CN102031517A - Titanium alloy surface laser-clad composite bioceramic coating material - Google Patents

Titanium alloy surface laser-clad composite bioceramic coating material Download PDF

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CN102031517A
CN102031517A CN 201010617930 CN201010617930A CN102031517A CN 102031517 A CN102031517 A CN 102031517A CN 201010617930 CN201010617930 CN 201010617930 CN 201010617930 A CN201010617930 A CN 201010617930A CN 102031517 A CN102031517 A CN 102031517A
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titanium alloy
coating
alloy surface
powder
surface laser
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王迎春
黄文旵
王翠霞
王德平
姚爱华
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Tongji University
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Tongji University
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Abstract

The invention belongs to the technical field of bioceramics, and relates to a titanium alloy surface laser-clad composite bioceramic coating material, which consists of the following bioactive ceramic materials in percentage by volume: 20 to 61 percent of hydroxyapatite, and the balance of mixture of tertiary calcium phosphate and calcium pyrophosphate. The titanium alloy surface laser-clad composite bioceramic coating material has a uniform fiber reinforced microstructure, high crystallinity, high biocompatibility, superior phase compositions and high mechanical properties; and the raw materials of the coating material are low in cost and readily available and have vast market application prospect and high commercial values.

Description

Titanium alloy surface laser melting coating Bioceramic Composite material
Technical field
The invention belongs to the biological ceramics technical field, relate to a kind of composite boilogical ceramic coated material.
Background technology
Repair the field at human body hard tissue, the purpose of bone alternate material implant into body is in order to remedy the bone defective, finally to be substituted by the human body area of new bone, so implant must biologically active and biodegradability.Calcium orthophosphate base bioceramic has identical chemical ingredients with human body natural's bone, is the focus that people study.The main products of calcium orthophosphate base bioceramic is hydroxyapatite ((Ca 10(PO 4) 6(OH) 2, HAP, tricalcium phosphate (Ca 3(PO 4) 2, TCP), Calcium Pyrophosphate (β-Ca 2P 2O 7, β-TTCP) etc.HAP is the main component of human body natural's bone, degraded hardly after a very long time that implants.Tricalcium phosphate, Calcium Pyrophosphate have good bone inducibility, are a kind of ideal degradable biological stupaliths, and physiological functions such as its bone formation performance are very near HAP.The comprehensive physiological property of the matrix material of HAP and degradable biological pottery will be better than single HAP biological ceramics.The intensity of calcium phosphate ceramic is low, the mechanical property of poor toughness has limited its widespread use.Preparation hydroxyl apatite bioceramic coated material is present domestic and international ongoing research focus on metallic matrix, and plasma spraying is the unique preparation technology who is adopted on the present clinical application goods.The main drawback of the bio-ceramic coating of plasma spraying method preparation can be summarized as:
1. the tissue of coating and degree of crystallinity are inhomogeneous, will reduce biological compatibility of coating and stability;
2. layer is relatively poor with the cohesive strength of matrix, will make coating peel off in clinical application.
At the problems referred to above that hydroxyl apatite bioceramic coating and plasma spray coating process still exist, the calcium phosphorus based biologic active ceramic coating that contains HAP with the laser melting and coating process preparation is developed in recent years.According to the difference of starting material, preparation laser apparatus, the research that at present domestic and international laser melting coating prepares Bioceramic Composite is divided into two main research directions:
1. using the Nd-YAG laser apparatus, is the raw material preparing bio-ceramic coating with HAP.Mainly be the research that the foreign scholar is engaged in this direction at present.But what these technology starting material adopted is the HAP powder, so cost is higher; In the laser cladding process, the easy decomposes of HAP powder, the content of HAP is restricted in the gained coating.
2. use CO 2Laser apparatus is with CaHPO 42H 2O, CaCO 3And a spot of rare earth composition mixed powder is starting material, and laser melting coating prepares Bioceramic Composite.This technology is with CaHPO 42H 2O and CaCO 3Mixed powder when being starting material, must in mixed powder, add rare earth composition (Y 2O 3Or CeO 2), could in cladding layer, obtain comprising the Bioceramic Composite of HAP composition.This kind method must be at starting material CaHPO 42H 2O and CaCO 3Add rare earth composition (Y in the powder 2O 3Or CeO 2), could in cladding layer, obtain comprising the Bioceramic Composite of HAP composition.Because the starting material mixed powder is to CO 2The specific absorption of laser is very high, and starting material take place to decompose and scaling loss; The laser cladding process temperature is too high simultaneously, and thermodynamics of reactions and reaction kinetics are unfavorable for the generation of HAP.
Find by literature search, Chinese patent application numbers 200510200011: laser melting coating prepares the material of gradient biologically active ceramic coating and the method for making of coating, this patent relates to the gradient biologically active ceramic coating material, and its production process is: (1) ground and mixed prepares CaHPO 42H 2O, CaCO 3With the mixed powder of rare earth oxide and titanium valve, the mixed powder that adding caking agent (2) will add caking agent is pressed into titanium alloy surface, carries out CO 2Laser Cladding Treatment obtains first gradient layer, and the like, the compacting second layer and the 3rd layer of mixed powder on first gradient layer, Laser Cladding Treatment obtains the gradient Bioceramic Composite.But because CO 2Laser melting coating does not possess the thermodynamics of reactions and the reaction kinetics of YAG laser, so the content of the HAP in the gradient biologically active ceramic coating material that this patent relates to is restricted, must add in the starting material simultaneously and contain a certain amount of rare earth oxide as catalyzer, otherwise will not contain bioceramic material in the coating, this will improve production cost, strengthen process complexity, be unfavorable for the industrialization of the material of gradient biologically active ceramic coating, limited its utilization on civilian industry.In addition, this gradient biologically active ceramic coating material, can not change according to clinical application so the variation range of its thickness is restricted flexibly owing to be to obtain by three compactings and laser melting coating.
