CN117229045A - Resin-infiltrated porous ceramic composite material and preparation method and application thereof - Google Patents
Resin-infiltrated porous ceramic composite material and preparation method and application thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 106
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 80
- 239000011521 glass Substances 0.000 claims abstract description 44
- 238000005245 sintering Methods 0.000 claims abstract description 41
- 239000011812 mixed powder Substances 0.000 claims abstract description 35
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003825 pressing Methods 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims description 39
- 229920005989 resin Polymers 0.000 claims description 39
- 238000002844 melting Methods 0.000 claims description 35
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- 239000005373 porous glass Substances 0.000 claims description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 238000009694 cold isostatic pressing Methods 0.000 claims description 10
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005452 bending Methods 0.000 claims description 5
- 238000001764 infiltration Methods 0.000 claims description 5
- 230000008595 infiltration Effects 0.000 claims description 5
- 238000009766 low-temperature sintering Methods 0.000 claims description 4
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 31
- 230000002950 deficient Effects 0.000 abstract description 21
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- 239000002994 raw material Substances 0.000 abstract description 5
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 13
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 13
- 239000000429 sodium aluminium silicate Substances 0.000 description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 13
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- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 229910007472 ZnO—B2O3—SiO2 Inorganic materials 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a resin-infiltrated porous ceramic composite material, a preparation method and application thereof, wherein the composite material takes mixed powder of leadless low-melting-point glass powder and silicate powder according to the mass ratio of 1-20:80-99 as raw materials, and adoptsTwice pressing and forming, sintering at 500-650 deg.c, vickers hardness of the material over 1.6GPa, elastic modulus over 25GPa and fracture toughness over 1.5MPa 1/2 The defective rate of the material in the production can be as low as 2.3 percent, compared with the prior ceramic resin composite material prepared by taking silicate powder as a raw material, the defective rate of the material is obviously reduced by about 50 percent, and the mechanical property of the material can be kept equal to or even better than the mechanical property of the prior 700-800 ℃ sintering at the sintering temperature of 500-650 ℃.
Description
Technical Field
The invention belongs to the technical field of dental restoration materials, and particularly relates to a resin-permeable porous ceramic composite material, and a preparation method and application thereof.
Background
The transformation of dental restoration materials from original gold, silver and copper noble metals to resin restoration materials is a great revolution in development, and composite resin restoration materials are widely applied due to attractive color, good physicochemical properties and easy processability. The dental Bis-GMA resin matrix material has clinical experience for more than 50 years, but according to clinical statistics data, the service life of the Bis-GMA resin matrix material is generally shorter (6-8 years), and the problems of large polymerization shrinkage, low mechanical strength, lower curing degree and the like mainly exist, so that the resin ceramic composite material is applied to solve the problems.
In the resin ceramic composite material, the ceramic is used as a reinforcing body, so that the mechanical properties such as strength and modulus of the resin composite material can be improved, the wear resistance can be improved, and the service life of the material can be prolonged, but the ceramic is too compact, and cannot provide enough communication aperture for resin permeation, and the reduction of sintering temperature can lead to the reduction of shrinkage and the reduction of mechanical properties, and the mechanical properties of the resin ceramic composite material are improved, but the improvement range is limited, and the modulus of the ceramic is generally far greater than that of a resin system, so that the condition that cracks or fractures are generated due to insufficient interface combination of the two is easy to occur, and the defective rate is high. Therefore, the resin ceramic composite material with high yield is researched, and particularly, the resin ceramic composite material with the mechanical property meeting the requirement can be obtained by low-temperature sintering, thereby being more beneficial to popularization and application.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides a resin-infiltrated porous ceramic composite material, and a preparation method and application thereof, and aims to discover that the ceramic resin composite material is prepared by mixing and granulating a leadless low-melting-point glass powder and a silicate powder according to the mass ratio of 1-20:80-99, so that the defective rate of the material can be reduced, and the composite material meeting the mechanical property requirement can be prepared at 500-650 ℃, thereby solving the technical problem that the defective rate of the dental repair material prepared by the conventional monosilicate powder is higher.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a resin-infiltrated porous ceramic composite material, comprising the steps of:
(1) Mixing and granulating lead-free low-melting glass powder of 50-500nm and silicate powder of 50-500nm according to a preset proportion to obtain mixed powder, and pressing twice to prepare a porous glass ceramic green body;
the mass ratio of the leadless low-melting point glass powder to the silicate powder is 1-20:80-99; the lead-free low-melting glass powder comprises the main components including but not limited to Bi 2 O 3 、ZnO、B 2 O 3 、SiO 2 、Al 2 O 3 、Na 2 O、ZrO2、SnCl 2 、Sb 2 O 3 、Li 2 O、BaO、K 2 O, the melting temperature is less than or equal to 500 ℃;
(2) And (3) sintering at low temperature: sintering the porous glass ceramic green body obtained in the step (1) at a low temperature of 500-650 ℃ to obtain a porous glass ceramic green body; and obtaining the resin-infiltrated porous ceramic composite material after resin infiltration and solidification.
