Environment-friendly wear-resistant ceramic and preparation method thereof

Abstract

The application discloses an environment-friendly wear-resistant ceramic and a preparation method thereof, and belongs to the technical field of ceramics.The environment-friendly wear-resistant ceramic comprises the following raw materials in parts by weight: 60-70 parts of aluminum oxide, 10-15 parts of boron nitride, 3-8 parts of a binder, 3-8 parts of a composite fluxing agent, 5-10 parts of a toughening agent, and 40-50 parts of deionized water.The environment-friendly wear-resistant ceramic prepared by the method has excellent wear resistance, bending strength and impact strength.

Description

Technical Field

[0001] This invention relates to the field of ceramic technology, specifically to an environmentally friendly wear-resistant ceramic and its preparation method. Background Technology

[0002] Ceramic materials are widely used in many fields due to their high hardness, excellent wear resistance, and chemical stability. However, the inherent brittleness and low fracture toughness of traditional ceramic materials, especially conventional ceramics made primarily from natural minerals, are the main factors limiting their application under impact and high-load conditions. In terms of mechanical strength, inherent defects such as pores and microcracks in the internal microstructure of ceramics easily become stress concentration points under instantaneous external loads, inducing cracks and causing their unstable propagation, thus leading to sudden brittle fracture of the material and reducing its impact and flexural strength.

[0003] Chinese invention patent CN118290120A discloses an environmentally friendly wear-resistant ceramic and its preparation method. The preparation method of the environmentally friendly ceramic is as follows: barium chloride and calcium chloride are dissolved in a solvent to obtain a mixed solution; kaolin and silicon dioxide are added to the mixed solution and stirred; aluminum silicate, barium titanate, zirconium oxide, alumina, silicon carbide, silicon nitride, and calcium carbonate are added to the mixed solution and mixed to obtain a mixed slurry; the mixed slurry is formed into a green body; the green body is placed in a sintering furnace and heated from room temperature to 180-260℃ and treated in a vacuum for 1.5-3 hours, then heated to a second temperature of 820-950℃ and treated in a vacuum for 3-8 hours; then the sintering furnace is heated to a third temperature of 1150-1320℃ and treated for 5-12 hours; finally, the sintering furnace is heated to a fourth temperature of 1450-1620℃ and treated for 0.5-3 hours. The prepared ceramic has high mechanical strength and good wear resistance, but its flexural strength and impact resistance need to be improved. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the purpose of this invention is to provide an environmentally friendly wear-resistant ceramic and its preparation method.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] An environmentally friendly, wear-resistant ceramic comprises the following raw materials in parts by weight:

[0007] Alumina 60-70 parts, boron nitride 10-15 parts, binder 3-8 parts, composite flux 3-8 parts, toughening agent 5-10 parts, deionized water 40-50 parts;

[0008] The adhesive is prepared by the following method:

[0009] S1: Glycylcysteine ​​reacts with 6-hydroxyhexanoic acid to form a diamide compound.

[0010] S2: The diamide compound reacts with triallyl isocyanurate to form a three-armed compound.

[0011] S3: The three-armed compound reacts with tert-butyl acetoacetate to generate an oxoester-modified three-armed compound.

[0012] S4: Oxyester-modified three-armed compounds react with amino-modified oligosiloxanes to form adhesives.

[0013] In step S1, the molar ratio of glycyl-cysteine ​​to 6-hydroxyhexanoic acid is 1:(1.05-1.1).

[0014] In step S2, the molar ratio of the diamide compound to triallyl isocyanurate is (3.1-3.2):1.

[0015] In step S3, the molar ratio of the three-arm compound to tert-butyl acetoacetate is 1:(3.05-3.2).

[0016] In step S4, the mass ratio of the oxyester-modified three-arm compound to the amino-modified oligosiloxane is 1:(2-3).

[0017] In step S4, the amino-modified oligosiloxane is prepared by reacting methyltrimethoxysilane with γ-aminopropyltriethoxysilane.

[0018] The molar ratio of methyltrimethoxysilane to γ-aminopropyltriethoxysilane is 1:1.

