Ceramic plug coating and method for its production, ceramic plug and use

Abstract

The application belongs to the technical field of ceramic processing, and particularly relates to a ceramic plug coating, a preparation method thereof, a ceramic plug and application. The ceramic plug coating comprises a transition layer and an outer surface layer; raw materials of a material of the transition layer comprise a first metal salt and a silane coupling agent; the first metal salt comprises a zirconium salt, a tungstate, a lanthanum salt and a yttrium salt. The ceramic plug coating provided by the application comprises a transition layer and an outer surface layer, the transition layer firmly connects the plug base body and the outer surface layer, the outer surface layer has strong bonding force with the ceramic plug base body, is not prone to peeling off after long-time use, and prolongs the service life of the ceramic plug.

Description

Technical Field

[0001] This invention belongs to the field of ceramic processing technology, specifically relating to a ceramic embolization coating and its preparation method, ceramic embolization, and its application. Background Technology

[0002] Embolists are classified by material into metal emboli (stainless steel, carbon steel, cemented carbide, etc.), ceramic emboli (zirconia, alumina, etc.), coated emboli (base (carbon steel) + surface plating of chromium (Cr), titanium nitride (TiN), etc.), and plastic emboli (polyetheretherketone, polytetrafluoroethylene, etc.). Among these, metal emboli corrode in strong acid / alkali environments and their hardness decreases at high temperatures, leading to deformation. The coating on coated emboli is prone to peeling off under high pressure, and after the coating wears down, the base metal is exposed, causing accelerated embolism failure and shortened service life. Plastic emboli have poor pressure resistance and wear resistance (the surface becomes rough after long-term use, affecting sealing). Ceramic emboli, on the other hand, possess ultra-high hardness, chemical inertness, high temperature resistance, and self-lubricating properties, effectively compensating for the shortcomings of metal emboli, coated emboli, and plastic emboli.

[0003] While ceramic emboli exhibit excellent corrosion resistance, wear resistance, and high-temperature stability, they are also brittle and have poor impact resistance, making them prone to fracture under impact loads or uneven stress. To address this issue, a coating is typically applied to the ceramic surface to reduce the brittleness of the ceramic embolization substrate and improve its impact resistance. However, due to differences between the ceramic embolization substrate and the coating material, as well as variations in the coating preparation process, the adhesion between the coating and the ceramic embolization substrate may be insufficient, leading to easy peeling; the coating may have high porosity, resulting in reduced corrosion resistance; and the sprayed coating may have a rough surface, failing to meet the requirements of precision emboli. Summary of the Invention

[0004] To address the aforementioned problems, this invention provides a ceramic embolization coating, its preparation method, a ceramic embolization plug, and its application. The ceramic embolization coating at least solves the technical problems of insufficient adhesion between the coating and the ceramic embolization plug substrate, and easy peeling.

[0005] This invention is achieved through the following technical solution: In a first aspect, the present invention provides a ceramic embolization coating, comprising a transition layer and an outer surface layer; The raw materials for the transition layer include a first metal salt and a silane coupling agent; The first metal salt includes zirconium salt, tungstate, lanthanum salt and yttrium salt.

[0006] In some possible implementations, the mass ratio of the first metal salt to the silane coupling agent is 1:(1.5~3).

[0007] In some possible implementations, the molar ratio of zirconium, tungsten, lanthanum and yttrium in the first metal salt is (1.5~2):(1.5~2):0.015:(0.05~0.12).

[0008] In some possible implementations, the raw material for the transition layer also includes a second metal salt.

[0009] In some possible implementations, the thickness of the transition layer is 10 μm to 30 μm.

[0010] In some possible implementations, the raw materials for the outer surface layer include a third metal salt and a silane coupling agent; The second metal salt includes aluminum salts, zirconium salts, tungstates, lanthanum salts, and yttrium salts.

[0011] In some possible implementations, the thickness of the outermost layer is 600 μm to 800 μm.

[0012] In some possible implementations, the total molar amount of metal elements in the second metal salt is 0.1% to 0.5% of the total molar amount of metal elements in the first metal salt.

