CN115745407A - Microcrystalline glass for tooth restoration material and preparation method thereof - Google Patents
Microcrystalline glass for tooth restoration material and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 9
- 229910018070 Li 2 O 10 Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 67
- 238000001816 cooling Methods 0.000 claims description 27
- 239000006064 precursor glass Substances 0.000 claims description 23
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 14
- 239000010431 corundum Substances 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 238000000265 homogenisation Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 5
- 208000005374 Poisoning Diseases 0.000 abstract description 3
- 239000002932 luster Substances 0.000 abstract description 3
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 239000012567 medical material Substances 0.000 abstract description 2
- 239000002241 glass-ceramic Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229940037003 alum Drugs 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 239000013065 commercial product Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 210000004763 bicuspid Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 239000006136 disilicate glass ceramic Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Abstract
The invention relates to the technical field of medical materials, in particular to microcrystalline glass for a tooth restoration material and a preparation method thereof. The preparation raw materials of the microcrystalline glass comprise: siO 2 2 60 wt%~75 wt%；Li 2 O 10 wt%~20 wt%；Al 2 O 3 1 wt%~10 wt%；P 2 O 5 2 wt%~10 wt%；K 2 O 4 wt%~11 wt%；CeO 2 1 wt%~5 wt%；Tb 4 O 7 0.1 wt%~1 wt%；Er 2 O 3 0.01 wt% to 0.1 wt%; the sum of the contents of the components is 100 percent. The microcrystalline glass provided by the invention does not contain vanadium, reduces the poisoning risk in the preparation or use process, still ensures the aesthetic requirement of the tooth restoration material, has the same color and luster as the situation of adding heavy metal, and has better mechanical property.
Description
Technical Field
The invention relates to the technical field of medical materials, in particular to microcrystalline glass for a tooth restoration material and a preparation method thereof.
Background
Glass-ceramics, also known as glass-ceramics, are multiphase solid materials comprising a crystalline phase and a glassy phase obtained by controlled devitrification of a matrix glass by thermal treatment techniques. In other words, the glass ceramic is a solid material which is prepared by melting, forming and heat treating at high temperature and has a composite of a crystal phase and glass. Among them, lithium disilicate (Li) 2 Si 2 O 5 LD) glass ceramics as a novel dental restorative material has many incomparable advantages such as high mechanical properties (bending strength of 300 to 400 MPa), wear resistance equivalent to that of natural teeth, aesthetic properties, good processability and the like compared with traditional polymer materials, metal materials and ceramics, and thus becomes a research and development hotspot in the field of current bone and dental restorative materials. In particular, it has a very wide range of applications in dental restorations, from single-tooth restorations to full-mouth restorations, including partial and full-tooth coverings using inlays, onlays, veneers and anterior/posterior crowns, and tooth replacements using fixed partial dentures, to second-generation premolars, implant abutments and implant crowns, to name a few.
The existing lithium disilicate glass-ceramic technology needs to adopt alum to adjust color so as to meet the aesthetic requirement of false teeth, but often heavy metal alum causes toxicity problems in the preparation process or the use process of patients more or less, and in addition, in the preparation process, platinum crucibles and other harsh preparation conditions can be adopted.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a microcrystalline glass for a dental restoration material and a preparation method thereof, which still ensure the aesthetic requirements of the dental restoration material on the basis of not adopting an alum component, are comparable to the situation of adding heavy metals in color and luster, and have excellent mechanical properties.
The invention provides microcrystalline glass for a tooth restoration material, which is prepared from the following raw materials:
SiO 2 60 wt%~75 wt%；
Li 2 O 10 wt%~20 wt%；
Al 2 O 3 1 wt%~10 wt%；
P 2 O 5 2 wt%~10 wt%；
K 2 O 4 wt%~11 wt%；
CeO 2 1 wt%~5 wt%；
Tb 4 O 7 0.1 wt%~1 wt%；
Er 2 O 3 0.01 wt%~0.1 wt%；
the sum of the contents of the components is 100 percent.