[0019] The composite flux is a mixture of spodumene and waste glass powder; the mixing weight ratio of spodumene to waste glass powder is 1:(1.5-2.5).

[0020] The toughening agent is zirconium oxide.

[0021] A method for preparing an environmentally friendly wear-resistant ceramic includes the following steps:

[0022] (1) Weigh out the following by weight: 60-70 parts alumina, 10-15 parts boron nitride, 3-8 parts binder, 3-8 parts composite flux, 5-10 parts toughening agent, and 40-50 parts deionized water;

[0023] (2) Place alumina, boron nitride, binder, composite flux and toughening agent into a ball mill, add deionized water, and ball mill to obtain a uniform slurry;

[0024] (3) Spray granulation of the slurry to obtain granular powder; after aging the powder in a closed environment for 24-48 hours, place it in a mold and press it to form a green body; place the green body in a sintering furnace, raise the temperature from room temperature to 450-500℃ and hold it for 30-40 minutes; then raise the temperature to 1200℃-1400℃ and hold it for 30-60 minutes; cool it naturally to room temperature to obtain environmentally friendly wear-resistant ceramics.

[0025] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include:

[0026] The environmentally friendly wear-resistant ceramic prepared by this invention has excellent wear resistance, flexural strength and impact strength. Detailed Implementation

[0027] The following description, in conjunction with specific embodiments, provides further details, but the present invention is not limited to these embodiments.

[0028] Example 1: Preparation of adhesive:

[0029] S1: Under nitrogen protection, 100 mL of dichloromethane, 0.105 mol of 6-hydroxyhexanoic acid, and 0.11 mol of 1-hydroxybenzotriazole were added to the reactor. The mixture was stirred at room temperature for 15 min. Then, 0.11 mol of dicyclohexylcarbodiimide was added under ice bath conditions, and the mixture was stirred for 15 min. Next, 0.1 mol of glycyl-cysteine ​​and 0.11 mol of triethylamine were added, and the mixture was reacted under ice bath conditions for 0.5 h. The mixture was then brought to room temperature and reacted for 10 h. After filtration, the filtrate was washed successively with 10 wt% citric acid solution (50 mL × 2), saturated sodium carbonate solution (50 mL × 2), and saturated sodium chloride solution (50 mL). The mixture was allowed to stand and separate into layers. The organic phase was dried with 20 g of anhydrous sodium sulfate for 2 h, filtered, distilled under reduced pressure at 30 °C for 2 h, and dried under vacuum at 40 °C for 12 h to obtain the diamide compound. The reaction equation is shown below:

[0030]

[0031] Its 1H NMR data are as follows: 1 H NMR (400 MHz, Acetone- d6) δ 7.38 (t, J = 6.0 Hz, 1H), 7.04 (t, J = 3.6 Hz, 1H), 3.83 (s, 2H), 3.54 (q, J = 5.8 Hz, 2H), 3.31 (td, J = 5.1, 3.6 Hz, 2H), 3.13 (t, J = 5.9 Hz, 1H), 2.66 (dt, J = 6.8, 5.1Hz, 2H), 2.22 (t, J = 8.4 Hz, 2H), 1.73 (t, J = 6.8 Hz, 1H), 1.63 – 1.36 (m,6H).

[0032] S2: Under nitrogen protection, add 500 mL of tetrahydrofuran, 0.1 mol of triallyl isocyanurate, 0.31 mol of diamide compound, and 0.6 g of photoinitiator 184 to the reactor, stir and mix thoroughly, and at room temperature, with an intensity of 8.4 mW / cm². 2 After irradiation under a 365nm UV LED lamp for 8 hours, the mixture was distilled under reduced pressure at 40℃ for 2 hours. The solution was then slowly added to 800mL of cold diethyl ether, stirred, and a precipitate formed. The precipitate was filtered, washed three times with 100mL of cold diethyl ether each time, and dried under vacuum at 40℃ for 12 hours to obtain the three-armed compound. The reaction equation is shown below:

[0033]

[0034] Its 1H NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.44 – 6.91 (m,6H), 3.97 – 3.78 (m, 12H), 3.54 (q, J = 5.8 Hz, 6H), 3.37 (q, J = 4.1 Hz,6H), 2.77 – 2.59 (m, 15H), 2.22 (t, J = 8.4 Hz, 6H), 1.82 (p, J = 6.8 Hz, 6H), 1.65 – 1.34 (m, 18H).

