Boron-silicon-titanium hybrid resin-based high-temperature resistant ceramic binders, their preparation and application

Abstract

This invention relates to the field of high-temperature ceramic bonding materials, specifically to a boron-silicon-titanium hybrid resin-based high-temperature resistant ceramic binder and its preparation and application. A boron-hybridized phenolic resin is obtained by hydroxymethylation of triphenyl borate and diphenyl borate, followed by a condensation and dealcoholization reaction with dialkoxysilane to prepare a silicon-hybridized boron-phenolic resin; or by an alcohol exchange reaction with titanate ester to prepare a titanium-hybridized boron-phenolic resin. This is then compounded with MQ silicone resin to obtain a crosslinkable and curable polymer base. Further mixing with a metal oxide flux, adding high-temperature resistant ceramic powder as the main material, using a coupling agent as an interface treatment agent, and supplemented with a solvent, yields a viscous paste-like high-temperature resistant ceramic binder. Ceramic bonding is then performed, followed by sintering at 1500℃ under normal pressure. The binder itself forms a ceramic phase, and the ceramic exhibits good compressive shear properties. This effectively reduces the sintering temperature of high-temperature ceramics and has potential applications in the aerospace materials field.

Description

Technical Field

[0001] This invention relates to boron-silicon-titanium hybrid resin-based high-temperature resistant ceramic binders, their preparation and application, and belongs to the field of ceramic materials technology. Background Technology

[0002] Ceramic binders are reagents that can bond ceramics. They are generally classified into three categories: organic ceramic binders, inorganic ceramic binders, and metal powder binders. Common organic ceramic binders mainly include epoxy-based ceramic binders and organosilicon-based ceramic binders. Their main performance difference from inorganic ceramic binders lies in their temperature resistance. Organic binders typically have a maximum temperature resistance between 100-250 degrees Celsius, generally not exceeding 400 degrees Celsius. In contrast, inorganic ceramic binders typically have a temperature resistance range between 600-1750 degrees Celsius. Organic ceramic binders can be either soft and elastic or hard and rigid, while inorganic ceramic binders are usually hard and rigid. Common metal powder ceramic binders mainly consist of low-melting-point metal powders, and their temperature resistance depends on the melting point of the metal powder.

[0003] Heat-resistant adhesives have a promising future in ceramic manufacturing due to their ability to withstand higher temperatures. It is generally believed that heat-resistant adhesives can be used at temperatures above 200℃, while the temperature limit of ordinary polymer materials is 350℃. As temperature increases, the molecular backbone decomposes, leading to a sharp decline in mechanical properties that fail to meet application requirements. Silicate or phosphate-based inorganic adhesives often have heat resistance temperatures as high as around 1000℃, but their high brittleness, strong corrosiveness to the substrate, poor adhesion, and poor thermal shock resistance prevent them from achieving strong bonded joints.

[0004] Pure phenolic resins, due to their poor toughness, poor peel strength, and high brittleness, have greatly limited their application in the aerospace field. Boron-hybrid phenolic resins, synthesized from formaldehyde, phenol, and boron modifiers, possess better heat resistance and ablation resistance. Their ablation resistance, instantaneous high-temperature resistance, thermal oxidation resistance, and neutron radiation protection are superior to ordinary phenolic resins. The long bond length and large bond angle of the Si-O-Si main chain structure of organosilicon materials give these materials excellent weather resistance. Furthermore, under high-temperature conditions, they can be transformed into a SiOC ceramic structure [Science Bulletin, 2007, 52(14):1625-1629]. In the pyrolysis products under nitrogen atmosphere conditions of 1050–1500℃, some β-SiC crystalline structures are gradually generated. With increasing treatment temperature, the crystallinity of silicon carbide and cristobalite significantly increases. This results in excellent high-temperature resistance and ablation resistance.

[0005] In recent years, a significant amount of research has been conducted on using polymer matrices and inorganic compounds (oxides, carbides, etc.) as fillers to prepare high-temperature resistant adhesives for bonding various ceramic materials through high-temperature treatment. This method has become an important approach for high-temperature resistant ceramic material adhesives. Zhang TS et al. prepared a novel silicone adhesive [Int.J.Adhes.Adhes.,2013,41:16-23], using silicone resin as the matrix and Al, low-melting-point glass, ZnO, and Fe2O3 powders as inorganic fillers. This adhesive was used to bond mullite fiber-reinforced silica aerogel and 1Cr18Ni9Ti steel. This adhesive solves the problem of joint failure caused by mismatched thermal expansion of different thermally expanding substrates under high-temperature conditions. Xingang Luan et al. used a novel high-temperature resistant adhesive, polyborosilicate, to bond Al2O3 ceramic materials [Mater. Sci. Eng., A, 2016, 651: 517-523]. After heat treatment at 1500℃ / 1.5KPa for 2 hours, the shear strength at room temperature reached 15.73MPa. When the temperature was increased to 800℃, the bond strength of the bonded parts increased to 12.91MPa. CN104726054A discloses a low-expansion, high-temperature resistant adhesive and its preparation method. The adhesive is a two-component adhesive composed of silicone resin, silane coupling agent, curing agent, high-temperature resistant filler (some metal powders, SiC, BC, Al2O3, CaO, CuO, ZrO2, etc.), inorganic fibers (short-cut basalt fibers, short-cut quartz fibers, and short glass fibers), and organic solvents (aromatics, cyclohexanone, etc.). It can be cured at room temperature and has low expansion, excellent thermal shock resistance and high-temperature stability. The room temperature shear strength can reach 5 MPa, and the shear strength at 1200℃ can reach 1.8 MPa. It has long-term heat resistance of 1200℃ and short-term heat resistance of 1700℃.

[0006] Generally, low- and medium-temperature curing polymer-based ceramic adhesives are characterized by low bonding operation temperatures and ease of use. However, their significant drawbacks include low bond strength (<10MPa) and poor high-temperature resistance (<1200℃), making them unsuitable for high-temperature environments exceeding 1500℃, such as high-Mach flight conditions where aerodynamic heating exposes the aircraft to extreme high-temperature environments. Traditional C / C and C / SiC high-temperature resistant composite materials are commonly used for many high-temperature structural components in aircraft. However, with the rapid development of hypersonic vehicles, these materials can no longer meet the urgent requirements of hypersonic vehicle external heat shield materials for high-temperature resistance, erosion resistance, and ablation resistance. Therefore, developing high-temperature resistant adhesives as simple joining materials for commonly used ceramics in aircraft to effectively solve the challenges of their engineering applications is of great significance. Furthermore, adding flux to ceramic adhesives to lower the sintering temperature of the ceramics not only enables ceramic bonding under high-temperature conditions but also contributes to energy conservation and emission reduction.

[0007] This invention employs a composite of high-temperature resistant resin-based polymers and alkaline earth metal oxides, facilitating bonding and molding at inorganic or metal interfaces. The resin polymer undergoes cross-linking and curing reactions under medium-to-low temperature conditions, resulting in early-stage strength in the composite binder and improving the yield of molded bonded products. During sintering at 1000-1200℃, a liquid-phase ceramic flux is formed. This fluxing component facilitates the high-temperature sintering of high-temperature resistant ceramic powders, including zirconium diboride, boron nitride, silicon nitride, and silicon carbide, thereby achieving ceramic bonding under high-temperature conditions. Lowering the sintering temperature of high-temperature ceramics not only yields high-performance, high-strength ceramic binders but also contributes to energy conservation and emission reduction. Therefore, this invention is proposed. Summary of the Invention

[0008] In view of the aforementioned state of the prior art, the inventors of this invention have conducted in-depth and extensive research in the field of ceramic binders, and discovered that using silicon / boron hybrid phenolic / silicone resin and titanium / boron hybrid phenolic / silicone resin as polymer bases to formulate ceramic binders not only provides good bonding strength and temperature resistance, but also lowers the ceramic sintering temperature. For high-temperature sintering ceramics such as boron nitride and silicon nitride, sintering at atmospheric pressure at 1500℃ can produce boron nitride and silicon nitride ceramic crystalline phases. This invention is based on the above findings.

[0009] Therefore, one object of the present invention is to provide a boron-silicon-titanium hybrid resin-based high-temperature resistant ceramic binder. This binder uses silicon / boron hybrid phenolic / silicone resin and titanium / boron hybrid phenolic / silicone resin as polymer bases, alkaline earth metal oxides such as calcium, magnesium, and aluminum as fluxing components for high-temperature resistant ceramic powders, and high-temperature resistant ceramic powders such as borides and nitrides such as silicon powder, silicon oxide, zirconium diboride, boron nitride, silicon nitride, and silicon carbide as the main high-temperature resistant ceramic binder. Organosilicon or organotitanium coupling agents are used as interface treatment agents. After uniform mixing, a paste-like resin-based / oxide / ceramic powder composite is obtained, which is the high-temperature resistant ceramic binder.

[0010] The second objective of this invention is to provide a method for preparing a borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder. A paste-like resin-based / oxide / ceramic powder composite is obtained by uniform mixing. Under low-temperature conditions, the high-temperature ceramic binder is applied to the ceramic sample to be bonded. After solvent removal and drying, it is sintered at 1500°C in a high-temperature furnace under normal pressure, thereby achieving high-temperature bonding of the ceramic sample, which features high bonding strength and thermal shock resistance.

