CN101053675B - Gradient biologically active ceramic coating material, broad band laser preparing method and product application - Google Patents
Gradient biologically active ceramic coating material, broad band laser preparing method and product application Download PDFInfo
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Abstract
The invention discloses a preparation method of gradient bioactive ceramics coating material, wide band laser and products application, calculating according to weight percent: it is made of 40-100% of composite ceramics powder and 60-0% titanium powder; wherein composite ceramics powder is composed of ceramics powder containing 72-80% of CaHPO4.2H2O and 20-28% of CaCO3, 0.4-0.8% of rare earth oxide. The invention adopts wide band laser cladding technology, gradient design is more reasonable, produced bioactive ceramics coating has a little crack and holes, high rigidity, well tenacity, without generating amorphous phase in coating, and content of titanium powder in the third gradient layer contacting with human body is null, higher HA content, biological activity and biocompatibility of products is improved obviously, it can be used for repairing femur osteonecrosis or hip joint, tooth defect, unable generating rejection reaction, and short repair time.
Description
Technical field: the present invention relates to a kind of gradient biologically active ceramic coating material, broad band laser preparation method and product and use, belong to the technical field of medical material.
Background technology: bioceramic is the important component part of bio-medical material, in the defect repair of human body hard tissue and rebuild and play an important role aspect the physiological function of having lost.The technology of preparing of bioactive ceramic coating generally speaking can be divided into dry method and wet method two big classes, and the laser cladding in the dry method is the CaHPO that applies certain proportioning on substrate material surface in advance
42H
2O and CaCO
3Mixed-powder is used CO then
2Laser-processing system is carried out the surface cladding processing to metal base, makes synthetic and apply hydroxyapatite (HA) coating to finish in one step of titanium alloy surface.Laser cladding is at the early-stage aspect preparation biological coating material, but has demonstrated huge superiority.The mechanical performance of HA bio-ceramic coating mainly depends on the sintered density and the microscopic structure of last sintered product, and the broadband laser cladding technological parameter can have a deep effect on the microscopic structure and the agglutinating property of bio-ceramic coating.Therefore, the inventor has carried out research in depth to the technology that broadband laser cladding prepares the gradient bio-ceramic coating, has applied for and obtained a patent of invention (patent No.: 2005102000115).
The material of the gradient biologically active ceramic coating that provides in the patent of invention 2005102000115 is: first gradient layer is 80～70 kilograms of titanium valves and 20～30 kilograms of composite ceramics, second gradient layer is 50～40 kilograms of titanium valves and 50～60 kilograms of composite ceramics, and the 3rd gradient layer is 20～10 kilograms of titanium valves and 80～90 kilograms of composite ceramics.As seen, titanium valve accounts for 10～20% of material gross weight in the 3rd gradient layer that contacts with human body.Because the biological activity and the biocompatibility of metallic titanium powder are poor, and there are excellent biological compatibility in HA and biological tissue.And from thermodynamic (al) result of calculation, the addition of necessary strict control titanium valve could reduce CaTiO as far as possible
3With the growing amount of CaO, increase substantially the growing amount of HA.Therefore, with coating material that human body contacts in the content of titanium valve low more, the content of HA is high more, then the biological activity of prepared bioactive ceramics and biocompatibility are good more.But in order to guarantee the physical chemistry compatibility between coating and the titanium alloy TC 4, with first gradient layer that titanium alloy TC 4 directly contacts in must add a certain amount of metallic titanium powder.For this reason, the inventor has carried out research more in depth to the gradient coating components in proportions on the basis of patent 2005102000115, has optimized the material of each gradient coating and has formed.
Summary of the invention:
The objective of the invention is to: provide a kind of gradient biologically active ceramic coating material, broad band laser preparation method and product to use, this coating material and method for making can not only guarantee to form stable bioactive ceramic coating on the surface of titanium alloy, and the biological activity of products obtained therefrom and biocompatibility obviously improve, can be used for human femur under loading necrosis or hip joint, reparation that tooth is damaged, rejection can not take place, and repair time is shorter.
The present invention constitutes like this: a kind of gradient biologically active ceramic coating material, and calculate according to percentage by weight: it is prepared from by 60～0% titanium valve and 40～100% composite ceramic; Wherein composite ceramic is the CaHPO by 72～80% percentage by weights
42H
2The CaCO of O and 20～28% percentage by weights
3Mix that rare earth oxide that the ceramics obtain adds 0.4～0.8% percentage by weight again forms.
