CN102942371B - Method for preparing fluorinated hydroxyapatite/ zirconium oxide (FHA/ZrO2) composite ceramic powder with good heat stability by hydrothermal synthesis - Google Patents

Method for preparing fluorinated hydroxyapatite/ zirconium oxide (FHA/ZrO2) composite ceramic powder with good heat stability by hydrothermal synthesis Download PDF

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CN102942371B
CN102942371B CN201210467107.8A CN201210467107A CN102942371B CN 102942371 B CN102942371 B CN 102942371B CN 201210467107 A CN201210467107 A CN 201210467107A CN 102942371 B CN102942371 B CN 102942371B
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李文旭
罗燕
邹靖
于德珍
王福平
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Harbin Institute of Technology
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Abstract

The invention provides a method for preparing fluorinated hydroxyapatite/ zirconium oxide (FHA/ZrO2) composite ceramic powder with good heat stability by hydrothermal synthesis, relates to a preparation method of the composite ceramic powder, and aims at solving the problems that all components in the composite ceramic powder are not evenly dispersed and mixed, and composite ceramic powder is poor in heat stability. The method comprises the steps of: 1, preparing yttrium-stabilized hydrous zirconium oxide powder Y2O3-Zr(OH)4; 2, preparing FHA/ZrO2 composite precursor powder by hydrothermal synthesis; and 3, carrying out heat treatment on the FHA/ZrO2 composite ceramic powder to obtain the FHA/ZrO2 composite ceramic powder with the phase composition including FHA and yttrium-stabilized tetragonal phase ZrO2. The method is applied to the field of preparing the composite ceramic powder by hydrothermal synthesis.

Description

The FHA/ZrO with good thermal stability 2the hydro-thermal synthetic preparation method of composite ceramic material
Technical field
The present invention relates to the preparation method of composite ceramic material.The invention belongs to inorganic bio field.
Background technology
Hydroxyapatite (Hydroxyapatite, be called for short HA) be the essential mineral composition of human body hard tissue bone and tooth, there is good biocompatibility and bone inducibility, after in implant into body, under the effect of body fluid, the calcium in component and the phosphorus material surface that can dissociate, by body tissue, absorbed, be organized in interface formation chemical bonds with skeleton, thereby the growth of inducing peripheral osseous tissue is implanted in human body and can produce rejection therefore can be used as the substitution material of sclerous tissues.Therefore, become one of the most promising generally acknowledged at present biological hard tissue substitution material.
But, to compare with natural bone tissue, pure HA embedded material exists serious weak point in mechanical property.The bending strength lower (20-100MPa) of HA, the poor (1.0-1.2MPam of toughness 1/2, people's bone is 2-12MPam 1/2).Thereby the pure HA embedded material of artificial preparation can not be used as large scale, the high bone of body planting material bearing a heavy burden and repair materials, only can be applied to nonbearing small-sized implantation body, as damaged in tooth root under people, otica, filling bone etc., this has limited its application in clinical treatment greatly.
In order to address this problem, method is that itself and inactive ceramic component are compounded to form to composite preferably at present, in numerous inactive ceramic, zirconium oxide has unique transformation toughening characteristic and the impayable mechanical performance of other inactive ceramic, can improve by a larger margin toughness and the intensity of composite ceramics, except the excellent part in mechanical performance, ZrO 2pottery is also one of the most permanent material of physiological property in tooth-planting material, has good physiological compatibility.
The conventional preparation method of composite ceramics is solid phase mixing method at present, is about to HA powder body and inactive ceramic powder body (as ZrO 2) both are mixed in proportion, and then through ball milling, dry supervisor, obtain composite granule, afterwards it are further become the operations such as base, sintering, the composite ceramics promoting to obtain mechanical property.Although this method is simple to operation, lower to the requirement of equipment, because material component itself there are differences, easily cause in composite granule each component to disperse inhomogeneous, be difficult to reach homogeneous and mix, thereby affect the stability of the mechaanical property of materials.