[0011] A third objective of this invention is to provide applications of borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binders. These binders are based on a polymer matrix with good plasticity and processability, providing the material with toughness and impact resistance. They can be applied to the bonding of high-temperature ceramics, especially high-temperature resistant ceramic materials for certain special applications.

[0012] The technical solution for achieving the above-mentioned objectives can be summarized as follows:

[0013] A borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder includes high-temperature resistant ceramic powder and ceramic flux crystallizer;

[0014] The raw materials for the ceramic flux crystals include: a composite material composed of polymer-based raw materials and metal oxides;

[0015] The polymer-based raw material is a mixture of at least one of boron-hybridized phenolic resin, silicon-boron-hybridized phenolic resin, and titanium-boron-hybridized phenolic resin with organosilicon resin.

[0016] According to the present invention, preferably, the high-temperature resistant ceramic powder is one or a mixture of two or more of silicon powder, silicon oxide, zirconium diboride, boron nitride, and silicon nitride;

[0017] Preferably, when the high-temperature resistant ceramic powder is a mixture of silicon nitride, boron nitride, and zirconium diboride, the molar ratio between silicon nitride, boron nitride, and zirconium diboride is 1.0:3.5:(2.0~4.0), and a high-temperature resistant ceramic binder with zirconium silicate and zirconium oxide as the main crystalline phases can be obtained by sintering at atmospheric pressure at 1500℃.

[0018] When the high-temperature resistant ceramic powder is a mixture of silicon powder, silicon oxide, and zirconium diboride, the molar ratio between silicon powder, silicon oxide, and zirconium diboride is (2.0~1.0):(2.0~1.0):(1.0~2.0). High-temperature resistant ceramic binder with zirconium diboride and zirconium oxide as the main crystalline phases can be obtained by sintering at atmospheric pressure at 1500℃.

[0019] According to the present invention, preferably, the mass ratio of high-temperature resistant ceramic powder to ceramic flux crystallizer is (1.2-3.5):1, and more preferably (1.5-3):1.

[0020] According to the present invention, preferably, the boron-hybridized phenolic resin in the ceramic flux crystal is diphenyl hydroxymethyl borate or / and triphenyl hydroxymethyl borate;

[0021] More preferably, the hydroxymethyl borate diphenyl ester has the following structure:

[0022]

[0023] More preferably, the hydroxymethylated triphenyl borate has the following structure:

[0024]

[0025] According to the present invention, preferably, the boron-hybridized phenolic resin in the ceramic flux crystal is prepared by reacting diphenyl borate or triphenyl borate with formaldehyde to obtain tetramethylolpropionic acid diphenyl ester or hexamethylolpropionic acid triphenyl ester.

[0026] More preferably, the molar ratio of diphenyl borate to formaldehyde is 1.0:4.0 to 1:4.5, and the molar ratio of triphenyl borate to formaldehyde is 1.0:6.0 to 1:7.0;

[0027] More preferably, the hydroxymethylation reaction is carried out using ammonia as a catalyst at a reaction temperature of 50–120°C.

[0028] According to the present invention, preferably, the silicon-boron hybrid phenolic resin in the ceramic flux crystal material is obtained by further reacting boron hybrid phenolic resin with diekoxysilane R. 1 R 2 Si(OR 3 )2 is obtained by chain extension reaction;

[0029] More preferably, the molar ratio of dialkoxysilane to boron-hybridized phenolic resin is 2.0:1.0 to 2.2:1.0, and the chain extension reaction temperature is 40-120℃;

[0030] More preferably, the silicon-boron hybrid phenolic resin has the following structure:

[0031]

[0032] More preferably, the diekoxysilane R 1 R 2 Si(OR 3 )2 is selected from at least one of dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylhydrodimethoxysilane, and methylhydrodiethoxysilane;

[0033] R 1 R 2 R 3 Each alkyl or phenyl group is independently selected from C1-C6, more preferably methyl, ethyl, or phenyl.

[0034] According to the present invention, preferably, the titanium boron hybrid phenolic resin in the ceramic flux crystal is obtained by further transesterification reaction of boron hybrid phenolic resin with titanate ester;

[0035] More preferably, the molar ratio of titanate to boron-hybridized phenolic resin is 4.0:1.0 to 4.2:1.0; and the transesterification reaction temperature is 20-30°C.

[0036] More preferably, the titanate is at least one selected from ethyl titanate, isopropyl titanate, n-butyl titanate, and poly(n-butyl titanate).

[0037] More preferably, the titanium-boron hybrid phenolic resin has the following structure:

[0038]

[0039] According to the present invention, preferably, the organosilicon resin in the ceramic flux crystal is MQ silicone resin, and more preferably at least one of methyl MQ silicone resin, methyl phenyl MQ silicone resin, methyl vinyl MQ silicone resin, and methyl hydrogen MQ silicone resin; preferably, the M / Q ratio in the MQ silicone resin is between 0.30 and 1.20.

[0040] According to the present invention, preferably, the weight ratio of boron-hybridized phenolic resin, silicon-boron-hybridized phenolic resin, or titanium-boron-hybridized phenolic resin to MQ silicone resin in the ceramic flux crystal is between 2:1 and 1:2.

[0041] According to the present invention, preferably, the metal oxide in the ceramic flux crystal material includes at least calcium oxide, magnesium oxide and aluminum oxide, or further includes at least one of silicon dioxide and boric acid (calculated as B2O3);

[0042] More preferably, the molar ratio of the oxides is: CaO:MgO:Al2O3:B2O3:SiO2=(0.50~0.8):(0.10~0.30):(0.63~0.85):(5.30~6.00):(0.200~0.500), wherein SiO2 and B2O3 generated from the polymer-based raw materials are included in the composition;

[0043] Preferably, the weight ratio of the total weight of the polymer base to the weight of metal oxides such as calcium, magnesium, and aluminum is 100:1 to 5:1, and more preferably 100:5 to 10:1.

[0044] Further preferably, the metal oxide is a fine powder with a particle size of 200 mesh or more.

[0045] According to the present invention, preferably, in the composite material composed of polymer-based raw material and metal oxide of ceramic flux crystal, the weight ratio of polymer-based raw material to metal oxide is 1:9 to 9:1, more preferably 2:8 to 4:6.

[0046] According to the present invention, preferably, the raw materials of the ceramic flux crystals further include a surface treatment agent of metal oxides;

[0047] More preferably, the surface treatment agent for the metal oxide is a silane coupling agent and / or a titanate coupling agent;

[0048] More preferably, the silane coupling agent is at least one of methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane, and the titanate coupling agent is at least one of ethyl titanate, isopropyl titanate, n-butyl titanate, and polyn-butyl titanate.

[0049] According to the present invention, preferably, the amount of the surface treatment agent of the metal oxide is 1% to 8% of the mass of the metal oxide.

[0050] According to the present invention, preferably, the ceramic flux crystal material comprises at least one of quartz, cristobalite, γ-phase alumina, and perovskite crystals, and has typical crystalline compound properties.

[0051] According to the present invention, the preparation method of the above-mentioned borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder includes the following steps:

[0052] The polymer-based raw material is dissolved in a solvent, and then a metal oxide is added, or a surface treatment agent of the metal oxide is added, followed by high-temperature resistant ceramic powder. The mixture is then stirred evenly to obtain a borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder.

[0053] According to the present invention, preferably, the solvent is a mixture of alcohol and aromatic hydrocarbon;

[0054] More preferably, the alcohol is methanol or ethanol; the aromatic hydrocarbon is toluene or xylene;

[0055] More preferably, the volume ratio of alcohol to aromatic hydrocarbon is between 2:1 and 1:2, and the amount of mixed solvent is 2 to 3 times the volume of polymer-based raw material.

[0056] According to the present invention, the above-mentioned borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder is used as a ceramic binder in the preparation of ceramic glazes and high-temperature resistant ceramics.

[0057] According to the present invention, preferably, the high-temperature resistant ceramic is at least one of zirconium silicate ceramic, zirconium boride ceramic, and zirconium oxide ceramic.

[0058] According to the present invention, a preferred method for applying the borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder is as follows:

[0059] (1) The borosilicate-titanium hybrid resin-based high-temperature resistant ceramic adhesive is used for ceramic bonding at room temperature. After solvent removal and drying, it is cured and crosslinked to form the initial bonding strength; or after solvent removal and drying, it is not cured and crosslinked.

[0060] (2) The material processed in step (1) is sintered at room temperature to 1500℃ under normal pressure to achieve ceramic bonding.

[0061] According to the present invention, preferably, the curing crosslinking temperature in step (1) is 150-200°C;

[0062] Preferably, the atmospheric pressure sintering conditions in step (2) are as follows: room temperature ~ 250℃ @ 3.0 ~ 4.0℃ / min and hold for 10 ~ 30 min, 250 ~ 1500℃ @ ~ 3.0℃ / min and hold for 30 ~ 120 min, and then the temperature is gradually reduced to below 100℃.

[0063] The beneficial effects of this invention are as follows:

[0064] 1. The boron-silicon-titanium hybrid resin-based high-temperature resistant ceramic binder of the present invention uses silicon / boron hybrid phenolic / silicone resin, or titanium / boron hybrid phenolic / silicone resin polymer, combined with alkaline earth metal oxides and high-temperature resistant ceramic powder, etc., which is easy to bond or form at the interface of inorganic materials or metals. Under medium and low temperature conditions, the resin polymer undergoes a cross-linking and curing reaction, thereby giving the composite binder early strength and improving the yield of bonded products after molding. Furthermore, when sintered at atmospheric pressure at 1500℃, a high-temperature resistant ceramic binder with zirconium diboride and zirconium oxide as the main crystalline phases, or zirconium silicate and zirconium oxide as the main crystalline phases, can be prepared for bonding high-purity alumina ceramic samples, which has high bonding strength and good thermal shock resistance.

