CN103751841A - Modified medical titanium metal material and preparation method thereof - Google Patents
Modified medical titanium metal material and preparation method thereof Download PDFInfo
- Publication number
- CN103751841A CN103751841A CN201410001001.8A CN201410001001A CN103751841A CN 103751841 A CN103751841 A CN 103751841A CN 201410001001 A CN201410001001 A CN 201410001001A CN 103751841 A CN103751841 A CN 103751841A
- Authority
- CN
- China
- Prior art keywords
- titanium metal
- medical titanium
- titanium
- metal material
- double bond
- 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.)
- Granted
Links
Images
Abstract
The invention discloses a modified medical titanium metal material and a preparation method thereof. The modified medical titanium metal material comprises a medical titanium metal, wherein a bioactive coating is applied to the surface of the medical titanium metal, and is formed by performing surface hydroxylation on the medical titanium metal, introducing silane coupling agent molecules with terminal double bonds and covalently grafting polyaniline in an in-situ polymerization manner. The modified medical titanium metal material has excellent biocompatibility, bacteriostasis and stability because the bioactive coating is applied to the surface of the medical titanium metal, and has an excellent bacteriostatic capability to common strains, such as escherichia coli and staphylococcus aureus, with the bacteriostasis rate of over 90 percent; the bioactive coating is in chemical bonding with a matrix material, is high in bonding strength and can not easily fall off, so that the stability of an implant can be improved, and the service life of the implant can be prolonged.
Description
Technical field
The invention belongs to medical titanium metal material technical field, be specifically related to a kind of modification medical titanium metal material, also relate to a kind of preparation method of modification medical titanium metal material simultaneously.
Background technology
Titanium and titanium alloy with its good biocompatibility, the elastic modelling quantity close with osseous tissue and under biotic environment good corrosion resistance, aspect artificial bone substitute materials, obtained broad research and application clinically.But titanium metal material belongs to bio-inert material in essence, itself does not possess biological activity, as not forming strong chemical synostosis between implant and osseous tissue, after life-time service, can have loosening phenomenon; In implantation process, implant may be brought the antibacterial of surrounding in addition, thereby causes the postoperative infection such as osteomyelitis.For merging at the interface of improving between implant and osseous tissue, and improve the biocidal property of implant, titanium and titanium alloy are carried out to surface modification and become one of current study hotspot of embedded material.
In prior art, improve the bioactive method of titanium and alloy surface thereof and be mainly to adopt and singly plant or multiplely there is bioactive inorganic matter to its modifying surface, hydroxyapatite for example, titanium dioxide etc.; General using silver ion, as antimicrobial component, is constructed bioactive coating material or the composite coating material with bacteriostasis, thereby realizes the biological activity combination between bone grafting material and sclerous tissues.These methods can significantly be improved life phase capacitive and the antibiotic property of titanium and alloy material thereof, but the weak problem of ubiquity coating and base material bond strength; Under the combined effect of stressed and body fluid, coating easily comes off and dissolving etc., causes coating to lose efficacy, and then causes that implant lost efficacy.
Summary of the invention
The object of this invention is to provide a kind of modification medical titanium metal material, solve the problem that existing medical titanium metal coating and base material bond strength are weak, coating easily comes off and dissolves.
Second object of the present invention is to provide a kind of preparation method of modification medical titanium metal material.
In order to realize above object, the technical solution adopted in the present invention is: a kind of modification medical titanium metal material, comprise medical titanium metal, described medical titanium metal surface has bioactivity coatings, described bioactivity coatings is that medical titanium metal is carried out after surface hydroxylation, introducing is with the silane coupled agent molecule of terminal double bond, then form by in-situ polymerization covalence graft polyaniline.
Described medical titanium metal is pure titanium or titanium alloy.
A preparation method for above-mentioned modification medical titanium metal material, comprises the following steps:
1) surface hydroxylation: the medical titanium metal after cleaning is placed in to piranha solution and carries out oxidation processes, rear taking-up, washes and dry, and obtains the medical titanium metal of surface hydroxylation;
2) surperficial terminal double bond: the medical titanium metal of step 1) gained surface hydroxylation is placed in to toluene, add the silane coupler with terminal double bond to carry out back flow reaction, after reaction 10～40h, take out, after cleaning, dry, obtain the medical titanium metal of surperficial terminal double bond;
3) Polyaniline Grafted: aniline, Ammonium persulfate. are added in ethanol and make mixed liquor, and the pH that controls mixed liquor is 1～3; By step 2) the medical titanium metal of gained surface terminal double bond is placed in described mixed liquor, under room temperature, reacts 1～24h, takes out, and after cleaning, dries, obtain.
The cleaning of the metal of medical titanium described in step 1) is for processing through polishing, polishing, ultrasonic cleaning successively.
The temperature of oxidation processes described in step 1) is 50～90 ℃, and the time is 2～60min.
Step 2) described in, with the silane coupler of terminal double bond, be any one in γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxysilane, vinyltrimethoxy silane, VTES.
Described is 1～10:100 with the silane coupler of terminal double bond and the volume ratio of toluene.
Described in step 3), in mixed liquor, the volume ratio of ethanol and aniline is 10～100:1.
Described in step 3), in mixed liquor, the addition of described Ammonium persulfate. is that every ml aniline adds 0.05～1g Ammonium persulfate..
Step 2) described in, cleaning is to clean with toluene; Described in step 3), clean is with ethanol, water, to clean to neutral successively.
The method of controlling the pH of mixed liquor in step 3) is to add any one in hydrochloric acid, sulphuric acid or perchloric acid to control.
Polyaniline is a kind of medical macromolecular materials with good biocompatibility, but has again synthetic simple and good biocidal property simultaneously concurrently.
Modification medical titanium metal material of the present invention, medical titanium metal is carried out after surface hydroxylation, introducing is with the silane coupled agent molecule of terminal double bond, again by in-situ polymerization by polyaniline molecule covalence graft in medical titanium metal surface, in medical titanium metal surface, form bioactivity coatings, there is good biocompatibility, biocidal property and stability; Common strain is all had to good bacteriostasis as escherichia coli, staphylococcus aureus, and bacteriostasis rate can reach more than 90%; Bioactivity coatings and base material chemical bonding, bond strength is high, and difficult drop-off has increased the stability of implant, has extended the service life of implant.
