CN100390051C - Preparation method of non-agglomeration nano-grade hydroxy apatite - Google Patents
Preparation method of non-agglomeration nano-grade hydroxy apatite Download PDFInfo
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- CN100390051C CN100390051C CNB2005101152657A CN200510115265A CN100390051C CN 100390051 C CN100390051 C CN 100390051C CN B2005101152657 A CNB2005101152657 A CN B2005101152657A CN 200510115265 A CN200510115265 A CN 200510115265A CN 100390051 C CN100390051 C CN 100390051C
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Abstract
The present invention particularly relates to a preparation method of non-agglomeration nano-grade hydroxyapatites with biological activity and biocompatibility, which belongs to the field of the preparation of non-metal biologic materials. Starches are added in the process of solution mixing and are used as obstructing agents, and the starches are removed through the calcining treatment to obtain non-agglomeration nano-grade powder. The present invention effectively solves the agglomeration problem of hydroxyapatite crystal particles in the solution-phase synthesis, and non-agglomeration nano-grade powder which has the advantages of safety, innocuity, good dispersancy and fine crystal grains is obtained. The process of the preparation method of the present invention is simple, desired raw materials can be obtained conveniently, and the present invention can be popularized and used for the prior arts, such as biomedicine, tissue repair, filtration and carrier materials, etc.
Description
Technical field
The invention belongs to the preparation field of nonmetal biomaterial, particularly be used to prepare the manufacture method of a kind of non-agglomeration nano-grade hydroxy apatite of biologically active and biocompatibility.
Background technology
Hydroxyapatite is one of modal biomineral of nature, is the main inorganic composition of bone and tooth, generally is white in color.Hydroxyapatite has been widely used in surgical repair and field of tissue engineering technology, and the superfine hydroxy apatite powder is because its special structure and surface property, except traditional biomedical sector, also shown new application prospect at chemical analysis and environment remediation field.The manufacture method of the liquid phase synthesizing superfine hydroxyapatite of report mainly contains at present:
(1) Chen Guanxiong, " making method of dense multicrystalline hydroxyl apatite particles " (publication number CN86108700) of silver-colored refined monarch's invention.The contriver is with Ca (NO
3)
24H
2O and (NH
4)
2HPO
4Dilute solution add NH
4After OH transfers to strong basicity, with (NH
4)
2HPO
4Slowly splash into Ca (NO
3)
2Synthesize, obtain hydroxyapatite particles through barreling and calcination processing again.
(2) technology of preparing in " nano-grade hydroxy apatite and preparation method and the application in toothpaste " (the publication number CN1429538) of Meng Xiangcai application.The contriver is at reaction forward direction Ca (OH)
2Middle adding is controlled the additive of elementary forming core and liquid is heated back adding Ca (H at a certain temperature in advance
2PO
4)
2H
2O can obtain needle-like or the granular hydroxyapatite of grain-size less than 100nm after super-dry or calcination processing.
(3) Rudin Vsevolod Nikolaevich, Komarov Vladimir Fedorovich, the manufacture method in the invention " Method for Producing Nano-SizedCrystalline Hydroxyapatite " (publication number WO0202461) of people such as Melikhov Igor Vitallevich application.The contriver places the calcium hydroxide and the phosphoric acid of liquid phase first reaction vessel (reactor) mixing 0.2 ~ 0.8s and regulates pH value to 8 to 9 according to certain stoichiometric ratio, then mixed solution is placed second reaction vessel to take place to change 10～20s rapidly mutually, repeat above-mentioned step after after afterwards mixed solution being placed the 3rd reaction vessel and adding a certain amount of calcium hydroxide liquid being continued to place first reaction vessel.The mixed solution that present method requires all volumes is according to above-mentioned step cycle 10 to 20 times, and all circulations will finish in 10% by the hydroxyapatite content in mixed solution, otherwise serious reunion can take place resultant hydroxyapatite.
(4) Huang Jianfeng, " a kind of preparing nano hydroxyapatite powder " (patent No. ZL200310105951.7) of Cao Liyun invention.The contriver is with Ca (NO
3)
24H
2O and (NH
4)
2HPO
4Mix by certain molar ratio, utilize multifrequency chemistry producer to synthesize under certain temperature and ultrasonic frequency after adding the urea powder, nano hydroxyapatite powder better crystallinity degree, the particle that obtains behind the cleaning-drying is little, uniform particles, nothing are reunited.
