An interfacial activator, a preparation method and application thereof and an application method

Abstract

This invention belongs to the field of dental restoration technology, and provides an interface activator, its preparation method, application, and application method, solving the problems of weak bonding or insufficient long-term bonding stability of dental zirconia. The interface activator is prepared from raw materials containing the following molar fractions: 50-60 mol% silica, 10-30 mol% alumina, 10-30 mol% magnesium oxide, and 1-6 mol% zirconia. The raw materials are mixed and sequentially melted and crystallized to obtain microcrystalline glass; the microcrystalline glass, solvent, and colorant are then mixed to obtain the interface activator. The activator of this invention, through optimized composition, lowers the temperature during crystallization heat treatment during use; and after application and further heat treatment, it effectively improves bonding strength and durability, reduces the possibility of chipping and detachment of ceramic dentures, and effectively enhances the fracture load and deformation resistance of ceramic dentures.

Description

Technical Field

[0001] This invention relates to the field of dental restoration technology, and in particular to an interface activator, its preparation method, application, and application method. Background Technology

[0002] Since its introduction into the field of oral medicine in the early 1990s, zirconia ceramics have become an important material for the fabrication of dental ceramic restorations due to their excellent biocompatibility, mechanical properties, and aesthetic characteristics. Zirconia exhibits excellent stability in the oral environment, does not cause allergic reactions, does not alter normal taste, and demonstrates particularly outstanding fracture toughness. These characteristics make zirconia an ideal dental restorative material, widely used in various dental restorations, especially in aesthetic restorations.

[0003] Although zirconia ceramics are increasingly used in dentistry, their strong chemical stability makes it difficult to form effective chemical bonds with traditional adhesives. This limits the effectiveness of conventional surface treatment methods in improving shear bond strength. For example, while methods such as hydrofluoric acid etching, silane coupling agents, or primers have been used, they have failed to significantly enhance the bond strength of zirconia ceramics. Currently, zirconia ceramic dentures often experience weak bonding or detachment during clinical use, affecting their long-term stability.

[0004] The surface properties of zirconia, including its chemical composition, microstructure, and roughness, directly affect its bonding performance. Current research on improving the bonding strength of zirconia primarily focuses on surface treatment techniques, with common methods including mechanical and physical treatments and chemical modification. Physical methods, such as Al₂O₃ blasting, can improve surface roughness to some extent, but this method may generate microcracks on the zirconia ceramic surface, thus affecting its mechanical properties. Chemical treatment methods, such as preparing lithium silicon coatings and using adhesives containing acidic functional monomers, can improve shear bond strength, but the performance improvement from these methods is limited and may lead to adhesive degradation, increasing the frequency of follow-up visits and the burden on patients. Summary of the Invention

[0005] The purpose of this invention is to solve the problems of weak bonding or insufficient long-term bonding stability of dental zirconia, and to provide an interface activator, its preparation method, application, and application method.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides an interface activator, prepared from raw materials comprising the following molar fractions:

[0008] 50–60 mol% silicon dioxide, 10–30 mol% aluminum oxide, 10–30 mol% magnesium oxide, and 1–6 mol% zirconium oxide.

[0009] Preferably, the raw materials of the interface activator include colorants;

[0010] The colorant is one or more of carmine, anthocyanin, methylene blue, indigo, and beetroot red.

[0011] The present invention also provides a method for preparing the interface activator, comprising the following steps:

[0012] (1) The raw materials are mixed and then sequentially melted and crystallized to obtain microcrystalline glass;

[0013] (2) The interface activator is obtained by mixing microcrystalline glass, solvent and colorant.

[0014] Preferably, the melting temperature in step (1) is 1500-1600°C and the melting time is 2-5 hours.

[0015] Preferably, the heating rate of the crystallization treatment in step (1) is 1 to 10 °C / min; the first target temperature is 700 to 800 °C, and the holding time at the first target temperature is 1 to 3 h; the second target temperature is 900 to 1000 °C, and the holding time at the second target temperature is 2 to 4 h.