Preferably, the preparation method of the resin-infiltrated porous ceramic composite material comprises the steps of preparing the leadless low-melting glass powder, wherein the main component of the leadless low-melting glass powder comprises Bi 2 O 3 、ZnO、B 2 O 3 、SiO 2 、Al 2 O 3 、Na 2 O, where Bi 2 O 3 :ZnO:B 2 O 3 :SiO 2 :Al 2 O 3 :Na 2 The mass ratio of O is 49:20.5 (25.5-26.5) to 3.5 (0.5-1.5).
Preferably, the mass ratio of the leadless low-melting point glass powder to the silicate powder is 5-15:85-95.
Preferably, the low-temperature sintering in the step (2) is performed at 550-600 ℃ for 2-3 hours.
Preferably, the twice pressing in the step (1) comprises pre-pressing and cold isostatic pressing, wherein the pre-pressing pressure is 4-6t, and the pressing time is 15-40s; the pressure of the cold isostatic pressing is 200-400MPa, and the pressing time is 1-5min.
According to another aspect of the present invention, there is also provided a resin-infiltrated porous ceramic composite material prepared according to the preparation method of the present invention.
Preferably, the resin-infiltrated porous ceramic composite material has a Vickers hardness average of 1.6GPa or more, an elastic modulus average of 25GPa or more, and a fracture toughness average of 1.5MPa.m 1/2 The above.
Preferably, the resin-infiltrated porous ceramic composite material, the composite material thereof has a vickers hardness average value of greater than 2.0GPa, an elastic modulus average value of greater than 34GPa, and a fracture toughness average value of greater than 2.0mpa.m 1/2 The bending strength is more than 160Mpa.
According to another aspect of the present invention there is also provided the use of a resin infiltrated porous ceramic composite according to the present invention in dental restorations.
Preferably, the use of the resin-infiltrated porous ceramic composite in dental restorations, including artificial teeth, veneers, inlays and crowns; wherein crown restorations include full crown, single crown and continuous crown restorations.
