CN103951191B - The tooth devitrified glass of color gradient change between the Huang of two kinds of frit compounds/white - Google Patents

The tooth devitrified glass of color gradient change between the Huang of two kinds of frit compounds/white Download PDF

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Publication number
CN103951191B
CN103951191B CN201410179282.6A CN201410179282A CN103951191B CN 103951191 B CN103951191 B CN 103951191B CN 201410179282 A CN201410179282 A CN 201410179282A CN 103951191 B CN103951191 B CN 103951191B
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powder
glass frit
frit
white
yellow
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CN103951191A (en
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姚树玉
董亚群
曲有志
韩野
王萍
邵丹
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Shandong University of Science and Technology
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Shandong University of Science and Technology
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Abstract

The invention discloses the tooth devitrified glass of color gradient change between a kind of Huang of two kinds of frit compounds/white, first it prepare the yellow frit different with white two kinds of colors, then white micro-crystals glass frit and yellow microcrystalline glass frit are mixed respectively according to a certain percentage, cloth on request, sintering Crystallizing treatment, cooling, trimming, polishing and forming process.The devitrified glass outward appearance prepared yellow in various degree can be carried out change according to different distributing modes and be regulated, thus regulates artificial tooth color and luster, with the color and luster requirement of satisfied different tooth.

