CN117417180B - Preparation method of alpha-alumina powder, artificial joint ceramic powder and preparation method - Google Patents

Abstract

The present invention relates to the technical field of artificial joint materials, and specifically to a preparation method of α-alumina powder, an artificial joint ceramic powder and a preparation method. The preparation method of the α-alumina powder of the present invention uses γ-alumina as a raw material, adds water and an organic acid for soaking, sand-grinds the slurry for filtering and washing the filter cake to obtain wet alumina; the wet alumina material and the modified resin coating liquid loaded with magnesium are stirred and mixed, spray-dried and granulated to obtain modified resin-coated alumina; the dried alumina is calcined and ground to obtain α-alumina powder. The method can be used for the preparation of artificial joint ceramic powder. The test results show that the obtained artificial joint has high bending strength, fracture toughness and wear resistance, and excellent comprehensive performance.

Description

Preparation method of alpha-alumina powder, artificial joint ceramic powder and preparation method

Technical Field

The invention relates to the technical field of artificial joint materials, in particular to a preparation method of alpha-alumina powder, artificial joint ceramic powder and a preparation method thereof.

Background

Many patients suffering from bone joint diseases are suffering from aging population, diseases, wounds and the like, and patients who need artificial joint replacement are increasing. Alumina has the advantages of stable chemical property, good biocompatibility, higher hardness, wear resistance and the like, and gradually becomes an important raw material for preparing artificial joints.

The key point of the preparation of the artificial joint ceramic sintered body with excellent performance is to obtain high-quality alpha-Al ₂O₃ powder and ceramic powder formula. The alpha-alumina powder prepared by calcining and crystal-transferring the gamma-alumina which is cheap and easy to obtain is used as a raw material, so that a large amount of alpha-alumina powder can be rapidly obtained, but the alpha-alumina powder prepared by the process has the problems of high content of harmful impurity sodium, coarse particles, uneven particle size distribution and the like.

Based on the above, the application aims to improve the prior art, prepare and obtain the alpha-Al ₂O₃ powder with superfine, narrower particle size distribution and good dispersibility by taking gamma-alumina as a raw material, and obtain the artificial joint ceramic powder with excellent performance by taking the alpha-Al ₂O₃ powder as a raw material for formula design.

Disclosure of Invention

The first object of the present invention is to provide a method for preparing alpha-alumina powder, which can use existing production line, is convenient for process implementation and application, and can obtain alpha-Al ₂O₃ powder with fine particle size, narrow particle size distribution and good dispersibility by calcining at a lower temperature.

The second purpose of the invention is to provide the artificial joint ceramic powder which can be used for firing the artificial joint, and the artificial joint obtained by firing has higher bending strength, fracture toughness and wear resistance and has excellent comprehensive performance.

The third object of the invention is to provide a preparation method of the artificial joint ceramic powder, which has simple process, convenient implementation and application, and the artificial joint obtained by firing has higher bending strength, fracture toughness and wear resistance and excellent comprehensive performance.

In order to achieve the above purpose, the invention adopts the following technical scheme:

the first object of the application is to provide a method for preparing alpha-alumina powder, comprising the following steps:

s1, taking gamma-alumina as a raw material, adding water and organic acid, soaking at 20-80 ℃, sanding at 50-90 ℃, filtering the slurry, and washing a filter cake to obtain an alumina wet material;

s2, stirring and mixing the alumina wet material obtained in the step S1 and the modified resin coating liquid loaded with magnesium, and performing spray drying granulation to obtain modified resin coated alumina;

The magnesium-loaded modified resin coating liquid is prepared by uniformly stirring and dispersing magnesium hydroxide in an ethanol solution of polyacrylic acid, and then mixing and modifying with phenolic resin;

S3, drying the S2 to obtain alumina, and calcining and grinding to obtain alpha-alumina powder.

Further, the ratio of the feed liquid adopted in the soaking in the S1 is 1:1.2-2.6;

The organic acid in the 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-2 mol/L;

The using amount of the organic acid in the S1 is 1% -5% of the mass of the gamma-alumina.

Further, the soaking time of the S1 is 60-180 min, and the sanding time is 2-4 h.

The washing method of S1 is that the filter cake is washed by proper amount of water and then is washed by proper amount of absolute ethyl alcohol.

Further, the inlet temperature of spray drying adopted in the spray granulation in the step S2 is 160-170 ℃ and the outlet temperature is 70-80 ℃.

