Processing technology of zirconia ceramic with antibacterial property

Abstract

The invention discloses a processing technology of zirconia ceramic with an antibacterial property. The invention relates to the technical field of zirconia ceramics, which comprises two processing technologies, the first processing technology specifically comprises the following steps: step 1, uniformly mixing zirconia powder and an antibacterial material, then carrying out dry ball milling, and then sieving; step 2, adding a binder and a dispersant, and stirring until the mixture is uniformly mixed; and step 3, loading the preformed material into a sheath, performing sealing treatment, then putting the sheath into a high-pressure container in an isostatic pressing machine, and increasing the pressure at the pressure increasing speed of 1-5MPa / min. According to the processing technology of the zirconia ceramic with the antibacterial property, the antibacterial materials are mixed and added, so that the antibacterial materials release zinc ions or gallium ions in a ceramic system, the released ions can interact with groups with negative electricity on bacterial cell membranes, the integrity and permeability of the cell membranes are destroyed, bacterial contents are leaked, and the antibacterial property of the zirconia ceramic is improved. And the bacteria are killed.

Description

Technical Field

[0001] The invention relates to the technical field of zirconia ceramics, in particular to a processing technology of zirconia ceramics with antibacterial properties. Background Art

[0002] Pure zirconium oxide is a white solid. It will appear gray or light yellow when it contains impurities. It can also show various other colors by adding colorants. The molecular weight of pure zirconium oxide is 123.22, and the theoretical density is 5.89g / cm 3 , melting point is 2715℃; usually contains a small amount of hafnium oxide, which is difficult to separate, but has no significant effect on the performance of zirconium oxide. Zirconia has three crystal forms: monoclinic, tetragonal, and cubic. At room temperature, zirconium oxide only appears in the monoclinic phase, which turns into the tetragonal phase when heated to about 1100℃, and turns into the cubic phase when heated to a higher temperature.

[0003] Existing antibacterial ceramics are generally made by attaching metals or metal compound materials with antibacterial activity to the surface of the ceramic, such as metallic silver. However, metallic silver is relatively expensive and costly, and is easily oxidized when exposed to air. Therefore, the present invention proposes a processing technology for zirconia ceramics with antibacterial properties to solve the above-mentioned problems. Summary of the invention

[0004] 1. Technical issues to be resolved

[0005] In view of the deficiencies in the prior art, the present invention provides a processing technology for antibacterial zirconia ceramics, which solves the problems mentioned in the above background technology.

[0006] (II) Technical solution

[0007] To achieve the above objectives, the present invention is implemented by the following technical solutions: A processing technology for antibacterial zirconia ceramics includes two processing technologies, and the first processing technology specifically includes the following steps:

[0008] Step 1: Mix the zirconium oxide powder and the antibacterial material evenly, then use dry ball milling and then sieve;

[0009] Step 2: Add binder and dispersant, and stir until mixed evenly;

[0010] Step 3: Put the preformed material into the bag, seal it, and then put it into the high-pressure container in the isostatic press. Increase the pressure at a rate of 1-5 MPa / min. After reaching the target pressure value, maintain the pressure for 30-60 minutes, and then reduce the pressure at a rate of 1-3 MPa / min until the pressure value is zero.

[0011] Step 4: Place the material after isostatic pressing into a calcining furnace, heat it to 1400° C., and sinter it for 2 hours to obtain zirconia ceramics with antibacterial properties.

[0012] Preferably, the weight proportions of the components added are: 93-97 parts of zirconium oxide powder, 3-7 parts of antibacterial material, 2.5-4 parts of binder, and 4-7 parts of dispersant.

[0013] Preferably, in step 1, the antibacterial material is selected from any one of zinc oxide and gallium oxide.

[0014] Preferably, in the step 2, the binder is polyvinyl alcohol; and the dispersant is ammonium citrate.

[0015] Preferably, in step 4, the heating rate is 5-10°C / min.