Description

The tooth devitrified glass of color gradient change between the Huang of two kinds of frit compounds/white
Technical field
The present invention relates to medical in the devitrified glass of tooth, is specifically the tooth devitrified glass of color gradient change between a kind of Huang/white.
Background technology
Devitrified glass is used as teeth repairing material and has good physical strength, chemical stability, biocompatibility, plays more and more important effect in clinical medicine.
" Liaoning University's journal (natural science edition) " periodical third phase Yang Donghui in 2006 discloses one " application of devitrified glass on teeth repairing material " article, its conclusion is: tooth devitrified glass repair materials is started late in China, but it has become one of problem developed jointly in materialogy and medical circle, believes that it can become the preferred material of people on Dental Erosion in the near future." Shaanxi Tech Univ's journal " periodical the 6th summer phase in 2004 proud, seedling swan goose, Li Yongqiang discloses one " technical study of the toughness reinforcing bio-microcrystal glass material of dental Y-TZP " article, its conclusion is: prepared devitrified glass has the character such as the strong and chemical stability of coking property Hao ﹑ density Gao ﹑ wear resistance is good, substantially meets the performance requriements of biomaterial.Therefore, devitrified glass is used as teeth repairing material is feasible technically.
But the color and luster of tooth devitrified glass is difficult to the requirement meeting natural teeth at present.After some patients grow permanent teeth, former tooth and artificial tooth color have larger difference, affect attractive in appearance.According to the color and luster of the tooth of patient, prepare the devitrified glass of color gradient change between a kind of Huang/white, make it meet the color and luster requirement of different tooth.
China Patent Publication No. CN102098979A discloses a kind of formed body be made up of form stable formed material, described material comprises at least one first component and a second component, and second component has different from described first component painted, and described second component is arranged on the inside of described first component, form interface, make described interface present curved surface in space; First component and second component are by dense sintering or porous sintered stupalith or plastic material formed body.First component and second component formed body in conjunction with time, first with machinery firmly or with binding agent by polycomponent compacting or be bonded to one, 700-800 DEG C by binder removal after at 1200 DEG C of sintering.Due to formed body be first suppressed by the intermediate molded object of multiple different colours or be bonded to one, then sintering form, this technology is made to there is following defect: one is when as dental prosthesis material, because everyone color of teeth is different, even if also there is color distortion in the tooth of same person, this just causes needs in advance to prepare the intermediate molded object of not fixed number, then the graded arrangement as required of multiple formed body is shaping, complex process is be difficult to as dental prosthesis material in reality; Two are interfaces between each intermediate molded object is weak links, the poor compatibility of interface bi-material, final molding body interface place is caused to there is performance gradient change, just as a bowl broken, by adhesives to sintering together and doing the knot that integrally reburns in advance, the performance of end product is uneven.
Summary of the invention
In order to overcome existing tooth devitrified glass complicated process of preparation, the technological deficiency that the color and luster that the product colour prepared is difficult to satisfied different tooth requires, the invention provides a kind of technique simple possible, color naturally has Huang/white between the tooth devitrified glass of color gradient change, the color of this devitrified glass is closer to the natural tooth color and luster of grownup.
For achieving the above object, tooth devitrified glass of the present invention is prepared from by following methods:
The first step: preparation white micro-crystals glass frit:
1.1st step: accurately take SiO in proportion 255-70 part, CaO15-25 part, Na 2o8-15 part, wherein Na 2o is converted into Na 2cO 3after weigh; Mixing is poured in stirrer, stirs 1 hour;
1.2nd step: poured into by the powder raw material stirred in the kiln of 1530-1580 DEG C, found 2-4 hour, shrend, takes out post-drying and forms white micro-crystals glass frit;
Second step: prepare yellow microcrystalline glass frit:
2.1st step: accurately take SiO in proportion 240-50 part, Al 2o 31-5 part, CaO8-13 part, BaO1-4 part, MgO1-5 part, B 2o 30.3-2 part, Na 2o+K 2o10-15 part, CaF 20.3-2 part, P 2o 51-5 part, ZnO1-5 part, Sb 2o 30.3-1 part, colorant 1-5 part, wherein BaO, Na 2o+K 2o is converted into BaCO 3, Na 2cO 3+ K 2cO 3after weigh, mixing pour in stirrer, stir 1 hour;
Described colorant is CeO 2and/or TiO 2;
2.2nd step: poured into by the powder raw material stirred in the kiln of 1500-1550 DEG C, found 2-4 hour, shrend, takes out post-drying and forms yellow microcrystalline glass frit;
3rd step: the devitrified glass of color gradient change between preparation is yellow/white
3.1st step: white micro-crystals glass frit and yellow microcrystalline glass frit are crushed to below 200 orders respectively, reduce gradually according to white micro-crystals glass frit powder proportions, trend that yellow microcrystalline glass frit powder increases gradually weighs respectively, mixing, stir, formed and organize mixed powder more, the thickness of every layer of frit powder is 2-10mm;
3.2nd step: cloth
Forming mould is first laid one deck white micro-crystals glass frit powder, and then above successively lay organize mixed powder more; When laying many group mixed powders, carry out according to frit powder proportions yellow in mixed powder principle from less to more, finally re-lay one deck yellow microcrystalline glass frit powder, the thickness of every layer of powder is 2-10mm;
3.3rd step: sintering
Mixed frit powder sintering processes in crystallization furnace by laying: rise in 1050-1150 DEG C of temperature range with the temperature rise rate of 2-10 DEG C/min, insulation 1-2 hour;
4th step: cooling;
5th step: trimming, polishing, carries out forming process.
Above-mentioned number is weight part.
Requirement; The white micro-crystals glass prepared is to visible light reflectance ≮ 50% of all wavelengths; Be 430-450nm to the optimal absorption scope of visible wavelength in yellow microcrystalline glass, best is 570-580nm through scope.
Vickers' hardness ≮ 5.80GPa (HV that flexural strength ≮ 80MPa, FM-700 type microhardness tester that the material utilizing the present invention to be prepared into is tested on WDW3100 type electronic universal tester are tested 0.5).Can medically for teeth repairing material.
Advantage of the present invention is:
Positively effect of the present invention is: 1. an existing proportioning is founded and the once sintered method preparing heterogeneous devitrified glass by the present invention, make into two kinds of frits respectively proportioning found and be mixed in proportion sintering, make the sintering crystallization treatment temp of two kinds of frits interval consistent, ensure that compatibility during two kinds of frit sintering; If 2. the present invention needs to change the color of material, without the need under again founding Huang, white dichromatism glass ceramics frit prerequisite, by changing the blending ratio of two kinds of frits in mixed powder, the tooth devitrified glass of the color that meets the requirements just can be prepared.3. the present invention can by adjustment frit composition proportion or the blending ratio changing two kinds of frit powder, the devitrified glass close to different crowd color of teeth can be prepared, the factor that preparation technology is pind down is little, process controllability and strong operability, is convenient to promote the use of.4. the mixed frit of different ratio is pulverized and mixed by the present invention, then lays sintering according to the variation tendency of the color of teeth of people, and make the strong mechanical property prepared, intensity is high, color nature.
Accompanying drawing explanation
Fig. 1 is the microstructure picture of the crystallite glass of example one of the present invention formula.
Embodiment
Technical scheme of the present invention is further illustrated below for several different devitrified glass
Embodiment one
White micro-crystals glass frit is founded by the raw material of following weight part and is formed: SiO 267.5 parts, CaO20 part, Na 2o12.5 part;
Yellow microcrystalline glass frit is founded by the raw material of following weight part and is formed: SiO 246 parts, Al 2o 33.3 parts, CaO13 part, BaO2 part, MgO3.6 part, B 2o 32 parts, Na 2o+K 2o13 part, CaF 20.6 part, P 2o 54.5 parts, ZnO3 part, Sb 2o 31 part, CeO 21 part, TiO 20.5 part.
Preparation method is as follows:
The first step: preparation white micro-crystals glass frit
1. take white frit raw material by above-mentioned weight part, mixing is poured in stirrer, stirs 1 hour; 2. pour in the kiln of 1570 DEG C, found 2 hours, shrend, dry, form white micro-crystals glass frit;
Second step: prepare yellow microcrystalline glass frit
1. take yellow frit raw material by above-mentioned weight part, mixing is poured in stirrer, stirs 1 hour; 2. pour in the kiln of 1550 DEG C, found 2 hours, shrend, dry and form yellow microcrystalline glass frit;
3rd step: the devitrified glass of color gradient change between preparation is yellow/white