The invention also provides a preparation method of the microcrystalline glass for the tooth restoration material, which comprises the following steps:
a) Uniformly mixing the preparation raw materials, melting, and homogenizing to obtain precursor glass;
b) Heating the precursor glass to 450-550 ℃ for first heat preservation, heating to 600-700 ℃ for second heat preservation, and cooling;
c) Sintering the glass material obtained in the step B) to obtain the microcrystalline glass.
Preferably, in step a), the melting is carried out in a corundum crucible;
the melting temperature is 1500 to 1550 ℃, and the time is 3 to 5h.
Preferably, in step a), the homogenization is carried out in a corundum crucible;
the homogenization temperature is 1250 to 1550 ℃, and the time is 0.5 to 2.5 hours.
Preferably, in the step B), the precursor glass is heated to 450-550 ℃ at a heating rate of 3~5 ℃/min;
heating the precursor glass to 450-550 ℃ and keeping the temperature for the first time for 1-3h.
Preferably, in the step B), the temperature is increased to 600 to 700 ℃ again, and the heating rate is 3~5 ℃/min;
then heating to 600-700 ℃ and keeping the temperature for the second time for 1.5-2h.
Preferably, in step C), the sintering method comprises:
c1 Carrying out heat preservation on the glass material obtained in the step B) at the temperature of 350-450 ℃ for 4-8 min;
c2 Heating to 810-830 ℃ at a heating rate of 85-95 ℃/min, and keeping the temperature for 8-12 s;
c3 Heating to 840 to 860 ℃ at a heating rate of 25 to 35 ℃/min, and keeping the temperature for 5 to 9 min.
Preferably, step C) further comprises, after the sintering: and (6) cooling.
The invention provides microcrystalline glass for a tooth restoration material, which is prepared from the following raw materials: siO 2 2 60 wt%~75 wt%；Li 2 O 10 wt%~20 wt%；Al 2 O 3 1 wt%~10 wt%；P 2 O 5 2 wt%~10 wt%；K 2 O 4 wt%~11 wt%；CeO 2 1 wt%~5 wt%；Tb 4 O 7 0.1 wt%~1 wt%；Er 2 O 3 0.01 wt% to 0.1 wt%; the sum of the contents of the components is 100 percent. The microcrystalline glass for the tooth restoration material provided by the invention does not contain vanadium element, and the alum-free formula greatly reduces heavy metal damage, thereby reducing the poisoning risk in the preparation or use process. Meanwhile, the invention still ensures the aesthetic requirement of the tooth restoration material on the basis of not adopting alum component, has the same color as the situation of adding heavy metal, and has better physical and chemical properties such as mechanics, etc. In addition, the corundum crucible is adopted in the melting process, so that the limitation of melting conditions is further reduced, the traditional noble metal crucible is replaced, and the manufacturing cost is saved.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides microcrystalline glass for a tooth restoration material, which is prepared from the following raw materials:
SiO 2 60 wt%~75 wt%；
Li 2 O 10 wt%~20 wt%；
Al 2 O 3 1 wt%~10 wt%；
P 2 O 5 2 wt%~10 wt%；
K 2 O 4 wt%~11 wt%；
CeO 2 1 wt%~5 wt%；
Tb 4 O 7 0.1 wt%~1 wt%；
Er 2 O 3 0.01 wt%~0.1 wt%；
the sum of the contents of the components is 100 percent.
In the microcrystalline glass, siO 2 The content of the compound is 60 wt% -75 wt%. In certain embodiments of the invention, the SiO 2 Is 70.9 wt%, 69.6 wt% or 62 wt%.
In the microcrystalline glass, li 2 The content of O is 10 wt% -20 wt%. In certain embodiments of the present invention, the Li 2 The O content is 15 wt% or 18 wt%.