In general, compared with the prior art, the technical proposal of the invention adopts the mixed powder of silicate powder and low-melting glass powder as raw materials, wherein the mass ratio of the leadless low-melting glass powder to the silicate powder is 1-20:80-99, and the following technical effects can be achieved:
according to the preparation method of the resin-infiltrated porous ceramic composite material, as the low-melting-point glass powder in the raw materials can enable the ceramic matrix in the resin infiltrated ceramic to have better combination property with the resin network, cracking is prevented, the defective rate is effectively reduced, compared with the existing defective rate (5-6%), the defective rate can be reduced to 2.3%, and the defective rate is reduced by about 50%; and the sintering temperature is reduced to 500-650 ℃, the mechanical property of the material is equivalent to that of the existing sintering temperature of 700-800 ℃, even better, the sintering temperature of the ceramic matrix can be reduced while the integral mechanical property is ensured, and the effects of energy conservation and emission reduction can be achieved.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The mechanical properties of the dental restoration material in clinical application should meet the following requirements: the bending strength is more than 150MPa, the elastic modulus is about 20GPa, and the Vickers hardness is about 2.00 GPa. At present, the sintering temperature of the independent silicate powder ceramic block is about 800 ℃, and although the mechanical property of the existing material can meet the requirement of clinical application, the existing material needs to be further improved, and the existing defective rate is higher (the defective rate is 5-6%). In order to further improve the mechanical properties of materials, the existing research usually adopts a temperature of more than 1000 ℃ for sintering, while patent CN201910597419.2 is a low-temperature sintered alumina black ceramic and a preparation method thereof, the sintering is carried out by adopting a mode of gradually heating at low temperature for a long time, but the sintering process is that the temperature is firstly increased to 500-500 ℃ and the temperature is kept for 2-5 hours; heating to 700-950 ℃, and preserving heat for 2-5 h; and then heating to 1100-1250 ℃, preserving heat for 5-15 h, wherein the sintering time is long, the sintering process is complex, the final sintering temperature is still above 1000 ℃, the sintering temperature is high, the ceramic block is easy to be excessively high in compactness, resin is difficult to permeate, continuous production is not facilitated, and the efficiency is low.
The invention discovers that ceramic resin composite material is prepared by taking mixed powder with the mass ratio of leadless low-melting point glass powder to silicate powder of 1-20:80-99 as raw materials, and discovers that dental repair material meeting the mechanical property requirement can be obtained by sintering at the low temperature of 500-650 ℃ and the defective rate of the repair material is obviously reduced.
The invention provides a preparation method of a resin-infiltrated porous ceramic composite material, which comprises the following steps:
(1) Fully mixing the lead-free low-melting glass powder with the mass ratio of (1-20) to (80-99) of the silicate powder with the mass ratio of (50-500) to (50-500), and granulating to obtain mixed powder; the main composition of the lead-free low-melting glass powder is not limited to Bi 2 O 3 、ZnO、B 2 O 3 、SiO 2 、Al 2 O 3 、Na 2 O、ZrO2、SnCl 2 、Sb 2 O 3 、Li 2 O、BaO、K 2 Two or more of O, preferably Bi 2 O 3 -ZnO-B 2 O 3 -SiO 2 -Al 2 O 3 -Na 2 The mass ratio of the O to the components is 49:20.5 (25.5-26.5) to 3.5 (0.5-1.5); the melting temperature is less than or equal to 500 ℃.
(2) Twice pressing, specifically as follows:
and (5) one-step prepressing and forming: mixing the powder at 4-6t pressure, and pressing for 15-40s;
cold isostatic pressing secondary pressing: the cold isostatic pressing pressure is 200-400MPa, and the porous glass ceramic green body is obtained after pressing for 1-5 min;
(3) And (3) sintering at low temperature: sintering the porous glass ceramic green body obtained in the step (2) at 500-650 ℃ to obtain a porous glass ceramic green body;
experiments show that the mechanical property of the material can be obviously improved by adding 1-20% of the leadless low-melting glass powder into the mixed powder, mainly because the leadless low-melting glass powder can enhance the interfacial binding force of the resin and the ceramic, and the defective rate can be reduced; although the shrinkage and the mechanical property are reduced due to the reduction of the sintering temperature, the glass powder is in a molten state at 500-650 ℃, and the glass powder in the molten state can form 'welding spots' among silicate powder particles so as to play a role of a binder, so that the bonding effect among silicate particles can be improved, and the unexpected finding that the mechanical property of the material is unchanged although the sintering temperature is reduced, and meets the requirements of clinical application.
(4) And (3) carrying out resin infiltration and curing on the porous glass ceramic blank obtained in the step (3) to obtain the resin infiltrated porous ceramic composite material.
The porous glass ceramic blank is sintered at a lower sintering temperature, so that the internal void of the porous glass ceramic blank can provide enough communication aperture for resin permeation, and the leadless low-melting glass powder added into silicate can reduce the exothermic peak temperature of the resin curing reaction, and can reduce the linear expansion coefficient and shrinkage rate of the cured product, thereby eliminating the internal stress of the cured product, further preventing cracking and reducing the defective rate.
