3-5 wt% of mixed powder, 0.5-3 wt% of corrosion inhibitor, 0.5-3 wt% of curing agent, 0.5-5 wt% of filler and the like, 0.1-2 wt% of dispersant and the balance of water. The aggregate is hexagonal boron nitride BN, and the granularity is 500-800 meshes; the preparation method of the coating comprises the following steps: firstly, 60mol percent of polyvinyl alcohol and 40mol percent of boric acid are prepared into polyvinyl alcohol borate gel according to a sol-gel method, and the polyvinyl alcohol borate gel is cracked at the temperature of 400-600 ℃ under the air condition to obtain carbon and B 2 O 3 Powder; then mixing the aluminum dihydrogen phosphate, the corrosion inhibitor, the curing agent, the dispersing agent and the filler with water to obtain turbid liquid mainly containing aluminum dihydrogen phosphate (the concentration is 10-50 wt%); finally, ball milling the turbid liquid and BN powder for 22-26h to obtain the BN coating combined with the aluminum dihydrogen phosphate. The coating has the advantages of good dispersibility and fluidity, easy coating, strong adhesion with a substrate, stable high-temperature chemical structure and excellent thermal shock resistance.)

1. The coating for smelting the aluminum lithium alloy crucible is characterized in that the binder accounts for 40-90 wt% of the coating, and the aggregate BN accounts for 10-60 wt%; wherein the binder comprises (10-50 wt%) aluminum dihydrogen phosphate powder, (3-5 wt%) c-B₂O₃(0.5-3 wt%) corrosion inhibitor, (0.5-3 wt%) curing agent, (0.5-5 wt%) filler, (0.1-2 wt%) dispersing agent and the rest is water.

2. The coating for smelting the crucible of aluminum-lithium alloy as claimed in claim 1, wherein the binder is a composite binder, and the main components are aluminum dihydrogen phosphate (with a particle size of 150-200 meshes and a mass fraction of 10-50 wt%) and c-B₂O₃(3-5 wt%). Wherein c-B₂O₃The preparation method is characterized in that polyvinyl alcohol borate gel is prepared from polyvinyl alcohol (60 mol%) and boric acid (40 mol%) according to a sol-gel method, and then the polyvinyl alcohol borate gel is cracked at the temperature of 400-600 ℃ under the air condition.

3. The coating for smelting the aluminum-lithium alloy crucible as recited in claim 1, wherein the aggregate is hexagonal BN, and the granularity is 500-800 meshes.

4. The coating for melting aluminum lithium alloy crucibles according to claim 2, wherein the additives in the binder comprise: the corrosion inhibitor is sodium aluminate or sodium molybdate, the curing agent is MgO or magnesium aluminate spinel, the filler is SiC fiber, and the dispersant is sepiolite or calcium phosphate; wherein the granularity of MgO or magnesium aluminate spinel is 500-800 meshes, the granularity of sodium aluminate or sodium molybdate is 200-300 meshes, the granularity of sepiolite is 500-800 meshes, the diameter of SiC fiber is 5-10 microns, and the length-diameter ratio is 20.

5. The method for preparing the coating for smelting the aluminum lithium alloy crucible as claimed in claim 1, wherein aluminum dihydrogen phosphate, c-B₂O₃Mixing the corrosion inhibitor, the curing agent, the dispersing agent and the filler into water to obtain turbid liquid mainly containing aluminum dihydrogen phosphate (with the concentration of 10-50 wt%); and ball-milling the turbid liquid and BN powder for 22-26h to obtain the BN slurry coating.

6. A method of applying a coating prepared according to the method of claim 5 to a graphite crucible, comprising: removing impurities on the inner surface of the graphite crucible, and heating to 65-95 ℃; the coating is coated on the inner surface of the crucible in various modes of brushing and spraying; after air drying, heating to 800-.

7. The coating method according to claim 6, characterized in that the thickness of the coating is 50-80 microns.

Technical Field

The invention belongs to the field of material processing, and particularly relates to a coating formula for smelting an aluminum-lithium alloy crucible, and a preparation method and a coating method thereof.

Technical Field

The aluminum-lithium alloy has the advantages of low density, high elastic modulus, high specific stiffness, high specific strength, low fatigue crack propagation rate, excellent corrosion resistance and the like, and is an ideal material in the fields of aerospace, aviation, navigation, unmanned aerial vehicles and the like. However, the alloy melt has high reactivity and the melting process is very challenging. In particular to the harsh requirement on the service performance of the crucible for smelting the aluminum lithium alloy. In contrast, the high-purity graphite crucible has higher stability than a ceramic crucible and a common graphite-clay crucible, and is one of the first-choice crucibles for smelting aluminum-lithium alloy at present. However, the study of gunn macros and the like in the aeronautical newspaper (2003, 9(2), 81-84) shows that: because the radius of lithium ions is small, the lithium ions are easy to seep out from the loose part of the graphite crucible, and lithium and carbon are easy to react to generate lithium carbide under the long-time smelting and heat preservation states. This not only results in a reduction in the purity and performance of the aluminum lithium alloy; meanwhile, the crucible is in danger of aluminum leakage after being corroded, and the service life is reduced.

