CN103539478B - A kind of preparation method of calcium metaphosphate porous bio-ceramic - Google Patents

A kind of preparation method of calcium metaphosphate porous bio-ceramic Download PDF

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CN103539478B
CN103539478B CN201210234006.6A CN201210234006A CN103539478B CN 103539478 B CN103539478 B CN 103539478B CN 201210234006 A CN201210234006 A CN 201210234006A CN 103539478 B CN103539478 B CN 103539478B
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powder body
calcium
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calcium metaphosphate
dalcium biphosphate
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CN103539478A (en
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张垠
姚能健
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Nanjing Tech University
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Abstract

The present invention relates to a kind of preparation method of calcium metaphosphate porous ceramics, it is characterized in that, with calcium oxide and phosphoric acid for initial reactant, adopting isothermal crystal chemical precipitation method, first synthesize a water dalcium biphosphate (Ca (H according to calcium metaphosphate formation mechenism 2pO 4) 2h 2o, MCPM) powder body; Again with this powder body for raw material, heat-treat at different temperature respectively to synthesize dalcium biphosphate (Ca (H 2pO 4) 2, MCPA) and calcium dihydric pyrophosphate (CaH 2p 2o 7, CDPP) and powder body; Under the condition controlling moulding process and calcining system (typed pressure as samples, initial stage heat treated heating rate), calcium metaphosphate porous ceramics is prepared with the powder body synthesized respectively.Calcium metaphosphate porous ceramics prepared by the present invention utilizes the different water of crystallization contained by raw material self to decompose the gas of release as pore creating material, realizes with the preparation technology of the synthetic method and porous body that control powder body.

Description

A kind of preparation method of calcium metaphosphate porous bio-ceramic
Technical field
The present invention relates to a kind of preparation method of calcium metaphosphate porous bio-ceramic.
Technical background
At present, biomaterial mainly comprises medical metal material, ceramic material and medical macromolecular materials and composite four major types thereof.Strength of Metallic Materials is high and be easy to be processed into complicated shape, and common medical metal material comprises cobalt-chromium alloy, titanium alloy and rustless steel etc.Medical macromolecular materials have the feature of easily degraded, comprise the various polymer such as polylactic acid, polyethylene, polypropylene of natural derivative chitosan, collagen, various protein and synthetic.Ceramic material has the two character concurrently, and be often used as orthopedic implants and dental materials, Typical Representative has aluminium oxide, calcium phosphate and bio-vitric.
Calcium metaphosphate (Calciummetaphosphate, CMP) there is the advantages such as excellent biocompatibility, biological activity, biodegradability, bone conductibility and osteoinductive, be applied in bone tissue engineer as bone impairment renovation material or bone alternate material.
Research shows [non-patent reference 1,2,3]: dense form bioceramic is unfavorable for material degraded in vivo, and its higher firing temperature will reduce its biological activity; And porous type bioceramic is conducive to growing into of body fluid and cell tissue due to its loose structure, for bone defect healing provides useful physical arrangement, and huge specific surface area can promote material degraded in vivo.Microcellular structure in porous bio-ceramic is more conducive to the immersion of body fluid and growing into of bone and its cells, fixedly provides good physical support to the reparation of Cranial defect and early stage.Meanwhile, because hole is stress concentration point, the induction of stress can increase degraded, and porosity turn increases the specific surface area of implant, and the envirment factor for water and oxide isolation etc. provides more broken site.As the porous ceramics of bone substitute, its pore volume capacity, average pore size and be interconnected the mechanical property that channel size not only determines it, also determine its biology performance.So, for producing the bone alternate material with superior function, need to carry out these parameters accurately to control.Therefore, increasing research concentrates on the research of multiporous biological degraded pottery.
The manufacture method of porous ceramics emerges in an endless stream, and the stuctures and properties of porous ceramics controlled by its preparation technology: porous ceramics as obtained in the foam process in powder sintering and slurry sintering process mostly is hole-closing structure; The porous ceramics that organic foam dipping technique obtains is then full communicating open-celled structure, and porosity is high and aperture is large; And the most applicable micropore ceramics of preparing of sol-gel technology, the little and even pore distribution [non-patent reference 4] in its aperture.