(1) white micro-crystals glass frit and yellow microcrystalline glass frit are crushed to below 200 orders respectively, weigh respectively according to the ratio of 7: 3,5: 5,3: 7, mixing, stirs, forms three groups of mixed frit powder;
(2) cloth: first lay white micro-crystals glass frit powder on forming mould, and then thereon according to yellow powder ratio principle from less to more in mixed frit powder, lay mixing frit powder end respectively, finally re-lay yellow microcrystalline glass frit powder, every layer of frit powder thickness is 6mm; That is: from the bottom up, white micro-crystals glass frit powder is followed successively by, 7: 3 mixed frit powder, 5: 5 mixed frit powder, 3: 7 mixed frit powder and yellow microcrystalline glass frit powder,
(3) sintering processes in crystallization furnace: rise in 1110 DEG C of temperature ranges with the temperature rise rate of 5 DEG C/min, be incubated 1.5 hours;
4th step: cooling;
5th step: trimming, polishing, carries out forming process, and the appearance color of prepared devitrified glass is by presenting graded to Huang in vain.Wherein the white micro-crystals glass that goes out of white praducing frits is to visible light reflectance ≮ 50% of all wavelengths; Is 580-590nm to visible wavelength in the yellow microcrystalline glass that yellow praducing frits goes out through scope, CeO in change colorant 2, TiO 2ratio, thereupon changing through scope of this wavelength, corresponding yellow degree also changes for it.
Be the Vickers' hardness that 93.1MPa, FM-700 type microhardness tester are tested by the flexural strength in the prepared devitrified glass of test on WDW3100 type electronic universal tester be 6.14GPa (HV 0.5), can medically for teeth repairing material, Fig. 1 is shown in by the microstructure picture of the devitrified glass of preparation.
Microstructure picture as can be seen from Fig. 1: have A and B two kinds of crystal in devitrified glass of the present invention, wherein A crystal is the crystalline phase introduced by white frit, and B crystal is the crystalline phase introduced by yellow frit; Separate out two kinds of crystal after two kinds of frit mixing, wherein A, B crystalline phase and glass basis merge mutually, compatible good, pore-free, dense structure.
Embodiment two, change blending ratio
The preparation method of embodiment 2 is substantially identical with embodiment 1, unlike, the ratio that white micro-crystals glass frit and yellow frit mix mutually is respectively 6: 4,5: 5,4: 6.The white micro-crystals glass that white micro-crystals glass frit is prepared is to visible light reflectance ≮ 50% of all wavelengths; Be 430-450nm to the optimal absorption scope of visible wavelength in the yellow microcrystalline glass that yellow microcrystalline glass frit is prepared, best is 570-580nm through scope.
The appearance color of prepared devitrified glass is by presenting graded to Huang in vain.
Be the Vickers' hardness that 91.9MPa, FM-700 type microhardness tester are tested by the flexural strength in the prepared devitrified glass of test on WDW3100 type electronic universal tester be 6.21GPa (HV 0.5), basically identical with the performance of example one.Can medically for teeth repairing material.
Embodiment three, simultaneously change blending ratio and fabric thickness prepare devitrified glass
The preparation method of embodiment 3 is substantially identical with embodiment 1, unlike, the ratio that white micro-crystals glass frit and yellow microcrystalline glass frit mix mutually is respectively 8: 2,6: 4,5: 5,4: 6,2: 8, and the thickness that white micro-crystals glass frit powder, yellow microcrystalline glass frit powder, each mixed microcrystalline glass frit powder are laid is 4mm.The white micro-crystals glass that white praducing frits goes out is to visible light reflectance ≮ 50% of all wavelengths; Be 430-450nm to the optimal absorption scope of visible wavelength in the yellow microcrystalline glass that yellow praducing frits goes out, best is 570-580nm through scope.
The appearance color of prepared devitrified glass is by presenting graded to Huang in vain, and the change of gradient color is milder.
Be the Vickers' hardness that 94.7MPa, FM-700 type microhardness tester are tested by the flexural strength in the prepared devitrified glass of test on WDW3100 type electronic universal tester be 6.16GPa (HV 0.5), can medically for teeth repairing material.
As can be seen from above-mentioned three embodiments: no matter the present invention is the proportioning by changing each component in two kinds of glass ceramics frits, or by the ratio that change white micro-crystals glass frit and yellow frit mix mutually, or change blending ratio and fabric thickness simultaneously, the devitrified glass performance prepared does not have great change, it is little that this has also confirmed the factor that preparation technology of the present invention pind down, process controllability and strong operability, be convenient to promote the use of.
Number in embodiment is weight part.