[0035] S3: Under nitrogen protection, 800 mL of xylene, 0.1 mol of the three-arm compound, 0.305 mol of tert-butyl acetoacetate, and 0.01 mol of dibutyltin oxide were added to the reactor. The mixture was stirred and stirred until homogeneous. After reflux for 6 h (tert-butanol was removed using a water separator during the reaction), the mixture was cooled to room temperature, washed three times with saturated brine (200 mL each time), dried with 20 g of anhydrous magnesium sulfate for 30 min, filtered, and the filtrate was distilled under reduced pressure at 80 °C for 3 h and dried under vacuum at 70 °C for 12 h to obtain the oxoester-modified three-arm compound. The reaction equation is shown below:

[0036]

[0037] Its 1H NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.37 – 6.97 (m,6H), 4.14 (t, J = 6.2 Hz, 6H), 3.94 – 3.80 (m, 12H), 3.51 (s, 6H), 3.37 (q, J= 4.2 Hz, 6H), 2.73 – 2.61 (m, 12H), 2.27 – 2.17 (m, 15H), 1.88 – 1.40 (m, 24H).

[0038] S4: Add 10g of oxyester-modified three-arm compound and 20g of amino-modified oligomeric siloxane to the reactor, stir and mix well, and melt-stir at 120℃ for 20min; then cure under vacuum at 100℃ for 12h to obtain the adhesive; the reaction equation is shown below:

[0039]

[0040] Example 2: Preparation of adhesive:

[0041] S1: Under nitrogen protection, 100 mL of dichloromethane, 0.108 mol of 6-hydroxyhexanoic acid, and 0.11 mol of 1-hydroxybenzotriazole were added to the reactor. The mixture was stirred at room temperature for 15 min. 0.11 mol of dicyclohexylcarbodiimide was added under ice bath conditions. The mixture was stirred for 15 min. 0.1 mol of glycyl-cysteine ​​and 0.11 mol of triethylamine were added. The mixture was reacted under ice bath conditions for 0.5 h. The mixture was then brought to room temperature and reacted for 9 h. The mixture was filtered. The filtrate was washed successively with 10 wt% citric acid solution (50 mL × 2), saturated sodium carbonate solution (50 mL × 2), and saturated sodium chloride solution (50 mL). The mixture was allowed to stand and separate into layers. The organic phase was dried with 20 g of anhydrous sodium sulfate for 2 h. The mixture was filtered, distilled under reduced pressure at 30 °C for 2 h, and dried under vacuum at 40 °C for 12 h to obtain the diamide compound.

[0042] S2: Under nitrogen protection, add 500 mL of tetrahydrofuran, 0.1 mol of triallyl isocyanurate, 0.315 mol of diamide compound, and 0.6 g of photoinitiator 184 to the reactor, stir and mix thoroughly, and at room temperature, with an intensity of 8.4 mW / cm². 2 After irradiation under a 365nm UV LED lamp for 7 hours, the mixture was distilled under reduced pressure at 40℃ for 2 hours, then slowly added to 800mL of cold diethyl ether, stirred, and the precipitate was precipitated. The precipitate was filtered, washed three times with cold diethyl ether (100mL each time), and dried under vacuum at 40℃ for 12 hours to obtain the three-armed compound.

[0043] S3: Under nitrogen protection, 800 mL of xylene, 0.1 mol of the three-arm compound, 0.312 mol of tert-butyl acetoacetate, and 0.01 mol of dibutyltin oxide were added to the reactor. The mixture was stirred and stirred until homogeneous. After reflux for 7 h (tert-butanol was removed using a water separator during the reaction), the mixture was cooled to room temperature, washed three times with saturated brine (200 mL each time), dried with 20 g of anhydrous magnesium sulfate for 30 min, filtered, and the filtrate was distilled under reduced pressure at 80 °C for 3 h and dried under vacuum at 70 °C for 12 h to obtain the oxyester-modified three-arm compound.

