CN101575726B - Method for preparing bioactive gradient film of fluor-hydroxyapatite - Google Patents
Method for preparing bioactive gradient film of fluor-hydroxyapatite Download PDFInfo
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- CN101575726B CN101575726B CN2009101455234A CN200910145523A CN101575726B CN 101575726 B CN101575726 B CN 101575726B CN 2009101455234 A CN2009101455234 A CN 2009101455234A CN 200910145523 A CN200910145523 A CN 200910145523A CN 101575726 B CN101575726 B CN 101575726B
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Abstract
The invention relates to a bioactive modification method of medical titanium materials, which is characterized by adopting a segmented micro-arc oxidation technology and directly in-situ forming a bioactive gradient film containing TiO2/FHA/HA on the surfaces of titanium and titanium alloy. The method comprises the following steps: preparing electrolyte solution containing phosphate ions, calciumions and fluoride ions; taking the titanium material as an anode and stainless steel as a cathode; adopting a DC pulse power supply to carry out micro-arc oxidation on the titanium and titanium alloyin the manner of segmented oxidation. The bioactive gradient film containing TiO2/FHA/HA prepared by the invention has good bioactivity and can apply the titanium to the field of dental restoration widely. The invention features simple process and lower cost, has no special requirements on material shapes, is particularly suitable for matrices with complex shapes and effectively expands the application range of the materials.
Description
Technical field
The present invention relates to medical titanium metallic substance bioactivation method of modifying, particularly a kind of preparation method who is used for the fluoridated hydroxyapatite bioactive gradient film of tooth section.
Background technology
The titanium metal biomaterial is because its higher intensity and toughness, better biocompatibility and erosion resistance and be widely used in orthopaedics and shaping field.But because titanium metal is a bio-inert material, can not produce Chemical bond with the main body bone behind the implant into body, have a strong impact on the implantation effect, therefore be necessary titanium metal is carried out the bioactivation modification.Prepare the research focus that the bioactive ceramics rete becomes surface of metal titanium modification in recent years in surface of metal titanium.
The chemical ingredients of hydroxyapatite is similar to the inorganic components of the osseous tissue of human body and hard tooth tissue, but the inorganic components of human body hard tissue also contains other zwitterions, as: F
-, Ba
2+Deng, form fluorapatite behind the hydroxyl in the fluorion substituted hydroxy phosphatic rock, make the structure of phosphatic rock more stable, as oral cavity material the time, can reduce sticking of bacterium, preventing dental caries.
At present the main method for preparing bioactive film in surface of metal titanium has plasma spraying method, sol-gel method and micro arc oxidizing compounding process method etc.Tsui Y C etc., at titanium matrix surface plasma spraying hydroxyapatite, bio-medical material, 1998,22,2031-2043.Disclose the employing plasma spraying method and prepared fluoridated hydroxyapatite, but the spraying process temperature is too high, fluorine volatilizees easily, and the rete of formation is formed difficult control, and plasma spraying is streamlined process, is difficult to obtain uniform coating on complex-shaped matrix.Zhu's type extensively waits people, titanium alloy surface TiO
2The preparation of-FHA-HA gradient bio-ceramic coating, silicate circular, 2007,26,812-815.Disclose and adopted sol-gel method to prepare the bio-ceramic coating of titanium dioxide/fluoridated hydroxyapatite/alloy/hydroxylapatite gradient structure at the pretreated titanium matrix surface of differential arc oxidation, the result shows that the bioactive gradient coating has significantly improved and is coated with basic bonding force, and because of the fluorine hydroxyapatite littler than the dissolution rate of hydroxyapatite, and improved the implantation life-span, but there is contraction in gel in the later stage sintering process, and the production cycle is longer relatively.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of and be coated with the film-substrate binding strength height in the titanium or titanium alloy surface preparation, stability and biological activity are good, and the relative preparation method of short fluoridated hydroxyapatite bioactive gradient film of production cycle.
Above-mentioned purpose of the present invention reaches by following measure.