Although porous bio-ceramic has many excellent biological properties, receive the close concern of people nearly recent decades always and study widely, but in application process, still have many problems to need to solve [non-patent reference 5,6,7]: it is not difficult that (1) prepares merely the porosity much higher hole bioceramic, but obtain that there is certain pore size distribution and porous ceramics that is connective and three dimensional structure, also need at present to carry out a large amount of Exploration & stu dy; (2) implant degrade gradually until during being replaced by newborn autologous tissue completely mechanical property unsatisfactory, cannot provide support for cambium; (3) need the surface nature improving porous bio-ceramic, for cell adhesion, sprawl and move good environment is provided.
Because pore creating material legal system also exists the uneven shortcoming of pore creating material dispersion for porous ceramics, and the mechanical property defect of material may be caused thus.And in-situ method is prepared porous ceramics and is similar to pore creating material method, is form loose structure by the process such as decomposition, gasification, volatilization of pore creating material equally.But original position does not need additional pore former from foaming legal system for porous ceramics, but produce gas formation loose structure by the decomposition of material self water of crystallization, utilize the decomposition of material self water of crystallization to produce gas, so there is not the shortcoming such as pore creating material skewness and pore creating material (Organic substance) decomposes generation harmful gas, and its even air hole distribution, the mechanical property defect of material therefore can not be caused because of the skewness in hole.
But there is not report to original position from the method for legal system for porous ceramics that foam at present.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of calcium metaphosphate porous bio-ceramic, the method is for initial reactant with phosphoric acid and calcium oxide, adopting isothermal crystal chemical precipitation method, is the crystal type one water dalcium biphosphate Ca (H of less than 10 μm according to calcium metaphosphate formation mechenism synthesis particle diameter 2pO 4) 2h 2o (MCPM) powder body.Again with MCPM powder body for preparing the raw material of calcium metaphosphate porous body, prepare calcium metaphosphate porous ceramics with the preparation technology of the synthesis condition and porous body that control powder body (briquetting pressure as samples, initial stage heat treated heating rate).The present invention is realized by the following technical programs, and a kind of preparation method of calcium metaphosphate porous bio-ceramic, comprises following process.
1. a water dalcium biphosphate Ca (H 2pO 4) 2h 2the preparation of O (MCPM) powder body
By Ca/Pmol than be 0.5 calcium oxide and phosphoric acid and pure water add respectively in container and mix, mixed solution after fully stirring, precipitation, dry, pulverize for subsequent use, diameter of particle controls below 100 μm.
Isothermal crystal chemical precipitation method prepares the theory reaction of powder body as shown in equation (1).
CaO+2H 3PO 4＝Ca(H 2PO 4) 2·H 2O(1)
2. dalcium biphosphate Ca (H 2pO 4) 2and calcium dihydric pyrophosphate CaH (MCPA) 2p 2o 7(CDPP) preparation of powder body
Get water dalcium biphosphate (MCPM) powder body of a certain amount of above-mentioned 1 synthesis, respectively 140 DEG C of heat treatments 1 hour, synthesis dalcium biphosphate Ca (H 2pO 4) 2(MCPA); 250 DEG C of heat treatments 0.5 hour, synthesis calcium dihydric pyrophosphate CaH 2p 2o 7(CDPP); Powder body after heat treatment is pulverized for subsequent use respectively, and diameter of particle controls below 100 μm.
3. the preparation of calcium metaphosphate porous ceramics
MCPM, MCPA, CDPP powder body that above-mentioned 1 and 2 are synthesized respectively respectively with a certain amount of polyvinyl alcohol (PVA) binding agent Homogeneous phase mixing, pelletize, sieve, use dry pressure formed.Dry-pressing formed under lower than the pressure of 2MPa respectively for MCPM, MCPA powder body, be then heated to 500 DEG C with the heating rate being less than 0.5 DEG C/min; Can heat under any pressure compacted under and any heating rate for CDPP powder body.Be heated to 920 ~ 980 DEG C with the calcining system of 5 ~ 10 DEG C/min again after being heated to 500 DEG C, and 920 ~ 980 DEG C of Isothermal sinter 1 ~ 3 hour, be cooled to room temperature and namely obtain calcium metaphosphate porous bio-ceramic.
