CN100457972C - Production of composite biological ceramic coating by laser coating home position - Google Patents

Production of composite biological ceramic coating by laser coating home position Download PDF

Info

Publication number
CN100457972C
CN100457972C CNB2005100301175A CN200510030117A CN100457972C CN 100457972 C CN100457972 C CN 100457972C CN B2005100301175 A CNB2005100301175 A CN B2005100301175A CN 200510030117 A CN200510030117 A CN 200510030117A CN 100457972 C CN100457972 C CN 100457972C
Authority
CN
China
Prior art keywords
laser
calcium salt
coating
composite powder
synthetic method
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB2005100301175A
Other languages
Chinese (zh)
Other versions
CN1778989A (en
Inventor
王迎春
李建国
周尧和
俞海良
黄延禄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jiaotong University
Original Assignee
Shanghai Jiaotong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Jiaotong University filed Critical Shanghai Jiaotong University
Priority to CNB2005100301175A priority Critical patent/CN100457972C/en
Publication of CN1778989A publication Critical patent/CN1778989A/en
Application granted granted Critical
Publication of CN100457972C publication Critical patent/CN100457972C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

A method of producing complex bioceramic coat by laser in situ synthesis which includes such steps as calcium salt powder preparation, piling the powder directly on surface of metallic matrix to form a prefabricate coat, high-energy laser beam melting, fused bath forming instantly, calcium salt powder turnning into complex bioceramic coat with HAP and beta-Ca2P2O7 as its essential component by regulating laser parameter. Advantages of this method are as follows: high combination intensity between coat and metallic matrix, complex bioceramic coat with high quality being obtained by using cheap raw materials.

