CN1390607A - Modified hydroxyphosphorite as substitute of bone and its preparing process and application - Google Patents
Modified hydroxyphosphorite as substitute of bone and its preparing process and application Download PDFInfo
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- CN1390607A CN1390607A CN 01118777 CN01118777A CN1390607A CN 1390607 A CN1390607 A CN 1390607A CN 01118777 CN01118777 CN 01118777 CN 01118777 A CN01118777 A CN 01118777A CN 1390607 A CN1390607 A CN 1390607A
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Abstract
A modified hydroxyphosphorite used as bone substitute, its preparing process and its application in repairing bone in situ are disclosed. Said bone substitute is prepared from the phosphate bone cement containing the radical of carbonic acid and the cations of metal except Ca, and solidifying liquid through proportional mixing.
Description
The present invention relates to a kind of generation bone material, its preparation method and solidify the application of repairing in the osseous tissue in position.More specifically, the invention provides a kind of phosphate bone cement that contains the metal cation beyond carbonate and the deliming, this bone cement and consolidation liquid are mixed in proportion curing after, can make modified hydroxylapatite for bone material.Above-mentioned material can be directly used in in-situ solidifying reparation osseous tissue in the clinical operation.
Hydroxyapatite (HAP) is the main mine material that constitutes skeleton and tooth, so its various forms is widely used as for bone material.Hydroxyapatite belongs to difficulty soluble salt, log (K
Sp) be 58.6 at 37 ℃, its crystal is the most stable with hexagonal crystal system, grows up into needle-like or bar-shaped crystal easily.Mineralogical study shows that the basic structure of hydroxyapatite is Ca
10(PO
4)
6(OH)
2, the PO in the crystal
4 3-Ion can be by CO
3 2-, SiO
4 2-, and SO
4 2-Replace etc. the anion homophase, and calcium ion can be by magnesium ion, potassium ion, sodium ion, cation homophases such as manganese (II) ion replace.The part chemistry and the crystal structure that change hydroxyapatite are to improve its bioactive fundamental way.
Behind hydroxyapatite fine powder plastotype, through high temperature sintering typing more than 1000 ℃, be bioceramic.Sintering makes the HAP crystalline solid become big, and mechanical property is better, but can not degrade, and is used as the substitute of tooth and bone more, especially is suitable as the tooth substitute.
Bone cement is meant the mixture that comprises various phosphate fine powders.During use and consolidation liquid reconcile into pastel, in clinical operation, be filled into the defect of bone, original position is cured and is reacted into as a wholely under body temperature, the end product of reaction is a hydroxyapatite, in order to repairing bone defect.
Brown, W.E. have provided the Ca (OH) with directive significance in US4518430 and US4612053
2-H
3PO
4-H
2The dissolubility phasor of O system is easy in view of the above by general phosphate synthesizing hydroxylapatite bone cement.But bone cement is the system of a complexity, and its different composition is for its presetting period, initial strength, and final strength, biocompatibility, bone conversion speed in vivo, and finally can degrade fully and all has a significant impact.Therefore, people are carrying out extensive studies work always, at different purposes, seek the better bone cement of performance.In addition, desirable material also should have following feature: be easy to produce, have long storage period, use easily and operate.
US4880610 discloses preparation intensity greater than the spongy bone (method of 30～40MPa) material among US5009898 and the CN1003053A.East China University of Science has also been studied with Ca
4P
2O
9Be hydraulicity phosphate, synthesizing hydroxylapatite is for the method for bone material.In these research work, synthetic end product is a hydroxyapatite, for the intensity after strengthening bone cement and solidifying, and has reduced the porosity of material, thus influenced osseous tissue grow into and promptly solidify for bone material after the degradation speed of bone cement.
Medical research shows that the mineral facies of skeleton are not by pure hydroxyapatite Ca
10(PO
4)
6(OH)
2Form, wherein also contain 6% the carbonate of having an appointment, 0.7% sodium ion, and small amount of magnesium, fluorine, chlorine, elements such as potassium.Discover that important effect is being brought into play in the existence of carbonate, for example, carbonate can suppress HAP grain growth (Blumenthal, et al., Calcif.Tissue Int., 1984,36:439-441; LeGeros, et al., " Phosphate Minerals inHuman Tissues ", in Phosphate Minerals (Berlin), J.Nriagu (eds): Springer, 1984, pp351-385), and the form that makes mineral facies from needle-like and bar-shaped become spherical, change the inner tensions of HAP and the chemical stability (LeGeros of apatite, et al., the same, 1984; LeGeros, et al., the same, 1989).Therefore, the HAP of carbonate replacement has littler crystal grain and better dissolubility.