[0013] In some possible implementations, the second metal salt includes at least one of iron salt, ferrous salt, and manganese salt.

[0014] In some possible implementations, the mass ratio of the third metal salt to the silane coupling agent is 1:(1.5~3).

[0015] In some possible implementations, the molar ratio of aluminum, zirconium, tungsten, lanthanum and yttrium in the third metal salt is (0.5~1.2):(0.5~1.2):(0.5~2):0.1:(0.02~0.035).

[0016] Secondly, the present invention provides a method for preparing the above-mentioned ceramic embolization coating, comprising the following steps: A transition layer and an outer layer were prepared on the surface of a ceramic embolization substrate, respectively.

[0017] In some possible implementations, the preparation of the transition layer includes the following steps: coating a first slurry onto the surface of an acid-treated ceramic embolization substrate and then sintering it; the first slurry includes a metal salt raw material for the transition layer and a silane coupling agent.

[0018] In some possible implementations, the preparation of the outer surface layer includes the following steps: acidifying the transition layer, coating it with a second slurry, and then sintering it; the second slurry includes a metal salt raw material for the outer surface layer and a silane coupling agent.

[0019] In some possible implementations, the preparation of the first slurry includes the following steps: dispersing the metal salt raw material of the transition layer in the silane coupling agent and adding water dropwise.

[0020] In some possible implementations, the preparation of the second slurry includes the following steps: dispersing the metal salt raw material of the outer layer in a silane coupling agent and adding water dropwise.

[0021] In some possible implementations, the volume ratio of silane coupling agent to water in the first slurry is 1:(0.01~0.1).

[0022] In some possible implementations, the volume ratio of silane coupling agent to water in the second slurry is 1:(0.01~0.1).

[0023] Thirdly, the present invention provides a ceramic embolization, including the above-described ceramic embolization coating.

[0024] Fourthly, the present invention provides an application of the above-mentioned ceramic embolism in an embolism pump or a high-pressure pump.

[0025] The ceramic embolic coating and its preparation method provided by this invention have at least the following beneficial technical effects compared with the prior art: (1) The ceramic embolization coating provided by the present invention includes a transition layer and an outer layer. The transition layer firmly connects the embolization substrate and the outer layer, so that the outer layer and the ceramic embolization substrate have a strong bonding force and are not easy to peel off after long-term use, thus extending the service life of the ceramic embolization.

[0026] (2) The ceramic embolization coating provided by the present invention is a composite of various wear-resistant materials, and the resulting ceramic embolization coating has high wear resistance, high hardness, corrosion resistance and high temperature stability.

[0027] (3) The method for preparing ceramic embolization coating provided by the present invention uses silane coupling agent to form O-Si-O chemical bonds between the ceramic matrix and the transition layer, and between the transition layer and the outer surface layer, so that the transition layer and the ceramic embolization matrix have strong interfacial bonding force, and are not easy to peel off after long-term use, thus extending the service life of the ceramic embolization. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of this drawing or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this drawing. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0029] Figure 1This is a schematic diagram of the ceramic embolization coating provided in an embodiment of the present invention.

[0030] Figure reference numerals: 1-Ceramic embolization matrix; 2-Transition layer; 3-Outer surface layer.

[0031] The purpose, features, and advantages of this accompanying drawing will be further explained in conjunction with the embodiments and with reference to the accompanying drawing. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the invention is described and illustrated below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. All other embodiments obtained by those skilled in the art based on the embodiments provided by this invention without inventive effort are within the scope of protection of this invention.

[0033] Obviously, the following description is merely some examples or embodiments of the present invention. Those skilled in the art can apply the present invention to other similar scenarios without any inventive effort. Furthermore, it is understood that although the effort involved in such development may be complex and lengthy, for those skilled in the art related to the content disclosed in this invention, modifications to design, manufacturing, or production based on the technical content disclosed in this invention are merely conventional technical means and should not be construed as insufficient disclosure of the present invention.

[0034] However, there may be instances where unnecessary detailed descriptions are omitted. For example, detailed descriptions of well-known matters or repetitive descriptions of essentially the same structures may be omitted. This is to avoid making the following description unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the following description is provided to enable those skilled in the art to fully understand the invention and is not intended to limit the subject matter of the claims.