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

Further, the preparation method of the modified resin coating liquid loaded with magnesium in S2 comprises the following steps:

1) According to the formula amount, adding polyacrylic resin into absolute ethyl alcohol with the ratio of 1/10-2/10, and heating to 50-60 ℃ under the stirring of 500r/min to dissolve the polyacrylic resin in the ethyl alcohol to obtain a polyacrylic acid solution;

2) Adding magnesium hydroxide into the polyacrylic acid solution in the step 1), and stirring for 20-40 min to obtain a magnesium-loaded polyacrylic acid mixed solution;

3) Adding the rest of absolute ethyl alcohol into phenolic resin, stirring and mixing for 35-50 min at 800r/min, adding the magnesium-loaded polyacrylic acid mixed solution obtained in the step 2), and continuously stirring and mixing for 30-50 min at 300r/min to obtain the magnesium-loaded polyacrylic acid mixed solution.

Further, the phenolic resin in S2 is a thermosetting phenolic resin.

The second object of the application is to provide an alpha-alumina artificial joint ceramic powder, which is prepared from the following raw materials:

an alpha-alumina powder prepared according to the method of any one of claims 1 to 8;

3.8-4.4% of chromium oxide by mass of the alpha-alumina powder;

The alpha-alumina powder comprises 1.7% -2.3% of yttrium-stabilized zirconia, wherein the content of yttrium oxide in the yttrium-stabilized zirconia is 1% -5%.

The third object of the application is to provide the preparation method of the alpha-alumina artificial joint ceramic powder, which is characterized in that the alpha-alumina powder, the chromium oxide and the yttrium-stabilized zirconia are subjected to ball milling and uniformly mixing according to parts by weight.

Compared with the prior art, the invention has the beneficial effects that:

(1) According to the preparation method of the alpha alumina powder, the magnesium-loaded modified resin glue solution is used as the particle protecting agent for alumina calcination, the acting force between hydroxyl groups in magnesium hydroxide molecules and carboxyl groups in a polyacrylic resin structure is utilized to enable magnesium hydroxide to be combined on polyacrylic resin, and then the good compatibility between the polyacrylic resin and phenolic resin is utilized to prepare the uniform modified resin glue solution. The selected phenolic resin has good thermal stability, has long-time particle protection effect on alumina in the calcination process, and effectively reduces the agglomeration phenomenon of the alumina in the calcination process. Meanwhile, by means of the dispersion effect of the modified resin glue solution, magnesium loaded in the glue solution can be uniformly distributed on the surface of aluminum oxide, and magnesium oxide formed by decomposing magnesium in calcination is used as a seed crystal inducer, so that the phase transition temperature of alpha-aluminum oxide can be effectively reduced, the coarsening condition of crystal grains caused by powder sintering is improved, the height Wen Tuanju of the powder is improved, and alpha-Al ₂O₃ powder with fine particle size, narrow particle size distribution and good dispersibility is obtained by calcination at a lower temperature.

(2) The invention takes cheap gamma-alumina as raw material, adds organic acid and water for soaking and sand grinding at high temperature, and refines the granularity of powder by utilizing the crushing effect of sand grinding, thereby being beneficial to separating out impurities, and the separated impurities are removed by subsequent filtering and washing. In addition, the organic acid added in the sand grinding can also prevent the secondary agglomeration of the powder generated among grains in the sand grinding process, so that the alumina powder has better dispersibility in the subsequent mixing with the modified resin glue solution.

(3) The alpha-alumina artificial joint ceramic powder provided by the invention is suitable for firing the artificial joint ceramic body, and the obtained artificial joint has higher bending strength, fracture toughness and wear resistance and excellent comprehensive performance.

Detailed Description

The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

The gamma-alumina raw material adopted in the embodiment of the invention has a D50 of 20 μm and a chemical composition (weight) of ：Al₂O₃ 94.82％、SiO₂ 0.024％、Fe₂O₃ 0.026％、Na₂O 0.32％、CaO0.02％、MgO0.01％、K₂O 0.021％、 and a reduction of 4.759%.

The methods are conventional methods unless otherwise specified, and the starting materials are commercially available from the public sources unless otherwise specified.