A kind of preparation method of fluoridated hydroxyapatite bioactive gradient film is characterized in that: adopt the segmentation differential arc oxidization technique, directly contain titanium dioxide (TiO in the generation of titanium or titanium alloy surface in situ
2The bioactive gradient film of)/fluoridated hydroxyapatite (FHA)/hydroxyapatite (HA), the preparation method comprises the steps and technology:
Step 1: pre-treatment
With titanium or titanium alloy sanding and polishing, ultrasonic cleaning;
Step 2: preparation electrolyte solution
Prepare a kind of electrolyte solution that includes phosphate anion, fluorion and calcium ion;
Step 3: differential arc oxidation
Be anode with titanium or titanium alloy in above-mentioned electrolyte solution, stainless steel is a negative electrode, adopts direct current pulse power source, the sectional type differential arc oxidation;
Described sectional type differential arc oxidation comprises preoxidation and differential arc oxidation; Preoxidation voltage is 200～250V, and preoxidation time is 2～5min; Differential arc oxidation voltage is 350～500V, and the differential arc oxidation time is 5～20min; Oxidising process electrolyte solution temperature keeps 30～40 ℃, and frequency is 50～100HZ, and dutycycle is 5～30%.
The concentration range of phosphate anion is 0.02～0.12mol/L in the described electrolyte solution of step 2, and the concentration range of calcium ion is 0.10～0.40mol/L, and the concentration range of fluorion is 0.01～0.04mol/L.
For the described electrolyte solution of step 2 provides the ionogen of phosphate anion preferably from chemical reagent SODIUM PHOSPHATE, MONOBASIC or sodium; The ionogen that calcium ion is provided is a lime acetate; The ionogen that fluorion is provided is preferably from Sodium Fluoride or Calcium Fluoride (Fluorspan).
The present invention compared with prior art has following outstanding advantage and significant effect:
1, the present invention adopts and contains special pharmacological effect Sodium Fluoride or Calcium Fluoride (Fluorspan), as the ionogen that fluorion is provided.Form the fluorine hydroxyapatite behind the hydroxyl in containing the electrolyte solution of fluorion in the fluorion substituted hydroxy phosphatic rock, make the structure of hydroxyapatite more stable, as oral cavity material the time, can reduce sticking of bacterium, preventing dental caries.
2, the fluoridated hydroxyapatite bioactive gradient film of the present invention's preparation is compared with single hydroxyapatite film layer, solubleness is less in simulated body fluid, the life-span is expected to prolongation and is coated with base in conjunction with good after making the material implant into body, provides possibility for titanium metal is widely used in tooth reparation field.
3, the present invention directly generates the fluoridated hydroxyapatite bioactive gradient film in the surface of metal titanium original position to compare with sol-gel method, and gained rete and substrate combinating strength are higher, does not exist problem such as rete shrinkage cracking and production cycle shorter relatively.Technology is simple and cost is also lower.
4, the present invention compares with plasma spraying method, and it is too high to have overcome the spraying process temperature, and fluorine volatilizees easily, and the rete of formation is formed problem more rambunctious.
5, material shape is not had particular requirement, be specially adapted to complex-shaped matrix, enlarged the range of application of material effectively.
6, the present invention adopts the sectional type differential arc oxidation, and first preoxidation voltage is that low-voltage micro arc oxidation is at the fine and close TiO of matrix surface preparation
2Layer effectively suppresses separating out of harmful metal ion; Back differential arc oxidation adopts high voltage, at fine and close TiO
2The preparation vesicular structure contains the bioactive film of FHA and HA on the basis of layer, helps growing into of osseous tissue.
Description of drawings
Fig. 1 is the SEM picture of the fluoridated hydroxyapatite bioactive gradient film of embodiment 1
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
Step 1: pre-treatment
10 * 10 * 1mm3 titanium sheet successively with 180#, 280#, 360#, 600#, 800#, 1000# sand papering polishing, is used 99.5% acetone, 99.7% dehydrated alcohol, each ultrasonic cleaning 20min of deionized water then successively.
