High-efficiency antibacterial zirconia powder and preparation method thereof

Abstract

The application relates to the technical field of antibacterial ceramics, in particular to high-efficiency antibacterial zirconia powder and a preparation method thereof. The high-efficiency antibacterial zirconia powder is prepared from the following raw materials in parts by mass: zirconium oxychloride octahydrate 50-150 parts, nano-silicon dioxide 10-20 parts, yttrium oxide 0.1-1 part, liquid crystal emulsifier 10-20 parts, tetrabutyl titanate 10-30 parts, triethanolamine 10-20 parts and dendritic polyamide-amine 1-2 parts. The nano-titanium dioxide generated by hydrolysis of the tetrabutyl titanate is combined with the zirconia crystal boundary in a chemical bonding mode, the photocatalytic activity of the nano-titanium dioxide is derived from the oxidative damage of the valence band hole pair to the microbial cell membrane, non-dissolution type antibacterial is realized, and persistent antibacterial is achieved. Meanwhile, the preparation method is simple, and is suitable for large-scale popularization and application.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of antibacterial ceramics, in particular to high-efficiency antibacterial zirconia powder and a preparation method thereof. BACKGROUND

[0002] As a representative of new functional ceramic materials, zirconia has a broad application prospect in high-end medical fields such as dental implants and joint prostheses due to its excellent mechanical properties, chemical stability and biocompatibility.

[0003] However, the current zirconia powder preparation technology still faces the following challenges: (1) although the traditional preparation method (such as coprecipitation and sol-gel method) can realize the synthesis of nano-zirconia powder, the hard agglomeration phenomenon is easily caused due to the excessively high surface energy of the particles in the process, resulting in uneven particle size distribution of the final powder, and the actual particle size is significantly increased due to the agglomerates, and the particle size dispersion is as high as 30% or more, which seriously affects the uniformity of the subsequent forming process; although the existing dispersion technology (such as surfactant coating and mechanical ball milling) can partially alleviate the agglomeration, there are problems such as organic residue densification and short dispersion stability aging, which are difficult to meet the strict requirements of medical materials on purity and long-term stability; (2) the current antibacterial modification technology mainly relies on silver / copper ion loading or metal oxide composite, which has significant limitations, and the continuous release of metal ions in the body fluid may cause cytotoxicity, which conflicts with the requirement of biocompatibility; and the insufficient bonding strength between the antibacterial components and the matrix will also cause poor persistence.

[0004] Therefore, developing a zirconia powder preparation technology with nano-level dispersion stability and long-acting antibacterial function has become a key breakthrough for promoting the upgrading of biomedical materials. SUMMARY

[0005] The application aims to solve the problems in the prior art and provides high-efficiency antibacterial zirconia powder and a preparation method thereof.

[0006] The high-efficiency antibacterial zirconia powder comprises, by mass fraction, 50-150 parts of zirconium oxychloride octahydrate, 10-20 parts of nano-silicon dioxide, 0.1-1 part of yttrium oxide, 10-20 parts of liquid crystal emulsifier, 10-30 parts of tetrabutyl titanate, 10-20 parts of triethanolamine and 1-2 parts of dendritic polyamide-amine.

[0007] Preferably, the liquid crystal emulsifier is a phospholipid liquid crystal emulsifier.

[0008] Preferably, the liquid crystal emulsifier comprises hydrogenated lecithin, behenyl alcohol and cetyl alcohol, and the mass ratio of the hydrogenated lecithin, behenyl alcohol and cetyl alcohol is 2-4:1-2:1-2.

[0009] Preferably, the antibacterial rate of the zirconia powder is greater than 99%.

[0010] Preferably, the particle size distribution coefficient of the zirconium oxide powder is ≤1.35.

[0011] Preferably, the specific surface area of the zirconium oxide powder is ≥190m 2 / g.