[0016] Preferably, the particle size of the microcrystalline glass in step (2) is 0.2 to 30 μm;

[0017] The solvent mentioned in step (2) is one or more of water, styrene, pentane and butanediol;

[0018] The mass of the colorant mentioned in step (2) is 0.1% to 0.5% of the mass of the solvent;

[0019] The mass of the microcrystalline glass in step (2) is 0.5 to 5.0% of the mass of the solvent.

[0020] The present invention also provides the application of the aforementioned interface activator in dental zirconia ceramic bonding.

[0021] The present invention also provides a method for applying the aforementioned interface activator in dental zirconia ceramic bonding, comprising the following steps:

[0022] (a) The interface activator is coated onto the bonding surface of the zirconia green blank and heat-treated to obtain a heat-treated sample;

[0023] (b) The surface of the heat-treated sample coated with the interface activator was sequentially acid-etched and silanized, and then bonded.

[0024] Preferably, the temperature of the heat treatment in step (a) is 1350–1550 °C.

[0025] Preferably, the heat treatment time in step (a) is 2 to 4 hours.

[0026] This invention provides an interface activator prepared from raw materials comprising the following molar fractions: 50-60 mol% silica, 10-30 mol% alumina, 10-30 mol% magnesium oxide, and 1-6 mol% zirconium oxide. The raw materials are mixed and sequentially melted and crystallized to obtain microcrystalline glass. The microcrystalline glass, solvent, and colorant are then mixed to obtain the interface activator. This invention's activator, through optimized composition, lowers the temperature required for crystallization heat treatment during use, saving production costs. Furthermore, when applied to the bonding surface of a dental zirconia ceramic (restoration) green body followed by further heat treatment, it effectively improves the bonding strength and durability of dental zirconia ceramic dentures, reduces the possibility of chipping and detachment, and effectively enhances the fracture load and deformation resistance of the ceramic denture.

[0027] This invention employs high-strength, high-temperature microcrystalline glass as a pre-permeation activator for the bonding interface of dental zirconia ceramics. By applying this activator to the bonding side of the green zirconia ceramic and then subjecting it to a single heat treatment step, the shear bond strength of the zirconia ceramic can be effectively improved, thus effectively solving the problem of insufficient bonding strength of current dental zirconia ceramics. Simultaneously, the activator also promotes the sintering of the zirconia green body, further enhancing the fracture strength and deformation resistance of the zirconia ceramic. This innovative method not only improves the bonding strength and mechanical properties of zirconia restorations but also simplifies the traditional fabrication process of zirconia ceramic dentures, providing an efficient and reliable solution for dental restorations. Attached Figure Description

[0028] Figure 1 The XRD pattern of the interfacial activator in Example 1;

[0029] Figure 2 This is a scanning electron microscope image of the interface between the interface activator and the zirconium oxide in Example 1;

[0030] Figure 3 The displacement-load curves are for the repair materials of Example 3, Comparative Example 1, and Comparative Example 2. Detailed Implementation

[0031] This invention provides an interface activator, prepared from raw materials comprising the following molar fractions:

[0032] 50–60 mol% silicon dioxide, 10–30 mol% aluminum oxide, 10–30 mol% magnesium oxide, and 1–6 mol% zirconium oxide.

[0033] In this invention, the preferred molar fraction of silicon dioxide is 52 mol%, 54 mol%, 56 mol%, or 58 mol%.

[0034] In this invention, the molar fraction of the alumina is preferably 15 mol%, 20 mol%, or 25 mol%.

[0035] In this invention, the molar fraction of magnesium oxide is preferably 15 mol%, 20 mol%, or 25 mol%.

[0036] In this invention, the molar fraction of zirconium oxide is preferably 2 mol%, 3 mol%, 4 mol%, or 5 mol%.

[0037] In this invention, the raw materials of the interface activator include a colorant.

[0038] In this invention, the colorant is one or more of carmine, anthocyanin, methylene blue, indigo and beetroot red.

[0039] The present invention also provides a method for preparing the interface activator, comprising the following steps:

[0040] (1) The raw materials are mixed and then sequentially melted and crystallized to obtain microcrystalline glass;

[0041] (2) The interface activator is obtained by mixing microcrystalline glass, solvent and colorant.

