CN110438484A - A kind of preparation method of HA nano-array bioactivity coatings - Google Patents
A kind of preparation method of HA nano-array bioactivity coatings Download PDFInfo
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- CN110438484A CN110438484A CN201910626363.9A CN201910626363A CN110438484A CN 110438484 A CN110438484 A CN 110438484A CN 201910626363 A CN201910626363 A CN 201910626363A CN 110438484 A CN110438484 A CN 110438484A
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- nano
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- lye
- bioactivity coatings
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/64—Treatment of refractory metals or alloys based thereon
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- Inorganic Chemistry (AREA)
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- Thermal Sciences (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a kind of preparation methods of HA nano-array bioactivity coatings, first using deionized water as solvent, using sodium hydroxide as solute, prepare lye, and polished titanium sheet is soaked in lye and is pre-processed to get netted Na is arrived2Ti3O7Coating；Then using deionized water as solvent, it is 11-12.5 that pH value of solution is adjusted using calcium salt and microcosmic salt as solute, after mixing, then netted Na2Ti3O7Painting is placed in solution is reacted using solvent-thermal method, obtains HA nano-array bioactivity coatings in titanium alloy surface after reaction.The present invention prepares the good hydroxyapatite nano stick coating of bioactivity on titanium surface using sodium hydroxide lye immersion-hydro-thermal composite algorithm, simplifies experimental technique, has saved manufacturing cost.
Description
Technical field
The present invention relates to the field of surface modification of titanium and titanium alloy member, and in particular to a kind of HA nano-array bioactivity
The preparation method of coating.
Background technique
With aging of population, hip replacement and tooth mobility have seriously affected people's lives quality, therefore plant
The development prospect of body is huge, and Titanium is biologically inert, and one layer of fibr tissue, In can be formed on its surface after implanting
Under biggish stress, with bone tissue the changing of the relative positions can occur for fibr tissue, so as to cause loosening, so must be modified.Hydroxyl phosphorus
Lime stone is the main inorganic composition of human body bone, since its composition is similar with nature bone, will not generate irritation after being implanted into organism
And rejection, and the ability with good induction new bone formation, planting body coating material is often used as to improve cell
Response and osteoconductive.And nano-array is similar with the collagen fiber structure of body bone tissue is constituted, nanoscale pattern is also more
Close to the pattern of natural bone tissue, the bionics effect having had, while can also pass through change material surface protein
Conformation, provide site for the attachment of protein, and then promote the adherency of subsequent osteoblast, sprawl.
The method of synthesizing hydroxylapatite has at present: vapour deposition process, sol-gel method, differential arc oxidation-hydro-thermal are compound
Method, differential arc oxidation-electrophoretic deposition composite algorithm etc., but above method the defects of there are complex process, at high cost, poor bonding strength,
To limit its application in sclerous tissues' implantation material.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of HA nano-array bioactivity coatings, to overcome existing skill
Art there are the problem of.The present invention is good in titanium alloy surface preparation bioactivity using sodium hydroxide lye immersion-hydro-thermal composite algorithm
Good HA nano-array, simplifies experimental technique, has saved manufacturing cost.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of preparation method of HA nano-array bioactivity coatings, comprising the following steps:
Step 1: preparing lye, and polished titanium sheet is soaked in lye and is pre-processed to get netted titanium is arrived
Chromate coatings；
Step 2: using deionized water as solvent, it is 11-12.5 that pH value of solution is adjusted using calcium salt and microcosmic salt as solute, after mixing,
Then netted titanate painting is placed in solution and is reacted using solvent-thermal method, obtaining surface after reaction is HA nanometers
Array internal layer is the bioactivity coatings of titanate.
Further, lye is using deionized water as solvent, using sodium hydroxide or potassium hydroxide as solute in step 1.
Further, the concentration of lye is 1-10mol/L in step 1.
Further, pretreated temperature is 30-40 DEG C in step 1, time 1-2h.
Further, calcium salt described in step 2 is calcio-disodium edetate.
Further, microcosmic salt described in step 2 is the mixture of diammonium hydrogen phosphate, ammonium hydrogen phosphate or both.
Further, the concentration of calcium salt is 0.167-0.334mol/L in acquired solution in step 2, and microcosmic salt concentration is
0.1mol/L。
Further, the temperature reacted in step 2 is 180-240 DEG C, time 3-20h.
Compared with prior art, the invention has the following beneficial technical effects:
The main method that document report prepares HA at present is differential arc oxidation-hydro-thermal composite algorithm, and differential arc oxidation will be used largely
Sodium β-glycerophosphate, it is expensive, and micro-arc oxidation process will be completed in special equipment, and the device is complicated.And this
Invention is prepared for HA nano-array using dipping by lye-hydro-thermal composite algorithm, provides one kind more just for the preparation of HA nano-array
Prompt scheme.The Lattice Matching degree of the titanate obtained after dipping by lye and HA crystal is higher, and HA is easier on titanate surface
Forming core growth.The HA nano-array of this method preparation has higher biology living while guaranteeing coating binding force and intensity
Property, have great importance in the application of hard tissue implanting material.