Description

The synthetic method for preparing Bioceramic Composite of Laser Cladding in-situ
Technical field
What the present invention relates to is a kind of method of technical field of ceramic material, specifically is the synthetic method for preparing Bioceramic Composite of a kind of Laser Cladding in-situ.
Background technology
The medical bio pottery is just at flourish biomaterial.The biological ceramics of calcium orthophosphate base is the most extensive in clinical application at present, and its main products is hydroxyapatite, calcium phosphate, β-Ca 2P 2O 7Deng.Hydroxyapatite (molecular formula Ca 10(PO 4) 6(OH) 2, be called for short HAP), claim that again calcium phosphate powder is the important component part of bone, its product is mainly used in substituting and repairing of human body bone, tooth.β-Ca 2P 2O 7Having good bone inducibility, is a kind of ideal degradable biological stupalith, and physiological functions such as its bone formation performance are very near hydroxyapatite.At present, 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 research focus on metallic matrix, multiple preparation technology is arranged, as plasma spraying, pulsed laser deposition deposition, ion sputtering, physical chemistry vapour deposition etc.Plasma spraying is the unique preparation technology who is adopted on the present clinical application goods.
Find through literature search prior art, " the Hydroxyapatite-alumina composites andbone-bonding " that J.Li delivers on " Biomaterials " (" biomaterial ") 15 (5) (1995) 417-422 (" hydroxyapatite-aluminium sesquioxide mixture is connected with bone "), this article adopts plasma spraying method to prepare the bio-ceramic coating material on metallic matrix, but the bio-ceramic coating that obtains, the shortcoming that exists mainly is: coating structure pattern and crystalline ununiformity, reduced biocompatibility and stability; The bonding strength of coating and matrix is relatively poor, causes phenomenon such as occur in the clinical application coming off.The starting material that technology adopted such as plasma spraying all are based on hydroxyapatite basically, and cost is higher; Coating and matrix are mechanical bond, and bonding strength is lower.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of Laser Cladding in-situ the synthetic method for preparing Bioceramic Composite, make it can prepare homogeneous microstructure, composite boilogical ceramic coating that crystal property is good; Coating and substrate combinating strength height are the chemical metallurgy combination; Starting material price is cheap, conveniently is easy to get.
The present invention is achieved by the following technical solutions, the present invention at first prepare 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 prefabricated coating.Because the water content of powder is qualified, the most energy of laser will be absorbed by prefabricated coating and metallic surface thin layer in the laser processing procedure, with high energy laser beam calcium salt composite powder and metallic matrix are carried out the laser melting and coating process processing, under photothermal laser mechanics and photochemical effect, calcium salt composite powder and metal base surface thin layer are in microsecond～nanosecond (10 -6～10 -9S) fusing, produce the molten bath, under suitable laser technical parameters,, thereby make calcium salt composite powder reaction in generate HAP and β-Ca 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 2P 2O 7Be the composite boilogical ceramic coating of main component, coating presents fibre-reinforced microstructure, and biocompatibility is good.
Described preparation calcium salt composite powder is specially: adopt weight percent 70% secondary calcium phosphate CaHPO 42H 2O, 28% lime carbonate CaCO 3With 2% sodium stearate as starting material, secondary calcium phosphate and calcium carbonate powders are put into open containers through mixing, add the dispersion agent sodium stearate and leave standstill dehydration, again mix, leave standstill and strengthen dehydration, mixer mixes, and preparing average particle diameter is 20 μ m, and water content is 6.2% calcium salt composite powder.
Described secondary calcium phosphate CaHPO 42H 2O is 200 orders, analytical pure.Described lime carbonate CaCO 3, be 200 orders, analytical pure.Described sodium stearate is an analytical pure.
Described matrix is 316L medical stainless steel (the national standard model is 00Cr17Ni14Mo2).
Described calcium salt composite powder directly heap is overlying on the 316L medical stainless steel matrix, is coated with layer height 1.6～2mm.
Described laser melting and coating process, parameter is: spot diameter 3mm, output rating 800～1200W, scanning speed 3～6mm/s, shielding gas are argon gas.
The present invention adopts simple directly heap to cover the composite powder of adding additives not as prefabricated coating, laser processing procedure, directly prefabricated powder is carried out processing treatment with certain laser technical parameters, obtained to be distributed in the bar-shaped β-Ca of mutual overlap joint with tiny granular HAP 2P 2O 7Among the composite boilogical ceramic coating structure.
Compared with prior art, the present invention has following effect: (1) can prepare homogeneous microstructure, composite boilogical ceramic coating that crystal property is good; (2) main component of coating is the hydroxyapatite of stable in properties and the composite boilogical ceramic of degradable Calcium Pyrophosphate; (3) coating and substrate combinating strength height are the chemical metallurgy combination; (4) from making, cost of material is cheap, and it is convenient to buy, and is easy to store.The present invention has increased a kind of new preparation technology again and has opened up new research direction for preparing the hydroxyl apatite bioceramic coating both at home and abroad.
Embodiment