Simultaneously, carbonate is an osteoblast, and osteoclast and other osteocyte permeate necessary between bone.Because mineral replace and the skeleton reconstruction all relates to osteoblast, osteoclast etc., so the hydroxyapatite implant of synthetic preferably is the hydroxyapatite that contains carbonate in essence.
WO94/08458 discloses a kind of hydroxyapatite bone material and application thereof that contains carbonate.But use Ca in this technology
4P
2O
9As hydraulicity phosphate, need to add solid orthophosphoric acid in the reaction.And ortho-phosphoric adding is escaped the carbonate in the carbonate easily, reacts wayward, and its storage like this, application etc. are all inconvenient.
In order to overcome the problems referred to above, the purpose of this invention is to provide a kind of generation bone material, this generation bone material be to form with the curing of consolidation liquid mix homogeneously by the phosphate bone cement that contains the metal cation beyond carbonate and the deliming.Because in this,, bone material more approached the mineral facies of skeleton in generation, therefore after solidify at the damaged place of bone, had good dissolubility, was easy to the growth of tissue apposition and osseous tissue.
Another object of the present invention provides the preparation method of above-mentioned modified hydroxylapatite for bone material.
Another purpose of the present invention be above-mentioned generation bone material be used for the clinical repair osseous tissue.
The present invention relates to a kind of modified hydroxylapatite for bone material, it is characterized in that, contain the metal ion beyond carbonate and the deliming in this hydroxyapatite, this in generation bone material have following general formula:
Ca
10-xyM
wH
v(PO
4)
6-x(CO
3)
x(OH)
2-xWherein: M is Li
+, Na
+Or K
+Etc. the monovalence metal cation,
X represents the replacement amount of carbonate, is 0＜x≤1,
Y represents that a carbonate replaces the calcium room number that is produced behind the phosphate radical, and is relevant with Ca/P, is 1.33～1.67 positive number,
V represents to be used for the unbalanced hydrionic quantity of compensation charge,
W is 0.10～0.30 positive number, and
w+v＝2x(y-1)。
According to a preferred embodiment of the present invention, the M in above-mentioned general formula is a sodium ion.
The invention still further relates to micropowder modification bone cement, is a kind of phosphate bone cement that contains carbonate and deliming metal cation in addition, comprising phosphate, carbonate, the salt that contains the M metal, particular certain cancers, this bone cement mixes with consolidation liquid when using and solidifies.
In the described phosphate, with α-Ca
3(PO
4)
2As hydraulicity phosphate, constitute the major part of bone cement, its content based on the bone cement gross weight is 75～92wt%.Also comprise in the described phosphate and be selected from other phosphate, for example CaHPO
4, CaHPO
42H
2O, Ca (H
2PO
4)
2Or Ca (H
2PO
4)
2H
2Among the O one or more, other phosphatic content is surplus.
In principle, unrestricted to described carbonate, but preferably use calcium carbonate, its content based on the bone cement gross weight is 2～17wt%.
Described sodium salt can be various salt or the hydrated salts that contain sodium ion, or its combination in any, but preferably uses sodium carbonate, sodium bicarbonate, and one or more in tertiary sodium phosphate and the hypophosphite monohydrate sodium salt, its content based on the bone cement gross weight is 1～5wt%.
Each component in the bone cement comprises phosphate, and carbonate contains the slaine of M element, and other component of for example sodium salt, and ubi infra all grinds to form fine powder.The mean diameter of the fine powder that grinding obtains is about 0.5 μ m～30 μ m, preferred 1 μ m～10 μ m, more preferably 1 μ m～5 μ m.Solid particle is ground to form micropowder can carry out according to various known methods.
According to one embodiment of the invention, also contain calcium oxide in the described modification bone cement, its content based on the bone cement gross weight is 0～3wt%.
According to one embodiment of the invention, also contain anti-rare powder in the described modification bone cement, this anti-rare powder is selected from sodium alginate and sodium fulvate, and its content based on the bone cement gross weight is 0～0.5wt%.