Detailed description of the invention
Fig. 1 is the netted Na that the embodiment of the present invention 1 obtains2Ti3O7The SEM photograph of coating；
Fig. 2 is the netted Na that the embodiment of the present invention 1 obtains2Ti3O7The XRD spectra of coating；
Fig. 3 is the SEM photograph for the HA nanometer rods that the embodiment of the present invention 1 obtains；
Fig. 4 is the XRD spectra for the HA nanometer rods that the embodiment of the present invention 1 obtains；
Fig. 5 is the film substrate bond strength for the coating that the embodiment of the present invention 1 obtains；
Fig. 6 is the biological evaluation for the coating that the embodiment of the present invention 1 obtains.
Specific embodiment
Present invention is further described in detail below:
A kind of preparation method of HA nano-array bioactivity coatings, comprising the following steps:
Step 1: using deionized water as solvent, sodium hydroxide or potassium hydroxide are solute, prepare lye, wherein hydroxide
Sodium or concentration of potassium hydroxide are 1-10mol/L.It polished titanium sheet is soaked in lye is placed in 30-40 DEG C of insulating box and carry out
Pretreatment, reaction time 1-2h.After reaction, netted titanate coating is obtained；
Step 2: solvent-thermal method is utilized, using deionized water as solvent, (wherein, calcium salt is second as solute using calcium salt and microcosmic salt
Ethylenediamine tetraacetic acid (EDTA) calcium sodium, microcosmic salt are the mixture of diammonium hydrogen phosphate, ammonium hydrogen phosphate or both), the concentration of calcium salt is 0.167-
0.334mol/L, microcosmic salt concentration are 0.1mol/L.The pH value for adjusting solution is 11-12.5.By solution and pretreated sample
It is placed in reaction kettle and is reacted, reaction temperature is 180-240 DEG C, time 3-20h.It is obtained after reaction with array junctions
The HA nanometer rods of structure.
Below with reference to embodiment, the present invention will be described in detail:
Embodiment 1
Step 1: sodium hydroxide is solute using deionized water as solvent, 10mol/L lye is prepared.By polished titanium sheet
It is soaked in be placed in 37 DEG C of insulating boxs in lye and be pre-processed, reaction time 1h.After reaction, it obtains netted
Na2Ti3O7Coating；
Step 2: 15ml is prepared using calcio-disodium edetate, diammonium hydrogen phosphate as the solution of solute, wherein ethylenediamine
The concentration of tetraacethyl calcium sodium is 0.2338mol/L, and the concentration of diammonium hydrogen phosphate is 0.1mol/L.It is adjusted with sodium hydroxide lye molten
The pH to 12.5 of liquid.Above-mentioned solution is transferred in 50mL high-temperature high-pressure reaction kettle, pretreated sample is then placed in reaction
In kettle, 20h is kept the temperature under the conditions of 240 DEG C, the HA nano-array that diameter is 30nm or so can be prepared.
Titanium alloy surface after pretreated as can be seen from Figure 1 is in reticular structure, and is evenly distributed.In conjunction with the XRD of Fig. 2
Spectrogram can be seen that Na2Ti3O7Mutually occur, this is that lye occurs to chemically react phase generated with pure titanium.It can from Fig. 3
The nano-array that diameter is 30nm or so is generated after hydro-thermal reaction out.It can be seen that occurred HA's in conjunction with the XRD spectra of Fig. 4
Object phase, therefore nano-array is hydroxyapatite.The minimum film substrate bond strength that human body hard tissue is implanted into material is 14N, from Fig. 5
It can be seen that the film substrate bond strength of HA nano-array is greater than 28.5N, meets implantation and require.Fig. 6 is fibroblast in coating
The fluorescent staining of actin and nucleus after surface culture 3d, it can be seen that HA nano-array has good bioactivity.
Embodiment 2
Step 1: potassium hydroxide is solute using deionized water as solvent, 1mol/L lye is prepared.By polished titanium sheet
It is soaked in lye to be placed in 40 DEG C of insulating boxs, reaction time 2h.After immersion, netted K is obtained2Ti3O7Coating；
Step 2: 15ml is prepared using calcio-disodium edetate, diammonium hydrogen phosphate and ammonium hydrogen phosphate mixture as solute
Solution utilizes solvent-thermal method, wherein the concentration of calcio-disodium edetate is 0.167mol/L, diammonium hydrogen phosphate and ammonium hydrogen phosphate
The concentration of mixture is 0.1mol/L.The pH value of solution is adjusted to 11.Above-mentioned solution is transferred in 50mL high-temperature high-pressure reaction kettle,
Then pretreated sample is placed in reaction kettle, keeps the temperature 3h under the conditions of 180 DEG C, it is 10nm or so that diameter, which can be prepared,
HA nano-array.
