CN101358370A - Electrochemical method for preparing hydroxylapatite granule thin coating on metallo-implantation surface - Google Patents

Electrochemical method for preparing hydroxylapatite granule thin coating on metallo-implantation surface Download PDF

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Publication number
CN101358370A
CN101358370A CNA2008100636011A CN200810063601A CN101358370A CN 101358370 A CN101358370 A CN 101358370A CN A2008100636011 A CNA2008100636011 A CN A2008100636011A CN 200810063601 A CN200810063601 A CN 200810063601A CN 101358370 A CN101358370 A CN 101358370A
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China
Prior art keywords
implant
metal
electrochemical
electrolytic solution
metal implant
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CNA2008100636011A
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Chinese (zh)
Inventor
王小祥
江勇
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Zhejiang University ZJU
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Zhejiang University ZJU
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Priority to CNA2008100636011A priority Critical patent/CN101358370A/en
Publication of CN101358370A publication Critical patent/CN101358370A/en
Pending legal-status Critical Current

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Abstract

The invention discloses an electrochemical method for preparing a hydroxylapatite particle thin coating on the surface of a metal implant, which comprises the following steps: electrolyte is put into a container equipped with a constant temperature heating system and heated to be 30 DEG C to 95 DEG C, and then the temperature is kept; platinum is taken as the anode and evenly distributed around the container, and the metal implant is taken as the cathode, put in the middle of the container and totally soaked in the electrolyte; DC voltage of 2V to 4V is added between the anode and the cathode, the surface of the metal implant has cathode reduction reaction, the pH value is increased and the supersaturation degree of the hydroxylapatite is also increased, so as to crystalize on the surface of titanium; after 0.5h to 5h of deposition, a layer of hydroxylapatite particle thin coating which can be excellently adhered to the matrix metal is formed on the surface of the implant. The hydroxylapatite particle thin coating prepared by the method is thin and even, is not easy to fall off during the operation process, can guide the bone tissue to quickly grow to the surface after being implanted into the bone tissue, so as to greatly improve the clinical success rate of the implant.

