Preparation method of α-aluminum oxide powder, artificial joint ceramic powder and preparation method

Abstract

The present invention relates to the technical field of artificial joint materials, and specifically relates to a preparation method of α-aluminum oxide powder, artificial joint ceramic powder and a preparation method thereof. The preparation method of the α-aluminum oxide powder of the present invention uses γ-aluminum oxide as a raw material, adds water and organic acid for soaking, grinds the slurry, filters it, and washes the filter cake to obtain wet aluminum oxide; the wet aluminum oxide and a modified resin coating solution loaded with magnesium are stirred and mixed, and spray drying granulation is carried out to obtain modified resin-coated aluminum oxide; the dried aluminum oxide is calcined and ground to obtain α-aluminum oxide powder. This method can be used for the preparation of artificial joint ceramic powder. The test results show that the obtained artificial joint has high flexural strength, fracture toughness and wear resistance, and excellent comprehensive performance.

Description

Technical Field

[0001] The present invention relates to the technical field of artificial joint materials, and particularly to a preparation method of α-aluminum oxide powder, artificial joint ceramic powder and a preparation method thereof. Background Art

[0002] Due to reasons such as population aging, diseases, and traumas, there are many patients with osteoarticular diseases, and the number of patients in need of artificial joint replacement is increasing day by day. Alumina has gradually become an important raw material for artificial joint preparation due to its advantages such as stable chemical properties, good biocompatibility, high hardness, and wear resistance.

[0003] The key to preparing artificial joint ceramic sintered bodies with excellent performance lies in obtaining high-quality α-Al2O3 powder and ceramic powder formulations. Calcining and transforming γ-aluminum oxide, which is cheap and easily available, into α-aluminum oxide powder can quickly obtain a large amount of α-aluminum oxide powder. However, the α-aluminum oxide powder prepared by this process has problems such as high sodium content of harmful impurities, large particle size, and uneven particle size distribution.

[0004] Based on this, the present application aims to improve the above existing process, prepare α-Al2O3 powder with ultra-fine, narrow particle size distribution, and good dispersibility using γ-aluminum oxide as a raw material, and design a formulation using this α-Al2O3 powder as a raw material to obtain artificial joint ceramic powder with excellent performance. Summary of the Invention

[0005] The first object of the present invention is to provide a preparation method of α-aluminum oxide powder. This method can use the existing production line, which is convenient for the implementation and application of the process, and can obtain α-Al2O3 powder with fine particle size, narrow particle size distribution, and good dispersibility by calcining at a lower temperature.

[0006] The second object of the present invention is to provide an artificial joint ceramic powder, which can be used for firing artificial joints. The artificial joints obtained by firing have high flexural strength, fracture toughness, and wear resistance, and excellent comprehensive performance.

[0007] The third object of the present invention is to provide a preparation method of artificial joint ceramic powder. This method has a simple process, is convenient for implementation and application, and the artificial joints obtained by firing have high flexural strength, fracture toughness, and wear resistance, and excellent comprehensive performance.

[0008] In order to achieve the above objects, the present invention adopts the following technical solutions:

[0009] The first object of the present application is to provide a preparation method of α-aluminum oxide powder, including the following steps:

[0010] S1. Using γ-aluminum oxide as raw material, add water and organic acid, soak at 20°C to 80°C, then perform sand grinding at 50°C to 90°C. Filter the slurry and wash the filter cake to obtain wet aluminum oxide material;

[0011] S2. Stir and mix the wet aluminum oxide material obtained in S1 and the modified resin coating solution loaded with magnesium, and perform spray drying granulation to obtain modified resin-coated aluminum oxide;

[0012] Among them, the modified resin coating solution loaded with magnesium is obtained by uniformly stirring and dispersing magnesium hydroxide in an ethanol solution of polyacrylic acid, and then mixing and modifying with phenolic resin;

[0013] S3. Calcinate and grind the aluminum oxide obtained by drying in S2 to obtain α-aluminum oxide powder.