[0035] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions, and all technical features and optional technical features of the present invention can be combined with each other to form new technical solutions.

[0036] A first aspect of the present invention provides a ceramic embolization coating, comprising a transition layer and an outer surface layer; The raw materials for the transition layer include a first metal salt and a silane coupling agent; The first metal salt includes zirconium salt, tungstate, lanthanum salt and yttrium salt.

[0037] The ceramic embolization coating provided in this invention features a transition layer that chemically bonds the embolization substrate and the outer surface layer, resulting in strong adhesion between the outer surface layer and the ceramic embolization substrate. This ensures that the coating is not easily peeled off even after prolonged use, thus extending the service life of the ceramic embolization. Furthermore, zirconium salts and yttrium salts decompose at high temperatures to yield zirconium oxide and yttrium oxide, respectively. Zirconium oxide exhibits strong chemical inertness and high chemical stability, making it suitable for extreme environments. Yttrium oxide stabilizes the zirconium oxide structure, further extending the service life of the ceramic embolization. Tungstate decomposes at high temperatures to form tungsten oxide, which possesses excellent high-temperature resistance. When the raw materials also contain carbon, tungsten oxide further reacts with carbon at high temperatures to form tungsten carbide. The ultra-high hardness, wear resistance, high-temperature stability, and excellent chemical inertness of tungsten carbide further enhance the wear resistance and corrosion resistance of the transition layer, thereby further extending the service life of the ceramic embolization.

[0038] In some embodiments, the mass ratio of the first metal salt to the silane coupling agent is 1:1.5~3.

[0039] In some embodiments, the zirconium salt includes at least one of zirconium nitrate, zirconium sulfate, and tetrabutyl zirconate.

[0040] In some embodiments, tungstates include sodium tungstate (Na₂WO₄), magnesium tungstate (MgWO₄), and ammonium paratungstate ((NH₄)₂). 10 W 12 O 41 At least one of the following.

[0041] In some embodiments, lanthanum salts include lanthanum nitrate (La(NO3)3), lanthanum chloride (LaCl3), lanthanum oxalate (La2(C2O4)3), lanthanum acetylacetone (La(C5H7O2)3), and lanthanum stearate (La(C5H7O2)3). 17 H 35 At least one of COO3).

[0042] In some embodiments, the yttrium salt includes at least one of yttrium stearate, yttrium chloride, yttrium nitrate, and yttrium oxalate.

[0043] In some embodiments, the molar ratio of zirconium, tungsten, lanthanum and yttrium in the first metal salt is (1.5~2):(1.5~2):0.015:(0.05~0.12).

[0044] In some embodiments, the raw material for the transition layer also includes a second metal salt.

[0045] In some embodiments, the total molar amount of metal elements in the second metal salt is 0.1% to 0.5% of the total molar amount of metal elements in the first metal salt.

[0046] In some embodiments, the second metal salt includes at least one of iron salt, ferrous salt, and manganese salt.

[0047] In some embodiments, iron salts include ferric nitrate, ferric chloride, ferric acetylacetone (Fe(C5H7O2)3), ferric citrate (FeC6H5O7), and ferric stearate (Fe(C5H7O2)3). 17 H 35 At least one of COO3).

[0048] In some embodiments, the molar amount of iron in the iron salt is 0.2% to 0.5% of the total molar amount of metal elements in the first metal salt.

[0049] In some embodiments, the ferrous salt includes at least one of ferrous sulfate, ferrous oxalate, and ferrous chloride.

[0050] In some embodiments, the molar amount of ferrous iron in the ferrous salt is 0.2% to 0.5% of the total molar amount of metal elements in the first metal salt.

[0051] In some embodiments, the manganese salt includes at least one of manganese nitrate, manganese oxalate, manganese stearate, and manganese citrate.

[0052] In some embodiments, the molar amount of manganese in the manganese salt is 0.1% to 0.2% of the total molar amount of metal elements in the first metal salt.

[0053] In some embodiments, the thickness of the transition layer is 10 μm to 30 μm.