[0044] S4: Add 10g of oxyester-modified three-arm compound and 25g of amino-modified oligosiloxane to the reactor, stir and mix well, melt and stir at 120℃ for 20min; then cure under vacuum at 100℃ for 12h to obtain the adhesive.

[0045] Example 3: Preparation of adhesive:

[0046] S1: Under nitrogen protection, 100 mL of dichloromethane, 0.11 mol of 6-hydroxyhexanoic acid and 0.11 mol of 1-hydroxybenzotriazole were added to the reactor. The mixture was stirred at room temperature for 15 min. 0.11 mol of dicyclohexylcarbodiimide was added under ice bath and stirred for 15 min. 0.1 mol of glycyl-cysteine ​​and 0.11 mol of triethylamine were added. The mixture was reacted under ice bath for 0.5 h. After being brought to room temperature and reacted for 8 h, the mixture was filtered. The filtrate was washed successively with 10 wt% citric acid solution (50 mL × 2), saturated sodium carbonate solution (50 mL × 2), and saturated sodium chloride solution (50 mL). The mixture was allowed to stand and separate into layers. The organic phase was dried with 20 g of anhydrous sodium sulfate for 2 h. The mixture was filtered, distilled under reduced pressure at 30 °C for 3 h, and dried under vacuum at 40 °C for 12 h to obtain the diamide compound.

[0047] S2: Under nitrogen protection, add 500 mL of tetrahydrofuran, 0.1 mol of triallyl isocyanurate, 0.32 mol of diamide compound, and 0.6 g of photoinitiator 184 to the reactor, stir and mix thoroughly, and at room temperature, with an intensity of 8.4 mW / cm². 2After irradiation under a 365nm UV LED lamp for 6 hours, the mixture was distilled under reduced pressure at 40℃ for 2 hours, then slowly added to 800mL of cold diethyl ether, stirred, and the precipitate was precipitated. The precipitate was filtered, washed three times with cold diethyl ether (100mL each time), and dried under vacuum at 40℃ for 12 hours to obtain the three-armed compound.

[0048] S3: Under nitrogen protection, 800 mL of xylene, 0.1 mol of the three-arm compound, 0.32 mol of tert-butyl acetoacetate, and 0.01 mol of dibutyltin oxide were added to the reactor. The mixture was stirred and stirred until homogeneous. After reflux for 8 h (tert-butanol was removed using a water separator during the reaction), the mixture was cooled to room temperature, washed three times with saturated brine (200 mL each time), dried with 20 g of anhydrous magnesium sulfate for 30 min, filtered, and the filtrate was distilled under reduced pressure at 80 °C for 3 h and dried under vacuum at 70 °C for 12 h to obtain the oxyester-modified three-arm compound.

[0049] S4: Add 10g of oxyester-modified three-arm compound and 30g of amino-modified oligosiloxane to the reactor, stir and mix well, melt and stir at 120℃ for 20min; then cure under vacuum at 100℃ for 12h to obtain the adhesive.

[0050] Example 4: The preparation method of amino-modified oligomeric siloxanes is as follows:

[0051] 0.6 mol of deionized water, 100 mL of anhydrous ethanol, 0.1 mol of γ-aminopropyltriethoxysilane, and 0.1 mol of methyltrimethoxysilane were added to a reactor. The mixture was stirred and stirred until homogeneous. After reacting at 60 °C for 12 h, the mixture was distilled under reduced pressure at 60 °C for 2 h to obtain amino-modified oligomeric siloxanes. The reaction process is illustrated below:

[0052]

[0053] Example 5: Preparation of environmentally friendly wear-resistant ceramics:

[0054] (1) Weigh out: 600g of alumina, 100g of boron nitride, 30g of binder (prepared in Example 1), 30g of composite flux (12g of spodumene and 18g of waste glass powder), 50g of toughening agent (zirconia), and 400g of deionized water;

