CN103405806B

CN103405806B - Method used for surface bio-activation of porous anodic alumina (PAA)

Info

Publication number: CN103405806B
Application number: CN201310311849.6A
Authority: CN
Inventors: 倪似愚; 李晓宏; 李长艳; 于晓伟
Original assignee: Donghua University
Current assignee: Donghua University; National Dong Hwa University
Priority date: 2013-07-23
Filing date: 2013-07-23
Publication date: 2014-12-10
Anticipated expiration: 2033-07-23
Also published as: CN103405806A

Abstract

The invention relates to a method used for surface bio-activation of porous anodic alumina (PAA). The method comprises following steps: porous anodic alumina (PAA) is immersed in a modifying solution containing phosphorus for 2 to 6h; after that, porous anodic alumina (PAA) is taken out from the solution, is subjected to vacuum drying and calcining, and is cooled to room temperature naturally and washed so as to obtain modified PAA. Production cost of the method is low, operation is simple, and effects are obvious. Activated PAA possesses excellent capability of inducing the formation of bone like apatite, and possesses positive meanings on the research of surface activation of biomaterials.

Description

A kind of method to porous anodic aluminium oxide PAA surface biological activation modification

Technical field

The invention belongs to porous anodic aluminium oxide PAA method of modifying field, particularly a kind of method to porous anodic aluminium oxide PAA surface biological activation modification.

Background technology

PAA surface has orderly cellular porous structure, there is excellent abrasion-proof rust-preventing performance and biocompatibility, and after implanting, there is good biological safety, have no side effect, be therefore expected to the face coat as a kind of novel biomedical metallic material.But due to the PAA Al-OH group positively charged that its surface forms in body fluid environment, the ability itself without induction osteoid apatite deposition, is biologically inert (J Ceram Soc Jpn, 2001,109 (4): S49-S57), therefore after implant into body, be that mechanical embedding connects with surrounding bone tissue, and inanimate combination is lower with the bond strength of bone, easily there is loosening and the (J.Bimed.Mater.Res. that comes off, 1997,37:267-275), limit its application and development.Therefore, if bioactivation modification is carried out in PAA surface, can under physiological environment, induce osteoid apatite generate, thereby just may realize and osseous tissue between chemical bonding.Have scholar apply the ceramic coating that induced activity group produces in vivo or directly apply active group at inertia biomaterial surface, compound go out all good novel hard tissue materials of biological activity and mechanical property.Therefore, utilize surface active modification technology not only can improve stability and the wearability of metal surface, can also give implant biological activity.PAA surface, after bioactivation modification, is desirably in and under physiological environment, can induces bone like apatite layer deposition, thereby be conducive to sticking and breed of correlation function cell, promotion implant in early days, synosteosis firmly.This is having very important meaning aspect clinical plastic surgery operations.

The people such as He (Materials Science and Engineering A367 (2004) 51-56) plate certain thickness Al film by magnetron sputtering physical vapor deposition (PVD) technology on Ti sheet metal, then containing carrying out anodic oxidation in the electrolyte of Ca, P, by the PAA thin film hydrothermal treatment consists under certain conditions after anodic oxidation, finally on Ti sheet, obtain CaP(polymer fibrous, nanoporous)/Al ₂o ₃composite biological coating, this composite biological material, except having good biological activity, also shows good biochemistry stability, high strength and excellent wear-resisting erosion resistance, has good clinical practice potentiality.The people such as Erin (Biomaterials2005,26:1969-1976) strengthened osteoblast in the ability of sticking of material surface and the expression of associated protein by the fixing RGDC polypeptide of physical absorption vitronectin and covalency on PAA, and the matched group PAA of unmodified do not have these significant effects.The people such as Wu (Materials Letters, 2007,61:2952-2955) have synthesized HAP/Al by methods such as physical vapour deposition (PVD), anodic oxidation, gas phase treatment, electro-deposition and hydrothermal treatment consists in Ti substrate ₂o ₃composite biological coating, this composite biological coating has the ability that good induction osteoid apatite generates in SBF, but this material also has unsatisfactory part, the equipment complexity that preparation method requires, cost is had relatively high expectations relatively, energy consumption is larger, and structure, crystalline phase and the performance of coating is subject to the impact of many technological parameters, is difficult to promote on a large scale.

Summary of the invention

Technical problem to be solved by this invention is to provide a kind of method to porous anodic aluminium oxide PAA surface biological activation modification, and the method preparation cost is low, simple to operate, and effect is remarkable; The PAA of activated state possesses the ability that good induction osteoid apatite forms, and biomaterial surface activation study on the modification is had to very positive meaning.