Example 1

The embodiment provides a preparation method of alpha-alumina powder, which comprises the following steps:

S1, adding a gamma-alumina raw material, water and 1.5mol/L oxalic acid solution into a sand mill, soaking for 120min at 50 ℃, wherein the adopted feed-liquid ratio is 1:2, the use amount of the oxalic acid solution is 3% of the mass of the gamma-alumina raw material, heating after soaking, sanding for 3h at 85 ℃, filtering the sanded slurry, washing a filter cake with a proper amount of water, and washing with a proper amount of absolute ethyl alcohol to obtain an alumina wet material;

s2, adding the alumina wet material obtained in the step S1 into the modified resin coating liquid loaded with magnesium in a mixing tank, and stirring and mixing for 30min at the stirring rotating speed of 500r/min to obtain a mixture. Wherein the weight ratio of the modified resin coating liquid loaded with magnesium to the gamma-alumina raw material in S1 is 8:1, and the mixture is subjected to spray drying to obtain modified resin coated alumina, wherein the inlet temperature adopted by the spray drying is 160-170 ℃ and the outlet temperature is 70-80 ℃;

The preparation method of the magnesium-loaded modified resin coating liquid comprises the steps of adding 1 part of polyacrylic resin with the molecular weight of 20 ten thousand into 10 parts of absolute ethyl alcohol, heating to 55 ℃, stirring at the stirring speed of 500r/min for more than 30min to enable polyacrylic acid to be dissolved in the ethyl alcohol to obtain a polyacrylic acid solution, adding 0.1 part of magnesium hydroxide into the polyacrylic acid ethyl alcohol solution, continuously stirring and mixing for 20min to obtain a magnesium-loaded polyacrylic acid mixed liquid, adding 10 parts of thermosetting phenolic resin into 90 parts of absolute ethyl alcohol in another container, stirring and mixing for 40min at the stirring speed of 800r/min, adding the prepared magnesium-loaded polyacrylic acid mixed liquid, and stirring and mixing for 35min at the stirring speed of 300r/min to obtain the magnesium-loaded polyacrylic acid mixed liquid.

S3, calcining the alumina obtained by drying the S2 in a calciner, heating to 800 ℃ at the speed of 3 ℃ per minute, preserving heat for 30 minutes, heating at the speed of 8 ℃ per minute, preserving heat for 3 hours at the temperature of 1100 ℃, calcining, grinding for 1 hour in a ball mill after cooling, and obtaining the alpha-alumina powder named AYHL-1100.

Example 2

The embodiment provides a preparation method of alpha-alumina powder, which comprises the following steps:

S1, adding a gamma-alumina raw material, water and 2mol/L oxalic acid solution into a sand mill, soaking for 120min at 50 ℃, wherein the adopted feed-liquid ratio is 1:2.5, the use amount of the oxalic acid solution is 2.5% of the mass of the gamma-alumina raw material, heating after soaking, sanding for 3h at 85 ℃, filtering the sanded slurry, washing a filter cake with a proper amount of water, and washing with a proper amount of absolute ethyl alcohol to obtain an alumina wet material;

S2, adding the alumina wet material obtained in the step S1 into the magnesium-loaded modified resin coating liquid in a mixing tank, and stirring and mixing for 30min at the stirring rotating speed of 500r/min to obtain a mixture. Wherein the weight ratio of the modified resin coating liquid loaded with magnesium to the gamma-alumina raw material in S1 is 8:1, and the mixture is subjected to spray drying to obtain modified resin coated alumina, wherein the inlet temperature adopted by the spray drying is 160-170 ℃ and the outlet temperature is 70-80 ℃;

The preparation method of the magnesium-loaded modified resin coating liquid comprises the steps of adding 1 part of polyacrylic resin with the molecular weight of 20 ten thousand into 20 parts of absolute ethyl alcohol, heating to 55 ℃, stirring at the stirring speed of 500r/min for more than 30min to enable polyacrylic acid to be dissolved in the ethyl alcohol to obtain a polyacrylic acid solution, adding 0.2 part of magnesium hydroxide into the polyacrylic acid ethyl alcohol solution, continuously stirring and mixing for 20min to obtain a magnesium-loaded polyacrylic acid mixed liquid, adding 10 parts of thermosetting phenolic resin into 80 parts of absolute ethyl alcohol in another container, stirring and mixing for 40min at the stirring speed of 800r/min, adding the prepared magnesium-loaded polyacrylic acid mixed liquid, and stirring and mixing for 35min at the stirring speed of 300r/min to obtain the magnesium-loaded modified resin coating liquid.

S3, calcining the alumina obtained by drying the S2 in a calciner, heating to 800 ℃ at the speed of 3 ℃ per minute, preserving heat for 30 minutes, heating at the speed of 8 ℃ per minute, preserving heat for 3 hours at the temperature of 1100 ℃, calcining, grinding for 1 hour in a ball mill after cooling, and obtaining the alpha-alumina powder named AYHL-1050.