Following examples employing equipment is iLS-YC-30A YAG type laser apparatus, and matrix is the 316L medical stainless steel.
Embodiment 1:
(1) weigh per-cent is 70%CaHPO 42H 2O, 28%CaCO 3With 2% sodium stearate.
Above-mentioned powder is put into open containers to above-mentioned powder to be left standstill dehydration through mixing, add the dispersion agent sodium stearate, mixes again, leaves standstill to strengthen and dewater, mixer mixes, preparing average particle diameter is that 20 μ m water content are 6.2%, the calcium salt composite powder of mean diameter 20～50 μ m.
(2) calcium salt composite powder heap is overlying on the stainless steel base thickness 1.6.At shielding gas is argon gas; spot diameter 3mm; output rating 800W; under the processing parameter of scanning speed 3mm/s; with high energy laser beam cladding powder and metallic matrix are carried out the laser melting and coating process processing; cladding powder and metal base surface thin layer melt in microsecond～nanosecond, form cladding coating.The coating that obtains is that chemical metallurgy combines with matrix, and bonding strength is 30.2Mpa, but has only a spot of HAP in the coating.
Embodiment 2:
(1) weigh per-cent is 70%CaHPO 42H 2O, 28%CaCO 3With 2% sodium stearate.
Above-mentioned powder is put into open containers to above-mentioned powder and is left standstill dehydration through mixing, add the dispersion agent sodium stearate, mixes again, leaves standstill to strengthen and dewater, mixer mixes, preparing average particle diameter is that 20 μ m water content are 6.2%, the calcium salt composite powder of mean diameter 20～50 μ m.
(2) calcium salt composite powder heap is overlying on the stainless steel base thickness 1.9mm.At spot diameter 3mm, output rating 800W under the processing parameter of scanning speed 5mm/s, utilizes high energy laser beam that cladding powder and metallic matrix are carried out the laser melting and coating process processing, cladding powder and metal base surface thin layer melt in microsecond～nanosecond, form cladding coating.The coating that obtains is that chemical metallurgy combines with matrix, and bonding strength is 30.1Mpa, and the composition in the coating is 18.6% HAP and β-Ca 2P 2O 7
Embodiment 3:
(1) weigh per-cent is 70%CaHPO 42H 2O, 28%CaCO 3With 2% sodium stearate.
Above-mentioned powder is put into open containers to above-mentioned powder to be left standstill dehydration through mixing, add the dispersion agent sodium stearate, mixes again, leaves standstill to strengthen and dewater, mixer mixes, preparing average particle diameter is that 20 μ m water content are 6.2%, the calcium salt composite powder of mean diameter 20～50 μ m.
(2) calcium salt composite powder heap is overlying on the stainless steel base thickness 2mm.At spot diameter 3mm, output rating 1000W under the processing parameter of scanning speed 6mm/s, can obtain suitable reaction kinetics and thermodynamics of reactions.Utilize high energy laser beam that cladding powder and metallic matrix are carried out Laser Cladding Treatment, cladding powder and metal base surface thin layer melt in microsecond～nanosecond, under photothermal laser mechanics and photochemical effect, calcium salt composite powder reaction in generates HAP.The main component of the coating that obtains is HAP, and content is about 52.3%, and coating combines with the chemical metallurgy that is combined into of matrix, and bonding strength is 29.8Mpa.
Embodiment 4:
(1) weigh per-cent is 70%CaHPO 42H 2O, 28%CaCO 3With 2% sodium stearate.
Above-mentioned powder is put into open containers to above-mentioned powder to be left standstill dehydration through mixing, add the dispersion agent sodium stearate, mixes again, leaves standstill to strengthen and dewater, mixer mixes, preparing average particle diameter is that 20 μ m water content are 6.2%, the calcium salt composite powder of mean diameter 20～50 μ m.
(2) calcium salt composite powder heap is overlying on the stainless steel base thickness 2.0mm.At spot diameter 3mm, output rating 1200W under the processing parameter of scanning speed 3mm/s, can obtain suitable reaction kinetics and thermodynamics of reactions.Utilize high energy laser beam that cladding powder and metallic matrix are carried out Laser Cladding Treatment, cladding powder and metal base surface thin layer melt in microsecond～nanosecond, under photothermal laser mechanics and photochemical effect, calcium salt composite powder reaction in generates HAP.Composition in the coating that obtains is 15.6% HAP and β-Ca 2P 2O 7,, coating combines with the chemical metallurgy that is combined into of matrix, and bonding strength is 26.7Mpa.
Embodiment 5:
(1) weigh per-cent is 70%CaHPO 42H 2O, 28%CaCO 3With 2% sodium stearate.
Above-mentioned powder is put into open containers to above-mentioned powder to be left standstill dehydration through mixing, add the dispersion agent sodium stearate, mixes again, leaves standstill to strengthen and dewater, mixer mixes, preparing average particle diameter is that 20 μ m water content are 6.2%, the calcium salt composite powder of mean diameter 20～50 μ m.
(2) calcium salt composite powder heap is overlying on the stainless steel base thickness 1.8mm.At spot diameter 3mm, output rating 1200W under the processing parameter of scanning speed 6mm/s, can obtain suitable reaction kinetics and thermodynamics of reactions.Utilize high energy laser beam that cladding powder and metallic matrix are carried out Laser Cladding Treatment, cladding powder and metal base surface thin layer melt in microsecond～nanosecond, under photothermal laser mechanics and photochemical effect, calcium salt composite powder reaction in generates HAP.Composition in the coating that obtains is a spot of HAP% and β-Ca 2P 2O 7,, coating combines with the chemical metallurgy that is combined into of matrix, and bonding strength is 21.8Mpa.
By to the composition of embodiment and comparing of bonding strength, can find that the resulting effect of processing parameter of embodiment 3 is best.