According to one embodiment of the invention, also contain in the described modification bone cement in advance at the synthetic carbonato crystal seed of aqueous phase, this crystal seed is by soluble calcium salt, phosphate, the carbonate reaction preparation, wherein:
(1) calcium salt is calcium oxalate and/or lime nitrate, is the aqueous solution of 0.01～0.04M;
(2) phosphate is sodium hydrogen phosphate, sodium dihydrogen phosphate, and one or more in tertiary sodium phosphate and the triammonium phosphate are the aqueous solution of 0.01～0.5M;
(3) carbonate is sodium carbonate and/or sodium bicarbonate, is the aqueous solution of 0.01～0.5M.The content of carbonate reaches as high as～20wt% in the crystal seed, and the content of crystal seed in bone cement is 0～20wt%.
Because in the hydroxyapatite of the common synthetic carbonating of hydraulicity phosphate curing reaction, contain the carbonate of the 2%～4wt% that has an appointment, and content instability, so in order to obtain more HAP near the skeleton mineral facies, promptly contained the HAP of 6% carbonate approximately, can be taked certain measure.According to the present invention,, improved the carbonate content in the bone cement after solidifying effectively by in bone cement, adding carbonato crystal seed.And, can regulate the content of modification for the carbonate in the bone material by the content of regulating carbonate in the crystal seed and/or the consumption of regulating crystal seed in the bone cement.
Described consolidation liquid is that sodium phosphate and/or sodium carbonate are dissolved in the solution that is made in the deionized water, its concentration 0.1～0.4M.When using bone cement, this consolidation liquid and bone cement is even by the mixed of 0.3～1ml/g, be filled to the bone defect and carry out in-situ solidifying.
According to another embodiment of the invention, when containing sodium phosphate and/or sodium carbonate in the described modification bone cement, consolidation liquid can only be a deionized water also.
The invention still further relates to the preparation method of described bone cement, wherein elder generation grinds to form fine powder respectively with each component of bone cement, then according to the aforementioned ratio mix homogeneously.
The invention still further relates to the preparation method of described modified hydroxylapatite for bone material, is the modification bone cement to be mixed with consolidation liquid be cured and obtain, and described consolidation liquid and modification bone cement are by the mixed of 0.3～1ml/g.
The invention still further relates to described modified hydroxylapatite for the application of bone material in repairing osseous tissue.Described modification bone cement and described consolidation liquid are mixed in proportion, fill in clinical operation or be expelled to both injured bones tissue place, in-situ solidifying becomes modified hydroxylapatite for bone material, repairing bone defect.
Modified hydroxylapatite of the present invention for the crystal of bone material and chemical composition than agglomerating and general hydroxyapatite more near skeleton mineral facies (seeing accompanying drawing 1a and 1b).Infrared spectrum shows that carbonate has wherein replaced the phosphate radical in the hydroxyapatite structure, rather than has (seeing accompanying drawing 2a and 2b) with the impurity form.Because modified hydroxylapatite of the present invention is for carbonate that contains high level in the bone material and sodium ion, and the chemical bond that combines with carbonate and sodium ion relative a little less than, make crystal begin dissolving and degraded easily from these places.In addition,, make that the crystal grain of HAP is littler, also improved the dissolubility of HAP owing to contain more carbonate and sodium ion.Therefore, modified hydroxylapatite of the present invention has better dissolubility and degradability for bone material, helps new bone and substitutes and the bone integration.Body is implanted into experiment and shows that modified hydroxylapatite of the present invention combines with bone interface closely in vivo for bone material, and material is partly dissolved after 16 weeks, and new bone is grown in the material.
Each component in the bone cement of the present invention all adopts grinder to grind, and granularity is very little, thus the injection of material and anti-rare diffusing functional, good operation performance.In addition, the curing reaction of bone cement is obviously accelerated, and comprcssive strength obviously improves, like this, the faster molding of operation back bone substitute can be shortened patient's postoperative and repose the time, thereby minimizing patient health skeleton and muscle is not because of bearing for a long time the chance that atrophy does not take place load.
Bone cement of the present invention is a solid powder material, and in principle, as long as isolated dampness, it can be stored indefinitely.When using, bone cement of the present invention and consolidation liquid are mixed in proportion and can use, very convenient.
The accompanying drawing summary:
Fig. 1 a is the X-ray diffraction spectrogram that contains the modified hydroxylapatite of carbonate and sodium ion for bone material of the present invention;
Fig. 1 b is the X-ray diffraction spectrogram of human body spongy bone mineral facies;
Fig. 2 a is the infrared spectrum that contains the modified hydroxylapatite of carbonate and sodium ion for bone material of the present invention;
Fig. 2 b is the infrared spectrum of human body cortical bone mineral facies.
