CN1031040C - Biological active coating-Ti alloy man-made bone, joint and its preparation - Google Patents
Biological active coating-Ti alloy man-made bone, joint and its preparation Download PDFInfo
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- CN1031040C CN1031040C CN 89108653 CN89108653A CN1031040C CN 1031040 C CN1031040 C CN 1031040C CN 89108653 CN89108653 CN 89108653 CN 89108653 A CN89108653 A CN 89108653A CN 1031040 C CN1031040 C CN 1031040C
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- bioactive
- bone
- ground
- titanium alloy
- coat enamel
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Abstract
The present invention relates to a biological active coating layer--a Ti alloy man-made bone, a man-made joint and a preparation method thereof, which is characterized in that a layer of base enamel is coated on the handles and the acetabulum parts of the Ti-alloy man-made bone and the man-made joint, a layer of bioactive materials is coated on the outer surface of the base enamel, and the bioactive materials are composed of carboxyl apatite and bioactive microcrystalline glass. Synostosis is built between the bioactive materials and human body bones after the man-made bone or the man-made joint is embedded in a human body to realize biological fixation in order to prevent a false body from loosening and sinking and prolong the service life of the man-made bone and the man-made joint.
Description
The present invention relates to medical titanium alloy cmposite artificial bone and artificial joint and preparation method.
Behind people's the skeletal injury, often to replace corresponding site with medical alloy.The method of attachment of medical alloy and people's bone has: the bullet alloy is pressed into medullary cavity inlays fixing; Screw is fixed; Fixing etc. with polymethyl methacrylate.Above method all belongs to the mechanical fixation between alloy and the people's bone.Along with the prolongation of the time of implantation, under the effect of alloy administration of human bone pressure, damage will appear in people's bone, is absorbed, thereby causes becoming flexible, sinking.This is a problem anxious to be solved in artificial bone, the artificial joint replacement.
The method of useful plasma spraying at alloy surface, is made foraminous surface to the material coated of aluminium oxide or tungstenic, phosphorus in the prior art.Its objective is the osseous tissue that makes the people grow into realize in the hole fixing.But the hole that plasma spraying method forms has only 50 microns, and osseous tissue is difficult to grow into.
Occurred in recent years alloy surface is made coralliform and cellular, and will osseous tissue can be grown in the hole, bone and alloy be chimeric mutually, and its effect is better than additive method.But because the alloy non-activity, osseous tissue and alloy interface still machinery are chimeric, and its effect can not make people satisfied.
The purpose of this invention is to provide a kind of bioactivity coatings-titanium alloy artificial bone, artificial joint and preparation method, on existing titanium alloy artificial bone, artificial joint basis, composite at its surperficial coated one deck biologically active, set up a kind of synostosis with making after artificial bone or the artificial joint implant into body between bioactive materials and the human body bone and realize biological fixation, prevent prosthetic loosening, sinking, prolong the service life of artificial bone and artificial joint.
First technical solution of the present invention is titanium alloy artificial bone and artificial joint shank and acetabular bone portion surface coated one deck ground-coat enamel, the multiple one deck bioactive materials of this ground-coat enamel outer surface repaste,
The chemical constituent scope (weight %) of a, titanium alloy ground-coat enamel is: SiO
235～45, B
2O
35～25, K
2O6～18, Na
2O4～8, MgO1～6, CaO5～9, P
2O
54～10, Li
2O1～5, CaF
20.5～3, Al
2O
31～3, MnO0.5～2, NiO0.5～2.5, CoO0.5～3,
B, bioactive materials are made up of hydroxyapatite and bioactive devitrified glass, and wherein hydroxyapatite accounts for 38～45% (weight ratios).
The chemical constituent scope (weight %) of C, bioactive devitrified glass is: SiO
230～60, CaO10～40, P
2O
57～20, B
2O
35～10, K
2O2～7, Na
2O4～9, Li
2O1～5, MgO1～4, TiO
21～4, CaF
20.5～2.
Another technical solution of the present invention is the preparation method of bioactivity coatings-titanium alloy artificial bone and artificial joint, and its preparation technology is as follows:
(1) adopts analytical pure or chemical pure raw material, mix in proportion, fusion under 1400 ℃ of temperature, shrend, adding mill again adds agent and makes the ground-coat enamel slip, mill adds agent and is made up of Suzhou soil and sodium carbonate, and each composition of ground-coat enamel slip and content are ground-coat enamel 52.5%, Suzhou soil 7%, sodium carbonate 0.5%, water 40% (weight ratio).