Described titanium valve is 20～80 μ m, and composite ceramic is 30～50 μ m, and rare earth oxide is 1～5 μ m.
Say exactly: composite ceramic is the CaHPO by 78% percentage by weight
42H
2The CaCO of O and 22% percentage by weight
3Mix that rare earth oxide that the ceramics obtain adds 0.6% percentage by weight again forms; Described titanium valve is 40 μ m, and composite ceramic is 36 μ m, and rare earth oxide is 4 μ m.
Above-described rare earth oxide is CeO
2, La
2O
3Or Y
2O
3
The broad band laser preparation method of gradient biologically active ceramic coating of the present invention is: ceramics and rare earth oxide are mixed, ground 3 hours, with titanium valve mixed grinding 3 hours, make it abundant mixing again, obtain the coated powder material; The coated powder material for preparing is mixed with binding agent, then it is pressed in advance the surface of titanium alloy TC 4, the coating layer thickness of precompressed is 0.4～0.6mm; Adopt broadband laser cladding technology, at first at titanium alloy TC 4 surface cladding first gradient layer, clear up surperficial residue, clean specimen surface, again the coated powder material for preparing is pressed in advance the surface of titanium alloy TC 4, cladding second gradient layer, clear up surperficial residue again, clean specimen surface, then the coated powder material for preparing is pressed in advance surface cladding the 3rd gradient layer of titanium alloy TC 4, finally make gradient biologically active ceramic on the titanium alloy TC 4 surface.
Wherein, the broadband laser cladding technological parameter is: output P=2.1～2.9kW, scan velocity V=120～200mm/min, spot size D=16～30mm * 1～4mm.Used binding agent is 1～5 milliliter a Semen sojae atricolor alkyd; The pressure of coated powder material precompressed is 50kg/cm
2, the coating layer thickness of precompressed is 0.5mm; The laser melting coating device therefor is TJ-HL-5000 type 5kW CO
2Laser instrument, TJ-LTM-VI type five coordinate three-shaft linkage Laser Processing Digit Control Machine Tools and JKF-6 type laser broadband scanning mirror.
Preferred broadband laser cladding technological parameter is: output P=2.5kW, scan velocity V=150mm/min, spot size D=16mm * 2mm.
The coated powder material that is pressed in titanium alloy TC 4 surface first gradient layer in advance is: the titanium valve of 60% percentage by weight mixes, grinds and make with the composite ceramic of 40% percentage by weight, the coated powder material of second gradient layer is: the titanium valve of 30% percentage by weight mixes, grinds and make with the composite ceramic of 70% percentage by weight, and the coated powder material of the 3rd gradient layer is: 100% composite ceramic mixes, grinds and make.
The application of the gradient biologically active ceramic that the broad band laser preparation method of gradient biologically active ceramic coating of the present invention prepares in the damaged reparation of human femur under loading necrosis or hip joint, tooth.
The inventor has studied the influence of rare earth oxide content to Bioceramic Composite phase structure, tissue topography and cracking sensitivity by experiment, rare earth oxide content is got 0.2%, 0.4%, 0.6%, 0.8%, 1.0% respectively and is experimentized, rare earth oxide content reaches at 0.4～0.6% o'clock as a result, the quantity maximum of catalysis synthesizing hydroxylapatite and beta-calcium phosphate, and rare earth oxide content reaches at 0.8% o'clock, and the quantity of catalysis synthesizing hydroxylapatite and beta-calcium phosphate descends on the contrary.Conclusion: rare earth oxide content is having a deep effect on the formation of biological activity phase hydroxyapatite and beta-calcium phosphate, when rare earth oxide content reaches 0.4～0.6%, and the quantity maximum of catalysis synthesizing hydroxylapatite and beta-calcium phosphate; Add rare earth oxide bio-ceramic coating organize the obvious refinement of the tissue that does not add rare earth oxide, the tissue of this refinement helps improving the mechanical property of bioceramic; The bio-ceramic coating cracking sensitivity that adds rare earth oxide is less, and the coating that does not add has bigger cracking sensitivity.