[0014] Further, the material-liquid ratio used in the soaking in S1 is 1:1.2 to 2.6;

[0015] The organic acid in S1 is one or more of acetic acid, citric acid, oxalic acid, and acrylic acid, and the concentration of the organic acid is 1 mol / L to 2 mol / L;

[0016] The usage amount of the organic acid in S1 is 1% to 5% of the mass of the γ-aluminum oxide.

[0017] Further, the soaking time in S1 is 60 min to 180 min; the sand grinding time is 2 h to 4 h.

[0018] Further, the washing method in S1 is to first wash the filter cake with an appropriate amount of water and then wash it with an appropriate amount of absolute ethanol.

[0019] Further, the inlet temperature of the spray drying used in the spray granulation in S2 is 160°C to 170°C, and the outlet temperature is 70°C to 80°C.

[0020] Further, the mass ratio of the polyacrylic acid resin, the phenolic resin, the magnesium hydroxide, and the ethanol in S2 is 1 to 2:8 to 10:0.1 to 0.2:100.

[0021] Further, the preparation method of the modified resin coating solution loaded with magnesium in S2 is:

[0022] 1) According to the formula amount, add polyacrylic acid resin to 1 / 10 to 2 / 10 of anhydrous ethanol, and heat up to 50°C to 60°C under stirring at 500 r / min to dissolve the polyacrylate resin in ethanol to obtain a polyacrylic acid solution;

[0023] 2) Add magnesium hydroxide to the polyacrylic acid solution in step 1) and stir for 20 min to 40 min to obtain a magnesium-loaded polyacrylic acid mixed solution;

[0024] 3) Add the remaining anhydrous ethanol to the phenolic resin and stir. After mixing at 800 r / min for 35 min to 50 min, add the magnesium-loaded polyacrylic acid mixed solution described in step 2) above, and continue to stir and mix at 300 r / min for 30 min to 50 min to obtain the product.

[0025] Further, the phenolic resin in S2 is a thermosetting phenolic resin.

[0026] The second object of the present application is to provide an α-aluminum oxide artificial joint ceramic powder, and its preparation raw materials include:

[0027] α-aluminum oxide powder, and the α-aluminum oxide powder is prepared by the method according to any one of claims 1-8;

[0028] 3.8% to 4.4% by mass of chromium oxide in the α-aluminum oxide powder;

[0029] 1.7% to 2.3% by mass of yttrium-stabilized zirconia in the α-aluminum oxide powder; wherein, the content of yttrium oxide in the yttrium-stabilized zirconia is 1% to 5%.

[0030] The third object of the present application is to provide a preparation method of the above-mentioned α-aluminum oxide artificial joint ceramic powder. According to parts by weight, the α-aluminum oxide powder, the chromium oxide, and the yttrium-stabilized zirconia are ball-milled and mixed evenly to obtain the product.

[0031] Compared with the prior art, the beneficial effects of the present invention are:

[0032] (1) In the preparation method of the α-aluminum oxide powder provided by the present invention, by using the magnesium-loaded modified resin solution as the particle protective agent for the calcination of aluminum oxide, and utilizing the interaction between the hydroxyl groups in the magnesium hydroxide molecule and the carboxyl groups in the polyacrylic acid resin structure, the magnesium hydroxide is combined with the polyacrylic acid resin. Then, a uniform modified resin solution is prepared by using the good compatibility between the polyacrylic acid resin and the phenolic resin. The modified resin solution has good compatibility with aluminum oxide, and after removing the solvent by spray drying, a resin shell layer can be formed on the surface of the aluminum oxide particles. The selected phenolic resin has good thermal stability and has a long-term particle protection effect on aluminum oxide during the calcination process, effectively reducing the agglomeration phenomenon of aluminum oxide during the calcination process. At the same time, with the dispersion effect of the modified resin solution, the magnesium loaded in the solution can be evenly distributed on the surface of the aluminum oxide. Using magnesium oxide formed by the decomposition of magnesium during the calcination as a seed inducer can effectively reduce the phase transition temperature of α-aluminum oxide, improve the grain coarsening caused by the sintering of the powder, and improve the high-temperature agglomeration of the powder, and obtain α-Al2O3 powder with fine particle size, narrow particle size distribution, and good dispersion at a lower temperature during the calcination.