Description

Electrochemical method at metal implant surface preparation hydroapatite particles shallow layer
Technical field
The present invention relates to a kind of method for preparing the hydroapatite particles shallow layer, especially, relate to the method that a kind of method that adopts electrochemical electrolysis in the calcium that contains the citrate ion additive, phosphate radical solution makes metal implant surface fast deposition hydroapatite particles shallow layer.
Background technology
Metal implant is widely used in orthopaedics, Stomatological Department field, as joint prosthesis and tooth implant.The metal implant implant surgery can successful key be behind the implant implantable bone tissue can be apace to the implant surface growth and with surperficial mortise.The titanium or titanium alloy implant that uses healing growth for a long time at present could form securely with the surrounding bone tissue and combine, and has brought risk for the success of implant.Therefore, produce at the surface treatment method miscellaneous of this problem, purpose all is to quicken combining of implant and osseous tissue thereupon.The 60 to 70's of last century is mainly adopted hydroxyapatite coating layer in plasma spraying.Because spraying process must experience the high temperature more than 10000 ℃, there is very big interfacial stress between phase structure complexity, coating and the matrix of coating, in use coating and metal interface bonding force are not enough, and report is arranged when breaking away from the plantation failure that causes because of coating.Since the last century the nineties both at home and abroad study emphasis do not need the hydro-thermal of pyroprocess synthetic, collosol and gel, electrolysis or electrophoresis and biomimetic method prepare hydroxyapatite coating layer.Hydroxyapatite coating layer with these method preparations is greatly improved on composition is even.Wherein the electrochemical electrolysis method is a kind of coating technology fast and effectively, generally all uses Ca (NO 3) 2, NH 4(or Na) H 2PO 4As calcium, phosphorus source, add a certain amount of NH again 4(or Na) NO 3To improve the electroconductibility of electrolytic solution.As negative electrode, platinized platinum is as anode with the titanium metal implant, behind in addition certain volts DS, and surface of metal titanium generation evolving hydrogen reaction, the pH value raises, and the hydroxyapatite degree of supersaturation increases, thus crystallization is in surface of metal titanium.But the coating that obtains in the electrolytic solution that adopts in existing disclosed documents and materials exists that hydroapatite particles is big and low with the matrix metal bonding force, thick coating and shortcoming such as wayward, therefore never obtains the clinical application of reality.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of electrochemical method at metal implant surface preparation hydroapatite particles shallow layer is provided, make in the electrochemical electrolysis process metal titanium and titanium alloy surface fast growth obtain the hydroapatite particles coating, coating thin and with matrix metal bonding force height.
The objective of the invention is to be achieved through the following technical solutions: a kind of electrochemical method at metal implant surface preparation hydroapatite particles shallow layer, it is characterized in that, may further comprise the steps:
(1) electrolytic solution of in the container of having equipped the thermostatically heating system, packing into, and electrolytic solution is heated to 30~95 ℃ of constant temperature;
(2) platinum is evenly distributed on around the container as anode, metal implant places in the middle of the container as negative electrode, be immersed in the electrolytic solution fully, add volts DS 2~4V between the two poles of the earth, cathodic reduction reaction takes place in the metal implant surface, the pH value raises, and the hydroxyapatite degree of supersaturation increases, thereby crystallization is in surface of metal titanium;
(3) through after 0.5~5 hour deposition, can form one deck at implant surfaces and combine hydroapatite particles shallow layer good, that approach with matrix metal;
(4) take out cleaning, remove the electrolytic solution of surface attachment, dry in 60~100 ℃ loft drier.
Further, described electrolytic solution composition constitutes element, additive and conductive agent three parts by Hap to be formed, and its pH value is 5~12; It is Ca that described Hap constitutes element 2+And PO 4 3-, their concentration is respectively 0.3~6.0mM/L and 0.18~3.6mM/L, and Ca 2+/ PO 4 3-=1.67; Described additive is Citrate trianion C 6H 5O 7 3-, its concentration is 0.3~60mM/L, and C 6H 5O 7 3-/ Ca 2+=1~10; Described conductive agent is lactic acid salt C 3H 5O 3 -, nitrate NO 3 -Or acetate CH 3COO -, concentration is 0.01~1M/L.