[0016] Preferably, the second processing technology of the antibacterial zirconia ceramic specifically comprises the following steps:

[0017] S1. Add a stabilizer to the zirconium oxide, then pour it into a ball mill for ball milling, then put the powder into a bag, seal it, and then put it into a high-pressure container in an isostatic press, and increase the pressure at a pressure increase rate of 1-5MPa / min. After reaching the target pressure value, maintain the pressure for 30-60min, and then reduce the pressure at a pressure reduction rate of 1-3MPa / min until the pressure value is zero, to obtain a zirconium oxide block;

[0018] S2, placing the zirconia block in a calcining furnace, heating to 1000°C, and sintering for 2h;

[0019] S3. Immerse the sintered zirconium oxide block in an antibacterial solution, then take it out, place it in a calcining furnace, heat it to 1400° C., and sinter it for 2 hours to obtain zirconium oxide ceramics with antibacterial properties.

[0020] Preferably, the antibacterial solution is selected from any one of a zinc fluoride dispersion and a silver nitrate solution.

[0021] Preferably, in S2 and S3, the heating rate is 5-10°C / min.

[0022] (III) Beneficial effects

[0023] The present invention provides a processing technology for antibacterial zirconium oxide ceramics. Compared with the prior art, it has the following beneficial effects:

[0024] (1) The processing technology of the antibacterial zirconia ceramics is to release zinc ions or gallium ions in the ceramic system by mixing and adding antibacterial materials. The released ions can interact with negatively charged groups on bacterial cell membranes, destroy the integrity and permeability of the cell membranes, and cause the leakage of bacterial contents, thereby killing the bacteria. In addition, in the ceramic system in which zinc oxide or gallium oxide is mixed with zirconium oxide, when excited by external energy (such as light, mechanical vibration, etc.), zinc oxide or gallium oxide will undergo electronic transitions to produce some highly reactive substances, such as hydroxyl radicals (·OH), superoxide anion radicals (O 2 · - ) etc. These free radicals can attack bacterial cell membranes, proteins, nucleic acids and other biological macromolecules, causing bacterial damage and death.

[0025] (2) The processing technology of the zirconia ceramic with antibacterial properties is as follows: the zirconia block is immersed in a zinc fluoride solution, so that during the immersion process, the zinc ions and fluorine ions in the zinc fluoride solution will adhere to the surface of the zirconia ceramic, and some zinc ions will diffuse into the lattice of the zirconia ceramic, interact with phospholipids, proteins and other components on the bacterial cell membrane, destroy the integrity and permeability of the cell membrane, cause the bacterial contents to leak, and thus kill the bacteria; in addition, the zinc ions can also enter the bacteria, combine with various enzymes and proteins in the bacteria, inhibit the metabolism and reproduction process of the bacteria, and the fluorine ions combine with the cations on the surface of the bacterial cell membrane, change the charge distribution and permeability of the cell membrane, thereby inhibiting the growth of bacteria; and a modified layer containing elements such as zinc and fluorine is formed on the surface of the zirconia ceramic, which improves the hydrophilicity of the surface of the zirconia ceramic, making it more difficult for bacteria to adhere to and grow on the ceramic surface;

[0026] By immersing the zirconium oxide block in a silver nitrate solution, the silver ions in the silver nitrate solution adhere to the surface of the zirconium oxide ceramic, combine with the proteins and enzymes on the bacterial cell membrane, destroy the integrity and permeability of the cell membrane, cause the leakage of bacterial contents, and ultimately kill the bacteria. At the same time, after the silver ions enter the bacterial cells, they will combine with the bacterial DNA, hinder the replication and transcription of the DNA, and inhibit the reproduction of the bacteria. The silver ions will also interfere with the electron transport chain in the bacterial cells, affect the energy metabolism process, and make the bacteria unable to grow and reproduce normally due to lack of energy. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 A comparison chart of the antibacterial performance tests of Examples 1-3 and Comparative Example 1 provided by the present invention;

[0028] Figure 2 A comparison chart of the antibacterial performance tests of Examples 4-6 and Comparative Example 2 provided by the present invention;

[0029] Figure 3A comparison chart of the antibacterial performance test of Example 7 and Comparative Example 3 provided by the present invention;

