CN100445427C - A kind of method for preparing titanium and titanium alloy glass-ceramic coating - Google Patents

Abstract

The invention relates to a method for preparing titanium and titanium alloy glass-ceramic coatings. In the glass-ceramics used in the method, the total content of CaO and _P2O5 is 80-90mol% _, the content of _Na2O is 4-7mol%, and the rest For TiO ₂ and ZrO ₂ . Mix the raw materials evenly, heat and melt after drying, then take them out and pour them on the stainless steel plate to punch to prepare glass, grind the punched glass balls into powder, dissolve them in methanol to make a slurry. The pure titanium, Ti6Al4V, Ti29Nb13Ta4.6Zr and Ti24Nb4Zr7.6Sn alloys treated by alumina blasting are immersed in the mixed solution of glass ceramics and methanol for extraction, and then sintered at high temperature to obtain the glass ceramic coating. The coating does not contain SiO ₂ , no toxic elements, and has good biological activity. Hydroxyapatite will be formed after soaking in simulated human body fluid for 4 days, and its binding force with titanium and titanium alloy substrate is greater than 15MPa. The coating has a high Ca/P ratio and a composition similar to that of human hard tissue, which can induce the growth of new bone on the surface of the implant faster, and can be used as a replacement and repair material for human hard tissue.

Description

A kind of method for preparing titanium and titanium alloy glass-ceramic coating

Technical field:

The invention relates to the fields of biological coatings and glass ceramics, in particular to the field of preparation of surface active coatings when titanium and titanium alloys are used as hard tissue repair and replacement materials, specifically a method for preparing titanium and titanium alloy glass ceramic coatings.

Background technique:

生物玻璃(Na₂O-CaO-SiO₂-P₂O₅系)、Ceravital微晶玻璃(Na₂O-K₂O-MgO-CaO-P₂O₅-SiO₂系)、A-W生物玻璃陶瓷(MgO-CaO-SiO₂-P₂O₅系)、羟基磷灰石生物活性陶瓷(HA，组成为：Ca₁₀(PO₄)₆(OH)₂)等等植入生物体内，不会被纤维性膜包覆，能于骨形成牢固结合。见参考文献[3]：L.L.Hench.Bioceramics.Journal of American Ceramics Society.1998，81[7]：1705-1728。因此，如果能在钛及钛合金表面制备一层生物玻璃陶瓷涂层，则既能发挥金属优良的力学性能，又使表面具有生物相容性和生物活性等特点。等离子喷涂羟基磷灰石是临床上常用的制备活性涂层的方法。但是，等离子喷涂在高温下进行，涂层成分和晶体结构难于控制，并且设备要求高，成本昂贵，长期植入，有松动的倾向。见参考文献[4]：F.Li，Q.L.Feng

Z.Cui，H.D.Li and H.Schubert.A simple biomimeticmethod for calcium phosphate coating.Surface and Coatings Technology，2002，154：88-93。In developed countries, arthritis and fractures are one of the main reasons why the elderly cannot walk. In Japan, there are 100,000 cases of artificial hip joint replacement and artificial knee joint surgery every year. Therefore, it is of great significance to develop artificial joints and artificial bones with long-term stable quality in the market. See reference [1]: Li Qing. Titanium alloy surface coating applied to the study of biological bone. Bio-orthopedic materials and clinical research. 2004, 1[3]: 45-49. Titanium and titanium alloys have become important hard tissue repair and replacement materials due to their excellent mechanical properties, corrosion resistance and good biocompatibility. However, titanium and titanium alloys are biologically inert materials. When they are directly implanted as implants, the surface will be surrounded by biological collagen, which will isolate the implant from the biological bone. Long-term implantation will easily cause loosening, and it is difficult to form a firm structure with the biological bone. combined. The necessary condition for osseointegration of artificial implant and biological bone is that the surface of the artificial implant should form apatite similar to bone tissue in the living body. Once the apatite similar to the biological bone tissue is formed on the surface of the artificial implant, the biological cells will not be able to recognize it as a foreign body, but will regard it as the same kind of biological bone and grow together with the damaged biological bone, rapidly growing on the surface. Bone bud cells are implanted in the ground, and a firm chemical bond is formed between the apatite of the biological bone and the apatite on the surface of the artificial implant, and finally become one with the biological bone. See reference [2]: LL Hench, RJSplinter, WCAllen and TKGreenlee. Bonding mechanisms at the interface of ceramic prosthetic materials. Journal of Biomedical Materials Research Symposium. 1971, 2: 117-141. The study found that 45S5