In addition, the heat decomposition temperature of pure ha is about 1200 ℃, but when hydroxyapatite and second-phase compound tense, its heat decomposition temperature can reduce greatly, causes can generating β calcium phosphate (β-TCP) after HA decomposition.Because two kinds of materials exist larger difference at aspects such as density, biological activity and degradabilities, therefore very easily cause the change of final bone alternate material physicochemical properties, cause the reduction of the performances such as embedded material degradability, osteocyte absorbability and biological activity.
Summary of the invention
The present invention will solve in composite ceramic material that each component disperses to mix the problem of inhomogeneous and poor heat stability and the FHA/ZrO with good thermal stability that provides 2the hydro-thermal synthetic preparation method of composite ceramic material.
One, yttrium is stablized hydrous zirconium oxide(HZO) powder body Y 2o 3-Zr (OH) 4preparation: by ZrOCl 28H 2o and Y (NO 3) 38H 2o is dissolved in distilled water and makes mixed solution, to the ammonia of mixed solution and dripping mass percentage concentration 25%～28%, after ageing 1.5～2h, the precipitation obtaining after ageing is carried out to centrifugal, washing, obtains yttrium and stablizes hydrous zirconium oxide(HZO) powder body Y 2o 3-Zr (OH) 4; Wherein, ZrOCl in described mixed solution 2concentration is 0.19～0.21molL -1,, in described mixed solution, the mol ratio of Zr and Y is 100: 6;
Two, Hydrothermal Synthesis FHA/ZrO 2compound precursor powder body
A, press Ca/P mol ratio for (1.67～1.68): 1 mixes calcium nitrate aqueous solution with ammonium dibasic phosphate aqueous solution, obtain HA forerunner's system; Wherein, described calcium nitrate aqueous solution concentration is 0.50～0.55molL -1, described ammonium dibasic phosphate aqueous solution concentration is 0.30～0.35molL -1;
B, use distillation water as medium, stablize hydrous zirconium oxide(HZO) powder body Y by the yttrium of preparing in step 1 2o 3-Zr (OH) 4ultrasonic dispersion forms suspension, then in suspension, be added dropwise to HA forerunner's system of preparing in step a, add again ammonium fluoride, form FHA precursor solution, with the ammonia of mass percentage concentration 25%～28%, regulate the pH value of FHA precursor solution simultaneously, be prepared into composite granule hydro-thermal forerunner system; Wherein, described HA forerunner's system is to be (0.348～0.351) by the mol ratio of Zr and Ca: 1 adds, and described ammonium fluoride is (0.19～0.21) by F and Ca mol ratio: 1 adds;
C, by after the composite granule hydro-thermal forerunner system magnetic agitation 10～12h preparing in step b, put into the rustless steel hydro-thermal still of teflon lined, rustless steel hydro-thermal still is put into siliconit sintering furnace, then hydro-thermal reaction 6～6.5h at 180～185 ℃, after taking-up, use successively distilled water and absolute ethanol washing hydrothermal product, then filter, be drying to obtain FHA/ZrO 2compound precursor powder body;
Three, FHA/ZrO 2the heat treatment of composite ceramic material
By the FHA/ZrO making in step 2 2compound precursor powder body is placed in Muffle furnace, carries out sintering 2～2.1h at 1100～1120 ℃, obtains phase and consists of fluorine substituted hydroxy apatite and the stable tetragonal phase zirconium oxide FHA/ZrO of yttrium 2composite ceramic material.
Invention effect:
The present invention proposes to prepare the hydrothermal method of hydroxyapatite and zirconic composite nano-powder, introduces a small amount of fluorine element simultaneously in composite granule system, improves the heat stability of composite granule.The difference of ceramic powder provided by the invention and existing Preparation Technique of Powders is:
(1) adopt hydro-thermal method to prepare fluorine substituted hydroxy apatite/zirconium oxide composite granule, because each component is to be mixed by the microcosmic carrying out under ionic forms in liquid phase, therefore component distribution is more even.
(2) component of powder body is fluorine substituted hydroxy apatite and the yttrium stable zirconium oxide with well-crystallized, and these two kinds of phases can provide for the bioceramic material of follow-up preparation good biology performance and mechanical property.
(3) fluorion that liquid phase is introduced makes composite granule heat stability bring up to 1100 ℃ by 800 ℃, can guarantee not decompose at 1100 ℃ of temperature, has better thermal stability.