[0055] (2) Place alumina, boron nitride, binder, toughening agent and composite flux into a ball mill, add deionized water, use grinding balls with a diameter of 5 mm and grinding balls with a diameter of 3 mm, the weight ratio of 5 mm grinding balls to 3 mm grinding balls is 2:1, the ball-to-material ratio is 10:1, ball mill at 600 rpm for 15 min, stand for 15 min, circulate ball milling and stand for 4 times to obtain a uniform slurry;

[0056] (3) Spray granulation of slurry, with inlet air temperature of 180℃ and outlet air temperature controlled at 95-105℃, peristaltic pump speed of 60r / min and atomizer speed of 6000r / min to obtain granular powder; age the powder in a closed environment for 24h; place the aged powder in a mold (3mm×3mm×30mm) and press it under 20MPa pressure for 15min to obtain green body; place the green body in a sintering furnace and heat it from room temperature to 450℃ at a rate of 2℃ / min and hold it for 40min; then heat it to 1200℃ at a rate of 5℃ / min and hold it for 60min; finally cool it to room temperature with the furnace to obtain environmentally friendly wear-resistant ceramic.

[0057] Example 6: Preparation of environmentally friendly wear-resistant ceramics:

[0058] (1) Weigh out: 650g of alumina, 125g of boron nitride, 50g of binder (prepared in Example 2), 60g of composite flux (20g of spodumene and 40g of waste glass powder), 80g of toughening agent (zirconia), and 450g of deionized water;

[0059] (2) Place alumina, boron nitride, binder, toughening agent and composite flux into a ball mill, add deionized water, use grinding balls with a diameter of 5 mm and grinding balls with a diameter of 3 mm, the weight ratio of 5 mm grinding balls to 3 mm grinding balls is 2:1, the ball-to-material ratio is 10:1, ball mill at 500 rpm for 15 min, stand for 15 min, circulate ball milling and stand for 4 times to obtain a uniform slurry;

[0060] (3) Spray granulation of slurry, with inlet air temperature of 180℃ and outlet air temperature controlled at 95-105℃, peristaltic pump speed of 60r / min and atomizer speed of 6000r / min to obtain granular powder; age the powder in a closed environment for 32h; place the aged powder in a mold (3mm×3mm×30mm) and press it under 25MPa pressure for 15min to obtain green body; place the green body in a sintering furnace and heat it from room temperature to 480℃ at a rate of 2℃ / min and hold it for 35min; then heat it to 1300℃ at a rate of 5℃ / min and hold it for 40min; finally cool it to room temperature with the furnace to obtain environmentally friendly wear-resistant ceramic.

[0061] Example 7: Preparation of environmentally friendly wear-resistant ceramics:

[0062] (1) Weigh out: 700g of alumina, 150g of boron nitride, 80g of binder (prepared in Example 3), 80g of composite flux (23g of spodumene and 57g of waste glass powder), 100g of toughening agent (zirconia), and 500g of deionized water;

[0063] (2) Place alumina, boron nitride, binder, toughening agent and composite flux into a ball mill, add deionized water, use grinding balls with a diameter of 5 mm and grinding balls with a diameter of 3 mm, the weight ratio of 5 mm grinding balls to 3 mm grinding balls is 2:1, the ball-to-material ratio is 10:1, ball mill at 400 rpm for 15 min, stand for 15 min, circulate ball milling and stand for 4 times to obtain a uniform slurry;

[0064] (3) Spray granulation of slurry, with inlet air temperature of 180℃ and outlet air temperature controlled at 95-105℃, peristaltic pump speed of 60r / min and atomizer speed of 6000r / min to obtain granular powder; age the powder in a closed environment for 48h; place the aged powder in a mold (3mm×3mm×30mm) and press it under 30MPa pressure for 15min to obtain green body; place the green body in a sintering furnace and heat it from room temperature to 500℃ at a rate of 2℃ / min and hold it for 30min; then heat it to 1400℃ at a rate of 5℃ / min and hold it for 30min; finally cool it to room temperature with the furnace to obtain environmentally friendly wear-resistant ceramic.