The present invention has following technique effect: with method provided by the invention at the hydroxyapatite coating layer thin thickness of implant surfaces preparation and evenly, difficult drop-off in operative process, the energy inducting osseous tissue is fast to surface growth behind the implantable bone tissue, thereby improve early stage bonding strength, 0.5-1 a year back coating can be absorbed fully, improves the clinical success rate of implant greatly.
Description of drawings
Fig. 1 obtains the synoptic diagram of uniform hydroxylapatite particle shallow layer on the metal titanium surface for the embodiment of the invention 1;
Fig. 2 is 10 times of enlarged views of Fig. 1;
Fig. 3 obtains the synoptic diagram of uniform hydroxylapatite particle shallow layer on the metal titanium surface for the embodiment of the invention 2;
Fig. 4 is 10 times of enlarged views of Fig. 3.
Embodiment
The present invention adds a certain amount of citrate ion in traditional calcium, phosphate anion electrolytic solution, the effect of citrate ion is the bonding force that improves hydroapatite particles and matrix metal effectively, make the thin thickness of coating and be easy to control, the size of hydroapatite particles descends, shape becomes coniform or needle-like, the hydroapatite particles surface roughening that becomes.
The electrolytic solution composition constitutes element, additive and conductive agent three parts by effect by Hap to be formed, and their concrete content is as follows:
Hap constitutes element: Ca 2+0.3~6.0mM/L,
PO 4 3-0.18~3.6mM/L (making Ca/P=1.67),
pH=5~12;
Additive: Citrate trianion C 6H 5O 7 3-0.3~60mM/L,
(make C 6H 5O 7 3-/ Ca 2+=1-10),
Conductive agent: lactic acid salt C 3H 5O 3 -, or nitrate NO 3 -, or acetate CH 3COO -
0.01~1M/L。
By above-mentioned concentration requirement analytically pure all ingredients is dissolved in the distilled water one by one, with ammoniacal liquor the pH value of solution is transferred at last and require numerical value.The electrolytic solution of in high-quality stainless steel that is equipped with the thermostatically heating system or pure high score container of material, packing into, and electrolytic solution is heated to 30~95 ℃ of constant temperature, platinum is evenly distributed on around the container as anode, metal implant places as negative electrode in the middle of the container, is immersed in fully in the electrolytic solution, adds volts DS 2~4V between the two poles of the earth, cathodic reduction reaction takes place in the metal implant surface, the pH value raises, and the hydroxyapatite degree of supersaturation increases, thereby crystallization is in surface of metal titanium.Through after 0.5~5 hour deposition, can form one deck at implant surfaces and combine hydroxyapatite coating layer good, that approach with matrix metal, coating is made of column, taper and acicular hydroapatite particles.Take out to clean and remove the electrolytic solution of surface attachment, in 60~100 ℃ loft drier, promptly finish whole coating preparation process after the drying.
Describe embodiments of the invention below with reference to the accompanying drawings in detail, it is more obvious that purpose of the present invention and effect will become.
Embodiment 1
Bath composition:
Hap constitutes element: Ca (NO 3) 2---0.3mM/L,
NH 4H 2PO 4---0.18mM/L,
pH=5;
Additive: Na 3C 6H 5O 72H 2O---0.3mM/L
Conductive agent: NaNO 3---0.01M/L
Electrolyte temperature: 30 ℃
Depositing time: 0.5 hour
Deposition voltage: 2V
Obtain uniform hydroxylapatite particle shallow layer on the metal titanium surface, the Hap particle is coniform, and diameter reduces from bottom to top gradually, the about 50nm of top diameter, and the about 150nm of length, as shown in Figures 1 and 2.
Embodiment 2
Bath composition:
Hap constitutes element: C 6H 10CaO 6---6mM/L,
NH 4H 2PO 4---3.6mM/L,
pH=12;
Additive: Na 3C 6H 5O 72H 2O---60mM/L
Conductive agent: C 3H 5NaO 35H 2O---1M/L
Electrolyte temperature: 95 ℃
Depositing time: 5 hours
Deposition voltage: 4V
Above-mentioned bath composition is made of the physiology ion fully, has got rid of nitrate ion (NO in the example 1 3 -) disadvantageous effect to biocompatibility that may bring.Obtain uniform hydroxylapatite particle shallow layer on the metal titanium surface, the Hap particle is irregular column, the about 150nm of diameter, and surface irregularity is shown in accompanying drawing 3 and accompanying drawing 4.
The foregoing description is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.

