CN100560505C - The in-situ preparation method of nano zircite and hydroxyapatite composite powder - Google Patents
The in-situ preparation method of nano zircite and hydroxyapatite composite powder Download PDFInfo
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- CN100560505C CN100560505C CNB2007100455100A CN200710045510A CN100560505C CN 100560505 C CN100560505 C CN 100560505C CN B2007100455100 A CNB2007100455100 A CN B2007100455100A CN 200710045510 A CN200710045510 A CN 200710045510A CN 100560505 C CN100560505 C CN 100560505C
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Abstract
The in-situ preparation method of nano zircite of the present invention and hydroxyapatite composite powder, contain following steps: " original position is compound "---adopting basic zirconium chloride, nitrocalcite, DAP and ammoniacal liquor is raw material, place same reactor by proportioning, reaction pH value is controlled at alkaline range, under higher temperature of reaction, and under the effect of stirrer, react the precursor of preparation nano level zirconium white and hydroxy apatite powder;------" washing with alcohol "---" calcining "---" grinding " obtains nano zircite and hydroxyapatite composite powder to pass through " supersound process " again.Positively effect of the present invention is that the composite granule of preparation provides new approach for the modification of nano particle biomaterial: can prepare high performance biological ceramics, be used for the replacement of artificial growth body and joint prosthesis; Can form the nanocomposite filler of different-grain diameter and component, be used for the nano composite material of synthesized high-performance, in the application of medical material, have great meaning.
Description
[technical field]
The present invention relates to medical material tech field, specifically, be a kind of bio-medical material that is mainly used in, as alveolar ridge increase, planting body, tissue engineering bracket and Guan Qiao repair, and also can be used as the nano zircite (ZrO that filler carries out modification to existing polymkeric substance simultaneously
2) and the in-situ preparation method of hydroxyapatite (HA) composite granule.
[background technology]
At present, on technological layer, preparation nano zircite (ZrO
2) and hydroxyapatite (HA) composite granule mainly contain two kinds of methods:
A kind of is " solid phase method ", and it is with hydroxyapatite (HA) and zirconium white (ZrO
2) powder mixes according to a certain percentage, carries out mechanical ball milling then, obtains the method for nano level zirconium white and hydroxyapatite composite powder.
Another kind is " liquid-phase suspension process ", is by with zirconium white (ZrO
2) powder drops in the hydroxyapatite colloidal sols and prepare nano level zirconium white and hydroxyapatite (HA) composite ceramic material.
Preparation nano zircite (ZrO
2) and hydroxyapatite (HA) composite granule, mainly be in order to improve the toughness of hydroxyapatite, enlarge it in the scope of clinical application medically.But, according to the preparation method of existing nano zircite and hydroxyapatite composite powder, needing to add a large amount of zirconium whites, its common add-on is 30～50%, this can cause the sintering temperature of zirconium white and hydroxyapatite composite powder very high; And at high temperature, hydroxyapatite is easy to reunite and decompose, thereby causes its distinctive biological activity to reduce or forfeiture.
In addition, mainly be to adopt single filler utilizing Nano filling that polymkeric substance is carried out the technical of modification at present, adopt nanocomposite filler also few to the research that polymkeric substance carries out modification.(when material was subjected to external force generation tiny crack, the t-ZrO2 crystal of crack tip was stress induced following to more stable m-ZrO because of its distinctive stress-induced phase transformation toughening effect for nano zircite
2Change mutually, volumetric expansion of following and change of shape change the stress field of crack tip, stop the extension of crackle also to make crack propagation need higher external influence load), can be used to improve the toughness of traditional ceramics.And nanometer hydroxyapatite is a kind of typical biomaterial, have excellent biological compatibility and biological activity, the hydroxylapatite ceramic of synthetic and the affinity of human body are best, therefore, the synthetic method of nano hydroxyapatite powder has been carried out a large amount of research both at home and abroad, also obtain some progress, but in the research of nano zircite and hydroxyapatite composite powder in-situ preparing, also rarely had report.
[summary of the invention]
The objective of the invention is to overcome the deficiency of existing nano zircite and hydroxyapatite composite powder technology of preparing, the method for a kind of nano zircite and hydroxyapatite composite powder in-situ preparing is provided; By this preparation method can obtain that biological activity is good, the nano zircite of good dispersity and hydroxyapatite composite powder filler.