[0065] 2. The borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder of the present invention contains ceramic flux crystals, exhibiting significant crystal precipitation and a low melting temperature, which is highly beneficial for reducing the ceramic calcination temperature. High-temperature resistant ceramic binders with high compressive shear strength can be obtained at 1500℃, achieving energy saving and consumption reduction while obtaining high-temperature resistant, high-strength ceramic binder materials.

[0066] 3. The boron-silicon-titanium hybrid resin-based high-temperature resistant ceramic binder of the present invention is simple to prepare, easy to mold, and can significantly reduce the sintering temperature of high-temperature resistant ceramics. Attached Figure Description

[0067] Figure 1 The 1H NMR spectra of the products triphenyl hydroxymethylborate (II-A) and diphenyl hydroxymethylborate (II-B) in Example 2 ( 1 H NMR);

[0068] Figure 2 The 1H NMR spectrum of the silicon-boron hybrid phenolic resin (triphenyl ester) (III-A-Si) product in Example 3 ( 1 H NMR);

[0069] Figure 3 The 1H NMR spectrum of the titanium-boron hybrid phenolic resin (triphenyl ester) (III-A-Ti) product in Example 3 ( 1 H NMR);

[0070] Figure 4 Thermogravimetric spectra of boron-hybridized phenolic resin (triphenyl ester) (II-A), silicon-boron-hybridized phenolic resin (triphenyl ester) (III-A-Si), and titanium-boron-hybridized phenolic resin (triphenyl ester) (III-A-Ti) in Example 3;

[0071] Figure 5 Thermogravimetric spectra of boron-hybridized phenolic resin (diphenyl ester) (II-B), silicon-boron-hybridized phenolic resin (diphenyl ester) (III-B-Si), and titanium-boron-hybridized phenolic resin (diphenyl ester) (III-B-Ti) in Example 3;

[0072] Figure 6 Example 4 included boron-hybridized phenolic resin / methyl MQ silicone resin composites (1-1#), silicon-boron hybridized phenolic resin / methyl MQ silicone resin composites (1-2#), and titanium-boron hybridized phenolic resin / methyl MQ silicone resin composites (1-3#). Thermogravimetric analyses of these composites were also tested.

[0073] Figure 7 Thermogravimetric spectra of boron hybrid phenolic resin / MQ silicone resin / metal oxide composite (2-1#), silicon boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-2#), and titanium boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-3#) in Example 5;

[0074] Figure 8 A schematic diagram of heating program 1 in Example 5.

[0075] Figure 9 A schematic diagram of heating program 2 in Example 5.

[0076] Figure 10 A schematic diagram of heating program 3 in Example 5.

[0077] Figure 11 XRD patterns of the following samples treated at 600℃ in Example 5: boron hybrid phenolic resin / MQ silicone resin / metal oxide composite (2-1#), silicon boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-2#), and titanium boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-3#).

[0078] Figure 12XRD patterns of the following samples treated at 1020℃ in Example 5: boron hybrid phenolic resin / MQ silicone resin / metal oxide composite (2-1#), silicon boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-2#), and titanium boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-3#).

[0079] Figure 13 XRD patterns of the following samples treated at 1220℃ in Example 5: boron hybrid phenolic resin / MQ silicone resin / metal oxide composite (2-1#), silicon boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-2#), and titanium boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-3#).

[0080] Figure 14 TGA / DSC curves of high-temperature resistant ceramic binder samples 1#, 2#, and 3# in Example 6;

[0081] Figure 15 XRD pattern of the high-temperature resistant ceramic binder #3 sintered at 1500℃ in Example 6;

[0082] Figure 16 XRD pattern of the high-temperature resistant ceramic binder 9# sintered at 1500℃ in Example 7. Detailed Implementation

[0083] This invention uses boron-silicon-titanium hybrid phenolic resin / silicone resin as the polymer base, dissolved in an organic solvent, and mixed uniformly with alkaline earth metal oxides such as calcium, magnesium, and aluminum in the presence of an organosilicon or organotitanium interface surface treatment agent to obtain a paste-like resin-based metal oxide composite. This composite is easily bonded or molded at inorganic material or metal interfaces. Under medium-low temperature conditions, the resin polymer undergoes a cross-linking and curing reaction, resulting in early strength of the composite binder and improving the yield of molded bonded products. Further, when sintered at 1500℃ under normal pressure, a high-temperature resistant ceramic binder with zirconium diboride and zirconium oxide as the main crystalline phases, or zirconium silicate and zirconium oxide as the main crystalline phases, can be prepared for bonding high-purity alumina ceramic samples, exhibiting high bonding strength and excellent thermal shock resistance. The boron-silicon-titanium hybrid resin-based high-temperature resistant ceramic binder of this invention contains ceramic flux crystals, exhibiting significant crystal precipitation and a low melting temperature, which is highly beneficial for reducing the ceramic calcination temperature. A ceramic bond with high compressive shear strength was obtained at 1500℃, achieving energy saving and consumption reduction while obtaining a high-temperature resistant and high-strength ceramic bond material.

[0084] The ceramic flux crystallizer of this invention exhibits significant crystal precipitation, which is more conducive to inducing the ceramic phase during subsequent ceramic sintering and displays typical properties of crystalline ceramic compounds. This indicates that a crystalline phase is generated from the glass melt phase under high-temperature calcination, forming a crystallizable flux. Because this flux crystallizer has a low melting temperature, it is beneficial for reducing the ceramic calcination temperature. Furthermore, the preparation method of this invention is simple and easy to process and shape. For flux ceramic glazes or high-temperature resistant ceramic sintering, it can reduce the sintering temperature and save energy.

[0085] This invention is based on the good plasticity and processability of polymer matrix, which can provide toughness and impact resistance of materials. It develops a simpler and more efficient borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder, which is convenient to mold as an additive.

[0086] The boron-silicon-titanium hybrid resin-based high-temperature resistant ceramic binder of the present invention comprises high-temperature resistant ceramic powder and ceramic flux crystallizer;

[0087] The raw materials for the ceramic flux crystals include: a composite material composed of polymer-based raw materials and metal oxides;

[0088] The polymer-based raw material is a mixture of at least one of boron-hybridized phenolic resin, silicon-boron-hybridized phenolic resin, and titanium-boron-hybridized phenolic resin with organosilicon resin.

[0089] The high-temperature resistant ceramic powder involved in this invention includes silicon powder, silicon oxide, zirconium diboride, boron nitride, silicon nitride, etc., which are used as the main materials of high-temperature resistant ceramic binders. During the sintering process, the sintering temperature of these high-temperature ceramic powders is effectively reduced by the liquid glass phase formed by the metal oxides in the ceramic flux crystals at around 1200°C.

[0090] Therefore, in one or more preferred embodiments, the high-temperature resistant ceramic powder is one or a mixture of two or more of silicon powder, silicon oxide, zirconium diboride, boron nitride, and silicon nitride. When silicon nitride, boron nitride, and zirconium diboride are used as the main raw material formulation of the high-temperature resistant ceramic binder, the molar ratio between silicon nitride, boron nitride, and zirconium diboride is from 1.0:3.5:2.0 to 1.0:3.5:4.0, and a high-temperature resistant ceramic binder with zirconium silicate and zirconium oxide as the main crystalline phases can be obtained by sintering at atmospheric pressure at 1500°C. When silicon powder, silicon oxide, and zirconium diboride are used as the main raw material formulation of the high-temperature resistant ceramic binder, the molar ratio between silicon powder, silicon oxide, and zirconium diboride is from 2.0:2.0:1.0 to 1.0:1.0:2.0, and a high-temperature resistant ceramic binder with zirconium diboride and zirconium oxide as the main crystalline phases can be obtained by sintering at atmospheric pressure at 1500°C.

[0091] In one or more preferred embodiments, the mass ratio of high-temperature resistant ceramic powder to ceramic flux crystallizer is (1.2-3.5):1, more preferably (1.5-3):1. The high-temperature resistant ceramic powder used is a fine powder with a particle size of 200 mesh or larger.

[0092] The raw materials of the ceramic flux crystallizer of the present invention include: a composite material composed of polymer-based raw materials and metal oxides;

[0093] The polymer-based raw material is a mixture of at least one of boron-hybridized phenolic resin, silicon-boron-hybridized phenolic resin, and titanium-boron-hybridized phenolic resin with organosilicon resin.

[0094] The boron-modified phenolic resin of this invention comprises hydroxymethylated diphenyl borate and hydroxymethylated triphenyl borate (Formula 1). These two boron-modified phenolic resin sources can be prepared using diphenyl borate (Formula 2), triphenyl borate (Formula 3), and formaldehyde as raw materials, through a hydroxymethylation reaction according to the reference (Mohamed O. Abdalla, Adriane Ludwick, Temisha Mitchell. Boron-modified phenolic resins for high performance applications[J]. Polymer, 2003, 44(24):7353-7359). The preferred molar ratios of diphenyl borate and triphenyl borate to formaldehyde are 1.0:4.0 to 1:4.5 and 1.0:6.0 to 1:7.0, respectively, and the reaction is preferably carried out at 50–120°C under ammonia catalysis for 2–6 hours. The diphenyl borate and triphenyl borate of this invention can be prepared using a solid-phase borate esterification method according to existing technologies.