Example 3

The embodiment provides a preparation method of artificial joint ceramic powder, which comprises the following steps:

1) Preparing alpha-alumina AYHL-1100, weighing chromium oxide according to 4.4% of the alpha-alumina mass, and weighing yttrium-stabilized zirconia according to 1.7% of the alpha-alumina mass, wherein the content of yttrium oxide in the yttrium-stabilized zirconia is 2.5%.

2) And (3) performing ball milling and dispersing on the alpha-alumina powder, the chromium oxide and the yttrium stabilized zirconia in a ball mill for 2 hours to obtain the artificial joint ceramic powder which is named TCFT to 4417.

Example 4

The embodiment provides a preparation method of artificial joint ceramic powder, which comprises the following steps:

1) Preparing alpha-alumina AYHL-1050, weighing chromium oxide according to 3.8% of the alpha-alumina, weighing yttrium-stabilized zirconia according to 2.3% of the alpha-alumina, wherein the content of yttrium oxide in the yttrium-stabilized zirconia is 2.5%.

2) And (3) performing ball milling and dispersing on the alpha-alumina powder, the chromium oxide and the yttrium stabilized zirconia in a ball mill for 2 hours to obtain the artificial joint ceramic powder which is named TCFT-3823.

Comparative example 1

The procedure of example 1 was followed except that the gamma-alumina raw material S1 was prepared by adding gamma-alumina raw material and water in a sand mill at a ratio of 1:2.5, sand-dispersing at room temperature for 3 hours, filtering the slurry, washing the filter cake with a suitable amount of water, and washing with a suitable amount of absolute ethanol to give an alumina wet material, and the obtained alpha-alumina was designated AYHL-P1.

Comparative example 2

The procedure of example 1 was followed except that the procedures of S2 and S3 were as follows:

S2, adding 10 parts of thermosetting phenolic resin into 100 parts of absolute ethyl alcohol, and stirring and dispersing for 40 minutes at 800 r/min. Adding the alumina wet material obtained in the step S1 into phenolic resin feed liquid, stirring and mixing for 30min at the stirring speed of 500r/min according to the weight ratio of the phenolic resin to the gamma-alumina raw material in the step S1 to obtain a mixture, performing spray drying on the mixture to obtain resin coated alumina, and controlling the inlet temperature of spray drying to be 160-170 ℃ and the outlet temperature to be 70-80 ℃;

S3, adding magnesium oxide accounting for 0.5% of the weight of the aluminum oxide obtained by drying in the S2, uniformly mixing, calcining in a calciner, heating at the speed of 8 ℃ per minute, preserving heat for 3 hours at the temperature of 1100 ℃, calcining, grinding in a ball mill for 1 hour after cooling, and obtaining the alpha-aluminum oxide powder named AYHL-P2.

Comparative example 3

The method of example 1 was followed except that the calcination method used in S3 was one in which the temperature was directly raised to 1100℃at 8℃/min for 3h calcination, and the resulting alpha-alumina was milled in a ball mill for 1h after the temperature was lowered, and the resulting alpha-alumina was designated AYHL-P3.

Comparative example 4

The procedure of example 3 was followed except that alpha-alumina powder AYHL-P1 was used, and the resulting artificial joint ceramic powder was designated TCFT-P1.

Comparative example 5

The procedure of example 3 was followed except that alpha-alumina powder AYHL-P2 was used, and the resulting artificial joint ceramic powder was designated TCFT-P2.

Comparative example 6

The procedure of example 3 was followed except that alpha-alumina powder AYHL-P3 was used, and the resulting artificial joint ceramic powder was designated TCFT-P3.

Test example 1

The following performance tests were carried out on the alpha-alumina powder prepared by the methods of examples and comparative examples, the Na ₂ O content of the alpha-Al ₂O₃ powder was measured according to the GB/T6609.5 rule, the alpha-Al ₂O₃ alpha-phase conversion of the powder was measured according to the GB/T6609.32 rule, and the D50 and D90/D10 were measured by a laser particle size analysis method, and the test results are shown in Table 1 below.

TABLE 1 results of Performance test of alpha-alumina powder

Sample name	Na 2 O content	Alpha-phase conversion	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

As can be seen from Table 1, compared with comparative examples 1-3, the content of sodium oxide in the alpha-Al ₂O₃ powder AYHL-1100 and AYHL-1050 prepared by the embodiment of the application can be reduced to below 0.08%, the alpha-phase conversion rate of alumina is 95.9% -96.7% by adopting the calcining temperature of 1050-1100 ℃, the average particle diameter is less than 0.35 μm, and the particle diameter distribution is narrow.