[0042] In this invention, the melting temperature in step (1) is preferably 1500-1600℃, more preferably 1525℃, 1550℃, 1570℃, or 1590℃; the melting time is preferably 2-5h, more preferably 2.5h, 3h, 4h, or 4.5h.

[0043] In this invention, after melting is completed in step (1), water quenching is performed to obtain intermediate material, which is then subjected to crystallization treatment.

[0044] In this invention, the heating rate of the crystallization treatment is preferably 1-10℃ / min, more preferably 2℃ / min, 4℃ / min, 6℃ / min, or 8℃ / min; the first target temperature is preferably 700-800℃, more preferably 720℃, 740℃, 760℃, or 780℃; the holding time for the first target temperature is preferably 1-3h, more preferably 1.5h, 2h, or 2.5h; the second target temperature is preferably 900-1000℃, more preferably 920℃, 940℃, 960℃, or 980℃, and the holding time for the second target temperature is preferably 2-4h, more preferably 2.5h, 3h, or 3.5h.

[0045] In this invention, the obtained microcrystalline glass is crushed. The particle size of the microcrystalline glass in step (2) is preferably 0.2 to 30 μm, and more preferably 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, or 25 μm.

[0046] In this invention, the solvent in step (2) is one or more of water, styrene, pentane and butanediol.

[0047] In this invention, the mass of the colorant in step (2) is preferably 0.1% to 0.5% of the mass of the solvent, and more preferably 0.2%, 0.3%, or 0.4%.

[0048] In this invention, the mass of the microcrystalline glass in step (2) is preferably 0.5% to 5.0% of the solvent mass, and more preferably 1%, 2%, 3%, or 4%.

[0049] The present invention also provides the application of the aforementioned interface activator in dental zirconia ceramic bonding.

[0050] The present invention also provides a method for applying the aforementioned interface activator in dental zirconia ceramic bonding, comprising the following steps:

[0051] (a) The interface activator is coated onto the bonding surface of the zirconia green blank and heat-treated to obtain a heat-treated sample;

[0052] (b) The surface of the heat-treated sample coated with the interface activator was sequentially acid-etched and silanized, and then bonded.

[0053] In this invention, the area to be coated in step (a) is the entire bonding surface of the zirconia green blank.

[0054] In this invention, the heat treatment temperature in step (a) is preferably 1350-1550°C, and more preferably 1400°C, 1450°C, or 1500°C.

[0055] In this invention, the heat treatment time in step (a) is preferably 2 to 4 hours, and more preferably 2.5 hours, 3 hours, or 3.5 hours.

[0056] In this invention, the acid etching in step (b) is performed using hydrofluoric acid, the silanization treatment is performed by coating a silane coupling agent, and the bonding is performed using a resin-based adhesive, such as resin cement. In this invention, the acid etching, silanization treatment, and bonding are performed using methods conventional in the art.

[0057] In this invention, a magnesium olivine microcrystalline glass coating formed by an activator is used as a transition layer. On the one hand, it achieves a tight bond with the dental zirconia ceramic prosthesis, ensuring the bond strength between the two. On the other hand, after sintering the dental ceramic (restoration) coated with the surface activator, acid etching, silanization treatment, and adhesive coating are performed, the bond strength between the ceramic and the abutment tooth is guaranteed and improved, thereby reducing the bond loss rate of the dental zirconia ceramic prosthesis.

[0058] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0059] Example 1

[0060] The raw materials are mixed evenly according to the proportion. The mixed raw materials are placed in a crucible and melted at 1515℃ for 5 hours. Then, the mixture is water quenched to obtain an intermediate material. The intermediate material is placed back into a muffle furnace and heated to 750℃ at a rate of 5℃ / min. It is held at this temperature for 2 hours. After the holding time, the temperature is increased to 950℃ at a rate of 5℃ / min. It is held at this temperature for 3 hours to crystallize.