Embodiment 3
Step 1: sodium hydroxide is solute using deionized water as solvent, 5mol/L lye is prepared.By polished titanium sheet
It is soaked in lye to be placed in 30 DEG C of insulating boxs, reaction time 1.5h.After immersion, netted Na is obtained2Ti3O7Coating；
Step 2: preparing 15ml using calcio-disodium edetate, ammonium hydrogen phosphate as the solution of solute and utilize solvent-thermal method,
In, the concentration of calcio-disodium edetate is 0.334mol/L, and the concentration of ammonium hydrogen phosphate is 0.1mol/L.The pH value of solution is
12.Above-mentioned solution is transferred in 50mL high-temperature high-pressure reaction kettle, then pretreated sample is placed in reaction kettle, 200 DEG C
Under the conditions of keep the temperature 10h, the HA nano-array that diameter is 20nm or so can be prepared.
Claims (8)
1. a kind of preparation method of HA nano-array bioactivity coatings, which comprises the following steps:
Step 1: preparing lye, and polished titanium sheet is soaked in lye and is pre-processed to get netted titanate is arrived
Coating；
Step 2: using deionized water as solvent, it is 11-12.5 that pH value of solution is adjusted using calcium salt and microcosmic salt as solute, after mixing, then
Netted titanate painting is placed in solution and is reacted using solvent-thermal method, obtaining surface after reaction is HA nano-array
Internal layer is the bioactivity coatings of titanate.
2. a kind of preparation method of HA nano-array bioactivity coatings according to claim 1, which is characterized in that step
Lye is using deionized water as solvent, using sodium hydroxide or potassium hydroxide as solute in one.
3. a kind of preparation method of HA nano-array bioactivity coatings according to claim 1, which is characterized in that step
The concentration of lye is 1-10mol/L in one.
4. a kind of preparation method of HA nano-array bioactivity coatings according to claim 1, which is characterized in that step
Pretreated temperature is 30-40 DEG C in one, time 1-2h.
5. a kind of preparation method of HA nano-array bioactivity coatings according to claim 1, which is characterized in that step
Calcium salt described in two is calcio-disodium edetate.
6. a kind of preparation method of HA nano-array bioactivity coatings according to claim 1, which is characterized in that step
Microcosmic salt described in two is the mixture of diammonium hydrogen phosphate, ammonium hydrogen phosphate or both.
7. a kind of preparation method of HA nano-array bioactivity coatings according to claim 1, which is characterized in that step
The concentration of calcium salt is 0.167-0.334mol/L in acquired solution in two, and microcosmic salt concentration is 0.1mol/L.
8. a kind of preparation method of HA nano-array bioactivity coatings according to claim 1, which is characterized in that step
The temperature reacted in two is 180-240 DEG C, time 3-20h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112226767A (en) * | 2020-09-29 | 2021-01-15 | 西安交通大学 | Hydroxyapatite nanorod biological coating and preparation method thereof |
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| CN1695744A (en) * | 2005-06-14 | 2005-11-16 | 河北工业大学 | Biomedicine material of titanium or titanium alloy in use for artificial bones, and preparation method |
| CN101537208A (en) * | 2008-03-21 | 2009-09-23 | 中国科学院金属研究所 | Biological active coating on surface of titanium or titanium alloy and preparation method thereof |
| US20140377449A1 (en) * | 2011-11-14 | 2014-12-25 | Obl (Société Anonyme) | Method for the surface treatment of titanium bone implants using, in order, a sodium hydroxide bath and anodization |
| CN107130279A (en) * | 2017-04-20 | 2017-09-05 | 西安交通大学 | A kind of HA nanotubes bioactivity coatings preparation method |
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2019
- 2019-07-11 CN CN201910626363.9A patent/CN110438484A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1695744A (en) * | 2005-06-14 | 2005-11-16 | 河北工业大学 | Biomedicine material of titanium or titanium alloy in use for artificial bones, and preparation method |
| CN101537208A (en) * | 2008-03-21 | 2009-09-23 | 中国科学院金属研究所 | Biological active coating on surface of titanium or titanium alloy and preparation method thereof |
| US20140377449A1 (en) * | 2011-11-14 | 2014-12-25 | Obl (Société Anonyme) | Method for the surface treatment of titanium bone implants using, in order, a sodium hydroxide bath and anodization |
| CN107130279A (en) * | 2017-04-20 | 2017-09-05 | 西安交通大学 | A kind of HA nanotubes bioactivity coatings preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112226767A (en) * | 2020-09-29 | 2021-01-15 | 西安交通大学 | Hydroxyapatite nanorod biological coating and preparation method thereof |
| CN112226767B (en) * | 2020-09-29 | 2021-12-28 | 西安交通大学 | Hydroxyapatite nanorod biological coating and preparation method thereof |
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