Fig. 3 a is that the bone of making in the animal model is damaged;
Fig. 3 b is that bone is inserted carbonating apatite in damaged;
Fig. 3 c is the specimen that bone was inserted in damaged behind the carbonating apatite 5 days;
Fig. 3 d is the specimen that bone was inserted in damaged behind the carbonating apatite 16 days;
Fig. 3 e is an aneurysmal bone cyst;
Fig. 3 f is that bone is damaged seen in the art;
Fig. 3 g is this material of the damaged filling of bone;
Fig. 3 h is the postoperative X sheet.
Further elaborate the present invention below in conjunction with embodiment.
With 0.88g α-Ca
3(PO
4)
2, 0.09g CaCO
3, 0.01gNaHCO
3, 0.08gCa (H
2PO
4)
2H
2O, 0.03g CaO are milled down to below the 10 μ m, add the Na of 0.4ml 0.2M
3PO
4Aqueous solution stirs into pasty state, injects in the mould to solidify.In 100% humidity, 37 ℃ keep down the demoulding after half an hour, immerse in the deionized water comprcssive strength 53MPa after 5 days, Ca/P=1.67, CO
3 2-Replacement amount 4.32%, Na
2O content 0.8%.
The chemical constitution formula of material is Ca
8.9Na
0.26H
0.68(PO
4)
5.33(CO
3)
0.7(OH)
1.3Embodiment 2
0.78g α-Ca
3(PO
4)
2, the synthetic Ca of 0.10g
5(PO
4, CO
3)
3The OH crystal seed, other components and content, operation was surveyed comprcssive strength in 1, five day later on embodiment.In five parallel laboratory tests, comprcssive strength is 38MPa～48MPa, CO
3 2-Content 4.95%～5.3%, Na
2O content 0.8%.
Embodiment 3
With the prescription of embodiment 1, in fine powder, add the 5mg sodium alginate, stir into pasty state, rub into the dough shape after syringe is injected in 37 ℃ of warm water with have gentle hands, not rare diffusing, 10 minutes after fixing.
Embodiment 4
With 0.84g α-Ca
3(PO
4)
2, 0.123g CaCO
3, 0.01gNaHCO
3, 0.03gCa (H
2PO
4)
2H
2After the O fine powder mixes, add the Na of 0.4ml 0.2M
3PO
4Aqueous solution stirs into pasty state, injects in the mould to solidify.In 100% humidity, 37 ℃ keep down the demoulding after half an hour, immerse in the deionized water comprcssive strength 37MPa after 5 days.
Embodiment 5
Prescription and operation are with embodiment 4, and fine powder is crossed 400 mesh sieves (mean diameter is 23.6 μ m) after being respectively and grinding, the micropowder (mean diameter is 3.1 μ m) of crossing 600 mesh sieves (mean diameter is 12.3 μ m) and grinding through super grinder, the intensity of specimen.The intensity of micropowder is 51.042 ± 3.728MPa, and elastic modelling quantity is 15.23 ± 1.65, and the compressive strength of 600 orders and 400 order CHA is respectively 31.799 ± 3.621MPa and 23.817 ± 2.973MPa, and elastic modelling quantity is 13.61 ± 2.12 and 14.38 ± 1.92.Implementation column 6
Get the micropowder bone cement of embodiment 4 prescriptions and make sample, implant damaged (Fig. 3 a of hybrid dog distal femur bone, 3b), 5 days and 16 weeks back execution animal; get specimen and carry out cardinal principle, stereomicroscope, decalcification section and undecalcified sections observation, compare with baric acrylic acid bone cement (BCBC) in the experiment.Gross examination of skeletal muscle: CHA is good at the implant site in-situ solidifying in the time of 5 days, and the surface has the part area of new bone to form, and combines closely with the interface of bone, does not find that fibrous connective tissue forms.CHA and synosteosis are tight when 16 weeks, and tangent plane visible part CHA degraded and new bone are grown into.Matched group BCBC all is kept perfectly, and can see fibrous tissue formation between the interface of bone.The stereomicroscope testing result is presented at the volume of implanting back 5 days CHA in-situ solidifyings and is kept perfectly, and prolongation in time can obviously be observed CHA during 16 weeks and degrade gradually, new bone grow into gradually (Fig. 3 c, 3d).When 16 weeks, can obviously see formation one deck fibrous tissue between BCBC and the osseous tissue and implant the BCBC group.Half decalcification section HE dyeing testing result shows specimen through incomplete decalcification, can see portion C HA in section, does not find fiber, granulation tissue and inflammatory cell infiltration between the interface of bone and CHA all the time.Prolongation in time, visible CHA degraded, new bone is grown into gradually, and the bone island that new vessels forms occurs centering on, osteoblast secretion bone matrix, the visible osteoclast in interface.In the BCBC group, can be observed and form fibrous tissue between the interface.The fluorescence staining testing result shows that fluorescent material can deposit in the area of new bone, therefore adopts fluorescent labeling to can be observed the formation of area of new bone.From 4 weeks to 16 all materials and bone interface between tetracycline deposition is all arranged, show that there is mineralization process all the time in material surface.And the interface of BCBC and bone does not have tangible area of new bone to form.