[0061] After grinding the microcrystalline glass raw material to 10μm, it is formulated with butanediol and a colorant to form a stable interface activator. The colorant is methylene blue, and the mass of the colorant is 0.1% of the mass of butanediol. The mass of the microcrystalline glass is 0.8% of the mass of butanediol, and the mass of butanediol is 10g.

[0062] The interface activator was uniformly sprayed onto the bonding side of the zirconia green blank, and the sprayed blank was heat-treated at 1500℃ for 1.5h.

[0063] After heat treatment, the zirconia samples are sequentially acid-etched, silanized, and coated with adhesive, which allows for effective bonding.

[0064] The restorative material prepared above is bonded to the abutment tooth. The bonding method includes:

[0065] The restorative material prepared above was etched with 10% HF acid for 60 seconds to form a rough surface. Then, it was silanized with a silane coupling agent, coated with resin adhesive, and bonded to the abutment tooth.

[0066] The prepared interface activator was characterized, and the XRD pattern is shown below. Figure 1 As shown, by Figure 1 It can be seen that the crystal phase of the interface activator is magnesium olivine crystal.

[0067] Scanning electron microscope image of the interface between the interface activator and zirconium oxide penetration is shown below. Figure 2 As shown, Figure 2 In the image, the left side is the SEM image, and the right side is the EDS image; from Figure 2 It can be seen that infiltration occurred at the interface between the zirconia matrix and the microcrystalline glass infiltration layer.

[0068] Example 2

[0069] The raw materials are mixed evenly according to the proportion. The mixed raw materials are placed in a crucible and melted at 1525℃ for 5 hours. Then, the mixture is water quenched to obtain an intermediate material. The intermediate material is placed back into a muffle furnace and heated to 720℃ at a rate of 3℃ / min. It is held at this temperature for 1.5 hours. After the holding time, the temperature is increased to 900℃ at a rate of 3℃ / min. It is held at this temperature for 2 hours to crystallize.

[0070] After grinding the microcrystalline glass raw material to 15μm, it is formulated with butanediol and a colorant to form a stable interface activator. The colorant is methylene blue, and the mass of the colorant is 0.2% of the mass of butanediol. The mass of the microcrystalline glass is 0.5% of the mass of butanediol, and the mass of butanediol is 5g.

[0071] The interface activator was uniformly sprayed onto the bonding surface of the zirconia ceramic green body, and the sprayed green body was heat-treated at 1350℃ for 2.5h.

[0072] After heat treatment, the zirconia sample was sequentially acid-etched, silanized, and coated with adhesive before being bonded to the abutment tooth.

[0073] The restorative material prepared above is bonded to the abutment tooth. The bonding method includes:

[0074] The restorative material prepared above was etched with 10% HF acid for 60 seconds to form a rough zirconia surface. Then, it was silanized with a silane coupling agent, coated with resin adhesive, and bonded to the abutment tooth.

[0075] Example 3

[0076] The raw materials are mixed evenly according to the proportion. The mixed raw materials are placed in a crucible and melted at 1550℃ for 3 hours. Then, the mixture is water quenched to obtain an intermediate material. The intermediate material is placed back into a muffle furnace and heated to 760℃ at a rate of 4℃ / min. It is held at this temperature for 2.5 hours. After the holding time, the temperature is increased to 960℃ at a rate of 5℃ / min. It is held at this temperature for 2.5 hours to crystallize.

[0077] After grinding the microcrystalline glass raw material to 10μm, it was formulated with butanediol and a colorant to prepare a stable interface activator. The colorant was methylene blue, and the mass of the colorant was 0.3% of the mass of butanediol. The mass of the microcrystalline glass was 2% of the mass of butanediol, and the mass of butanediol was 3.33g.

[0078] The interface activator was uniformly sprayed onto the bonding surface of the zirconia green blank, and the sprayed blank was heat-treated at 1550℃ for 2 hours.

[0079] After heat treatment, the zirconia sample was sequentially acid-etched, silanized, and coated with adhesive before being bonded to the abutment tooth.