[0054] In some embodiments, the raw materials for the outer surface layer include a third metal salt and a silane coupling agent; The third metal salt includes aluminum salts, zirconium salts, tungstates, lanthanum salts, and yttrium salts. In this case, aluminum salts decompose at high temperatures to yield alumina, which can improve the corrosion resistance of ceramic emboli. Zirconium and yttrium salts decompose at high temperatures to yield zirconium oxide and yttrium oxide, respectively. Zirconium oxide is chemically inert and has high chemical stability, making it suitable for extreme environments; yttrium oxide can stabilize the zirconium oxide structure and extend the service life of ceramic emboli. Tungstates decompose at high temperatures to yield tungsten oxide, and the synergistic effect of tungsten oxide, alumina, and zirconium oxide can improve the wear resistance of ceramic emboli. Furthermore, the material of the outer layer is similar to that of the transition layer, which can improve the compatibility between the two layers.

[0055] In some embodiments, the mass ratio of the third metal salt to the silane coupling agent is 1:1.5~3.

[0056] In some embodiments, the molar ratio of aluminum, zirconium, tungsten, lanthanum and yttrium in the third metal salt is (0.5~1.2):(0.5~1.2):(0.5~2):0.1:(0.02~0.035).

[0057] In some embodiments, aluminum salts include aluminum chloride, aluminum nitrate, triethylaluminum (Al(C2H5)3), and aluminum stearate (Al(C2H5)3). 17 H 35 At least one of COO3).

[0058] In some embodiments, the thickness of the outer layer is 600 μm to 800 μm.

[0059] In some embodiments, the raw material for the outer surface layer also includes a fourth metal salt.

[0060] In some embodiments, the fourth metal salt includes at least one of iron salt, ferrous salt, and manganese salt.

[0061] In some embodiments, the total molar amount of metal elements in the fourth metal salt is 0.1% to 0.5% of the total molar amount of metal elements in the second metal salt.

[0062] In some embodiments, the molar amount of iron in the iron salt is 0.2% to 0.5% of the total molar amount of metal elements in the second metal salt.

[0063] In some embodiments, the molar amount of ferrous iron in the ferrous salt is 0.2% to 0.5% of the total molar amount of metal elements in the second metal salt.

[0064] In some embodiments, the molar amount of manganese in the manganese salt is 0.1% to 0.2% of the total molar amount of metal elements in the second metal salt.

[0065] In some embodiments, the silane coupling agent includes at least one of 3-methacryloyloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.

[0066] A second aspect of this invention provides a method for preparing the above-mentioned ceramic embolic coating, comprising the following steps: S10. A transition layer and an outer layer are prepared on the surface of the ceramic embolization substrate, respectively.

[0067] The ceramic embolization coating preparation method provided in this invention produces a ceramic embolization coating with high wear resistance, high hardness, corrosion resistance, and high temperature stability.

[0068] In some embodiments, in step S10 above, the material of the ceramic embolization matrix includes at least one of alumina, zirconium oxide, silicon carbide, and silicon nitride.

[0069] In some embodiments, in step S10 above, the preparation of the transition layer includes the following steps: S101. The first slurry is coated onto the surface of the acid-treated ceramic plug substrate and then sintered. The first slurry includes a metal salt raw material for the transition layer and a silane coupling agent.

[0070] In some embodiments, the acidification step in step S101 above includes: S1010. Immerse the ceramic embolization matrix in dilute phosphoric acid for acidification.

[0071] In some embodiments, in step S1010 above, the concentration of dilute phosphoric acid is 10% to 30%.

[0072] In some embodiments, the acidification time in step S1010 is 1h to 2h.

[0073] In some embodiments, in step S101 above, the preparation of the first slurry includes the following steps: S1011. Disperse the metal salt raw material of the transition layer in the silane coupling agent, and add water dropwise; The volume ratio of silane coupling agent to water is 1:(0.01~0.1).