For achieving the above object, the in-situ preparation method of nano zircite of the present invention and hydroxyapatite composite powder is characterized in that, contains following steps:
(1) original position is compound
Adopting basic zirconium chloride, nitrocalcite, Secondary ammonium phosphate and ammonia soln is raw material, but they are placed same reacting by heating bottle, control reaction pH value and temperature react under the effect of stirrer, the precursor of preparation nano level zirconium white and hydroxy apatite powder;
Its concrete technology is:
Nitrocalcite Ca (NO with the 0.0334mol/L of 40～60mL
3)
2Put into reactor, again with the Secondary ammonium phosphate (NH of the 0.02mol/L of 40～60mL
4)
2HPO
4Put into separating funnel, make calcium (Ca)/phosphorus (P) mol ratio be 1.67, and Secondary ammonium phosphate be splashed in the reactor with the speed of per minute 2～3mL; Temperature of reaction is 60～90 ℃; Agitator is stirred to Secondary ammonium phosphate (NH
4)
2HPO
4Drip off back 3 hours;
In same reactor, put into the basic zirconium chloride (ZrOCl of 80mL 0.1mol/L then
2), 40mL0.6mol/L ammoniacal liquor is put into separating funnel, making zirconium (Zr) and nitrogen (N) mol ratio is 1: 3, and with the speed of per minute 2～3mL ammoniacal liquor is splashed in the reaction flask; Temperature of reaction is 60～90 ℃;
Utilize the ammoniacal liquor of 0.6mol/L that reaction pH value is controlled between 7～10;
Agitator is stirred to ammoniacal liquor and drips off back 3 hours, gets white depositions.
(2) sonic oscillation
Deionized water repetitive scrubbing precursor is used in the precursor that " original position is compound " step is made ageing 24 hours in former reactor then, all will carry out sonic oscillation to precursor in each washing process, be neutrality until supernatant liquor, uses AgNO
3Detecting no chlorion exists.
(3) washing with alcohol
In precursor, added the dehydrated alcohol ultra-sonic oscillation 10 minutes again, the unnecessary ethanol of centrifugal then removal, dry sediment under the room temperature.
(4) calcining
To put into the high-temperature calcination stove by the precursor that " original position is compound ", " sonic oscillation ", " washing with alcohol " step make and calcine, the incinerating temperature is 500～700 ℃, and calcination time is 4 hours.
(5) grind
To calcine cooled object and in mortar, grind 20 minutes, obtain the nano zircite and the hydroxyapatite composite powder of white.
In the concrete technology of described original position composite steps, temperature of reaction is 75～85 ℃; Utilize ammoniacal liquor that reaction pH value is controlled between 8～9.
In the concrete technology of described original position composite steps, temperature of reaction is 80 ℃; Utilize ammoniacal liquor that reaction pH value is controlled to be 9.
In described calcining step, calcining temperature is 550 ℃.
Positively effect of the present invention is: the nano zircite of preparation and hydroxyapatite composite powder provide new approach for the modification of nano particle biomaterial: on the one hand, it under certain condition sintering, prepare high performance biological ceramics, be used for the replacement of biological hard tissues such as artificial growth body and joint prosthesis; On the other hand, it is compound with the particle in-situ of two kinds of materials, can form the nanocomposite filler of different-grain diameter and component, is used for the nano composite material of synthesized high-performance, and it has great meaning in the application of medical material.
[embodiment]
The specific embodiment of the present invention below is provided.
The in-situ preparation method of nano zircite of the present invention and hydroxyapatite composite powder comprises following production stage:
(1) original position is compound
Here said " original position is compound ", purpose are the zirconium white (ZrO that will be less than 10%
2) be dispersed in the hydroxyapatite (HA), like this, can reduce the sintering temperature of composite granule, the biological activity of reservation hydroxyapatite, can make the compounded mix of good dispersity again.
Adopt the basic zirconium chloride (ZrOCl of 0.1mol/L
2), the nitrocalcite Ca (NO of 0.0334mol/L
3)
2, 0.02mol/L Secondary ammonium phosphate (NH
4)
2HPO
4With the ammoniacal liquor of 0.6mol/L be raw material, they are placed same reactor, reaction pH value is 8～9, temperature of reaction is 80 ℃, reaction is 6 hours under the effect of magnetic stirrer, the precursor of preparation nano level zirconium white and hydroxy apatite powder;
Its concrete technology is:
Nitrocalcite Ca (NO with the 0.0334mol/L of 40～60mL
3)
2Put into reactor, again with the Secondary ammonium phosphate (NH of the 0.02mol/L of 40～60mL
4)
2HPO
4Put into separating funnel, control calcium (Ca) and phosphorus (P) mol ratio are 1.67, and with the speed of per minute 2～3mL Secondary ammonium phosphate are splashed in the reactor; Temperature of reaction is 80 ℃; Magnetic stirrer is to Secondary ammonium phosphate (NH
4)
2HPO
4Drip off back 3 hours;
In same reactor, put into the basic zirconium chloride (ZrOCl of 80mL 0.1mol/L then
2), 40mL0.6mol/L ammoniacal liquor is put into separating funnel, control zirconium (Zr) and nitrogen (N) mol ratio are 1: 3, and with the speed of per minute 2～3mL ammoniacal liquor are splashed in the reactor; Temperature of reaction is 80 ℃;
For the presoma that prevents zirconium white and hydroxyapatite influences each other, produces agglomeration in reactor, pH value when the present invention reacts by control avoids it to influence each other, utilize the ammoniacal liquor of 0.6mol/L that reaction pH value is controlled between 8～9, make it depart from the iso-electric point of solution, the micelle surface has the electric charge of jack per line, repels mutually between micelle; So the stability of micelle improves, good dispersity;
Agitator is stirred to ammoniacal liquor and drips off back 3 hours, gets white depositions.