Embodiment 7
Get experimental model and the experiment material of embodiment 6, in material, imbed metallic screw during operation, respectively 5 days after surgery and 16 all animal, biomechanics bond strengths between test material and the bone interface of putting to death.The biomechanics testing result shows, separation test: the adhesion between the normal distal part of femur spongy bone is 322 ± 17N.Implanting CHA rear interface adhesion 5 days only was 56N, and the plane of disruption is between bone and CHA, along with the prolongation adhesion of time strengthens gradually, reaches 281N when 16 weeks, plane of disruption major part still between the interface, is considered to be worth doing with spongy bone but can observe portion C HA surface.The interface binding power of implanting the baric bone cement reached 288.5N in 5 days, but along with the prolongation of time, adhesion is dwindled gradually, and adhesion is reduced to 228N during 16 weeks, and as seen short broken face has fibrous tissue to form.Pull: the withdrawal force of 5 days CHA groups of postoperative screw only is 250N, between bone and CHA interface, rupture, the solidified CHA of screw complete covering one deck in surface, along with the prolongation of time, the screw withdrawal force increases gradually, and the withdrawal force of CHA reaches 512.5N when 16 weeks, the plane of disruption is still at the interface of CHA and bone, but CHA can not be kept perfectly, the visible part fracture, and the surface is with a large amount of Grafting Cancellous Bone Bolt bits.5 days baric bone cements of postoperative group screw withdrawal force reaches 753N, but prolongation along with the time, the power of pulling out is dwindled gradually, pull out power during 16 weeks and reduce to 603N, the plane of disruption is between baric bone cement and spongy bone, the visible fibrous tissue in interface forms, and the screw surface covers the complete baric bone cement of one deck all the time.
Embodiment 8
Get the material of embodiment 4 prescriptions, strict sterile working makes down, and packing is through cobalt
60Sterilization is equipped with clinical use.Case 1, women, 15 years old, the proximal tibia aneurysmal bone cyst, MRI shows tumor intrusion soft tissue, strikes off tumor in the art, abrasive drilling grinding tumor bed, carbonating hydroxyapatite solid-liquid is mixed mutually, insert bone damaged in, solidified in about ten minutes, the postoperative X line shows, damaged filling is satisfied, otch normally heal (Fig. 3 e-3h).Case 2, the women, 49 years old, the proximal tibia giant cell tumor of bone was struck off tumor in the art, abrasive drilling grinding tumor bed mixes carbonating hydroxyapatite solid-liquid mutually, insert bone damaged in, solidified in about ten minutes, the postoperative X line shows that damaged filling is satisfied, otch normally heals.
Original operation is being filled in the cavity of affected part from body bone or allograph bone fragment the patient, there is the gap for (1) in its shortcoming in charges and between charges and the chamber wall, (2) no pressure resistance degree, (3) foreign body rejection, (4) patient must accept the misery (autologous bone transplanting) that autologous bone transplanting causes, (5) pathophoresis (allogenic bone transplantation).
The front is illustrated the present invention and effect thereof in conjunction with the embodiments.Yet, it should be appreciated by those skilled in the art, in this specific method of discussing and result, only be in order to demonstrate the invention, rather than limitation of the present invention, the present invention will be more completely open by claim subsequently.Under the situation that does not break away from spirit of the present invention, to any modification of the present invention and modification, all within the scope of the present invention.