[0033] (2) The present invention uses inexpensive γ-aluminum oxide as raw material, adds organic acid and water for soaking and performs sand grinding at high temperature. By means of the crushing effect of sand grinding, the particle size of the powder is refined, which is conducive to the precipitation of impurities. The precipitated impurities are removed through subsequent filtration and washing. In addition, the organic acid added during sand grinding can also prevent secondary agglomeration between grains during the sand grinding process of the powder. Therefore, when the alumina powder is mixed with the modified resin sizing agent subsequently, it has better dispersibility.

[0034] (3) The α-aluminum oxide artificial joint ceramic powder provided by the present invention is suitable for firing artificial joint ceramic bodies. The obtained artificial joints have high flexural strength, fracture toughness and wear resistance, and excellent comprehensive performance. Detailed implementation manners

[0035] Next, in combination with the embodiments of the present invention, the technical solutions of the present invention will be described clearly and completely. The described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

[0036] The γ-aluminum oxide raw material used in the embodiment of the present invention has a D50 of 20 μm, and its chemical composition (by weight) is: Al2O3 94.82%, SiO2 0.024%, Fe2O3 0.026%, Na2O 0.32%, CaO 0.02%, MgO 0.01%, K2O 0.021%, and the loss on ignition is 4.759%.

[0037] Unless otherwise specified, the methods are all conventional methods, and unless otherwise specified, the raw materials can all be obtained from public commercial channels.

[0038] Example 1

[0039] This example provides a preparation method of α-aluminum oxide powder, including the following steps:

[0040] S1. Add γ-aluminum oxide raw material, water and 1.5 mol / L oxalic acid solution into a sand mill, soak at 50 °C for 120 min, with a material-liquid ratio of 1:2, and the usage amount of the oxalic acid solution is 3% of the mass of the γ-aluminum oxide raw material. After soaking, raise the temperature, perform sand grinding at 85 °C for 3 h, filter the sand grinding slurry, wash the filter cake with appropriate amount of water and then with appropriate amount of absolute ethanol to obtain wet alumina material;

[0041] S2. In the mixing tank, add the wet alumina material obtained in S1 to the modified resin coating solution loaded with magnesium. Stir and mix for 30 min at a stirring speed of 500 r / min to obtain a mixed material. Among them, the weight ratio of the modified resin coating solution loaded with magnesium to the γ-alumina raw material in S1 is 8:1. The mixed material is spray-dried to obtain modified resin-coated alumina. Among them, the inlet temperature used for spray drying is 160°C to 170°C, and the outlet temperature is 70°C to 80°C;

[0042] The preparation method of the above-mentioned modified resin coating solution loaded with magnesium is as follows: Add 1 part of polyacrylic acid resin with a molecular weight of 200,000 to 10 parts of absolute ethanol, heat up to 55°C, and stir at a stirring speed of 500 r / min for more than 30 min to dissolve polyacrylic acid in ethanol to obtain a polyacrylic acid solution; Add 0.1 part of magnesium hydroxide to the polyacrylic acid ethanol solution, and continue to stir and mix for 20 min to obtain a magnesium-loaded polyacrylic acid mixed solution; In another container, add 10 parts of thermosetting phenolic resin to 90 parts of absolute ethanol and stir and mix at 800 r / min for 40 min. Add the above-prepared magnesium-loaded polyacrylic acid mixed solution thereto, and stir and mix at a stirring speed of 300 r / min for 35 min to obtain it.

[0043] S3. Calcinate the alumina obtained by drying in S2 in a calcination furnace. First, heat up to 800°C at a speed of 3°C / min, keep it warm for 30 min, then heat up at a speed of 8°C / min, and calcine at 1100°C for 3 h. After cooling, grind it in a ball mill for 1 h. The obtained α-alumina powder is named AYHL-1100.