(2) with after titanium alloy artificial bone or the artificial joint cleaning, adopt to soak and ward off method extension ground-coat enamel slip, under 850～900 ℃ of temperature, burn till and be incubated 5～10 minutes after drying and take out cooling.
(3) adopt analytical pure or chemical pure raw material, mix in proportion fusion under 1400～1500 ℃ of temperature, shrend, drying, insulation is 4 hours under 900 ℃ of temperature conditions, and controlled micro crystallization is handled, natural cooling, through pulverizing, sieve (160～200 order), bioactive devitrified glass.
(4) hydroxylapatite powder and bioactive devitrified glass powder are mixed in proportion bioactive materials, % adds bioactive materials 50% by weight again, sucrose 5%, water 45% are made the biological activity slip.
(5) will scribble the titanium alloy artificial bone of ground-coat enamel or artificial joint and coat bioactive materials with the method for soaking the method for warding off or cast, drying was sent in the electric furnace in 850～890 ℃ of temperature and reducing atmosphere sintering 5 minutes, stopped to heat natural cooling then.During the sintering bioactive materials, with water vapour or water, carbon monoxide, hydrogen keep reducing atmosphere in electric furnace.
Bioactive coating material must possess biological activity, so its composition is limited in certain scope.Like this, it is very big that its coefficient of expansion and titanium alloy differ, and adherence is also bad, and directly coated is at titanium alloy surface.Transition zone must be arranged, be about to ground-coat enamel and be coated in titanium alloy surface earlier, and then the bioactive materials sintering on the ground-coat enamel surface.
Requirement to ground-coat enamel is that its composition is to the human body avirulence; Good biocompatibility; Its coefficient of expansion should be 60～80% of the titanium alloy coefficient of expansion; Its firing temperature should be a little more than the firing temperature of bioactive composite material.The coefficient of expansion of ground-coat enamel of the present invention is 307 * 10
-7/ ℃ its firing temperature is 900 ℃.
The hydroxyapatite that this method is used adopts lime nitrate, potassium phosphate, potassium hydroxide reaction to synthesize.
Synthetic product at first generates decentralized photo, generates hydroxyapatite through revulsive crystallization again.With the product drying, calcining back crushing screening (160～200 order).
Hydroxyapatite has superior bioactive.But the sintering difficulty, and intensity is low, is difficult to independent coated at titanium alloy surface.For this reason, bioactive devitrified glass and hydroxyapatite mixed sintering, improving sintering character, and improve intensity.Crystalline phases such as the composition energy precipitation of phosphorus lime stone of this bioactive devitrified glass and wollastonite.The coefficient of expansion of bioactive devitrified glass should be 60～70% of a titanium alloy, and the coefficient of expansion of bioactive devitrified glass of the present invention is 287 * 10
-7/ ℃.Form pore diameter range after this bioactive materials sintering and pick up micron to 400 microns hole for number, porosity is 20～30%.Therefore, people's bone after bioactivity coatings-titanium alloy artificial bone or the artificial joint implant into body can be grown into form synostosis in the hole of bioactive materials and realize biological fixation.
Bioactive materials good biocompatibility of the present invention, and the hole that has osseous tissue to grow into, after bioactivity coatings-titanium alloy artificial bone or artificial joint implant into body, the human body bone can be grown in the hole of bioactivity composite coating.Old friend's body and artificial bone or artificial joint become one, and set up synostosis, have realized biological fixation, have solved the problem of prosthetic loosening and sinking after the implanting prosthetic preferably.
Description of drawings:
Fig. 1 is the sketch map in the artificial joint of the present invention.
Fig. 2 is bioactive composite material and osseous tissue interface's stereoscan photograph.
Fig. 3 is the stereoscan photograph of the bone collagen fiber in the bioactive composite material.
Fig. 4 sees the stereoscan photograph of osteocyte for the bioactive composite material surface.
Fig. 5 is the bonded section photo of bioactive composite material and osseous tissue.
Fig. 6 is bioactive composite material and osseous tissue combination interface electronic probe component analysis figure.
Fig. 7 is a bioactive materials section hole photo.
Fig. 8 is a crystal microphotograph under the bioactive materials quadrature.