The present invention adopts hydro-thermal method liquid phase to synthesize fluorine substituted hydroxy apatite/zirconium oxide (FHA/ZrO 2) composite granule, because this method is each component of while synthetic composite material in liquid phase, therefore can make material mixing uniformity be greatly improved, farthest improve the mechanical property of composite; In order to improve the heat stability of hydroxyapatite in composite granule, in composite granule system, take ammonium fluoride as raw material introducing fluorine element simultaneously.Object is that the bone reparation pottery that has excellent mechanical performances, excellent biology performance and heat stability for further preparing concurrently provides reliable raw material.
Accompanying drawing explanation
Fig. 1 is the XRD figure of composite ceramic material in test 1; Wherein a is 70FHA/30ZrO 2, b is 70HA/30ZrO 2, c is PDF#09-0169 β-TCP, and d is PDF#09-0432HA, and e is PDF#50-1089ZrO 2,
Figure BDA00002427345300031
for HA, ◇.for ZrO 2; ★for β-TCP.
The specific embodiment
The specific embodiment one: the FHA/ZrO with good thermal stability of present embodiment 2the hydro-thermal synthetic preparation method of composite ceramic material is realized according to the following steps:
One, yttrium is stablized hydrous zirconium oxide(HZO) powder body Y 2o 3-Zr (OH) 4preparation: by ZrOCl 28H 2o and Y (NO 3) 38H 2o is dissolved in distilled water and makes mixed solution, to the ammonia of mixed solution and dripping mass percentage concentration 25%～28%, after ageing 1.5～2h, the precipitation obtaining after ageing is carried out to centrifugal, washing, obtains yttrium and stablizes hydrous zirconium oxide(HZO) powder body Y 2o 3-Zr (OH) 4; Wherein, ZrOCl in described mixed solution 2concentration is 0.19～0.21molL -1,, in described mixed solution, the mol ratio of Zr and Y is 100: 6;
Two, Hydrothermal Synthesis FHA/ZrO 2compound precursor powder body
A, press Ca/P mol ratio for (1.67～1.68): 1 mixes calcium nitrate aqueous solution with ammonium dibasic phosphate aqueous solution, obtain HA forerunner's system; Wherein, described calcium nitrate aqueous solution concentration is 0.50～0.55molL -1, described ammonium dibasic phosphate aqueous solution concentration is 0.30～0.35molL -1;
B, use distillation water as medium, stablize hydrous zirconium oxide(HZO) powder body Y by the yttrium of preparing in step 1 2o 3-Zr (OH) 4ultrasonic dispersion forms suspension, then in suspension, be added dropwise to HA forerunner's system of preparing in step a, add again ammonium fluoride, form FHA precursor solution, with the ammonia of mass percentage concentration 25%～28%, regulate the pH value of FHA precursor solution simultaneously, be prepared into composite granule hydro-thermal forerunner system; Wherein, described HA forerunner's system is to be (0.348～0.351) by the mol ratio of Zr and Ca: 1 adds, and described ammonium fluoride is (0.19～0.21) by F and Ca mol ratio: 1 adds;
C, by after the composite granule hydro-thermal forerunner system magnetic agitation 10～12h preparing in step b, put into the rustless steel hydro-thermal still of teflon lined, rustless steel hydro-thermal still is put into siliconit sintering furnace, then hydro-thermal reaction 6～6.5h at 180～185 ℃, after taking-up, use successively distilled water and absolute ethanol washing hydrothermal product, then filter, be drying to obtain FHA/ZrO 2compound precursor powder body;
Three, FHA/ZrO 2the heat treatment of composite ceramic material
By the FHA/ZrO making in step 2 2compound precursor powder body is placed in Muffle furnace, carries out sintering 2～2.1h at 1100～1120 ℃, obtains phase and consists of fluorine substituted hydroxy apatite and the stable tetragonal phase zirconium oxide FHA/ZrO of yttrium 2composite ceramic material.
Present embodiment effect:
Present embodiment proposes to prepare the hydrothermal method of hydroxyapatite and zirconic composite nano-powder, introduces a small amount of fluorine element simultaneously in composite granule system, improves the heat stability of composite granule.The ceramic powder that present embodiment provides and the difference of existing Preparation Technique of Powders are:
(1) adopt hydro-thermal method to prepare fluorine substituted hydroxy apatite/zirconium oxide composite granule, because each component is to be mixed by the microcosmic carrying out under ionic forms in liquid phase, therefore component distribution is more even.