[0065] Comparative Example 1

[0066] An environmentally friendly wear-resistant ceramic, with the same raw material composition and preparation method as in Example 6, differs in that the binder is replaced with an equal weight of binder prepared by the following method:

[0067] The preparation method of the adhesive is basically the same as that in Example 2, except that 6-hydroxyhexanoic acid in step S1 is replaced with an equimolar amount of 3-hydroxypropionic acid.

[0068] Comparative Example 2

[0069] An environmentally friendly wear-resistant ceramic, with the same raw material composition and preparation method as in Example 6, differs in that the binder is replaced with an equal weight of binder prepared by the following method:

[0070] The preparation method of the adhesive is basically the same as that in Example 2, except that 6-hydroxyhexanoic acid in step S1 is replaced with an equimolar amount of 9,10-dihydroxystearic acid.

[0071] Comparative Example 3

[0072] An environmentally friendly wear-resistant ceramic, with the same raw material composition and preparation method as in Example 6, differs in that the binder is replaced with an equal weight of binder prepared by the following method:

[0073] The preparation method of the adhesive is basically the same as that in Example 2, except that the diamide compound in step S2 is replaced with an equimolar amount of 12-mercaptododecane-1-ol.

[0074] Comparative Example 4

[0075] An environmentally friendly wear-resistant ceramic, with the same raw material composition and preparation method as in Example 6, differs in that the binder is replaced with an equal weight of binder prepared by the following method:

[0076] The preparation method of the adhesive is basically the same as that in Example 2, except that the triallyl isocyanurate in step S2 is replaced with an equimolar amount of diallyl isocyanurate.

[0077] Comparative Example 5

[0078] An environmentally friendly wear-resistant ceramic, with the same raw material composition and preparation method as in Example 6, differs in that the binder is replaced with an equal weight of binder prepared by the following method:

[0079] The preparation method of the adhesive is basically the same as that in Example 2, except that the triallyl isocyanurate in step S2 is replaced with an equimolar amount of 1,3,5-trivinylbenzene.

[0080] Comparative Example 6

[0081] An environmentally friendly wear-resistant ceramic, with the same raw material composition and preparation method as in Example 6, differs in that the binder is replaced with an equal weight of binder prepared by the following method:

[0082] The preparation method of the adhesive is basically the same as that in Example 2, except that the amino-modified oligosiloxane in step S4 is replaced with an equal mass of 1,7-diaminoheptane.

[0083] The main components of the waste glass powder used in the embodiments and comparative examples of this application include: SiO2 (72.3 wt%), CaO (11.8 wt%), Na2O (12.5 wt%), with an average particle size of 400 mesh; the main components of spodumene include: Li2O (8.0 wt%), Al2O3 (27.3 wt%), SiO2 (64.5 wt%), with an average particle size of 200 mesh; and the CAS number of glycyl-cysteine ​​is 106463-34-7.

[0084] The environmentally friendly wear-resistant ceramics prepared in Examples 5-7 and Comparative Examples 1-6 were tested for wear resistance, flexural strength and impact resistance. The results are shown in Table 1.

[0085] Wear resistance test: The ceramic was subjected to wear tests under dry sliding conditions using a multi-functional tribology and wear testing machine (MFT-5000) at room temperature (25℃) and relative humidity (30%). The test adopted a reciprocating linear motion mode with ball-to-surface contact. The friction pair consisted of Si3N4 balls (5.76mm in diameter). During the test, the applied normal load was 30N, the sliding frequency was 3Hz, the wear time was 30min, and the sliding distance was 4mm. The wear volume was measured using a super depth-of-field microscope (VHX-2000C), and the wear rate was determined by the volumetric method, using the following formula:

[0086]

[0087] In the formula, W—wear rate (mm) 3 / (N·m));

[0088] L—Total sliding distance (mm);

[0089] V—Wear volume (mm) 3 );

[0090] —Normal load (N), 30N in this experiment.