Bio-glass (Na ₂ O-CaO-SiO ₂ -P ₂ O ₅ series), Ceravital glass-ceramics (Na ₂ OK ₂ O-MgO-CaO-P ₂ O ₅ -SiO ₂ series), AW bio-glass ceramics (MgO -CaO-SiO ₂ -P ₂ O ₅ series), hydroxyapatite bioactive ceramics (HA, composed of: Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ), etc. implanted in the body, will not be affected by fibrous Covered by a membrane, it can form a firm bond with the bone. See reference [3]: LL Hench. Bioceramics. Journal of American Ceramics Society. 1998, 81 [7]: 1705-1728. Therefore, if a layer of biological glass-ceramic coating can be prepared on the surface of titanium and titanium alloys, it can not only exert the excellent mechanical properties of the metal, but also make the surface have the characteristics of biocompatibility and bioactivity. Plasma spraying of hydroxyapatite is a commonly used method for preparing active coatings in clinical practice. However, plasma spraying is carried out at high temperature, and the composition and crystal structure of the coating are difficult to control, and the equipment requirements are high, the cost is high, and the long-term implantation tends to loosen. See reference [4]: F.Li, QLFeng

Z. Cui, HDLi and H. Schubert. A simple biomimetic method for calcium phosphate coating. Surface and Coatings Technology, 2002, 154: 88-93.

The present invention is based on the existing glass ceramics (patent application number: 200510047283.6, application date: 2005.9.28), and prepares glass ceramic coatings on the surface of titanium and titanium alloys with simple technology and cheap equipment. The glass ceramic coating does not contain SiO ₂ , no toxic elements, and has good biological activity. At the same time, the coating has a high Ca/P ratio and a composition similar to that of human hard tissue, and can be used as a replacement and repair material for human hard tissue. When the coating is implanted as an implant, it is expected to exert the excellent mechanical properties of titanium and titanium alloys and the good biological activity of the coating, and is expected to guide the growth of new bone faster and stronger.

Invention content:

组织替代和修复材料。The purpose of the present invention is to provide a method for preparing titanium and titanium alloy glass ceramic coating. The coating obtained by this method does not contain SiO ₂ , no toxic elements, and has good biological activity. It has similar components to human hard tissues and can be used as a

Tissue replacement and restorative materials.

Technical scheme of the present invention is:

The invention provides a method for preparing a titanium and titanium alloy glass-ceramic coating. The preparation of the coating includes the preparation of glass-ceramic powder, titanium and titanium alloy pretreatment, and coating and sintering of the coating. The specific steps are as follows:

(1) Preparation of glass ceramic powder

陶瓷粉末；The glass ceramic used is CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ glass ceramic powder, the composition of the glass ceramic powder is: the total content of CaO and P ₂ O ₅ is 80-90 mol%, and the content of Na ₂ O 4~7mol%, the rest is TiO ₂ and ZrO ₂ , the molar ratio of Ca to P is 0.5~1.5, and the content of ZrO ₂ is 0.5~10mol%; CaCO ₃ , Na ₂ CO ₃ , TiO ₂ , ZrO ₂ and H _3. PO ₄ is the raw material. Mix the raw materials evenly according to the above ingredients, prepare glass slurry, grind it into 5-10 μm powder after drying, heat it to 1300-1400 ° C to melt and keep it warm for 0.5-1 hour; then take it out Pour it on a stainless steel plate and punch it to get glass ceramics, and grind the obtained glass balls into 1-10 μm powder to get glass ceramics.

ceramic powder;

(2) Titanium and titanium alloy pretreatment

Titanium and titanium alloys are subjected to alumina blasting treatment to achieve a surface roughness of 1-5 μm;

(3) Coating and sintering of the coating

The glass-ceramic powder obtained by ball milling is made into methanol slurry, and the sandblasted titanium and titanium alloys are completely immersed, then extracted, dried naturally in the air, and then sintered in a resistance furnace.

The glass ceramics methanol solution has a concentration of 0.01-2M, an extraction speed of 0.5-5mm/s, a sintering temperature of 700-900°C and a sintering time of 0.5-3 hours.

The titanium and titanium alloys of the present invention adopt pure titanium, Ti6Al4V, Ti29Nb13Ta4.6Zr or Ti24Nb4Zr7.6Sn.

The main components of the coating prepared by the method of the invention are β-Ca ₃ (PO ₄ ) ₂ and β-Ca ₂ P ₂ O ₇ after being sintered at 700°C, 800°C and 900°C.