[0095]

[0096]

[0097]

[0098] In one or more preferred embodiments, the boron-hybridized phenolic resin is diphenyl hydroxymethyl borate or / and triphenyl hydroxymethyl borate;

[0099] Preferably, the hydroxymethyl borate diphenyl ester has the following structure:

[0100]

[0101] Preferably, the hydroxymethylated triphenyl borate has the following structure:

[0102]

[0103] In one or more preferred embodiments, the boron-hybridized phenolic resin is prepared by reacting diphenyl borate or triphenyl borate with formaldehyde to obtain tetramethylolpropionate or hexamethylolpropionate.

[0104] Preferably, the molar ratio of diphenyl borate to formaldehyde is 1.0:4.0 to 1:4.5, and the molar ratio of triphenyl borate to formaldehyde is 1.0:6.0 to 1:7.0.

[0105] Preferably, the hydroxymethylation reaction is carried out using ammonia as a catalyst at a reaction temperature of 50–120°C.

[0106] The silicon-boron hybrid phenolic resin of this invention is obtained by further reacting boron hybrid phenolic resin (diphenyl hydroxymethyl borate, triphenyl hydroxymethyl borate) with dialkoxysilane R. 1 R 2 Si(OR 3 )2 undergoes chain extension reaction to prepare silicon boron hybrid phenolic resin (4); and boron hybrid phenolic resin (hydroxymethyl borate diphenyl ester, hydroxymethyl borate triphenyl ester) is further subjected to transesterification reaction with titanate to prepare titanium boron hybrid phenolic resin (5).

[0107]

[0108]

[0109] Boron-hybridized phenolic resin is further reacted with diekoxysilane R 1 R 2 Si(OR 3 In the chain extension reaction, the molar ratio of dialkoxysilane to boron-hybridized phenolic resin is preferably 2.0:1.0 to 2.2:1.0, and the chain extension reaction is preferably carried out at a temperature of 40-120°C. After solvent separation, silicon-boron hybridized phenolic resin is obtained. The dialkoxysilane preferably includes: dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylhydrodimethoxysilane, methylhydrodiethoxysilane, etc. When the boron-hybridized phenolic resin further undergoes an ester exchange reaction with a titanate, the molar ratio of titanate to boron-hybridized phenolic resin is preferably 4.0:1.0 to 4.2:1.0, and the ester exchange reaction is carried out at room temperature. After solvent separation, titanium-boron hybridized phenolic resin is obtained. The titanate preferably includes: ethyl titanate, isopropyl titanate, n-butyl titanate, polyn-butyl titanate, etc.

[0110] In one or more preferred embodiments, the silicon-boron hybrid phenolic resin is obtained by further reacting a boron hybrid phenolic resin with a diekoxysilane R. 1 R 2Si(OR 3 )2 is obtained by chain extension reaction;

[0111] Preferably, the molar ratio of dialkoxysilane to boron-hybridized phenolic resin is 2.0:1.0 to 2.2:1.0, and the chain extension reaction temperature is 40-120°C;

[0112] Preferably, the silicon-boron hybrid phenolic resin has the following structure:

[0113]

[0114] Preferably, the dialkoxysilane R 1 R 2 Si(OR 3 )2 is selected from at least one of dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylhydrodimethoxysilane, and methylhydrodiethoxysilane;

[0115] Where: R 1 R 2 R 3 Each alkyl or phenyl group is independently selected from C1-C6, more preferably methyl, ethyl, or phenyl.

[0116] In one or more preferred embodiments, the titanium-boron hybrid phenolic resin is obtained by further transesterification of boron hybrid phenolic resin with titanate ester.

[0117] Preferably, the molar ratio of titanate to boron-hybridized phenolic resin is 4.0:1.0 to 4.2:1.0; the transesterification reaction temperature is 20-30°C.

[0118] Preferably, the titanate is at least one selected from ethyl titanate, isopropyl titanate, n-butyl titanate, and poly(n-butyl titanate).

[0119] Preferably, the titanium-boron hybrid phenolic resin has the following structure:

[0120]

[0121]

[0122] The organosilicon resin described in this invention is an MQ silicone resin prepared using an alkoxysilane monomer / water glass process. MQ silicone resin is a type of polysiloxane, a mature commercially available product, and can also be prepared using existing technologies. MQ silicone resin is an organosilicon resin composed of monofunctional Si-O units (M units) and tetrafunctional Si-O units (SiQZ, abbreviated as Q units), exhibiting a tightly packed, bilayered spherical structure. In the MQ silicone resin used in this invention, the alkoxysilane monomer preferably includes: methyltrimethoxysilane or methyltriethoxysilane, as well as any one of phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, trimethoxysilane, and triethoxysilane. The M / Q ratio is preferably between 0.30 and 1.20. Depending on the type of alkoxysilane monomer, the MQ silicone resin can be methylMQ silicone resin, methylphenylMQ silicone resin, methylvinylMQ silicone resin, and methylhydroMQ silicone resin, etc.

[0123] The polymer-based raw material described in this invention is a composite of at least one of the aforementioned boron-hybridized phenolic resin, silicon-boron-hybridized phenolic resin, and titanium-boron-hybridized phenolic resin with MQ silicone resin, wherein the weight ratio of boron-hybridized phenolic resin, silicon-boron-hybridized phenolic resin, or titanium-boron-hybridized phenolic resin to MQ silicone resin is between 2:1 and 1:2.

[0124] In one or more preferred embodiments, the silicone resin is an MQ silicone resin, more preferably at least one of methyl MQ silicone resin, methyl phenyl MQ silicone resin, methyl vinyl MQ silicone resin, and methyl hydrogen MQ silicone resin; preferably, the M / Q ratio in the MQ silicone resin is between 0.30 and 1.20.

[0125] In one or more preferred embodiments, the weight ratio of boron-hybridized phenolic resin, silicon-boron-hybridized phenolic resin, or titanium-boron-hybridized phenolic resin to MQ silicone resin is between 2:1 and 1:2.

[0126] The metal oxides described in this invention include: calcium oxide, magnesium oxide, aluminum oxide, or aluminum hydroxide (calculated as aluminum oxide), silicon dioxide, and boric acid (calculated as a B2O3 source), etc. These metal oxides readily form a glassy phase or glass-ceramic under sintering conditions. This invention draws upon the theories and experiences of successful glass-ceramic preparations both domestically and internationally, introducing CaO, MgO, Al2O3, B2O3, and SiO2 as excellent high-temperature flux components, and using fine powders with a particle size of 200 mesh or larger for the metal oxides. When these oxides are combined in a certain molar ratio, for example: CaO:MgO:Al2O3:B2O3:SiO2=(0.50~0.8):(0.10~0.30):(0.63~0.85):(5.30~6.00):(0.200~0.500) (SiO2 and B2O3, the sintering products of the polymer base, are included in the composition), a molten and softened glass phase or glass ceramic can be formed in the range of calcination temperature of 250-1250℃, preferably 600-1250℃, and most preferably 1000-1250℃.

[0127] In one or more preferred embodiments, the metal oxide includes at least calcium oxide, magnesium oxide and aluminum oxide, or further includes at least one of silicon dioxide and boric acid (denoted as B2O3);

[0128] Preferably, the molar ratio of the oxides is: CaO:MgO:Al2O3:B2O3:SiO2=(0.50~0.8):

[0129] (0.10~0.30):(0.63~0.85):(5.30~6.00):(0.200~0.500), wherein SiO2 and B2O3 generated from polymer-based raw materials are included in the composition;

[0130] In one or more preferred embodiments, the total weight ratio of the polymer base to the weight ratio of metal oxides such as calcium, magnesium, and aluminum is 100:1 to 5:1, with a more preferred range of 100:5 to 10:1.

[0131] Preferably, the metal oxide is a fine powder with a particle size of 200 mesh or more.

[0132] The ceramic flux crystallizer described in this invention is mainly a composite material composed of polymer-based raw materials and metal oxides.

[0133] In one or more preferred embodiments, the weight ratio of the polymer-based raw material to the metal oxide in the composite material is 1:9 to 9:1, more preferably 2:8 to 4:6.

[0134] In the ceramic flux crystallizer raw material described in this invention, the metal oxide is preferably treated with an interface treatment agent. Organosilicon or organotitanium interface treatment agents can be used, including coupling agents such as methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane, or coupling agents such as isopropyl titanate, n-butyl titanate, and polyn-butyl titanate. This improves the dispersibility of the metal oxide during the polymer composite process, resulting in a more uniform and efficient sintering material.

[0135] In one or more preferred embodiments, the raw material of the ceramic flux crystal further includes a surface treatment agent of a metal oxide; more preferably, the surface treatment agent of the metal oxide is a silane coupling agent and / or a titanate coupling agent;

[0136] More preferably, the silane coupling agent is at least one of methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane, and the titanate coupling agent is at least one of ethyl titanate, isopropyl titanate, n-butyl titanate, and polyn-butyl titanate.

[0137] In one or more preferred embodiments, the amount of the surface treatment agent for the metal oxide is 1% to 8% of the mass of the metal oxide.