[0012] The preparation method of the high-efficiency antibacterial zirconium oxide powder comprises the following steps:

[0013] S1, adding zirconium oxychloride octahydrate, nano-silicon dioxide, yttrium oxide and liquid crystal emulsifier into water, stirring at 40-50 DEG C for 1-2h, refluxing and stirring at 80-90 DEG C for 1-2h to obtain a preform a;

[0014] S2, adding tetrabutyl titanate into an aqueous ethanol solution, adding triethanolamine and stirring uniformly to obtain a preform b;

[0015] S3, under the stirring state, adding the preform b into the preform a dropwise, continuing to stir for 1-2h after the dropwise addition is completed, continuing to spray an aqueous ammonium bicarbonate solution into the preform under the stirring state, stopping the spraying when the pH value of the system is 7-7.5, adding dendritic polyamide-amine and continuing to stir for 1-4h, standing for 5-15h, filtering, washing, drying to constant weight, ball milling, calcining at 800-900 DEG C for 1-3h and reducing to room temperature.

[0016] Preferably, in S2, the mass fraction of the aqueous ethanol solution is 40-60%.

[0017] Preferably, in S3, the concentration of the aqueous ammonium bicarbonate solution is 1-2mol / L.

[0018] Preferably, in S3, the drying temperature for drying to constant weight is 100-120 DEG C.

[0019] Beneficial effects:

[0020] In the application, yttrium oxide is combined with nano-silicon dioxide, yttrium oxide is used as a crystal form stabilizer, by forming yttrium stabilized zirconia solid solution, the crystal lattice distortion caused by high temperature phase transition can be inhibited, nano-silicon dioxide provides heterogeneous nucleation sites, cooperates with the three-dimensional steric hindrance effect of dendritic polyamide-amine, limits the migration distance of crystal nucleus, cooperates with phospholipid liquid crystal emulsifier to form an ordered lamellar structure, guides the directional arrangement of particles through the hydrophobic-hydrophilic balance effect, avoids secondary agglomeration, and under the comprehensive action, the product has small particle size and concentrated distribution, and the powder dispersity is significantly reduced.

[0021] In the application, nano-titanium dioxide generated by the hydrolysis of tetrabutyl titanate is combined with the zirconium oxide grain boundary in a chemical bonding form, the photocatalytic activity of the nano-titanium dioxide is derived from the oxidative damage of the valence band hole pair to the microbial cell membrane, non-dissolution type antibacterial is realized, and persistent antibacterial is exhibited.

[0022] This invention utilizes the combination of nano-silica and nano-titanium dioxide in zirconium oxide powder to create a stress-reinforcing toughening effect, resulting in not only excellent wear resistance but also... 3+ The oxygen vacancy defects formed by doping can capture active oxygen in corrosive media, significantly enhancing corrosion resistance.

[0023] The preparation method of this invention is simple and suitable for large-scale application. Attached Figure Description

[0024] Figure 1 This is a comparison chart of the particle size and specific surface area of ​​the zirconia powders obtained in Example 5 and Comparative Examples 1-3.

[0025] Figure 2 The graph shows a comparison of the corrosion resistance and wear resistance of discs made from zirconia powder obtained in Example 5 and Comparative Examples 1-3.

[0026] Figure 3 The diagram shows a comparison of the antibacterial durability of discs made from zirconium oxide powder obtained in Example 5 and Comparative Examples 1-3. Detailed Implementation

[0027] The dendritic polyamide-amines used below were purchased from Hangzhou Mouqiao Biotechnology Co., Ltd., and are third-generation dendritic polyamide-amines.

[0028] The present invention will be further explained below with reference to specific embodiments.

[0029] Example 1

[0030] A highly efficient antibacterial zirconium oxide powder, the raw materials of which include: 50g zirconium oxychloride octahydrate, 10g nano silica, 0.1g yttrium oxide, 10g liquid crystal emulsifier, 10g tetrabutyl titanate, 10g triethanolamine, and 1g dendritic polyamide-amine.

[0031] The liquid crystal emulsifier is composed of hydrogenated lecithin, behenol, and cetyl alcohol in a mass ratio of 1:1:1.

[0032] The preparation method of the above-mentioned high-efficiency antibacterial zirconia powder includes the following steps:

[0033] S1. Add zirconium oxychloride octahydrate, nano silica, yttrium oxide, and liquid crystal emulsifier to 500g of deionized water, stir at 40℃ for 1h at a stirring speed of 500r / min, and reflux at 80℃ for 1h to obtain preform a.

