CN1557263A - Teeth correcting wire with surface deposited calcium phosphorus biological ceramic and its preparation method - Google Patents

Teeth correcting wire with surface deposited calcium phosphorus biological ceramic and its preparation method Download PDF

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CN1557263A
CN1557263A CNA2004100139237A CN200410013923A CN1557263A CN 1557263 A CN1557263 A CN 1557263A CN A2004100139237 A CNA2004100139237 A CN A2004100139237A CN 200410013923 A CN200410013923 A CN 200410013923A CN 1557263 A CN1557263 A CN 1557263A
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wire
tooth
calcium phosphate
ion
bionical
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CN1283213C (en
Inventor
储成林
林萍华
浦跃朴
薛小燕
沈刚
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Yangzhou Yahua Biological Technology Development Co Ltd
Southeast University
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Yangzhou Yahua Biological Technology Development Co Ltd
Southeast University
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Abstract

The present invention is one kind of teeth correcting wire with excellent biocompatibility biological Ca-P ceramic coating and its making process. On the metal substrate, is one layer of excellent biocompatibility biological Ca-P ceramic coating in double-layered structure comprising a non-crystal calcium phosphate base layer contacting with the metal substance of the teeth correcting wire and a crystalline bone-like apatite surface layer. The non-crystal calcium phosphate base layer is 1-10 micron thick and the crystalline bone-like apatite surface layer is 10-50 micron thick. The preparation process includes machining the teeth correcting wire of Ni-Ti memory alloy or stainless material; the surface activating treatment of the teeth correcting wire; and two steps of bionic deposition to form the biological Ca-P ceramic layer comprising the non-crystal calcium phosphate base layer and the crystalline bone-like apatite surface layer.

Description

Wire for correcting shape of tooth of surface deposition calcium phosphate bioceramic and preparation method thereof
Technical field
The present invention relates to the wire for correcting shape of tooth of a kind of mouth cavity orthodontic treatment usefulness, particularly relate to the wire for correcting shape of tooth and preparation method thereof that a kind of surface has the calcium phosphate bioceramic coating of good biocompatibility, belong to technical field of medical instruments.
Background technology
The dental appliance that is used for the mouth cavity orthodontic treatment mainly comprises bracket, buccal tube and wire for correcting shape of tooth etc., and wherein, wire for correcting shape of tooth is a critical component, run through bracket and need the tooth of shaping round all.Wire for correcting shape of tooth is usually with preparations such as Ultimum Ti or stainless steel materials, although these materials have good decay resistance, but because the orthodontic treatment cycle is longer, generally more than half a year, in the orthodontic treatment process because of the corrosiveness of oral environment to wire for correcting shape of tooth, have metal ion and from orthopedic wire, constantly discharge, cause halitosis.In addition, wire for correcting shape of tooth generally is placed in the exposure position in the oral cavity, its outward appearance is the color of metal itself or surface film oxide usually, be metallic luster or lead, with the white of tooth very big contrast is arranged visually, life-time service to the patient particularly the face appearance of female patient bring bigger influence, this can bring mental pressure to the patient undoubtedly.
The main inanimate matter of tooth is calcium phosphate, hydroxyapatite, mix CO 3 2-Ca-P ceramics such as ionic osteoid apatite and OCP, if at wire for correcting shape of tooth surface-coated one deck calcium phosphate bioceramic, can reduce the stripping of wire for correcting shape of tooth metal ion under oral environment, improve biocompatibility and the decay resistance of orthopedic wire in the oral cavity.Simultaneously, the color and the tooth of Ca-P ceramic are close, can make the wire for correcting shape of tooth outward appearance present ideal cream white.Usually, the Ca-P ceramic coating adopts the plasma spraying method preparation, but the wire for correcting shape of tooth that this method pair cross-section diameter generally is less than 0.5mm is obviously improper, and particularly the high-temperature process of this process can change the memory performance and the super-elasticity of Ultimum Ti orthopedic wire.Therefore, the ideal wire for correcting shape of tooth that does not also have the surface to have the calcium phosphate bioceramic coating at present can be used.
