CN102000358A - Nd2O3-containing gradient bioactive ceramic coating material and preparation method thereof - Google Patents
Nd2O3-containing gradient bioactive ceramic coating material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an Nd2O3-containing gradient bioactive ceramic coating material and a preparation method thereof. The coating material comprises the following raw materials in parts by weight: 0 to 70 parts of titanium powder and 30 to 100 parts of compound ceramic powder, wherein the compound ceramic powder is prepared through the steps of mixing 72 to 80 parts of CaHPO4.2H2O with 28 to 20 parts of CaCO3 so as to obtain 100 parts of ceramic powder, and then adding 0.1 to 0.8 parts of Nd2O3 powder into the obtained ceramic powder. In the invention, because of adding the Nd2O3 powder into the ceramic powder, the ceramic coating has the function of catalyzing the synthesis of hydroxyapatite and beta-calcium phosphate, and compared with the actions of the ceramic powder added with CeO2, La2O3 and Y2O3 powder, a biological ceramic coating prepared by adding Nd2O3 powder has better biocompatibility and biological activity, has the function of anticoagulation and can prevent canceration; meanwhile, compared with the action of the ceramic powder added with CeO2, La2O3 and Y2O3 powder, more micro-pores are formed on the surface of the biological ceramic coating prepared through adding Nd2O3 powder, thereby providing more channels for a bone tissue ingrowth coating.
Description
Technical field
The present invention relates to a kind of Nd of containing
2O
3Gradient biologically active ceramic coating material and preparation method, belong to medical material tech field.
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, dry method is to carry out various reactions and deposition, for example plasma spraying method, physical vaporous deposition, chemical vapour deposition technique, hot spray process, laser cladding and ion implantation etc. in gas phase.Thereby wet method is to utilize the technology that various reactions deposited coatings on base material takes place in the liquid phase, such as sol-gel process, electrochemical deposition, self-assembled monolayer embrane method etc.Laser cladding 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.At present, the subject matter of Laser Clad Bioceramic Coating existence is: the laser of narrowband hot spot that adopt (1) is very little, and (φ 1～3mm), and overlap and remelting area are too many, causes that bioceramic decomposes again with decrystallized, influences the uniformity and the stability of coating; (2) the laser of narrowband energy is Gauss distribution, easily causes the bigger thermograde of molten bath middle section, can produce more crackle in the coating after the weld pool solidifies crystallization; (3) rare earth oxide content lacks research to bio-ceramic coating organizational structure and Effect on Performance rule.
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 in depth research to the technology that broadband laser cladding prepares the gradient bio-ceramic coating, and has studied the impact of rare earth oxide content to the Bioceramic Composite institutional framework.
The applicant has applied for and the patent of invention (ZL2005102000115, ZL2007102006271, ZL2007102006286, ZL2007102006318, ZL2007102006322) of obtaining the authorization provides laser melting coating to prepare the material of gradient biologically active ceramic coating and the method for making of coating, and the rare earth oxide that mixes in its ceramic powder is Y
2O
3, CeO
2Or La
2O
3Y
2O
3, CeO
2Or La
2O
3In laser cladding process, can catalyze and synthesize hydroxyapatite (HA) and beta-calcium phosphate.The inventor finds after further research, not only can mix Y in the ceramic powder
2O
3, CeO
2, La
2O
3, can also mix other rare earth oxide.
Summary of the invention
The objective of the invention is to: a kind of Nd of containing is provided
2O
3Gradient biologically active ceramic coating material and preparation method, this new coating material and its method for making can guarantee to form stable bioactive ceramic coating on the surface of titanium alloy, the product human implantable that obtains is interior as bone, osteoarticular substitute, rejection can not take place, have blood coagulation resisting function and can prevent canceration.