(2) sonic oscillation
Utilize ultransonic cavitation effect, on the one hand reaction residue is impacted completely from throw out, can break up the particle that condenses together by electrostatic attraction and Van der Waals force on the other hand, improve dispersed.
Deionized water repetitive scrubbing precursor is used in the precursor that " original position is compound " step is made ageing 24 hours in former reactor then, all will carry out sonic oscillation to precursor in each washing process, be neutrality until supernatant liquor, uses AgNO
3Detecting no chlorion exists.
(3) washing with alcohol
In precursor, added the dehydrated alcohol ultra-sonic oscillation 10 minutes again, the unnecessary ethanol of centrifugal then removal, dry sediment under the room temperature.
The present invention carries out absolute ethanol washing to precursor, pass through absolute ethanol washing, the non-bridge formation hydroxyl of precursor is replaced by oxyethyl group, ethanol molecule can not link to each other with hydrogen bond with particle surface, in the ethanol volatilization process, the adjacent oxyethyl group reaction of same particle forms ether, and resolves into two ethene and water rapidly, do not have key between particle, eliminate the purpose of reuniting thereby reach.
(4) calcining
To put into the high-temperature calcination stove by the precursor that " original position is compound ", " sonic oscillation ", " washing with alcohol " step make and calcine, the incinerating temperature is 500～700 ℃, and preferable calcining temperature is 550 ℃; Calcination time is 4 hours.
(5) grind
To calcine cooled object and in mortar, grind 20 minutes, obtain the nano zircite and the hydroxyapatite composite powder of white.
Show after tested, when the mol ratio of calcium (Ca) and zirconium (Zr) is 1: 5, zirconium white (ZrO
2) and hydroxyapatite (HA) composite granule be spheroidal particle not of uniform size, big spheroidal particle is hydroxyapatite (HA), diameter is about 40 nanometers (nm), little spheroidal particle is zirconium white (ZrO
2), diameter is about 5 nanometers (nm), both good dispersitys.
When the mol ratio of calcium (Ca) and zirconium (Zr) is 1: 10, zirconium white (ZrO
2) and hydroxyapatite (HA) composite granule become two kinds of particles not of uniform size, big spheroidal particle is hydroxyapatite (HA), shape is flat slightly, is about rice (nm) in 50, little spheroidal particle is zirconium white (ZrO
2), diameter is about 5 nanometers (nm), but both dispersivenesses are poor slightly.
When the mol ratio of calcium (Ca) and zirconium (Zr) is 1: 20, zirconium white (ZrO
2) and hydroxyapatite (HA) composite granule be the nano particle of two kinds of shapes, a kind of is the hydroxyapatite (HA) of corynebacterium, being about is rice (nm) in 90, wide 10 nanometers (nm) that are about; Another kind is spheric zirconium white (ZrO
2), diameter is about 5 nanometers (nm).
At last, the transmission electron microscope and the examination of infrared spectrum that carry out of the sample of nano zircite that the in-situ preparation method that adopts nano zircite and hydroxyapatite composite powder is made and hydroxyapatite composite powder shows: the optimum mole ratio of calcium (Ca) and zirconium (Zr) is 1: 5.