[0138] This invention also provides a method for preparing a borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder, comprising the following steps:

[0139] The polymer-based raw material is dissolved in a solvent, and then a metal oxide is added, or a surface treatment agent of the metal oxide is added, followed by high-temperature resistant ceramic powder. The mixture is then stirred evenly to obtain a borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder.

[0140] The solvent described in this invention is an organic solvent, which can be a mixture of methanol or ethanol with aromatic hydrocarbons such as toluene or xylene. The volume ratio of alcohol to aromatic solvent is between 2:1 and 1:2, and the amount used is 2 to 3 times the volume of the polymer-based raw material. It exhibits good solubility for silicon-boron hybrid phenolic resin or titanium-boron hybrid phenolic resin with MQ silicone resin. The paste-like resin-based composite formed with the metal oxide has excellent workability, and at temperatures above 150°C, the hydroxymethyl and silanol groups contained in the two resins will further undergo a condensation reaction to generate a thermosetting crosslinked resin.

[0141] In one or more preferred embodiments, the solvent is a mixture of alcohol and aromatic hydrocarbon;

[0142] Preferably, the alcohol is methanol or ethanol; the aromatic hydrocarbon is toluene or xylene.

[0143] Preferably, the volume ratio of alcohol to aromatic hydrocarbon is between 2:1 and 1:2, and the amount of mixed solvent is 2 to 3 times the volume of polymer-based raw material.

[0144] The ceramic flux crystallizer of this invention is a composite of polymer-based raw materials and alkaline earth metal oxides, which facilitates bonding or molding at inorganic material or metal interfaces. Under medium-low temperature conditions, the resin polymer undergoes a cross-linking and curing reaction, resulting in early strength of the composite binder and improving the yield of molded bonded products. Further sintering at the specified temperature yields a flux crystallizer containing quartz, cristobalite, γ-phase alumina, and calcium titanate crystals, exhibiting typical crystalline compound properties. Based on these properties, the boron-silicon-titanium hybrid resin-based high-temperature resistant ceramic binder of this invention will help reduce the sintering temperature of ceramics, achieving energy conservation and reduced consumption while obtaining high-temperature resistant, high-strength ceramic materials.

[0145] In the application of the silicon-titanium-boron hybrid resin-based high-temperature resistant ceramic binder of this invention, the resin curing and sintering processes involved are as follows: 1) The prepared high-temperature resistant ceramic binder is used for ceramic bonding under low-temperature conditions. After solvent removal and drying, it is first cured and cross-linked at 180°C to form initial bonding strength. This step can also be omitted from directly sintering the dried bonded ceramic sample; 2) After the bonded ceramic sample is cross-linked and cured, it is sintered in a high-temperature furnace at room temperature to 1500°C under normal pressure to achieve ceramic bonding. The simplest normal pressure sintering method is used in a tubular high-temperature furnace. During the sintering process, with the pyrolysis of the silicon-titanium-boron hybrid resin, there will be some chemical reactions between the polymer's decomposed components and the metal oxides. Therefore, the heating rate is generally set to be less than 5°C / min during the reaction sintering stage. The specific sintering conditions are as follows: room temperature to 250℃ @ 3.0 to 4.0℃ / min and hold for 10 to 30 min, 250 to 1500℃ @ 3.0℃ / min and hold for 30 to 120 min, and then the temperature is gradually reduced to below 100℃ to obtain the bonded ceramic sample.

[0146] The high-temperature resistant ceramic binder of this invention performs ceramic bonding under low-temperature conditions. After solvent removal and drying, it is first cured and cross-linked at 180°C to form initial bonding strength. Then, it is sintered in a high-temperature furnace at ambient temperature to 1500°C under normal pressure to achieve ceramic bonding. Because this high-temperature ceramic binder contains ceramic flux crystallizer, it can effectively reduce the ceramic calcination temperature and obtain higher bonding strength.

[0147] The present invention will be further described below with reference to specific embodiments and accompanying drawings, but is not limited thereto.

[0148] Example 1

[0149] This embodiment provides a method for preparing triphenyl borate and diphenyl borate, the specific steps of which are as follows:

[0150] In a reactor equipped with a stirrer, thermometer, and water separator, 1.000 kg of phenol and 2.190 kg of boric acid were added after nitrogen purging, along with a suitable amount of alkaline catalyst. Nitrogen gas was introduced, and the temperature was gradually raised to approximately 50°C until the solid phenol melted. The temperature was then rapidly increased to 150°C and reacted for 30 minutes, followed by a slow increase to 170°C. The water separator was connected to a -0.01 MPa vacuum dehydration system. The temperature was then increased by 10°C every hour until reaching 180°C, at which point the reaction was stopped after 2 hours. The material was then transferred out at approximately 120°C, yielding triphenyl borate with a yield of 93%.

[0151] In the preparation of diphenyl borate, 3.280 kg of boric acid was added, and the remaining materials and synthesis process were the same as above. The product obtained was triphenyl borate, with a yield of 95%.

[0152] Example 2

[0153] This embodiment provides a method for preparing boron-hybridized phenolic resins, namely diphenyl hydroxymethyl borate (II-B) and triphenyl hydroxymethyl borate (II-A), the specific steps of which are as follows:

[0154] In a reactor equipped with a stirrer, thermometer, and reflux + water separation device, 0.580 kg of triphenyl borate and 1.260 kg of 36% formaldehyde solution (or depolymerized paraformaldehyde), 100 mL of toluene, and an appropriate amount of ammonia water as a catalyst were added. The mixture was heated to 50°C with stirring until the reactants formed a homogeneous solution, then further heated to 70°C and reacted for 1 hour, followed by a further increase to 90°C and a reaction time of 2 hours, and finally at 120°C for 2 hours. The reactants were then rotary evaporated to obtain hydroxymethylated triphenyl borate with a yield of 95.5%.

[0155] In the preparation of hydroxymethylated diphenyl borate, 0.580 kg of triphenyl borate and 0.840 kg of 36% formaldehyde solution (or depolymerized paraformaldehyde) were added, and the remaining materials and synthesis process were the same as above. The product obtained was hydroxymethylated diphenyl borate, with a yield of 96.1%.

[0156] 1H NMR spectra of diphenyl hydroxymethylborate and triphenyl hydroxymethylborate products ( 1 H NMR) such as Figure 1 As shown.

[0157] Example 3

[0158] This embodiment provides a method for preparing silicon-boron hybrid phenolic resin, the specific steps of which are as follows:

[0159] In a reactor equipped with a stirrer, thermometer, and reflux + water separation device, 0.470 kg of boron-hybridized phenolic resin (triphenyl hydroxymethyl borate (II-A)) was dissolved in 200 mL of methanol / toluene (volume ratio 2:1). 0.060 kg of dimethyldimethoxysilane and an appropriate amount of tetramethylammonium hydroxide were added as catalysts. The mixture was heated to approximately 50 °C for 1 h under stirring, and then further heated to 80 °C for 4 h to separate some methanol. Afterward, rotary evaporation was performed, with the temperature and vacuum gradually increased. Under a vacuum of -0.094 MPa, the temperature was raised to 120 °C and held for 30 min before distillation was stopped, yielding silicon-boron hybridized phenolic resin (III-A-Si) with a yield of 97.2%.

[0160] This embodiment also provides a method for preparing titanium-boron hybrid phenolic resin, the specific steps of which are as follows:

[0161] In a reactor equipped with a stirrer, thermometer, and reflux + water separation device, 0.470 kg of boron-hybridized phenolic resin (triphenyl hydroxymethyl borate (II-A)) was dissolved in 200 mL of a methanol / toluene (volume ratio 2:1) mixed solvent. 0.085 kg of tetrabutyl titanate was added, and the reaction was stirred at room temperature and reacted exothermically at approximately 40 °C for 1 h. The temperature was then further increased to 80 °C for 2 h to separate some methanol. Afterward, rotary evaporation was performed, with the temperature and vacuum gradually increased. Under a vacuum of -0.094 MPa, the temperature was raised to 110 °C and held for 30 min before distillation was stopped to obtain titanium-boron hybridized phenolic resin (III-A-Ti) with a yield of 98.3%.

[0162] The 1H NMR spectrum of the silicon-boron hybrid phenolic resin (triphenyl ester) product in this embodiment ( 1 H NMR) such as Figure 2 As shown, the 1H NMR spectrum of the titanium boron hybrid phenolic resin (triphenyl ester) product is... 1 H NMR) such as Figure 3 As shown.

[0163] Thermogravimetric spectra of boron-hybridized phenolic resin (triphenyl ester) (II-A), silicon-boron-hybridized phenolic resin (triphenyl ester) (III-A-Si), and titanium-boron-hybridized phenolic resin (triphenyl ester) (III-A-Ti) were tested, as follows: Figure 4 As shown.

[0164] Thermogravimetric spectra of boron-hybridized phenolic resin (diphenyl ester) (II-B), silicon-boron-hybridized phenolic resin (diphenyl ester) (III-B-Si), and titanium-boron-hybridized phenolic resin (diphenyl ester) (III-B-Ti) were tested, as follows: Figure 5 As shown.

