CN103964692B - A/W bio-microcrystal glass with machinability and preparation method thereof - Google Patents
A/W bio-microcrystal glass with machinability and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of A/W bio-microcrystal glass with machinability and preparation method thereof, the single wollastonite that it utilizes glass matrix identical respectively and the glass ceramics frit that single phosphatic rock is crystalline phase, by sintering method be prepared from after mixing with mica frit.Because devitrified glass of the present invention overcomes processing difficulties containing wollastonite crystalline phase and the lower technological deficiency of mica glass ceramic intensity simultaneously, and the biocompatibility advantage remained containing phosphatic rock crystalline phase devitrified glass, thus make it have certain mechanical property and biocompatibility, there is again good machinability.
Description
Technical field
The invention belongs to inorganic materials manufacture field, relate to and a kind of there is devitrified glass of biological activity, machinability and mechanical property and preparation method thereof simultaneously; Relate to a kind of single phosphatic rock (W utilizing glass matrix identical specifically, wollastonite) glass ceramics frit of crystalline phase and single wollastonite (A, apatite) frit, be prepared from by sintering method after mixing with mica frit, there is certain mechanical property and biocompatibility and devitrified glass and preparation method thereof of easy machining.
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.
In devitrified glass, the devitrified glass containing wollastonite crystalline phase has higher mechanical property, but processing is more difficult; Devitrified glass containing phosphatic rock crystalline phase has certain biocompatibility.Mica glass ceramic is due to the anisotropy of crystal height on one dimension or two-dimensional directional, and determine mica glass ceramic and have good machinability, therefore mica glass ceramic also becomes the important research object of dentistry factorial lumber material.Last century the seventies, the Corning company of the U.S. is at first by the commercialization of dentistry devitrified glass, and its main products Dicor and Macor is just using four silicon micas and fluorophlogopite as principal crystalline phase respectively, and uses till today.It is because this material can imitate out the translucency of natural teeth that mica glass ceramic is introduced as another major reason of full ceramic restoration material in Oral Repair field, has good aesthetic property.But because the intensity of mica glass ceramic is relatively low, which limits it and be engaged the larger backteeth district of strength, the use in district of especially grinding one's teeth in sleep.
Nineteen eighty-two, the Kokubo etc. of Japan utilizes scorification to develop AW bioactive devitrified glass containing phosphatic rock, wollastonite crystalline phase and glassy phase, its good biocompatibility, after goods implant, safe, nontoxic, without untoward reactions such as rejections; Because devitrified glass contains wollastonite crystalline phase, therefore there is higher mechanical property.But mechanical property is higher means that processing is more difficult, and when utilizing scorification to prepare shape of product and performance wayward.
Afterwards, along with going deep into of research, researchist proposes to adopt the Production of A/W Glass-Ceramic by Sol-Gel Method.Such as: a kind of preparation method of novel bioactive glass-ceramic-wollastonite/phosphatic rock (AW) glass-ceramic disclosed in Chinese Patent Application No. 2005100211840, it is take tetraethoxy as silicon source, triethyl phosphate is phosphorus source, Ca (NO
3)
24H
2o, Mg (NO
3)
26H
2o, NH
4hF
2for calcium, magnesium, fluorine source, deionized water, ethanol are solvent, HNO
3for catalyzer and regulation system pH value, prepare colloidal sol at a certain temperature, colloidal sol obtains submicron order high reactivity precursor powder after ageing, drying, pre-burning; Precursor powder prepares AW glass-ceramic through granulation, shaping, high temperature sintering." functional materials " periodical first phase in 2009, Xue Ming, Zhou great Li, Cao Juhui, Wang Hongtao, Yang Weizhong disclosed one " preparation of apatite-wollastonite porous glass ceramics and crystal phase structure are studied " article.Although this technology overcomes scorification prepare the defect that AW bioactive devitrified glass exists, due in the preparation, wollastonite and phosphatic rock crystalline phase in same formula, be prepared from simultaneously; The defect caused: one is the product performance poor controllability finally made, once product performance are undesirable, need again to prepare, risk is larger; Two is that processing requirement is harsher, if a certain component proportion needs adjustment, causes whole system proportioning all must adjust, pulls one hair and move the whole body, be unfavorable for industrial application; Three are: when preparing the devitrified glass of tooth in this way, cause the mechanical property of the finished product to adjust in time; Four is processing difficulties.
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.
