CN101249280B

CN101249280B - Bionics method preparation of pure magnesium surface agustite coating

Info

Publication number: CN101249280B
Application number: CN200810047195XA
Authority: CN
Inventors: 王欣宇; 龚沛; 李世普; 闫玉华; 陈晓明; 韩颖超; 江昕; 李建华
Original assignee: Wuhan University of Technology WUT
Current assignee: Wuhan University of Technology WUT
Priority date: 2008-03-31
Filing date: 2008-03-31
Publication date: 2011-06-08
Anticipated expiration: 2028-03-31
Also published as: CN101249280A

Abstract

The present invention provides a method for preparing an apatite coating on a pure magnesium surface. The specific proposal is adopting a two-step acid and alkali method, which comprises the steps of activating the surface of a buffed and cleaned pure magnesium substrate, soaking the substrate in the solvent of CaCl2 and K2HPO4 for pre-calcification treatment, forming a layer of unformed calcium phosphate on the pure magnesium surface, putting the pure magnesium substrate into a calcium phosphorus saturated solution for certain time, and forming a layer of even apatite coating on the surface of the pure magnesium substrate.

Description

The biomimetic method preparation of pure magnesium surface apatite coating

Technical field

The present invention relates to a kind of method for preparing apatite coating at pure magnesium surface.

Background technology

The bio-medical metal material is occupying an important position aspect alternative and the repairing human body hard tissue owing to its good mechanical performance and processability.Yet its biology performance but can not be satisfactory, adds wearability and corrosion resistance that it is relatively poor, becomes the shortcoming of this material in engineering in medicine field application facet.(Hydroxyapatite, the composite that HA) prepares have fully utilized the biology performance of metal material excellent mechanical property and hydroxyapatite excellence, are ideal bone alternate materials to apply hydroxyapatite at metal base surface.

99124034.0,03117835.9,200510021026.5), laser cladding (Chinese application number: 200510030117.5), sol-gal process, electrophoretic deposition (Chinese application number: 200610055168.8) and bionical solwution method etc. at present the preparation apatite coating has a lot of methods, as: plasma spraying method (Chinese application number:.Biomimetic Solution Method for Preparing Apatite Coating is the new method of the preparation apatite coating that gets up of development in recent years.Bionical synthetic unique technological advantage that has, it is suitable for preparation phosphorus ash stone coating on the matrix of various material, different shape.Form apatite film with biomimetic method at material surface, need the group of elder generation usually in its surface formation energy induced nuclei generation, as-OH ,-COOH ,-NH ₂,-PO ₄H ₂Deng.These active groups easily combine with calcium, phosphonium ion in simulated body fluid and induce to form and examine, and then growth forms coating.

The present invention at first adopts the soda acid two-step method that pure magnesium is carried out surface activation process, again it is immersed CaCl ₂And K ₂HPO ₄Solution carries out pre-calcification to be handled, and goes out one deck amorphous calcium phosphate in surperficial preformed precipitate, and the amorphous calcium phosphate of formation can be induced the formation of apatite nucleus at matrix surface rapidly.

Summary of the invention

The invention provides a kind of new method for preparing apatite coating at pure magnesium surface.This method may further comprise the steps:

(1) with waterproof abrasive paper that pure magnesio sheet specimen surface polishing is coarse, again it is used successively distilled water, anhydrous propanone, distilled water ultrasonic cleaning, take out after finishing, air-dry standby;

(2) the pure magnesio sheet of step (1) cleaning-drying being crossed immerses the HCl solution soaking, takes out behind the acid etching 3min, cleans up in distilled water, and is air-dry standby;

(3) the pure magnesio sheet of step (2) cleaning-drying being crossed immerses in the NaOH solution of 0.5mol/L and soaks, and temperature is 100 ℃, and the time takes out after being no less than 30min, cleans up with distilled water, and is air-dry standby;

(4) use CaCl ₂Solution and K ₂HPO ₄Solution carries out pre-calcification to pure magnesio sheet surface to be handled

The CaCl of preparation 0.1mol/L ₂The K of solution and 0.1mol/L ₂HPO ₄Solution will place CaCl through the pure magnesio sheet that handled step (3) ₂In the solution, then to wherein dropwise adding isopyknic K ₂HPO ₄Solution constantly stirs in the process, is added dropwise to complete the back and continues to stir more than the 10min, after this leaves standstill more than the 1h, takes out with distilled water at last to clean up;

(5) will immerse through the pure magnesio sheet that handled step (4) and take out after being no less than 12d in the calcium phosphorus saturated solution (CalciumPhosphate supersaturated solution), after washed with de-ionized water, promptly obtain uniform apatite coating on pure magnesio sheet surface.

To cut into 10 * 10 * 5mm with 200#, 400# waterproof abrasive paper in the above-mentioned preparation method step (1) ³The polishing of pure magnesium sample coarse, again it is used successively distilled water, anhydrous propanone, distilled water ultrasonic cleaning 10min, taking-up is air-dry standby finishing after.Be no less than 1h drying time.

HCl solution described in the step (2) is 1mol/L HCl solution.

Treatment temperature described in the step (3) is necessary for 100 ℃, and the time is no less than 30min;

Calcium phosphorus saturated solution described in the step (5) is prepared as follows, is example to join 1000ml: dissolve 8.035g NaCl, 0.347g K successively ₂HPO ₄3H ₂O, 39ml 1.0M-HCl, 0.438g CaCl ₂And 6.118g (CH ₂OH) ₃CNH ₂In ultra-pure water, with 1.0M-HCl and (CH ₂OH) ₃CNH ₂Regulating pH value is 7.4.

The solution of HCl described in the present invention, NaOH solution, CaCl ₂Solution and K ₂HPO ₄Solution etc. all refer to the aqueous solution of this material, except as otherwise noted.