Technical scheme of the present invention: a kind of Nd that contains
2O
3The gradient biologically active ceramic coating material, according to listed as parts by weight, it is to be prepared from by 30～100 parts of 70～0 parts of titanium valves and composite ceramics; Described composite ceramic is by 72～80 parts of CaHPO
42H
2O and 28～20 parts of CaCO
3Mix 100 parts of the ceramic powders obtain and add again 0.1～0.8 part of Nd
2O
3Powder constituent.
Aforementioned coating comprises three gradient layers, the coating material of first gradient layer that contacts with titanium alloy TC 4 is mixed, grinds and make with 50～30 parts of composite ceramics by 50～70 parts of titanium valves, the coating material of second gradient layer is mixed, grinds and make with 90～30 parts of composite ceramics by 10～70 parts of titanium valves, and the coating material of the 3rd gradient layer that contacts with human body is mixed, grinds and make with 100～90 parts of composite ceramics by 0～10 part of titanium valve.
Preferred each gradient layer coating material is: the coating material of first gradient layer is mixed, grinds and make with 30 parts of composite ceramics by 70 parts of titanium valves, the coating material of second gradient layer is mixed, grinds and make with 70 parts of composite ceramics by 30 parts of titanium valves, the coating material of the 3rd gradient layer by 100 parts of mixing of composite ceramic, grind and make.
Aforementioned titanium valve is 20～80 μ m, and composite ceramic is 30～50 μ m, Nd
2O
3Powder is 1～5 μ m.
Preferred composite ceramic is by 78 parts of CaHPO
42H
2O and 22 parts of CaCO
3Mix the ceramic powder that obtains and add again 0.4～0.6 part of Nd
2O
3Powder constituent; Preferred titanium valve is 40 μ m, and composite ceramic is 36 μ m, Nd
2O
3Powder is 3 μ m.
The Nd that contains with aforementioned coating material
2O
3The preparation method of gradient biologically active ceramic coating is: with ceramic powder and Nd
2O
3Powder stirred 8～12 hours with star-like ball mill, with titanium valve mixed grinding 4 hours, made it abundant mixing again, obtained 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 0.3～0.6mm, adopts broadband laser cladding technology, at first at titanium alloy TC 4 surface cladding first gradient layer, clear up surperficial residue, clean specimen surface, again precompressed, cladding second gradient layer, clear up surperficial residue, clean specimen surface, then precompressed, cladding the 3rd gradient layer namely make gradient biologically active ceramic coating on the titanium alloy TC 4 surface.
In the preceding method, the broadband laser cladding technological parameter is: output P=2.0～2.9kW, scan velocity V=120～240mm/min, spot size D=16～30mm * 1～4mm.
In the preceding method, used binding agent is a Semen sojae atricolor alkyd; The pressure of coated powder material precompressed is 50kg/cm
2, the coating layer thickness of precompressed is 0.4mm.
In the preceding method, 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.
Aforementioned broadband laser cladding optimal process parameter is: output P=2.4kW, scan velocity V=180mm/min, spot size D=16mm * 2mm.
Prepare during thereby gradient biologically active ceramic that gradient biologically active ceramic coating makes can be used for the defect repair of human body hard tissue or replace with material of the present invention and method; Specifically, can be used for human femur under loading necrosis or hip joint, reparation that tooth is damaged.
The inventor finds CeO in the research in early stage
2, La
2O
3, Y
2O
3In laser cladding process, has the biologically active of catalyzing and synthesizing phase HA+ β-TCP (β-Ca
3(PO
4)
2) effect, and this rare earth biological ceramic coating has good biocompatibility and biologically active.In the periodic table of elements, La, Ce, Pr, Nd, Pm, Sm, Eu belong to light rare earth, CeO
2, La
2O
3In the research work in early stage, demonstrated good biocompatibility and biologically active, and the antiinflammatory action of Nd compounds is stronger than other rare-earth actions, so the inventor infers Nd
2O
3Should have better biological property, and carry out relevant experimental study and investigation for this reason.