To solve the above problems, the most effective means is to apply a coating material to the inner surface of the crucibleOne of them is applied. Because of the higher activity of the aluminum-lithium alloy melt, the traditional refractory coating Al₂O₃，ZnO，ZrO₂The aluminum-lithium alloy is easy to wet and has reduction reaction, thereby polluting alloy components and reducing alloy performance. Therefore, it is important to develop a novel crucible coating which is non-wetting and non-reactive with aluminum lithium alloy. Through thermodynamic calculation, the materials chemically stable in the aluminum lithium alloy liquid (i.e. not reacted with the aluminum lithium alloy liquid) are MgO and Y₂O₃SiC and BN, etc.

It has been found that plasma spraying Al onto graphite crucible₂O₃Then coating MgO and smelting an aluminum lithium alloy; the method has the defects of high cost, low adhesion between MgO and a graphite substrate, large difference with the thermal expansion coefficient of graphite, poor thermal shock resistance at high temperature and the like. Generally, only 1-2 furnaces are smelted.

The patents CN109020554A and CN110172627A adopt a spray gun spraying mode to respectively coat SiC and Y on the inner wall of a stainless steel crucible₂O₃And (4) coating. The method is high in cost, and the coating can be wetted or permeated by the aluminum lithium alloy melt, so that the service life of the coating is greatly shortened.

Patent CN112521778A shows that hexagonal BN has the property of being non-wetting and non-reactive with aluminum lithium alloys and can be used up to 850 ℃ in an oxidizing atmosphere and 1372 ℃ in a non-oxidizing atmosphere. Considering the crystal structure of boron nitride similar to graphite, high thermal conductivity and thermal expansion coefficient (about 5.85 x 10)^-6K^-1) (Zhousherong, preparation and performance research of nitride fiber reinforced boron nitride ceramic matrix wave-transparent composite, doctor's paper of national defense science and technology university, 2016) and graphite (about 2 x 10)^-6K^-1) And more matched. Therefore, the coating aggregate is suitable for the graphite crucible for smelting the aluminum lithium alloy.

However, without an efficient binder, the firm adhesion of the boron nitride coating on the graphite surface cannot be achieved, and the multiple use requirements such as high-temperature structural stability cannot be met. In view of this, inorganic binders are undoubtedly the best choice. Chenyang et al indicated that inorganic binders such as silicates and sol-gels have good high temperature properties in refractory materials (2018, 52, 154-157), but silicates are prone to react with aluminum-lithium alloys. Therefore, the use in aluminum lithium alloy melting crucibles is limited. The sol-gel type binder is difficult to form a film, and needs to be used in combination with other film-forming substances. However, phosphates (aluminum phosphate, magnesium phosphate, etc.) can overcome the above disadvantages. In particular, the aluminum dihydrogen phosphate can be dissolved in water at room temperature to form uniform colloid, and has good fluidity and film forming property. Meanwhile, the aluminum dihydrogen phosphate binder gradually forms orthogonal aluminum phosphate with a three-dimensional network structure through glycidyl polymerization at the temperature of 400-. The orthogonal aluminum phosphate was then further raised to 1600 c to convert it to a structurally stable cristobalite aluminum phosphate (hearowa, preparation of phosphate-based high temperature binders and their adhesion performance studies, tianjin university, master article, 2012). Therefore, the aluminum dihydrogen phosphate is a bonding agent with good film forming property at room temperature and stable three-dimensional network structure at high temperature. However, the aluminum dihydrogen phosphate binder and the graphite substrate mainly have physical bonding force, lack chemical bonding force and still have the problem of low adhesive force. Therefore, the present invention proposes a new solution to the above-mentioned problems.