The present invention proposes a kind of devitrified glass simultaneously with biological activity, machinability and mechanical property, it is the glass ceramics frit that the single wollastonite that utilizes glass matrix identical respectively and single phosphatic rock are crystalline phase, by sintering method is prepared from after mixing with mica frit; By changing the blending ratio of three kinds of frits, devitrified glass can be made both to have had higher force and physiologically acceptable performance, there is again good processing characteristics; Through retrieval, there is no patent and the paper report of this matrix material at present.
Summary of the invention
The object of this invention is to provide a kind of A/W bio-microcrystal glass with machinability, this devitrified glass overcomes processing difficulties containing wollastonite crystalline phase and the lower technological deficiency of mica glass ceramic intensity simultaneously, and the biocompatibility advantage remained containing phosphatic rock crystalline phase devitrified glass, thus make it have certain mechanical property and biocompatibility, there is again good machinability.
The present invention provides a kind of method preparing this tooth devitrified glass simultaneously.
For achieving the above object, devitrified glass of the present invention is by the identical wollastonite glass ceramics frit of glass matrix and phosphatic rock glass ceramics frit, mix with mica frit, sinter and come, detailed preparation method is as follows:
The first step: prepare phosphatic rock glass ceramics frit powder
1.1st step: accurately take SiO in proportion
240-50 part, Al
2o
31-5 part, CaO5-13 part, BaO1-4 part, MgO1-5 part, B
2o
30.3-2 part, Na
2o+K
2o5-15 part, CaF
20.3-2 part, P
2o
51-5 part, ZnO1-5 part, Sb
2o
30.3-1 part, wherein BaO, Na
2o+K
2o is converted into BaCO
3, Na
2cO
3+ K
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 frit, pulverize, granularity ≯ 1 μm;
Second step: prepare wollastonite glass ceramics frit powder
2.1st step: accurately take SiO in proportion
240-50 part, Al
2o
31-5 part, CaO15-30 part, BaO1-4 part, MgO1-5 part, B
2o
30.3-2 part, Na
2o+K
2o5-15 part, CaF
20.3-2 part, ZnO1-5 part, Sb
2o
30.3-1, wherein BaO, Na
2o+K
2o is converted into BaCO respectively
3, Na
2cO
3+ K
2cO
3after weigh; Mixing is poured in stirrer, stirs 1 hour;
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 frit, pulverize, granularity ≯ 1 μm;
3rd step: prepare mica glass ceramic frit powder
3.1st step: accurately take SiO in proportion
240-50 part, Al
2o
35-10 part, CaO1-5 part, MgO5-10 part, B
2o
30.2-2 part, Na
2o+K
2o5-15 part, MgF
210-20 part, P
2o
51-5 part, ZnO1-3 part, Sb
2o
30.2-1 part, wherein Na
2o+K
2o is converted into Na
2cO
3+ K
2cO
3after weigh; Mixing is poured in stirrer, stirs 1 hour;
3.2nd step: poured into by the powder raw material stirred in the kiln of 1500-1550 DEG C, found 2-4 hour, shrend, dries and pulverizes, granularity ≯ 1 μm;
4th step: prepare mixed frit powder
By wollastonite glass ceramics frit powder, phosphatic rock glass ceramics frit powder and mica glass ceramic frit powder according to (1 ~ 5): (5 ~ 1): the ratio of (4 ~ 1) is weighed respectively, mixing, stirs;
5th step: cloth
Forming mould is laid mixed frit powder;
6th step: sintering processes in crystallization furnace
Rise in 1050-1150 DEG C of temperature range with the temperature rise rate of 2-10 DEG C/min, insulation 1-2 hour;
7th step: cooling, trimming, polishing, carries out forming process.
Above-mentioned number is weight part.
Vickers' hardness ≮ 5.50GPa (HV that flexural strength ≮ 60MPa, FM-700 type microhardness tester that the material use WDW3100 type electronic universal tester utilizing the present invention to be prepared into is tested are tested
0.5).Can be used as medical material.