Summary of the invention
Technical problem: the objective of the invention is at present wire for correcting shape of tooth above shortcomings, wire for correcting shape of tooth of a kind of surface deposition calcium phosphate bioceramic and preparation method thereof is provided, this wire for correcting shape of tooth outward appearance is ideal cream white, its surperficial calcium phosphate bioceramic coating has ideal double-decker, can effectively reduce the stripping of metal ion in the orthopedic wire under the oral environment, improve biocompatibility and the decay resistance of orthopedic wire in the oral cavity.
Technical scheme; The present invention is realized by the following technical programs:
The wire for correcting shape of tooth of surface deposition calcium phosphate bioceramic, its metal base surface have the good calcium phosphate bioceramic coating of one deck biocompatibility, and outward appearance is cream white.The calcium phosphate bioceramic coating of being addressed has double-decker, is made up of calcium phosphate amorphous underlayer that contacts with the wire for correcting shape of tooth metallic matrix and osteoid apatite crystalline phase surface layer, and calcium phosphate amorphous underlayer thickness is 1-10 μ m; Osteoid apatite crystalline phase surface layer thickness is 10-50 μ m.
The preparation method of the wire for correcting shape of tooth of surface deposition calcium phosphate bioceramic of the present invention comprises the steps:
1) at first processes wire for correcting shape of tooth with Ultimum Ti or stainless steel material;
2) wire for correcting shape of tooth is carried out surface activation process, go on foot bionical deposition processes by two then, obtain the calcium phosphate bioceramic layer of forming successively by calcium phosphate amorphous underlayer and osteoid apatite crystalline phase surface layer on the wire for correcting shape of tooth surface;
Described in the above-mentioned preparation method and wire for correcting shape of tooth make with Ultimum Ti or rustless steel, its version can be any or form that other is new of the prior art, the present invention repeats no more.
The bionics method for preparation of calcium phosphate bioceramic coating of the present invention is simple, need not special equipment, whole process is all finished at a lower temperature, is specially adapted to the Ultimum Ti wire for correcting shape of tooth, and the memory performance and the super-elasticity of Ultimum Ti orthopedic wire are not had influence.
It is the ebullient H of 10-60% that described surface activation process adopts concentration 2O 2Aqueous solution, the processing time is 10-90 minute, take out flushing after, be immersed in temperature again and be 30-80 ℃, concentration and be in the NaOH aqueous solution of 1-10M 6-48 hour.
Described bionical deposition processes of two steps comprises the steps:
1) the bionical calcifying solution A of preparation: bionical calcifying solution A presses the active constituent content of ionometer:
Sodium ion 500-850mM, magnesium ion 4.5-6.0mM, calcium ion 10.0-13.5mM, chloride ion 500-800mM, phosphoric acid hydrogen radical ion 4.0-6.0mM, bicarbonate ion 15.0-30.0mM;
2) the bionical calcifying solution B of preparation: bionical calcifying solution B presses the active constituent content of ionometer:
Sodium ion 100.0-180.0mM, potassium ion 4.0-5.5mM, magnesium ion 3.0-4.5mM, calcium ion 2.0-3.5mM, chloride ion 80.0-150.0mM, phosphoric acid hydrogen radical ion 0.5-1.5mM, bicarbonate ion 6.5-12.0mM, sulfate ion 0.5-1.0mM;
3) the bionical deposition processes of calcium phosphate amorphous underlayer: the wire for correcting shape of tooth immersion temperature that surface activation process is crossed is among the 10-30 ℃ of bionical calcifying solution A, under stirring condition, take out after bionical deposition processes 12-36 hour, clean, drying, wire for correcting shape of tooth surface obtain the calcium phosphate amorphous layer of thickness 1-10 μ m, densification;
4) the bionical deposition processes of osteoid apatite crystalline phase surface layer: the wire for correcting shape of tooth immersion temperature that the surface is had the calcium phosphate amorphous layer is among the 30-50 ℃ of molten B of bionical calcification, took out in bionical deposition processes 12-72 hour, clean, drying, further deposit thickness is 10-50 μ m, porous osteoid apatite crystalline phase surface layer on the wire for correcting shape of tooth surface phosphoric acid calcium amorphous underlayer.
