CN103422089A - Nd-YAG laser cladding method for preparing thickness adjustable biological ceramic composite coating adopting bone-like structure - Google Patents
Nd-YAG laser cladding method for preparing thickness adjustable biological ceramic composite coating adopting bone-like structure Download PDFInfo
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- CN103422089A CN103422089A CN2013103101315A CN201310310131A CN103422089A CN 103422089 A CN103422089 A CN 103422089A CN 2013103101315 A CN2013103101315 A CN 2013103101315A CN 201310310131 A CN201310310131 A CN 201310310131A CN 103422089 A CN103422089 A CN 103422089A
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Abstract
The invention discloses an Nd-YAG laser cladding method for preparing a thickness adjustable biological ceramic composite coating adopting a bone-like structure. The method includes the following steps: 1, proportionally mixing rare earth, CaHPO4.2H2O and CaCO3 to prepare composite powder; 2, piling the composite powder obtained in step 1 on the surface of a titanium alloy basal body to form a precast coating; 3, performing Nd-YAG laser cladding to the composite powder; so as to obtain the biological ceramic composite coating with high binding force. According to the invention, the rare earth added in raw material improves the stability of an HAP phase structure; the obtained coating is high in bonding strength when bonded with the metal basal body, and is bonded with chemical metal to solve the problem that the biological ceramic coating is easy to fall off; in addition, the raw material is low in price, convenient to purchase and easy to store; the preparing technology is simple, the implementation is easy, and the metal has favorable market application prospect and commercial value.
Description
Technical field
The present invention relates to the bioceramic material field, especially relate to the method for the adjustable class bone structure Bioceramic Composite of a kind of Nd-YAG laser melting coating thickness.
Background technology
Hydroxyapatite (the Ca come out since the seventies
10(PO
4)
6(OH)
2, HAP) the medical bio pottery is front both at home and abroad just at flourish biomaterial at present.The embedded material prepared by the HAP micro-crystalline ceramic can with the good combination of human body natural's bone, be the best bioceramic material of biocompatibility of having found.The biological ceramics of calcium orthophosphate base is most widely used in clinical application at present, and its main products is HAP, tricalcium phosphate (Ca
3(PO
4)
2, TCP), Calcium Pyrophosphate (β-Ca
2P
2O
7, β-TTCP) etc.Tricalcium phosphate, Calcium Pyrophosphate have good bone inducibility, are a kind of desirable degradable biological stupaliths, and the physiological functions such as its bone formation performance approach HAP very much.The comprehensive physiological property of the matrix material be comprised of HAP and degradable biological pottery will be better than single HAP biological ceramics.During clinical application at present, be to utilize the method for plasma spraying that it is sprayed on metallic matrix and forms coating this bioceramic material.Clinical use discovery, the main drawback of bio-ceramic coating prepared by plasma spraying method is: 1, the tissue of coating and degree of crystallinity are inhomogeneous, and this will reduce biocompatibility and the stability of coating; 2, the cohesive strength of coating and matrix is poor, makes coating occur peeling off in clinical application.
Still the problems referred to above that exist for hydroxyl apatite bioceramic coating and plasma spray coating process, the calcium phosphorus based biologic active ceramic coating with the laser melting and coating process preparation containing HAP is developed in recent years.Use CO in traditional laser melting coating preparation technology
2Laser apparatus, to add rare earth
With CaCO
3Mixed powder be that starting material can obtain the Bioceramic Composite that comprises the HAP composition in cladding layer.It should be noted that due to CO
2Laser is due to the wavelength absorption characteristic of self, CO
2Laser melting coating does not add rare earth composition
With CaCO
3Can't obtain bio-ceramic coating during composition.Nd: the wavelength of YAG solid statelaser is 1.064 μ m, with CO
2Gas laser (wavelength is 10.64 μ m) is compared, and the wavelength of its output is shorter.But, for metallic substance, optical maser wavelength is shorter, uptake factor larger (a and b place in figure), but for pottery and glass material (A and B place in figure), situation is just in time contrary, as shown in Figure 1, so (1) work as CO
2Laser melting coating
With CaCO
3When mixed powder prepares bio-ceramic coating, mixed powder is to CO
2The specific absorption of laser will be far away higher than metallic matrix, starting material
Ablation or decomposition, the generation content of HAP in the reduction coating, the HAP composition of simultaneously preparing easily decomposes, and the content of gained HAP reduces; In contrast, during Nd-YAG laser melting coating mixed powder, metallic matrix will be far away higher than mixed powder to the specific absorption of Nd-YAG laser.(2) transmission ofenergy mode: in the Nd-YAG laser cladding process, the energy of mixed powder synthesising biological pottery carrys out self-absorption Nd-YAG laser beam energy and the molten metal matrix, and this existence for HAP in laser cladding process provides processing and thermodynamic condition.