Claims (6)
1, the in-situ preparation method of nano zircite and hydroxyapatite composite powder is characterized in that, contains following steps:
(1) original position is compound
Adopting basic zirconium chloride, nitrocalcite, Secondary ammonium phosphate and ammonia soln is raw material, but they are placed same reacting by heating bottle, control reaction pH value and temperature react under the effect of stirrer, the precursor of preparation nano level zirconium white and hydroxy apatite powder;
Its concrete technology is:
The nitrocalcite of the 0.0334mol/L of 40～60mL is put into reactor, again the Secondary ammonium phosphate of the 0.02mol/L of 40～60mL is put into separating funnel, making calcium/phosphorus mol ratio is 1.67, and with the speed of per minute 2～3mL Secondary ammonium phosphate is splashed in the reactor; Temperature of reaction is 60～90 ℃; Agitator is stirred to Secondary ammonium phosphate and drips off back 3 hours;
Put into the basic zirconium chloride of 80mL 0.1mol/L then in same reactor, 40mL0.6mol/L ammoniacal liquor is put into separating funnel, making zirconium/nitrogen mol ratio is 1: 3, and with the speed of per minute 2～3mL ammoniacal liquor is splashed in the reaction flask; Temperature of reaction is 60～90 ℃;
Utilize the ammoniacal liquor of 0.6mol/L that reaction pH value is controlled between 7～10;
Agitator is stirred to ammoniacal liquor and drips off back 3 hours, gets white depositions;
(2) sonic oscillation
Deionized water repetitive scrubbing precursor is used in the precursor that " original position is compound " step is made ageing 24 hours in former reactor then, all will carry out sonic oscillation to precursor in each washing process, be neutrality until supernatant liquor, uses AgNO
3Detecting no chlorion exists;
(3) washing with alcohol
In precursor, added the dehydrated alcohol ultra-sonic oscillation 10 minutes again, the unnecessary ethanol of centrifugal then removal, dry sediment under the room temperature;
(4) calcining
To put into the high-temperature calcination stove by the precursor that " original position is compound ", " sonic oscillation ", " washing with alcohol " step make and calcine, the incinerating temperature is 500～700 ℃, and calcination time is 4 hours;
(5) grind
To calcine cooled object and in mortar, grind 20 minutes, obtain the nano zircite and the hydroxyapatite composite powder of white.
2, the in-situ preparation method of nano zircite according to claim 1 and hydroxyapatite composite powder is characterized in that, in the concrete technology of described original position composite steps, temperature of reaction is 75～85 ℃; Utilize ammoniacal liquor that reaction pH value is controlled between 8～9.
3, the in-situ preparation method of nano zircite according to claim 1 and hydroxyapatite composite powder is characterized in that, in the concrete technology of described original position composite steps, temperature of reaction is 80 ℃.
4, the in-situ preparation method of nano zircite according to claim 1 and hydroxyapatite composite powder is characterized in that, in the concrete technology of described original position composite steps, utilizes ammoniacal liquor that reaction pH value is controlled to be 9.
5, the in-situ preparation method of nano zircite according to claim 1 and hydroxyapatite composite powder is characterized in that, in described calcining step, calcining temperature is 550 ℃.
6, the in-situ preparation method of nano zircite according to claim 1 and hydroxyapatite composite powder is characterized in that, the optimum mole ratio of calcium and zirconium is 1: 5.
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|---|---|---|---|---|
| CN102232907A (en) * | 2010-04-28 | 2011-11-09 | 国立台北科技大学 | Composite bioceramic material with biological activity, tooth root implant body and preparation method thereof |
| CN102424581A (en) * | 2011-09-15 | 2012-04-25 | 广州倍绣生物技术有限公司 | Hydroxyapatite bioceramic for bone connection and bone repair and preparation method thereof |
| CN103073279A (en) * | 2013-01-14 | 2013-05-01 | 陕西科技大学 | Preparation method for sodium-carbon-silicon composite doped HA biological ceramics |
| CN106800408A (en) * | 2016-12-31 | 2017-06-06 | 广东金鹿陶瓷实业有限公司 | Can be used for the preparation method of the hydroxyapatite composite material of Bone China production |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001231849A (en) * | 2000-02-24 | 2001-08-28 | Matsushita Electric Works Ltd | Calcium phosphate coated zirconia biomaterial and its preparation |
| CN1699270A (en) * | 2005-05-17 | 2005-11-23 | 杭州市萧山区中医院 | Preparation method of hydroxyapatite/zirconium dioxide biological ceramic composite material and its products |
| CN1709829A (en) * | 2005-06-29 | 2005-12-21 | 上海大学 | Hydroxyapatite-zirconium dioxide composite bioceramic material and its preparing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001231849A (en) * | 2000-02-24 | 2001-08-28 | Matsushita Electric Works Ltd | Calcium phosphate coated zirconia biomaterial and its preparation |
| CN1699270A (en) * | 2005-05-17 | 2005-11-23 | 杭州市萧山区中医院 | Preparation method of hydroxyapatite/zirconium dioxide biological ceramic composite material and its products |
| CN1709829A (en) * | 2005-06-29 | 2005-12-21 | 上海大学 | Hydroxyapatite-zirconium dioxide composite bioceramic material and its preparing method |
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