The wavelength of Nd: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 short more, uptake factor big more (a and b place among the figure), but for pottery and glass material (A and B place among the figure), situation is just in time opposite, as shown in Figure 1, so (1) works as CO 2Laser melting coating CaHPO 42H 2O and CaCO 3When mixed powder prepared bio-ceramic coating, mixed powder was to CO 2The specific absorption of laser will be higher than metallic matrix, CaHPO far away 42H 2O takes place to ablate or decompose; Only in mixed powder, add rare earth composition simultaneously, just can prepare the bio-ceramic coating that main component is HAP; In contrast, during Nd-YAG laser melting coating mixed powder, metallic matrix will be higher than mixed powder far away to the specific absorption of Nd-YAG laser.The contriver has observed Nd-YAG laser for CaHPO in the laser melting coating experiment in early stage 42H 2O and CaCO 3Characteristics with perviousness.(2) transmission ofenergy mode: in the Nd-YAG laser cladding process, the energy of mixed powder synthesising biological pottery is from absorption of N d-YAG laser beam energy and the molten metal matrix, and this existence for HAP in the laser cladding process provides processing and thermodynamic condition.
Summary of the invention
The present invention is directed to deficiency of the prior art and defective, a kind of titanium alloy surface laser melting coating Bioceramic Composite material is provided.
The present invention is achieved by the following technical solutions:
A kind of titanium alloy surface laser melting coating Bioceramic Composite material, (β-TTCP) three kinds of biological active ceramic materials are formed by hydroxyapatite (HAP), tricalcium phosphate (TCP) and Calcium Pyrophosphate.
The volume percent of described HAP is 20～70%, and its surplus is TCP and β-Ca 2P 2O 7Mixture.
The thickness of described titanium alloy surface laser melting coating Bioceramic Composite material is 0～2mm.
The starting material of described Bioceramic Composite material are CaHPO 42H 2O powder and CaCO 3Powder.
Described CaHPO 42H 2O powder and CaCO 3The weight percent of powder is: 70%: 30%～75%: 25%.
At first preparation mix, good fluidity, calcium salt composite powder that water content is low, powder under the situation of adding additives not directly heap be overlying on metal base surface and form preset coating, be coated with layer height 0～2mm.Because CaHPO 42H 2O and CaCO 3Mixed powder is to unique absorption characteristics of Nd-YAG laser, and the water content of powder is qualified simultaneously, and during the laser melting coating mixed powder, metallic matrix will be higher than mixed powder far away to the specific absorption of Nd-YAG laser.The most energy of laser will be absorbed by the metallic surface thin layer in the laser processing procedure, the preset coating energy will be from the metallic surface thin layer of melted state, under suitable photothermal laser mechanics and photochemical effect, calcium salt composite powder and metal base surface thin layer are 10 -6～10 -9The S fusing.Under suitable laser technical parameters, because high energy laser beam (wavelength of YAG laser apparatus is 1.06 μ m) has unique thermodynamics of reactions and reacting dynamics condition in laser processing procedure, thereby make calcium salt composite powder reaction in generate HAP/ tricalcium phosphate/β-Ca 2P 2O 7Be the composite boilogical ceramic coating of main component, coating presents fibre-reinforced microstructure, and biological compatibility of coating is good.
Described titanium alloy surface laser melting coating Bioceramic Composite preparation methods comprises step:
(1) employing equipment is iLS-YC-30AYAG type laser apparatus, and used starting material are secondary calcium phosphate (CaHPO 42H 2O, 200 orders, analytical pure), with lime carbonate (CaCO 3, 200 orders, analytical pure), composition proportion (weight percent, following same) is: 72% and 28%.Matrix is the Ti6Al4V titanium alloy.
(2) above-mentioned powder is put into open containers and strengthen dehydration through mixing, mix again, leaving standstill, mixer mixes, and preparing average particle diameter is 50 μ m, and water content is 6.2% calcium salt composite powder.
(3) the direct heap of calcium salt composite powder is overlying on the Ti6Al4V titanium alloy substrate thickness 0～2mm.Regulate suitable processing parameter, obtain suitable reaction kinetics and thermodynamics, cladding powder and metallic matrix are carried out the laser melting and coating process processing with high energy laser beam.The metal base surface thin layer is 10 -6～10 -9Fusing in the S, the calcium salt composite powder obtains suitable thermodynamics of reactions and reacting dynamics condition, and the original position synthetic ingredient is HAP/ tricalcium phosphate/β-Ca 2P 2O 7The composite boilogical ceramic coating, coating is that chemical metallurgy combines with matrix, the bonding strength height is 25～38Mpa.Laser technical parameters is (shielding gas is an argon gas): spot diameter 3mm, output rating 900～1200W, scanning speed 1～3mm/s.
Under this experiment condition, the thing of bio-ceramic coating coordinates and is divided into 20～70%HAP (volume percent), and its surplus is TCP and β-Ca 2P 2O 7Mixture, the thing phase composition of bio-ceramic coating, mechanical property and Nd-YAG laser cladding technological parameter fixed light spot sizes such as microhardness, scanning speed, laser output power is closely related.
Preparation method of the present invention has following effect:
(1) since Nd-YAG laser to CaHPO 42H 2O and CaCO 3Mixed powder has the characteristics of perviousness, so in the Ti6Al4V titanium alloy surface Nd-YAG laser cladding process, thereby make calcium salt composite powder reaction under the situation that does not add caking agent generate the composite boilogical ceramic coating, the calcium salt mixed powder can obtain to prepare the thermodynamics of reactions and the reaction kinetics of the uniqueness of HAP biological ceramics, so can prepare homogeneous microstructure, composite boilogical ceramic coating that crystal property is good at titanium alloy surface.
(2) main component of coating is the composite boilogical ceramic of hydroxyapatite, tricalcium phosphate and the degradable Calcium Pyrophosphate of stable in properties, the biocompatibility excellence.
(3) coating and substrate combinating strength height are the chemical metallurgy combination, are 25～38Mpa, can solve the problem that bio-ceramic coating comes off in human body easily; Bio-ceramic coating cross section microhardness is significantly improved, and is 600～1200HV, for the 3-6 of titanium alloy metallic matrix doubly; With titanium alloy metallic matrix bonding strength height, thickness is controlled in 0～2mm, can be used for substituting and repairing of human body hard tissue.
(4) from making, cost of material is cheap, and it is convenient to buy, and is easy to store; Need not add rare earth composition in the starting material; Technology is simple and convenient, and is easy to implement, has better market prospect and commercial value.
Description of drawings
Fig. 1 is the specific absorption synoptic diagram of material to different wavelength of laser.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1:
The thing phase composite of coating is 20%HAP (volume percent), and its excess is TCP and β-Ca mutually 2P 2O 7Mixture, thickness 0.5mm is that chemical metallurgy combines with matrix, bonding strength is 25～38Mpa, the coatings cross-section microhardness is the Bioceramic Composite of 600～1200HV.
(1) weighing composition proportion is 72%CaHPO 42H 2O and 28%CaCO 3Above-mentioned powder put into open containers through mix, leave standstill dehydration, mix again, leave standstill strengthen dehydration, mixer mixes, preparing average particle diameter is 50 μ m, water content is 6.2% calcium salt composite powder.
(2) calcium salt composite powder heap is overlying on the Ti6Al4V alloy substrate thickness 0.5mm.At shielding gas is argon gas, spot diameter 3mm, and output rating 800W under the processing parameter of scanning speed 3mm/s, carries out the laser melting and coating process processing with the Nd-YAG high energy laser beam to cladding powder and metallic matrix, and the metal base surface thin layer is 10 -6～10 -9Fusing in the S forms titanium alloy surface Nd-YAG laser melting coating Bioceramic Composite.The coating structure that obtains is even, and crystal property is good, and coat-thickness 0.5mm is that chemical metallurgy combines with matrix, and bonding strength is 25～38Mpa, and the thing phase composite of coating is 20%HAP (volume percent), and its excess is TCP and β-Ca mutually 2P 2O 7Mixture.This bio-ceramic coating cross section microhardness is significantly improved, and is 600～1200HV, for the 3-6 of titanium alloy metallic matrix doubly.
Embodiment 2:
The thing phase composite of coating is 53%HAP (volume percent), and its excess is TCP and β-Ca mutually 2P 2O 7Mixture, thickness 2mm is that chemical metallurgy combines with matrix, bonding strength is 25～38Mpa, the coatings cross-section microhardness is the Bioceramic Composite of 600～1200HV.
(1) weighing composition proportion is 72%CaHPO 42H 2O and 28%CaCO 3Above-mentioned powder is put into open containers through mixing, leave standstill dehydration, mixing again, leave standstill and strengthen dehydration, and mixer mixes, and preparing average particle diameter is 50 μ m, and water content is 6.2% calcium salt composite powder.
(2) calcium salt composite powder heap is overlying on the Ti6Al4V alloy substrate thickness 2mm.At spot diameter 3mm, output rating 1000W under the processing parameter of scanning speed 1mm/s, can obtain suitable reaction kinetics and thermodynamics of reactions.Utilize the Nd-YAG high energy laser beam that cladding powder and metallic matrix are carried out the laser melting and coating process processing, the metal base surface thin layer is 10 -6～10 -9Fusing in the S forms titanium alloy surface Nd-YAG laser melting coating Bioceramic Composite cladding coating.The coating structure that obtains is even, and crystal property is good, and thickness 2mm is that chemical metallurgy combines with matrix, and bonding strength is 25-38Mpa, and the thing phase composite of coating is 53%HAP (volume percent), and its excess is TCP and β-Ca mutually 2P 2O 7Mixture.This bio-ceramic coating cross section microhardness is significantly improved, and is 600～1200HV, for the 3-6 of titanium alloy metallic matrix doubly.
Embodiment 3:
The thing phase composite of coating is 61%HAP (volume percent), and its excess is TCP and β-Ca mutually 2P 2O 7Mixture, thickness 2mm is that chemical metallurgy combines with matrix, bonding strength is 25-38Mpa, the coatings cross-section microhardness is the Bioceramic Composite of 600～1200HV.
(1) weighing composition proportion is 72%CaHPO 42H 2O and 28%CaCO 3Above-mentioned powder is put into open containers through mixing, leave standstill dehydration, mixing again, leave standstill and strengthen dehydration, and mixer mixes, and preparing average particle diameter is 50 μ m, and water content is 6.2% calcium salt composite powder.
(2) calcium salt composite powder heap is overlying on the Ti6Al4V alloy substrate thickness 2mm.At spot diameter 3mm, output rating 1200W under the processing parameter of scanning speed 1mm/s, can obtain suitable reaction kinetics and thermodynamics of reactions.Utilize the Nd-YAG high energy laser beam that cladding powder and metallic matrix are carried out the laser melting and coating process processing, the metal base surface thin layer is 10 -6～10 -9Fusing in the S forms titanium alloy surface Nd-YAG laser melting coating Bioceramic Composite.The Bioceramic Composite homogeneous microstructure that obtains, crystal property is good, and thickness 2mm is that chemical metallurgy combines with matrix, and bonding strength is 25～38Mpa, and the thing phase composite of coating is 61%HAP (volume percent), its excess is TCP and β-Ca mutually 2P 2O 7Mixture.This bio-ceramic coating cross section microhardness is significantly improved, and is 600～1200HV, for the 3-6 of titanium alloy metallic matrix doubly.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.