Disclosure of Invention

The invention aims to provide a graphite crucible coating for smelting an aluminum-lithium alloy and a preparation and coating method thereof. According to the invention, the aluminum dihydrogen phosphate is gradually dehydrated and condensed in the heating process, the aluminum dihydrogen phosphate is gradually converted into the orthogonal aluminum phosphate with a stable three-dimensional network structure at the medium-high temperature of 400-; in order to further improve the binding force between the aluminum dihydrogen phosphate binder and the graphite substrate, the invention is based on a sol-gel method, polyvinyl alcohol and boric acid are used as raw materials to synthesize polyvinyl borate gel, and carbon and B are obtained by cracking at the temperature of 400-600 ℃ in the air₂O₃Mixture of (2) (abbreviated to c-B)₂O₃) Principle (Fei Zhang, boron carbide powder)Low temperature synthesis, university of great graduate, 2011, master thesis); and then according to B₂O₃The glass phase formed at high temperature can be wetted with the graphite substrate (arbitrary rock, graphite material surface ZrB₂Preparation and performance research of a SiC-based high-temperature and ultrahigh-temperature oxidation resistant protective coating, university of Chinese science and technology, doctor's paper, 2021); and B₂O₃Can form B on the graphite surface under the reducing nitrogen atmosphere and at a lower temperature (1300℃)₄The principle of chemical bond such as C (Fei in Zhang, low temperature synthesis of boron carbide powder, university of university, 2011, Master thesis) is adopted in the invention₂O₃The BN coating and aluminum dihydrogen phosphate are prepared into a composite binder, so that the chemical binding force and the adhesive force of the BN coating and a graphite substrate are further improved.

The coating for smelting the aluminum lithium alloy crucible is characterized in that the binder accounts for 40-90 wt% of the coating, and the aggregate BN accounts for 10-60 wt%; wherein the binder comprises (10-50 wt%) aluminum dihydrogen phosphate powder, (3-5 wt%) c-B₂O₃(0.5-3 wt%) corrosion inhibitor, (0.5-3 wt%) curing agent, filler (0.5-5 wt%), dispersing agent (0.1-2 wt%) and the rest is water.

Further, the aggregate is hexagonal BN, and the granularity is 500-800 meshes.

Further, the main component in the binder is aluminum dihydrogen phosphate (with the granularity of 150-200 meshes), and the mass fraction is 10-50 wt%; c-B used in binders₂O₃Preparing polyvinyl alcohol borate gel from polyvinyl alcohol (60 mol%) and boric acid (40 mol%) by a sol-gel method, and cracking the polyvinyl alcohol borate gel at the temperature of 400-600 ℃ under the air condition to obtain B₂O₃Carbon-blended powder (c-B for short)₂O₃)。

In addition to good adhesion, the dispersibility and flowability of the coating are also of critical importance. The paint has no excellent dispersibility and flowability, and the storage of the paint and the uniformity of the coating cannot be guaranteed. In order to obtain a boron nitride coating with uniform dispersion and good fluidity, the invention is based on the characteristics of good rheological property and thickening effect of sepiolite, network structure (ruhohcan, zhui gold, lie, xixianpan, schie chen, lirirong, wang jiadong, cement slurry suspending agent research progress, oilfield chemistry, 2014, 31(2), 307-.

Further, the dispersing agent used in the binder is sepiolite or calcium phosphate, and the granularity is 500-800 meshes.

Further, the binder also comprises various additives: the corrosion inhibitor is sodium aluminate or sodium molybdate, the curing agent is MgO or magnesia-alumina spinel, and the filler is SiC fiber; wherein the particle size of MgO or magnesium aluminate spinel is 500-800 meshes, the particle size of sodium aluminate or sodium molybdate is 200-300 meshes, the diameter of SiC fiber is 5-10 microns, and the length-diameter ratio is 20.

The preparation method of the coating for smelting the aluminum lithium alloy crucible is characterized in that aluminum dihydrogen phosphate, c-B₂O₃Mixing the corrosion inhibitor, the curing agent, the dispersing agent and the filler into water to obtain turbid liquid mainly containing aluminum dihydrogen phosphate (with the concentration of 10-50 wt%); and ball-milling the turbid liquid and BN powder for 22-26h to obtain the BN slurry coating.

A method for coating the coating prepared by the method on the graphite crucible is characterized in that impurities on the inner surface of the graphite crucible are removed, and the graphite crucible is heated to 65-95 ℃; the coating is coated on the inner surface of the crucible in various modes of brushing and spraying; after air drying, heating to 800-.

Further, the thickness of the coating is 50-80 microns.