In the microcrystalline glass, al 2 O 3 The content of the compound is 1 wt% -10 wt%. In certain embodiments of the present invention, the Al 2 O 3 Is 2.6 wt%, 3.5 wt% or 8 wt%.
In the above microcrystalline glass, P 2 O 5 The content of the compound is 2 wt% -10 wt%. In certain embodiments of the invention, the P 2 O 5 Is 3 wt%, 4 wt% or 8 wt%.
In the microcrystalline glass, K 2 The content of O is 4 wt% -11 wt%. In certain embodiments of the invention, the K 2 The O content is 4 wt% or 10 wt%.
In the microcrystalline glass, ceO 2 The content of the additive is 1 wt% -5 wt%. In certain embodiments of the invention, the CeO 2 Is 1.8 wt%, 1.6 wt% or 5 wt%.
In the microcrystalline glass, tb 4 O 7 The content of (b) is 0.1 wt% -1 wt%. In the inventionIn certain embodiments, the Tb 4 O 7 Is 0.4 wt%, 0.3 wt% or 0.8 wt%.
In the microcrystalline glass, er 2 O 3 The content of the compound is 0.01 wt% -0.1 wt%. In certain embodiments of the present invention, said Er 2 O 3 The content of (A) is 0.1 wt% or 0.05 wt%.
The raw materials for preparing the microcrystalline glass do not contain vanadium.
The invention also provides a preparation method of the microcrystalline glass for the tooth restoration material, which comprises the following steps:
a) Uniformly mixing the preparation raw materials, melting, and homogenizing to obtain precursor glass;
b) Heating the precursor glass to 450-550 ℃ for first heat preservation, heating to 600-700 ℃ for second heat preservation, and cooling;
c) Sintering the glass material obtained in the step B) to obtain the microcrystalline glass.
In step A):
and uniformly mixing the preparation raw materials, melting, and homogenizing to obtain the precursor glass.
In some embodiments of the invention, the melting temperature is 1500 to 1550 ℃, in particular 1500 ℃; the time is 3 to 5 hours, specifically 3 hours. The melting is carried out in a corundum crucible.
In certain embodiments of the invention, the temperature of the homogenization is 1250 to 1550 ℃, in particular 1250 ℃; the time is 0.5 to 2.5 hours, specifically 0.5 hour. The homogenization is carried out in a corundum crucible.
In step B):
and heating the precursor glass to 450-550 ℃ for first heat preservation, heating to 600-700 ℃ for second heat preservation, and cooling.
In some embodiments of the invention, the precursor glass is heated to 450 to 550 ℃ at a heating rate of 3~5 ℃/min; specifically, the temperature can be increased to 450 ℃ or 500 ℃ at 3 ℃/min or 5 ℃/min.
In some embodiments of the invention, the precursor glass is heated to 450 to 550 ℃ and the total time of the first heat preservation is 1 to 3h; specifically, the time is 1h or 3h.
In some embodiments of the invention, the temperature rise rate of the temperature rise to 600 to 700 ℃ is 3~5 ℃/min; specifically, the temperature can be increased to 600 ℃ or 660 ℃ at 3 ℃/min or 5 ℃/min.
In some embodiments of the invention, the temperature is raised to 600 to 700 ℃ and the total time of the second heat preservation is 1.5 to 2h; specifically, the time is 2h.
In certain embodiments of the invention, step B) is performed in an annealing furnace, and the cooling is furnace cooling.
In step C):
sintering the glass material obtained in the step B) to obtain the microcrystalline glass.
In certain embodiments of the invention, the method of sintering comprises:
c1 Carrying out heat preservation on the glass material obtained in the step B) at the temperature of 350-450 ℃ for 4-8 min;
c2 Heating to 810-830 ℃ at a heating rate of 85-95 ℃/min, and keeping the temperature for 8-12 s;
c3 Heating to 840 to 860 ℃ at a heating rate of 25 to 35 ℃/min, and keeping the temperature for 5 to 9 min.