[0091] Flexural strength test: The flexural strength of the samples was determined using a KZJ-30 electric flexural strength tester. The calculation formula is as follows:

[0092]

[0093] In the formula, —Flexural strength (MPa);

[0094] P—The load (N) at which the specimen breaks;

[0095] L—Distance between support blades (mm), 30mm in this experiment;

[0096] B—Width of the fracture surface of the sample (mm);

[0097] H—Height at the fracture surface of the sample (mm);

[0098] K—coefficient, take K=1.

[0099] Impact strength test: The test was conducted according to GB / T 38494-2020. The test results are shown in Table 1.

[0100] Table 1 Performance Indicators of Environmentally Friendly Wear-Resistant Ceramic

[0101]

[0102] As can be seen from the data in Examples 5, 6 and 7 of Table 1, the environmentally friendly wear-resistant ceramics prepared in this application have excellent wear resistance, flexural strength and impact strength.

[0103] The binder added to the environmentally friendly wear-resistant ceramic prepared in this invention has a three-dimensional network structure with isocyanurate rings as rigid crosslinking centers and siloxane as the backbone. During the green body forming stage, the rigidity of the isocyanurate rings in the binder acts as a strong crosslinking point, effectively resisting the bending stress generated during powder pressing and subsequent processing, preventing deformation or cracking of the green body. Simultaneously, the siloxane backbone (Si-O-Si) achieves strong interfacial chemical bonding between the binder and inorganic particles through condensation or strong hydrogen bonding between its terminal silanol groups (-Si-OH) and the hydroxyl groups on the surface of ceramic particles, enhancing interfacial adhesion and improving the strength of the green body. In the early stages of the sintering process, the three-dimensional network of the binder provides support. As the temperature rises, the internal stress of the green body begins to change. At this time, the flexible long chains in the binder effectively absorb and release this energy through the extension and rotation of chain segments, preventing the formation of microcracks. The polar groups such as amide bonds (-CO-NH-) and silanol groups (-Si-OH) in the binder constitute a dynamic "hydrogen bond network." When the material is subjected to thermal stress, these dynamic hydrogen bonds can undergo reversible breakage and recombination, actively dissipating energy while the covalent backbone remains intact, thus preventing the initiation and propagation of microcracks and avoiding instantaneous brittle fracture of the material. During sintering, the silica generated by the pyrolysis of siloxanes in the binder can undergo a solid-phase reaction with the surface of ceramic particles to form a silicate interface layer with strong chemical bonds. On the other hand, as a sintering aid, it melts at the sintering temperature to form a liquid phase, which fills the pores between particles through viscous flow, forming a dense glassy phase network that effectively transfers and disperses stress, thereby inhibiting crack initiation and improving flexural strength.

[0104] In summary, the synergistic effect of multiple functional groups simultaneously achieves rigid support against flexural strength and effective dissipation of impact energy, ultimately forming an environmentally friendly ceramic with a dense structure and excellent mechanical properties.

[0105] The main reason for the decline in the performance of the environmentally friendly wear-resistant ceramic prepared in Comparative Example 2 is that the dihydroxy structure of the 9,10-dihydroxystearic acid used affects the network structure of the final product. The second hydroxyl group in the middle of its molecule will generate significant steric hindrance, reduce the efficiency of subsequent transesterification reaction, and result in insufficient crosslinking density. At the same time, it destroys the molecular regularity and forms stress concentration defects in the network, resulting in a decrease in impact resistance and flexural strength.

[0106] The main reason for the decline in the performance of the environmentally friendly wear-resistant ceramic prepared in Comparative Example 3 is that the lack of amide bonds in the binder weakens the hydrogen bonding with the ceramic surface, reduces the cohesive strength of the binder, and leads to a decrease in impact resistance and flexural strength.

[0107] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.