The preparation method of modification medical titanium metal material of the present invention, adopt successively the technique of surface hydroxylation, molecular self-assembling terminal double bond and in-situ polymerization covalence graft polyaniline, in medical titanium metal surface, form evenly, the polyaniline molecule of chemical graft, realize the chemical bond of bioactivity coatings and base material; Gained bioactivity coatings good stability, high with base material bond strength, solved the problem that existing medical titanium metal coating and base material bond strength are weak, coating easily comes off and dissolves; Technique is simple, easy to operate, and without special installation, production cost is low, is easy to realize large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of preparation method of the modification medical titanium metal material of embodiment 1, m<50 wherein, n<50;
Fig. 2 is the scanning electron microscope (SEM) photograph of pure titanium sheet;
Fig. 3 is the scanning electron microscope (SEM) photograph of the titanium sheet of embodiment 2 gained surface hydroxylations;
Fig. 4 is the scanning electron microscope (SEM) photograph of the titanium sheet of embodiment 2 gained surface terminal double bonds;
Fig. 5 is the scanning electron microscope (SEM) photograph of the titanium sheet of embodiment 2 gained Polyaniline Grafteds;
Fig. 6 is different titanium metal material surface contact angle schematic diagrams, wherein (a) is pure titanium sheet, (b) be the titanium sheet of embodiment 5 gained surface hydroxylations, (c) the titanium sheet of embodiment 5 gained surface terminal double bonds, (d) is the titanium sheet of embodiment 5 gained Polyaniline Grafteds;
Fig. 7 is the X-ray diffractogram of different titanium metal materials in embodiment 8;
Fig. 8 is pure titanium sheet biocidal property experimental result scanning electron microscope (SEM) photograph;
Fig. 9 is pure titanium sheet biocidal property experiment count of bacteria schematic diagram;
Figure 10 is the biocidal property experimental result scanning electron microscope (SEM) photograph of the titanium sheet of embodiment 10 gained Polyaniline Grafteds;
Figure 11 is the biocidal property experiment count of bacteria schematic diagram of the titanium sheet of embodiment 10 gained Polyaniline Grafteds;
Figure 12 is that the titanium sheet osteoblastic proliferation of embodiment 2 gained Polyaniline Grafteds is tested the scanning electron microscope (SEM) photograph after 1 day;
Figure 13 is that the titanium sheet osteoblastic proliferation of embodiment 2 gained Polyaniline Grafteds is tested the scanning electron microscope (SEM) photograph after 4 days;
Figure 14 is that the titanium sheet osteoblastic proliferation of embodiment 2 gained Polyaniline Grafteds is tested the scanning electron microscope (SEM) photograph after 10 days.
The specific embodiment
Below in conjunction with the specific embodiment, the present invention is further illustrated.
The modification medical titanium metal material of the present embodiment, comprise medical titanium metal, described medical titanium metal surface has bioactivity coatings, described bioactivity coatings is that medical titanium metal is carried out after surface hydroxylation, introducing is with the silane coupled agent molecule of terminal double bond, then form by in-situ polymerization covalence graft polyaniline.
Described medical titanium metal is pure titanium.
The preparation method of the modification medical titanium metal material of the present embodiment, as shown in Figure 1, comprises the following steps:
1) clean: getting dimensions is the pure titanium sheet of 10mm * 10mm * 1mm, and successively through polishing, polishing, ultrasonic cleaning, the titanium sheet obtaining after cleaning is standby;
2) surface hydroxylation: the titanium sheet after cleaning is placed in to piranha solution and carries out oxidation processes, the temperature of oxidation processes is 50 ℃, takes out after processing 60min, with deionized water, cleans and dries, and obtains the titanium sheet of surface hydroxylation;
3) surperficial terminal double bond: the titanium sheet of step 1) gained surface hydroxylation is placed in to 100ml toluene, add γ-methacryloxypropyl trimethoxy silane of 1ml to carry out back flow reaction, after reaction 40h, take out, with toluene, clean, under room temperature, dry, obtain the titanium sheet of surperficial terminal double bond;
4) Polyaniline Grafted: successively 5ml aniline, 1g Ammonium persulfate. are added in 50ml ethanol and make mixed liquor, the pH that adds sulphuric acid to control mixed liquor is 1; By step 2) the titanium sheet of gained surface terminal double bond is placed in described mixed liquor, under room temperature, reacts 1h, takes out, and cleans to neutral successively with ethanol, water, under room temperature, dries, and obtains the titanium sheet of Polyaniline Grafted.
Embodiment 2
The modification medical titanium metal material of the present embodiment, comprise medical titanium metal, described medical titanium metal surface has bioactivity coatings, described bioactivity coatings is that medical titanium metal is carried out after surface hydroxylation, introducing is with the silane coupled agent molecule of terminal double bond, then form by in-situ polymerization covalence graft polyaniline.
Described medical titanium metal is pure titanium.
The preparation method of the modification medical titanium metal material of the present embodiment, comprises the following steps:
1) clean: getting dimensions is the pure titanium sheet of 10mm * 10mm * 1mm, and successively through polishing, polishing, ultrasonic cleaning, the titanium sheet obtaining after cleaning is standby;
2) surface hydroxylation: the titanium sheet after cleaning is placed in to piranha solution and carries out oxidation processes, the temperature of oxidation processes is 90 ℃, takes out after processing 2min, with deionized water, cleans and dries, and obtains the titanium sheet of surface hydroxylation;
3) surperficial terminal double bond: the titanium sheet of step 1) gained surface hydroxylation is placed in to 100ml toluene, add γ-methacryloxypropyl trimethoxy silane of 10ml to carry out back flow reaction, after reaction 10h, take out, with toluene, clean, under room temperature, dry, obtain the titanium sheet of surperficial terminal double bond;
4) Polyaniline Grafted: successively 0.5ml aniline, 0.05g Ammonium persulfate. are added in 50ml ethanol and make mixed liquor, the pH that adds hydrochloric acid to control mixed liquor is 3; By step 2) the titanium sheet of gained surface terminal double bond is placed in described mixed liquor, under room temperature, reacts 24h, takes out, and cleans to neutral successively with ethanol, water, under room temperature, dries, and obtains the titanium sheet of Polyaniline Grafted.