Claims (7)

1, the synthetic method for preparing Bioceramic Composite of a kind of Laser Cladding in-situ is characterized in that, at first with weight percent 70% secondary calcium phosphate CaHPO 42H 2O, 28% lime carbonate CaCO 3Prepare the calcium salt composite powder with 2% sodium stearate, the direct heap of calcium salt composite powder is overlying on metal base surface forms prefabricated coating, with high energy laser beam calcium salt composite powder and metallic matrix are carried out the laser melting and coating process processing then, under photothermal laser mechanics and photochemical effect, calcium salt composite powder and metal base surface thin layer melt in microsecond～nanosecond, produce the molten bath, regulate laser technical parameters, utilize thermodynamics of reactions and the reacting dynamics condition of high energy laser beam in laser processing procedure, make calcium salt composite powder reaction in generate HAP and β-Ca 2P 2O 7Composite boilogical ceramic coating for main component.
2, the synthetic method for preparing Bioceramic Composite of Laser Cladding in-situ according to claim 1, it is characterized in that, described calcium salt composite powder preparation process is specially: secondary calcium phosphate and calcium carbonate powders are put into open containers through mixing, add the dispersion agent sodium stearate and leave standstill dehydration, again mix, leave standstill and strengthen dehydration, mixer mixes, and preparing average particle diameter is that 20 μ m water content are 6.2% calcium salt composite powder.
3, the synthetic method for preparing Bioceramic Composite of Laser Cladding in-situ according to claim 2 is characterized in that described secondary calcium phosphate CaHPO 42H 2O is 200 orders, analytical pure, described lime carbonate CaCO 3, be 200 orders, analytical pure, described sodium stearate is an analytical pure.
4, the synthetic method for preparing Bioceramic Composite of Laser Cladding in-situ according to claim 1 is characterized in that, described laser melting and coating process, and parameter is: spot diameter 3mm, output rating 800～1200W, scanning speed 3～6mm/s.
5, according to claim 1 or the synthetic method for preparing Bioceramic Composite of 4 described Laser Cladding in-situ, it is characterized in that described laser melting and coating process, shielding gas are argon gas.
6, the synthetic method for preparing Bioceramic Composite of Laser Cladding in-situ according to claim 1 is characterized in that described matrix is the 316L medical stainless steel.
7, according to claim 1 or the synthetic method for preparing Bioceramic Composite of 2 described Laser Cladding in-situ, it is characterized in that, described calcium salt composite powder, directly heap is overlying on the 316L medical stainless steel matrix, is coated with layer height 1.6～2mm.
CNB2005100301175A 2005-09-29 2005-09-29 Production of composite biological ceramic coating by laser coating home position Expired - Fee Related CN100457972C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2005100301175A CN100457972C (en) 2005-09-29 2005-09-29 Production of composite biological ceramic coating by laser coating home position

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2005100301175A CN100457972C (en) 2005-09-29 2005-09-29 Production of composite biological ceramic coating by laser coating home position

Publications (2)

Publication Number Publication Date
CN1778989A CN1778989A (en) 2006-05-31
CN100457972C true CN100457972C (en) 2009-02-04

Family

ID=36769444

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2005100301175A Expired - Fee Related CN100457972C (en) 2005-09-29 2005-09-29 Production of composite biological ceramic coating by laser coating home position

Country Status (1)