A kind of method to porous anodic aluminium oxide PAA surface biological activation modification of the present invention, comprising:

(1) porous anodic aluminium oxide PAA is placed in to phosphorous modified solution and floods 2-6h, wherein temperature maintains 0-5 DEG C;

(2) take out after porous anodic aluminium oxide PAA, carry out vacuum drying, calcining, then naturally cools to room temperature, and washing, to remove unconjugated PO in PAA surface and hole ₄ ^3-group, obtains the PAA after modification.

In described step (1), the aperture of PAA is 50-200nm, and pore wall thickness is 15-60nm.

In described step (1), phosphorous modified solution is phosphoric acid solution, ammonium phosphate solution or ammonium hydrogen phosphate solution; In phosphorous modified solution, the concentration of phosphate radical or phosphoric acid hydrogen radical ion is 0.1-0.5M.

In described step (2), vacuum drying temperature is 100-130 DEG C, and the time is 10-15h.

While calcining in described step (2), heating rate is 1-3 DEG C/min, and calcining heat is 500-600 DEG C, and calcination time is 3-6h.

The present invention is by PAA dipping, dry, after calcination processing, introduces PO on its surface ₄ ^3-group, makes the oxide-film of the passivation state of former inertia be converted into activated state oxide-film, and the PAA of this activated state possesses the ability that good induction osteoid apatite forms, and biomaterial surface activation study on the modification is had to very positive meaning.

The sign of material and Bioactivity evaluation

Before and after modification, FTIR, the EDS of PAA characterize:

Before and after modification shown in Fig. 2, the EDS collection of illustrative plates of PAA has illustrated that the PAA after modification is mixed with P element; Adopt FTIR to characterize the characteristic group on PAA surface before and after modification, as shown in Figure 3,1078cm ^-1the strong absworption peak at place belongs to the peculiar P-O absworption peak of modification PAA, illustrates on PAA surface and has introduced PO ₄ ^3-group.

The simulated body fluid immersion test of modification PAA

The present invention selects a kind of ion concentration close with human plasma, pH value is 7.4 simulated body fluid (Simulated Body Fluid, SBF) study the Bioactivity of modification PAA, the composition of simulated body fluid is as shown in table 1, and the preparation of simulated body fluid is by analytical reagent NaCl, NaHCO ₃, KCl, K ₂hPO ₄.3H ₂o, MgCl ₂.6H ₂o, CaCl ₂and Na ₂sO ₄be dissolved in deionized water, then use hydrochloric acid (HCl) and Tris ((CH ₂oH) ₃cNH ₂) be buffered to pH=7.4, it is conformed to the pH of human plasma.

The ion concentration (mM) of table 1 simulated body fluid and human plasma

PAA after modification is placed in to the each ultrasonic cleaning 10min of deionized water, and natural drying, then puts into PAA the SBF of 37 DEG C, respectively at 1 day, 3 days and taking-up afterwards in 7 days, with natural drying after washed with de-ionized water, in experimentation, changes a SBF every 24h.Use the field emission scanning electron microscope (FESEM) with X-ray energy spectrum to observe the modification of surface morphology of specimen surface after SBF soaks different time, the experimental result that SBF soaks shows: modification PAA immersed after SBF1 days, and heterogeneous nucleation growth occurs calcium phosphorus crystal on functionalized surface; Along with the prolongation of soak time, the bone like apatite layer that modification PAA surface forms is more and more finer and close, microcellular structure is covered by bone like apatite layer gradually, show that modification PAA has good biological activity, analyze modification PAA by Fourier transform infrared spectroscopy (FTIR) and soak different time rear surface chemical composition through SBF and change, what its result had further confirmed to form in the PAA surface of modification and hole is osteoid apatite.

As can be seen here, can effectively in PAA surface and hole, introduce PO by PAA surface being carried out to bonderizing ₄ ^3-group, shows that by SBF immersion test the PAA of modification has good biological activity subsequently, can be used as the coating material with good biological activity, has good practical value.

beneficial effect

(1) preparation cost of the present invention is low, simple to operate, and effect is remarkable;

(2) PAA of the activated state of gained of the present invention possesses the ability that good induction osteoid apatite forms, and biomaterial surface activation study on the modification is had to very positive meaning;

(3) the activated state PAA surface of gained of the present invention is expected to as a kind of face coat of novel Artificial Intervention material and is applied to technical field of biological material.