(2) component of powder body is fluorine substituted hydroxy apatite and the yttrium stable zirconium oxide with well-crystallized, and these two kinds of phases can provide for the bioceramic material of follow-up preparation good biology performance and mechanical property.
(3) fluorion that liquid phase is introduced makes composite granule heat stability bring up to 1100 ℃ by 800 ℃, can guarantee not decompose at 1100 ℃ of temperature, has better thermal stability.
Present embodiment adopts the synthetic fluorine substituted hydroxy apatite/zirconium oxide (FHA/ZrO of hydro-thermal method liquid phase 2) composite granule, because this method is each component of while synthetic composite material in liquid phase, therefore can make material mixing uniformity be greatly improved, farthest improve the mechanical property of composite; In order to improve the heat stability of hydroxyapatite in composite granule, in composite granule system, take ammonium fluoride as raw material introducing fluorine element simultaneously.Object is that the bone reparation pottery that has excellent mechanical performances, excellent biology performance and heat stability for further preparing concurrently provides reliable raw material.
The specific embodiment two: present embodiment is different from the specific embodiment one: centrifugal in step 1 is centrifugal 3～5min under 5000～8000r/min condition.Other step and parameter are identical with the specific embodiment one.
The specific embodiment three: present embodiment is different from the specific embodiment one or two: the washing in step 1 is used distilled water to wash.Other step and parameter are identical with the specific embodiment one or two.
The specific embodiment four: present embodiment is different from one of specific embodiment one to three: in step 2 b, the pH value of FHA precursor solution is 9.8～10.2.Other step and parameter are identical with one of specific embodiment one to three.
The specific embodiment five: present embodiment is different from one of specific embodiment one to four: in step 2 b, ultrasonic jitter time is 10～15min.Other step and parameter are identical with one of specific embodiment one to four.
The specific embodiment six: present embodiment is different from one of specific embodiment one to five: dry in step 2 c is at 75～85 ℃ of dry 20～24h.Other step and parameter are identical with one of specific embodiment one to five.
The specific embodiment seven: present embodiment is different from one of specific embodiment one to six: the volume of the composite granule hydro-thermal forerunner system of putting in rustless steel hydro-thermal still in step 2 c be rustless steel hydro-thermal kettle long-pending 75%.Other step and parameter are identical with one of specific embodiment one to six.
By following verification experimental verification the present invention
Test 1:
One, yttrium is stablized hydrous zirconium oxide(HZO) powder body Y 2o 3-Zr (OH) 4preparation: by zirconium oxychloride ZrOCl 28H 2o and Yttrium trinitrate Y (NO 3) 38H 2o is dissolved in and in distilled water, is prepared into mixed solution, to the ammonia of the excessive mass percentage concentration 25%～28% of mixed solution and dripping until do not produce precipitation, after ageing 2h, centrifugal 5min, distilled water wash precipitation under 5000r/min condition, repeated multiple times, get supernatant 0.1molL at every turn -1silver nitrate solution check, until produce without white precipitate, obtains yttrium and stablizes hydrous zirconium oxide(HZO) powder body Y 2o 3-Zr (OH) 4; Wherein, ZrOCl in described mixed solution 2concentration is 0.2molL -1,, in described mixed solution, the mol ratio of Zr and Y is 100: 6;
Two, Hydrothermal Synthesis FHA/ZrO 2compound precursor powder body