[0044] Example 2

[0045] This example provides a preparation method of α-alumina powder, including the following steps:

[0046] S1. Add γ-alumina raw material, water, and 2 mol / L oxalic acid solution to a sand mill and soak at 50°C for 120 min. The material-liquid ratio used is 1:2.5, and the usage amount of the oxalic acid solution is 2.5% of the mass of the γ-alumina raw material. After soaking, heat up and sand mill at 85°C for 3 h. Filter the sand mill slurry, wash the filter cake with an appropriate amount of water and then with an appropriate amount of absolute ethanol to obtain a wet alumina material;

[0047] S2. In the mixing tank, add the wet alumina material obtained in S1 to the modified resin coating solution loaded with magnesium. Stir and mix for 30 min at a stirring speed of 500 r / min to obtain a mixed material. Among them, the weight ratio of the modified resin coating solution loaded with magnesium to the γ-alumina raw material in S1 is 8:1. The mixed material is spray-dried to obtain modified resin-coated alumina. Among them, the inlet temperature used for spray drying is 160°C to 170°C, and the outlet temperature is 70°C to 80°C;

[0048] The preparation method of the above-mentioned modified resin coating solution loaded with magnesium is as follows: Add 1 part of polyacrylic acid resin with a molecular weight of 200,000 to 20 parts of absolute ethanol, heat up to 55°C, and stir at a stirring speed of 500 r / min for more than 30 min to dissolve polyacrylic acid in ethanol to obtain a polyacrylic acid solution; Add 0.2 part of magnesium hydroxide to this polyacrylic acid ethanol solution, and continue to stir and mix for 20 min to obtain a magnesium-loaded polyacrylic acid mixed solution; In another container, add 10 parts of thermosetting phenolic resin to 80 parts of absolute ethanol and stir and mix at 800 r / min for 40 min. Add the above-prepared magnesium-loaded polyacrylic acid mixed solution thereto, and stir and mix at a stirring speed of 300 r / min for 35 min to obtain it.

[0049] S3. Calcinate the alumina obtained by drying in S2 in a calcination furnace. First, heat up to 800°C at a rate of 3°C / min, keep it warm for 30 min, then heat up at a rate of 8°C / min, and calcine at 1100°C for 3 h. After cooling, grind it in a ball mill for 1 h. The obtained α-alumina powder is named AYHL-1050.

[0050] Example 3

[0051] This example provides a preparation method of artificial joint ceramic powder, including the following steps:

[0052] 1) Prepare α-alumina AYHL-1100, weigh chromium oxide according to 4.4% of the mass of α-alumina, and weigh yttrium-stabilized zirconia according to 1.7% of the mass of α-alumina. Among them, the content of yttrium oxide in yttrium-stabilized zirconia is 2.5%.

[0053] 2) Perform ball milling and dispersion of the α-alumina powder, chromium oxide, and yttrium-stabilized zirconia in a ball mill for 2 h to obtain it. The obtained artificial joint ceramic powder is named TCFT0-4417.

[0054] Example 4

[0055] This example provides a preparation method of artificial joint ceramic powder, including the following steps:

[0056] 1) Prepare α-aluminum oxide AYHL-1050. Weigh chromium oxide according to 3.8% of the mass of α-aluminum oxide, and weigh yttrium-stabilized zirconia according to 2.3% of the mass of α-aluminum oxide. The content of yttrium oxide in the yttrium-stabilized zirconia is 2.5%.

[0057] 2) Ball mill and disperse the α-aluminum oxide powder, chromium oxide, and yttrium-stabilized zirconia in a ball mill for 2 h to obtain the artificial joint ceramic powder, which is named TCFT5-3823.

[0058] Comparative Example 1

[0059] According to the method of Example 1, the difference is that the method of γ-aluminum oxide raw material S1 is as follows: Add γ-aluminum oxide raw material and water into a sand mill, with a material-to-water ratio of 1:2.5, and perform sand milling and dispersion at room temperature for 3 h. Filter the slurry, wash the filter cake with an appropriate amount of water and then with an appropriate amount of absolute ethanol to obtain wet alumina, and the obtained α-aluminum oxide is named AYHL-P1.