[0074] In the preparation of the first slurry, the metal salt raw material (first metal salt, or, first metal salt and second metal salt) of the transition layer is dispersed in a silane coupling agent, and then a small amount of water is added to partially hydrolyze the silane coupling agent. This process ensures that the metal ions are uniformly dispersed in the slurry, resulting in a transition layer with uniform thickness and composition after coating and sintering within the metal oxide silicon oxide framework. Furthermore, it increases the viscosity of the first slurry, facilitating subsequent coating. Additionally, the silanol obtained from the hydrolysis of the silane coupling agent is grafted onto the H atoms on the surface of the (acidified) ceramic embolization substrate, ensuring that the first slurry is uniformly and stably coated on the surface of the ceramic embolization substrate. Moreover, after coating and sintering, silicon forms O-Si-O with the O atoms in the substrate and the transition layer, resulting in a chemical bond. This creates a strong interfacial bond between the transition layer and the ceramic embolization substrate, preventing peeling even after prolonged use and extending the service life of the ceramic embolization.

[0075] In some embodiments, in step S101 above, the coating includes the following steps: S1012. The first slurry is coated onto the surface of the ceramic plug substrate using high-pressure airless spraying.

[0076] High-pressure airless spraying is a high-efficiency, high-quality spraying technology. It uses a high-pressure embolism pump to pressurize the paint to a high-pressure state, causing it to be sprayed out of the nozzle at high speed and violently collide with the air to form atomized particles that are uniformly deposited on the surface of the object being coated.

[0077] In some embodiments, in step S1012 above, the spraying pressure in high-pressure airless spraying is 15MPa~20MPa.

[0078] In some embodiments, the sintering step in step S101 above includes: S1013. Heat to 1200℃~1500℃ at a heating rate of 2℃ / min~5℃ / min and then hold at that temperature.

[0079] In this case, during sintering, the metal salt raw material of the transition layer decomposes to generate metal oxides (and metal carbides). The silicon in the silane coupling agent chemically bonds with the O in the ceramic plug matrix and the O in the first slurry, respectively, improving the bonding force between the transition layer and the ceramic matrix; heat preservation promotes the densification of the coating and grain growth.

[0080] In some embodiments, the heat preservation time in step S1013 is 30 min to 60 min.

[0081] In some embodiments, in step S10 above, preparing the outer surface layer includes the following steps: S102. After acidifying the transition layer, coat it with the second slurry and then sinter it; The second slurry includes the metal salt raw material and silane coupling agent for the outer layer.

[0082] In some embodiments, the acidification treatment in step S102 is the same as the acidification step of the ceramic embolization matrix, and will not be described again here.

[0083] In some embodiments, in step S102 above, the preparation of the second slurry includes the following steps: S1021. Disperse the metal salt raw material of the outer layer in a silane coupling agent, and add water dropwise; The volume ratio of silane coupling agent to water is 1:(0.01~0.1).

[0084] In some embodiments, the coating and sintering steps in step S102 are the same as those for the coating and sintering of the first slurry, and will not be described again here.

[0085] A third aspect of the present invention provides a ceramic embolization, including the ceramic embolization coating provided in the embodiments of the present invention.

[0086] The following is a further explanation with reference to specific embodiments. For ease of explanation, unless otherwise specified, the material of the ceramic embolization matrix in the following embodiments or comparative examples is zirconium oxide.

[0087] Example 1 Example 1 provides a ceramic embolization coating, which consists of a transition layer and an outer layer; The transition layer material is composed of zirconium nitrate, ammonium paratungstate, lanthanum nitrate, yttrium nitrate, and 3-methacryloyloxypropyltrimethoxysilane; the molar ratio of zirconium, tungsten, lanthanum, and yttrium is 1.5:1.5:0.015:0.12; the total mass ratio of zirconium nitrate, ammonium paratungstate, lanthanum nitrate, and yttrium nitrate to the mass ratio of 3-methacryloyloxypropyltrimethoxysilane is 1:2.

[0088] The outer layer material is composed of aluminum chloride, zirconium nitrate, ammonium paratungstate, lanthanum nitrate, yttrium nitrate, and 3-methacryloyloxypropyltrimethoxysilane; the molar ratio of aluminum, zirconium, tungsten, lanthanum, and yttrium is 0.8:0.8:1:0.1:0.03; the total mass ratio of aluminum chloride, zirconium nitrate, ammonium paratungstate, lanthanum nitrate, and yttrium nitrate to the mass ratio of 3-methacryloyloxypropyltrimethoxysilane is 1:2.