The coating prepared by the method of the invention has good biological activity, and hydroxyapatite can be formed after soaking in simulated human body fluid (SBF) for 4 days.

The bonding force between the coating prepared by the method of the invention and the titanium and titanium alloy substrate is greater than 15MPa.

The beneficial effects of the present invention are:

The glass-ceramic coating of the present invention does not contain SiO ₂ , no toxic elements, and has good biological activity. Hydroxyapatite will be formed after soaking in simulated human body fluid for 4 days; the coating has a high bond with titanium and titanium alloy substrates Force (greater than 15MPa). The coating has a high Ca/P ratio and a composition similar to that of human hard tissue, and can be used as a replacement and repair material for human hard tissue. When the coating is implanted as an implant, it is expected to exert the excellent mechanical properties of titanium and titanium alloys and the good biological activity of the coating, and is expected to guide the growth of new bone faster and stronger.

Description of drawings:

Figure 1 The physical appearance of glass powder 2# coated on the surface of pure titanium after sandblasting and sintered at 700 °C;

Figure 2 The surface X-ray diffraction pattern of glass powder 2# coated on the surface of pure titanium after sandblasting and sintered at 700 ° C;

Figure 3 Glass powder 4# is coated on the surface of the Ti6Al4V alloy sheet after sandblasting and sintered at 900 ° C and the surface X-ray diffraction pattern;

Fig. 4 The surface X-ray diffraction pattern of glass powder 9# coated on the surface of the Ti24Nb4Zr7.6Sn alloy sheet after sandblasting and sintered at 800 °C;

Figure 5 is the surface topography of glass powder 9# coated on the surface of the Ti24Nb4Zr7.6Sn alloy sheet after sandblasting and sintered at 800 °C;

Figure 6 is the surface topography of glass powder 9# coated on the surface of the Ti24Nb4Zr7.6Sn alloy sheet after sandblasting and sintered at 800 ° C and then soaked in simulated human body fluid (SBF) for 4 days;

Figure 7 is the surface topography of glass powder 3# coated on the surface of the Ti29Nb13Ta4.6Zr alloy sheet after sandblasting and sintered at 800 ° C and then soaked in simulated human body fluid (SBF) for 4 days;

Figure 8 is the surface X-ray diffraction pattern of glass powder 3# coated on the surface of Ti29Nb13Ta4.6Zr alloy sheet after sandblasting, sintered at 800°C and soaked in simulated human body fluid (SBF) for 4 days.

Detailed ways:

Example 1

Use analytically pure CaCO ₃ , Na ₂ CO ₃ , TiO ₂ , ZrO ₂ and H ₃ PO ₄ (weight concentration 85%) as raw materials to prepare glass slurry with ingredients 1 to 10# as described in Table 1, and use an electric mixer to mix the raw materials evenly , and then placed in a 50°C drying oven for 24 hours. Pound the dried raw material into powder (with a particle size of 5-10 μm) and place it in a platinum crucible at 1350°C for 0.5h, take it out immediately, pour it on a stainless steel plate, and press it quickly to obtain glass.

Table 1CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ glass components

Example 2

The obtained glass 2# is ball-milled into powder (with a particle size of 1-10 μm). The glass-ceramic powder is made into 0.01M methanol slurry, and the pure titanium rod is sandblasted with alumina with a particle size of 0.5mm (surface roughness is 1μm), and then suspended with a thin wire, lifted at a speed of 1mm/s, and placed in the air. After natural drying in medium temperature, keep it in a resistance furnace at 700°C for 1 hour, and then cool down with the furnace. The macro image of the real object is shown in Figure 1, and the X-ray diffraction pattern of the coating surface is shown in Figure 2.

Example 3

The obtained glass 4# is ball-milled into powder (with a particle size of 1-10 μm). The glass ceramic powder is made into 2M methanol slurry, the Ti6Al4V alloy sheet is sandblasted with alumina with a particle size of 3mm (surface roughness is 5μm), and then suspended with a thin wire, lifted at a speed of 5mm/s, and naturally in the air After drying, keep it in a resistance furnace at 900°C for 1 hour, and then cool down with the furnace. The X-ray diffraction pattern of the coating surface is shown in Figure 3.