Country Link
CN (1) CN100457972C (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102031517A (en) * 2010-12-30 2011-04-27 同济大学 Titanium alloy surface laser-clad composite bioceramic coating material
CN103422089A (en) * 2013-07-23 2013-12-04 河南工业大学 Nd-YAG laser cladding method for preparing thickness adjustable biological ceramic composite coating adopting bone-like structure
CN113816770B (en) * 2021-06-25 2022-10-04 西北工业大学 Preparation method for improving surface activity of aluminum oxide-zirconium oxide composite ceramic

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1546372A (en) * 2003-12-04 2004-11-17 上海交通大学 Method for in situ synthesis of calcium salt composite powder of bioceramic coating

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1546372A (en) * 2003-12-04 2004-11-17 上海交通大学 Method for in situ synthesis of calcium salt composite powder of bioceramic coating

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
激光熔覆原位合成制备生物陶瓷涂层. 王迎春，李飞群，李延民等.激光技术，第28卷第6期. 2004
激光熔覆原位合成制备生物陶瓷涂层. 王迎春，李飞群，李延民等.激光技术，第28卷第6期. 2004 *

Also Published As

Publication number Publication date
CN1778989A (en) 2006-05-31

Similar Documents

Publication Publication Date Title
Khor et al. Microstructure and mechanical properties of plasma sprayed HA/YSZ/Ti–6Al–4V composite coatings
Demnati et al. Hydroxyapatite coating on titanium by a low energy plasma spraying mini-gun
Zhang et al. Rapidly sintering of interconnected porous Ti-HA biocomposite with high strength and enhanced bioactivity
Qaid et al. Micro-arc oxidation of bioceramic coatings containing eggshell-derived hydroxyapatite on titanium substrate
Zheng et al. Microstructure and in vitro bioactivity of laser-cladded bioceramic coating on titanium alloy in a simulated body fluid
Um et al. Robust hydroxyapatite coating by laser‐induced hydrothermal synthesis
WO2010135873A1 (en) Method for preparing bioactive glass coating by hot-spraying in liquid phase
CN100457972C (en) Production of composite biological ceramic coating by laser coating home position
Yoganand et al. Characterization and in vitro-bioactivity of natural hydroxyapatite based bio-glass–ceramics synthesized by thermal plasma processing
CN102031518A (en) method for preparing material with biological ceramic composite coating laser-clad on surface of titanium alloy
Su et al. Ca-P bioactive coating prepared by combining microwave-hydrothermal and supersonic atmospheric plasma spraying methods
CN102851664B (en) Method for preparing hydroxy apatite biological ceramic coating containing fluorine
CN103418030A (en) Osteoid structure biological ceramic composite material with adjustable coating thickness
Choy et al. In situ synthesis of osteoconductive biphasic ceramic coatings on Ti6Al4V substrate by laser-microwave hybridization
de Almeida Filho et al. Bioactive coating on titanium implants modified by Nd: YVO4 laser
Su et al. In-situ synthesis and characterization of calcium phosphate coatings on rapidly solidified zirconia toughened alumina eutectic bioceramics by laser cladding
Xiao et al. Bioactive glass-ceramic coatings synthesized by the liquid precursor plasma spraying process
Galindo-Valdes et al. Laser deposition of bioactive coatings by in situ synthesis of pseudowollastonite on Ti6Al4V alloy
Verné et al. Bioverit® I base glass/Ti particulate biocomposite:“in situ” vacuum plasma spray deposition
Lv et al. Phase evolution in calcium phosphate coatings obtained by in situ laser cladding
Loginov et al. Sintered Ti–Ti3P–CaO electrodes and their application for pulsed electrospark treatment of titanium
Hu et al. In situ synthesis and fabrication of tricalcium phosphate bioceramic coating on commercially pure titanium by laser rapid forming
Roy et al. Laser surface modification of electrophoretically deposited hydroxyapatite coating on titanium
Dos Santos et al. Sol–gel based calcium phosphates coatings deposited on binary Ti–Mo alloys modified by laser beam irradiation for biomaterial/clinical applications
Barabás et al. Fluorhydroxyapatite Coatings Obtained by Flame‐Spraying Deposition

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20090204

Termination date: 20110929