Find by literature search, Chinese Patent Application No.: 200510030117.5, title: the synthetic method for preparing Bioceramic Composite of Laser Cladding in-situ, this patent relates to the preparation technology of Nd-YAG laser melting coating Bioceramic Composite, and the composite boilogical ceramic coated material that it relates to is mainly by HAP and β-Ca
2P
2O
7Form, but and then there is not rare earth composition in the composite boilogical ceramic coating that this patent relates in the composite boilogical ceramic coating starting material that relate to of this patent owing to not adding rare earth composition in starting material.The interpolation of starting material middle-weight rare earths in laser cladding process, the formation of the calcium phosphorus base bioceramic phases such as energy catalysis HAP also can suppress it and decompose, and improves the stability of HAP phase structure.Rare earth, in Bioceramic Coating by Laser Cladding, is distributed in intracrystalline on a small quantity in addition, and major part is distributed between local grain.The doping of rare earth, promote grain refining, has the features such as irregularity that natural bone organizes crystal grain and fibrous tissue.In the Nd-YAG laser cladding process, under laser technical parameters and composition of raw material same case, the bio-ceramic coating that adds rare earth reduces 5-10 doubly than the grain fineness number of the bio-ceramic coating that does not add rare earth, tissue has the features such as the irregularity of class osseous tissue and fibrous tissue, bonding strength improves 30%-50%, during phase forms, the content of hydroxyapatite improves 10-30%, and the process parameters range of synthesizing hydroxylapatite enlarges.
Summary of the invention
The object of the invention is to for existing CO
2Laser melting coating prepares the deficiency of bio-ceramic coating, provides a kind of to have added rare earth composition
With CaCO
3Mixed powder be the Nd-YAG laser melting coating preparation method that starting material are made the adjustable composite boilogical ceramic coating with class bone structure of coat-thickness.
For achieving the above object, the present invention can take following technical proposals:
The method of the class bone structure Bioceramic Composite that Nd-YAG laser melting coating thickness of the present invention is adjustable, comprise the steps:
The first step, by rare earth,
With CaCO
3Be mixed in proportion and be prepared into composite powder;
Second step, overlay on titanium alloy-based surface by the first step gained composite powder heap and form prefabricated coating;
The 3rd step, Nd-YAG laser melting coating composite powder, can obtain the high-bond Bioceramic Composite.
In described second step, heap overlays on the compound coating thickness≤2mm of titanium alloy-based surface.
Described titanium alloy substrate is Ti6Al4V, Ti-5Al-2.5Fe, Ti-6Al-7Nb, Ti-13Nb-13Zr or Ti-12Nb-6Zr-2Fe.
The preparation method of described composite powder is: by rare earth,
With CaCO
3Press rare earth 1-2%,
70-74%, CaCO
3After the weight percent of 24-29% takes, put into that container mixes, standing dehydration, and then mixing, standing strengthen dewatering, enter in mixer and mix, can obtain median size 50-100 μ m, the mixed powder of water content 5.8 ~ 6.8%.Processing parameter condition during described laser melting coating is: shielding gas is argon gas, spot diameter 3mm, output rating 800～1200W, scanning speed 1～3mm/s.
During described laser melting coating, the wavelength of laser is 1.06 μ m.
Thickness≤the 2mm of described Bioceramic Composite, during its phase forms, the volume fraction of HAP accounts for 30～70%, and all the other are TCP, β-Ca
2P
2O
7Mixture with calcium titanate; The bonding strength of compound coating and titanium alloy substrate is 30-45Mpa.