A, by Ca/P mol ratio, be sour calcium aqueous solution to be mixed with ammonium dibasic phosphate aqueous solution in 1.67: 1, obtain hydroxyapatite HA forerunner system; Wherein, described calcium nitrate aqueous solution concentration is 0.50molL -1, described ammonium dibasic phosphate aqueous solution concentration is 0.30molL -1;
B, use distillation water as medium, stablize hydrous zirconium oxide(HZO) powder body Y by the yttrium of preparing in step 1 2o 3-Zr (OH) 4ultrasonic dispersion 30min forms suspension, then in suspension, is added dropwise to the hydroxyapatite HA forerunner system of preparing in step a, then adds ammonium fluoride to introduce the OH in F-substituted hydroxy apatite HA -, form FHA precursor solution, with the ammonia of mass percentage concentration 25%～28%, regulate the pH value to 10 of FHA precursor solution simultaneously, be prepared into composite granule hydro-thermal forerunner system; Wherein, described HA forerunner's system is to be to add at 0.35: 1 by the mol ratio of Zr and Ca, and described ammonium fluoride is to add at 0.2: 1 by F and Ca mol ratio;
C, by after the about 11h of composite granule hydro-thermal forerunner system magnetic agitation preparing in step b, put into volume filling rate and be the rustless steel hydro-thermal still of 75% teflon lined, rustless steel hydro-thermal still is put into siliconit sintering furnace, then hydro-thermal reaction 6h at 180 ℃, after taking-up, use successively distilled water and absolute ethanol washing hydrothermal product, then filtration, 80 ℃ of dry 22h obtain FHA/ZrO 2compound precursor powder body;
Three, FHA/ZrO 2the heat treatment of composite ceramic material
By the FHA/ZrO making in step 2 2compound precursor powder body is placed in Muffle furnace, by the heating rate of 5 ℃/min, Muffle furnace is heated up, and carries out sintering 2h at 1100 ℃, obtains that phase consists of fluorine substituted hydroxy apatite and yttrium is stablized tetragonal phase zirconium oxide FHA/ZrO 2composite ceramic material.
Fig. 1 calcines 2h at 1100 ℃, the XRD figure of the composite ceramic material before and after resulting fluorine adds.As can be seen from the figure, appear at 2 θ=25.8 °, 31.7 °, 32.1 ° and 33.0 ° of crystal face diffraction maximums that the diffraction maximum of locating is hydroxyapatite (HA), in 2 θ=30.2 °, 35.2 °, 50.4 ° and 60.1 ° of diffraction maximums of locating are tetragonal phase zirconium oxide (ZrO 2) crystal face diffraction maximum; And in 2 θ=25.8 °, 27.7 °, 31.0 ° and the 34.3 ° diffraction maximums that occur bata-tricalcium phosphate (β-TCP).The appearance of β-TCP shows that composite granule is after 1100 ℃ of calcinings, and the hydroxyapatite not adding in the composite granule of fluorine starts to occur thermal decomposition.But the 70FHA/30ZrO that fluorine replaces 2in composite granule, there is not the diffraction maximum of β-TCP, illustrate that this composition powder body can stable existence at 1100 ℃.
Table 1 is to utilize I in XRD figure β-TCP/ (I hAp+ I β-TCP) relative intensity of diffraction maximum calculates the content ratio of β-TCP in powder body, analyzes the degree of decomposition of hydroxyapatite in composite granule, the data obtained is as shown in table 1,70FHA/30ZrO 2represent 70%FHA (fluorine substituted hydroxy apatite) and 30%ZrO 2composite granule (weight ratio); 70HA/30ZrO 2represent 70%HA (not adding the hydroxyapatite of fluorine) and 30%ZrO 2composite granule (weight ratio);
Calcium phosphate diffraction maximum relative intensity in table 1 powder body
Powder body title I β-TCP/(I HAp+I β-TCP)
70HA/30ZrO 2 69.1％
70FHA/30ZrO 2 0.8％
As can be seen from Table 1: before not adding fluorine, the content of β-TCP that in powder body, hydroxyapatite decomposition generates is 69.1%, and after adding fluorine, in powder body, β-TCP has been difficult for being detected, and content is only 0.8%.The introducing that proves thus F-can effectively hinder the decomposition of hydroxy apatite powder when high temperature sintering, improves the heat stability of composite granule.