Test example 2

After ball milling, granulating and press molding of the artificial joint ceramic powders obtained in examples and comparative examples, the sintered bodies were heat-preserved at 1350 ℃ for 3 hours, and the performance of the sintered bodies was tested according to the method in ISO6474, and the results of the performance test are shown in table 2 below.

TABLE 2 Performance test results of sintered bodies

As can be seen from Table 2, the sintered bodies prepared by using the artificial joint ceramic powders of examples TCFT to 4417 and TCFT to 3823 of the present application have a sintered body density of 3.93g/cm ³ or more, a flexural strength of >335MPa, a fracture toughness of 4.73 MPa.m ^0.5 or more, a wear amount of less than 0.089mm ³, and excellent overall properties.

It should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present application may be modified or some technical features may be equivalently replaced, and all the modifications are included in the scope of the technical solution of the present application.

Claims (9)

1. The preparation method of the alpha-alumina powder is characterized by comprising the following steps of:

s1, taking gamma-alumina as a raw material, adding water and organic acid, soaking at 20-80 ℃, sanding at 50-90 ℃, filtering the slurry, and washing a filter cake to obtain an alumina wet material;

s2, stirring and mixing the alumina wet material obtained in the step S1 and the modified resin coating liquid loaded with magnesium, and performing spray drying granulation to obtain modified resin coated alumina;

The magnesium-loaded modified resin coating liquid is prepared by uniformly stirring and dispersing magnesium hydroxide in an ethanol solution of polyacrylic resin, and then mixing and modifying with phenolic resin;

the phenolic resin is thermosetting phenolic resin;

S3, drying the S2 to obtain alumina, and calcining and grinding to obtain alpha-alumina powder.

2. The method for preparing alpha-alumina powder according to claim 1, wherein the ratio of feed to liquid used for soaking in S1 is 1:1.2-2.6;

The organic acid in the 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-2 mol/L;

The using amount of the organic acid in the S1 is 1% -5% of the mass of the gamma-alumina.

3. The method for preparing the alpha-alumina powder according to claim 1, wherein the S1 soaking time is 60-180 min, and the sanding time is 2-4 h.

4. The method for preparing α -alumina powder according to claim 1, wherein the washing step S1 is performed by washing the filter cake with a proper amount of water and then with a proper amount of absolute ethanol.

5. The method for preparing α -alumina powder according to claim 1, wherein the spray drying used in the spray granulation of S2 has an inlet temperature of 160 ℃ to 170 ℃ and an outlet temperature of 70 ℃ to 80 ℃.

6. The method for preparing α -alumina powder according to claim 1, wherein the mass ratio of the polyacrylic resin, the phenolic resin, the magnesium hydroxide and the ethanol is 1-2:8-10:0.1-0.2:100.

7. The method for producing an α -alumina powder according to claim 1 or 6, wherein the method for producing the magnesium-supporting modified resin coating liquid of S2 comprises:

1) According to the formula amount, adding polyacrylic resin into absolute ethyl alcohol with the ratio of 1/10-2/10, and heating to 50-60 ℃ under the stirring of 500r/min to dissolve the polyacrylic resin in the ethyl alcohol to obtain an ethanol solution of the polyacrylic resin;

2) Adding magnesium hydroxide into the ethanol solution of the polyacrylic resin in the step 1), and stirring for 20-40 min to obtain a magnesium-loaded polyacrylic resin mixed solution;

3) Adding the rest of absolute ethyl alcohol into phenolic resin, stirring and mixing for 35-50 min at 800r/min, adding the magnesium-loaded polyacrylic resin mixed solution obtained in the step 2), and continuously stirring and mixing for 30-50 min at 300 r/min.

8. The alpha-alumina artificial joint ceramic powder is characterized by comprising the following raw materials:

An alpha-alumina powder prepared according to the method of any one of claims 1 to 7;

3.8-4.4% of chromium oxide by mass of the alpha-alumina powder;

The alpha-alumina powder comprises 1.7% -2.3% of yttrium-stabilized zirconia, wherein the content of yttrium oxide in the yttrium-stabilized zirconia is 1% -5%.

9. The method for preparing the alpha-alumina artificial joint ceramic powder according to claim 8, which is characterized in that the alpha-alumina powder, the chromium oxide and the yttrium-stabilized zirconia are subjected to ball milling and uniformly mixing according to parts by weight.