Advantage applies of the present invention is in the following aspects:
First, because Nd-YAG laser (wavelength 1.06 μ m) has the characteristics of perviousness to the biological ceramics mixed powder, therefore carry out in laser cladding process with titanium alloy-based surface, mixed powder can obtain thermodynamics of reactions and the reaction kinetics of the uniqueness of preparation HAP biological ceramics, therefore can the good composite boilogical ceramic coating of processability in titanium alloy-based surface;
The second, added rare earth and (comprised Y in starting material
2O
3, Ce
2O
3, La
2O
3Deng) composition, improved the stability of HAP phase structure.Rare earth composition can promote grain refining, has the features such as irregularity that natural bone organizes crystal grain and fibrous tissue; The hydroxyapatite that in composite boilogical ceramic coating prepared by cladding, main component is stable in properties, tricalcium phosphate, degradable Calcium Pyrophosphate and calcium titanate, the biocompatibility excellence; Under identical Nd-YAG laser technical parameters and composition of raw material same case, the bio-ceramic coating that in starting material prepared by the interpolation rare earth reduces 5-10 doubly than the grain fineness number of the bio-ceramic coating that does not add rare earth, tissue has the features such as the irregularity of class osseous tissue and fibrous tissue, and during phase forms, the content of hydroxyapatite improves 10-30%.
The 3rd, coating and metallic matrix bonding strength are high, are the chemical metallurgy combination, can solve bio-ceramic coating and hold caducous problem in human body; Under identical Nd-YAG laser technical parameters and composition of raw material same case, the bio-ceramic coating that in starting material prepared by the interpolation rare earth improves 30%-50% than the bonding strength of the bio-ceramic coating that does not add rare earth, and the process parameters range of synthesizing hydroxylapatite enlarges.
The 4th, the prices of raw and semifnished materials are cheap, and it is convenient to buy, and are easy to store; Preparation technology is simple, easy to implement, has good market application foreground and commercial value.
The accompanying drawing explanation
Fig. 1 is the specific absorption schematic diagram of material to the laser of different wave length.
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated.
Embodiment 1:
The first step, by Y
2O
3,
With CaCO
3Ratio (weight percent) in 1:72:27 takes, and puts into that container mixes, standing dehydration, and then mixing, standing strengthen dewatering, enters in mixer and mixes, and obtains median size 50-100 μ m, the mixed powder of water content 6.2%;
Second step, overlay on Ti6Al4V alloy substrate surface (adopt other titanium alloy substrate effect identical), thickness 0.5mm by the first step gained mixed powder heap;
The 3rd step; adopt iLS-YC-30A YAG type laser apparatus; at shielding gas, it is argon gas; spot diameter 3mm; output rating 900W; under the processing parameter of scanning speed 2mm/s, with the Nd-YAG high energy laser beam, mixed powder and metallic matrix are carried out to the laser melting and coating process processing, form titanium alloy surface Nd-YAG laser melting coating Bioceramic Composite.After tested, the coated grains refinement of acquisition, have the features such as irregularity that natural bone organizes crystal grain and fibrous tissue.Coat-thickness 0.5mm is combined for chemical metallurgy between metallic matrix, and bonding strength is 35Mpa, and the phase of coating consists of the 37%HAP(volume percent), all the other phases are TCP, β-Ca
2P
2O
7, calcium titanate mixture.(under identical Nd-YAG laser technical parameters and composition of raw material same case, the bio-ceramic coating that adds rare earth reduces 5-10 doubly than the grain fineness number of the bio-ceramic coating that does not add rare earth, tissue has the features such as the irregularity of class osseous tissue and fibrous tissue, bonding strength improves 30%-50%, and during phase forms, the content of hydroxyapatite improves 10-30%.And the process parameters range of synthesizing hydroxylapatite enlarges.）
Embodiment 2:
The first step, with embodiment 1.
Second step, overlay on Ti6Al4V alloy substrate surface (adopt other titanium alloy substrate effect identical), thickness 1.0mm by the first step gained mixed powder heap;
The 3rd step; adopt iLS-YC-30A YAG type laser apparatus; at shielding gas, it is argon gas; spot diameter 3mm; output rating 1000W; under the processing parameter of scanning speed 2mm/s, with the Nd-YAG high energy laser beam, mixed powder and metallic matrix are carried out to the laser melting and coating process processing, form titanium alloy surface Nd-YAG laser melting coating Bioceramic Composite.After tested, the coated grains of acquisition is even, and crystal property is good, has the features such as irregularity that natural bone organizes crystal grain and fibrous tissue.Coat-thickness 1.0mm is combined for chemical metallurgy between metallic matrix, and bonding strength is 37Mpa, and the phase of coating consists of the 43%HAP(volume percent), all the other phases are TCP, β-Ca
2P
2O
7, calcium titanate mixture.