Step 2: preparation electrolyte solution
Be mixed with the electrolyte solution of phosphorus-containing acid ion and calcium ion, fluorion respectively with SODIUM PHOSPHATE, MONOBASIC, lime acetate, Calcium Fluoride (Fluorspan) with deionized water, the concentration that makes phosphate anion in the electrolyte solution is 0.02mol/L, the concentration of calcium ion is 0.10mol/L, and the concentration of fluorion is 0.01mol/L.
Step 3: differential arc oxidation
With the titanium sheet is anode, and stainless steel is a negative electrode, adopts direct current pulse power source, and dutycycle is 5%, and frequency is 50HZ, and preoxidation voltage is 200V, and preoxidation time is 5min; Differential arc oxidation voltage is 500V, and the differential arc oxidation time is 10min, and keeping the electrolyte solution temperature is 30～40 ℃.
Make the fluoridated hydroxyapatite bioactive gradient film behind the sectional type differential arc oxidation, this bioactive gradient film is the generation of surface of metal titanium original position and contains TiO
2The bioactive gradient film of/FHA/HA, its SEM picture as shown in Figure 1, display surface forms vesicular structure, the aperture is 1～5um; Being coated with film-substrate binding strength is 47MPa.It is immersed in the simulated body fluid takes out the surface behind the 12h and promptly have one deck white film to generate, shown good biological activity.
Embodiment 2
Step 1: pre-treatment
10 * 10 * 1mm3 titanium sheet successively with 180#, 280#, 360#, 600#, 800#, 1000# sand papering polishing, is used 99.5% acetone, 99.7% dehydrated alcohol, each ultrasonic cleaning 20min of deionized water then successively.
Step 2: preparation electrolyte solution
Be mixed with the electrolyte solution of phosphorus-containing acid ion and calcium ion, fluorion respectively with sodium, lime acetate, Sodium Fluoride with deionized water, the concentration that makes phosphate anion in the electrolyte solution is 0.06mol/L, the concentration of calcium ion is 0.20mol/L, and the concentration of fluorion is 0.02mol/L.
Step 3: differential arc oxidation
With the titanium sheet is anode, and stainless steel is a negative electrode, adopts direct current pulse power source, and dutycycle is 15%, frequency is 80HZ, and preoxidation voltage is 250V, and preoxidation time is 3min, differential arc oxidation voltage is 450V, and the differential arc oxidation time is 15min, and keeping the electrolyte solution temperature is 30～40 ℃.
Make the fluoridated hydroxyapatite bioactive gradient film behind the sectional type differential arc oxidation, this bioactive gradient film is the generation of surface of metal titanium original position and contains TiO
2The bioactive gradient film of/FHA/HA, its SEM picture display surface forms vesicular structure, and the aperture is 1～5um; Being coated with film-substrate binding strength is 42MPa.It is immersed in the simulated body fluid takes out the surface after 1 day and promptly have one deck white film to generate, shown good biological activity.
Embodiment 3
Step 1: pre-treatment
The tooth reparation is polished with 180#, 280#, 360#, 600#, 800#, 1000# sand papering successively with titanium metal substrates, use 99.5% acetone, 99.7% dehydrated alcohol, each ultrasonic cleaning 20min of deionized water then successively.
Step 2: preparation electrolyte solution
Be mixed with the electrolyte solution of phosphorus-containing acid ion and calcium ion, fluorion respectively with sodium, lime acetate, Sodium Fluoride with deionized water, the concentration that makes phosphate anion in the electrolyte solution is 0.12mol/L, the concentration of calcium ion is 0.40mol/L, and the concentration of fluorion is 0.04mol/L.
Step 3: differential arc oxidation
With the titanium metal is anode, and stainless steel is a negative electrode, adopts direct current pulse power source, and dutycycle is 30%, and frequency is 100HZ, and preoxidation voltage is 250V, and preoxidation time is 2min; Differential arc oxidation voltage is 350V, and the differential arc oxidation time is 20min, and keeping the electrolyte solution temperature is 30～40 ℃.