Claims (10)
1. a modified hydroxylapatite is characterized in that for bone material, contains the metal ion beyond carbonate and the deliming in this hydroxyapatite, this in generation bone material have following general formula:
Ca
10-xyM
wH
v(PO
4)
6-x(CO
3)
x(OH)
2-xWherein: M is Li
+, Na
+Or K
+Etc. the monovalence metal cation,
X represents the replacement amount of carbonate, is 0＜x≤1,
Y represents that a carbonate replaces the calcium room number that is produced behind the phosphate radical, and is relevant with Ca/P, is 1.33～1.70 positive number,
V represents to be used for the unbalanced hydrionic quantity of compensation charge,
W is 0.10～0.30 positive number, and
w+v＝2x(y-1)。
2. modified hydroxylapatite according to claim 1 is characterized in that for bone material described M is a sodium ion.
3. a modified hydroxylapatite as claimed in claim 1 is for the preparation method of bone material, is the modification bone cement to be mixed with consolidation liquid be cured and obtain, and described consolidation liquid and modification bone cement are by the mixed of 0.3～1ml/g.
4. preparation method according to claim 3, it is characterized in that described consolidation liquid is that sodium phosphate and/or sodium carbonate are dissolved in the solution that is made in the deionized water, its concentration is 0.1～0.4M, when perhaps containing sodium phosphate and/or sodium carbonate in bone cement, described consolidation liquid is a deionized water.
5. preparation method according to claim 3 is characterized in that, described modification bone cement is by containing calcium phosphate, calcium carbonate, and the slaine that contains the M element is formed, and each constituent content is by weight percentage:
(1) contain calcium phosphate: 78～95%,
(2) calcium carbonate: 2～17%,
(3) contain the slaine of M element: 1～5%,
And will become mean diameter by the blended improved grinding of above-mentioned composition proportioning is the fine powder of 0.5～30 μ m, makes the modification bone cement.
6. preparation method according to claim 5 is characterized in that, the described calcium phosphate that contains is hydraulicity calcium phosphate α-Ca
3(PO
4)
2Be selected from CaHPO
4, CaHPO
42H
2O, Ca (H
2PO
4)
2Or Ca (H
2PO
4)
2H
2Other synthos of among the O one or more, and hydraulicity calcium phosphate content is 75～92% of bone cement gross weight, and surplus is the content of other synthos.
7. preparation method according to claim 5 is characterized in that, the slaine of the described M of containing element is the carbonate of M metal, bicarbonate, one or more in tricresyl phosphate salt and the hydrated phosphate.
8. according to any described preparation method in the claim 5～7, it is characterized in that also contain in the described modification bone cement in advance at the synthetic carbonato crystal seed of aqueous phase, the content of crystal seed in bone cement is 0～20wt%.
9. claim 1 or 2 modified hydroxylapatite are for the application of bone material in repairing human body bone (tooth) tissue.
10. the application of claim 9 is characterized in that behind bone cement and the consolidation liquid mix homogeneously, injects or directly be filled into both injured bones (tooth) position clinically.
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|---|---|---|---|
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|---|---|---|---|
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| CN1189220C CN1189220C (en) | 2005-02-16 |
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| CN101491691B (en) * | 2009-02-18 | 2012-08-29 | 重庆大学 | Hydroxyapatite reinforcing material for metal matrix composite |
| CN106552293A (en) * | 2016-11-24 | 2017-04-05 | 南京航空航天大学 | A kind of preparation method of the gluconic acid modified hydroxyapatite bone cement of high intensity |
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2001
- 2001-06-12 CN CNB011187778A patent/CN1189220C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101223105B (en) * | 2005-07-19 | 2011-04-06 | 法恩扎Fin-陶瓷股份公司 | Process for the preparation of a biomimetic bone substitute and its uses |
| CN101491691B (en) * | 2009-02-18 | 2012-08-29 | 重庆大学 | Hydroxyapatite reinforcing material for metal matrix composite |
| CN106552293A (en) * | 2016-11-24 | 2017-04-05 | 南京航空航天大学 | A kind of preparation method of the gluconic acid modified hydroxyapatite bone cement of high intensity |
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| CN106946486A (en) * | 2017-04-19 | 2017-07-14 | 东南大学 | Synthetic method for the calcium containing compound additive of calcium phosphate bone cement |
| CN106946486B (en) * | 2017-04-19 | 2019-09-10 | 东南大学 | The synthetic method of calcium containing compound additive for calcium phosphate bone cement |
| CN111194204A (en) * | 2017-06-02 | 2020-05-22 | 西澳大利亚大学 | Method for producing a calcified tissue substitute |
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| CN108144126B (en) * | 2017-11-23 | 2021-05-18 | 四川大学华西医院 | Lithium-doped nano hydroxyapatite composite material and preparation method and application thereof |
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