[0034] S2. Add tetrabutyl titanate to 200g of 40% ethanol aqueous solution, add triethanolamine and stir evenly to obtain preform b;

[0035] S3. Under stirring, add preform b dropwise to preform a. After the addition is complete, continue stirring for 1 hour at a stirring speed of 200 r / min. Continue spraying a 1 mol / L ammonium bicarbonate aqueous solution into the mixture while stirring. Stop spraying when the pH of the system reaches 7-7.5. Add dendritic polyamide-amine and continue stirring for 1 hour. Let stand for 5 hours, filter, wash, dry at 100℃ to constant weight, ball mill, calcine at 800℃ for 1 hour, and cool to room temperature.

[0036] Example 2

[0037] A highly efficient antibacterial zirconium oxide powder, the raw materials of which include: 150g zirconium oxychloride octahydrate, 20g nano silica, 1g yttrium oxide, 20g liquid crystal emulsifier, 30g tetrabutyl titanate, 20g triethanolamine, and 2g dendritic polyamide-amine.

[0038] The liquid crystal emulsifier is composed of hydrogenated lecithin, behenol, and cetyl alcohol in a mass ratio of 4:1:1.

[0039] The preparation method of the above-mentioned high-efficiency antibacterial zirconia powder includes the following steps:

[0040] S1. Add zirconium oxychloride octahydrate, nano silica, yttrium oxide, and liquid crystal emulsifier to 1000g of deionized water, stir at 50℃ for 2h at a stirring speed of 1000r / min, and reflux at 90℃ for 2h to obtain preform a.

[0041] S2. Add tetrabutyl titanate to 500g of 60% ethanol aqueous solution, add triethanolamine and stir evenly to obtain preform b;

[0042] S3. Under stirring, add preform b dropwise to preform a. After the addition is complete, continue stirring for 2 hours at a stirring speed of 600 r / min. Continue spraying a 2 mol / L ammonium bicarbonate aqueous solution into the mixture while stirring. Stop spraying when the pH of the system reaches 7-7.5. Add dendritic polyamide-amine and continue stirring for 4 hours. Let stand for 15 hours, filter, wash, dry at 120℃ to constant weight, ball mill, calcine at 850℃ for 3 hours, and cool to room temperature.

[0043] Example 3

[0044] A highly efficient antibacterial zirconium oxide powder, the raw materials of which include: 80g zirconium oxychloride octahydrate, 18g nano silica, 0.3g yttrium oxide, 17g liquid crystal emulsifier, 15g tetrabutyl titanate, 18g triethanolamine, and 1.3g dendritic polyamide-amine.

[0045] The liquid crystal emulsifier is composed of hydrogenated lecithin, behenol, and cetyl alcohol in a mass ratio of 7:3:3.

[0046] The preparation method of the above-mentioned high-efficiency antibacterial zirconia powder includes the following steps:

[0047] S1. Add zirconium oxychloride octahydrate, nano silica, yttrium oxide, and liquid crystal emulsifier to 700g of deionized water, stir at 48℃ for 80min at a stirring speed of 900r / min, and reflux at 82℃ for 100min to obtain preform a;

[0048] S2. Add tetrabutyl titanate to 300g of 55% ethanol aqueous solution, add triethanolamine and stir evenly to obtain preform b;

[0049] S3. Under stirring, add preform b dropwise to preform a. After the addition is complete, continue stirring for 80 minutes at a stirring speed of 500 r / min. Continue to spray a 1.5 mol / L ammonium bicarbonate aqueous solution into the mixture while stirring. Stop spraying when the pH of the system reaches 7-7.5. Add dendritic polyamide-amine and continue stirring for 2 hours. Let stand for 12 hours, filter, wash, dry at 105℃ to constant weight, ball mill, calcine at 900℃ for 1.5 hours, and cool to room temperature.

[0050] Example 4

[0051] A highly efficient antibacterial zirconium oxide powder, the raw materials of which include: 120g zirconium oxychloride octahydrate, 12g nano silica, 0.7g yttrium oxide, 13g liquid crystal emulsifier, 25g tetrabutyl titanate, 12g triethanolamine, and 1.7g dendritic polyamide-amine.