The sintering is performed in a sintering furnace.
In step c 1):
in certain embodiments, the incubation temperature is 350 ℃ or 400 ℃ for 6 min or 8 min.
In step c 2):
in certain embodiments, the ramp rate is 85 ℃/min or 90 ℃/min, the hold temperature is 810 ℃ or 820 ℃, and the time is 10 s or 12 s.
In step c 3):
in some embodiments, the temperature rise rate is 25 ℃/min or 30 ℃/min, the temperature for heat preservation is 840 ℃ or 850 ℃, and the time is 7 min or 9 min.
In some embodiments of the present invention, after sintering, further comprises: and (6) cooling.
The cooling comprises the following steps:
cooling to 600-700 ℃ along with the furnace, then opening the furnace door, and cooling to room temperature.
In certain embodiments of the invention, the furnace is cooled to 650 ℃ or 700 ℃.
The source of the above-mentioned raw materials is not particularly limited, and the raw materials may be generally commercially available.
Has the advantages that:
1) Dental restorative materials such as dentures are worn in the mouth of a patient for a long time, and thus, materials containing heavy metals have problems in that vanadium is absorbed by the human body and thus damages the human body. The microcrystalline glass for the tooth restoration material provided by the invention does not contain vanadium element, and the alum-free formula greatly reduces heavy metal damage, thereby reducing the poisoning risk in the preparation or use process.
2) The invention still ensures the aesthetic requirement of the tooth restoration material on the basis of not adopting alum component, has the same color and luster as the situation of adding heavy metal, and simultaneously obtains better flexural strength.
3) The corundum crucible is adopted in the melting process, so that the limitation of melting conditions is further reduced, the traditional noble metal crucible is replaced, and the manufacturing cost is saved.
In order to further illustrate the present invention, the following will describe in detail a microcrystalline glass for dental restorative material and a method for preparing the same, which are provided by the present invention, with reference to the following examples, but should not be construed as limiting the scope of the present invention.
Example 1
The microcrystalline glass for the tooth restoration material is prepared from the following raw materials:
SiO 2 70.9 wt%；
Li 2 O 15 wt%；
Al 2 O 3 2.6 wt%；
P 2 O 5 3 wt%；
K 2 O 4 wt%；
CeO 2 1.8 wt%；
Tb 4 O 7 0.4 wt%；
Er 2 O 3 0.1 wt%。
the preparation method of the microcrystalline glass for the tooth restoration material comprises the following steps:
1) Uniformly mixing the above prepared raw materials, putting into a corundum crucible, feeding into a furnace, melting at 1500 ℃ for 3h, and homogenizing at 1250 ℃ for 0.5h to obtain precursor glass;
2) Heating the precursor glass to 500 ℃ at a speed of 5 ℃/min in an annealing furnace, and keeping the temperature, wherein the total time of heating and keeping the temperature is 1h;
heating to 660 ℃ at the speed of 5 ℃/min, preserving heat, wherein the total time of heating and preserving heat is 2h, and cooling along with the furnace;
3) Preserving the heat of the glass material obtained in the step 2) for 6 min at 400 ℃ in a sintering furnace;
heating to 820 ℃ at the heating rate of 90 ℃/min, and preserving the heat by 10 s;
heating to 850 ℃ at the heating rate of 30 ℃/min, preserving heat for 7 min, cooling to 650 ℃ along with the furnace, then opening the furnace door, and cooling to room temperature to obtain the glass ceramics.