Claims (7)

1. the FHA/ZrO with good thermal stability 2the hydro-thermal synthetic preparation method of composite ceramic material, is characterized in that FHA/ZrO 2the hydro-thermal synthetic preparation method of composite ceramic material is realized according to the following steps:
One, yttrium is stablized hydrous zirconium oxide(HZO) powder body Y 2o 3-Zr (OH) 4preparation: by ZrOCl 28H 2o and Y (NO 3) 38H 2o is dissolved in distilled water and makes mixed solution, to the ammonia of mixed solution and dripping mass percentage concentration 25%～28%, after ageing 1.5～2h, the precipitation obtaining after ageing is carried out to centrifugal, washing, obtains yttrium and stablizes hydrous zirconium oxide(HZO) powder body Y 2o 3-Zr (OH) 4; Wherein, ZrOCl in described mixed solution 2concentration is 0.19～0.21molL -1,, in described mixed solution, the mol ratio of Zr and Y is 100: 6;
Two, Hydrothermal Synthesis FHA/ZrO 2compound precursor powder body
A, by Ca/P mol ratio, be 1.67～1.68: 1 calcium nitrate aqueous solution to be mixed with ammonium dibasic phosphate aqueous solution, obtain HA forerunner's system; Wherein, described calcium nitrate aqueous solution concentration is 0.50～0.55molL -1, described ammonium dibasic phosphate aqueous solution concentration is 0.30～0.35molL -1;
B, use distillation water as medium, stablize hydrous zirconium oxide(HZO) powder body Y by the yttrium of preparing in step 1 2o 3-Zr (OH) 4ultrasonic dispersion forms suspension, then in suspension, be added dropwise to HA forerunner's system of preparing in step a, add again ammonium fluoride, form FHA precursor solution, with the ammonia of mass percentage concentration 25%～28%, regulate the pH value of FHA precursor solution simultaneously, be prepared into composite granule hydro-thermal forerunner system; Wherein, described HA forerunner's system is to be to add at 0.348～0.351: 1 by the mol ratio of Zr and Ca, and described ammonium fluoride is 0.19～0.21 by F and Ca mol ratio: 1 adds;
C, by after the composite granule hydro-thermal forerunner system magnetic agitation 10～12h preparing in step b, put into the rustless steel hydro-thermal still of teflon lined, rustless steel hydro-thermal still is put into siliconit sintering furnace, then hydro-thermal reaction 6～6.5h at 180～185 ℃, after taking-up, use successively distilled water and absolute ethanol washing hydrothermal product, then filter, be drying to obtain FHA/ZrO 2compound precursor powder body;
Three, FHA/ZrO 2the heat treatment of composite ceramic material
By the FHA/ZrO making in step 2 2compound precursor powder body is placed in Muffle furnace, carries out sintering 2～2.1h at 1100～1120 ℃, obtains phase and consists of fluorine substituted hydroxy apatite and the stable tetragonal phase zirconium oxide FHA/ZrO of yttrium 2composite ceramic material.
2. the FHA/ZrO with good thermal stability according to claim 1 2the hydro-thermal synthetic preparation method of composite ceramic material, is characterized in that centrifugal in step 1 is centrifugal 3～5min under 5000～8000r/min condition.
3. the FHA/ZrO with good thermal stability according to claim 1 2the hydro-thermal synthetic preparation method of composite ceramic material, is characterized in that the washing in step 1 is used distilled water to wash.
4. the FHA/ZrO with good thermal stability according to claim 1 2the hydro-thermal synthetic preparation method of composite ceramic material, the pH value that it is characterized in that FHA precursor solution in step 2 b is 9.8～10.2.
5. the FHA/ZrO with good thermal stability according to claim 1 2the hydro-thermal synthetic preparation method of composite ceramic material, is characterized in that in step 2 b, ultrasonic jitter time is 10～15min.
6. the FHA/ZrO with good thermal stability according to claim 1 2the hydro-thermal synthetic preparation method of composite ceramic material, is characterized in that dry in step 2 c is at 75～85 ℃ of dry 20～24h.
7. the FHA/ZrO with good thermal stability according to claim 1 2the hydro-thermal synthetic preparation method of composite ceramic material, the volume that it is characterized in that the composite granule hydro-thermal forerunner system put in rustless steel hydro-thermal still in step 2 c be rustless steel hydro-thermal kettle long-pending 75%.
CN201210467107.8A 2012-11-19 2012-11-19 Method for preparing fluorinated hydroxyapatite/ zirconium oxide (FHA/ZrO2) composite ceramic powder with good heat stability by hydrothermal synthesis Expired - Fee Related CN102942371B (en)

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