Claims (5)

1. a titanium alloy surface laser melting coating Bioceramic Composite material is characterized in that: be made up of hydroxyapatite, tricalcium phosphate and three kinds of biological active ceramic materials of Calcium Pyrophosphate.
2. titanium alloy surface laser melting coating Bioceramic Composite material according to claim 1, it is characterized in that: the volume percent of described hydroxyapatite is 20～70%, its surplus is the mixture of tricalcium phosphate and Calcium Pyrophosphate.
3. titanium alloy surface laser melting coating Bioceramic Composite material according to claim 1 is characterized in that: the thickness of described titanium alloy surface Nd-YAG laser melting coating Bioceramic Composite material is 0～2mm.
4. titanium alloy surface laser melting coating Bioceramic Composite material according to claim 1, it is characterized in that: the starting material of described Bioceramic Composite material are CaHPO 42H 2O powder and CaCO 3Powder.
5. titanium alloy surface laser melting coating Bioceramic Composite material according to claim 4 is characterized in that: described CaHPO 42H 2O and CaCO 3Weight percent be: 70%: 30%～75%: 25%.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107233618A (en) * 2017-06-30 2017-10-10 湖北大学 A kind of method that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy

Citations (1)

* Cited by examiner, † Cited by third party
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《激光技术》 20041231 王迎春等 激光熔覆原位合成制备生物陶瓷涂层 572-574页 第28卷, 第6期 2 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107233618A (en) * 2017-06-30 2017-10-10 湖北大学 A kind of method that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy

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Application publication date: 20110427