Beneficial effect: advantage of the present invention and good effect are as follows:
(1) the wire for correcting shape of tooth outward appearance of surface deposition calcium phosphate bioceramic of the present invention presents ideal cream white, its surperficial calcium phosphate bioceramic coating can effectively reduce the stripping of metal ion in the orthopedic wire under the oral environment, improves the biocompatibility and the decay resistance of orthopedic wire.
(2) the calcium phosphate bioceramic coating on wire for correcting shape of tooth of the present invention surface has ideal double-decker: calcium phosphorus amorphous underlayer is thin and fine and close, combine firmly with metallic matrix, and can be used as the deposition growing of " nucleus basal plane " promotion osteoid apatite crystalline phase surface layer.The bond strength height of this calcium phosphate bioceramic coating and orthopedic wire metallic matrix.
(3) bionics method for preparation of calcium phosphate bioceramic coating of the present invention is simple, need not special equipment, whole process is all finished under lower temperature, is specially adapted to the Ultimum Ti wire for correcting shape of tooth, and the memory performance and the super-elasticity of Ultimum Ti orthopedic wire are not had influence.
The instantiation mode
Embodiment 1
The Ultimum Ti wire for correcting shape of tooth of surface deposition calcium phosphate bioceramic, on the result, the metal base surface of this Ultimum Ti wire for correcting shape of tooth has the good calcium phosphate bioceramic coating of one deck biocompatibility, and outward appearance is cream white.The calcium phosphate bioceramic coating has double-decker, is made up of calcium phosphate amorphous underlayer that contacts with nickel-titanium memory alloy-based body and osteoid apatite crystalline phase surface layer, and calcium phosphate amorphous underlayer thickness is 1.5-2.0 μ m; The osteoid apatite surface layer thickness is 15-20 μ m.Its preparation process is as follows:
1) at first processes wire for correcting shape of tooth with medical Ultimum Ti;
2) wire for correcting shape of tooth surface activation process: after the Ultimum Ti wire for correcting shape of tooth used acetone, 70% ethanol, distilled water ultrasonic cleaning successively, adopting concentration was 20% ebullient H 2O 2Aqueous solution is handled, and the processing time is 45 minutes, take out flushing after, be immersed in temperature again and be in 30-50 ℃, the NaOH aqueous solution of 4M after 24-36 hour, take out distilled water flushing, 70 ℃ of dryings.
3) the bionical deposition processes of calcium phosphate amorphous underlayer: the wire for correcting shape of tooth immersion temperature that surface activation process is crossed is that bionical calcifying solution A is among 20 ℃ of bionical calcifying solution A by the active constituent content of ionometer: sodium ion 610mM, magnesium ion 4.5mM, calcium ion 12.5mM, chloride ion 610.0mM, phosphoric acid hydrogen radical ion 5.0mM, bicarbonate ion 18.0mM.Bionical calcifying solution A employing magnetic stirring apparatus stirs, takes out after bionical deposition processes 12-24 hour, and the distilled water ultrasonic cleaning, drying at room temperature, the wire for correcting shape of tooth surface obtains the calcium phosphate amorphous layer of thickness 1.5-2.0 μ m, densification.