[0165] Depend on Figure 4 , Figure 5It can be seen that, compared with boron hybrid phenolic resins II-A and II-B, silicon boron hybrid phenolic resins III-A-Si and III-B-Si exhibit slower thermal degradation rates at 500–700 °C, while titanium boron hybrid phenolic resins III-A-Ti and III-B-Ti maintain essentially unchanged thermal degradation rates at 500–700 °C. Furthermore, the residual amounts of boron hybrid phenolic resins II-A and II-B at 800 °C are higher than those of the corresponding silicon boron hybrid phenolic resins III-A-Si, III-B-Si, and titanium boron hybrid phenolic resins III-A-Ti and III-B-Ti.

[0166] Example 4

[0167] This embodiment provides methods for preparing boron-hybridized phenolic resin, silicon-boron-hybridized phenolic resin, and titanium-boron-hybridized phenolic resin composites with MQ silicone resin, respectively. The specific steps are as follows:

[0168] Accurately weigh boron-hybridized phenolic resin (II-A), silicon-boron-hybridized phenolic resin (III-A-Si), and titanium-boron-hybridized phenolic resin (III-A-Ti), and mix them with methyl MQ silicone resin (M:Q = 0.8) according to the following weight ratio:

[0169] Boron-hybridized phenolic resin / methyl MQ silicone resin = 0.75 / 0.25, silicon-boron hybridized phenolic resin / methyl MQ silicone resin = 0.50 / 0.50, titanium-boron hybridized phenolic resin / methyl MQ silicone resin = 0.25 / 0.75, and the total amount of each polymer base material is 100.0g; each is dissolved and mixed evenly in 50mL of methanol / toluene mixed solvent, with the corresponding volume ratios of methanol / toluene mixed solvent for each polymer base material as follows: 4:1, 1:2, and 1:1.

[0170] The following composites were obtained: boron-hybridized phenolic resin / methyl MQ silicone resin composites (1-1#), silicon-boron hybridized phenolic resin / methyl MQ silicone resin composites (1-2#), and titanium-boron hybridized phenolic resin / methyl MQ silicone resin composites (1-3#). Thermogravimetric analyses of these composites were then performed. Figure 6 As shown.

[0171] Depend on Figure 6 It can be seen that by varying the formulation ratio of boron, silicon, and titanium hybrid phenolic resin to MQ silicone resin, the thermal degradation rate and pyrolysis residual weight of the composite resin sample can be effectively controlled. This is mainly due to the condensation reaction between the hydroxyl groups of the boron, silicon, and titanium hybrid phenolic resin and the MQ silicone resin.

[0172] Example 5

[0173] This embodiment provides a method for preparing ceramic flux crystallizers, the specific steps of which are as follows:

[0174] Accurately weigh 5.00 g of boron-hybridized phenolic resin (II-A), 5.00 g of methyl MQ silicone resin with M:Q = 0.8, and 5 mL of a mixed solvent of methanol / toluene at a volume ratio of 1:2. After dissolving the resin base, add 4.68 g of calcium oxide, 0.64 g of magnesium oxide, 14.68 g of aluminum oxide, and 1.50 g of methyltrimethoxysilane. Mix thoroughly and then grind evenly in an agate mortar to form a viscous resin paste for later use.

[0175] Accurately weigh 5.00 g of silicon boron hybrid phenolic resin (triphenyl ester) (III-A-Si), 5.00 g of methyl MQ silicone resin with M:Q = 0.8, and 5 mL of a mixed solvent of methanol / toluene at a volume ratio of 1:2. After dissolving the resin base, add 4.68 g of calcium oxide, 0.64 g of magnesium oxide, 14.68 g of aluminum oxide, and 1.50 g of methyltrimethoxysilane. Mix thoroughly and then grind evenly with an agate mortar to form a viscous resin paste for later use.

[0176] Accurately weigh 5.00 g of titanium boron hybrid phenolic resin (triphenyl ester) (III-A-Ti), 5.00 g of methyl MQ silicone resin with M:Q = 0.8, and 5 mL of a mixed solvent of methanol / toluene with a volume ratio of 1:2. After dissolving the resin base, add 4.68 g of calcium oxide, 0.64 g of magnesium oxide, 14.68 g of aluminum oxide, and 1.50 g of methyltrimethoxysilane. Mix thoroughly and grind evenly with an agate mortar to form a viscous resin paste for later use.

[0177] All of the above metal oxides are fine powders with a mesh size of 200 or higher.

[0178] Molding and drying: The above three resin polymer-based / metal oxide pastes are placed in a 20mm×10mm×10mm fluoroplastic strip mold, placed in a room temperature drying oven to evaporate and remove the solvent, and then transferred to a 50℃ oven for further evaporation and drying.

[0179] After drying, the following samples were obtained: boron-hybridized phenolic resin / MQ silicone resin / metal oxide composite (2-1#), silicon-boron hybridized phenolic resin (triphenyl ester) / methylMQ silicone resin / metal oxide composite (2-2#), and titanium-boron hybridized phenolic resin (triphenyl ester) / methylMQ silicone resin / metal oxide composite (2-3#). Thermogravimetric spectra of the above three samples were tested, as follows: Figure 7 As shown.

[0180] Depend on Figure 7 It can be seen that the thermal weight loss of composite materials 2-2# and 2-3# slows down significantly above 100℃, while the thermal weight loss rate of composite material 2-1# is relatively high between 100 and 600℃. It is speculated that the thermal stability of the reaction products between the polymer groups and metal oxides in composite materials 2-2# and 2-3# is significantly improved.

[0181] Sintering preparation: The three types of dried resin polymer-based / metal oxide samples were transferred to high-purity alumina ceramic boats and placed in a tube furnace. Sintering was carried out at 600℃, 1020℃, and 1220℃ using the following temperature program settings. After sintering, silicon / titanium / hybrid boron phenolic resin / MQ silicon resin-based ceramic flux crystallizer was obtained.

[0182] Temperature ramp-up program 1: Room temperature to 250℃ for 100 minutes and hold for 60 minutes, then 250℃ to 600℃ for 100 minutes and hold for 10 minutes, followed by a ramp-down program of 600℃ to 200℃ for 100 minutes, and then natural cooling to below 100℃. For example... Figure 8 As shown.

[0183] Temperature program 2: Room temperature to 250℃ for 100 minutes and hold for 60 minutes, then 250℃ to 1020℃ for 300 minutes and hold for 20 minutes, followed by a temperature decrease program of 1020℃ to 200℃ for 400 minutes, and then natural cooling to below 100℃. Figure 9 As shown.

[0184] Temperature program 3: Room temperature to 250℃ for 100 minutes and hold for 60 minutes, then 250℃ to 1220℃ for 400 minutes and hold for 20 minutes, followed by a temperature decrease program of 1220℃ to 200℃ for 500 minutes, and then natural cooling to below 100℃. Figure 10 As shown.

[0185] XRD patterns of samples treated at 600℃: boron-hybridized phenolic resin / MQ silicone resin / metal oxide composite (2-1#), silicon-boron hybridized phenolic resin (triphenyl ester) / methylMQ silicone resin / metal oxide composite (2-2#), and titanium-boron hybridized phenolic resin (triphenyl ester) / methylMQ silicone resin / metal oxide composite (2-3#). Figure 11 As shown. By Figure 11 It can be seen that when treated at 600℃, a small amount of quartz crystal phase appears in the pyrolysis products of composite materials 2-1#, 2-2#, and 2-3#.

[0186] XRD patterns of samples treated at 1020℃: boron-hybridized phenolic resin / MQ silicone resin / metal oxide composite (2-1#), silicon-boron hybridized phenolic resin (triphenyl ester) / methylMQ silicone resin / metal oxide composite (2-2#), and titanium-boron hybridized phenolic resin (triphenyl ester) / methylMQ silicone resin / metal oxide composite (2-3#). Figure 12 As shown. By Figure 12It can be seen that when treated at 1020℃, the pyrolysis products of composite materials 2-1# and 2-2# contain a small amount of quartz crystal phase, as well as a small amount of alumina and cristobalite crystal phase respectively; while 2-3# produces a large amount of quartz and cristobalite crystal phase and a small amount of calcium titanate crystal phase.

[0187] XRD patterns of samples treated at 1220℃: boron-hybridized phenolic resin / MQ silicone resin / metal oxide composite (2-1#), silicon-boron hybridized phenolic resin (triphenyl ester) / methylMQ silicone resin / metal oxide composite (2-2#), and titanium-boron hybridized phenolic resin (triphenyl ester) / methylMQ silicone resin / metal oxide composite (2-3#). Figure 13 As shown. By Figure 13 It can be seen that when treated at 1220℃, a large amount of quartz crystal phase material was generated in the pyrolysis products of composite materials 2-1#, 2-2# and 2-3#, and a small amount of cristobalite crystal phase material was also generated.

[0188] Example 6

[0189] This embodiment provides a specific preparation method for a silicon-titanium-boron hybrid resin-based high-temperature resistant ceramic binder, the specific steps of which are as follows:

[0190] Accurately weigh 5.00g of triphenyl hydroxymethylborate and 5.00g of methyl MQ silicone resin (M:Q = 0.65) and place them in an agate mortar. Add 0.50g of calcium oxide, 0.10g of magnesium oxide, 1.05g of aluminum oxide, 7.30g of silicon nitride, 4.80g of boron nitride, 12.00g of zirconium diboride, and 1.50g of methyltrimethoxysilane. Mix them in the agate mortar and grind them thoroughly until homogeneous. Transfer the mixture to a tubular container and add 10mL of a methanol / toluene mixture (volume ratio 1:2). Stir until a viscous resin paste (No. 1) is formed. Set aside for later use.