Claims

1. An environmentally friendly wear-resistant ceramic, characterized in that, The ingredients include the following parts by weight: Alumina 60-70 parts, boron nitride 10-15 parts, binder 3-8 parts, composite flux 3-8 parts, toughening agent 5-10 parts, deionized water 40-50 parts; The adhesive is prepared by the following method: S1: Under nitrogen protection, dichloromethane, 6-hydroxyhexanoic acid, and 1-hydroxybenzotriazole were added to the reactor and stirred at room temperature. Dicyclohexylcarbodiimide was added under ice bath and stirred. Glycine-cysteine ​​and triethylamine were added and reacted under ice bath. The reaction was then brought up to room temperature. The mixture was filtered, and the filtrate was washed successively with citric acid solution, saturated sodium carbonate solution, and saturated sodium chloride solution. The mixture was allowed to stand and separate into layers. The organic phase was dried with anhydrous sodium sulfate, filtered, distilled under reduced pressure, and dried under vacuum to obtain the diamide compound. S2: Under nitrogen protection, tetrahydrofuran, triallyl isocyanurate, diamide compound, and photoinitiator 184 were added to the reactor and stirred to mix. The mixture was then irradiated under ultraviolet LED light at room temperature and distilled under reduced pressure. The mixture was slowly added to cold diethyl ether and stirred to precipitate. The precipitate was filtered, washed with cold diethyl ether, and dried under vacuum to obtain the three-armed compound. S3: Under nitrogen protection, xylene, three-arm compound, tert-butyl acetoacetate, and dibutyltin oxide were added to the reactor, stirred and mixed, refluxed, cooled to room temperature, washed with saturated brine, dried with anhydrous magnesium sulfate, filtered, distilled under reduced pressure, and dried under vacuum to obtain the oxyester-modified three-arm compound. S4: Add the oxoester-modified three-arm compound and the amino-modified oligosiloxane to the reactor, stir and mix well, melt and stir; vacuum solidify to obtain the binder; The CAS number of glycyl-cysteine ​​mentioned in step S1 is 106463-34-7; In step S4, the amino-modified oligosiloxane is prepared by the following method: Deionized water, anhydrous ethanol, γ-aminopropyltriethoxysilane, and methyltrimethoxysilane were added to the reactor, stirred and mixed, heated and reacted, and then distilled under reduced pressure to obtain amino-modified oligosiloxanes. The composite flux is a mixture of spodumene and waste glass powder; the mixing weight ratio of spodumene to waste glass powder is 1:(1.5-2.5).

2. The environmentally friendly wear-resistant ceramic according to claim 1, characterized in that, In step S1, the molar ratio of glycyl-cysteine ​​to 6-hydroxyhexanoic acid is 1:(1.05-1.1).

3. The environmentally friendly wear-resistant ceramic according to claim 1, characterized in that, In step S2, the molar ratio of the diamide compound to triallyl isocyanurate is (3.1-3.2):

1.

4. The environmentally friendly wear-resistant ceramic according to claim 1, characterized in that, In step S3, the molar ratio of the three-arm compound to tert-butyl acetoacetate is 1:(3.05-3.2).

5. The environmentally friendly wear-resistant ceramic according to claim 1, characterized in that, In step S4, the mass ratio of the oxyester-modified three-arm compound to the amino-modified oligosiloxane is 1:(2-3).

6. The environmentally friendly wear-resistant ceramic according to claim 1, characterized in that, The molar ratio of methyltrimethoxysilane to γ-aminopropyltriethoxysilane is 1:

1.

7. The environmentally friendly wear-resistant ceramic according to claim 1, characterized in that, The toughening agent is zirconium oxide.

8. A method for preparing the environmentally friendly wear-resistant ceramic according to any one of claims 1-7, characterized in that, Includes the following steps: (1) Weigh out the following by weight: 60-70 parts alumina, 10-15 parts boron nitride, 3-8 parts binder, 3-8 parts composite flux, 5-10 parts toughening agent, and 40-50 parts deionized water; (2) Place alumina, boron nitride, binder, composite flux and toughening agent into a ball mill, add deionized water, and ball mill to obtain a uniform slurry; (3) Spray granulation of the slurry to obtain granular powder; after aging the powder in a closed environment for 24-48 hours, place it in a mold and press it to form a green body; place the green body in a sintering furnace, raise the temperature from room temperature to 450-500℃ and hold it for 30-40 minutes; then raise the temperature to 1200℃-1400℃ and hold it for 30-60 minutes; cool it naturally to room temperature to obtain environmentally friendly wear-resistant ceramics.

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