In summary, the present invention is based on the stability of MgO in aluminum lithium alloy melts; the improvement effect of the SiC fibers on thermal shock stability (Chengfeng, research on corrosion resistance and thermal shock resistance of carbon-silicon fibers, Suzhou university, 2012) and the stability of the SiC fibers on aluminum-lithium alloy; corrosion inhibition of sodium aluminate on aluminum alloy melt(Wanwenzhong, metal corrosion inhibitor and its application, electroplating and environmental protection, 2007, 6, 43-44), and relative to CrO₃And zinc chrome yellow (CN109020554A and CN110172627A) are more environment-friendly; and preparing the BN coating. The components in the coating can mutually cooperate, the non-wetting and non-reactivity of BN to the aluminum lithium alloy melt and the characteristic that aluminum dihydrogen phosphate generates stable aluminum phosphate with a three-dimensional network structure at high temperature are fully exerted, and B₂O₃In-situ formation of B on graphite surface₄The principle of C chemical bond can increase the adhesive force and high-temperature stability of the coating. In addition, in the preparation process of the coating, sepiolite or calcium phosphate is used as a dispersing agent, so that the suspension stability of the coating can be considered, and the high-temperature performance of the coating can be further enhanced; the SiC fiber is not only stable to the aluminum lithium alloy melt, but also can improve the thermal shock resistance stability of the coating; MgO does not react with the aluminum-lithium alloy, and can further reduce the curing temperature of the aluminum dihydrogen phosphate (Hehezuhua, preparation of phosphate-based high-temperature binder and research on its binding properties, Tianjin university, Master thesis, 2012). Therefore, the components in the invention can fully play a synergistic role, and the boron nitride coating with good dispersion, low curing temperature, firm adhesion, stable high-temperature performance and good thermal shock resistance is obtained.

The characteristic of the coating of the invention is that BN is used as aggregate, and the BN coating is prepared by utilizing the characteristic that BN is not influenced by most of molten metal, slag and scum and is not infiltrated with the molten metal, slag and scum, and the service life of the graphite crucible is prolonged. In addition, the boron nitride coating can be used in a reducing atmosphere at 1372 ℃ and in an oxidizing atmosphere at 850 ℃, and has excellent thermal shock resistance, high-temperature lubricity and corrosion resistance.

The invention is characterized in that the adhesive is selected from aluminum dihydrogen phosphate and c-B₂O₃The composite binder adopts MgO as a curing agent and SiC fiber as a filler, so that the boron nitride coating and the graphite substrate have good physical and chemical binding force, and have the characteristics of low curing temperature, good thermal shock resistance, strong corrosion resistance and stable high-temperature performance. And ball-milling and mixing the slurry for 24 hours to prepare the crucible coating for smelting the aluminum-lithium alloy.

The key process in the invention is the regulation and control of the BN coating. The sepiolite or calcium phosphate used has excellent dispersing performance and is a key additive for successfully preparing the BN coating. They can make BN powder in aluminium dihydrogen phosphate and c-B₂O₃The suspension of the composite binder has the characteristics of uniform dispersion and good flow property.

The BN coating of the present invention is provided in a liquid form that is easily paintable, can be diluted with water to a consistency suitable for spraying and brushing, and is suitable for application to a variety of permeable and impermeable substrates including graphite. Has the advantages of simple and convenient operation.

In the coating method, the temperature rise speed is 5-10 ℃/min when the temperature rises to 800-.

Further, a thermal shock test is carried out on the graphite crucible with the BN coating, the graphite crucible is heated to 750 ℃ firstly, then is cooled to room temperature, the thermal shock resistance test is repeatedly carried out for 6 times, and the coating does not crack or fall off, so that the coating has good thermal shock resistance; when the aluminum-lithium alloy is immersed in the melt for 1 hour, no aluminum diffuses in the graphite crucible, which indicates that the coating has good chemical stability.

Drawings

FIG. 1 is a rheological curve of BN coating of a graphite crucible for melting an aluminum lithium alloy of example 1 of the present invention;

FIG. 2 is an SEM image of sintered graphite crucible coating for smelting aluminum-lithium alloy in example 1 of the present invention.

Detailed Description

Aluminum dihydrogen phosphate, sodium aluminate, sepiolite, magnesium oxide, silicon carbide fiber and boron nitride adopted in the embodiment of the invention are commercial products.

The polyvinyl alcohol and boric acid in the examples of the present invention are commercially available products.

c-B in the examples of the invention₂O₃Is prepared by preparing polyvinyl alcohol and boric acid into polyvinyl alcohol borate through a sol-gel method and cracking the polyvinyl alcohol borate in air at the temperature of 400-600 ℃.

The crucible in the embodiment of the invention is a high-purity graphite crucible.

In the embodiment of the invention, a glass container is adopted for mixing the materials.

The water used in the examples of the present invention is deionized water.

In the embodiment of the invention, aluminum dihydrogen phosphate and sodium aluminate in the raw materials are dissolved in water in the process of preparing the coating.

In the embodiment of the invention, the SiC raw material is fibrous, the diameter is 5-10 microns, and the length-diameter ratio is 20.