The inventor studies show that through thermodynamics and kinetics: the technological parameter of strict control laser melting coating could generate hydroxyapatite (HA).Therefore, for guaranteeing effect of the present invention, the inventor has carried out preferably the technological parameter of laser melting coating, and is specific as follows:
The broadband laser cladding parameters Optimization:
Want in cladding coating to obtain to contain the calcium phosphorio bioactive ceramics phase of HA, and coating there is good binding with base material, must the suitable laser cladding technological parameter of selection.Discovering laser output power that control is lower and higher scanning speed, is the key that obtains phosphoric acid calcium active ceramic coating.But output is crossed low or scanning speed is too fast, can not make matrix and cladding material fusing or can only local melting, makes cladding layer and matrix bond not firm, influences its bond strength.Therefore this experiment is determined best laser cladding technological parameter by changing output P and scan velocity V.Specific practice is: first fixed light spot size D and scan velocity V change output P; Fixed light spot size D, output P change scan velocity V again.Optimize optimal processing parameter by analysis to macro morphology, microstructure and the microhardness of sample.
1. output P's determines
Fixed light spot size D and scanning speed, change output, at first roughly determine the scope of output, by repeatedly experiment, after examining the quality of the situation that combines of coating and base material and coating surface, preliminary definite broad band laser output power range is 2.0～3.0kW, and then the contrived experiment scheme, and is as shown in table 1.
The technological parameter of table 1 broadband laser cladding gradient bio-ceramic coating
(1) output is to the influence of ceramic composite coating tissue
Under this experiment condition, find that No. 111 sample surfaces of low-power preparation are the bead shape, do not generate bio-ceramic coating.This is that the laser energy that is absorbed on the sample unit are is specific energy E because output is low
bToo low, be not enough to due to titanium alloy surface formation molten bath.No. 112 the sample surface is more smooth, has formed bio-ceramic coating.No. 113～No. 115 specimen surface has also formed bio-ceramic coating, but apparent mass variation gradually is the poorest with No. 115 sample apparent masses especially.This is that the laser energy that is absorbed on the sample unit are is specific energy E owing to the increase gradually along with laser output power
bAlso increase, the temperature of melt increases gradually in the molten bath thereupon, and then weld pool surface becomes big by the leading tension gradient of thermograde thereupon.The tension gradient of weld pool surface is bigger, and then the convection current of melt aggravates in the molten bath in, causes behind the solidification and crystallization apparent mass variation gradually.Matrix is born of the same parents' shape crystalline substance in the bio-ceramic coating of No. 112 samples, is distributed with the tiny granule of white on it, and also there is accumulative white particle group in the part; And bio-ceramic coating dense structure, hole is less.Begun to have occurred more hole in the bio-ceramic coating of No. 113 samples, examine and also can find some white ultrafine dusts that distribute in the bio-ceramic coating, utilize power spectrum and electron probing analysis to find that white fine particle mainly is the oxide that is rich in Ti and Ca mutually.The existence of these white ultrafine dusts can improve the toughness of bioceramic.More hole occurred in the bio-ceramic coating microscopic structure of No. 114 samples, the compactness of tissue is poorer.Some hole in the bio-ceramic coating of No. 115 samples connects mutually, has formed macroscopic void or crackle, and this organizational structure will inevitably reduce its mechanical property.
As seen, along with the increase of output P, the compactness of bio-ceramic coating tissue descends.This is because of the increase along with output, has also promptly improved ceramic sintering temperature.Along with the rising of sintering temperature, the crystal grain that forms pottery is grown up gradually, makes the corner angle of crystal grain become slick and sly simultaneously, and little crystal grain is interconnection and form big crystal grain, and at this moment the glassy state liquid phase at crystal boundary place is filled intercrystalline space and bonding little crystal grain; Little crystal grain is further grown up again, and with the temperature glassy state liquid phase the forms further filling pore again that raises, grain growth and liquid phase are filled continuous reciprocation cycle and carried out like this, finally sintering and form pottery.But with usually sintering process is different, because laser melting coating is Fast Heating and cooling procedure fast, when output is big, also be sintering temperature when high, formed crystallite dimension is bigger, and to have little time to fill the hole that forms also bigger owing to liquid phase; On the other hand, because output is big, the thermal stress that produces in the sintering process is also bigger, so also forms bigger cavity and crackle easily.And the prepared bioceramic of the present invention requires that certain voidage is arranged, so that the growing into of osseous tissue.According to above-mentioned experimental result, when output P=2.5KW, the existing certain density of prepared ceramic surface has certain voidage again, thereby is optimum process parameters.