Example 2
The microcrystalline glass for the tooth restoration material is prepared from the following raw materials:
SiO 2 69.6 wt%；
Li 2 O 15 wt%；
Al 2 O 3 3.5 wt%；
P 2 O 5 4 wt%；
K 2 O 4 wt%；
CeO 2 1.6 wt%；
Tb 4 O 7 0.3 wt%；
Er 2 O 3 0.1 wt%。
the preparation method of the microcrystalline glass for the tooth restoration material comprises the following steps:
1) Uniformly mixing the above prepared raw materials, putting into a corundum crucible, feeding into a furnace, melting at 1500 ℃ for 3h, and homogenizing at 1250 ℃ for 0.5h to obtain precursor glass;
2) Heating the precursor glass to 500 ℃ at a speed of 5 ℃/min in an annealing furnace, and keeping the temperature, wherein the total time of heating and keeping the temperature is 1h;
heating to 660 ℃ at the speed of 5 ℃/min, preserving heat, wherein the total time of heating and preserving heat is 2h, and cooling along with the furnace;
3) Preserving the heat of the glass material obtained in the step 2) for 6 min at 400 ℃ in a sintering furnace;
heating to 820 ℃ at the heating rate of 90 ℃/min, and preserving the heat by 10 s;
heating to 850 ℃ at the heating rate of 30 ℃/min, preserving heat for 7 min, cooling to 650 ℃ along with the furnace, then opening the furnace door, and cooling to room temperature to obtain the glass ceramics.
Example 3
The microcrystalline glass for the tooth restoration material is prepared from the following raw materials:
SiO 2 62 wt%；
Li 2 O 18 wt%；
Al 2 O 3 8 wt%；
P 2 O 5 8 wt%；
K 2 O 10 wt%；
CeO 2 5 wt%；
Tb 4 O 7 0.8 wt%；
Er 2 O 3 0.05 wt%。
the preparation method of the microcrystalline glass for the tooth restoration material comprises the following steps:
1) Uniformly mixing the above prepared raw materials, putting into a corundum crucible, feeding into a furnace, melting at 1500 ℃ for 3h, and homogenizing at 1250 ℃ for 0.5h to obtain precursor glass;
2) Heating the precursor glass to 500 ℃ at a speed of 5 ℃/min in an annealing furnace, and keeping the temperature, wherein the total time of heating and keeping the temperature is 1h;
heating to 660 ℃ at the speed of 5 ℃/min, preserving heat, wherein the total time of heating and preserving heat is 2h, and cooling along with the furnace;
3) Preserving the heat of the glass material obtained in the step 2) for 6 min at 400 ℃ in a sintering furnace;
heating to 820 ℃ at a heating rate of 90 ℃/min, and preserving the heat by 10 s;
heating to 850 ℃ at the heating rate of 30 ℃/min, preserving heat for 7 min, cooling to 650 ℃ along with the furnace, then opening the furnace door, and cooling to room temperature to obtain the glass ceramics.
Example 4
The difference from example 1 is that:
in the step 2), heating the precursor glass to 450 ℃ at a speed of 3 ℃/min in an annealing furnace, and preserving heat, wherein the total time of heating and preserving heat is 3h;
then heating to 600 ℃ at the speed of 3 ℃/min, preserving heat, wherein the total time of heating and preserving heat is 2h, and cooling along with the furnace.
Example 5
The difference from example 1 is that:
3) Preserving the heat of the glass material obtained in the step 2) for 8 min at 350 ℃ in a sintering furnace;
heating to 810 ℃ at the heating rate of 85 ℃/min, and preserving heat for 12 s;
heating to 840 ℃ at the heating rate of 25 ℃/min, preserving heat for 9 min, cooling to 700 ℃ along with the furnace, then opening the furnace door, and cooling to room temperature to obtain the microcrystalline glass.