Embodiment 3
The modification medical titanium metal material of the present embodiment, comprise medical titanium metal, described medical titanium metal surface has bioactivity coatings, described bioactivity coatings is that medical titanium metal is carried out after surface hydroxylation, introducing is with the silane coupled agent molecule of terminal double bond, then form by in-situ polymerization covalence graft polyaniline.
Described medical titanium metal is pure titanium.
The preparation method of the modification medical titanium metal material of the present embodiment, comprises the following steps:
1) clean: getting dimensions is the pure titanium sheet of 10mm * 10mm * 1mm, and successively through polishing, polishing, ultrasonic cleaning, the titanium sheet obtaining after cleaning is standby;
2) surface hydroxylation: the titanium sheet after cleaning is placed in to piranha solution and carries out oxidation processes, the temperature of oxidation processes is 75 ℃, takes out after processing 30min, with deionized water, cleans and dries, and obtains the titanium sheet of surface hydroxylation;
3) surperficial terminal double bond: the titanium sheet of step 1) gained surface hydroxylation is placed in to 100ml toluene, add γ-methacryloxypropyl trimethoxy silane of 5ml to carry out back flow reaction, after reaction 20h, take out, with toluene, clean, under room temperature, dry, obtain the titanium sheet of surperficial terminal double bond;
4) Polyaniline Grafted: successively 3ml aniline, 0.4g Ammonium persulfate. are added in 50ml ethanol and make mixed liquor, the pH that adds perchloric acid to control mixed liquor is 2; By step 2) the titanium sheet of gained surface terminal double bond is placed in described mixed liquor, under room temperature, reacts 12h, takes out, and cleans to neutral successively with ethanol, water, under room temperature, dries, and obtains the titanium sheet of Polyaniline Grafted.
Embodiment 4
The modification medical titanium metal material of the present embodiment, comprise medical titanium metal, described medical titanium metal surface has bioactivity coatings, described bioactivity coatings is that medical titanium metal is carried out after surface hydroxylation, introducing is with the silane coupled agent molecule of terminal double bond, then form by in-situ polymerization covalence graft polyaniline.
Described medical titanium metal is pure titanium.
The preparation method of the modification medical titanium metal material of the present embodiment, comprises the following steps:
1) clean: getting dimensions is the pure titanium sheet of 10mm * 10mm * 1mm, and successively through polishing, polishing, ultrasonic cleaning, the titanium sheet obtaining after cleaning is standby;
2) surface hydroxylation: the titanium sheet after cleaning is placed in to piranha solution and carries out oxidation processes, the temperature of oxidation processes is 90 ℃, takes out after processing 2min, with deionized water, cleans and dries, and obtains the titanium sheet of surface hydroxylation;
3) surperficial terminal double bond: the titanium sheet of step 1) gained surface hydroxylation is placed in to 100ml toluene, add γ-methacryloxypropyl triethoxysilane of 10ml to carry out back flow reaction, after reaction 10h, take out, with toluene, clean, under room temperature, dry, obtain the titanium sheet of surperficial terminal double bond;
4) Polyaniline Grafted: successively 0.5ml aniline, 0.05g Ammonium persulfate. are added in 50ml ethanol and make mixed liquor, the pH that adds hydrochloric acid to control mixed liquor is 3; By step 2) the titanium sheet of gained surface terminal double bond is placed in described mixed liquor, under room temperature, reacts 24h, takes out, and cleans to neutral successively with ethanol, water, under room temperature, dries, and obtains the titanium sheet of Polyaniline Grafted.
Embodiment 5
The modification medical titanium metal material of the present embodiment, comprise medical titanium metal, described medical titanium metal surface has bioactivity coatings, described bioactivity coatings is that medical titanium metal is carried out after surface hydroxylation, introducing is with the silane coupled agent molecule of terminal double bond, then form by in-situ polymerization covalence graft polyaniline.
Described medical titanium metal is pure titanium.
The preparation method of the modification medical titanium metal material of the present embodiment, comprises the following steps:
1) clean: getting dimensions is the pure titanium sheet of 10mm * 10mm * 1mm, and successively through polishing, polishing, ultrasonic cleaning, the titanium sheet obtaining after cleaning is standby;
2) surface hydroxylation: the titanium sheet after cleaning is placed in to piranha solution and carries out oxidation processes, the temperature of oxidation processes is 50 ℃, takes out after processing 60min, with deionized water, cleans and dries, and obtains the titanium sheet of surface hydroxylation;
3) surperficial terminal double bond: the titanium sheet of step 1) gained surface hydroxylation is placed in to 100ml toluene, add γ-methacryloxypropyl triethoxysilane of 1ml to carry out back flow reaction, after reaction 40h, take out, with toluene, clean, under room temperature, dry, obtain the titanium sheet of surperficial terminal double bond;
4) Polyaniline Grafted: successively 5ml aniline, 1g Ammonium persulfate. are added in 50ml ethanol and make mixed liquor, the pH that adds hydrochloric acid to control mixed liquor is 1; By step 2) the titanium sheet of gained surface terminal double bond is placed in described mixed liquor, under room temperature, reacts 1h, takes out, and cleans to neutral successively with ethanol, water, under room temperature, dries, and obtains the titanium sheet of Polyaniline Grafted.
Embodiment 6
The modification medical titanium metal material of the present embodiment, comprise medical titanium metal, described medical titanium metal surface has bioactivity coatings, described bioactivity coatings is that medical titanium metal is carried out after surface hydroxylation, introducing is with the silane coupled agent molecule of terminal double bond, then form by in-situ polymerization covalence graft polyaniline.