Under identical Nd-YAG laser technical parameters and composition of raw material same case, the bio-ceramic coating that adds rare earth reduces 5-10 doubly than the grain fineness number of the bio-ceramic coating that does not add rare earth, tissue has the features such as the irregularity of class osseous tissue and fibrous tissue, bonding strength improves 30%-50%, and during phase forms, the content of hydroxyapatite improves 10-30%.And the process parameters range of synthesizing hydroxylapatite enlarges.
Embodiment 3:
The first step, by Ce
2O
3,
With CaCO
3Ratio (weight percent) in 2:74:24 takes, and puts into that container mixes, standing dehydration, and then mixing, standing strengthen dewatering, enters in mixer and mixes, and obtains median size 50-100 μ m, the mixed powder of water content 6.2%;
Second step, overlay on Ti6Al4V alloy substrate surface (adopt other titanium alloy substrate effect identical), thickness 1.5mm by the first step gained mixed powder heap;
The 3rd step; adopt iLS-YC-30A YAG type laser apparatus; at shielding gas, it is argon gas; spot diameter 3mm; output rating 1000W; under the processing parameter of scanning speed 1mm/s, with the Nd-YAG high energy laser beam, mixed powder and metallic matrix are carried out to the laser melting and coating process processing, form titanium alloy surface Nd-YAG laser melting coating Bioceramic Composite.After tested, the coated grains of acquisition is thin, has the features such as irregularity that natural bone organizes crystal grain and fibrous tissue.Coat-thickness 1.5mm is combined for chemical metallurgy between metallic matrix, and bonding strength is 43Mpa, and the phase of coating consists of the 47%HAP(volume percent), all the other phases are TCP, β-Ca
2P
2O
7, calcium titanate mixture.
Under identical Nd-YAG laser technical parameters and composition of raw material same case, the bio-ceramic coating that adds rare earth reduces 5-10 doubly than the grain fineness number of the bio-ceramic coating that does not add rare earth, tissue has the features such as the irregularity of class osseous tissue and fibrous tissue, bonding strength improves 30%-50%, and during phase forms, the content of hydroxyapatite improves 10-30%.And the process parameters range of synthesizing hydroxylapatite enlarges.
Embodiment 4:
The first step, with embodiment 3;
Second step, overlay on Ti6Al4V alloy substrate surface (adopt other titanium alloy substrate effect identical), thickness 2.0mm by the first step gained mixed powder heap;
The 3rd step; adopt iLS-YC-30A YAG type laser apparatus; at shielding gas, it is argon gas; spot diameter 3mm; output rating 1200W; under the processing parameter of scanning speed 1mm/s, with the Nd-YAG high energy laser beam, mixed powder and metallic matrix are carried out to the laser melting and coating process processing, form titanium alloy surface Nd-YAG laser melting coating Bioceramic Composite.After tested, the coated grains of acquisition is thin, has the features such as irregularity that natural bone organizes crystal grain and fibrous tissue.Coat-thickness 2.0mm is combined for chemical metallurgy between metallic matrix, and bonding strength is 45Mpa, and the phase of coating consists of the 67%HAP(volume percent), all the other phases are TCP, β-Ca
2P
2O
7, calcium titanate mixture.
Under identical Nd-YAG laser technical parameters and composition of raw material same case, the bio-ceramic coating that adds rare earth reduces 5-10 doubly than the grain fineness number of the bio-ceramic coating that does not add rare earth, tissue has the features such as the irregularity of class osseous tissue and fibrous tissue, bonding strength improves 30%-50%, and during phase forms, the content of hydroxyapatite improves 10-30%.And the process parameters range of synthesizing hydroxylapatite enlarges.
Embodiment 5:
The first step, by La
2O
3,
With CaCO
3Press
1:70:29Ratio (weight percent) take, put into that container mixes, standing dehydration, and then mixing, standing strengthen dewatering, enter in mixer and mix, obtain median size 50-100 μ m, the mixed powder of water content 6.2%;
Second step, overlay on Ti6Al4V alloy substrate surface (adopt other titanium alloy substrate effect identical), thickness 2.0mm by the first step gained mixed powder heap;
The 3rd step; adopt iLS-YC-30A YAG type laser apparatus; at shielding gas, it is argon gas; spot diameter 3mm; output rating 1200W; under the processing parameter of scanning speed 2mm/s, with the Nd-YAG high energy laser beam, mixed powder and metallic matrix are carried out to the laser melting and coating process processing, form titanium alloy surface Nd-YAG laser melting coating Bioceramic Composite.After tested, the coated grains of acquisition is thin, has the features such as irregularity that natural bone organizes crystal grain and fibrous tissue.Coat-thickness 2.0mm is combined for chemical metallurgy between metallic matrix, and bonding strength is 42Mpa, and the phase of coating consists of the 61%HAP(volume percent), all the other phases are TCP, β-Ca
2P
2O
7, calcium titanate mixture.