[0060] Comparative Example 2

[0061] According to the method of Example 1, the difference lies in that the methods of S2 and S3 are as follows:

[0062] S2: Add 10 parts of thermosetting phenolic resin into 100 parts of absolute ethanol, and stir and disperse at 800 r / min for 40 min. Add the wet alumina obtained from S1 into the phenolic resin solution, and stir and mix at a stirring speed of 500 r / min according to the weight ratio of phenolic resin to γ-aluminum oxide raw material in S1 of 10:1 for 30 min to obtain a mixture. Spray dry the mixture to obtain resin-coated alumina, and control the inlet temperature of spray drying to be 160 °C - 170 °C and the outlet temperature to be 70 °C - 80 °C;

[0063] S3: Add 0.5% of magnesium oxide by weight to the alumina obtained by drying in S2 and mix evenly. Calcinate in a calcination furnace, heat up at a speed of 8 °C / min, keep the temperature at 1100 °C for 3 h for calcination, cool down and grind in a ball mill for 1 h to obtain the α-aluminum oxide powder, which is named AYHL-P2.

[0064] Comparative Example 3

[0065] According to the method of Example 1, the difference is that the calcination method used in S3 is to directly heat up to 1100 °C at a speed of 8 °C / min, keep the temperature at 1100 °C for 3 h for calcination, cool down and grind in a ball mill for 1 h to obtain the α-aluminum oxide, which is named AYHL-P3.

[0066] Comparative Example 4

[0067] According to the method of Example 3, the difference is that α-aluminum oxide powder AYHL-P1 is used, and the obtained artificial joint ceramic powder is named TCFT-P1.

[0068] Comparative Example 5

[0069] According to the method of Example 3, the difference is that α-aluminum oxide powder AYHL-P2 is used, and the obtained artificial joint ceramic powder is named TCFT-P2.

[0070] Comparative Example 6

[0071] According to the method of Example 3, the difference is that α-aluminum oxide powder AYHL-P3 is used, and the obtained artificial joint ceramic powder is named TCFT-P3.

[0072] Test Example 1

[0073] The α-aluminum oxide powders prepared by the methods of the examples and comparative examples were subjected to the following performance tests. The Na2O content of the α-Al2O3 powder was determined according to GB / T6609.5, the α-phase conversion rate of the powder α-Al2O3 was measured according to the provisions of GB / T6609.32, and D50 and D90 / D10 were measured by laser particle size analysis method. The test results are shown in Table 1 below.

[0074] Table 1: Performance test results of α-aluminum oxide powder

[0075] Sample Name <![CDATA[Sodium oxide content]]> α-Phase Conversion Rate D50 D90 / D10 AYHL-1100 0.07％ 96.7％ 0.35μm 2.51 AYHL-1050 0.08％ 95.9％ 0.32μm 2.23 AYHL-P1 0.13％ 92.1％ 0.58μm 2.57 AYHL-P2 0.11％ 93.5％ 0.41μm 3.04 AYHL-P3 0.08％ 96.2％ 0.54μm 2.98

[0076] It can be seen from Table 1 that compared with Comparative Examples 1 to 3, the sodium oxide content in the α-Al2O3 powders AYHL-1100 and AYHL-1050 prepared in the examples of the present application can be reduced to less than 0.08%. With a calcination temperature of 1050-1100 °C, the α-phase conversion rate of alumina is 95.9% - 96.7%, the average particle size < 0.35 μm, and the particle size distribution is narrow.

[0077] Test Example 2

[0078] After ball milling, granulating, and pressing into shape the artificial joint ceramic powders obtained in the examples and comparative examples, they were sintered at 1350 °C for 3 h, and the performance of the sintered body was tested according to the method in ISO6474. The performance test results are shown in Table 2 below.

[0079] Table 2: Performance test results of sintered body

[0080]

[0081]

[0082] As can be seen from Table 2, for the sintered bodies prepared from the artificial joint ceramic powders of TCFT0-4417 and TCFT5-3823 in the embodiments of the present application, the density of the sintered bodies is above 3.93 g / cm 3 ³, the flexural strength > 335 MPa, and the fracture toughness is above 4.73 MPa·m 0.5 ³, and the wear amount is less than 0.089 mm 3 , and the comprehensive performance is excellent.