A kind of calcium metaphosphate porous ceramics of even air hole distribution can be prepared by this method.
Ultimate principle prepared by calcium metaphosphate porous ceramics is as follows:
Calcium metaphosphate porous ceramics prepared by the present invention utilizes the different water of crystallization contained by raw material self to decompose the gas of release as pore creating material, and the synthetic method of control powder body and the preparation technology of porous body realize.Simultaneously because CDPP water content (pore-creating dosage) is minimum, and between 250 DEG C ~ 450 DEG C, be one raise and process weightless continuously with temperature, air release is slow, and therefore aperture is little and distribute narrow; But there is the process of following equation (3) and the pore-creating of (4) two release gas in MCPA, both also exist obvious difference, formula (3) is the reaction occurred at specified temp 250 DEG C, compared with (4), reaction is violent, air release is rapid, and therefore aperture and pore-size distribution are all large than CDPP; And the process of a MCPM equation (2) release more than MCPA gas pore-creating, aperture and distribution thereof expand further.Therefore, preparing in porous body process, according to above theory, the porous material of different pore size distribution can be prepared.Therefore, during for pottery synthesizing porous with MCPM, MCPA powder body, must at the pressure compacted under lower than 2.0MPa, and heating rate must be less than 0.5 DEG C/min; And the calcium metaphosphate porous ceramics of regular shape can be synthesized under any pressure and heating rate for CDPP.
Powder body heat treatment chemical equation is as follows:
[non-patent reference 1] BitouM, OkamotoM.Fabricationofporous3-Dstructurefrompoly (l-lactide)-basednano-compositefoams.Effectoffoamstructureonenzymati cdegradation [J] .PolymerDegradationandStability, 2008,93 (6): 1081-1087.
[non-patent reference 2] OhSH, ParkIK, KimJMetal.InvitroandinvivocharacteristicsofPCLscaffoldsw ithporesizegradientfabricatedbyacentrifugationmethod [J] .Biomaterials, 2007,28 (9): 1664-1671.
[non-patent reference 3] vanTienenTG, HeijkantsRG.J.C, BumaPetal.Tissueingrowthanddegradationoftwobiodegradable porouspolymerswithdifferentporositiesandporesizes [J] .Biomaterials, 2002,23 (8): 1731-1738.
[non-patent reference 4] Liu Peisheng. porous material draws opinion [M]. Beijing: publishing house of Tsing-Hua University, 2004.
[non-patent reference 5] Ren Xuetan, Zeng Lingke, Wang Hui. the discussion [J] of foamed ceramics preparation technology. Materials Science and Engineering, 2001, (01): 102-103+108.
[non-patent reference 6] Zhu Qingxia, beam Hua Yin, Ding Zhijian. the fabrication & properties [J] of porous mullite fiber ceramics. Chinese pottery, 2006, (10): 7-9.
[non-patent reference 7] HsuFY, ChuehS-C, WangYJ.Microspheresofhydroxyapatite/reconstitutedcollage nassupportsforosteoblastcellgrowth [J] .Biomaterials, 1999,20 (20): 1931-1936.
Detailed description of the invention
Embodiment 1
Step one: Ca (H 2pO 4) 2h 2the preparation of O (MCPM) precursor
It is in the phosphoric acid solution of 3.0mol that Ca/Pmol is added 500.0ml concentration than the calcium oxide 42.06g being 0.5, use magnetic stirrer solution 48 hours postprecipitations, precipitate is put into electric heating constant-temperature blowing drying box, and dried powder body is also crushed to less than 50 μm by drying at 60 DEG C.Namely Ca (H is obtained 2pO 4) 2h 2o (MCPM) precursor powder.Products C a (H 2pO 4) 2h 2o (MCPM) powder body X-ray diffraction collection of illustrative plates is as shown in Figure of description 1.