Make the fluoridated hydroxyapatite bioactive gradient film behind the sectional type differential arc oxidation, this bioactive gradient film is the generation of surface of metal titanium original position and contains TiO
2The bioactive gradient film of/FHA/HA, its SEM picture display surface forms vesicular structure, and the aperture is 1～5um; Being coated with film-substrate binding strength is 36MPa.It is immersed in the simulated body fluid takes out the surface after 2 days and promptly have one deck white film to generate, shown good biological activity.
Claims (2)
1. the preparation method of a fluoridated hydroxyapatite bioactive gradient film is characterized in that: adopt the segmentation differential arc oxidization technique, directly contain TiO in the generation of titanium or titanium alloy surface in situ
2The bioactive gradient film of/FHA/HA, the preparation method comprises the steps and processing condition:
Step 1: pre-treatment
With titanium or titanium alloy sanding and polishing, ultrasonic cleaning;
Step 2: preparation electrolyte solution
Prepare a kind of electrolyte solution that includes phosphate anion, fluorion and calcium ion, the concentration range of phosphate anion is 0.02～0.12mol/L in the described electrolyte solution, the concentration range of calcium ion is 0.10～0.40mol/L, and the concentration range of fluorion is 0.01～0.04mol/L;
Step 3: differential arc oxidation
Be anode with titanium or titanium alloy in above-mentioned electrolyte solution, stainless steel is a negative electrode, adopts direct current pulse power source, the sectional type differential arc oxidation;
Described sectional type differential arc oxidation comprises preoxidation and differential arc oxidation; Preoxidation voltage is 200～250V, and preoxidation time is 2～5min; Differential arc oxidation voltage is 350～500V, and the differential arc oxidation time is 5～20min; Oxidising process electrolyte solution temperature keeps 30～40 ℃, and frequency is 50～100HZ, and dutycycle is 5～30%.
2. the preparation method of a kind of fluoridated hydroxyapatite bioactive gradient film according to claim 1 is characterized in that: describedly be selected from chemical reagent SODIUM PHOSPHATE, MONOBASIC or sodium for the step 2 electrolyte solution provides the ionogen of phosphate anion; The ionogen that calcium ion is provided is a lime acetate; Provide the ionogen of fluorion to be selected from Sodium Fluoride or Calcium Fluoride (Fluorspan).
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| CN101914799B (en) * | 2010-07-13 | 2012-01-25 | 中国科学院上海硅酸盐研究所 | Method for preparing calcium fluoride coating on surface of titanium and alloy thereof and application thereof |
| CN102409382A (en) * | 2011-11-10 | 2012-04-11 | 上海理工大学 | Bioactive coating of metal implant and preparation method thereof |
| CN102579145B (en) * | 2012-02-23 | 2014-05-14 | 中国人民解放军第四军医大学 | Dental implant and preparation method thereof |
| CN102605410A (en) * | 2012-03-21 | 2012-07-25 | 西安理工大学 | Method for preparing bioactive composite film layer containing hydroxyapatite on titanium metal surface |
| CN103046102B (en) * | 2013-01-29 | 2015-05-20 | 哈尔滨工业大学 | Method for preparing macroscopical porous micro-arc oxidation coating based on two-step process |
| CN103315915B (en) * | 2013-06-20 | 2014-11-05 | 北京大学 | Tooth repairing and whitening material and preparation method thereof |
| CN103315916B (en) * | 2013-06-20 | 2014-12-17 | 北京大学 | Dental prosthetic material and preparation method thereof |
| CN104726921B (en) * | 2015-02-15 | 2017-05-31 | 周建宏 | Titanium dioxide/hydroxyapatite bioactive nano-composite coating of fluorine containing strontium and its preparation method and application |
| CN105597157B (en) * | 2015-12-28 | 2018-07-27 | 周建宏 | One kind can promote vascularization and anti-infection bio active coating and its preparation method and application |
| CN105862096B (en) * | 2016-06-02 | 2017-12-12 | 烟台工程职业技术学院 | A kind of preparation method of FHA bioactivity coatings |
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