[0089] This embodiment also provides a method for preparing the ceramic embolization coating provided in this embodiment, the steps of which are as follows: E10. Acid-treated ceramic embolization matrix The ceramic embolization matrix was immersed in 10% dilute phosphoric acid for 2 hours for acidification.

[0090] E20. Preparation of the first slurry Zirconium nitrate, ammonium paratungstate, lanthanum nitrate, and yttrium nitrate were dispersed in 3-methacryloyloxypropyltrimethoxysilane, and deionized water was added dropwise. The volume ratio of 3-methacryloyloxypropyltrimethoxysilane to deionized water was 1:0.08.

[0091] E30. Preparation of transition layer E301. The first slurry is coated on the surface of the ceramic plug substrate using a high-pressure airless spraying method; wherein the spraying pressure is 20 MPa.

[0092] E302. Heat to 1300℃ at a heating rate of 4℃ / min and hold for 40min to obtain the transition layer.

[0093] E40. Acidification treatment transition layer The transition layer was immersed in 10% dilute phosphoric acid for 2 hours to acidify it.

[0094] E50. Preparation of the second slurry Aluminum chloride, zirconium nitrate, ammonium paratungstate, lanthanum nitrate, and yttrium nitrate were dispersed in 3-methacryloyloxypropyltrimethoxysilane, and deionized water was added dropwise. The volume ratio of 3-methacryloyloxypropyltrimethoxysilane to deionized water was 1:0.08.

[0095] E60. Preparation of outer surface layer E601. The second slurry is coated onto the surface of the ceramic plug substrate using high-pressure airless spraying; wherein the spraying pressure is 20 MPa.

[0096] E602. Heat to 1300℃ at a heating rate of 4℃ / min and hold for 40min to obtain the outer surface layer.

[0097] Example 2 Example 2 provides a ceramic embolization coating, which consists of a transition layer and an outer layer; The transition layer material is composed of zirconium nitrate, ammonium paratungstate, lanthanum nitrate, yttrium nitrate, ferric chloride, and 3-methacryloyloxypropyltrimethoxysilane. The molar ratio of zirconium, tungsten, lanthanum, and yttrium is 1.5:1.5:0.015:0.12, and the molar amount of iron is 0.3% of the total molar amount of zirconium, tungsten, lanthanum, and yttrium. The total mass ratio of zirconium nitrate, ammonium paratungstate, lanthanum nitrate, yttrium nitrate, and ferric chloride to the mass ratio of 3-methacryloyloxypropyltrimethoxysilane is 1:2.

[0098] The outer layer material is composed of aluminum chloride, zirconium nitrate, ammonium paratungstate, lanthanum nitrate, manganese oxalate, yttrium nitrate, and 3-methacryloyloxypropyltrimethoxysilane; the molar ratio of aluminum, zirconium, tungsten, lanthanum, and yttrium is 0.8:0.8:1:0.1:0.03; the molar amount of manganese is 0.1% of the total molar amount of zirconium, tungsten, lanthanum, and yttrium; the mass ratio of the total mass of aluminum chloride, zirconium nitrate, ammonium paratungstate, lanthanum nitrate, manganese oxalate, and yttrium nitrate to the mass of 3-methacryloyloxypropyltrimethoxysilane is 1:2.

[0099] This embodiment also provides a method for preparing the ceramic embolization coating provided in this embodiment. The steps are basically the same as those in Embodiment 1, except that: In step E20, the first slurry also contains ferric chloride.

[0100] In step 302, the temperature is increased to 1500℃ at a heating rate of 5℃ / min and then held for 30min to obtain the transition layer.

[0101] In step 50, the second slurry also contains manganese oxalate.

[0102] In step 602, the temperature is increased to 1400℃ at a heating rate of 3℃ / min and then held for 50min to obtain the outer surface layer.