[0030] Figure 4 The antibacterial performance test comparison between Example 8 and Comparative Example 4 provided by the present invention. DETAILED DESCRIPTION

[0031] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] Example 1

[0033] A processing technology for antibacterial zirconia ceramics specifically comprises the following steps:

[0034] Step 1: Mix 93 g of zirconium oxide powder and 7 g of zinc oxide evenly, then dry-mill and sieve;

[0035] Step 2: Add 4g of polyvinyl alcohol and 7g of ammonium citrate and stir until the mixture is evenly mixed;

[0036] Step 3: Put the preformed material into the bag, seal it, and then put it into the high-pressure container in the isostatic press. Increase the pressure at a pressure increase rate of 1 MPa / min. After reaching the target pressure value, maintain the pressure for 30 minutes, and then reduce the pressure at a pressure reduction rate of 1 MPa / min until the pressure value is zero.

[0037] Step 4: Place the material after isostatic pressing into a calcining furnace, heat it to 1400° C. at a heating rate of 5° C. / min, and sinter for 2 hours to obtain zirconia ceramics with antibacterial properties.

[0038] Example 2

[0039] A processing technology for antibacterial zirconia ceramics specifically comprises the following steps:

[0040] Step 1: Mix 95 g of zirconium oxide powder and 5 g of zinc oxide evenly, then dry-mill and sieve;

[0041] Step 2: Add 3.5 g of polyvinyl alcohol and 5 g of ammonium citrate and stir until well mixed;

[0042] Step 3: Put the preformed material into the bag, seal it, and then put it into the high-pressure container in the isostatic press. Increase the pressure at a pressure increase rate of 35 MPa / min. After reaching the target pressure value, maintain the pressure for 45 minutes, and then reduce the pressure at a pressure reduction rate of 2 MPa / min until the pressure value is zero.

[0043] Step 4: Place the isostatically pressed material into a calcining furnace, heat it to 1400° C. at a heating rate of 6° C. / min, and sinter for 2 hours to obtain antibacterial zirconia ceramics.

[0044] Example 3

[0045] A processing technology for antibacterial zirconia ceramics specifically comprises the following steps:

[0046] Step 1: Mix 93 g of zirconium oxide powder and 7 g of zinc oxide evenly, then dry-mill and sieve;

[0047] Step 2: Add 2.5 g of polyvinyl alcohol and 4 g of ammonium citrate and stir until well mixed;

[0048] Step 3: Put the preformed material into the bag, seal it, and then put it into the high-pressure container in the isostatic press. Increase the pressure at a pressure increase rate of 5 MPa / min. After reaching the target pressure value, maintain the pressure for 60 minutes, and then reduce the pressure at a pressure reduction rate of 3 MPa / min until the pressure value is zero.

[0049] Step 4: Place the isostatically pressed material into a calcining furnace, heat it to 1400° C. at a heating rate of 10° C. / min, and sinter for 2 hours to obtain antibacterial zirconia ceramics.

[0050] Example 4

[0051] A processing technology for antibacterial zirconia ceramics specifically comprises the following steps:

[0052] Step 1: Mix 99 g of zirconium oxide powder and 1 g of gallium oxide evenly, then dry-mill and sieve;

[0053] Step 2: Add 4g of polyvinyl alcohol and 7g of ammonium citrate and stir until the mixture is evenly mixed;

[0054] Step 3: Put the preformed material into the bag, seal it, and then put it into the high-pressure container in the isostatic press. Increase the pressure at a pressure increase rate of 1 MPa / min. After reaching the target pressure value, maintain the pressure for 30 minutes, and then reduce the pressure at a pressure reduction rate of 1 MPa / min until the pressure value is zero.

[0055] Step 4: Place the material after isostatic pressing into a calcining furnace, heat it to 1400° C. at a heating rate of 5° C. / min, and sinter for 2 hours to obtain zirconia ceramics with antibacterial properties.