Described medical titanium metal is pure titanium.
The preparation method of the modification medical titanium metal material of the present embodiment, comprises the following steps:
1) clean: getting dimensions is the pure titanium sheet of 10mm * 10mm * 1mm, and successively through polishing, polishing, ultrasonic cleaning, the titanium sheet obtaining after cleaning is standby;
2) surface hydroxylation: the titanium sheet after cleaning is placed in to piranha solution and carries out oxidation processes, the temperature of oxidation processes is 75 ℃, takes out after processing 30min, with deionized water, cleans and dries, and obtains the titanium sheet of surface hydroxylation;
3) surperficial terminal double bond: the titanium sheet of step 1) gained surface hydroxylation is placed in to 100ml toluene, add γ-methacryloxypropyl triethoxysilane of 5ml to carry out back flow reaction, after reaction 20h, take out, with toluene, clean, under room temperature, dry, obtain the titanium sheet of surperficial terminal double bond;
4) Polyaniline Grafted: successively 3ml aniline, 0.4g Ammonium persulfate. are added in 50ml ethanol and make mixed liquor, the pH that adds hydrochloric acid to control mixed liquor is 2; By step 2) the titanium sheet of gained surface terminal double bond is placed in described mixed liquor, under room temperature, reacts 12h, takes out, and cleans to neutral successively with ethanol, water, under room temperature, dries, and obtains the titanium sheet of Polyaniline Grafted.
Embodiment 7
The modification medical titanium metal material of the present embodiment, comprise medical titanium metal, described medical titanium metal surface has bioactivity coatings, described bioactivity coatings is that medical titanium metal is carried out after surface hydroxylation, introducing is with the silane coupled agent molecule of terminal double bond, then form by in-situ polymerization covalence graft polyaniline.
Described medical titanium metal is pure titanium.
The preparation method of the modification medical titanium metal material of the present embodiment, comprises the following steps:
1) clean: getting dimensions is the pure titanium sheet of 10mm * 10mm * 1mm, and successively through polishing, polishing, ultrasonic cleaning, the titanium sheet obtaining after cleaning is standby;
2) surface hydroxylation: the titanium sheet after cleaning is placed in to piranha solution and carries out oxidation processes, the temperature of oxidation processes is 75 ℃, takes out after processing 30min, with deionized water, cleans and dries, and obtains the titanium sheet of surface hydroxylation;
3) surperficial terminal double bond: the titanium sheet of step 1) gained surface hydroxylation is placed in to 100ml toluene, add the vinyltrimethoxy silane of 5ml to carry out back flow reaction, after reaction 20h, take out, with toluene, clean, under room temperature, dry, obtain the titanium sheet of surperficial terminal double bond;
4) Polyaniline Grafted: successively 3ml aniline, 0.4g Ammonium persulfate. are added in 50ml ethanol and make mixed liquor, the pH that adds hydrochloric acid to control mixed liquor is 2; By step 2) the titanium sheet of gained surface terminal double bond is placed in described mixed liquor, under room temperature, reacts 12h, takes out, and cleans to neutral successively with ethanol, water, under room temperature, dries, and obtains the titanium sheet of Polyaniline Grafted.
Embodiment 8
The modification medical titanium metal material of the present embodiment, comprise medical titanium metal, described medical titanium metal surface has bioactivity coatings, described bioactivity coatings is that medical titanium metal is carried out after surface hydroxylation, introducing is with the silane coupled agent molecule of terminal double bond, then form by in-situ polymerization covalence graft polyaniline.
Described medical titanium metal is pure titanium.
The preparation method of the modification medical titanium metal material of the present embodiment, comprises the following steps:
1) clean: getting dimensions is the pure titanium sheet of 10mm * 10mm * 1mm, and successively through polishing, polishing, ultrasonic cleaning, the titanium sheet obtaining after cleaning is standby;
2) surface hydroxylation: the titanium sheet after cleaning is placed in to piranha solution and carries out oxidation processes, the temperature of oxidation processes is 90 ℃, takes out after processing 2min, with deionized water, cleans and dries, and obtains the titanium sheet of surface hydroxylation;
3) surperficial terminal double bond: the titanium sheet of step 1) gained surface hydroxylation is placed in to 100ml toluene, add the vinyltrimethoxy silane of 10ml to carry out back flow reaction, after reaction 10h, take out, with toluene, clean, under room temperature, dry, obtain the titanium sheet of surperficial terminal double bond;
4) Polyaniline Grafted: successively 0.5ml aniline, 0.05g Ammonium persulfate. are added in 50ml ethanol and make mixed liquor, the pH that adds hydrochloric acid to control mixed liquor is 3; By step 2) the titanium sheet of gained surface terminal double bond is placed in described mixed liquor, under room temperature, reacts 24h, takes out, and cleans to neutral successively with ethanol, water, under room temperature, dries, and obtains the titanium sheet of Polyaniline Grafted.
Embodiment 9
The modification medical titanium metal material of the present embodiment, comprise medical titanium metal, described medical titanium metal surface has bioactivity coatings, described bioactivity coatings is that medical titanium metal is carried out after surface hydroxylation, introducing is with the silane coupled agent molecule of terminal double bond, then form by in-situ polymerization covalence graft polyaniline.
Described medical titanium metal is pure titanium.