[0052] The liquid crystal emulsifier is composed of hydrogenated lecithin, behenol, and cetyl alcohol in a mass ratio of 5:3:3.

[0053] The preparation method of the above-mentioned high-efficiency antibacterial zirconia powder includes the following steps:

[0054] S1. Add zirconium oxychloride octahydrate, nano silica, yttrium oxide, and liquid crystal emulsifier to 900g of deionized water, stir at 42℃ for 100min at a stirring speed of 700r / min, and reflux at 88℃ for 80min to obtain preform a.

[0055] S2. Add tetrabutyl titanate to 400g of 45% ethanol aqueous solution, add triethanolamine and stir evenly to obtain preform b.

[0056] S3. Under stirring, add preform b dropwise to preform a. After the addition is complete, continue stirring for 100 min at a stirring speed of 300 r / min. Continue stirring while spraying a 1.5 mol / L ammonium bicarbonate aqueous solution until the pH of the system is 7-7.5. Stop spraying, add dendritic polyamide-amine, continue stirring for 3 h, let stand for 8 h, filter, wash, dry at 115℃ to constant weight, ball mill, calcine at 850℃ for 2.5 h, and cool to room temperature.

[0057] Example 5

[0058] A highly efficient antibacterial zirconium oxide powder, the raw materials of which include: 100g zirconium oxychloride octahydrate, 15g nano silica, 0.5g yttrium oxide, 15g liquid crystal emulsifier, 20g tetrabutyl titanate, 15g triethanolamine, and 1.5g dendritic polyamide-amine.

[0059] The liquid crystal emulsifier is composed of hydrogenated lecithin, behenol, and cetyl alcohol in a mass ratio of 2:1:1.

[0060] The preparation method of the above-mentioned high-efficiency antibacterial zirconia powder includes the following steps:

[0061] S1. Add zirconium oxychloride octahydrate, nano silica, yttrium oxide, and liquid crystal emulsifier to 800g of deionized water, stir at 45℃ for 90min at a stirring speed of 800r / min, and reflux at 85℃ for 90min to obtain preform a;

[0062] S2. Add tetrabutyl titanate to 350g of 50% ethanol aqueous solution, add triethanolamine and stir evenly to obtain preform b;

[0063] S3. Under stirring, add preform b dropwise to preform a. After the addition is complete, continue stirring for 90 minutes at a stirring speed of 400 r / min. Continue to spray a 1.5 mol / L ammonium bicarbonate aqueous solution into the mixture while stirring. Stop spraying when the pH of the system reaches 7-7.5. Add dendritic polyamide-amine and continue stirring for 2.5 hours. Let stand for 10 hours, filter, wash, dry at 110℃ to constant weight, ball mill, calcine at 850℃ for 2 hours, and then cool to room temperature.

[0064] Comparative Example 1

[0065] A highly efficient antibacterial zirconium oxide powder, the raw materials of which include: 100g zirconium oxychloride octahydrate, 15g nano silica, 0.5g yttrium oxide, 15g OP-10, 20g tetrabutyl titanate, 15g triethanolamine, and 1.5g dendritic polyamide-amine.

[0066] The preparation method of the above-mentioned high-efficiency antibacterial zirconia powder includes the following steps:

[0067] S1. Add zirconium oxychloride octahydrate, nano silica, yttrium oxide, and OP-10 to 800g of deionized water, stir at 45℃ for 90min at a stirring speed of 800r / min, and then reflux at 85℃ for 90min to obtain preform a.

[0068] S2. Add tetrabutyl titanate to 350g of 50% ethanol aqueous solution, add triethanolamine and stir evenly to obtain preform b;

[0069] S3. Under stirring, add preform b dropwise to preform a. After the addition is complete, continue stirring for 90 minutes at a stirring speed of 400 r / min. Continue to spray a 1.5 mol / L ammonium bicarbonate aqueous solution into the mixture while stirring. Stop spraying when the pH of the system reaches 7-7.5. Add dendritic polyamide-amine and continue stirring for 2.5 hours. Let stand for 10 hours, filter, wash, dry at 110℃ to constant weight, ball mill, calcine at 850℃ for 2 hours, and then cool to room temperature.