[0056] Example 5

[0057] A processing technology for antibacterial zirconia ceramics specifically comprises the following steps:

[0058] Step 1: Mix 99.5 g of zirconium oxide powder and 0.5 g of gallium oxide evenly, then dry-mill and sieve;

[0059] Step 2: Add 3.5 g of polyvinyl alcohol and 6 g of ammonium citrate and stir until well mixed;

[0060] Step 3: Put the preformed material into the bag, seal it, and then put it into the high-pressure container in the isostatic press. Increase the pressure at a pressure increase rate of 3 MPa / min. After reaching the target pressure value, maintain the pressure for 45 minutes, and then reduce the pressure at a pressure reduction rate of 2 MPa / min until the pressure value is zero.

[0061] Step 4: Place the isostatically pressed material into a calcining furnace, heat it to 1400° C. at a heating rate of 6° C. / min, and sinter for 2 hours to obtain antibacterial zirconia ceramics.

[0062] Example 6

[0063] A processing technology for antibacterial zirconia ceramics specifically comprises the following steps:

[0064] Step 1: 99.8 g of zirconium oxide powder and 0.2 g of gallium oxide are mixed evenly, then dry-milled and sieved;

[0065] Step 2: Add 2.5 g of polyvinyl alcohol and 4 g of ammonium citrate and stir until well mixed;

[0066] Step 3: Put the preformed material into the bag, seal it, and then put it into the high-pressure container in the isostatic press. Increase the pressure at a pressure increase rate of 5 MPa / min. After reaching the target pressure value, maintain the pressure for 60 minutes, and then reduce the pressure at a pressure reduction rate of 3 MPa / min until the pressure value is zero.

[0067] Step 4: Place the isostatically pressed material into a calcining furnace, heat it to 1400° C. at a heating rate of 10° C. / min, and sinter for 2 hours to obtain antibacterial zirconia ceramics.

[0068] Example 7

[0069] A processing technology for antibacterial zirconia ceramics specifically comprises the following steps:

[0070] S1. Add a stabilizer to the zirconium oxide, then pour it into a ball mill for ball milling, then put the powder into a bag, seal it, and then put it into a high-pressure container in an isostatic press, and increase the pressure at a pressure increase rate of 5 MPa / min. After reaching the target pressure value, maintain the pressure for 60 minutes, and then reduce the pressure at a pressure reduction rate of 3 MPa / min until the pressure value is zero, to obtain a zirconium oxide block;

[0071] S2, placing the zirconia block in a calcining furnace, heating to 1000°C, and sintering for 2h;

[0072] S3. Immerse the sintered zirconium oxide block in a zinc fluoride solution, then take it out, place it in a calcining furnace, heat it to 1400° C., and sinter it for 2 hours to obtain zirconium oxide ceramics with antibacterial properties.

[0073] Example 8

[0074] A processing technology for antibacterial zirconia ceramics specifically comprises the following steps:

[0075] S1. Add a stabilizer to the zirconium oxide, then pour it into a ball mill for ball milling, then put the powder into a bag, seal it, and then put it into a high-pressure container in an isostatic press, and increase the pressure at a pressure increase rate of 1-5MPa / min. After reaching the target pressure value, maintain the pressure for 30-60min, and then reduce the pressure at a pressure reduction rate of 1-3MPa / min until the pressure value is zero, to obtain a zirconium oxide block;

[0076] S2, placing the zirconia block in a calcining furnace, heating to 1000°C, and sintering for 2h;

[0077] S3. Immerse the sintered zirconium oxide block in a silver nitrate solution, then take it out, place it in a calcining furnace, heat it to 1400° C., and sinter it for 2 hours to obtain zirconium oxide ceramics with antibacterial properties.

[0078] Comparative Example 1

[0079] Compared with Example 1, the difference is that zinc oxide is not added; the rest remains unchanged.

[0080] Comparative Example 2

[0081] Compared with Example 4, the difference is that gallium oxide is not added; the rest remains unchanged.

[0082] Comparative Example 3

[0083] Compared with Comparative Example 7, the difference is that no zinc fluoride solution is added; the rest remains unchanged.