The inventor finds by X-ray diffraction studies, uses CeO before
2, La
2O
3, Y
2O
3All contain the CaO phase in the synthetic bio-ceramic coating, and use Nd instead
2O
3After, all there is not the CaO phase in the prepared bio-ceramic coating, so that bio-ceramic coating has better biologically active.And: Nd
2O
3Addition through behind the broadband laser cladding, has catalyzed and synthesized the HA+ β-TCP that more has the biologically active phase and (has added respectively the Y of 0.6wt.% when 0.6wt.% in the bio-ceramic coating
2O
3, CeO
2, La
2O
3, Nd
2O
3, the HA+ β that synthesizes in the ceramic coating-TCP percentage composition is respectively 13%, 15%, 17%, 28%); Find by the simulated body fluid experiment, contain Nd
2O
3Bio-ceramic coating surface can (contain Y by the more calcium phosphorus base class osteolith of deposition
2O
3, CeO
2, La
2O
3, Nd
2O
3The calcium phosphorus base class osteolith of bio-ceramic coating surface deposition be respectively 70%, 79%, 85%, 95%), the performance of this result in clinical is to promote combining closely of rare earth biological pottery and bone tissue; By to containing 0.6wt.%Nd
2O
3Bio-ceramic coating carry out electric polarization and process also and find the abiotic Activity Phase of some in the coating such as CaTiO
3, Ca
4Ti
3O
10, α-TCP, Ca
4O (PO
4)
2, Ca
2P
2O
7Can transform to having bioactive HA.This shows, add Nd
2O
3The bioactive ceramic coating that makes and CeO
2, La
2O
3, Y
2O
3Compare and have better biocompatibility and biologically active.
Using Nd
2O
3In the process of preparation bioactive ceramic coating, main problem is exactly how with Nd
2O
3Powder is distributed in the ceramic powder opisthosoma equably.Through experimental study, screening, select at last star-like ball mill uniform stirring compound, mixing time can reach homodisperse purpose more than 8 hours.
The inventor has also studied Nd by experiment
2O
3Content is to the impact of Bioceramic Composite phase structure, tissue topography and cracking sensitivity, Nd
2O
3Content is got respectively 0.1%, 0.2%, 0.4%, 0.6%, 0.8%, 1.0% and is tested, as a result Nd
2O
3When content reached 0.4～0.6%, the amount that catalyzes and synthesizes hydroxyapatite and beta-calcium phosphate was maximum, and Nd
2O
3When content reached 0.8%, the amount that catalyzes and synthesizes hydroxyapatite and beta-calcium phosphate descended on the contrary.Conclusion: Nd
2O
3Content is having a deep effect on the formation of biologically active phase hydroxyapatite and beta-calcium phosphate, works as Nd
2O
3When content reached 0.4～0.6%, the amount that catalyzes and synthesizes hydroxyapatite and beta-calcium phosphate was maximum; Add Nd
2O
3Organizing of bio-ceramic coating do not add Nd
2O
3The obvious refinement of tissue, the tissue of this refinement is conducive to improve the mechanical property of bioceramic; Add Nd
2O
3The bio-ceramic coating cracking sensitivity a little less than, and the coating that does not add has stronger cracking sensitivity.
In addition, in rare earth element, Y is a heavy rare earth, and Nd is a light rare earth, and light rare earth compound has blood coagulation resisting function preferably for heavy rare earth compound.Because light rare earth ion proportion ionic radius of rare earth is more near the calcium ion radius, light rare earth ion is Duoed a positive charge than calcium ion, because light rare earth ion replaces calcium ion, thus the effect of effective competition inhibition calcium ion in coagulation process.Therefore, add Nd in the ceramic powder of the present invention
2O
3The effect that catalyzes and synthesizes hydroxyapatite and beta-calcium phosphate is not only arranged, and prepared bio-ceramic coating also has blood coagulation resisting function and can prevent canceration.