[0103] Example 3 Example 3 provides a ceramic embolization coating with a composition that is basically the same as that of Example 1, except that; In the transition layer material, the molar ratio of zirconium, tungsten, lanthanum and yttrium is 2:2:0.015:0.10; the total mass ratio of zirconium nitrate, ammonium paratungstate, lanthanum nitrate and yttrium nitrate to 3-methacryloyloxypropyltrimethoxysilane is 1:3.

[0104] In the raw materials of the outer layer, the molar ratio of aluminum, zirconium, tungsten, lanthanum and yttrium is 0.5:1:2:0.1:0.035; the total mass ratio of aluminum chloride, zirconium nitrate, ammonium paratungstate, lanthanum nitrate and yttrium nitrate to 3-methacryloyloxypropyltrimethoxysilane is 1:1.5.

[0105] Example 4 Example 4 provides a ceramic embolization coating with a composition basically the same as that of Example 1, except that: In the transition layer material, the molar ratio of zirconium, tungsten, lanthanum and yttrium is 1.5:1:0.015:0.05; the total mass ratio of zirconium nitrate, ammonium paratungstate, lanthanum nitrate and yttrium nitrate to the mass ratio of 3-methacryloyloxypropyltrimethoxysilane is 1:1.5.

[0106] In the raw materials of the outer layer, the molar ratio of aluminum, zirconium, tungsten, lanthanum and yttrium is 1:0.5:0.5:0.1:0.02; the total mass ratio of aluminum chloride, zirconium nitrate, ammonium paratungstate, lanthanum nitrate and yttrium nitrate to 3-methacryloyloxypropyltrimethoxysilane is 1:3.

[0107] Example 5 Example 5 provides a ceramic embolization coating with a composition basically the same as that of Example 1, except that: In the raw materials of the transition layer material, the lanthanum salt is lanthanum oxalate and the yttrium salt is yttrium oxalate.

[0108] In the raw materials of the outer layer material, the lanthanum salt is lanthanum oxalate and the yttrium salt is yttrium oxalate.

[0109] Comparative Example 1 Comparative Example 1 provides a ceramic embolization coating, composed of raw materials of the following: Zirconium nitrate, ammonium paratungstate, lanthanum nitrate, yttrium nitrate, and silicone oil.

[0110] The molar ratio of zirconium, tungsten, lanthanum and yttrium is 1.5:1.5:0.015:0.12; the total mass ratio of zirconium nitrate, ammonium paratungstate, lanthanum nitrate and yttrium nitrate to silicone oil is 1:2.

[0111] This comparative example also provides a method for preparing the ceramic embolization coating provided in this comparative example, the steps of which are as follows: D10. Zirconium nitrate, ammonium paratungstate, lanthanum nitrate, yttrium nitrate and silicone oil are mixed and coated onto the surface of a ceramic embolization substrate using a high-pressure airless spraying method; the spraying pressure is 20 MPa.

[0112] D20. The temperature was increased to 1300℃ at a heating rate of 4℃ / min and then held for 40 min to obtain the ceramic embolization coating provided in this comparative example.

[0113] Comparative Example 2 Comparative Example 2 provides a method for preparing a ceramic embolism coating, the steps of which are basically the same as those in Example 1, except that: The ceramic embolization matrix and transition layer are not acidified.

[0114] Comparative Example 3 Comparative Example 3 provides a method for preparing a ceramic embolization coating, the steps of which are basically the same as those in Example 1, except that: The volume ratio of 3-methacryloyloxypropyltrimethoxysilane to deionized water is 1:2.

[0115] To verify the advancement of the ceramic plug coating and its preparation method according to embodiments of the present invention, the ceramics or prepared coatings provided in the embodiments and comparative examples of the present invention were subjected to the following wear resistance and corrosion resistance tests. The results are shown in Table 1 below.

[0116] (1) Abrasion resistance test: The wear resistance of ceramic surfaces was tested using a Taber abrasion tester.

[0117] The grinding wheel type is CS-10; the rotation speed is 60 rpm; the load is 500g~1000g; the friction cycle is 500rpm~1000rpm; and the friction time is 10min.