[0080] The restorative material prepared above is bonded to the abutment tooth. The bonding method includes:

[0081] The restorative material prepared above was etched with 10% HF acid for 60 seconds to form a rough zirconia surface. Then, it was silanized with a silane coupling agent, coated with resin adhesive, and bonded to the abutment tooth.

[0082] Example 4

[0083] The raw materials are mixed evenly according to the proportion. The mixed raw materials are placed in a crucible and melted at 1575℃ for 3 hours. Then, the mixture is water quenched to obtain an intermediate material. The intermediate material is placed back into a muffle furnace and heated to 740℃ at a rate of 7℃ / min. It is held at this temperature for 3 hours. After the holding period, the temperature is increased to 980℃ at a rate of 4℃ / min. It is held at this temperature for 2.5 hours to crystallize.

[0084] After grinding the microcrystalline glass raw material to 5μm, it is formulated with butanediol and a colorant to prepare a stable interface activator. The colorant is methylene blue, and the mass of the colorant is 0.4% of the mass of butanediol. The mass of the microcrystalline glass is 4% of the mass of butanediol, and the mass of butanediol is 2.5g.

[0085] The interface activator was uniformly sprayed onto the bonding side of the zirconia green blank, and the sprayed blank was heat-treated at 1400℃ for 4 hours.

[0086] After heat treatment, the zirconia sample was sequentially acid-etched, silanized, and coated with adhesive before being bonded to the abutment tooth.

[0087] The restorative material prepared above is bonded to the abutment tooth. The bonding method includes:

[0088] The restorative material prepared above was etched with 10% HF acid for 60 seconds to form a rough zirconia surface. Then, it was silanized with a silane coupling agent, coated with resin adhesive, and bonded to the abutment tooth.

[0089] Example 5

[0090] The raw materials are mixed evenly according to the proportion. The mixed raw materials are placed in a crucible and melted at 1600℃ for 2 hours. Then, the mixture is water quenched to obtain an intermediate material. The intermediate material is placed back into a muffle furnace and heated to 770℃ at a rate of 8℃ / min. It is held at this temperature for 2.6 hours. After the holding time, the temperature is increased to 930℃ at a rate of 7℃ / min. It is held at this temperature for 3.5 hours to crystallize.

[0091] After grinding the microcrystalline glass raw material to 10μm, it is formulated with butanediol and a colorant to form a stable interface activator. The colorant is methylene blue, and the mass of the colorant is 0.5% of the mass of butanediol. The mass of the microcrystalline glass is 3% of the mass of butanediol, and the mass of butanediol is 2g.

[0092] The interface activator was uniformly sprayed onto one side of the bonding surface of the zirconia green blank, and the sprayed blank was heat-treated at 1450℃ for 4 hours.

[0093] After heat treatment, the zirconia sample was sequentially acid-etched, silanized, and coated with adhesive before being bonded to the abutment tooth.

[0094] The restorative material prepared above is bonded to the abutment tooth. The bonding method includes:

[0095] The restorative material prepared above was etched with 10% HF acid for 60 seconds to form a rough zirconia surface. Then, it was silanized with a silane coupling agent, coated with resin adhesive, and bonded to the abutment tooth.

[0096] Comparative Example 1

[0097] This comparative example provides a treatment method for improving the bonding performance of the inner surface of dental zirconia. The dental zirconia is the same as that in Examples 1-5, except that this comparative example does not undergo any treatment and is directly bonded to the abutment tooth.

[0098] Comparative Example 2

[0099] This comparative example provides a treatment method for improving the bonding performance of the inner surface of dental zirconia. The dental zirconia is the same as that in Examples 1-5, except that the prepared interfacial bonding agent is not sprayed in this comparative example, but the other steps, such as acid etching, are the same. After treatment, it is bonded to the abutment tooth.

[0100] The raw materials used in Examples 1 to 5 are shown in Table 1.