Step 2: the preparation of calcium metaphosphate porous ceramics
Get the Ca (H of the above-mentioned synthesis of 5g 2pO 4) 2h 2after O (MCPM) is mixed homogeneously with the PVA binding agent of 4wt%, pelletize is sieved, use dry pressing at 2Mpa pressure compacted under, then 500 DEG C are heated to 0.5 DEG C/min heating rate, 940 DEG C are heated to again with the heating rate of 5.0 DEG C/min, and 940 DEG C of Isothermal sinter 2.5 hours, after natural cooling, namely obtain the calcium metaphosphate porous ceramics of regular shape.The calcium metaphosphate porous ceramics of regular shape is as shown in Figure of description 2 (a).
Embodiment 2
Step one: Ca (H 2pO 4) 2h 2the preparation of O (MCPM) precursor
It is in the phosphoric acid solution of 1.0mol that Ca/Pmol is added 500.0ml concentration than the calcium oxide 14.02g being 0.5, use magnetic stirrer solution 36 hours postprecipitations, precipitate is put into electric heating constant-temperature blowing drying box, and dried powder body is also crushed to less than 60 μm by drying at 50 DEG C.Namely Ca (H is obtained 2pO 4) 2h 2o (MCPM) precursor powder.Products C a (H 2pO 4) 2h 2o (MCPM) powder body X-ray diffraction collection of illustrative plates is as shown in Figure of description 1.
Step 2: the preparation of calcium metaphosphate porous ceramics
Get the Ca (H of a certain amount of above-mentioned synthesis 2pO 4) 2h 2o (MCPM) 140 DEG C of constant temp. heating process 1 hour, with and prepare Ca (H 2pO 4) 2(MCPA) powder body.Get 5gCa (H 2pO 4) 2(MCPA) after powder body is mixed homogeneously with the PVA binding agent of 5wt%, pelletize is sieved, use dry pressing at 2Mpa pressure compacted under, then 500 DEG C are heated to 0.5 DEG C/min heating rate, 950 DEG C are heated again with the heating rate of 7 DEG C/min, and 950 DEG C of Isothermal sinter 2 hours, after natural cooling, namely obtain the calcium metaphosphate porous ceramics of regular shape.The calcium metaphosphate porous ceramics of regular shape is as shown in Figure of description 2 (b).
Embodiment 3
Step one: Ca (H 2pO 4) 2h 2the preparation of O (MCPM) precursor
It is in the phosphoric acid solution of 2.0mol that Ca/Pmol is added 500.0ml concentration than the calcium oxide 28.04g being 0.5, use magnetic stirrer solution 60 hours postprecipitations, precipitate is put into electric heating constant-temperature blowing drying box, and dried powder body is also crushed to less than 70 μm by drying at 55 DEG C.Namely Ca (H is obtained 2pO 4) 2h 2o (MCPM) precursor powder.Products C a (H 2pO 4) 2h 2o (MCPM) powder body X-ray diffraction collection of illustrative plates is as shown in Figure of description 1.
Step 2: the preparation of calcium metaphosphate porous ceramics
Get the Ca (H of a certain amount of above-mentioned synthesis 2pO 4) 2h 2o (MCPM) 250 DEG C of constant temp. heating process 0.5 hour, with and prepare CaH 2p 2o 7(CDPP) powder body.Get 5gCaH 2p 2o 7(CDPP) after powder body is mixed homogeneously with the PVA binding agent of 4.5wt%, pelletize is sieved, be used in molded method at 40.0Mpa pressure compacted under, then 500 DEG C are heated to 3.0 DEG C/min heating rate, 960 DEG C are risen to again with the heating rate of 10 DEG C/min, and at 960 DEG C of Isothermal sinter 1.5h, after natural cooling, namely obtain the calcium metaphosphate porous ceramics of regular shape.The calcium metaphosphate porous ceramics of regular shape is as shown in Figure of description 2 (c).