4) the bionical deposition processes of osteoid apatite crystalline phase surface layer: the wire for correcting shape of tooth immersion temperature that the surface is had the calcium phosphate amorphous layer is that bionical calcifying solution B presses the active constituent content of ionometer among 30 ℃ of bionical calcifying solution B: sodium ion 120.0mM, potassium ion 5.0mM, magnesium ion 3.5mM, calcium ion 2.5mM, chloride ion 120.0mM, phosphoric acid hydrogen radical ion 1.0mM, bicarbonate ion 11.0mM, sulfate ion 0.5mM.Took out in bionical deposition processes 12-36 hour, the distilled water ultrasonic cleaning, drying at room temperature, further deposit thickness is 15-20 μ m, porous osteoid apatite crystalline phase surface layer on the wire for correcting shape of tooth surface phosphoric acid calcium amorphous underlayer.
5) last, the cleaning of Ultimum Ti wire for correcting shape of tooth, the sterilization, standby that will have the calcium phosphate bioceramic coating.
Embodiment 2
A kind of rustless steel wire for correcting shape of tooth of surface deposition calcium phosphate bioceramic, on the result, the metal base surface of this rustless steel wire for correcting shape of tooth has the good calcium phosphate bioceramic coating of one deck biocompatibility, and outward appearance is cream white.The calcium phosphate bioceramic coating has double-decker, is made up of calcium phosphate amorphous underlayer that contacts with stainless steel base and osteoid apatite crystalline phase surface layer, and calcium phosphate amorphous underlayer thickness is 7.5-9.0 μ m; The osteoid apatite surface layer thickness is 40-50 μ m.Its preparation process is as follows:
1) at first uses the good wire for correcting shape of tooth of medical stainless steel materials processing;
2) wire for correcting shape of tooth surface activation process: after the rustless steel wire for correcting shape of tooth used acetone, 70% ethanol, distilled water ultrasonic cleaning successively, adopting concentration was 50% ebullient H 2O 2Aqueous solution is handled, and the processing time is 60 minutes, take out flushing after, be immersed in temperature again and be 30-40 ℃, concentration and be in the NaOH aqueous solution of 2M 12-24 hour.
3) the bionical deposition processes of calcium phosphate amorphous underlayer: the wire for correcting shape of tooth immersion temperature that surface activation process is crossed is that bionical calcifying solution A is among 30 ℃ of bionical calcifying solution A by the active constituent content of ionometer: sodium ion 610mM, magnesium ion 4.5mM, calcium ion 12.5mM, chloride ion 610.0mM, phosphoric acid hydrogen radical ion 5.0mM, bicarbonate ion 18.0mM.Bionical calcifying solution A employing magnetic stirring apparatus stirs, takes out after bionical deposition processes 30-36 hour, and the distilled water ultrasonic cleaning, drying at room temperature, the wire for correcting shape of tooth surface obtains the calcium phosphate amorphous layer of thickness 7.5-9.0 μ m, densification.
4) the bionical deposition processes of osteoid apatite crystalline phase surface layer: the wire for correcting shape of tooth immersion temperature that the surface is had the calcium phosphate amorphous layer is that bionical calcifying solution B presses the active constituent content of ionometer among 50 ℃ of molten B of bionical calcification: sodium ion 120.0mM, potassium ion 5.0mM, magnesium ion 3.5mM, calcium ion 2.5mM, chloride ion 120.0mM, phosphoric acid hydrogen radical ion 1.0mM, bicarbonate ion 11.0mM, sulfate ion 0.5mM.Took out in bionical deposition processes 64-72 hour, the distilled water ultrasonic cleaning, drying at room temperature, further deposit thickness is 40-50 μ m, porous osteoid apatite crystalline phase surface layer on the wire for correcting shape of tooth surface phosphoric acid calcium amorphous underlayer.
5) last, the cleaning of rustless steel wire for correcting shape of tooth, the sterilization, standby that will have the calcium phosphate bioceramic coating.