[0191] Accurately weigh 5.00g of silicon-hybrid boron phenolic resin (triphenyl ester) and 5.00g of methyl MQ silicone resin with M:Q = 0.8 into an agate mortar. Mix 0.50g of calcium oxide, 0.10g of magnesium oxide, 1.05g of aluminum oxide, 7.30g of silicon nitride, 4.80g of boron nitride, 12.00g of zirconium diboride, and 1.50g of methyltrimethoxysilane in the agate mortar and grind them thoroughly until homogeneous. Transfer the mixture to a tubular container and add 10mL of a methanol / toluene mixture with a volume ratio of 1:2. Stir until a viscous resin paste (No. 2) is formed. Set aside for later use.

[0192] Accurately weigh 5.00g of titanium-boron hybrid phenolic resin (triphenyl ester) and 5.00g of methyl MQ silicone resin (M:Q = 0.65) and place them in an agate mortar. Mix 0.50g of calcium oxide, 0.10g of magnesium oxide, 1.05g of aluminum oxide, 7.30g of silicon nitride, 4.80g of boron nitride, 12.00g of zirconium diboride, and 1.50g of isopropyl titanate in the agate mortar and grind them thoroughly until homogeneous. Transfer the mixture to a tubular container and add 10mL of a methanol / toluene mixture (volume ratio 1:2). Stir until a viscous resin paste (No. 3) is formed. Set aside for later use.

[0193] All of the above metal oxides are fine powders with a mesh size of 200 or higher, while silicon nitride, boron nitride, and zirconium diboride are fine powders with a mesh size of 300 or higher.

[0194] Drying: Approximately 1.0 g of each of the three resin-based high-temperature resistant ceramic binder pastes (1#, 2#, and 3#) was placed in a 20mm × 10mm × 10mm fluoroplastic strip mold. After evaporating and removing the solvent in a room-temperature drying oven, the samples were transferred to a 50℃ oven for further evaporation until dry. The TGA and DSC curves of the high-temperature resistant ceramic binder samples 1#, 2#, and 3# are shown below. Figure 14 .Depend on Figure 14 It can be seen that samples 1#, 2#, and 3# of the high-temperature resistant ceramic binder all experienced rapid degradation thermogravimetric loss (mainly polymer-based) and endothermic reaction near 250℃; near 700℃, the polymer thermal degradation was completed, showing a second thermal degradation plateau period, and the DSC curve showed an exothermic peak, which is presumably caused by the thermal melting reaction between the polymer-based thermal degradation products and the flux metal oxide; in the range of 800-1300℃, the thermogravimetric loss curves all showed a relatively stable plateau period, and their DSC curves all showed an endothermic peak near 1350℃, which is presumably caused by endothermic crystallization due to crystal transformation; at the end of sintering, accompanied by the crystal transformation process, samples 1# and 2# showed a thermogravimetric loss of ~6%, while sample 3# basically no longer experienced thermogravimetric loss.

[0195] Crosslinking curing, high-temperature sintering bonding, and preparation of high-temperature sintered materials for bonded ceramic specimens (for XRD analysis):

[0196] 1) The aforementioned high-temperature resistant ceramic adhesive viscous paste 1# to 3# was used to bond high-purity alumina ceramic test blocks (test block size: 20mm×10mm×10mm, each cleaned with acetone and dried before bonding). Each high-temperature resistant ceramic adhesive bonded 6 sets of test blocks. After evaporating and removing the solvent in a room temperature drying oven, they were transferred to a 50℃ oven for further evaporation and drying.

[0197] 2) Take three sets of each of the above-mentioned dried high-temperature resistant ceramic adhesive bonding test blocks, put them in an oven and heat them to 180°C for 60 minutes for curing reaction. After taking them out and letting them stand at room temperature for 24 hours, measure the compressive shear strength (GB / T 31541-2015 Test method for tensile and shear bond strength of fine ceramic interfaces).

[0198] 3) Take about 0.80g each of the dried high-temperature resistant ceramic binders 1#, 2# and 3#, transfer them to a high-purity alumina ceramic boat, place them in a tube furnace, and sinter them at atmospheric pressure at 600℃, 1000℃, 1200℃ and 1500℃ respectively using programmed temperature control. The high-temperature resistant ceramic binder material obtained after sintering is used for XRD testing.

[0199] 4) Take three sets of each of the dried high-temperature resistant ceramic binder test blocks and transfer them in batches to high-purity alumina ceramic boats. Place them in a tube furnace and sinter them at 1500℃ under normal pressure using programmed temperature control. After sintering, the high-temperature resistant ceramic binder test blocks are obtained. After being placed at room temperature for 24 hours, the compressive shear strength is measured (test standard is the same as above).

[0200] After curing at 180℃ for 60 minutes, the compressive shear strengths of the high-temperature resistant ceramic adhesive test blocks No. 1, No. 2, and No. 3 were 1.03 MPa, 1.56 MPa, and 1.44 MPa, respectively. This indicates that the resin-based material in the high-temperature resistant ceramic adhesive test blocks No. 1, No. 2, and No. 3 has a certain strength after cross-linking and curing, which can prevent deformation or damage during the transfer process.

[0201] The sintered binder material of the above-mentioned high-temperature resistant ceramic binder #3, which was sintered at atmospheric pressure, is shown in the XRD patterns of the sintered material at different temperatures. Figure 15 .Depend on Figure 15 It can be seen that the crystals at 600℃ are mainly the raw materials zirconium diboride and boron nitride; the crystals at 1000℃ retain a small amount of boron nitride, while zirconium diboride is transformed into zirconium oxide crystals; at 1000℃, in addition to retaining some zirconium oxide crystals, it further reacts with silicon oxide to transform into crystals mainly composed of zirconium silicate; and at 1500℃, a ceramic material mainly composed of zirconium silicate is obtained.

[0202] The compressive shear strength of the high-temperature resistant ceramic binder test blocks No. 1, No. 2, and No. 3 after sintering at 1500℃ for 60 min is shown in Table 1.

[0203] Table 1

[0204] Project / Number 1# 2# 3# Compressive shear strength / MPa 8.21 14.32 15.60 Compression shear deformation / % 0.38 0.65 0.71 Compressive shear modulus / GPa 2.16 2.20 2.19

[0205] As shown in Table 1, using a mixture of resin-based materials and calcium oxide, magnesium oxide, and alumina as flux, and employing silicon nitride, boron nitride, and zirconium diboride high-temperature resistant ceramic binders for high-temperature bonding and sintering of high-purity alumina ceramic specimens, it is possible to obtain bonded ceramic specimens with a compressive shear strength as high as 15.60 MPa and a compressive shear modulus above 2.16 GPa. Among these, the titanium hybrid boron phenolic resin / methyl MQ silicone resin polymer-based binder is superior to the silicon hybrid boron phenolic resin / methyl MQ silicone resin polymer-based binder.

[0206] Example 7

[0207] This embodiment provides a specific preparation method for a silicon-titanium-boron hybrid resin-based high-temperature resistant ceramic binder, the specific steps of which are as follows:

[0208] Accurately weigh 5.00g of triphenyl hydroxymethyl borate and 5.00g of methyl MQ silicone resin (M:Q = 0.80) and place them in an agate mortar (the resin base composition is abbreviated as A). Add 0.22g of calcium oxide, 0.10g of magnesium oxide, 0.44g of aluminum oxide, 4.34g of silica powder, 8.70g of silicon oxide, 6.65g of zirconium diboride, and 1.50g of methyltrimethoxysilane. Mix them in the agate mortar and grind them thoroughly until homogeneous. Transfer the mixture to a tubular container and add 10mL of a methanol / toluene mixture with a volume ratio of 1:2. Stir until a viscous resin paste (4#) is formed. Separately prepare a high-temperature resistant ceramic binder resin paste (5#) (the formula is the same as 4#, but without the fluxing components calcium oxide, magnesium oxide, and aluminum oxide) for later use.

[0209] Accurately weigh 5.00g of silicon-hybrid boron phenolic resin (triphenyl ester), 5.00g of methyl MQ silicone resin with M:Q = 0.8 and place them in an agate mortar (the resin base composition is abbreviated as B). Mix 0.22g of calcium oxide, 0.10g of magnesium oxide, 0.44g of aluminum oxide, 4.34g of silica powder, 8.70g of silicon oxide, 6.65g of zirconium diboride, and 1.50g of methyltrimethoxysilane in the agate mortar and grind them thoroughly until uniform. Transfer the mixture to a tubular container and add 10mL of a methanol / toluene mixture with a volume ratio of 1:2. Stir until a viscous resin paste (6#) is formed. Separately prepare a high-temperature resistant ceramic binder resin paste (7#) (the formula is the same as 6#, but without the fluxing components calcium oxide, magnesium oxide, and aluminum oxide) for later use.

[0210] Accurately weigh 5.00g of titanium-hybrid boron phenolic resin (triphenyl ester), 5.00g of methyl MQ silicone resin with M:Q = 0.8 and place them in an agate mortar (the resin base composition is abbreviated as C). Mix 0.22g of calcium oxide, 0.10g of magnesium oxide, 0.44g of aluminum oxide, 4.34g of silica powder, 8.70g of silicon oxide, 6.65g of zirconium diboride, and 1.50g of methyltrimethoxysilane in the agate mortar and grind them thoroughly until uniform. Transfer the mixture to a tubular container and add 10mL of a methanol / toluene mixture with a volume ratio of 1:2. Stir until a viscous resin paste (No. 8) is formed. Separately prepare a high-temperature resistant ceramic binder resin paste (No. 9) (the formula is the same as No. 8, but without the fluxing components calcium oxide, magnesium oxide, and aluminum oxide) for later use.