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 power output is crossed low or sweep speed is too fast, can not make matrix and cladding material fusing or can only local melting, makes cladding layer and matrix in conjunction with not firm, affects its bond strength.Therefore this experiment is determined best laser cladding technological parameter by changing power 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 the 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 2.0～2.9kW, 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 absorbs on the sample unit are is specific energy E because power 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 absorbs on the sample unit are is specific energy E owing to the gradually increase 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 institutional framework will inevitably reduce its mechanical property.
As seen, along with the increase of power output P, the compactness of bio-ceramic coating tissue descends.This is because of the increase along with power output, has also namely improved ceramic sintering temperature.Along with the rising of sintering temperature, the crystal grain that forms pottery is grown up gradually, makes simultaneously the corner angle of crystal grain become slick and sly, and little crystal grain is connected to each other and forms big crystal grain, and at this moment the glassy state liquid phase of grain boundaries is filled intercrystalline space and bonding little crystal grain; Little crystal grain is further grown up again, and with the temperature more further filling pore of the glassy state liquid phase forms 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 quick cooling procedure, when power 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 power output is big, the thermal stress that produces in the sintering process is also bigger, so also forms easily bigger cavity and crackle.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=2.4KW, 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 porosity
Use the IAS-4 quantitative iamge analysis system, respectively No. 112～No. 115 sample bioceramic layer porosities are 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=2.2KW, i.e. the porosity minimum of No. 112 samples, when P=2.8kW, 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, power output P=2.4KW is 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. 213 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 sweep 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 so that its density increases, intensity and hardness increase.When scan velocity V=180mm/min, the ceramic layer density is high and be combined with matrix.
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=2.4kW, scan velocity V=180mm/min, spot size D=16mm * 2mm.
Compared with prior art, prepared gradient biologically active ceramic coating crackle and the hole of the present invention is few, the hardness height, good toughness, no amorphous phase produces in the coating, product can implant into body in as bone, osteoarticular substitute, rejection can not take place, have blood coagulation resisting function and can prevent canceration.The present invention uses the gradient design philosophy, adopts wide band laser cladding technology, directly at titanium alloy surface cladding CaHPO
42H
2O+CaCO
3+ Ti powder (being one-step method) had so both improved the bond strength at interface, can make coating have excellent biological compatibility again.The Gaussian Energy Distribution of broad band laser becomes rectangular energy and distributes after handling through the broadband scanning tilting mirror, and energy is evenly distributed.This rectangular energy is distributed in bath temperature is evenly distributed, molten bath middle section thermograde descends, crack sensitivity reduces, and can utilize again the thermograde of melt tank edge to form suitable surface tension field, plays the stirring melt and makes the equally distributed effect of alloying element; Also can increase the cladding width, reduce to overlap number of times, enhance productivity.The present invention adds Nd in ceramic powder
2O
3The effect that catalyzes and synthesizes hydroxyapatite and beta-calcium phosphate is not only arranged, prepared bio-ceramic coating and CeO
2, La
2O
3, Y
2O
3Compare and have better biocompatibility and biologically active, also have blood coagulation resisting function and can prevent canceration.And, add Nd
2O
3Than adding Y
2O
3The formed micropore in bio-ceramic coating surface many, can provide more passage for the bone tissue coating of growing into.
The specific embodiment
The following stated umber is weight portion.
Embodiments of the invention 1: a kind of Nd that contains
2O
3The gradient biologically active ceramic coating material: be prepared from by 30～100 parts of the composite ceramics of 70～0 parts of the titanium valves of 40 μ m and 36 μ m, wherein composite ceramic is by 78 parts of CaHPO
42H
2O and 22 parts of CaCO
3Mix the 100 parts of Nd that add again 3 μ m of ceramic powder that obtain
2O
30.6 part of composition of powder.
The coating material of first gradient layer that contacts with titanium alloy TC 4 is mixed, grinds and make with 30 parts of composite ceramics by 70 parts of titanium valves, the coating material of second gradient layer is mixed, grinds and make with 70 parts of composite ceramics by 30 parts of titanium valves, the coating material of the 3rd gradient layer that contacts with human body by 100 parts of mixing of composite ceramic, grind and make.