Preferably, the mixed powder is mixed according to the mass ratio of lead-free low-melting glass powder to silicate powder of (5-15) (85-95); more preferably, the low-temperature sintering temperature is 550-600 ℃, the Vickers hardness average value of the obtained material is more than 1.6GPa, the elastic modulus average value is more than 25GPa, and the fracture toughness average value is 1.5MPa.m 1/2 The above.
In some embodiments, the composite material obtained by mixing the leadless low-melting glass powder and the silicate powder according to the mass ratio of 8:92 and sintering at 600 ℃ for 2 hours has good mechanical property, the average value of the Vickers hardness is more than 2.0GPa, the average value of the elastic modulus is more than 34GPa, and the average value of the fracture toughness is more than 2.0MPa.m 1/2 The bending strength is more than 160Mpa, and the defective rate of the finished product is as low as 2.3 percent.
In addition, the invention also provides a resin-infiltrated porous ceramic composite material which is prepared by the preparation method.
The composite material has the average value of Vickers hardness of more than 1.6GPa, the average value of elastic modulus of more than 25GPa and the average value of fracture toughness of 1.5MPa.m 1/2 The above; preferably, the average value of the Vickers hardness is more than 2.15GPa, the average value of the elastic modulus is more than 34GPa, and the average value of the fracture toughness is more than 2.0MPa 1/2 The bending strength is more than 160Mpa.
The invention also provides the application of the resin-infiltrated porous ceramic composite material in dental restorations, including artificial teeth, veneers, inlays and crowns; wherein crown restorations include full crown, single crown and continuous crown restorations.
The following are examples:
the lead-free low-melting-point glass powder in the embodiment of the invention mainly comprises Bi as the components 2 O 3 -ZnO-B 2 O 3 -SiO 2 -Al 2 O 3 -Na 2 O, where Bi 2 O 3 :ZnO:B 2 O 3 :SiO 2 :Al 2 O 3 :Na 2 The mass ratio of O is 49:20.5: (25.5-26.5): 3.5: (0.5-1.5), fully and uniformly mixing the lead-free low-melting glass powder with the mass ratio of (1-20) to (80-99) of 50-500nm to the sodium aluminosilicate powder in a powder mixing machine to obtain mixed powder, denoted as AX, wherein X is the mass content of the lead-free low-melting glass powder, namely the X accounts for the mass percent of the mixed powder, if A1 represents the mass content of the lead-free low-melting glass powder is 1%, and mixing the mixed powder with a binder solution such as PVA liquid in sequence to granulate the glass powder of A1-A20.
Example 1
(1) Fully and uniformly mixing the lead-free low-melting glass powder with the thickness of 50-500nm and the sodium aluminosilicate powder with the thickness of 50-500nm according to the mass ratio of 1:99, and granulating to obtain mixed powder which is marked as A1.
(2) And (3) twice pressing mixed powder:
and (5) one-step prepressing and forming: transferring the powder A1 prepared in the step (1) into a die, forming a porous ceramic blank by hydraulic pressure of a hydraulic machine, setting the pressure of the hydraulic machine to be 6t, and maintaining the pressure for 30s;
cold isostatic pressing secondary pressing: and (3) placing the porous ceramic blank into a sealing protective film, and performing cold isostatic pressing treatment, wherein the pressure increasing rate of the cold isostatic pressing is 200MPa/min, the pressure is maintained at 200MPa for 3min, and then the porous ceramic blank is taken out after depressurization, so that the porous glass ceramic blank is obtained.
(3) Sintering the porous ceramic blank at low temperature: sintering the porous glass ceramic blank obtained in the step (2) at 500 ℃, 550 ℃, 600 ℃ and 650 ℃ respectively, wherein the heating rate is 5 ℃/min, and preserving heat for 2 hours; and (3) drying the mixture for 2 hours at 110 ℃ in a vacuum drying oven after sintering, or modifying the mixture by adopting a silane coupling agent and then drying the mixture in vacuum after sintering.