Comparative example 1
The microcrystalline glass for the tooth restoration material is prepared from the raw material components and the content of the raw material adopted in the patent CN113716872A in the embodiment 3;
the preparation method of the microcrystalline glass for the tooth restoration material comprises the following steps:
1) Uniformly mixing the above prepared raw materials, putting into a corundum crucible, feeding into a furnace, melting at 1500 ℃ for 3h, and homogenizing at 1250 ℃ for 0.5h to obtain precursor glass;
2) Heating the precursor glass to 500 ℃ at a speed of 5 ℃/min in an annealing furnace, and keeping the temperature, wherein the total time of heating and keeping the temperature is 1h;
heating to 660 ℃ at the speed of 5 ℃/min, preserving heat for 2 hours, and cooling along with the furnace;
3) Preserving the heat of the glass material obtained in the step 2) for 6 min at 400 ℃ in a sintering furnace;
heating to 820 ℃ at a heating rate of 90 ℃/min, and preserving the heat by 10 s;
heating to 850 ℃ at the heating rate of 30 ℃/min, preserving heat for 7 min, cooling to 650 ℃ along with the furnace, then opening a furnace door, and cooling to room temperature to obtain the microcrystalline glass.
Comparative example 2
The difference from example 1 is that:
adding CeO 2 Replacement by Fe 3 O 4 。
Comparative example 3
The difference from example 1 is that:
CeO is added 2 Replacement to MnO 2 。
Comparative example 4
The difference from example 1 is that:
tb in example 1 4 O 7 And Er 2 O 3 Are all replaced by CeO 2 。
The microcrystalline glasses prepared in example 1~5 and comparative example 1~4 were subjected to fracture property test:
1) Sample preparation
5 specimens (glass ceramics) were prepared for each example, the specimen size being 18mm × 5mm × 2mm. Each sample was ground to give a final sample in the form of a rectangular parallelepiped having a width of 4 mm. + -. 0.25mm, a thickness of 1.2 mm. + -. 0.2mm and a length of at least 18 mm. Grinding the sample on a diamond grinding plate of 30-40 mu m, and finally polishing the sample by using a diamond grinding plate of 15-20 mu m to ensure that two opposite surfaces of the sample are flat and the error of parallelism is less than 0.05mm. The sample was thoroughly cleaned to ensure that all grinding debris was removed.
2) Test procedure
The cross-sectional dimensions of each specimen were measured to the nearest 0.01 mm, the specimens were centered on the support point of a universal material testing machine, a load was applied to the specimen surface of 4mm width in a direction perpendicular to the long axis of the specimen, and the load required for specimen fracture was determined to the nearest 0.1N with a testing machine crosshead speed of (1 ± 0.5) mm/min. The above steps were repeated to test the remaining samples.
3) Intensity calculation
The flexural strength σ was calculated according to equation (1) in megapascals (MPa).
in equation (1):
P: breaking load in units of N;
l: test span (distance between the centers of the two support cylinders) in mm;
ω: the width of the sample, the dimension of the side perpendicular to the direction of the load, in mm;
b: the thickness of the test piece, the dimension of the side parallel to the direction of the load, is given in mm.
The average flexural strength was recorded and the results are shown in table 1.
TABLE 1 average values of flexural Strength of crystallized glass prepared in example 1~5 and comparative example 1~4
The microcrystalline glasses prepared in examples 1 and 2 were subjected to a color test:
and testing the color and the chromatic aberration of the microcrystalline glass by adopting a chromatic aberration meter, automatically comparing the color difference between the sample plate and the detected product, outputting three groups of CIE L, a and b data and four groups of chromatic aberration numerical values of Delta L, delta a and Delta b after the color comparison, and providing a reference scheme for color matching. Each set of data was tested once at three different locations on the glass ceramic, and the average was taken.
The output CIE L, a, b of the glass ceramics of example 1 are shown in table 2 and table 3. Table 2 shows the output values of the microcrystalline glass matte surface (unpolished surface), and table 3 shows the output values of the microcrystalline glass reflective surface (polished surface).
TABLE 2 CIE L, a, b three sets of data for matte surface output of microcrystalline glass of example 1
Table 3 CIE L, a, b three sets of data for the output of the reflective surface of the nucleated glass of example 1
The microcrystalline glass of example 2 has three sets of CIE L, a, b outputs as shown in tables 4 and 5. Table 4 shows the output values of the microcrystalline glass matte surface (unpolished surface), and table 5 shows the output values of the microcrystalline glass reflective surface (polished surface).