The preparation method of this gradient biologically active ceramic coating is: with ceramic powder and Nd
2O
3Powder stirred 10 hours with star-like ball mill, with titanium valve mixed grinding 4 hours, made it abundant mixing again, obtained the coated powder material, and the coated powder material for preparing is mixed with soybean alkyd, then it was used 50kg/cm
2Pressure be pressed in advance the surface of titanium alloy TC 4, 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 wide-band scanning rotary mirror carry out broadband laser cladding, the melting and coating process parameter is: power output P=2.4kW, scan velocity V=180mm/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 specimen surface in advance, cladding second gradient layer is cleared up surperficial residue again, cleans specimen surface, then the coated powder material for preparing is pressed in specimen surface cladding the 3rd gradient layer in advance, namely makes gradient biologically active ceramic coating on the titanium alloy TC 4 surface.
Embodiments of the invention 2: a kind of Nd that contains
2O
3The gradient biologically active ceramic coating material: be prepared from by 35～95 parts of the composite ceramics of 65～5 parts of the titanium valves of 20 μ m and 30 μ m, wherein composite ceramic is by 72 parts of CaHPO
42H
2O and 28 parts of CaCO
3Mix the 100 parts of Nd that add again 1 μ m of ceramic powder that obtain
2O
30.4 part of composition of powder.
The coating material of first gradient layer that contacts with titanium alloy TC 4 is mixed, grinds and make with 35 parts of composite ceramics by 65 parts of titanium valves, the coating material of second gradient layer is mixed, grinds and make with 65 parts of composite ceramics by 35 parts of titanium valves, and the coating material of the 3rd gradient layer that contacts with human body is mixed, grinds and make with 95 parts of composite ceramics by 5 parts of titanium valves.
The preparation method of this gradient biologically active ceramic coating is: with ceramic powder and Nd
2O
3Powder stirred 8 hours with star-like ball mill, with titanium valve mixed grinding 4 hours, made it abundant mixing again, obtained the coated powder material, and the coated powder material for preparing is mixed with soybean alkyd, then it was used 50kg/cm
2Pressure be pressed in advance the surface of titanium alloy TC 4, 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 wide-band scanning rotary mirror carry out broadband laser cladding, the melting and coating process parameter is: power output P=2.2kW, 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 specimen surface in advance, cladding second gradient layer is cleared up surperficial residue again, cleans specimen surface, then the coated powder material for preparing is pressed in specimen surface cladding the 3rd gradient layer in advance, namely makes gradient biologically active ceramic coating on the titanium alloy TC 4 surface.
Embodiments of the invention 3: a kind of Nd that contains
2O
3The gradient biologically active ceramic coating material: be prepared from by 40～98 parts of the composite ceramics of 60～2 parts of the titanium valves of 80 μ m and 50 μ m, wherein composite ceramic is by 80 parts of CaHPO
42H
2O and 20 parts of CaCO
3Mix the 100 parts of Nd that add again 5 μ m of ceramic powder that obtain
2O
30.2 part of composition of powder.
The coating material of first gradient layer that contacts with titanium alloy TC 4 is mixed, grinds and make with 40 parts of composite ceramics by 60 parts of titanium valves, the coating material of second gradient layer is mixed, grinds and make with 75 parts of composite ceramics by 25 parts of titanium valves, and the coating material of the 3rd gradient layer that contacts with human body is mixed, grinds and make with 98 parts of composite ceramics by 2 parts of titanium valves.
The preparation method of this gradient biologically active ceramic coating is: with ceramic powder and Nd
2O
3Powder stirred 12 hours with star-like ball mill, again with titanium valve mixed grinding 4 hours, make it abundant mixing, obtain the coated powder material, the coated powder material for preparing is mixed with soybean alkyd, 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, the melting and coating process parameter is: power output P=2.8kW, scan velocity V=240mm/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 precompressed, cladding second gradient layer are cleared up surperficial residue, clean specimen surface, then precompressed, cladding the 3rd gradient layer namely make gradient biologically active ceramic coating 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.