(2) output is to the influence of ceramic composite coating face porosity
Use the IAS-4 quantitative iamge analysis system, respectively the face porosity in No. 112～No. 115 sample bioceramic floor is measured, the results are shown in Table 2.Concrete steps are as follows: at first gather the bio-ceramic coating image, ash value image is carried out processing such as shadow correction, figure image intensifying, so that observe hole more clearly; Then the image thresholding is cut apart, carried out measuring the area percentage of hole after the binary Images Processing; At last the diverse location porosity of bio-ceramic coating is measured, got its meansigma methods.
The porosity of table 2 various sample (%) test result
As shown in Table 2, along with the increase of output P, the porosity in the bio-ceramic coating increases gradually.When P=2.3KW, i.e. the porosity minimum of No. 112 samples, when P=2.9kW, i.e. porosity maximum in No. 115 sample bio-ceramic coatings.Respectively the microhardness of No. 112 and No. 115 sample gradient bio-ceramic coatings is measured, as a result the height of the microhardness value of the bio-ceramic coating of No. 112 samples than No. 115.This is the dense structure because of No. 112 sample bio-ceramic coatings, due to porosity is low.And that No. 115 samples are organized is not fine and close, and porosity is big, and this will inevitably make the microhardness value of bioceramic descend.Therefore, no matter still analyze from the hardness aspect from porosity, output P=2.5KW is an optimal parameter.
2. scan velocity V determines
Fixedly output changes scanning speed, and the contrived experiment scheme is as shown in table 3.
The technological parameter of table 3 broadband laser cladding gradient bio-ceramic coating
The result as seen, the hole maximum in No. 211 bio-ceramic coatings, some hole also connects and is linked to be a line, coating structure compactness is the poorest.The hole minimum of No. 214 bio-ceramic coatings, coating structure is the finest and close.Because after optimum output power was selected, prepared ceramic coating tissue topography was greatly improved.Scanning speed does not have the output influence big to the influence of ceramic surface pattern.Increase with scanning speed, the density of pottery tissue increases, and porosity reduces.This is that the light beam time of staying is shorter, also is that sintering time shortens because increase with scanning speed, and crystal grain has little time to grow up and frozenly rapidly gets off, and makes crystal grain obtain refinement, and its density is increased; Moreover when scanning speed was big, the resulting power density of material surface diminished, and its thermal stress is reduced, and hole that it produced and crackle also will reduce like this.Thereby make its density increase, intensity and hardness increase.When scan velocity V=150mm/min, the ceramic layer density high and with matrix bond might as well.
Comprehensive above result of study and analysis, the best broadband laser cladding technological parameter that obtains under this experimental condition is: laser output power P=2.5kW, scan velocity V=150mm/min, spot size D=16mm * 2mm.
In theory, titanium powder content is high more in first gradient layer of ceramic coating, the physical chemistry compatibility between coating and the titanium alloy TC 4 is good more, and the application with compare in first to file 2005102000115, titanium powder content in first gradient layer has reduced by 10%, for this reason, the inventor has carried out a large amount of contrast experiments.Experimental result shows that titanium powder content is at 60% o'clock, and coating still is metallurgical binding with combining of base material, and its interface bond strength is higher.As seen, this proportioning does not influence the physical chemistry compatibility between coating and the titanium alloy TC 4.
In addition, because titanium powder content is zero in the 3rd gradient layer of ceramic coating of the present invention, (HA) is more for the hydroxyapatite that generates in the laser cladding process, experimental result shows that the pure HA that composite ceramic obtained of laser melting coating 100% is about about 20%, make that the HA content in the coating is higher, thereby its biological activity and biocompatibility are significantly improved with comparing in first to file 2005102000115.
Compared with prior art, the present invention adopts wide band laser cladding technology, the gradient design is more reasonable, prepared bioactive ceramic coating not only crackle and hole is few, the hardness height, good toughness, no amorphous phase produces in the coating, and titanium powder content is zero in the 3rd gradient layer that contacts with human body, and the content of HA is higher, the biological activity and the biocompatibility of products obtained therefrom are obviously improved, can be used for human femur under loading necrosis or hip joint, rejection can not take place in the reparation that tooth is damaged, and repair time short (with compare in first to file 2005102000115, approximately can shorten for 1～3 week, concrete condition is with individual relevant).