[0084] Comparative Example 4

[0085] Compared with Comparative Example 7, the difference is that no silver nitrate solution is added; the rest remains unchanged.

[0086] Antibacterial performance test: The antibacterial performance of Examples 1-6, Example 8, Comparative Examples 1-2, and Comparative Example 4 was tested with reference to ISO 22196:2011; the concentration of Escherichia coli was 6x10 5 CFU / mL, the antibacterial properties were evaluated by CCK-8 staining. Figure 1 , Figure 2 as well as Figure 4 As shown;

[0087] Example 7 and Comparative Example 3 used Streptococcus mutans to test their antibacterial properties; the concentration of Streptococcus mutans was 10 7 CFU / mL, the antibacterial properties were evaluated by CCK-8 staining. Figure 3 shown.

[0088] Meanwhile, the contents not described in detail in this specification belong to the prior art known to those skilled in the art.

[0089] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0090] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A processing technology for antibacterial zirconia ceramics, comprising two processing technologies, characterized in that: The first processing technology specifically includes the following steps: Step 1: Mix the zirconium oxide powder and the antibacterial material evenly, then use dry ball milling and then sieve; Step 2: Add binder and dispersant, and stir until mixed evenly; Step 3: Put the preformed material into the bag, seal it, and then put it into the high-pressure container in the isostatic press. Increase the pressure at a rate of 1-5 MPa / min. After reaching the target pressure value, maintain the pressure for 30-60 minutes, and then reduce the pressure at a rate of 1-3 MPa / min until the pressure value is zero. Step 4: Place the material after isostatic pressing into a calcining furnace, heat it to 1400° C., and sinter it for 2 hours to obtain zirconia ceramics with antibacterial properties.

2. The processing technology of the antibacterial zirconia ceramic according to claim 1, characterized in that: In the step 1, the antibacterial material is selected from any one of zinc oxide and gallium oxide.

3. The processing technology of the antibacterial zirconia ceramic according to claim 1, characterized in that: in, When the antibacterial material is zinc oxide, the weight proportions of each component added are: 93-97 parts of zirconium oxide powder, 3-7 parts of antibacterial material, 2.5-4 parts of binder, and 4-7 parts of dispersant; When the antibacterial material is gallium oxide, the weight proportions of each component added are: 99-99.8 parts of zirconium oxide powder, 0.2-1 parts of antibacterial material, 2.5-4 parts of binder, and 4-7 parts of dispersant.

4. The processing technology of the antibacterial zirconia ceramic according to claim 1, characterized in that: In the step 2, the binder is polyvinyl alcohol; and the dispersant is ammonium citrate.

5. The processing technology of the antibacterial zirconia ceramic according to claim 1, characterized in that: In the step 4, the heating rate is 5-10°C / min.

6. The processing technology of the antibacterial zirconia ceramic according to claim 1, characterized in that: The second processing technology of the antibacterial zirconia ceramic specifically comprises the following steps: S1. Add a stabilizer to the zirconium oxide, then pour it into a ball mill for ball milling, then put the powder into a bag, seal it, and then put it into a high-pressure container in an isostatic press, and increase the pressure at a pressure increase rate of 1-5MPa / min. After reaching the target pressure value, maintain the pressure for 30-60min, and then reduce the pressure at a pressure reduction rate of 1-3MPa / min until the pressure value is zero, to obtain a zirconium oxide block; S2, placing the zirconia block in a calcining furnace, heating to 1000°C, and sintering for 2h; S3. Immerse the sintered zirconium oxide block in an antibacterial solution, then take it out, place it in a calcining furnace, heat it to 1400° C., and sinter it for 2 hours to obtain zirconium oxide ceramics with antibacterial properties.

7. The processing technology of the antibacterial zirconia ceramic according to claim 6, characterized in that: The antibacterial solution is selected from any one of a zinc fluoride dispersion and a silver nitrate solution.

8. The processing technology of the antibacterial zirconia ceramic according to claim 6, characterized in that: In S2 and S3, the heating rate is 5-10°C / min.

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