Test example:
(1) gradient biologically active ceramic that embodiment 1 is prepared (contains 0.6wt.%Nd in the coating
2O
3) with coating in do not contain Nd
2O
3The gradient biologically active ceramic healthy dog femur of implant growing up, after 6 weeks, 12 weeks and 24 weeks, the physiological reactions such as irritated, rejection and pathology appear; Have no the symptoms such as obvious fiber kystis, chronic inflammation, tissue topography's sex change, necrosis on the histotomy; Contain 0.6wt.%Nd
2O
3Gradient biologically active ceramic coating in 2-3 week just with new bone tissue bonding has taken place the time, and almost very close to each other between bone tissue and the coating; And do not contain Nd
2O
3Even gradient biologically active ceramic coating after having experienced 24 week growths, still not and produce bonding between the bone tissue.This explanation contains 0.6wt.%Nd
2O
3Gradient biologically active ceramic coating have better biologically active and biocompatibility.
(2) 0.6wt.%Nd will be contained in the coating
2O
3Gradient biologically active ceramic and coating in contain 0.6wt.% CeO
2, La
2O
3, Y
2O
3Gradient biologically active ceramic implant respectively the healthy dog femur of growing up, the physiological reactions such as irritated, rejection and pathology appearred after 6 weeks, 12 weeks and 24 weeks; Have no the symptoms such as obvious fiber kystis, chronic inflammation, tissue topography's sex change, necrosis on the histotomy; By histotomy as can be known, contain 0.6wt.%Nd
2O
3Gradient biologically active ceramic coating with dog femoral gapless between bone tissue and the coating, and its excess-three kind rare earth (CeO have taken place closely to be combined in 4 whens week
2, La
2O
3, Y
2O
3) though ceramic coating with bone tissue bonding taken place, and not yet reaches the degree of combining closely.Show and contain Nd
2O
3The gradient biologically active ceramic coating ratio contain CeO
2, La
2O
3, Y
2O
3Gradient biologically active ceramic coating have better biologically active and biocompatibility.
Claims (10)
1. one kind contains Nd
2O
3The gradient biologically active ceramic coating material, according to listed as parts by weight, it is to be prepared from by 30～100 parts of 70～0 parts of titanium valves and composite ceramics; It is characterized in that: described composite ceramic is by 72～80 parts of CaHPO
42H
2O and 28～20 parts of CaCO
3Mix 100 parts of the ceramic powders obtain and add again 0.1～0.8 part of Nd
2O
3Powder constituent.
2. according to the described Nd that contains of claim 1
2O
3The gradient biologically active ceramic coating material, it is characterized in that: described coating comprises three gradient layers, the coating material of first gradient layer that contacts with titanium alloy TC 4 is mixed, grinds and make with 50～30 parts of composite ceramics by 50～70 parts of titanium valves, the coating material of second gradient layer is mixed, grinds and make with 90～30 parts of composite ceramics by 10～70 parts of titanium valves, and the coating material of the 3rd gradient layer that contacts with human body is mixed, grinds and make with 100～90 parts of composite ceramics by 0～10 part of titanium valve.
3. according to the described Nd that contains of claim 2
2O
3The gradient biologically active ceramic coating material, it is characterized in that: the coating material of first gradient layer is mixed, grinds and make with 30 parts of composite ceramics by 70 parts of titanium valves, the coating material of second gradient layer is mixed, grinds and make with 70 parts of composite ceramics by 30 parts of titanium valves, the coating material of the 3rd gradient layer by 100 parts of mixing of composite ceramic, grind and make.
4. according to the described Nd that contains of claim 3
2O
3The gradient biologically active ceramic coating material, it is characterized in that: described titanium valve is 20～80 μ m, composite ceramic is 30～50 μ m, Nd
2O
3Powder is 1～5 μ m.