Brief description of the drawings

Fig. 1 is low power (a) and high power (b) the FESEM figure on PAA surface before modification;

Fig. 2 be before modification and modification after the EDS collection of illustrative plates on PAA surface;

Fig. 3 be before modification and modification after the FTIR collection of illustrative plates on PAA surface;

Fig. 4 is that modification PAA soaks low power (a) and high power (b) the FESEM figure after SBF1 days;

Fig. 5 is that modification PAA soaks low power (c) and high power (d) the FESEM figure after SBF3 days;

Fig. 6 is that modification PAA soaks low power (e) and high power (f) the FESEM figure after SBF7 days;

Fig. 7 is that modification PAA soaks the EDS collection of illustrative plates after SBF1 days;

Fig. 8 is that modification PAA soaks the EDS collection of illustrative plates after SBF3 days;

Fig. 9 is that modification PAA soaks the EDS collection of illustrative plates after SBF7 days;

Figure 10 is that modification PAA soaks SBF1, the FTIR collection of illustrative plates after 3,7 days;

Figure 11 is that modification PAA soaks the XRD figure spectrum after SBF7 days.

Detailed description of the invention

Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.

Embodiment 1

(1) preparation phosphoric acid modification solution, wherein the concentration of phosphoric acid is 0.4M, is 130nm by aperture, and the PAA that pore wall thickness is 36nm is placed in phosphoric acid modification solution and floods 4h, and the temperature of system maintains 0 DEG C;

(2) take out the PAA in above-mentioned modified solution, then at 110 DEG C vacuum drying 10h;

(3) PAA after vacuum drying is proceeded to calcining at 500 DEG C in Muffle furnace, its heating rate is 2 DEG C/min, and temperature retention time is 5h, naturally cools to room temperature, sample after treatment rinses PAA surface repeatedly through deionized water, removes unconjugated PO in PAA surface and hole ₄ ^3-group.

(4) modification PAA carries out Bioactivity research: the PAA after modification is completed soaks after 1 day and carries out FESEM, EDS and FTIR sign in SBF, and its result is as shown in Fig. 4, Fig. 7 and Figure 10.

Embodiment 2

(1) preparation ammonium phosphate modified solution, wherein the concentration of ammonium phosphate is 0.3M, is 160nm by aperture, and the PAA that pore wall thickness is 45nm is placed in ammonium phosphate modified solution and floods 3h, and the temperature of system maintains 3 DEG C;

(2) take out the PAA in above-mentioned modified solution, then at 120 DEG C vacuum drying 12h;

(3) PAA after vacuum drying is proceeded to calcining at 550 DEG C in Muffle furnace, its heating rate is 1 DEG C/min, and temperature retention time is 3h, naturally cools to room temperature, sample after treatment rinses PAA surface repeatedly through deionized water, removes unconjugated PO in PAA surface and hole ₄ ^3-group.

(4) modification PAA carries out Bioactivity research: the PAA after modification is completed soaks after 3 days and carries out FESEM, EDS and FTIR sign in SBF, and its result is as shown in Fig. 5, Fig. 8 and Figure 10.

Embodiment 3

(1) preparation ammonium hydrogen phosphate modified solution, wherein the concentration of ammonium hydrogen phosphate is 0.5M, is 180nm by aperture, and the PAA that pore wall thickness is 55nm is placed in ammonium hydrogen phosphate modified solution and floods 5h, and the temperature of system maintains 4 DEG C;

(2) take out the PAA in above-mentioned modified solution, then at 100 DEG C vacuum drying 14h;

(3) PAA after vacuum drying is proceeded to calcining at 600 DEG C in Muffle furnace, its heating rate is 3 DEG C/min, naturally cools to room temperature, and sample after treatment rinses PAA surface repeatedly through deionized water, removes unconjugated PO in PAA surface and hole ₄ ^3-group.

(4) modification PAA carries out Bioactivity research: the PAA after modification is completed soaks after 7 days and carries out FESEM, EDS, FTIR and XRD sign in SBF, and its result is as shown in Fig. 6, Fig. 9, Figure 10 and Figure 11.

Claims

1. the method to porous anodic aluminium oxide PAA surface biological activation modification, comprising:

(1) porous anodic aluminium oxide PAA is placed in to phosphorous modified solution and floods 2-6h, wherein temperature maintains 0-5 DEG C; Wherein the aperture of PAA is 50-200nm, and pore wall thickness is 15-60nm; Phosphorous modified solution is phosphoric acid solution, ammonium phosphate solution or ammonium hydrogen phosphate solution; In phosphorous modified solution, the concentration of phosphate radical or phosphoric acid hydrogen radical ion is 0.1-0.5M;

(2) take out after porous anodic aluminium oxide PAA, carry out vacuum drying, calcining, then naturally cools to room temperature, and washing, obtains the PAA after modification.

2. a kind of method to porous anodic aluminium oxide PAA surface biological activation modification according to claim 1, is characterized in that: in described step (2), vacuum drying temperature is 100-130 DEG C, and the time is 10-15h.

3. a kind of method to porous anodic aluminium oxide PAA surface biological activation modification according to claim 1, it is characterized in that: while calcining in described step (2), heating rate is 1-3 DEG C/min, calcining heat is 500-600 DEG C, and calcination time is 3-6h.