TABLE 4 CIE L, a, b three sets of data for microcrystalline glass output of example 2
TABLE 5 microcrystalline glass output CIE L, a, b three sets of data for example 2
Lab values of the commercial product e-max were tested and compared to the Lab values of example 1~2, with Table 6 being the matte output value of the commercial product e-max and Table 7 being the retroreflective output value of the commercial product e-max.
TABLE 6 microcrystalline glass output CIE L, a, b three sets of data for e-max
TABLE 7 microcrystalline glass output CIE L, a, b three sets of data for e-max
Comparing tables 2 and 3 with e-max output tables 6 and 7, the values are not very different, indicating that the color of the sample prepared in example 1 is not substantially different from the commercially available product.
Comparing tables 4 and 5 with e-max output tables 6 and 7, the values are not very different, indicating that the color of the sample prepared in example 2 is not substantially different from the commercially available product.
According to the data result displayed after the color measurement of the color difference meter, the following analysis is carried out:
Δ L = Δ L sample- Δ L standard (lightness difference)
Δ a = a sample-a standard (red/green difference)
Δ b = b sample-b standard (yellow/blue difference)
The analysis result shows that the L values in the example 1 and the example 2 do not differ from the e-max by more than 2,a by more than 0.5, and the b values do not differ from 1. Therefore, the microcrystalline glass provided by the invention has no difference with the color of the products sold in the market. The contrast between the matte surface and the reflective surface is a numerical value for representing the color by data more comprehensively.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The microcrystalline glass for the tooth restoration material is prepared from the following raw materials:
SiO 2 60 wt%~75 wt%；
Li 2 O 10 wt%~20 wt%；
Al 2 O 3 1 wt%~10 wt%；
P 2 O 5 2 wt%~10 wt%；
K 2 O 4 wt%~11 wt%；
CeO 2 1 wt%~5 wt%；
Tb 4 O 7 0.1 wt%~1 wt%；
Er 2 O 3 0.01 wt%~0.1 wt%；
the sum of the contents of the components is 100 percent.
2. A preparation method of microcrystalline glass for a tooth restoration material comprises the following steps:
a) Uniformly mixing the preparation raw materials, melting, and homogenizing to obtain precursor glass;
b) Heating the precursor glass to 450-550 ℃ for first heat preservation, heating to 600-700 ℃ for second heat preservation, and cooling;
c) Sintering the glass material obtained in the step B) to obtain the microcrystalline glass.
3. A method according to claim 2, wherein in step a), the melting is carried out in a corundum crucible;
the melting temperature is 1500 to 1550 ℃, and the time is 3 to 5h.
4. A method according to claim 2, wherein in step A), the homogenization is carried out in a corundum crucible;
the homogenization temperature is 1250 to 1550 ℃, and the time is 0.5 to 2.5 hours.
5. The preparation method according to claim 2, wherein in the step B), the precursor glass is heated to 450 to 550 ℃ at a heating rate of 3~5 ℃/min;
heating the precursor glass to 450-550 ℃ and keeping the temperature for the first time for 1-3h.
6. The preparation method according to claim 2, wherein in the step B), the temperature rise rate of the temperature rise to 600 to 700 ℃ is 3~5 ℃/min;
then heating to 600-700 ℃ and keeping the temperature for the second time for 1.5-2h.
7. The method of manufacturing according to claim 2, wherein in step C), the method of sintering comprises:
c1 Carrying out heat preservation on the glass material obtained in the step B) at the temperature of 350-450 ℃ for 4-8 min;
c2 Heating to 810-830 ℃ at a heating rate of 85-95 ℃/min, and keeping the temperature for 8-12 s;
c3 Heating to 840 to 860 ℃ at a heating rate of 25 to 35 ℃/min, and keeping the temperature for 5 to 9 min.
8. The method according to claim 2, wherein the step C) further comprises, after the sintering: and (6) cooling.
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