The effect that adds rare earth oxide in the ceramics of the present invention is catalysis synthesizing hydroxylapatite and a beta-calcium phosphate in laser cladding process, improves the mechanical property of bioceramic, reduces the cracking sensitivity of ceramic coating.Add CeO
2Or La
2O
3Bio-ceramic coating also have blood coagulation resisting function and can prevent canceration, and more at the formed micropore of coating surface, can be the osseous tissue coating of growing into more passage be provided.
The specific embodiment:
Embodiments of the invention 1: a kind of gradient biologically active ceramic coating material: the composite ceramic by the titanium valve of 40 μ m, 60～0% percentage by weights and 36 μ m, 40～100% percentage by weights is prepared from, and wherein composite ceramic is the CaHPO by 78% percentage by weight
42H
2The CaCO of O and 22% percentage by weight
3Mix the rare earth oxide CeO that the ceramics that obtains adds 4 μ m, 0.6% percentage by weight again
2Be prepared into.
The coated powder material that is pressed in titanium alloy TC 4 surface first gradient layer in advance is: the titanium valve of 60% percentage by weight mixes, grinds and make with the composite ceramic of 40% percentage by weight, the coated powder material of second gradient layer is: the titanium valve of 30% percentage by weight mixes, grinds and make with the composite ceramic of 70% percentage by weight, and the coated powder material of the 3rd gradient layer is: 100% composite ceramic mixes, grinds and make.
The broadband laser cladding preparation method of this gradient biologically active ceramic coating: with ceramics and rare earth oxide CeO
2Mix, ground 3 hours, with titanium valve mixed grinding 3 hours, make it abundant mixing again, obtain the coated powder material, the coated powder material that the prepares Semen sojae atricolor alkyd with 3 milliliters is mixed, then it is used 50kg/cm
2Pressure be pressed in the surface of titanium alloy TC 4 in advance, the coating layer thickness of precompressed is 0.5mm; With TJ-HL-5000 type 5kW CO
2Laser instrument, TJ-LTM-VI type five coordinate three-shaft linkage Laser Processing Digit Control Machine Tools and JKF-6 type laser broadband scanning mirror carry out broadband laser cladding, the melting and coating process parameter is: output P=2.5kW, scan velocity V=150mm/min, spot size D=16mm * 2mm; At first at titanium alloy TC 4 surface cladding first gradient layer, clear up surperficial residue, clean specimen surface, again the coated powder material for preparing is pressed in advance the surface of titanium alloy TC 4, cladding second gradient layer is cleared up surperficial residue again, cleans specimen surface, then the coated powder material for preparing is pressed in advance surface cladding the 3rd gradient layer of titanium alloy TC 4, finally makes gradient biologically active ceramic on the titanium alloy TC 4 surface.
Embodiments of the invention 2: a kind of gradient biologically active ceramic coating material: the composite ceramic by the titanium valve of 20 μ m, 60～0% percentage by weights and 30 μ m, 40～100% percentage by weights is prepared from, and wherein composite ceramic is the CaHPO by 72% percentage by weight
42H
2The CaCO of O and 28% percentage by weight
3Mix the rare earth oxide Y that the ceramics that obtains adds 1 μ m, 0.4% percentage by weight again
2O
3Be prepared into.
The coated powder material that is pressed in each gradient layer of titanium alloy TC 4 surface in advance is with embodiment 1.
The broadband laser cladding preparation method of this gradient biologically active ceramic coating: with ceramics and rare earth oxide Y
2O
3Mix, ground 3 hours, with titanium valve mixed grinding 3 hours, make it abundant mixing again, obtain the coated powder material, the coated powder material that the prepares Semen sojae atricolor alkyd with 1 milliliter is mixed, then it is used 50kg/cm
2Pressure be pressed in the surface of titanium alloy TC 4 in advance, the coating layer thickness of precompressed is 0.4mm; With TJ-HL-5000 type 5kW CO
2Laser instrument, TJ-LTM-VI type five coordinate three-shaft linkage Laser Processing Digit Control Machine Tools and JKF-6 type laser broadband scanning mirror carry out broadband laser cladding, the melting and coating process parameter is: output P=2.1kW, scan velocity V=120mm/min, spot size D=16mm * 1mm; At first at titanium alloy TC 4 surface cladding first gradient layer, clear up surperficial residue, clean specimen surface, again the coated powder material for preparing is pressed in advance the surface of titanium alloy TC 4, cladding second gradient layer is cleared up surperficial residue again, cleans specimen surface, then the coated powder material for preparing is pressed in advance surface cladding the 3rd gradient layer of titanium alloy TC 4, finally makes gradient biologically active ceramic on the titanium alloy TC 4 surface.