Embodiment 3
A kind of Ultimum Ti wire for correcting shape of tooth of surface deposition calcium phosphate bioceramic, on the result, the metal base surface of this Ultimum Ti wire for correcting shape of tooth has the good calcium phosphate bioceramic coating of one deck biocompatibility, and outward appearance is cream white.The calcium phosphate bioceramic coating has double-decker, is made up of calcium phosphate amorphous underlayer that contacts with nickel-titanium memory alloy-based body and osteoid apatite crystalline phase surface layer, and calcium phosphate amorphous underlayer thickness is 7.5-9.0 μ m; The osteoid apatite surface layer thickness is 40-50 μ m.Its preparation process is as follows:
1) at first processes wire for correcting shape of tooth with medical Ultimum Ti;
2) wire for correcting shape of tooth surface activation process: after the Ultimum Ti wire for correcting shape of tooth used acetone, 70% ethanol, distilled water ultrasonic cleaning successively, adopting concentration was 30% ebullient H 2O 2Aqueous solution is handled, and the processing time is 90 minutes, take out flushing after, be immersed in temperature again and be 60-70 ℃, concentration and be in the NaOH aqueous solution of 8M 24-36 hour.
3) the bionical deposition processes of calcium phosphate amorphous underlayer: the wire for correcting shape of tooth immersion temperature that surface activation process is crossed is that bionical calcifying solution A is among 30 ℃ of bionical calcifying solution A by the active constituent content of ionometer: sodium ion 610mM, magnesium ion 4.5mM, calcium ion 12.5mM, chloride ion 610.0mM, phosphoric acid hydrogen radical ion 5.0mM, bicarbonate ion 18.0mM.Bionical calcifying solution A employing magnetic stirring apparatus stirs, takes out after bionical deposition processes 24-36 hour, and the distilled water ultrasonic cleaning, drying at room temperature, the wire for correcting shape of tooth surface obtains the calcium phosphate amorphous layer of thickness 7.5-9.0 μ m, densification.
4) the bionical deposition processes of osteoid apatite crystalline phase surface layer: the wire for correcting shape of tooth immersion temperature that the surface is had the calcium phosphate amorphous layer is that bionical calcifying solution B presses the active constituent content of ionometer among 50 ℃ of molten B of bionical calcification: sodium ion 120.0mM, potassium ion 5.0mM, magnesium ion 3.5mM, calcium ion 2.5mM, chloride ion 120.0mM, phosphoric acid hydrogen radical ion 1.0mM, bicarbonate ion 11.0mM, sulfate ion 0.5mM.Took out in bionical deposition processes 48-64 hour, the distilled water ultrasonic cleaning, drying at room temperature, further deposit thickness is 40-50 μ m, porous osteoid apatite crystalline phase surface layer on the wire for correcting shape of tooth surface phosphoric acid calcium amorphous underlayer.
5) last, the cleaning of Ultimum Ti wire for correcting shape of tooth, the sterilization, standby that will have the calcium phosphate bioceramic coating.
Obviously, the above embodiment of the present invention only is in order to clearly demonstrate example of the present invention, and is not to be qualification to embodiments of the present invention.For those of ordinary skill in the field; also can make other changes in different forms on the basis of the above description; here need not also can't give all embodiments exhaustive, and these belong to conspicuous variation or the change that spirit of the present invention amplified out and still are in protection scope of the present invention.

Claims (4)

1. the wire for correcting shape of tooth of a surface deposition calcium phosphate bioceramic, the metal base surface that it is characterized in that wire for correcting shape of tooth has the good calcium phosphate bioceramic coating of one deck biocompatibility, described calcium phosphate bioceramic coating has double-decker, promptly be made up of calcium phosphate amorphous underlayer that contacts with the wire for correcting shape of tooth metallic matrix and osteoid apatite crystalline phase surface layer, calcium phosphate amorphous underlayer thickness is 1-10 μ m; Osteoid apatite crystalline phase surface layer thickness is 10-50 μ m.