[0070] Comparative Example 2

[0071] A highly efficient antibacterial zirconium oxide powder, the raw materials of which include: 100g zirconium oxychloride octahydrate, 15g nano silica, 0.5g yttrium oxide, 16.5g liquid crystal emulsifier, 20g tetrabutyl titanate, and 15g triethanolamine.

[0072] The liquid crystal emulsifier is composed of hydrogenated lecithin, behenol, and cetyl alcohol in a mass ratio of 2:1:1.

[0073] The preparation method of the above-mentioned high-efficiency antibacterial zirconia powder includes the following steps:

[0074] S1. Add zirconium oxychloride octahydrate, nano silica, yttrium oxide, and liquid crystal emulsifier to 800g of deionized water, stir at 45℃ for 90min at a stirring speed of 800r / min, and reflux at 85℃ for 90min to obtain preform a;

[0075] S2. Add tetrabutyl titanate to 350g of 50% ethanol aqueous solution, add triethanolamine and stir evenly to obtain preform b;

[0076] S3. Under stirring, add preform b dropwise to preform a. After the addition is complete, continue stirring for 90 minutes at a stirring speed of 400 r / min. Continue to spray a 1.5 mol / L ammonium bicarbonate aqueous solution into the mixture while stirring. Stop spraying when the pH of the system reaches 7-7.5. Continue stirring for 2.5 hours, let stand for 10 hours, filter, wash, dry at 110℃ to constant weight, ball mill, calcine at 850℃ for 2 hours, and then cool to room temperature.

[0077] Comparative Example 3

[0078] A highly efficient antibacterial zirconium oxide powder, the raw materials of which include: 100g zirconium oxychloride octahydrate, 0.5g yttrium oxide, 20g liquid crystal emulsifier, 30g tetrabutyl titanate, 15g triethanolamine, and 1.5g dendritic polyamide-amine.

[0079] The liquid crystal emulsifier is composed of hydrogenated lecithin, behenol, and cetyl alcohol in a mass ratio of 2:1:1.

[0080] The preparation method of the above-mentioned high-efficiency antibacterial zirconia powder includes the following steps:

[0081] S1. Add zirconium oxychloride octahydrate, yttrium oxide, and liquid crystal emulsifier to 800g of deionized water, stir at 45℃ for 90min at a stirring speed of 800r / min, and reflux at 85℃ for 90min to obtain preform a;

[0082] S2. Add tetrabutyl titanate to 350g of 50% ethanol aqueous solution, add triethanolamine and stir evenly to obtain preform b;

[0083] S3. Under stirring, add preform b dropwise to preform a. After the addition is complete, continue stirring for 90 minutes at a stirring speed of 400 r / min. Continue to spray a 1.5 mol / L ammonium bicarbonate aqueous solution into the mixture while stirring. Stop spraying when the pH of the system reaches 7-7.5. Add dendritic polyamide-amine and continue stirring for 2.5 hours. Let stand for 10 hours, filter, wash, dry at 110℃ to constant weight, ball mill, calcine at 850℃ for 2 hours, and then cool to room temperature.

[0084] The particle size of the zirconia powders obtained in Example 5 and Comparative Examples 1-3 was tested using a laser particle size analyzer, and D10, D50, and D90 were statistically analyzed to calculate the particle size distribution coefficient. The specific surface area of ​​the zirconia powders obtained in Example 5 and Comparative Examples 1-3 was measured using a BET analyzer.

[0085] Particle size distribution coefficient = (D90 - D10) ÷ D50.

[0086] like Figure 1 As shown, the zirconia powder obtained in Example 5 has the smallest particle size distribution coefficient, indicating that the zirconia powder obtained in Example 5 is more uniform and has the largest specific surface area, which is better than Comparative Examples 1-3 (P<0.05).