Comparative example 1
Step one: Ca (H 2pO 4) 2h 2the preparation of O (MCPM) precursor
It is in the phosphoric acid solution of 3.0mol that Ca/Pmol is added 500.0ml concentration than the calcium oxide 42.06g being 0.5, use magnetic stirrer solution 48 hours postprecipitations, precipitate is put into electric heating constant-temperature blowing drying box, and dried powder body is also crushed to less than 50 μm by drying at 60 DEG C.Namely Ca (H is obtained 2pO 4) 2h 2o (MCPM) precursor powder.
Step 2: the preparation of calcium metaphosphate porous ceramics
Get the Ca (H of the above-mentioned synthesis of 5g 2pO 4) 2h 2after O (MCPM) is mixed homogeneously with the PVA binding agent of 4wt%, pelletize is sieved, use dry pressing at 10Mpa pressure compacted under, then 500 DEG C are heated to 1 DEG C/min heating rate, 940 DEG C are heated to again with the heating rate of 5 DEG C/min, and 940 DEG C of Isothermal sinter 2.5 hours, be calcium metaphosphate porous ceramics in irregular shape by what obtain after natural cooling.Calcium metaphosphate porous ceramics in irregular shape is as shown in Figure of description 2 (d).
Comparative example 2
Step one: Ca (H 2pO 4) 2h 2the preparation of O (MCPM) precursor
It is in the phosphoric acid solution of 1.0mol that Ca/Pmol is added 500.0ml concentration than the calcium oxide 14.02g being 0.5, use magnetic stirrer solution 36 hours postprecipitations, precipitate is put into electric heating constant-temperature blowing drying box, and dried powder body is also crushed to less than 60 μm by drying at 50 DEG C.Namely Ca (H is obtained 2pO 4) 2h 2o (MCPM) precursor powder.
Step 2: the preparation of calcium metaphosphate porous ceramics
Get a certain amount of Ca (H 2pO 4) 2h 2o (MCPM) powder body 140 DEG C of constant temp. heating process 1.0 hours, with and prepare Ca (H 2pO 4) 2(MCPA) powder body.Get the Ca (H of 5g 2pO 4) 2(MCPA) after powder body is mixed homogeneously with the PVA binding agent of 5wt%, pelletize is sieved, use dry pressing at 20Mpa pressure compacted under, then 500 DEG C are heated to 2 DEG C/min heating rate, 950 DEG C are heated to again with the heating rate of 7 DEG C/min, and 950 DEG C of Isothermal sinter 1.5 hours, be calcium metaphosphate porous ceramics in irregular shape by what obtain after natural cooling.Calcium metaphosphate porous ceramics in irregular shape is as shown in Figure of description 2 (e).
Accompanying drawing explanation
The X-ray diffraction collection of illustrative plates of the different powder body of Fig. 1 synthesized by the specific embodiment of the invention.Different X-diffracted rays is respectively
Ca (H 2pO 4) 2h 2o (MCPM) and Ca (H 2pO 4) 2h 2o (MCPM) is the XRD diffracted ray of heat treatment powder body at 140 DEG C, 250 DEG C and 300 DEG C respectively.Wherein nonheat-treated Ca (H 2pO 4) 2h 2o (MCPM), 140 DEG C of heat treatments 1 hour, 250 DEG C of heat treatments sample of 0.5 hour respectively with PdfNo.71-656Ca (H 2pO 4) 2h 2o (MCPM), PdfNo.9-390Ca (H 2pO 4) 2(MCPA), PdfNo.44-747Ca 2h 2p 2o 7(CDPP) corresponding, show Ca (H 2pO 4) 2h 2o (MCPM) really generates Ca (H after 140 DEG C and 250 DEG C of heat treatments 2pO 4) 2and Ca (MCPA) 2h 2p 2o 7(CDPP).
Fig. 2 is the calcium metaphosphate porous ceramics sample photo that the specific embodiment of the invention and comparative example obtain.Wherein, (a), (b), (c) are respectively sample prepared by embodiment; D (), (e) are respectively sample prepared by comparative example.