Positively effect of the present invention is: 1. the difference of wollastonite and phosphatic rock frit formula is CaO content, only CaO content need be changed like this on original formula basis, just can obtain the frit containing wollastonite and phosphatic rock crystalline phase respectively, formulating of recipe is simple, is convenient to industrialization promotion; 2. wollastonite is identical with the glass matrix of phosphatic rock frit, and interval consistent with the sintering crystallization treatment temp of mica frit, is conducive to when three kinds of frits sinter compatible; 3. the blending ratio of wollastonite frit is changed separately, the mechanical property of adjustable devitrified glass; The blending ratio of independent change phosphatic rock frit, the biocompatibility of adjustable devitrified glass; The blending ratio of independent change mica frit, the machinability of adjustable devitrified glass; If 4. the present invention needs the performance changing devitrified glass simultaneously, under the prerequisite without the need to again preparing glass ceramics frit, by changing the blending ratio between three kinds of frits, just can prepare the devitrified glass of different performance, the factor that preparation technology is pind down is little, process controllability and strong operability, be convenient to promote the use of.5. because devitrified glass of the present invention overcomes processing difficulties containing wollastonite crystalline phase and the lower technological deficiency of mica glass ceramic intensity simultaneously, and the biocompatibility advantage remained containing phosphatic rock crystalline phase devitrified glass, thus make it have certain mechanical property and biocompatibility, there is again good machinability.
Accompanying drawing explanation
The X ray diffracting spectrum of Fig. 1 devitrified glass prepared by example one of the present invention;
The X ray diffracting spectrum of Fig. 2 devitrified glass prepared by example two of the present invention;
The X ray diffracting spectrum of Fig. 3 devitrified glass prepared by example three of the present invention;
The middle and lower part of Fig. 1, Fig. 2 and Fig. 3 is respectively wollastonite (CaSiO
3), phosphatic rock (Ca
5(PO
4)
3and mica (KMg F)
3(Si
3al) O
10f
2) the standard X-ray diffraction collection of illustrative plates of three kinds of crystalline phases, the diffracting spectrum that top obtains after being actual sintered end of processing.
Embodiment
Technical scheme of the present invention is further illustrated below for several different devitrified glass
Embodiment one: the devitrified glass for the ratio preparation improving mica frit with free-cutting machinability
Phosphatic rock glass ceramics 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;
Wollastonite glass ceramics frit is founded by the raw material of following weight part and is formed: SiO
246 parts, Al
2o
33.3 parts, CaO19 part, BaO2 part, MgO3.6 part, B
2o
32 parts, Na
2o+K
2o13 part, CaF
20.6 part, ZnO3 part, Sb
2o
31 part;
Mica glass ceramic frit is calcined by the raw material of following weight part and is formed: SiO
245 parts, Al
2o
38 parts, CaO2 part, MgO10 part, B
2o
31 part, Na
2o+K
2o8 part, MgF
219 parts, P
2o
55 parts, ZnO1 part, Sb
2o
31 part.
Concrete preparation method is as follows:
(1) prepare phosphatic rock glass ceramics frit powder: 1. take phosphatic rock 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, pulverize and form frit powder, granularity ≯ 1 μm;
(2) prepare wollastonite glass ceramics frit powder: 1. take wollastonite 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, pulverize and form frit powder, granularity ≯ 1 μm;
(3) prepare mica glass ceramic frit powder: 1. accurately take mica frit raw material in proportion, mixing is poured in stirrer, stirs 1 hour; 2. the powder raw material stirred is poured in the kiln of 1530 DEG C, calcine 2 hours, cooling, pulverize after taking out, granularity ≯ 1 μm;
(4) prepare mixed frit powder: by phosphatic rock frit powder, wollastonite frit powder and mica frit powder according to 3: 3: 4 ratio weigh respectively, mixing, stir;
(5) cloth: lay mixed frit powder on forming mould;
(6) sintering processes in crystallization furnace: rise in 1050-1150 DEG C of temperature range with the temperature rise rate of 2-10 DEG C/min, insulation 1-2 hour;
(7) cool;
(8) trimming, polishing, carry out forming process.
The X ray diffracting spectrum of the devitrified glass of preparation is shown in Fig. 1, as can be seen from Figure 1: containing wollastonite, phosphatic rock and mica three kinds of crystalline phases in prepared devitrified glass, find through contrast: the main diffraction peak of mica is the highest, illustrate that mica is principal crystalline phase, wollastonite and phosphatic rock are paracrystalline phase, and such devitrified glass has good machinability.
Be the Vickers' hardness that 64.9MPa, 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 5.63GPa (HV
0.5), can medically for the filling of Cranial defect.
Embodiment two: to prepare the teeth repairing material devitrified glass with higher force performance
Embodiment two is compared with embodiment one, difference be the mutual blending ratio that have changed three kinds of frit powder, namely phosphatic rock frit powder, wollastonite frit powder and mica frit powder according to 2: 5: 1 ratio weigh respectively, mixing, stir.Other is identical with embodiment.