[0083] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application and are not intended to limit them; although the present application has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that it is still possible to modify the specific implementation manners of the present application or perform equivalent replacements for some technical features, and they should all be covered within the scope of the technical solutions claimed in the present application.

Claims

1. A method for preparing α-aluminum oxide powder, characterized in that, It includes the following steps: S1. Using γ-aluminum oxide as the raw material, adding water and organic acid, soaking at 20°C to 80°C, then performing sand grinding at 50°C to 90°C, filtering the slurry and washing the filter cake to obtain wet aluminum oxide; S2. Stirring and mixing the wet aluminum oxide obtained in S1 and the modified resin coating solution loaded with magnesium, and performing spray drying granulation to obtain modified resin-coated aluminum oxide; Among them, the modified resin coating solution loaded with magnesium is obtained by uniformly stirring and dispersing magnesium hydroxide in an ethanol solution of polyacrylic acid resin, and then mixing and modifying it with phenolic resin; The phenolic resin is a thermosetting phenolic resin; S3. Calcining and grinding the aluminum oxide obtained by drying in S2 to obtain α-aluminum oxide powder.

2. The preparation method of α-aluminum oxide powder according to claim 1, characterized in that, The material-liquid ratio used in the soaking in S1 is 1:1.2 to 2.6; The organic acid in S1 is one or more of acetic acid, citric acid, oxalic acid, and acrylic acid, and the concentration of the organic acid is 1 mol / L to 2 mol / L; The usage amount of the organic acid in S1 is 1% to 5% of the mass of the γ-aluminum oxide; 3. The preparation method of the α-aluminum oxide powder according to claim 1, wherein The soaking time in S1 is 60 min to 180 min; the sand grinding time is 2 h to 4 h.

4. The preparation method of α-aluminum oxide powder according to claim 1, characterized in that The washing method in S1 is to first wash the filter cake with an appropriate amount of water and then wash it with an appropriate amount of absolute ethanol.

5. The preparation method of α-aluminum oxide powder according to claim 1, characterized in that, The inlet temperature of the spray drying used in the spray granulation in S2 is 160°C to 170°C, and the outlet temperature is 70°C to 80°C.

6. The preparation method of the α-aluminum oxide powder according to claim 1, characterized in that, The mass ratio of the polyacrylic acid resin, the phenolic resin, the magnesium hydroxide, and the ethanol in S2 is 1 to 2:8 to 10:0.1 to 0.2:

100.

7. The preparation method of the α-aluminum oxide powder according to claim 1 or 6, characterized in that, The preparation method of the modified resin coating solution loaded with magnesium in S2 is: 1) According to the formula amount, adding polyacrylic acid resin to 1 / 10 to 2 / 10 of anhydrous ethanol, and heating to 50°C to 60°C under stirring at 500 r / min to dissolve the polyacrylic acid resin in ethanol to obtain an ethanol solution of polyacrylic acid resin; 2) Adding magnesium hydroxide to the ethanol solution of polyacrylic acid resin in step 1) and stirring for 20 min to 40 min to obtain a magnesium-loaded polyacrylic acid resin mixture; 3) Adding the remaining anhydrous ethanol to the phenolic resin and stirring and mixing at 800 r / min for 35 min to 50 min, then adding the magnesium-loaded polyacrylic acid resin mixture in step 2) above, and continuing to stir and mix at 300 r / min for 30 min to 50 min to obtain it.

8. An α-aluminum oxide artificial joint ceramic powder, characterized in that, Its preparation raw materials include: α-aluminum oxide powder, and the α-aluminum oxide powder is prepared by the method according to any one of claims 1-7; 3.8% to 4.4% of chromium oxide based on the mass of the α-aluminum oxide powder; 1.7% to 2.3% of yttrium-stabilized zirconia based on the mass of the α-aluminum oxide powder; among them, the content of yttrium oxide in the yttrium-stabilized zirconia is 1% to 5%.

9. The preparation method of the α-aluminum oxide artificial joint ceramic powder as described in claim 8, characterized in that, According to parts by weight, ball milling and mixing the α-aluminum oxide powder, the chromium oxide, and the yttrium-stabilized zirconia to obtain it.

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