The sintering temperature of the coating in the embodiment of the invention is 800-1300 ℃, and the heat preservation is carried out for 2 h. The main component of the coating after sintering at 1300 ℃ is BN, and the rest is mainly Al₂O₃-P₂O₅And the like.

The thickness of the sintered coating in the embodiment of the invention is 50-80 microns.

Example 1

The graphite crucible coating for smelting the aluminum-lithium alloy comprises the components of a binder and aggregate, wherein the binder accounts for 90 wt% of the total mass, and the balance is the aggregate; 10 wt% of aluminum dihydrogen phosphate and c-B in the binder according to mass percentage₂O₃3 wt%, MgO 0.8 wt%, sodium aluminate 1.5 wt%, sepiolite 0.5 wt%, SiC fiber 1 wt%, and water in balance; the aggregate is boron nitride with the granularity of 500-800 meshes and accounts for 10 wt% of the total mass;

the granularity of the aluminum dihydrogen phosphate is 150-200 meshes, the granularity of the MgO is 500-800 meshes, the granularity of the sodium aluminate is 200-300 meshes, and the granularity of the sepiolite is 500-800 meshes; the preparation method comprises the following steps:

(1) preparing polyvinyl alcohol borate gel from polyvinyl alcohol (60 mol%) and boric acid (40 mol%) by a sol-gel method, and cracking at 400-600 ℃ to obtain c-B₂O₃；

(2) Reacting aluminum dihydrogen phosphate, c-B₂O₃Mixing with sodium aluminate, magnesium oxide, sepiolite, SiC fiber, etc., adding water, heating to 50 deg.C under stirring to obtain mixed solution;

(3) adding BN powder into the mixed solution, and uniformly stirring to prepare slurry;

(4) ball-milling and mixing the slurry for 24 hours to prepare graphite crucible coating for smelting aluminum lithium alloy;

the coating method comprises the following steps:

removing impurities on the inner surface of the graphite crucible, and then heating the graphite crucible to 70 ℃; coating the graphite crucible coating for smelting the aluminum-lithium alloy on the inner surface of the graphite crucible in a brush coating or spraying manner, and then air-drying in the air for 1 h; heating the sprayed graphite crucible to 1300 ℃, keeping the temperature at the heating speed of 5 ℃/min for 1h, and cooling to normal temperature along with the furnace to obtain the graphite crucible with the surface coated with the coating and used for smelting the aluminum-lithium alloy; the coating thickness is 50-80 microns.

Example 2

The method is the same as example 1, except that:

(1) the binder accounts for 40% of the total mass of all the components; 30 wt% of aluminum dihydrogen phosphate and c-B in the adhesive according to mass percentage₂O₃3 wt%, MgO 2 wt%, sodium aluminate 1 wt%, SiC fiber 2 wt%, and water in balance;

(2) heating to 60 ℃ under stirring; ball-milling and mixing the slurry for 24 hours;

(3) heating to 80 ℃ after polishing; air drying time is 0.5 h; after spraying, the temperature is raised to 1300 ℃, the temperature raising speed is 10 ℃/min, and the temperature is kept for 1.5 h;

example 3

The method is the same as example 1, except that:

(1) the binder accounts for 50 wt% of the total mass of all the components; 30 wt% of aluminum dihydrogen phosphate and c-B in the adhesive according to mass percentage₂O₃5 wt%, 2 wt% of MgO, 1.3 wt% of sodium aluminate, 2 wt% of sepiolite, 1 wt% of SiC fiber and the balance of water;

(2) heating to 80 ℃ under stirring; adding BN, and then ball-milling and mixing the slurry for 22 hours;

(3) heating to 90 ℃ after polishing; air drying time is 0.5 h; after spraying, the temperature is raised to 1300 ℃, the temperature raising speed is 5 ℃/min, and the temperature is kept for 2 h.

Example 4

The method is the same as example 3, except that:

(1) the binder component accounts for 6 of the mass of all the components0 wt%, 20 wt% of aluminum dihydrogen phosphate in the adhesive, c-B₂O₃4 wt%, MgO 1 wt%, sodium aluminate 1.3 wt%, SiC fiber 1 wt%, and the balance of water; the aggregate accounts for 40 wt% of the total components and is BN with the particle size of 500-800 meshes.

(3) Heating to 80 ℃ under the condition of stirring, and ball-milling and mixing the slurry for 23h

(4) After polishing, the mixture is heated to 90 ℃, air is dried for 0.5h, and after spraying, the temperature is raised to 1300 ℃ at the speed of 10 ℃/min. And keeping the temperature for 2 h.