In above-mentioned prior art, form coacervate easily though can access the tiny hydroxy apatite powder of crystal grain.Though the generation that the technology that has can suppress to reunite but production technique are comparatively complicated, to having relatively high expectations of production unit.And most prior aries need use additive or dispersion agent, leaves remnants in technological process easily, is unfavorable for obtaining the harmless hydroxy apatite powder of totally nontoxic.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of non-agglomeration nano-grade hydroxy apatite powder.It is characterized in that: prepare in the solution mixing process of hydroxyapatite at liquid phase synthesizing method, add starch, or the adding dispersion agent uses in the lump as barrier agent; The starch addition is 1%～10% of a solution total mass; Then resulting hydroxyapatite presoma is heated to remove starch;
The method that resulting hydroxyapatite presoma is added heat abstraction starch adopts any one in following two kinds of methods:
(1) temperature rise rate between 100 ℃～550 ℃ is no more than 2 ℃/min;
(2) be warmed up to 550 ℃ from room temperature, and at 550 ℃ of insulation 6～12h.
The starch of described barrier agent is common starch, Zulkovsky starch or water soluble starch.
Described dispersion agent is ammonium citrate, trisodium citrate, silane coupling agent or Viscotrol C.
The invention has the beneficial effects as follows and adopt starch, improve the reunion situation of institute's synthetic nanometer hydroxyapatite, can in liquid phase synthetic solution mixing process, add very easily as barrier agent and dispersion agent; The adding dispersion agent can reduce the grain-size of hydroxyapatite when eliminating reunion.And the calcination stage that can be comprised in most of liquid phase synthesis and preparation process removes, effectively solve liquid phase synthetic in the agglomeration traits of hydroxyapatite crystal grain, obtain safety non-toxic, non-agglomeration nano-grade powder that crystal grain is tiny.Manufacturing approach craft involved in the present invention is simple, and required raw material conveniently is easy to get, and is beneficial on numerous prior aries and promotes the use of.
Embodiment
The preparation method who the purpose of this invention is to provide a kind of non-agglomeration nano-grade hydroxy apatite powder.The ultimate principle of liquid phase synthesizing hydroxylapatite is the ion combination in liquid phase that contains calcium and phosphorus, separates out hydroxyapatite presoma (calcium/phosphorus ratio is 1.6 ~ 1.7 water-bearing phosphate calcium salt) by regulating pH value and calcium/phosphorus than precipitation.Synthetic forming core and the growth process of generally comprising of liquid phase, in order to obtain nano level hydroxyapatite, generally by using dispersion agent or employing to help nucleus dispersive liquid-phase system such as alcohol solution, and for example control rate of titration mechanically, methods such as stirring, ultra-sonic dispersion promote nucleus to form and suppress excessive grain growth.Though these methods can obtain tiny hydroxyapatite crystal grain, but can't prevent from effectively to reunite, the material that adopts starch at first can utilize the gelatination property of starch to form being in contact with one another of gel network obstruct nucleus in liquid phase as barrier agent and hinder between nucleus spreads and the inhibition excessive grain growth, thereby obtains nano-grade hydroxy apatite.
In addition, adopt liquid phase synthetic method to prepare hydroxyapatite, for the crystal that obtains the well-crystallized often will carry out calcination processing to the hydroxyapatite presoma.The hydroxyapatite presoma is often owing to the high temperature sintering effect formation coacervate that is bound up in this process, and the use of starch barrier agent can suppress the sintering problem in the calcination process well.This is because the starch gel network can be decomposed to form CO at high temperature
2Thereby the crystal grain that the formation of this decomposition and gas can separate even collapse out tight contact suppresses the agglomerating generation.In addition, the starch particle totally nontoxic mainly is carbon also even decompose the remnants that leave, thereby has guaranteed that prepared product safety is nontoxic.
The addition of finding suitable starch barrier agent by systematic research is 1%～10% of a solution total mass.Starch content is low excessively, is difficult to form gel network and brings into play iris action by decomposing; Starch content surpasses 10% does not have further beneficial effect to grain-size and inhibition reunion.No matter be that common starch, Zulkovsky starch or water soluble starch can be brought into play above-mentioned effect as barrier agent.Common starch is present in seed, stem tuber and the root of plant in a large number, its technology of preparing is very ripe, and with low cost,, starch finds that starch decomposes, burns and the final CO of formation by being studied the back in the behavior of pyrolytic decomposition between 100 ℃～550 ℃
2Suitable heat-up rate, as be lower than 2 ℃/min can make starch decompose fully and not have remnants, and heat-up rate is too fast to be unfavorable for that then starch drains fully.In addition, because about 550 ℃ of the temperature that amylolysis finishes, therefore also can be with the starch Ex-all 550 ℃ of insulation for some time, suitable soaking time is 6～12 hours.Soaking time is too short to be difficult to eliminate starch, and sintering takes place the oversize crystal grain of soaking time easily.
Exemplifying embodiment is below further specified the present invention.