The X ray diffracting spectrum preparing devitrified glass is shown in Fig. 2, as can be seen from Figure 2: containing wollastonite, phosphatic rock and mica three kinds of crystalline phases in prepared devitrified glass, find through contrast: the main diffraction peak of wollastonite is the highest, illustrate that wollastonite is principal crystalline phase, mica and phosphatic rock are paracrystalline phase, and such devitrified glass has good mechanical property.
Be the Vickers' hardness that 82.6MPa, 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 5.95GPa (HV
0.5); Can medically for teeth repairing material.
Contrast as can be seen from embodiment two and embodiment one: the present invention, not adjusting under three kinds of frits formula prerequisites, only changes the blending ratio of three kinds of frit powder, obtain devitrified glass mechanical property be significantly improved, can be used for the environment having higher hardness to require; In other words, the blending ratio suitably between adjustment frit, with regard to its function of adjustable, this illustrates that preparation method of the present invention is relatively more flexible, and the condition pind down in system is few, is applicable to Industry Promotion.
Embodiment three: to be prepared in medically for artificial bone substitute materials devitrified glass
Embodiment three and embodiment one are distinguished and are, have adjusted the content of CaO and the melt temperature of three kinds of frits in three kinds of frits, that is: the content of CaO in phosphatic rock glass ceramics frit are dropped to 10 parts by 13 parts; The content of wollastonite glass ceramics frit CaO is brought up to 24 parts by 19 parts; The content of mica glass ceramic frit CaO is brought up to 3 parts by 2 parts; The melt temperature preparing phosphatic rock glass ceramics frit is adjusted to 1580 DEG C; The melt temperature preparing wollastonite glass ceramics frit is adjusted to 1540 DEG C; The melt temperature preparing mica glass ceramic frit is adjustment 1530 DEG C.
The X ray diffracting spectrum preparing devitrified glass is shown in Fig. 3, as can be seen from Figure 3: containing wollastonite, phosphatic rock and mica three kinds of crystalline phases in prepared devitrified glass, find through contrast: the main diffraction peak of phosphatic rock is the highest, illustrate that phosphatic rock is principal crystalline phase, mica and wollastonite are paracrystalline phase, and such devitrified glass has good biocompatibility.
The flexural strength that WDW3100 type electronic universal tester is tested is the Vickers' hardness that 72.4MPa, FM-700 type microhardness tester are tested is 5.74GPa (HV
0.5), can medically for artificial bone substitute materials.
Contrast as can be seen from embodiment three and embodiment one: the present invention is under the prerequisite of blending ratio not adjusting three kinds of frits, as long as the ratio adjusting component calcium oxide a little equally can prepare the devitrified glass with biological activity and free-cutting machinability and certain mechanical property, confirm the advantage of preparation technology of the present invention further.
Claims (2)
1. have an A/W bio-microcrystal glass for machinability, it is characterized in that, it is by the identical wollastonite glass ceramics frit of glass matrix and phosphatic rock glass ceramics frit, mix with mica frit, sinter and come, detailed preparation method is as follows:
The first step: prepare phosphatic rock glass ceramics frit powder
1.1st step: accurately take SiO in proportion
240-50 part, Al
2o
31-5 part, CaO5-13 part, BaO1-4 part, MgO1-5 part, B
2o
30.3-2 part, Na
2o+K
2o5-15 part, CaF
20.3-2 part, P
2o
51-5 part, ZnO1-5 part, Sb
2o
30.3-1 part, wherein BaO, Na
2o+K
2o is converted into BaCO
3, Na
2cO
3+ K
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 frit, pulverize, granularity ≯ 1 μm;
Second step: prepare wollastonite glass ceramics frit powder
2.1st step: accurately take SiO in proportion
240-50 part, Al
2o
31-5 part, CaO15-30 part, BaO1-4 part, MgO1-5 part, B
2o
30.3-2 part, Na
2o+K
2o5-15 part, CaF
20.3-2 part, ZnO1-5 part, Sb
2o
30.3-1 part, wherein BaO, Na
2o+K
2o is converted into BaCO respectively
3, Na
2cO
3+ K
2cO
3after weigh; Mixing is poured in stirrer, stirs 1 hour;
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 frit, pulverize, granularity ≯ 1 μm;
3rd step: prepare mica glass ceramic frit powder
3.1st step: accurately take SiO in proportion
240-50 part, Al
2o
35-10 part, CaO1-5 part, MgO5-10 part, B
2o
30.2-2 part, Na
2o+K
2o5-15 part, MgF
210-20 part, P
2o
51-5 part, ZnO1-3 part, Sb
2o
30.2-1 part, wherein Na
2o+K
2o is converted into Na
2cO
3+ K
2cO
3after weigh; Mixing is poured in stirrer, stirs 1 hour;
3.2nd step: poured into by the powder raw material stirred in the kiln of 1500-1550 DEG C, found 2-4 hour, shrend, dries and pulverizes, granularity ≯ 1 μm;
4th step: prepare mixed frit powder
By wollastonite glass ceramics frit powder, phosphatic rock glass ceramics frit powder and mica glass ceramic frit powder according to (1 ~ 5): (5 ~ 1): the ratio of (4 ~ 1) is weighed respectively, mixing, stirs;
5th step: cloth
Forming mould is laid mixed frit powder;
6th step: sintering processes in crystallization furnace
Rise in 1050-1150 DEG C of temperature range with the temperature rise rate of 2-10 DEG C/min, insulation 1-2 hour;
7th step: cooling, trimming, polishing, carries out forming process;
Above-mentioned number is weight part.