Claims (5)

1. the electrochemical method at metal implant surface preparation hydroapatite particles shallow layer is characterized in that, may further comprise the steps:
(1) electrolytic solution of in the container of having equipped the thermostatically heating system, packing into, and electrolytic solution is heated to 30~95 ℃ of constant temperature.
(2) platinum is evenly distributed on around the container as anode, metal implant places in the middle of the container as negative electrode, be immersed in the electrolytic solution fully, add volts DS 2~4V between the two poles of the earth, cathodic reduction reaction takes place in the metal implant surface, the pH value raises, and the hydroxyapatite degree of supersaturation increases, thereby crystallization is in surface of metal titanium.
(3) through after 0.5~5 hour deposition, can form one deck at implant surfaces and combine hydroapatite particles shallow layer good, that approach with matrix metal.
(4) take out cleaning, remove the electrolytic solution of surface attachment, dry in 60~100 ℃ loft drier.
2. the electrochemical method at metal implant surface preparation hydroapatite particles shallow layer according to claim 1 is characterized in that, described electrolytic solution composition constitutes element, additive and conductive agent three parts by Hap to be formed, and its pH value is 5~12.
3. the electrochemical method at metal implant surface preparation hydroapatite particles shallow layer according to claim 2 is characterized in that, it is Ca that described Hap constitutes element 2+And PO 4 3-, their concentration is respectively 0.3~6.0mM/L and 0.18~3.6mM/L, and Ca 2+/ PO 4 3-=1.67.
4. the electrochemical method at metal implant surface preparation hydroapatite particles shallow layer according to claim 2 is characterized in that described additive is Citrate trianion C 6H 5O 7 3-, its concentration is 0.3~60mM/L, and C 6H 5O 7 3-/ Ca 2+=1~10.
5. the electrochemical method at metal implant surface preparation hydroapatite particles shallow layer according to claim 2 is characterized in that described conductive agent is lactic acid salt C 3H 5O 3 -, nitrate NO 3 -Or acetate CH 3COO -, concentration is 0.01~1M/L.
CNA2008100636011A 2008-06-25 2008-06-25 Electrochemical method for preparing hydroxylapatite granule thin coating on metallo-implantation surface Pending CN101358370A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102286764A (en) * 2011-07-01 2011-12-21 浙江大学 Method for preparing periodical absorbable Hyaluronic Acid/acyl carrier protein (HA/ACP) composite coating on titanium implant surface
CN102492974A (en) * 2011-12-30 2012-06-13 浙江大学 Method for preparing degradable magnesium-doped amorphous calcium phosphate coating on surface of titanium implant
CN102899698A (en) * 2012-09-29 2013-01-30 浙江大学 Electrochemical method for preparing hydroxyapatite dendritic micro nano composite coating on surface of metallic titanium
CN103014801A (en) * 2011-09-20 2013-04-03 天津市玄真生物医药科技发展有限公司 Electrodeposition preparation method for biomedical titanium base hydroxyapatite composite material
CN103088383A (en) * 2011-11-04 2013-05-08 电子科技大学 Electrochemical method for preparing citric acid-hydroxyapatite/zirconia transition coating on surface of biomedical titanium
CN105624753A (en) * 2015-12-24 2016-06-01 广州中国科学院先进技术研究所 Technology for uniform deposition of HA (hydroxyapatite) coatings on medical porous titanium and titanium alloy

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102286764A (en) * 2011-07-01 2011-12-21 浙江大学 Method for preparing periodical absorbable Hyaluronic Acid/acyl carrier protein (HA/ACP) composite coating on titanium implant surface
CN103014801A (en) * 2011-09-20 2013-04-03 天津市玄真生物医药科技发展有限公司 Electrodeposition preparation method for biomedical titanium base hydroxyapatite composite material
CN103088383A (en) * 2011-11-04 2013-05-08 电子科技大学 Electrochemical method for preparing citric acid-hydroxyapatite/zirconia transition coating on surface of biomedical titanium
CN102492974A (en) * 2011-12-30 2012-06-13 浙江大学 Method for preparing degradable magnesium-doped amorphous calcium phosphate coating on surface of titanium implant
CN102899698A (en) * 2012-09-29 2013-01-30 浙江大学 Electrochemical method for preparing hydroxyapatite dendritic micro nano composite coating on surface of metallic titanium
CN105624753A (en) * 2015-12-24 2016-06-01 广州中国科学院先进技术研究所 Technology for uniform deposition of HA (hydroxyapatite) coatings on medical porous titanium and titanium alloy
CN105624753B (en) * 2015-12-24 2018-08-07 广州中国科学院先进技术研究所 A kind of medical porous titanium or titanium alloy uniform deposition hydroxyapatite coating layer technique

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