Claims (4)

1. a preparation method for calcium metaphosphate porous bio-ceramic, is characterized in that:
(1) one water dalcium biphosphate Ca (H 2pO 4) 2h 2the preparation of O (MCPM) powder body
By Ca/Pmol than be 0.5 calcium oxide and phosphoric acid and pure water add respectively in beaker, use magnetic stirrer solution after 48 hours, beaker is put into electric heating constant-temperature blowing drying box, drying 7 days at 60 DEG C, by dried powder body ball milling, powder body is crossed 200 mesh sieves and is namely obtained a water dalcium biphosphate powder body;
(2) preparation of calcium metaphosphate porous ceramics
Water dalcium biphosphate powder body step (1) obtained again mixes evenly with the polyvinyl alcohol of 5.0wt%, pelletize is sieved, dry pressure formed under lower than the pressure of 2.0MPa again, 500 DEG C are heated to the heating rate being less than 0.5 DEG C/min, be heated to 935 DEG C of insulation 2.0h to sintering by the calcining system of 5.0 ~ 10.0 DEG C/min again, after natural cooling, namely obtain calcium metaphosphate porous bio-ceramic.
2. a preparation method for calcium metaphosphate porous bio-ceramic, is characterized in that:
(1) one water dalcium biphosphate Ca (H 2pO 4) 2h 2the preparation of O (MCPM) powder body
By Ca/Pmol than be 0.5 calcium oxide and phosphoric acid and pure water add respectively in beaker, use magnetic stirrer solution after 48 hours, beaker is put into electric heating constant-temperature blowing drying box, drying 7 days at 60 DEG C, by dried powder body ball milling, powder body is crossed 200 mesh sieves and is namely obtained a water dalcium biphosphate powder body;
(2) preparation of calcium metaphosphate porous ceramics
(21) get a water dalcium biphosphate powder body described in a certain amount of step (1) 140 DEG C of heat treatments 1.0 hours, synthesis dalcium biphosphate (MCPA), more namely ground 200 mesh sieves obtain dalcium biphosphate powder body;
(22) dalcium biphosphate powder body step (21) obtained again mixes evenly with the polyvinyl alcohol of 5.0wt%, pelletize is sieved, dry pressure formed under lower than the pressure of 2.0MPa again, 500 DEG C are heated to the heating rate being less than 0.5 DEG C/min, be heated to 935 DEG C of insulation 2.0h to sintering by the calcining system of 5.0 ~ 10.0 DEG C/min again, after natural cooling, namely obtain calcium metaphosphate porous bio-ceramic.
3. a preparation method for calcium metaphosphate porous bio-ceramic, is characterized in that:
(1) one water dalcium biphosphate Ca (H 2pO 4) 2h 2the preparation of O (MCPM) powder body
By Ca/Pmol than be 0.5 calcium oxide and phosphoric acid and pure water add respectively in beaker, use magnetic stirrer solution after 48 hours, beaker is put into electric heating constant-temperature blowing drying box, drying 7 days at 60 DEG C, by dried powder body ball milling, powder body is crossed 200 mesh sieves and is namely obtained a water dalcium biphosphate powder body;
(2) preparation of calcium metaphosphate porous ceramics
(21) get a water dalcium biphosphate powder body described in a certain amount of step (1) 250 DEG C of heat treatments 0.5 hour, synthesis calcium dihydric pyrophosphate (CDPP), more namely ground 200 mesh sieves obtain calcium dihydric pyrophosphate powder body;
(22) calcium dihydric pyrophosphate powder body step (21) obtained again mixes evenly respectively with the polyvinyl alcohol of 5.0wt%, pelletize is sieved, dry pressure formed under any pressure again, 500 DEG C are heated to arbitrary heating rate, be heated to 935 DEG C of insulation 2.0h to sintering by the calcining system of 5.0 ~ 10.0 DEG C/min again, after natural cooling, namely obtain calcium metaphosphate porous bio-ceramic.
4. according to claim 1 or 2 or 3 the preparation method of calcium metaphosphate porous bio-ceramic that describes, it is characterized in that the Ca/Pmol ratio of calcium metaphosphate is 0.5.
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