Under identical Nd-YAG laser technical parameters and composition of raw material same case, the bio-ceramic coating that adds rare earth reduces 5-10 doubly than the grain fineness number of the bio-ceramic coating that does not add rare earth, tissue has the features such as the irregularity of class osseous tissue and fibrous tissue, bonding strength improves 30%-50%, and during phase forms, the content of hydroxyapatite improves 10-30%.And the process parameters range of synthesizing hydroxylapatite enlarges.
Claims (7)
1. the method for the adjustable class bone structure Bioceramic Composite of a Nd-YAG laser melting coating thickness, is characterized in that: comprise the steps:
The first step, by rare earth,
With CaCO
3Be mixed in proportion and be prepared into composite powder;
Second step, overlay on titanium alloy-based surface by the first step gained composite powder heap and form prefabricated coating;
The 3rd step, Nd-YAG laser melting coating composite powder, can obtain the high-bond Bioceramic Composite.
2. the method for the adjustable class bone structure Bioceramic Composite of Nd-YAG laser melting coating thickness according to claim 1, it is characterized in that: in described second step, heap overlays on the compound coating thickness≤2mm of titanium alloy-based surface.
3. the method for the adjustable class bone structure Bioceramic Composite of Nd-YAG laser melting coating thickness according to claim 1, it is characterized in that: described titanium alloy substrate is Ti6Al4V, Ti-5Al-2.5Fe, Ti-6Al-7Nb, Ti-13Nb-13Zr or Ti-12Nb-6Zr-2Fe.
4. the method for the adjustable class bone structure Bioceramic Composite of Nd-YAG laser melting coating thickness according to claim 1, it is characterized in that: the preparation method of described composite powder is: by rare earth,
With CaCO
3Press rare earth 1-2%,
70-74%, CaCO
3After the weight percent of 24-29% takes, put into that container mixes, standing dehydration, and then mixing, standing strengthen dewatering, enter in mixer and mix, can obtain median size 50-100 μ m, the mixed powder of water content 5.8 ~ 6.8%.
5. the method for the adjustable class bone structure Bioceramic Composite of Nd-YAG laser melting coating thickness according to claim 1; it is characterized in that: processing parameter condition during described laser melting coating is: shielding gas is argon gas; spot diameter 3mm; output rating 800～1200W, scanning speed 1～3mm/s.
6. the method for the adjustable class bone structure Bioceramic Composite of Nd-YAG laser melting coating thickness according to claim 1, it is characterized in that: during described laser melting coating, the wavelength of laser is 1.06 μ m.
7. the method for the adjustable class bone structure Bioceramic Composite of Nd-YAG laser melting coating thickness according to claim 1, it is characterized in that: the thickness≤2mm of described Bioceramic Composite, during its phase forms, the HAP volume fraction accounts for 30～70%, and all the other are TCP, β-Ca
2P
2O
7Mixture with calcium titanate; The bonding strength of compound coating and titanium alloy substrate is 30-45Mpa.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1778989A (en) * | 2005-09-29 | 2006-05-31 | 上海交通大学 | Production of composite biological ceramic coating by laser coating home position |
| CN102031518A (en) * | 2010-12-30 | 2011-04-27 | 同济大学 | method for preparing material with biological ceramic composite coating laser-clad on surface of titanium alloy |
| CN102851664A (en) * | 2012-08-03 | 2013-01-02 | 华中科技大学 | Method for preparing hydroxy apatite biological ceramic coating containing fluorine |
-
2013
- 2013-07-23 CN CN2013103101315A patent/CN103422089A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1778989A (en) * | 2005-09-29 | 2006-05-31 | 上海交通大学 | Production of composite biological ceramic coating by laser coating home position |
| CN102031518A (en) * | 2010-12-30 | 2011-04-27 | 同济大学 | method for preparing material with biological ceramic composite coating laser-clad on surface of titanium alloy |
| CN102851664A (en) * | 2012-08-03 | 2013-01-02 | 华中科技大学 | Method for preparing hydroxy apatite biological ceramic coating containing fluorine |
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Application publication date: 20131204 |