2. the preparation method of the wire for correcting shape of tooth of a surface deposition calcium phosphate bioceramic as claimed in claim 1 is characterized in that the method for preparing is:
1) at first processes wire for correcting shape of tooth with Ultimum Ti or stainless steel material;
2) wire for correcting shape of tooth is carried out surface activation process, go on foot bionical deposition processes by two then, obtain the calcium phosphate bioceramic layer of forming successively by calcium phosphate amorphous underlayer and osteoid apatite crystalline phase surface layer on the wire for correcting shape of tooth surface;
3. the preparation method of the wire for correcting shape of tooth of surface deposition calcium phosphate bioceramic as claimed in claim 2 is characterized in that bionical deposition processes of two steps comprises the steps:
1) the bionical calcifying solution A of preparation: bionical calcifying solution A presses the active constituent content of ionometer:
Sodium ion 500-850mM, magnesium ion 4.5-6.0mM, calcium ion 10.0-13.5mM, chloride ion 500-800mM, phosphoric acid hydrogen radical ion 4.0-6.0mM, bicarbonate ion 15.0-30.0mM;
2) the bionical calcifying solution B of preparation: bionical calcifying solution B presses the active constituent content of ionometer:
Sodium ion 100.0-180.0mM, potassium ion 4.0-5.5mM, magnesium ion 3.0-4.5mM, calcium ion 2.0-3.5mM, chloride ion 80.0-150.0mM, phosphoric acid hydrogen radical ion 0.5-1.5mM, bicarbonate ion 6.5-12.0mM, sulfate ion 0.5-1.0mM;
3) the bionical deposition processes of calcium phosphate amorphous underlayer: the wire for correcting shape of tooth immersion temperature that surface activation process is crossed is among the 10-30 ℃ of bionical calcifying solution A, under stirring condition, take out after bionical deposition processes 12-36 hour, clean, drying, the wire for correcting shape of tooth surface obtains the calcium phosphate amorphous layer of thickness 1-10 μ m;
4) the bionical deposition processes of osteoid apatite crystalline phase surface layer: the wire for correcting shape of tooth immersion temperature that the surface is had the calcium phosphate amorphous layer is among the 30-50 ℃ of molten B of bionical calcification, took out in bionical deposition processes 12-72 hour, clean, drying, further deposit thickness is the osteoid apatite crystalline phase surface layer of 10-50 μ m on the wire for correcting shape of tooth surface phosphoric acid calcium amorphous underlayer.
4. the preparation method of the wire for correcting shape of tooth of surface deposition calcium phosphate bioceramic as claimed in claim 2 is characterized in that it is the ebullient H of 10-60% that surface activation process adopts concentration 2O 2Aqueous solution, the processing time is 10-90 minute, take out flushing after, be immersed in temperature again and be 30-80 ℃, concentration and be in the NaOH aqueous solution of 1-10M 6-48 hour.
CN 200410013923 2004-01-16 2004-01-16 Teeth correcting wire with surface deposited calcium phosphorus biological ceramic and its preparation method Expired - Fee Related CN1283213C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103572200A (en) * 2013-11-13 2014-02-12 南京医科大学 Salt bath nitrocarburizing modifying method for surface of orthodontics arch wire
CN106310393A (en) * 2016-08-05 2017-01-11 四川北极光口腔医疗器械有限公司 Orthopedic wire for correcting teeth
CN111603607A (en) * 2020-05-21 2020-09-01 武汉理工大学 Fibroin-calcium hydrogen phosphate compound obtained by induction with fibroin as template and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103572200A (en) * 2013-11-13 2014-02-12 南京医科大学 Salt bath nitrocarburizing modifying method for surface of orthodontics arch wire
CN106310393A (en) * 2016-08-05 2017-01-11 四川北极光口腔医疗器械有限公司 Orthopedic wire for correcting teeth
CN111603607A (en) * 2020-05-21 2020-09-01 武汉理工大学 Fibroin-calcium hydrogen phosphate compound obtained by induction with fibroin as template and preparation method thereof
CN111603607B (en) * 2020-05-21 2021-01-05 武汉理工大学 Fibroin-calcium hydrogen phosphate compound obtained by induction with fibroin as template and preparation method thereof

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