Reach example in conjunction with the accompanying drawings and further specify technical solution of the present invention:
(1) found ground-coat enamel: employing analytical pure or chemical pure raw material % are by weight got SiO respectively
242.83B
2O
311.79, Na
2O7.86, K
2O8.84, MgO3.73, CaO8.84, R
2O
57.86, Li
2O1.96, CaF
20.79, Al
2O
31.96, MnO0.79, Ni
2O0.79, CoO1.96 mix homogeneously, fusion is 2 hours under 1400 ℃ of temperature, and shrend gets the ground-coat enamel material.% adds ground-coat enamel 52.5% by weight then, Suzhou soil 7%, and sodium carbonate 0.5%, water 40% mix homogeneously grind and are the ground-coat enamel slip.
(2) synthesizing hydroxylapatite: with chemical pure 0.08MKOH, 0.04MCa (No
3)
2, 0.24MK
3PO
4Mix homogeneously stirs, and keeps PH 9 to make hydroxyapatite, drying, calcining back crushing screening (160～200 order).
(3) producing of bioactive devitrified glass: adopt analytical pure or chemical pure to get SiO by weight percentage
245.78, CaO20.36, P
2O
510.68, B
2O
38.14, Na
2O7.12MgO2.03, Li
2O2.03, CaF
21.83, TiO
2.03 mix homogeneously, 1450 ℃ of fusions insulation shrends after 1 hour, drying, insulation is 4 hours under 900 ℃ of temperature conditions, controlled micro crystallization is handled, natural cooling, through pulverizing, sieve (160～200 order), the bioactive devitrified glass powder.
(4) fire bioactivity coatings.
1. with after titanium alloy artificial bone or artificial joint shank and the cleaning of marrow mortar portion, hang ground-coat enamel, after drying, under 900 ℃ of temperature, burn till insulation and took out cooling in 5 minutes with soaking the method for warding off.
2. hydroxylapatite powder and bioactive devitrified glass powder are mixed in proportion and make bioactive materials.% adds bioactive materials 50%, sucrose 5%, water 45% by weight again, makes the biological activity slip.
3. will scribble the titanium alloy artificial bone of ground-coat enamel or artificial joint adopts and soaks the method for warding off and hang and be coated with the biological activity slurry, drying is sent into and is fed water vapour, water, carbon monoxide or hydrogen in the electric furnace kept in the reducing atmosphere sintering 5 minutes under 890 ℃ of temperature, stops to heat natural cooling then.
Can see the structure in the artificial joint of the present invention in the accompanying drawing 1,1 is the titanium alloy mortar among Fig. 1, and 2 is the titanium alloy lock nut, and 3 is high density polyethylene (HDPE), and 4 is the titanium alloy handle, and 5 is bio-active material coating.
The hole (Fig. 7) that can see the sintering shape and be dispersed in the bioactive materials agglomerate section electromicroscopic photograph of the present invention.After measured, pore diameter range picks up micron to 400 microns for number.Porosity is 20～30%.This material is measured through X-ray diffractometer, and its crystalline phase is mainly (Fig. 8) such as basic apatite, wollastonites.
Shared 75 rabbits of biological activity-titanium alloy composite material of the present invention and 4 Canis familiaris L.s have done zoopery, have carried out the observation in conjunction with situation of biocompatibility and bioactive composite material and osseous tissue respectively.
1, biocompatibility experiment:
Under 20% urethane general anesthesia, respectively bioactive composite material and ground-coat enamel and control material (titanium alloy sheet) are planted in the rabbit musculus sacrospinalis, respectively at 4 weeks, 8 weeks, 16 weeks, the sampling of 24 weeks, carry out pathological examination.The result: the test specimen surrounding tissue is not seen obvious inflammatory reaction, necrosis and corrosion phenomenon.Fibrous membrane thickness is no more than required standard (0.03mm) around the test specimen.
2, bioactive composite material combines situation with osseous tissue:
(1) histological examination:
With Harbin type white rabbit, body weight 2.5～3.0kg, 20% crow is drawn load anesthesia, ilium body otch, this material is implanted in raggle, sampling in the time of 38 days (Beijing Friendship Hospital assists film-making).The result: visible hypertrophy osteocyte and bone stem matter close attachment around this material, this edge of materials recess also has bone matrix to stretch into (Fig. 2).
(2) scanning electron microscopic observation:
Respectively this material is planted in rabbit femoral greater trochanter portion, ala of ilium; The artificial prosthesis of this material is implanted the proximal femur of Canis familiaris L., sampling by stages, the specimen of rabbit is made bulk, and the specimen of Canis familiaris L. is cut into cross section through water under high pressure, at scanning electron microscopic observation, implants and sees that the interface was unclear in back 83 days after digestion method is handled.Osseous tissue is the sawtooth sample and stretches in this material, have osseous tissue to grow in the micropore.Implant back 175 days visible area of new bone cells (Fig. 3,4,5).