Embodiment 1
Liquid-phase synthesis process with a kind of common nano-grade hydroxy apatite is an example, and its specific embodiment is: with (NH
4)
2HPO
4Solution and CaNO
3Solution mixed in 6: 10 in molar ratio, add ammoniacal liquor and regulate pH value to 11, to leave standstill behind the solution thorough mixing, after the solution generation co-precipitation colloidal sol oven dry is formed gelatinous hydroxyapatite presoma, gel can be obtained hydroxyapatite at 550 ℃ after carrying out 6 hours calcination processing.
With quality is water soluble starch adding CaNO before solution mixes of solution total mass 10%
3Solution, temperature rise rate are 1 ℃/min, and other process is consistent with above-mentioned synthetic method of giving an example.Detecting through XRD and to learn that resulting powder all is well-crystallized's a hydroxyapatite phase, is 52.9nm perpendicular to the average grain size of (004) crystal face.Adopt laser particle analyzer that the size of hydroapatite particles is measured, the result shows, d
10Be 35nm, d
50Be 65nm, d
90This powder dispersity is good as can be seen for 130nm, does not reunite.
Embodiment 2
With quality is Zulkovsky starch adding CaNO before solution mixes of solution total mass 5%
3The solution thorough mixing, other condition is with embodiment 1.It all is well-crystallized's hydroxyapatite phase that resulting powder detects through XRD, is 70.8nm perpendicular to the average grain size of (004) crystal face.Adopt laser particle analyzer that the size of hydroapatite particles is measured, the result shows, d
10Be 35nm, d
50Be 67nm, d
90Be 139nm, illustrate that this powder dispersity is good, do not reunite.
Embodiment 3
With quality is common starch adding CaNO before solution mixes of solution total mass 5%
3Thorough mixing after solution is heated to 80 ℃, other condition is with embodiment 1.It all is well-crystallized's hydroxyapatite phase that resulting powder detects through XRD, is 89.6nm perpendicular to the average grain size of (004) crystal face.Adopt laser particle analyzer that the size of hydroapatite particles is measured, the result shows, d
10Be 64nm, d
50Be 92nm, d
90Be 195nm, illustrate that this powder dispersity is good, do not reunite.
Embodiment 4
Insulation is 9 hours after being warmed up to 550 ℃ from room temperature with the temperature rise rate of 10 ℃/min, and other condition is with embodiment 1.It all is well-crystallized's hydroxyapatite phase that resulting powder detects through XRD, is 54.6nm perpendicular to the average grain size of (004) crystal face.Adopt laser particle analyzer that the size of hydroapatite particles is measured, the result shows, d
10Be 37nm, d
50Be 71nm, d
90Be 161nm, illustrate that this powder dispersity is good, do not reunite.
Embodiment 5
In liquid-phase mixing, also add other dispersion agent simultaneously, at (NH except adding the starch barrier agent
4)
2HPO
4Add the dispersion agent trisodium citrate of solution quality 2% in the solution, all the other steps are with embodiment 1.It all is well-crystallized's hydroxyapatite phase that resulting powder detects through XRD, is 82.9nm perpendicular to the average grain size of (004) crystal face.Adopt laser particle analyzer that the size of hydroapatite particles is measured, the result shows, d
10Be 35nm, d
50Be 66nm, d
90Be 137nm, illustrate that this powder dispersity is good, do not reunite.
Embodiment 6
Dispersion agent is an ammonium citrate, and addition is 1% of a solute quality, and all the other steps are with embodiment 5.It all is well-crystallized's hydroxyapatite phase that resulting powder detects through XRD, is 22.8nm perpendicular to the average grain size of (004) crystal face, and grain-size is significantly less than the embodiment that does not use dispersion agent.Adopt laser particle analyzer consistent with embodiment 5, not reunion of powder is described the dimensional measurement result of hydroapatite particles.
Embodiment 7
Dispersion agent is a Viscotrol C, and all the other conditions are with embodiment 6.It all is well-crystallized's hydroxyapatite phase that resulting powder detects through XRD, is 25.7nm perpendicular to the average grain size of (004) crystal face, and grain-size is significantly less than the embodiment that does not use dispersion agent.Adopt laser particle analyzer consistent with embodiment 5, not reunion of powder is described the dimensional measurement result of hydroapatite particles.
Embodiment 8
Dispersion agent is a silane coupling agent, and all the other conditions are with embodiment 6.It all is well-crystallized's hydroxyapatite phase that resulting powder detects through XRD, is 24.8nm perpendicular to the average grain size of (004) crystal face, and grain-size is significantly less than the embodiment that does not use dispersion agent.Adopt laser particle analyzer consistent with embodiment 5, not reunion of powder is described the dimensional measurement result of hydroapatite particles.