Embodiments of the invention 3: a kind of gradient biologically active ceramic coating material: the composite ceramic by the titanium valve of 80 μ m, 60～0% percentage by weights and 50 μ m, 40～100% percentage by weights is prepared from, and wherein composite ceramic is the CaHPO by 80% percentage by weight
42H
2The CaCO of O and 20% percentage by weight
3Mix the rare earth oxide La that the ceramics that obtains adds 5 μ m, 0.8% percentage by weight again
2O
3Be prepared into.
The coated powder material that is pressed in each gradient layer of titanium alloy TC 4 surface in advance is with embodiment 1.
The broadband laser cladding preparation method of this gradient biologically active ceramic coating: with ceramics and rare earth oxide La
2O
3Mix, ground 3 hours, again with titanium valve mixed grinding 3 hours, make it abundant mixing, obtain the coated powder material, the coated powder material that the prepares Semen sojae atricolor alkyd with 5 milliliters is mixed, then it is pressed in advance the surface of titanium alloy TC 4, the coating layer thickness of precompressed is 0.6mm; Adopt broadband laser cladding technology to process cladding, technological parameter is: output P=2.9kW, scan velocity V=200mm/min, spot size D=30mm * 4mm; At first at titanium alloy TC 4 surface cladding first gradient layer, clear up surperficial residue, clean specimen surface, again the coated powder material for preparing is pressed in advance the surface of titanium alloy TC 4, cladding second gradient layer is cleared up surperficial residue again, cleans specimen surface, then the coated powder material for preparing is pressed in advance surface cladding the 3rd gradient layer of titanium alloy TC 4, finally makes gradient biologically active ceramic on the titanium alloy TC 4 surface.
The binding agent Semen sojae atricolor alkyd that uses among the present invention is a kind of commercial goods; In addition, other harmless binding agent also can use.
Embodiments of the invention 4: the gradient biologically active ceramic that embodiment 2 is prepared (contains 0.4%Y in the coating
2O
3) with coating in do not contain Y
2O
3Gradient biologically active ceramic implant the adult healthy dog femoral, after 4 weeks, 8 weeks and 24 weeks, physiological reactions such as irritated, rejection and pathological changes appear; Do not see symptoms such as obvious fiber kystis, chronic inflammatory disease, tissue topography's degeneration, tissue necrosis on the tissue slice; Contain 0.4%Y
2O
3Gradient biologically active ceramic coating in 4 weeks just with new bone tissue bonding has taken place the time, and almost very close to each other between osseous tissue and the coating; And do not contain Y
2O
3Even gradient biologically active ceramic coating after having experienced 24 week growths, still not and produce bonding between the osseous tissue.
To (contain 0.4%Y in the coating at first to file 2005102000115 preparation-obtained gradient biologically active ceramics in addition
2O
3) implant the adult healthy dog femoral, physiological reactions such as allergy, rejection and pathological changes appear after 6 weeks, 12 weeks and 24 weeks; Do not see obvious fiber kystis, chronic inflammatory disease on the tissue slice, symptoms such as tissue topography's degeneration, tissue necrosis; Hyperosteogeny thickness increased gradually when the X-ray sheet showed for 6 weeks, and bonding has taken place for ceramic coating and new bone tissue.
Above experimental result shows: gradient biologically active ceramic coating of the present invention has better biological activity and biocompatibility, can shorten about 2 weeks with bonding time of osseous tissue.