The preparation method of the modification medical titanium metal material of the present embodiment, comprises the following steps:
1) clean: getting dimensions is the pure titanium sheet of 10mm * 10mm * 1mm, and successively through polishing, polishing, ultrasonic cleaning, the titanium sheet obtaining after cleaning is standby;
2) surface hydroxylation: the titanium sheet after cleaning is placed in to piranha solution and carries out oxidation processes, the temperature of oxidation processes is 50 ℃, takes out after processing 60min, with deionized water, cleans and dries, and obtains the titanium sheet of surface hydroxylation;
3) surperficial terminal double bond: the titanium sheet of step 1) gained surface hydroxylation is placed in to 100ml toluene, add the vinyltrimethoxy silane of 1ml to carry out back flow reaction, after reaction 40h, take out, with toluene, clean, under room temperature, dry, obtain the titanium sheet of surperficial terminal double bond;
4) Polyaniline Grafted: successively 5ml aniline, 1g Ammonium persulfate. are added in 50ml ethanol and make mixed liquor, the pH that adds hydrochloric acid to control mixed liquor is 1; By step 2) the titanium sheet of gained surface terminal double bond is placed in described mixed liquor, under room temperature, reacts 1h, takes out, and cleans to neutral successively with ethanol, water, under room temperature, dries, and obtains the titanium sheet of Polyaniline Grafted.
The modification medical titanium metal material of the present embodiment, comprise medical titanium metal, described medical titanium metal surface has bioactivity coatings, described bioactivity coatings is that medical titanium metal is carried out after surface hydroxylation, introducing is with the silane coupled agent molecule of terminal double bond, then form by in-situ polymerization covalence graft polyaniline.
Described medical titanium metal is pure titanium.
The preparation method of the modification medical titanium metal material of the present embodiment, comprises the following steps:
1) clean: getting dimensions is the pure titanium sheet of 10mm * 10mm * 1mm, and successively through polishing, polishing, ultrasonic cleaning, the titanium sheet obtaining after cleaning is standby;
2) surface hydroxylation: the titanium sheet after cleaning is placed in to piranha solution and carries out oxidation processes, the temperature of oxidation processes is 90 ℃, takes out after processing 2min, with deionized water, cleans and dries, and obtains the titanium sheet of surface hydroxylation;
3) surperficial terminal double bond: the titanium sheet of step 1) gained surface hydroxylation is placed in to 100ml toluene, add the VTES of 5ml to carry out back flow reaction, after reaction 20h, take out, with toluene, clean, under room temperature, dry, obtain the titanium sheet of surperficial terminal double bond;
4) Polyaniline Grafted: successively 0.5ml aniline, 0.05g Ammonium persulfate. are added in 50ml ethanol and make mixed liquor, the pH that adds hydrochloric acid to control mixed liquor is 3; By step 2) the titanium sheet of gained surface terminal double bond is placed in described mixed liquor, under room temperature, reacts 24h, takes out, and cleans to neutral successively with ethanol, water, under room temperature, dries, and obtains the titanium sheet of Polyaniline Grafted.
Embodiment 11
The modification medical titanium metal material of the present embodiment, comprise medical titanium metal, described medical titanium metal surface has bioactivity coatings, described bioactivity coatings is that medical titanium metal is carried out after surface hydroxylation, introducing is with the silane coupled agent molecule of terminal double bond, then form by in-situ polymerization covalence graft polyaniline.
Described medical titanium metal is pure titanium.
The preparation method of the modification medical titanium metal material of the present embodiment, comprises the following steps:
1) clean: getting dimensions is the pure titanium sheet of 10mm * 10mm * 1mm, and successively through polishing, polishing, ultrasonic cleaning, the titanium sheet obtaining after cleaning is standby;
2) surface hydroxylation: the titanium sheet after cleaning is placed in to piranha solution and carries out oxidation processes, the temperature of oxidation processes is 75 ℃, takes out after processing 30min, with deionized water, cleans and dries, and obtains the titanium sheet of surface hydroxylation;
3) surperficial terminal double bond: the titanium sheet of step 1) gained surface hydroxylation is placed in to 100ml toluene, add the VTES of 10ml to carry out back flow reaction, after reaction 40h, take out, with toluene, clean, under room temperature, dry, obtain the titanium sheet of surperficial terminal double bond;
4) Polyaniline Grafted: successively 3ml aniline, 0.4g Ammonium persulfate. are added in 50ml ethanol and make mixed liquor, the pH that adds hydrochloric acid to control mixed liquor is 2; By step 2) the titanium sheet of gained surface terminal double bond is placed in described mixed liquor, under room temperature, reacts 12h, takes out, and cleans to neutral successively with ethanol, water, under room temperature, dries, and obtains the titanium sheet of Polyaniline Grafted.
Embodiment 12
The modification medical titanium metal material of the present embodiment, comprise medical titanium metal, described medical titanium metal surface has bioactivity coatings, described bioactivity coatings is that medical titanium metal is carried out after surface hydroxylation, introducing is with the silane coupled agent molecule of terminal double bond, then form by in-situ polymerization covalence graft polyaniline.
Described medical titanium metal is pure titanium.
The preparation method of the modification medical titanium metal material of the present embodiment, comprises the following steps:
1) clean: getting dimensions is the pure titanium sheet of 10mm * 10mm * 1mm, and successively through polishing, polishing, ultrasonic cleaning, the titanium sheet obtaining after cleaning is standby;
2) surface hydroxylation: the titanium sheet after cleaning is placed in to piranha solution and carries out oxidation processes, the temperature of oxidation processes is 50 ℃, takes out after processing 60min, with deionized water, cleans and dries, and obtains the titanium sheet of surface hydroxylation;
3) surperficial terminal double bond: the titanium sheet of step 1) gained surface hydroxylation is placed in to 100ml toluene, add the VTES of 1ml to carry out back flow reaction, after reaction 40h, take out, with toluene, clean, under room temperature, dry, obtain the titanium sheet of surperficial terminal double bond;
4) Polyaniline Grafted: successively 5ml aniline, 1g Ammonium persulfate. are added in 50ml ethanol and make mixed liquor, the pH that adds hydrochloric acid to control mixed liquor is 1; By step 2) the titanium sheet of gained surface terminal double bond is placed in described mixed liquor, under room temperature, reacts 1h, takes out, and cleans to neutral successively with ethanol, water, under room temperature, dries, and obtains the titanium sheet of Polyaniline Grafted.
Experimental example 1
This experimental example is to embodiment 2 pure titanium sheet used, and the titanium sheet of the titanium sheet of gained surface hydroxylation, surperficial terminal double bond and the titanium sheet of Polyaniline Grafted carry out scanning electron microscope and energy spectrum analysis.