[0087] 0.48 g of the zirconia powder obtained in Example 5 and Comparative Examples 1-3 were weighed and poured into a pre-made cylindrical mold with an inner diameter of 15 mm. The mold was pressed at 25 MPa for 1 min on a powder press to form discs. These discs were then placed in a sealed space, vacuum-sealed, and statically pressed at 200 MPa for 1 min. The resulting discs were then calcined in a high-temperature sintering furnace, heated from room temperature to 1250 °C, held for 30 min, then heated to 1400 °C, held for 2 h, and cooled to room temperature. The calcined discs were then ground and polished, with a thickness of 0.50 mm. The corrosion resistance of each group of discs was then determined according to GB / T 10125-2021 "Artificial Atmosphere Corrosion Test - Salt Spray Test" and the wear resistance of each group of discs was determined according to GB / T 12444-2006 "Metallic Materials Wear Test Method - Test Ring-Block Sliding Wear Test".

[0088] like Figure 2 As shown, the discs obtained using the zirconia powder obtained in Example 5 all had the smallest mass loss, confirming that they had the strongest corrosion resistance and wear resistance, which were superior to Comparative Examples 1-3 (P<0.05).

[0089] The antibacterial properties and antibacterial durability of the above-mentioned discs were determined in accordance with JC / T 897-2014 "Antibacterial Properties of Antibacterial Ceramic Products", using Staphylococcus aureus (Staphylococcus aureus) as a test sample. Staphylococcus aureus The test strains are ATCC 6538, Escherichia coli ATCC 11229, and Candida albicans ATCC 10231.

[0090] In the antibacterial performance test, the antibacterial rates of each group of discs against Staphylococcus aureus, Escherichia coli and Candida albicans were all greater than 99%, showing excellent antibacterial performance.

[0091] And antibacterial durability such as Figure 3 As shown, the discs obtained using the zirconium oxide powder obtained in Example 5 exhibit the best antibacterial durability.

[0092] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A highly efficient antibacterial zirconium oxide powder, characterized in that, The raw materials, by weight, include: 50-150 parts zirconium oxychloride octahydrate, 10-20 parts nano silica, 0.1-1 parts yttrium oxide, 10-20 parts liquid crystal emulsifier, 10-30 parts tetrabutyl titanate, 10-20 parts triethanolamine, and 1-2 parts dendritic polyamide-amine. The liquid crystal emulsifiers include: hydrogenated lecithin, behenol, and cetyl alcohol; the mass ratio of hydrogenated lecithin, behenol, and cetyl alcohol is 2-4:1-2:1-2.

2. The high-efficiency antibacterial zirconia powder according to claim 1, characterized in that, The zirconium oxide powder has an antibacterial rate of >99%.

3. The high-efficiency antibacterial zirconia powder according to claim 1, characterized in that, The particle size distribution coefficient of the zirconia powder is ≤1.

35.

4. The high-efficiency antibacterial zirconia powder according to claim 1, characterized in that, The specific surface area of ​​the zirconium oxide powder is ≥190m². 2 / g.

5. A method for preparing the highly efficient antibacterial zirconia powder as described in any one of claims 1-4, characterized in that, Includes the following steps: S1. Add zirconium oxychloride octahydrate, nano silica, yttrium oxide, and liquid crystal emulsifier to water, stir at 40-50℃ for 1-2 hours, and reflux at 80-90℃ for 1-2 hours to obtain preform a; S2. Add tetrabutyl titanate to an aqueous ethanol solution, add triethanolamine and stir until homogeneous to obtain preform b; S3. Under stirring, add preform b dropwise to preform a. After the addition is complete, continue stirring for 1-2 hours. Continue spraying ammonium bicarbonate aqueous solution into the mixture while stirring until the pH of the system is 7-7.

5. Stop spraying, add dendritic polyamide-amine and continue stirring for 1-4 hours. Let stand for 5-15 hours, filter, wash, dry to constant weight, ball mill, calcine at 800-900℃ for 1-3 hours, and cool to room temperature.

6. The method for preparing the high-efficiency antibacterial zirconia powder according to claim 5, characterized in that, In S2, the mass fraction of the ethanol aqueous solution is 40-60%.

7. The method for preparing the high-efficiency antibacterial zirconia powder according to claim 5, characterized in that, In S3, the concentration of ammonium bicarbonate aqueous solution is 1-2 mol / L.

8. The method for preparing the high-efficiency antibacterial zirconia powder according to claim 5, characterized in that, In S3, the drying temperature for drying to constant weight is 100-120℃.

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