Comparative example 1
Do not add starch barrier agent or dispersion agent, other conditions are with embodiment 1.It all is well-crystallized's hydroxyapatite phase that resulting powder detects through XRD, is 93.4nm perpendicular to the average grain size of (004) crystal face.Adopt laser particle analyzer the size of hydroapatite particles to be measured statistical result showed, d
10Be 474nm, d
50Be 695nm, d
90Be 2128nm, the particle size of these particulate sizes in the embodiment 1～5, and all be far longer than the size of nanometer-size die, illustrate that nanocrystalline reunion is serious.
Comparative example 2
Be warming up to 550 ℃ of insulations 6 hours with 8 ℃/min of temperature rise rate, all the other conditions are with embodiment 1.Resulting powder is black but not common white, through secondary clacining after 6 hours black take off, illustrate that heat-up rate is too fast, or starch can not eliminated above 6 hours 550 ℃ of insulations.
Claims (4)
1. the manufacture method of a non-agglomeration nano-grade hydroxy apatite powder is characterized in that: in the solution mixing process of Prepared by Sol Gel Method hydroxyapatite, add starch as barrier agent, or add the starch barrier agent and dispersion agent uses in the lump; The starch addition is 1%～10% of a solution total mass; Then resulting hydroxyapatite presoma is heated to remove starch.
2. manufacture method as claimed in claim 1 is characterized in that: wherein add heat abstraction starch and adopt in following two kinds of methods any one:
(1) temperature rise rate between 100 ℃～550 ℃ is no more than 2 ℃/min;
(2) be warmed up to 550 ℃ from room temperature, and at 550 ℃ of insulation 9～12h.
3. manufacture method as claimed in claim 1 is characterized in that: the starch of described barrier agent is common starch or Zulkovsky starch.
4. manufacture method as claimed in claim 1 is characterized in that: described dispersion agent is ammonium citrate, trisodium citrate, silane coupling agent or Viscotrol C.
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| CN103919686A (en) * | 2013-01-11 | 2014-07-16 | 王青山 | Tooth repair nanometer hydroxyapatite composite material and preparation method thereof |
| CN104860284B (en) * | 2014-10-11 | 2017-07-04 | 北京大学口腔医学院 | A kind of preparation method of amorphous calcium phosphate nanosphere |
| CN111689481A (en) * | 2020-06-28 | 2020-09-22 | 山东泰星新材料股份有限公司 | Aluminum hypophosphite flame retardant ultrafine powder and preparation method and application thereof |
| CN115285957B (en) * | 2022-08-03 | 2023-09-12 | 景德镇陶瓷大学 | Method for preparing hydroxyapatite powder by non-aqueous precipitation process |
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| US6110851A (en) * | 1996-04-09 | 2000-08-29 | Wiedemann; Wolfgang | Process for producing a ceramic material based on calcium phosphate compounds and use of this material |
| CN1308016A (en) * | 2000-11-10 | 2001-08-15 | 中国科学院上海硅酸盐研究所 | Preparation of low temperature sinterable hydroxyapatite powder |
| US6426114B1 (en) * | 2000-05-02 | 2002-07-30 | The University Of British Columbia | Sol-gel calcium phosphate ceramic coatings and method of making same |
| CN1544318A (en) * | 2003-11-21 | 2004-11-10 | 陕西科技大学 | Nanometer hydroxyapatite powder preparation method |
| CN1587195A (en) * | 2004-07-28 | 2005-03-02 | 同济大学 | Method for synthesizing nano hydroxy-apatite micro powder contaniing carbonate radical |
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2005
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6110851A (en) * | 1996-04-09 | 2000-08-29 | Wiedemann; Wolfgang | Process for producing a ceramic material based on calcium phosphate compounds and use of this material |
| US6426114B1 (en) * | 2000-05-02 | 2002-07-30 | The University Of British Columbia | Sol-gel calcium phosphate ceramic coatings and method of making same |
| CN1308016A (en) * | 2000-11-10 | 2001-08-15 | 中国科学院上海硅酸盐研究所 | Preparation of low temperature sinterable hydroxyapatite powder |
| CN1544318A (en) * | 2003-11-21 | 2004-11-10 | 陕西科技大学 | Nanometer hydroxyapatite powder preparation method |
| CN1587195A (en) * | 2004-07-28 | 2005-03-02 | 同济大学 | Method for synthesizing nano hydroxy-apatite micro powder contaniing carbonate radical |
Non-Patent Citations (2)
| Title |
|---|
| Preparation of porous hydroxyapatite ceramics with starchadditives. Yang lei et al.Trans.Nonferrous Met. Soc. China,Vol.15 No.2. 2005 |
| Preparation of porous hydroxyapatite ceramics with starchadditives. Yang lei et al.Trans.Nonferrous Met. Soc. China,Vol.15 No.2. 2005 * |
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