Claims (7)
1. the broad band laser preparation method of a gradient biologically active ceramic coating, calculate according to percentage by weight: this coating is prepared from by 60～0% titanium valve and 40～100% composite ceramic; Wherein composite ceramic is by the CaHPO of 72～80% percentage by weights
42H
2The CaCO of O and 20～28% percentage by weights
3Mix the rare earth oxide that the ceramics that obtains adds 0.4～0.8% percentage by weight again: CeO
2, La
2O
3Or Y
2O
3Form; It is characterized in that: with ceramics and rare earth oxide: CeO
2, La
2O
3Or Y
2O
3Mix, ground 3 hours, with titanium valve mixed grinding 3 hours, make it abundant mixing again, obtain the coated powder material; The coated powder material for preparing is mixed with binding agent, then it is pressed in advance the surface of titanium alloy TC 4, the coating layer thickness of precompressed is 0.4～0.6mm; Adopt broadband laser cladding technology: output P=2.1～2.9kW, scan velocity V=120～200mm/min, spot size D=16～30mm * 1～4mm; At first at titanium alloy TC 4 surface cladding first gradient layer, clear up surperficial residue, clean specimen surface, again the coated powder material for preparing is pressed in advance the surface of titanium alloy TC 4, cladding second gradient layer is cleared up surperficial residue again, cleans specimen surface, then the coated powder material for preparing is pressed in advance surface cladding the 3rd gradient layer of titanium alloy TC 4, finally makes gradient biologically active ceramic coating on the titanium alloy TC 4 surface; The coated powder material that is pressed in titanium alloy TC 4 surface first gradient layer in advance is: the composite ceramic of the titanium valve of 60% percentage by weight and 40% percentage by weight is formed, the coated powder material of second gradient layer is: the composite ceramic of the titanium valve of 30% percentage by weight and 70% percentage by weight is formed, and the coated powder material of the 3rd gradient layer is: 100% composite ceramic is formed.
2. according to the broad band laser preparation method of the described gradient biologically active ceramic coating of claim 1, it is characterized in that: described titanium valve is 20～80 μ m, and composite ceramic is 30～50 μ m, and rare earth oxide is 1～5 μ m.
3. according to the broad band laser preparation method of the described gradient biologically active ceramic coating of claim 1, it is characterized in that: composite ceramic is the CaHPO by 78% percentage by weight
42H
2The CaCO of O and 22% percentage by weight
3Mix that rare earth oxide that the ceramics obtain adds 0.6% percentage by weight again forms.
4. according to the broad band laser preparation method of claim 1 or 2 described gradient biologically active ceramic coatings, it is characterized in that: described titanium valve is 40 μ m, and composite ceramic is 36 μ m, and rare earth oxide is 4 μ m.
5. according to the broad band laser preparation method of the described gradient biologically active ceramic coating of claim 1, it is characterized in that: used binding agent is 1～5 milliliter a Semen sojae atricolor alkyd; The pressure of coated powder material precompressed is 50kg/cm
2, the coating layer thickness of precompressed is 0.5mm; The laser melting coating device therefor is TJ-HL-5000 type 5kW CO
2Laser instrument, TJ-LTM-VI type five coordinate three-shaft linkage Laser Processing Digit Control Machine Tools and JKF-6 type laser broadband scanning mirror.
6. according to the broad band laser preparation method of claim 1 or 5 described gradient biologically active ceramic coatings, it is characterized in that: the broadband laser cladding technological parameter is: output P=2.5kW, scan velocity V=150mm/min, spot size D=16mm * 2mm.
7. the gradient biologically active ceramic coating for preparing as the broad band laser preparation method of each described gradient biologically active ceramic coating among the claim 1-6.
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| US12/252,958 US8206843B2 (en) | 2007-05-16 | 2008-10-16 | Bioceramic coating, method of making and use thereof |
| US13/533,477 US8623526B2 (en) | 2007-05-16 | 2012-06-26 | Bioceramic coating, method of making and use thereof |
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| CN100574726C (en) * | 2008-04-17 | 2009-12-30 | 上海交通大学 | Partial gradient pore space structure artificial arthrosis prosthesis and preparation method thereof |
| CN102000358A (en) * | 2010-11-18 | 2011-04-06 | 贵州大学 | Nd2O3-containing gradient bioactive ceramic coating material and preparation method thereof |
| CN102580150B (en) * | 2012-03-21 | 2014-04-16 | 贵州大学 | Gradient bioactive ceramic coating material containing samarium oxide and preparation method thereof |
| CN106390199B (en) * | 2016-09-27 | 2019-08-02 | 贵州大学 | A kind of calcium phosphor coating and preparation method thereof that rare earth ion is controllably precipitated |
| CN108705092B (en) * | 2018-06-15 | 2021-06-01 | 淮阴工学院 | 3D printing in-situ rare earth doped titanium-based composite material active bone implant and forming method |
| CN117418143B (en) * | 2023-12-19 | 2024-03-26 | 汕头大学 | Ceramic reinforced metal matrix composite gradient coating and preparation method and application thereof |
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