Scanning electron microscope result as shown in Figure 2-5.As seen from Figure 2, pure titanium plate surface is except fault location, and smooth surface is smooth; And the titanium sheet of surface hydroxylation as shown in Figure 3, surface integral presents regular small embossment, and surperficial convex-concave is regular; And when surface grafting (the titanium sheet of surperficial terminal double bond after the silane coupled agent molecule of terminal double bond, as shown in Figure 4), there is a series of circles in micro-meter scale or the discontinuous platform structure of sub-circular in surface, this platform size is greater than graphite oxide rat size, surperficial successful grafting has been described silane coupled agent molecule; When surface grafting after polyaniline macromole (as shown in Figure 5), because macromolecule is connected, the platform structure after silane coupled is linked together by macromolecular chain, by initial " island " structure, has become continuous " island " structure.
Power spectrum test result is as shown in table 1～4.
The EDAX results of the pure titanium sheet of table 1 (corresponding with Fig. 2)
The EDAX results of the titanium sheet of table 2 surface hydroxylation (corresponding with Fig. 3)
The EDAX results of the titanium sheet of the surperficial terminal double bond of table 3 (corresponding with Fig. 4)
The EDAX results of the titanium sheet of table 4 Polyaniline Grafted (corresponding with Fig. 5)
Further, by power spectrum test analysis, the surface major part of pure titanium sheet is titanium elements; And after oxidation, Surface Oxygen constituent content obviously increases; After silane coupled, titanium surface silicon constituent content obviously increases; And after polyaniline grafted, with silane coupled before compare, carbon content obviously increases.In conjunction with surface topography and the EDAX results of titanium sheet, illustrate that the method that the application provides has successfully realized the grafting of polyaniline on medical metallic titanium surface.
Experimental example 2
Contact angle changes very sensitive to modified sample surface nature, therefore by the test of contact angle, can reflect the modification information of material surface.This experimental example is tested the contact angle of embodiment 5 pure titanium sheet used, the titanium sheet of gained surface hydroxylation, the titanium sheet of surperficial terminal double bond and the titanium sheet of Polyaniline Grafted, and result as shown in Figure 6.
As can be seen from Figure 6, the titanium sheet (b) of surface hydroxylation is compared with pure titanium sheet (a), and contact angle is from 86 ° of 105 ° of increasing to titanium oxide sheet of pure titanium sheet, and contact angle increases; It is generally acknowledged the increase of content of surface oxygen, contact angle can diminish, but the scanning electron microscope analysis result of the hydroxylated titanium sheet of mating surface and pure titanium sheet is known, the contact angle of the titanium plate surface of surface hydroxylation increases, and can be attributed to oxidation titanium plate surface and form due to numerous regular small embossments.And the titanium sheet (c) of surperficial terminal double bond and the titanium sheet (b) of surface hydroxylation that form through silane coupler coupling are compared, contact angle obviously increases; From 105 ° of the titanium sheet of surface hydroxylation, increase to 130 ° of titanium sheet of surperficial terminal double bond, this can be attributed to titanium plate surface after silane coupled, and has introduced due to long hydrophobic chain on surface, causes its contact angle obviously to increase, shown silane coupled success, this is consistent with scanning electron microscope result.And after polyaniline grafted, the contact angle on the titanium sheet (d) of Polyaniline Grafted surface obviously reduces, from 130 °, 22 ° have been reduced to, this is the introducing due to polyaniline, at titanium plate surface, introduce a large amount of ends amino, its hydrophilic is strengthened, caused its contact angle to reduce.From contact angle test result, can further prove, utilize the method that the application provides can successfully realize polyaniline at the chemical graft of medical titanium metal surface, consistent with the scanning electron microscope result of experimental example 1.
Experimental example 3
X-ray diffraction technology is more responsive to the structure of material surface, by X-ray diffraction, tests, and can understand the structural information of material modified surface layer.This experimental example has carried out X-ray diffraction analysis to embodiment 8 pure titanium sheet used, the titanium sheet of gained surface hydroxylation, the titanium sheet of surperficial terminal double bond and the titanium sheet of Polyaniline Grafted, and result as shown in Figure 7.
As can be seen from Figure 7, for the Titanium material before and after modification, before and after its modification, the diffraction peak of titanium material surface does not occur obviously to change, change be that diffraction maximum is strong; Before these diffraction maximums and modification, at the bottom of titanio, diffraction peak is similar, illustrates that these diffraction maximums should belong to the titanium sheet of surface hydroxylation of substrate and the structure of Titanium; But on titanium surface, introduce after the silane coupled agent molecule that contains terminal double bond, diffraction maximum reduces by force compared with titanium oxide peak by force, and continues to introduce after polyaniline molecule, and diffraction maximum is strong further to be reduced; The increase that this can belong to surface modification layer thickness, the method that further illustrating the application provides has successfully realized at titanium surface grafting polyaniline molecule.
Experimental example 4
The biocidal property of the titanium sheet that this experimental example detects pure titanium sheet and embodiment 10 gained Polyaniline Grafteds to escherichia coli (E.coli).
Experimental technique is: with reference to standard GB/T/T4789.2, first titanium sheet is carried out to sterilization treatment, then 5ml concentration is about to the bacterium drop of 1000/mL at the sample surfaces of sterilizing, then by dripping, have the sample of bacterium liquid to put into 37 ℃ of calorstats cultivation 24h.Take out the sample that 24h cultivates, will after the dilution of bacterium liquid, be seeded on the agar plate that contains culture medium.Postvaccinal agar plate is put into 37 ℃ of constant incubators and is cultivated 24h; Then with blood cell counting plate, count.The calculating of bacteriostasis rate is calculated according to following formula:
K=(A-B)/A×100％ (1)
Wherein, K is bacteriostasis rate, and A is antibacterial average in the front bacterium liquid of test; B is the antibacterial average on test sample.