(4) Resin infiltration and curing: injecting the resin mixed solution into a mould, placing the porous glass ceramic obtained in the step (3) into the mould, setting the pressure to be 0.6MPa, and maintaining the pressure for 4 hours under the vacuum condition to fully soak the resin into the pores of the ceramic; packaging porous glass ceramic with high-temperature vacuum film after resin infiltration, placing into a high-pressure chamber after packaging, heating hydraulic oil in the high-pressure chamber to 70 ℃, raising the pressure to 120MPa, firstly preserving heat and maintaining pressure for 2 hours, then raising the temperature to 120 ℃, adjusting the pressure to 180MPa, preserving heat and maintaining pressure for 3 hours, and taking out.
The resin mixed solution is prepared and obtained according to the following method:
bisphenol A dimethacrylate (Bis-GMA) and dimethacrylate urethane (TEGDMA) are mixed according to the mass ratio of 1:1, stirred for 2 hours, added with 1wt% of curing agent (according to the mixing mass of Bis-GMA and TEGDMA) and continuously stirred for 2 hours, and resin mixed solution is obtained; in this example the curative is Benzoyl Peroxide (BPO).
When in use, the resin-infiltrated porous glass ceramic composite material obtained in the step (4) is polished, such as the redundant resin layer after being polished and solidified by sand paper, and animal hair or nut shells mixed with the polishing agent are polished.
The resin-infiltrated porous ceramic composite material prepared using the mixed powder A1 was tested and the results are shown in the following table:
TABLE 1 mechanical Properties and defective fraction of resin infiltrated porous ceramic composite
In Table 1, "150.27 (11.30)" means "150.27.+ -. 11.30" and the same applies.
As can be seen from Table 1, a ceramic composite material with a Vickers hardness average value of 1.41GPa and an elastic modulus average value of more than 25GPa can be obtained by adding 1% of lead-free low-melting-point glass powder and sintering at 500 ℃, and the fracture toughness average value of the material can reach 1.5MPa m 1/2 The defective rate is 5.3%, and the mechanical property of the material is in a trend of ascending and then descending along with the ascending of the sintering temperature.
Example 2
Fully and uniformly mixing lead-free low-melting glass powder with the thickness of 50-500nm and sodium aluminosilicate powder with the thickness of 50-500nm according to the mass ratio of 3:97 to obtain mixed powder, and marking the mixed powder as A3; otherwise, as in example 1, a resin-infiltrated porous ceramic composite material was prepared.
The resin-infiltrated porous ceramic composite material prepared with the mixed powder A3 was tested and the results are shown in the following table:
TABLE 2 mechanical Properties of resin infiltrated porous ceramic composite
Example 3
Fully and uniformly mixing lead-free low-melting glass powder with the thickness of 50-500nm and sodium aluminosilicate powder with the thickness of 50-500nm according to the mass ratio of 5:95 to obtain mixed powder, and marking the mixed powder as A5; otherwise, as in example 1, a resin-infiltrated porous ceramic composite material was prepared.
The resin-infiltrated porous ceramic composite material prepared with the mixed powder A5 was tested and the results are shown in the following table:
TABLE 3 mechanical Properties of resin infiltrated porous ceramic composite
Example 4
Fully and uniformly mixing lead-free low-melting glass powder with the thickness of 50-500nm and sodium aluminosilicate powder with the thickness of 50-500nm according to the mass ratio of 8:92 to obtain mixed powder, and marking the mixed powder as A8; otherwise, as in example 1, a resin-infiltrated porous ceramic composite material was prepared.
The resin-infiltrated porous ceramic composite material prepared with the mixed powder A8 was tested and the results are shown in the following table:
TABLE 4 mechanical Properties of resin infiltrated porous ceramic composite
Example 5
Fully and uniformly mixing lead-free low-melting glass powder with the thickness of 50-500nm and sodium aluminosilicate powder with the thickness of 50-500nm according to the mass ratio of 12:88 to obtain mixed powder, and marking the mixed powder as A12; otherwise, as in example 1, a resin-infiltrated porous ceramic composite material was prepared.