[0211] Silicon powder, silicon oxide, and zirconium diboride are all fine powders with a mesh size of 300 or higher.

[0212] Drying: Take about 1.0g of each of the above three resin-based high-temperature resistant ceramic binder pastes 4# to 9#, place them in a 20mm×10mm×10mm fluoroplastic strip mold, put them in a room temperature drying oven to evaporate and remove the solvent, then transfer them to a 50℃ oven for further evaporation and drying, and set aside for later use.

[0213] High-temperature sintering bonding of bonded ceramic specimens and preparation of high-temperature sintered materials (for XRD analysis):

[0214] 1) Take about 0.50g each of the dried high-temperature resistant ceramic binders 4# to 9# and transfer them to a high-purity alumina ceramic boat. Place the boat in a tube furnace and sinter at atmospheric pressure at 600℃, 1000℃, 1200℃, 1400℃ and 1500℃ respectively using programmed temperature control. The high-temperature resistant ceramic binder material obtained after sintering is used for XRD testing.

[0215] 2) The aforementioned high-temperature resistant ceramic adhesive viscous paste 4# to 9# was used to bond high-purity alumina ceramic test blocks (test block size: 20mm×10mm×10mm, each block was cleaned with acetone and dried before bonding). Three sets of test blocks were bonded to each high-temperature resistant ceramic adhesive. After the solvent was evaporated in a room temperature drying oven, the blocks were transferred to a 50℃ oven for further evaporation and drying.

[0216] 3) Each of the dried high-temperature resistant ceramic binder test blocks was transferred in batches to high-purity alumina ceramic boats and placed in a tube furnace. The boats were then sintered at 1500℃ under normal pressure using a programmed temperature control. After sintering, the high-temperature resistant ceramic binder test blocks were obtained. After being removed and left at room temperature for 24 hours, their compressive shear strength was measured (GB / T31541-2015 Test Method for Tensile and Shear Bond Strength of Fine Ceramics Interfaces).

[0217] The sintered binder material of the above-mentioned high-temperature resistant ceramic binder No. 9, which was sintered at atmospheric pressure, is shown in the XRD patterns of the sintered material at different temperatures. Figure 16 .Depend on Figure 16 It can be seen that the crystals at 600℃ are mainly quartz transformed from the raw material metallic silicon and silicon dioxide; at 1000℃, in addition to retaining a small amount of quartz, the crystals show the transformation of zirconium diboride into zirconium oxide; at 1200℃, the composition of zirconium oxide crystals increases and zirconium diboride crystals begin to appear; at 1400℃, the composition of zirconium oxide crystals decreases slightly, while more zirconium diboride crystals are produced; and at 1500℃, a ceramic material is obtained with zirconium diboride crystals as the main component, supplemented by some zirconium oxide and zirconium silicate crystals.

[0218] The compressive shear strength of the high-temperature resistant ceramic binder test blocks No. 4 to No. 9 after sintering at 1500℃ for 60 min is shown in Table 2.

[0219] Table 2

[0220]

[0221] Table 2 shows that, using different resin bases, the high-temperature bonded sintered samples of high-purity alumina ceramic blocks with silicon powder, silicon oxide, and zirconium diboride as fluxes exhibit higher compressive shear strength, compressive shear modulus, and compressive shear deformation than those without metal oxide as fluxes. Among these, the silicon-hybrid boron phenolic resin / methyl MQ silicone resin polymer-based binder is superior to the titanium-hybrid boron phenolic resin / methyl MQ silicone resin polymer-based binder.

Claims

1. A boron-silicon-titanium hybrid resin-based high-temperature resistant ceramic binder, characterized in that, The binder comprises high-temperature resistant ceramic powder and ceramic flux crystallizer; The raw materials for the ceramic flux crystallizer include: a composite material composed of polymer-based raw materials and metal oxides; The polymer-based raw material is a mixture of at least one of boron-hybridized phenolic resin, silicon-boron-hybridized phenolic resin, and titanium-boron-hybridized phenolic resin with organosilicon resin; The boron-hybridized phenolic resin mentioned in the ceramic flux crystallizer is diphenyl hydroxymethyl borate or / and triphenyl hydroxymethyl borate; The silicon-boron hybrid phenolic resin mentioned in the ceramic flux crystallizer is obtained by further reacting boron hybrid phenolic resin with diekoxysilane R. 1 R 2 Si(OR 3 )2 undergoes a chain extension reaction to obtain R 1 R 2 R 3 Alkyl or phenyl groups, each independently selected from C1-C6; The titanium-boron hybrid phenolic resin mentioned in the ceramic flux crystallizer is obtained by further transesterification reaction of boron hybrid phenolic resin with titanate ester. The organosilicon resin mentioned in the ceramic flux crystallizer is MQ silicone resin; The metal oxides in the ceramic flux crystallizer include calcium oxide, magnesium oxide, and aluminum oxide.

2. The borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder according to claim 1, characterized in that, The high-temperature resistant ceramic powder is one or a mixture of two or more of silicon powder, silicon oxide, zirconium diboride, boron nitride, and silicon nitride.

3. The borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder according to claim 2, characterized in that, When the high-temperature resistant ceramic powder is a mixture of silicon nitride, boron nitride, and zirconium diboride, the molar ratio between silicon nitride, boron nitride, and zirconium diboride is 1.0 : 3.5 : (2.0~4.0); when the high-temperature resistant ceramic powder is a mixture of silicon powder, silicon oxide, and zirconium diboride, the molar ratio between silicon powder, silicon oxide, and zirconium diboride is (2.0~1.0) : (2.0~1.0) : (1.0~2.0).

4. The borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder according to claim 1, characterized in that, The mass ratio of high-temperature resistant ceramic powder to ceramic flux crystallizer is (1.2-3.5):

1.

5. The borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder according to claim 1, characterized in that, The molar ratio of diekoxysilane to boron-hybridized phenolic resin is 2.0:1.0 to 2.2:1.0, and the chain extension reaction temperature is 40-120℃.

6. The borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder according to claim 1, characterized in that, The hydroxymethyl borate diphenyl ester has the following structure: ； The hydroxymethylated triphenyl borate has the following structure: ； The silicon-boron hybrid phenolic resin has the following structure: or ; or or .

7. The borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder according to claim 1, characterized in that, The dialkoxysilane R 1 R 2 Si(OR 3 )2 is selected from at least one of dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylhydrodimethoxysilane, and methylhydrodiethoxysilane; R 1 R 2 R 3 Each is independently selected from methyl, ethyl, and phenyl.

8. The borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder according to claim 1, characterized in that, The molar ratio of titanate to boron-hybridized phenolic resin is 4.0:1.0 to 4.2:1.0; the transesterification reaction temperature is 20-30℃.

9. The borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder according to claim 1, characterized in that, The titanate is at least one of ethyl titanate, isopropyl titanate, n-butyl titanate, and poly(n-butyl titanate); The titanium-boron hybrid phenolic resin has the following structure: or ; or or .

10. The borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder according to claim 1, characterized in that, The MQ silicone resin is at least one of methyl MQ silicone resin, methyl phenyl MQ silicone resin, methyl vinyl MQ silicone resin, and methyl hydrogen MQ silicone resin, and the M / Q ratio in the MQ silicone resin is between 0.30 and 1.

20.

11. The borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder according to claim 1, characterized in that, The weight ratio of boron-hybridized phenolic resin, silicon-boron-hybridized phenolic resin, or titanium-boron-hybridized phenolic resin to MQ silicone resin in the ceramic flux crystallizer is between 2:1 and 1:

2.

12. The borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder according to claim 1, characterized in that, The metal oxide in the ceramic flux crystallizer further includes at least one of silicon dioxide and boric acid (calculated as B2O3).

13. The borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder according to claim 1, characterized in that, In the composite material of ceramic flux crystallizer composed of polymer-based raw materials and metal oxides, the weight ratio of polymer-based raw materials to metal oxides is 1:9 to 9:

1.

14. A method for preparing the borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder according to any one of claims 1-13, comprising the following steps: The polymer-based raw material is dissolved in a solvent, and then a metal oxide is added, or a surface treatment agent of the metal oxide is added, followed by high-temperature resistant ceramic powder. The mixture is then stirred evenly to obtain a borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder.

15. The application of the borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder according to any one of claims 1-4, as a ceramic binder in the preparation of ceramic glazes and high-temperature resistant ceramics, wherein the high-temperature resistant ceramic is at least one of zirconium silicate ceramics, zirconium boride ceramics, and zirconium oxide ceramics.

16. The application of the borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder according to claim 15, characterized in that, The application method of borosilicate-titanium hybrid resin-based high-temperature resistant ceramic binder is as follows: (1) The borosilicate-titanium hybrid resin-based high-temperature resistant ceramic adhesive is used for ceramic bonding at room temperature. After solvent removal and drying, it is cured and crosslinked to form the initial bonding strength; or after solvent removal and drying, it is not cured and crosslinked. (2) The material processed in step (1) is sintered at room temperature to 1500℃ under normal pressure to achieve ceramic bonding.

Images