[0118] (2) The corrosion resistance of the ceramic surface was tested according to standard ISO 28706 (test conditions: the sample was immersed in HCl solution with a temperature of 60℃ and a concentration of 4% for 24 hours).

[0119] Table 1

[0120] It can be seen from Table 1 above: (1) The ceramic plug coating provided in the embodiments of the present invention has high wear resistance and corrosion resistance.

[0121] (2) In the method for preparing ceramic embolization coating provided in the embodiments of the present invention, the silane coupling agent in the first slurry and the second slurry is partially hydrolyzed. After coating and sintering, silicon forms O-Si-O with O in the matrix and O in the transition layer, which is a chemical bond. This results in a strong interfacial bonding force between the transition layer and the ceramic embolization matrix. It is not easy to peel off after long-term use, thus extending the service life of the ceramic embolization.

[0122] (3) The method for preparing ceramic embolization coating provided in the embodiments of the present invention, after acid treatment of ceramic embolization substrate and transition layer, the coating prepared has better wear resistance and corrosion resistance.

[0123] It should be noted that the present invention is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments that have the same structure and perform the same effects as the technical concept within the scope of the present invention are included within the scope of the present invention. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of the present invention, are also included within the scope of the present invention.

Claims

1. A ceramic embolization coating, characterized in that, Includes a transition layer and an outer layer; The raw materials for the transition layer include a first metal salt and a silane coupling agent; The first metal salt includes zirconium salts, tungstates, lanthanum salts, and yttrium salts; The raw materials for the outer surface layer include a third metal salt and a silane coupling agent, wherein the third metal salt includes aluminum salt, zirconium salt, tungstate, lanthanum salt, and yttrium salt; The preparation of the transition layer includes the following steps: coating a first slurry onto the surface of an acid-treated ceramic embolization substrate and then sintering it; the first slurry includes a metal salt raw material for the transition layer and a silane coupling agent; The preparation of the outer surface layer includes the following steps: acidifying the transition layer, coating it with a second slurry, and then sintering it; the second slurry includes a metal salt raw material for the outer surface layer and a silane coupling agent; The preparation of the first slurry includes the following steps: dispersing the metal salt raw material of the transition layer in the silane coupling agent, and adding water dropwise; in the first slurry, the volume ratio of silane coupling agent to water is 1:0.01~0.1; The preparation of the second slurry includes the following steps: dispersing the metal salt raw material of the outer surface layer in a silane coupling agent and adding water dropwise; in the second slurry, the volume ratio of silane coupling agent to water is 1:0.01~0.

1.

2. The ceramic embolic coating according to claim 1, characterized in that, The mass ratio of the first metal salt to the silane coupling agent is 1:1.5~3; And / or, in the first metal salt, the molar ratio of zirconium, tungsten, lanthanum and yttrium is 1.5~2:1.5~2:0.015:0.05~0.12; And / or, the raw material of the transition layer material further includes a second metal salt; And / or, the thickness of the transition layer is 10 μm to 30 μm; And / or, the thickness of the outermost layer is 600μm~800μm.

3. The ceramic embolic coating according to claim 2, characterized in that, In the raw materials of the transition layer, the total molar amount of metal elements in the second metal salt is 0.1% to 0.5% of the total molar amount of metal elements in the first metal salt; And / or, in the raw materials of the transition layer, the second metal salt includes at least one of ferrous salt, ferrous salt, and manganese salt.

4. The ceramic embolic coating according to any one of claims 1 to 3, characterized in that, The mass ratio of the third metal salt to the silane coupling agent is 1:1.5~3; And / or, in the third metal salt, the molar ratio of aluminum, zirconium, tungsten, lanthanum and yttrium is 0.5~1.2:0.5~1.2:0.5~2:0.1:0.02~0.

035.

5. A method for preparing a ceramic embolic coating as described in any one of claims 1 to 4, characterized in that, Includes the following steps: A transition layer and an outer layer were prepared on the surface of a ceramic embolization substrate, respectively.

6. A ceramic embolism, characterized in that, Includes the ceramic embolization coating as described in any one of claims 1 to 4.

7. The application of the ceramic embolizer as described in claim 6 in an embolization pump or a high-pressure pump.

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