The resin-infiltrated porous ceramic composite material prepared using the mixed powder a12 was tested and the results are shown in the following table:
TABLE 5 mechanical Properties of resin infiltrated porous ceramic composite
Example 6
Fully and uniformly mixing lead-free low-melting glass powder with the thickness of 50-500nm and sodium aluminosilicate powder with the thickness of 50-500nm according to the mass ratio of 15:85 to obtain mixed powder, and marking the mixed powder as A15; otherwise, as in example 1, a resin-infiltrated porous ceramic composite material was prepared.
The resin-infiltrated porous ceramic composite material prepared using the mixed powder a15 was tested and the results are shown in the following table:
TABLE 6 mechanical Properties of resin infiltrated porous ceramic composite
Example 7
Fully and uniformly mixing and granulating the lead-free low-melting glass powder with the thickness of 50-500nm and the sodium aluminosilicate powder with the thickness of 50-500nm according to the mass ratio of 20:80 to obtain mixed powder which is marked as A20; otherwise, as in example 1, a resin-infiltrated porous ceramic composite material was prepared.
The resin-infiltrated porous ceramic composite material prepared using the mixed powder a20 was tested and the results are shown in the following table:
TABLE 7 mechanical Properties of resin infiltrated porous ceramic composite
The composite material is prepared by adopting the mixed powder A1-A20, and test results show that the mechanical property and fracture toughness of the composite material can be obviously improved by adding the leadless low-melting-point glass powder, the defective rate can be reduced, and the yield can be improved, wherein the content of the leadless low-melting-point glass powder in the mixed powder is 8%, the sintering temperature is 600 ℃, the mechanical property of the prepared composite material is optimal, and the defective rate is lowest.
Comparative example 1
The porous ceramic composite material is prepared by adopting 50-500nm sodium aluminosilicate powder, wherein the sodium aluminosilicate powder is firstly mixed with a binder PVA liquid to prepare a pelleting body, then the pelleting body is pressed by coarse-pressure cold isostatic pressing, the high-temperature sintering temperature is 700-850 ℃, and the heat preservation is carried out for 2 hours, so that the pelleting body is marked as A0. Otherwise, as in example 1, a resin-infiltrated porous ceramic composite material was prepared. The obtained resin-infiltrated porous ceramic composite was tested, and the results thereof are shown in the following table:
TABLE 8 mechanical Properties of resin infiltrated porous ceramic composite
The comparative example 1 is the common sintering temperature for preparing the ceramic composite material by the prior monosilicate powder, although the mechanical property of the material meets the clinical use requirement, the defective rate is higher, the Vickers hardness of the material is 1.6-1.65 GPa, and the hardness of the material is still lower than that of the natural teeth.
Comparative example 2
The resin-infiltrated porous ceramic composite material is prepared by adopting 50-500nm sodium aluminosilicate powder, wherein the sodium aluminosilicate powder and a binder PVA liquid are mixed to prepare a pelleting body, and then the pelleting body is pressed by coarse-pressure isostatic cool pressing, the high-temperature sintering temperature is 500-650 ℃, and the heat preservation is carried out for 2 hours, so that the resin-infiltrated porous ceramic composite material is prepared by other methods in the example 1.
The obtained resin-infiltrated porous ceramic composite was tested, and the results thereof are shown in the following table:
TABLE 9 mechanical Properties of resin infiltrated porous ceramic composite
Comparative example 2 is a common process for preparing ceramic composite materials from the existing monosilicate powder, but the sintering temperature is reduced, the shrinkage of the ceramic matrix is reduced, the porosity is increased, the mechanical properties are reduced, and the defective rate is higher.