The titanium sheet that employing scanning electron microscope and blood cell counting plate have compared pure titanium sheet and Polyaniline Grafted is to colibacillary fungistatic effect, and result is as shown in Fig. 8～11.From Fig. 8,9, can find out, still intact in pure titanium plate surface ne ar, and adhere in a large number, show that pure titanium plate surface biocidal property effect is bad; And titanium plate surface after polyaniline molecule graft modification, under the same conditions through scanning electron microscopic observation, as shown in figure 10, surface has not had bacterial adhesion, and the titanium plate surface of Polyaniline Grafted has significant fungistatic effect.In counting chamber test after surface bacteria eluting, find, as shown in figure 11, the demonstration of the titanium plate surface of Polyaniline Grafted has reached more than 90% escherichia coli bacteriostasis rate, has shown the biocidal property that it is good; Biocidal property result has further proved that the polyaniline molecule with biocidal property has successfully been grafted on the surface of medical metallic titanium.
Experimental example 5
This experimental example carries out osteoblastic adhesion experiment the titanium sheet of Polyaniline Grafted described in embodiment 2, usings its index as evaluating material biocompatibility.
The method of testing of biocompatibility is: in 12 orifice plates by 1x10
4the MG63 osteoblast of individual/ml (cell resource center of life science institute of the Chinese Academy of Sciences) is inoculated in the titanium plate surface of embodiment 2 gained Polyaniline Grafteds, adds DMEM nutrient chemical, puts into 5%CO
2in incubator, under 37 ℃ of constant incubators and 95% relative humidity condition, carry out compound cultivation; Cultivate after certain hour, with PBS rinsing, remove not adherent cell of titanium plate surface, with 2.5% glutaraldehyde, at 4 ℃, fix, Gradient elution using ethanol, critical point drying, metal spraying are observed osteoblast form under SEM.
From scanning electron microscope result (Figure 12～14), can find out, after having cultivated 1 day, cell substantially all above adheres at " platform " of sample surfaces, and on " gully ", substantially there is no cell distribution, this regional structure that may be applicable to sprawling with cell is relevant, also may be relevant to area surfaces composition.In the time of the 4th day, osteoblast is fusiformis shape mostly, and projection is more, relatively independent between cell, and coating surface cell proliferation is vigorous, and on " gully ", sprawls gradually; And when cultivating by the 10th day, found a large amount of cell deaths.
Biocompatibility experiment shows, titanium sheet and the osteoblast of the application's Polyaniline Grafted have good biocompatibility.
Claims (10)
1. a modification medical titanium metal material, it is characterized in that: comprise medical titanium metal, described medical titanium metal surface has bioactivity coatings, described bioactivity coatings is that medical titanium metal is carried out after surface hydroxylation, introducing is with the silane coupled agent molecule of terminal double bond, then form by in-situ polymerization covalence graft polyaniline.
2. modification medical titanium metal material according to claim 1, is characterized in that: described medical titanium metal is pure titanium or titanium alloy.
3. a preparation method for modification medical titanium metal material as claimed in claim 1, is characterized in that: comprise the following steps:
1) surface hydroxylation: the medical titanium metal after cleaning is placed in to piranha solution and carries out oxidation processes, rear taking-up, washes and dry, and obtains the medical titanium metal of surface hydroxylation;
2) surperficial terminal double bond: the medical titanium metal of step 1) gained surface hydroxylation is placed in to toluene, add the silane coupler with terminal double bond to carry out back flow reaction, after reaction 10～40h, take out, after cleaning, dry, obtain the medical titanium metal of surperficial terminal double bond;
3) Polyaniline Grafted: aniline, Ammonium persulfate. are added in ethanol and make mixed liquor, and the pH that controls mixed liquor is 1～3; By step 2) the medical titanium metal of gained surface terminal double bond is placed in described mixed liquor, under room temperature, reacts 1～24h, takes out, and after cleaning, dries, obtain.
4. the preparation method of modification medical titanium metal material according to claim 3, is characterized in that: the cleaning of the metal of medical titanium described in step 1) is for processing through polishing, polishing, ultrasonic cleaning successively.
5. the preparation method of modification medical titanium metal material according to claim 3, is characterized in that: the temperature of oxidation processes described in step 1) is 50～90 ℃, and the time is 2～60min.
6. the preparation method of modification medical titanium metal material according to claim 3, is characterized in that: step 2) described in the silane coupler of terminal double bond, be any one in γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxysilane, vinyltrimethoxy silane, VTES.
7. according to the preparation method of the modification medical titanium metal material described in claim 3 or 6, it is characterized in that: described is 1～10:100 with the silane coupler of terminal double bond and the volume ratio of toluene.
8. the preparation method of modification medical titanium metal material according to claim 3, is characterized in that: described in step 3), in mixed liquor, the volume ratio of ethanol and aniline is 10～100:1.
9. the preparation method of modification medical titanium metal material according to claim 3, is characterized in that: described in step 3), in mixed liquor, the addition of described Ammonium persulfate. is that every ml aniline adds 0.05～1g Ammonium persulfate..