5. according to claim 1 or the 4 described Nd that contain
2O
3The gradient biologically active ceramic coating material, it is characterized in that: described composite ceramic is by 78 parts of CaHPO
42H
2O and 22 parts of CaCO
3Mix the ceramic powder that obtains and add again 0.4～0.6 part of Nd
2O
3Powder constituent; Described titanium valve is 40 μ m, and composite ceramic is 36 μ m, Nd
2O
3Powder is 3 μ m.
6. with the Nd that contains of each described coating material among the claim 1-5
2O
3The preparation method of gradient biologically active ceramic coating, it is characterized in that: with ceramic powder and Nd
2O
3Powder stirred 8～12 hours with star-like ball mill, with titanium valve mixed grinding 4 hours, made it abundant mixing again, obtained 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 0.3～0.6mm, adopts broadband laser cladding technology, at first at titanium alloy TC 4 surface cladding first gradient layer, clear up surperficial residue, clean specimen surface, again precompressed, cladding second gradient layer, clear up surperficial residue, clean specimen surface, then precompressed, cladding the 3rd gradient layer namely make gradient biologically active ceramic coating on the titanium alloy TC 4 surface.
7. according to the described Nd that contains of claim 6
2O
3The preparation method of gradient biologically active ceramic coating, it is characterized in that: the broadband laser cladding technological parameter is: power output P=2.0～2.9kW, scan velocity V=120～240mm/min, spot size D=16～30mm * 1～4mm.
8. according to claim 6 or the 7 described Nd that contain
2O
3The preparation method of gradient biologically active ceramic coating, it is characterized in that: used binding agent is soybean alkyd; The pressure of coated powder material precompressed is 50kg/cm
2, the coating layer thickness of precompressed is 0.4mm.
9. according to claim 6 or the 7 described Nd that contain
2O
3The preparation method of gradient biologically active ceramic coating, it is characterized in that: 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 wide-band scanning rotary mirror.
10. according to claim 6 or the 7 described Nd that contain
2O
3The preparation method of gradient biologically active ceramic coating, it is characterized in that: the broadband laser cladding technological parameter is: power output P=2.4kW, scan velocity V=180mm/min, spot size D=16mm * 2mm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580150A (en) * | 2012-03-21 | 2012-07-18 | 贵州大学 | Gradient bioactive ceramic coating material containing samarium oxide and preparation method thereof |
| CN103418030A (en) * | 2013-07-23 | 2013-12-04 | 河南工业大学 | Osteoid structure biological ceramic composite material with adjustable coating thickness |
| CN110975006A (en) * | 2019-12-25 | 2020-04-10 | 锐百顺涂层科技（苏州）有限公司 | Preparation method of HA coating on surface of titanium alloy substrate |
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| CN1840493A (en) * | 2005-12-30 | 2006-10-04 | 四川大学 | Preparation of magnetic glass ceramics with bioactivity by rare-earth doping |
| CN101053675A (en) * | 2007-05-16 | 2007-10-17 | 贵州大学 | Gradient biologically active ceramic coating material, broad band laser preparing method and product application |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1840493A (en) * | 2005-12-30 | 2006-10-04 | 四川大学 | Preparation of magnetic glass ceramics with bioactivity by rare-earth doping |
| CN101053675A (en) * | 2007-05-16 | 2007-10-17 | 贵州大学 | Gradient biologically active ceramic coating material, broad band laser preparing method and product application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580150A (en) * | 2012-03-21 | 2012-07-18 | 贵州大学 | Gradient bioactive ceramic coating material containing samarium oxide and preparation method thereof |
| CN103418030A (en) * | 2013-07-23 | 2013-12-04 | 河南工业大学 | Osteoid structure biological ceramic composite material with adjustable coating thickness |
| CN110975006A (en) * | 2019-12-25 | 2020-04-10 | 锐百顺涂层科技（苏州）有限公司 | Preparation method of HA coating on surface of titanium alloy substrate |
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