2. there is a preparation method for the A/W bio-microcrystal glass of machinability, it is characterized in that,
The first step: prepare phosphatic rock glass ceramics frit powder
1.1st step: accurately take SiO in proportion
240-50 part, Al
2o
31-5 part, CaO5-13 part, BaO1-4 part, MgO1-5 part, B
2o
30.3-2 part, Na
2o+K
2o5-15 part, CaF
20.3-2 part, P
2o
51-5 part, ZnO1-5 part, Sb
2o
30.3-1 part, wherein BaO, Na
2o+K
2o is converted into BaCO
3, Na
2cO
3+ K
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 frit, pulverize, granularity ≯ 1 μm;
Second step: prepare wollastonite glass ceramics frit powder
2.1st step: accurately take SiO in proportion
240-50 part, Al
2o
31-5 part, CaO15-30 part, BaO1-4 part, MgO1-5 part, B
2o
30.3-2 part, Na
2o+K
2o5-15 part, CaF
20.3-2 part, ZnO1-5 part, Sb
2o
30.3-1 part, wherein BaO, Na
2o+K
2o is converted into BaCO respectively
3, Na
2cO
3+ K
2cO
3after weigh; Mixing is poured in stirrer, stirs 1 hour;
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 frit, pulverize, granularity ≯ 1 μm;
3rd step: prepare mica glass ceramic frit powder
3.1st step: accurately take SiO in proportion
240-50 part, Al
2o
35-10 part, CaO1-5 part, MgO5-10 part, B
2o
30.2-2 part, Na
2o+K
2o5-15 part, MgF
210-20 part, P
2o
51-5 part, ZnO1-3 part, Sb
2o
30.2-1 part, wherein Na
2o+K
2o is converted into Na
2cO
3+ K
2cO
3after weigh; Mixing is poured in stirrer, stirs 1 hour;
3.2nd step: poured into by the powder raw material stirred in the kiln of 1500-1550 DEG C, found 2-4 hour, shrend, dries and pulverizes, granularity ≯ 1 μm;
4th step: prepare mixed frit powder
By wollastonite glass ceramics frit powder, phosphatic rock glass ceramics frit powder and mica glass ceramic frit powder according to (1 ~ 5): (5 ~ 1): the ratio of (4 ~ 1) is weighed respectively, mixing, stirs;
5th step: cloth
Forming mould is laid mixed frit powder;
6th step: sintering processes in crystallization furnace
Rise in 1050-1150 DEG C of temperature range with the temperature rise rate of 2-10 DEG C/min, insulation 1-2 hour;
7th step: cooling, trimming, polishing, carries out forming process;
Above-mentioned number is weight part.
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CN103964692B true CN103964692B (en) | 2016-01-13 |
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JPS6272540A (en) * | 1985-09-26 | 1987-04-03 | Nippon Electric Glass Co Ltd | Alkaliless crystallized glass for organism and its production |
US5634956A (en) * | 1995-06-19 | 1997-06-03 | Samjo Industrial Co., Ltd. | Bioceramics used in artificial bone and artificial dental implants and the process for the preparation thereof |
CN1168684C (en) * | 2001-12-18 | 2004-09-29 | 清华大学 | Tinct adjustable stomatic bioactive divitrified glass and its prepn |
CN1724431A (en) * | 2005-06-29 | 2006-01-25 | 四川大学 | Preparation of wollastonite/phosphatic rock (AW) biological activity glass ceramic by sol-gel method |
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