Comparative example 3
The resin-infiltrated porous ceramic composite material is prepared by adopting mixed powder of 50-500nm sodium aluminosilicate powder and low-melting-point glass powder, wherein the low-melting-point glass powder accounts for 8% of the mass of the mixed powder, the particle size is 50-500nm, the sintering temperature is 700-850 ℃, and the resin-infiltrated porous ceramic composite material is prepared by other steps in the same way as in the example 1.
The obtained resin-infiltrated porous ceramic composite was tested, and the results thereof are shown in the following table:
TABLE 10 mechanical Properties of resin infiltrated porous ceramic composite
In comparative example 3, when the sintering temperature is 700-850 ℃, the communication of the internal pore diameter is ensured under the condition that the ceramic matrix is as compact as possible, but the addition of low-melting glass powder at the sintering temperature can influence the connectivity of the pore diameter to a certain extent, so that the resin cannot completely permeate, a certain gap is generated, and the strength of the material is reduced.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the resin-infiltrated porous ceramic composite material is characterized by comprising the following steps of:
(1) Mixing lead-free low-melting glass powder with the thickness of 50-500nm and silicate powder with the thickness of 50-500nm according to a preset proportion to obtain mixed powder, and pressing twice to prepare a porous glass ceramic green body;
the mass ratio of the leadless low-melting point glass powder to the silicate powder is 1-20:80-99; the lead-free low-melting glass powder mainly comprises two or more components including but not limited to Bi 2 O 3 、ZnO、B 2 O 3 、SiO 2 、Al 2 O 3 、Na 2 O、ZrO2、SnCl 2 、Sb 2 O 3 、Li 2 O、BaO、K 2 O, the melting point of which is less than or equal to 500 ℃;
(2) And (3) sintering at low temperature: sintering the porous glass ceramic green body obtained in the step (1) at a low temperature of 500-650 ℃ to obtain a porous glass ceramic green body; and obtaining the resin-infiltrated porous ceramic composite material after resin infiltration and solidification.
2. The method for producing a resin-infiltrated porous ceramic composite according to claim 1, wherein the lead-free low-melting glass powder comprises Bi as a main component 2 O 3 、ZnO、B 2 O 3 、SiO 2 、Al 2 O 3 、Na 2 O, where Bi 2 O 3 :ZnO:B 2 O 3 :SiO 2 :Al 2 O 3 :Na 2 The mass ratio of O is 49:20.5:
(25.5-26.5):3.5:(0.5-1.5)。
3. the method for producing a resin-infiltrated porous ceramic composite according to claim 1 or 2, wherein the mass ratio of the leadless low-melting glass powder to the silicate powder is 5 to 15:85 to 95.
4. The method for preparing a resin-infiltrated porous ceramic composite according to claim 3, wherein the low-temperature sintering in step (2) is performed at a sintering temperature of 550 to 600 ℃ for a heat preservation time of 2 to 3 hours.
5. The method of preparing a resin-infiltrated porous ceramic composite of claim 4, wherein the twice pressing of step (1) comprises pre-press forming and cold isostatic pressing, wherein the pre-press forming is performed at a pressure of 4 to 6t for a pressing time of 15 to 40s; the pressure of the cold isostatic pressing is 200-400MPa, and the pressing time is 1-5min.
6. A resin-infiltrated porous ceramic composite prepared according to the method of any one of claims 1 to 5.
7. The resin-infiltrated porous ceramic composite of claim 6, wherein the composite has a vickers hardness average of 1.6GPa or greater, an elastic modulus average of 25GPa or greater, and a fracture toughness average of 1.5mpa m 1/2 The above.
8. The resin-infiltrated porous ceramic composite of claim 7, wherein the composite has a vickers hardness average of greater than 2.0GPa, an elastic modulus average of greater than 34GPa, and a fracture toughness average of greater than 2.0mpa m 1/2 The bending strength is more than 160Mpa.
9. Use of a resin-infiltrated porous ceramic composite according to any one of claims 6 to 8 in dental restorations.
10. Use of the resin-infiltrated porous ceramic composite of claim 9 in dental restorations, including artificial teeth, veneers, inlays and crowns; wherein crown restorations include full crown, single crown and continuous crown restorations.
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