Claims (2)

1. a tooth devitrified glass for color gradient change between the Huang/white of two kinds of frit compounds, it is characterized in that, it is prepared from by following methods:
The first step: preparation white micro-crystals glass frit:
1.1st step: accurately take SiO in proportion 255-70 part, CaO15-25 part, Na 2o8-15 part, wherein Na 2o is converted into Na 2cO 3after weigh; Mixing is poured in stirrer, stirs 1 hour;
1.2nd step: poured into by the powder raw material stirred in the kiln of 1530-1580 DEG C, found 2-4 hour, shrend, takes out post-drying and forms white micro-crystals glass frit;
Second step: prepare yellow microcrystalline glass frit:
2.1st step: accurately take SiO in proportion 240-50 part, Al 2o 31-5 part, CaO8-13 part, BaO1-4 part, MgO1-5 part, B 2o 30.3-2 part, Na 2o+K 2o10-15 part, CaF 20.3-2 part, P 2o 51-5 part, ZnO1-5 part, Sb 2o 30.3-1 part, colorant 1-5 part, wherein BaO, Na 2o+K 2o is converted into BaCO 3, Na 2cO 3+ K 2cO 3after weigh, mixing pour in stirrer, stir 1 hour;
Described colorant is CeO 2and/or TiO 2;
2.2nd step: poured into by the powder raw material stirred in the kiln of 1500-1550 DEG C, found 2-4 hour, shrend, takes out post-drying and forms yellow microcrystalline glass frit;
3rd step: the devitrified glass of color gradient change between preparation is yellow/white
3.1st step: white micro-crystals glass frit and yellow microcrystalline glass frit are crushed to below 200 orders respectively, reduce gradually according to white micro-crystals glass frit powder proportions, trend that yellow microcrystalline glass frit powder increases gradually weighs respectively, mixing, stirs, and is formed and organizes mixed powder more;
3.2nd step: cloth
Forming mould is first laid one deck white micro-crystals glass frit powder, and then above successively lay organize mixed powder more; When laying many group mixed powders, carry out according to frit powder proportions yellow in mixed powder principle from less to more, finally re-lay one deck yellow microcrystalline glass frit powder, the thickness of every layer of powder is 2-10mm;
3.3rd step: sintering
Mixed frit powder sintering processes in crystallization furnace by laying: rise in 1050-1150 DEG C of temperature range with the temperature rise rate of 2-10 DEG C/min, insulation 1-2 hour;
4th step: cooling;
5th step: forming process: trimming and polishing;
Above-mentioned number is weight part.
2. prepare a method for the tooth devitrified glass of color gradient change between the Huang of two kinds of frit compounds/white, it is characterized in that, method is as follows:
The first step: preparation white micro-crystals glass frit:
1.1st step: accurately take SiO in proportion 255-70 part, CaO15-25 part, Na 2o8-15 part, wherein Na 2o is converted into Na 2cO 3after weigh; Mixing is poured in stirrer, stirs 1 hour;
1.2nd step: poured into by the powder raw material stirred in the kiln of 1530-1580 DEG C, found 2-4 hour, shrend, takes out post-drying and forms white micro-crystals glass frit;
Second step: prepare yellow microcrystalline glass frit:
2.1st step: accurately take SiO in proportion 240-50 part, Al 2o 31-5 part, CaO8-13 part, BaO1-4 part, MgO1-5 part, B 2o 30.3-2 part, Na 2o+K 2o10-15 part, CaF 20.3-2 part, P 2o 51-5 part, ZnO1-5 part, Sb 2o 30.3-1 part, colorant 1-5 part, wherein BaO, Na 2o+K 2o is converted into BaCO 3, Na 2cO 3+ K 2cO 3after weigh, mixing pour in stirrer, stir 1 hour;
Described colorant is CeO 2and/or TiO 2;
2.2nd step: poured into by the powder raw material stirred in the kiln of 1500-1550 DEG C, found 2-4 hour, shrend, takes out post-drying and forms yellow microcrystalline glass frit;
3rd step: the devitrified glass of color gradient change between preparation is yellow/white
3.1st step: white micro-crystals glass frit and yellow microcrystalline glass frit are crushed to below 200 orders respectively, reduce gradually according to white micro-crystals glass frit powder proportions, trend that yellow microcrystalline glass frit powder increases gradually weighs respectively, mixing, stirs, and is formed and organizes mixed powder more;
3.2nd step: cloth
Forming mould is first laid one deck white micro-crystals glass frit powder, and then above successively lay organize mixed powder more; When laying many group mixed powders, carry out according to frit powder proportions yellow in mixed powder principle from less to more, finally re-lay one deck yellow microcrystalline glass frit powder, the thickness of every layer of powder is 2-10mm;
3.3rd step: sintering
Mixed frit powder sintering processes in crystallization furnace by laying: rise in 1050-1150 DEG C of temperature range with the temperature rise rate of 2-10 DEG C/min, insulation 1-2 hour;
4th step: cooling;
5th step: forming process: trimming and polishing;
Above-mentioned number is weight part.
CN201410179282.6A 2014-04-29 2014-04-29 The tooth devitrified glass of color gradient change between the Huang of two kinds of frit compounds/white Expired - Fee Related CN103951191B (en)

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CN112408800A (en) * 2020-11-25 2021-02-26 江西璞晶新材料股份有限公司 Method for preparing marble-like colored microcrystalline glass by using ceramic pigment

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1349944A (en) * 2001-12-18 2002-05-22 清华大学 Tinct adjustable stomatic bioactive divitrified glass and its prepn
CN103429546A (en) * 2010-12-17 2013-12-04 义获嘉伟瓦登特公司 Production of shaped dental parts composed of porous glass

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Publication number Priority date Publication date Assignee Title
DE102004026433A1 (en) * 2004-05-29 2005-12-22 Schott Ag Nanoglass powder and its use

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1349944A (en) * 2001-12-18 2002-05-22 清华大学 Tinct adjustable stomatic bioactive divitrified glass and its prepn
CN103429546A (en) * 2010-12-17 2013-12-04 义获嘉伟瓦登特公司 Production of shaped dental parts composed of porous glass

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