[0101] Table 1. Molar percentage of raw materials in Examples 1-5

[0102] Example 1 Example 2 Example 3 Example 4 Example 5 <![CDATA[SiO2(%)]]> 50.0 51.0 52.0 55.0 60.0 <![CDATA[Al2O3(%)]]> 22.0 21.6 21.15 19.7 17.25 MgO (%) 22.0 21.6 21.15 19.7 17.25 <![CDATA[ZrO2(%)]]> 6.0 5.8 5.7 5.6 5.5

[0103] The repair materials prepared in Examples 1-5 and Comparative Examples 1-2 were tested using the following methods:

[0104] Semi-permeability: The semi-permeability of the sample was tested using a haze meter.

[0105] Positioning accuracy: The ceramic prosthesis is scanned in three dimensions using an optical scanner. After scanning, a three-dimensional deviation (RMS) analysis is performed between the scanned data and the design data of the additively manufactured ceramic prosthesis.

[0106] Fracture load: The ceramic dentures were tested for ultimate fracture load using a universal testing machine.

[0107] Bond strength: The bond strength test of this invention was conducted according to the industry standard YY / T0518-2009. The test results are shown in Table 2.

[0108] Table 2 Performance Test Results

[0109]

[0110] As shown in Table 2, the semi-permeability, mechanical strength, and adhesive strength of the embodiment are all improved compared to the comparative example. Under the implementation conditions of Example 3, the sample exhibits the highest semi-permeability and shear adhesive strength; the three-dimensional positioning deviation is the smallest in the embodiment, and the accuracy is not significantly different from that of the comparative example. In summary, this method can improve the semi-permeability, mechanical strength, and adhesive strength of the sample, and Example 3 achieves the best overall performance in terms of semi-permeability, positioning accuracy, mechanical strength, and adhesive strength.

[0111] The displacement-load curves of the repair materials in Example 3, Comparative Example 1, and Comparative Example 2 are shown below. Figure 3 As shown, from Figure 3 As can be seen from the implementation conditions of Example 3, the mechanical strength of the sample is significantly improved compared with the comparative example.

[0112] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for applying an interface activator in dental zirconia ceramic bonding, characterized in that: The interface activator is prepared by mixing microcrystalline glass, solvent and colorant; The microcrystalline glass is prepared from the following raw materials in the following molar fractions: 50-60 mol% silicon dioxide, 10-30 mol% aluminum oxide, 10-30 mol% magnesium oxide, and 1-6 mol% zirconium oxide; The preparation method of the interface activator includes the following steps: (1) After mixing the raw materials, they are sequentially melted and crystallized to obtain microcrystalline glass; (2) The interface activator is obtained by mixing the microcrystalline glass, solvent and colorant; The heating rate of the crystallization treatment in step (1) is 1~10℃ / min; the first target temperature is 700~800℃, and the holding time of the first target temperature is 1~3h; the second target temperature is 900~1000℃, and the holding time of the second target temperature is 2~4h. The application method includes the following steps: (a) The interface activator is coated onto the bonding surface of the zirconia green blank and heat-treated to obtain a heat-treated sample; (b) The surface of the heat-treated sample coated with the interface activator was sequentially acid-etched and silanized, and then bonded.

2. The method of using the interface activator in the application of dental zirconia ceramic bonding according to claim 1, wherein, The colorant is one or more of carmine, anthocyanin, methylene blue, indigo, and beetroot red.

3. The method of using the interface activator of claim 2 in the application of dental zirconia ceramic bonding, characterized in that, The melting temperature in step (1) is 1500~1600℃ and the melting time is 2~5h.

4. The method of applying the interface activator as described in claim 3 in dental zirconia ceramic bonding, characterized in that, The particle size of the microcrystalline glass mentioned in step (2) is 0.2~30μm; The solvent mentioned in step (2) is one or more of water, styrene, pentane and butanediol; The mass of the colorant mentioned in step (2) is 0.1~0.5% of the mass of the solvent; The mass of the microcrystalline glass in step (2) is 0.5 to 5.0% of the mass of the solvent.

5. The method of applying the interface activator as described in claim 4 in dental zirconia ceramic bonding, characterized in that, The heat treatment temperature in step (a) is 1350~1550℃.

6. The method of applying the interface activator as described in claim 5 in dental zirconia ceramic bonding, characterized in that, The heat treatment time in step (a) is 2 to 4 hours.

Images