10. the preparation method of modification medical titanium metal material according to claim 3, is characterized in that: step 2) described in to clean be to clean with toluene; Described in step 3), clean is with ethanol, water, to clean to neutral successively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410001001.8A CN103751841B (en) | 2014-01-02 | 2014-01-02 | A kind of modification medical titanium metal material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410001001.8A CN103751841B (en) | 2014-01-02 | 2014-01-02 | A kind of modification medical titanium metal material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103751841A true CN103751841A (en) | 2014-04-30 |
| CN103751841B CN103751841B (en) | 2015-08-19 |
Family
ID=50519261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410001001.8A Expired - Fee Related CN103751841B (en) | 2014-01-02 | 2014-01-02 | A kind of modification medical titanium metal material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103751841B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104258462A (en) * | 2014-09-30 | 2015-01-07 | 广西中医药大学 | Medical stainless steel material and preparation method thereof |
| CN104817694A (en) * | 2015-04-24 | 2015-08-05 | 四川大学 | Method for rapidly preparing nanometer polyaniline sensor material |
| CN105130206A (en) * | 2015-08-26 | 2015-12-09 | 河南科技大学 | Method for preparing superhydrophobic and self-cleaning glass |
| CN108103428A (en) * | 2017-11-14 | 2018-06-01 | 上海交通大学 | A kind of surface treatment method of medical metal material |
| CN110230058A (en) * | 2019-05-31 | 2019-09-13 | 上海交通大学 | Promote the method for the medical titanium alloy surface building of growth of marrow mesenchyme stem cell differentiation |
| CN112789065A (en) * | 2018-10-01 | 2021-05-11 | 微仙美国有限公司 | Medical device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912335A (en) * | 2012-09-24 | 2013-02-06 | 河南科技大学 | Surface modified medical metal material and preparation method thereof |
-
2014
- 2014-01-02 CN CN201410001001.8A patent/CN103751841B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912335A (en) * | 2012-09-24 | 2013-02-06 | 河南科技大学 | Surface modified medical metal material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 廖梓珺等: "聚苯胺/钛酸钡复合粒子的合成及结构表征", 《材料工程》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104258462A (en) * | 2014-09-30 | 2015-01-07 | 广西中医药大学 | Medical stainless steel material and preparation method thereof |
| CN104258462B (en) * | 2014-09-30 | 2016-05-11 | 广西中医药大学 | A kind of medical stainless steel material and preparation method thereof |
| CN104817694A (en) * | 2015-04-24 | 2015-08-05 | 四川大学 | Method for rapidly preparing nanometer polyaniline sensor material |
| CN105130206A (en) * | 2015-08-26 | 2015-12-09 | 河南科技大学 | Method for preparing superhydrophobic and self-cleaning glass |
| CN105130206B (en) * | 2015-08-26 | 2018-05-25 | 河南科技大学 | A kind of preparation method of super-hydrophobic automatic cleaning glass |
| CN108103428A (en) * | 2017-11-14 | 2018-06-01 | 上海交通大学 | A kind of surface treatment method of medical metal material |
| CN112789065A (en) * | 2018-10-01 | 2021-05-11 | 微仙美国有限公司 | Medical device |
| US11590267B2 (en) | 2018-10-01 | 2023-02-28 | Microvention, Inc. | Medical devices |
| CN110230058A (en) * | 2019-05-31 | 2019-09-13 | 上海交通大学 | Promote the method for the medical titanium alloy surface building of growth of marrow mesenchyme stem cell differentiation |
| CN110230058B (en) * | 2019-05-31 | 2020-08-14 | 上海交通大学 | Method for constructing medical titanium alloy surface for promoting growth and differentiation of bone marrow mesenchymal stem cells |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103751841B (en) | 2015-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lin et al. | Thermo and light-responsive strategies of smart titanium-containing composite material surface for enhancing bacterially anti-adhesive property | |
| CN103751841B (en) | A kind of modification medical titanium metal material and preparation method thereof | |
| Encinas et al. | Submicrometer-sized roughness suppresses bacteria adhesion | |
| De Giglio et al. | An innovative, easily fabricated, silver nanoparticle-based titanium implant coating: development and analytical characterization | |
| CN111035803B (en) | Titanium implant material with anti-infection and osseointegration promoting functions and preparation method thereof | |
| CN107096068A (en) | A kind of preparation method of dentistry implant and its bioactivity antimicrobial surface | |
| Sun et al. | Electrophoretic deposition of colloidal particles on Mg with cytocompatibility, antibacterial performance, and corrosion resistance | |
| Ungureanu et al. | Enhancing antimicrobial activity of TiO2/Ti by torularhodin bioinspired surface modification | |
| Bhattarai et al. | A controlled surface geometry of polyaniline doped titania nanotubes biointerface for accelerating MC3T3-E1 cells growth in bone tissue engineering | |
| Zhang et al. | Sr/ZnO doped titania nanotube array: an effective surface system with excellent osteoinductivity and self-antibacterial activity | |
| CN102912335B (en) | Medical metal material of a kind of surface modification and preparation method thereof | |
| Du et al. | Preparation of vancomycin-loaded alginate hydrogel coating on magnesium alloy with enhanced anticorrosion and antibacterial properties | |
| Zheng et al. | Enhanced osteoblasts responses to surface-sulfonated polyetheretherketone via a single-step ultraviolet-initiated graft polymerization | |
| KR101461159B1 (en) | Preparation method of implant comprising drug delivery layer and implant compostion for living donor transplantation comprising the same | |
| Zhang et al. | Surface modification of Titanium implants by pH-Responsive coating designed for Self-Adaptive antibacterial and promoted osseointegration | |
| Huang et al. | Enhanced antibacterial activity and biocompatibility of zinc-incorporated organic-inorganic nanocomposite coatings via electrophoretic deposition | |
| Qiaoxia et al. | Hydroxyapatite/tannic acid composite coating formation based on Ti modified by TiO2 nanotubes | |
| CN104387832B (en) | A kind of compound fungistatic coating preparation method being loaded with small-molecule substance | |
| CN103540934B (en) | Surface-modified medical titanium metal material and preparation method thereof | |
| Si et al. | A heterogeneous TiO2/SrTiO3 coating on titanium alloy with excellent photocatalytic antibacterial, osteogenesis and tribocorrosion properties | |
| CN107937880A (en) | A kind of method of metal surface properties modification and products thereof and purposes | |
| Du et al. | A multifunctional hybrid inorganic-organic coating fabricated on magnesium alloy surface with antiplatelet adhesion and antibacterial activities | |
| Zhang et al. | Construction of multifunctional micro-patterned PALNMA/PDADMAC/PEGDA hydrogel and intelligently responsive antibacterial coating HA/BBR on Mg alloy surface for orthopedic application | |
| Liang et al. | Smart Implant with Bacteria Monitoring and Killing Ability for Orthopedic Applications | |
| Zhang et al. | pH responsive zwitterionic-to-cationic transition for safe self-defensive antibacterial application |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150819 Termination date: 20160102 |
|
| EXPY | Termination of patent right or utility model |