Example 4

The obtained glass 9# is ball-milled into powder (with a particle size of 1-10 μm). The glass ceramic powder is made into 0.05M methanol slurry, and the Ti24Nb4Zr7.6Sn alloy sheet is sandblasted with alumina with a particle size of 2mm (surface roughness is 2.5μm), then suspended with a thin wire, and lifted at a speed of 2mm/s. After natural drying in the air, keep it in an 800°C resistance furnace for 1 hour, and then cool down with the furnace. The X-ray diffraction pattern of the coating surface is shown in Figure 4.

Example 5

After soaking the glass-ceramic coating obtained in Example 4 in simulated human body fluid (Table 2) at 37° C. for 4 days, hydroxyapatite was formed on the surface. The microscopic appearance before soaking is shown in Figure 5, and the microscopic appearance after soaking is shown in Figure 6.

Table 2 Ion concentrations (mM) in plasma and simulated body fluid (SBF) in the human body

Example 6

The obtained glass 3# is ball-milled into powder (with a particle size of 1-10 μm). The glass ceramic powder is made into 0.05M methanol slurry, and the Ti29Nb13Ta4.6Zr alloy sheet is sandblasted with alumina with a particle size of 2mm (surface roughness is 2.5μm), and then suspended with a thin wire, and lifted at a speed of 1mm/s. After natural drying in the air, keep it in an 800°C resistance furnace for 1 hour, and then cool down with the furnace. Then, after soaking in simulated human body fluid (Table 2) at 37°C for 4 days, hydroxyapatite was formed on the surface, the morphology of which is shown in Figure 7, and the surface X-ray diffraction pattern is shown in Figure 8.

Example 7

The Ti24Nb4Zr7.6Sn alloy was processed into a 5×5×30mm sample, which was sandblasted with 1mm alumina (with a surface roughness of 1.5μm) and suspended with a thin wire into a 0.05M glass-ceramic slurry with a composition of 2#. Lift at a speed of 2mm/s, dry naturally in the air and keep warm in a resistance furnace at 800°C for 1 hour, then cool with the furnace. The coated surface is bonded to stainless steel of the same size and cured with epoxy resin E-44. The sample was tested on the MTS tensile testing machine, the breaking strength was 15MPa, and the breaking occurred on the side of the epoxy resin.

Claims (4)

1, a kind of method for preparing the titanium or titanium alloy glass ceramic coating is characterized in that: the preparation of coating comprises the coating and the sintering of the preparation of glass ceramic powder, titanium or titanium alloy pre-treatment and coating, and concrete steps are as follows:

(1) preparation of glass ceramic powder

Used glass-ceramic is CaO-P ₂O ₅-Na ₂O-TiO ₂-ZrO ₂Glass ceramic powder, the consisting of of glass ceramic powder: CaO and P ₂O ₅Total content is at 80～90mol%, Na ₂The content of O is at 4～7mol%, and all the other are TiO ₂And ZrO ₂, Ca and P mol ratio are 0.5～1.5, ZrO ₂Content at 0.5～10mol%; With CaCO ₃, Na ₂CO ₃, TiO ₂, ZrO ₂And H ₃PO ₄Be raw material, by described composition raw material mixed that the formulate glass slurries are smashed into 5～10 μ m powder after drying to pieces, be heated to 1300～1400 ℃ of fusions and insulation, soaking time is 0.5～1 hour; Take out then and be poured on that punching press gets glass-ceramic on the stainless-steel sheet, the gained glass sphere is worn into 1～10 μ m powder promptly get glass ceramic powder;

(2) titanium or titanium alloy pre-treatment

Through the aluminum oxide sandblasting, reaching surfaceness is 1～5 μ m with the titanium or titanium alloy alloy;

(3) coating of coating and sintering

Ball milling gained glass ceramic powder is made into methanol slurry, the titanium or titanium alloy after the sandblasting is immersed fully, lixiviate then, in air after the seasoning in resistance furnace sintering.

2, according to the described method for preparing the titanium or titanium alloy glass ceramic coating of claim 1, it is characterized in that: in the described step 2, the aluminum oxide particle diameter is 0.5～3mm.

3, according to the described method for preparing the titanium or titanium alloy glass ceramic coating of claim 1, it is characterized in that: in the described step 3, described glass-ceramic concentration of methanol solution is 0.01～2M, lixiviate speed is 0.5～5mm/s, sintering temperature is respectively 700～900 ℃, and sintering time is 0.5～3 hour.

4, according to the described method for preparing the titanium or titanium alloy glass ceramic coating of claim 1, it is characterized in that: titanium or titanium alloy adopts pure titanium, Ti6Al4V, Ti29Nb13Ta4.6Zr or Ti24Nb4Zr7.6Sn.

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