(3) electron probe test:
This material is implanted the right greater trochanter of femur of rabbit portion, and bulk is made in sampling by stages, and spray carbon is handled.Through Institute of Analysis of Harbin Institute of Technology, carry out line analysis at the interface of bone and this material with JC * A-733 electron probe.Analyze 100 points, 1 micron of every some distance.Check Ca, P, Si, the Strength Changes situation of Na element on analysis position, and on same position, carry out the quantitative analysis of Ca, P, Na, Si element.From the line analysis result, mutual migration (diffusion) phenomenon of element is arranged.Than high in this material, Ca, P in the near interface material spread in this material as Ca, P in the bone.Do not see that Na has tangible diffusing phenomenon.Ca, P approximately spread 20-25 microns (Fig. 6) in this material.
(4) X ray examination:
Under 20% crow is drawn load anesthesia, expose the right radius of rabbit stage casing, together with 1 centimetre of periosteum osteotomy, this material (suitable with amputation bone size) is embedded in damaged place, in be fastened with filamentary silver, in the closed wound.Carry out the inspection of taking pictures of X line, postoperative is in the time of 1,2 months by stages, and X-ray film is not seen significant change, sees material and bone intersection image fog in the time of 3 months, and during 5 first quarter moon photos, material and bone interface disappear, and are the bony union image after surgery.
(5) isotopic examination:
To implant this material in 6 of the rabbits of right greater trochanter portion, respectively from ear vein injection skeletal imaging agent 99mTC-MDP (99m-methylene diphosphonate) 12MBq/kg, after 3 hours earlier with PHO/GAMMA HP SKC-1 type scintiphotograph machine carry out the bilateral greater trochanter of femur be in bone video picture (the right side greater trochanter of femur is implanted this material).Put to death at intravenous rabbit injection air then.Get this material and the sclerotin bonded of right side greater trochanter of femur portion immediately, also take out the sclerotin that the position is suitable, size is similar in left side greater trochanter of femur portion simultaneously with it.Carry out radiometry with FJ-2003/50 type γ rabbit epidemic disease enumerator.Measure in every this material of gram and the greater trochanter of femur osseous tissue in per minute radiocounting (CPm/g).
From bone video picture result as seen, implant 6 months experimental side radioactivity of this material apparently higher than the control sides radioactivity.
Radiometry (postoperative 3 months and 6 months 6 rabbits) radiometry result
cpm/g
| Rabbit number | Implant the back time | Experimental side (this material) | Control sides (left side greater trochanter of femur) |
| 1 | 3 months | 561811 | 1100000 |
| 2 | ″ | 564814 | 1032186 |
| 3 | ″ | 1014760 | 1701112 |
| 4 | 6 months | 3233333 | 249829 |
| 5 | ″ | 2983927 | 430439 |
| 6 | ″ | 2449883 | 561646 |
From last table as seen, 3 this material of rabbit radioactivity of 3 months of postoperative are not high.And 3 this material of rabbit radioactivity of 6 months of postoperative are apparently higher than the radioactivity of control sides.
Nuclide examinations such as above bone video picture and radiometry prove that skeletal imaging agent 99mTC-MDP supplies to enter into this material by blood in the time of back 6 months in implantation, may be adsorbed on this material.
Product of the present invention is applied to clinical since in November, 1988, use 19 examples at orthopaedics, and in respect of multiple diseases such as bone bland necrosis, fracture, bone tumor and tumour-like lesion, osteomyelitis, tuberculosis of bone and joint and arthrodesiss, short-term effect is good.
Claims (3)
1, a kind of bioactivity coatings-titanium alloy artificial bone, artificial joint is characterized in that titanium alloy artificial bone and artificial joint shank and acetabular bone portion surface coated one deck ground-coat enamel, the multiple one deck bioactive materials of this end outer surface repaste,
The chemical constituent scope (weight %) of a, titanium alloy ground-coat enamel is: SiO
235～45, B
2O
35～25, K
2O6～18, Na
2O4～8, MgO1～6, CaO5～9, P
2O
54～10, Li
2O1～5, CaF
20.5～3, Al
2O
31～3, MnO0.5～2, NiO0.5～2.5, CoO0.5～3,
B, bioactive materials are made up of hydroxy-apatite face and bioactive devitrified glass, and wherein hydroxyapatite accounts for 38～45% (weight ratios),
The chemical constituent scope (weight %) of c, bioactive devitrified glass is: SiO
230～60, CaO10～40, P
2O
57～20, B
2O
35～10, K
2O2～7, Na
2O4～9, Li
2O1～5, MgO1～4, TiO
21～4, CaF
20.5～2.