Description of drawings

Unprocessed pure magnesio sheet sample of Fig. 1 and pure magnesio sheet soak the XRD figure spectrum of the sample behind the 12d in calcium phosphorus saturated solution

The undressed pure magnesio sheet sample surfaces SEM image of Fig. 2

The pure magnesio sheet of Fig. 3 floods the sample surfaces SEM image behind the 12d in calcium phosphorus saturated solution

The specific embodiment

The invention will be further described below by embodiment

Embodiment 1 prepares apatite coating at pure magnesium surface

The preparation method step is:

(1) preparation of pure magnesio sheet and pretreatment are that to cut into volume be 10 * 10 * 5mm for 99.9% the pure magnesium of as cast condition with purity ³Sheet (substrate), use 200#, 400# liquid honing surface then.With the sample of polishing ultrasonic cleaning 10min in distilled water, anhydrous propanone, distilled water successively, take out after finishing, air-dry standby;

(2) the pure magnesio sheet of step (1) cleaning-drying being crossed immerses 1mol/L HCl solution soaking, takes out behind the acid etching 3min, cleans up in distilled water, and is air-dry standby;

(3) soak in the NaOH solution of the pure magnesio sheet immersion 0.5mol/L that step (2) cleaning-drying is crossed, temperature is 100 ℃, takes out behind the 30min, cleans up with distilled water, and is air-dry standby;

(4) pre-calcification is handled, the CaCl of preparation 0.1mol/L ₂The K of solution and 0.1mol/L ₂HPO ₄Solution will place CaCl through the pure magnesio sheet that handled step (3) ₂In the solution, then to wherein dropwise adding isopyknic K ₂HPO ₄Solution constantly stirs in the process, is added dropwise to complete the back and continues to stir 10min, after this leaves standstill 1h, takes out with distilled water at last to clean up;

(5) immersion of pure magnesio sheet in calcium phosphorus saturated solution, preparation 1000ml calcium phosphorus saturated solution dissolves 8.035g NaCl, K O.347g successively ₂HPO ₄3H ₂O, 39ml 1.0M-HCl, CaCl O.438g ₂And 6.118g (CH ₂OH) ₃CNH ₂In ultra-pure water, with 1.0M-HCl and (CH ₂OH) ₃CNH ₂Regulating pH value is 7.4; Take out after will in calcium phosphorus saturated solution, soaking 12d through the pure magnesio sheet after step (4) is handled, clean its surface, clean the air-dry survey fully in back with ultra-pure water.

Carry out thin film XRD (Japan, D/MAX-RB type) test to dried sample with without the pure magnesio sheet that said method is handled, test condition is: the Cu target, running voltage is 35kv, operating current is 30MA, and the scope of taking measurement of an angle is 10～60 °, and rotating speed is 10 °/min.Test result as shown in Figure 1, treated as shown in Figure 1 pure magnesio sheet surface has hydroxyapatite crystal to form.

Untreated pure magnesio sheet sample is carried out SEM (Japanese JEOL company, JSM-5610LV type) observe, observed result as shown in Figure 2.

The pure magnesio sheet sample of handling through the inventive method is carried out SEM observe, observed result has formed the layer of even apatite coating on the treated as seen from the figure pure magnesio sheet as shown in Figure 3, and coated crystal in the form of sheets.

Claims

1. method for preparing apatite coating at pure magnesium surface.It is characterized in that this preparation method may further comprise the steps:

(1) with waterproof abrasive paper that pure magnesium sheet specimen surface polishing is coarse, again it is used successively distilled water, anhydrous propanone, distilled water ultrasonic cleaning, take out after finishing, air-dry standby;

(2) the pure magnesium sheet of step (1) cleaning-drying being crossed immerses 1mol/L HCl solution soaking, takes out behind the acid etching 3min, cleans up in distilled water rapidly, and is air-dry standby;

(3) the pure magnesium sheet of step (2) cleaning-drying being crossed immerses in the NaOH solution of 0.5mol/L and soaks, and temperature is 100 ℃, and the time takes out after being no less than 30min, cleans up with distilled water, and is air-dry standby;

(4) use CaCl ₂Solution and K ₂HPO ₄Solution carries out pre-calcification to pure magnesium sheet surface to be handled

The CaCl of preparation 0.1mol/L ₂The K of solution and 0.1mol/L ₂HPO ₄Solution will place CaCl through the pure magnesium sheet that handled step (3) ₂In the solution, then to wherein dropwise adding isopyknic K ₂HPO ₄Solution constantly stirs in the process, is added dropwise to complete the back and continues to stir more than the 10min, after this leaves standstill more than the 1h, takes out with distilled water at last to clean up;

(5) will immerse through the pure magnesium sheet that handled step (4) and take out after being no less than 12d in the calcium phosphorus saturated solution, after washed with de-ionized water, promptly obtain uniform apatite coating on pure magnesium sheet surface, wherein said calcium phosphorus saturated solution is prepared as follows, preparation 1000ml dissolves 8.035g NaCl, 0.347g K successively ₂HPO ₄3H ₂O, 39ml 1.0M-HCl, 0.438g CaCl ₂And 6.118g (CH ₂OH) ₃CNH ₂In ultra-pure water, with 1.0M-HCl and (CH ₂OH) ₃CNH ₂Regulating pH value is 7.4.

2. as claimed in claim 1ly prepare the method for apatite coating, it is characterized in that, will cut into 10 * 10 * 5mm with 200#, 400# waterproof abrasive paper in the described step (1) at pure magnesium surface ³The polishing of pure magnesium sample coarse, again it is used successively distilled water, anhydrous propanone, distilled water ultrasonic cleaning 10min, taking-up is air-dry standby finishing after.