2, the preparation method of bioactivity coatings-titanium alloy artificial bone, artificial joint in a kind of preparation claim 1 is characterized in that:
(1) adopts analytical pure or chemical pure raw material, proportionately divide the ratio mix homogeneously, fusion under 1400 ℃ of temperature, shrend, adding mill again adds agent and makes the ground-coat enamel slip, mill adds agent and is made up of Suzhou soil and sodium carbonate, and each composition of ground-coat enamel slip and content are ground-coat enamel 52.5%, Suzhou soil 7%, sodium carbonate 0.5%, water 40% (weight ratio)
(2) with after titanium alloy artificial bone or the joint cleaning, adopt to soak and ward off method extension ground-coat enamel slip, under 850～900 ℃ of temperature, burn till and be incubated 5～10 minutes after drying and take out cooling,
(3) adopt analytical pure or chemical pure raw material, mix in proportion fusion under 1400 ℃～1500 ℃ temperature, shrend, drying, insulation is 4 hours under 900 ℃ of temperature conditions, and controlled micro crystallization is handled, natural cooling, through pulverizing, sieve (160～200 order), bioactive devitrified glass
(4) hydroxylapatite powder and bioactive devitrified glass powder are mixed in proportion bioactive materials, % adds bioactive materials 50% sucrose 5%, water 45% by weight again, makes the bioactive materials slip,
(5) will scribble the titanium alloy artificial bone of ground-coat enamel or artificial joint and coat bioactive materials with the method for soaking the method for warding off or cast, drying was sent in the electric furnace in 850～890 ℃ of temperature and reducing atmosphere sintering 5 minutes, stopped to heat natural cooling then.
3,, when it is characterized in that the sintering bioactive materials, in electric furnace, keep reducing atmosphere with water vapour or water, carbon monoxide, hydrogen as the said method of claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89108653 CN1031040C (en) | 1989-11-16 | 1989-11-16 | Biological active coating-Ti alloy man-made bone, joint and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89108653 CN1031040C (en) | 1989-11-16 | 1989-11-16 | Biological active coating-Ti alloy man-made bone, joint and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1042067A CN1042067A (en) | 1990-05-16 |
| CN1031040C true CN1031040C (en) | 1996-02-21 |
Family
ID=4857667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89108653 Expired - Fee Related CN1031040C (en) | 1989-11-16 | 1989-11-16 | Biological active coating-Ti alloy man-made bone, joint and its preparation |
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| Country | Link |
|---|---|
| CN (1) | CN1031040C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315538C (en) * | 2003-01-23 | 2007-05-16 | 同济大学 | Glass based nano hydroxyapatite biologic cement and its preparation method |
| CN101347358B (en) * | 2008-09-10 | 2012-04-25 | 哈尔滨工业大学 | Method for producing titanium alloy artificial hip joint with abrasion-proof ceramic coat |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086591C (en) * | 1998-12-21 | 2002-06-26 | 冶金工业部钢铁研究总院 | Artificial joint coated with bone morphogenesis protein and its making method |
| CN1087633C (en) * | 1998-12-21 | 2002-07-17 | 冶金工业部钢铁研究总院 | Method for preparing bone morphogenesis protein and hydroxyapatite compound dosage form |
| CN1081071C (en) * | 1998-12-21 | 2002-03-20 | 冶金工业部钢铁研究总院 | Compounding method of bone morphogenesis protein to calcined bone |
| CN1311875C (en) * | 2005-01-06 | 2007-04-25 | 贵州大学 | Method for preparing materials and coating of gradient bioactive ceramic coating by laser cladding |
| CN104478218A (en) * | 2014-11-10 | 2015-04-01 | 苏州维泰生物技术有限公司 | Bioactive glass ceramic and preparation method thereof |
| CN104665960A (en) * | 2015-02-15 | 2015-06-03 | 张洋 | Orthopedic prosthesis for proximal radioulnar joint fusion |
-
1989
- 1989-11-16 CN CN 89108653 patent/CN1031040C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315538C (en) * | 2003-01-23 | 2007-05-16 | 同济大学 | Glass based nano hydroxyapatite biologic cement and its preparation method |
| CN101347358B (en) * | 2008-09-10 | 2012-04-25 | 哈尔滨工业大学 | Method for producing titanium alloy artificial hip joint with abrasion-proof ceramic coat |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1042067A (en) | 1990-05-16 |
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