CN103952745A - Method for preparing zinc phosphate conversion coating on surface of titanium - Google Patents
Method for preparing zinc phosphate conversion coating on surface of titanium Download PDFInfo
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- CN103952745A CN103952745A CN201410191307.4A CN201410191307A CN103952745A CN 103952745 A CN103952745 A CN 103952745A CN 201410191307 A CN201410191307 A CN 201410191307A CN 103952745 A CN103952745 A CN 103952745A
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- titanium
- chemical conversion
- zinc phosphate
- zinc
- phosphate conversion
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Abstract
The invention discloses a method for preparing a zinc phosphate conversion coating on the surface of titanium. The method comprises the following steps: mixing a phosphorous compound, a zinc-containing compound, a calcium-containing compound and an accelerant together to form a chemical conversion basic liquid; performing activating treatment and surface adjustment on a pure titanium substrate; putting the treated pure titanium substrate in the chemical conversion basic liquid and applying an electric current field, wherein the pure titanium substrate is taken as a cathode, while platinum is taken as an anode; and obtaining the zinc phosphate conversion coating on the surface of titanium after chemical conversion. In such a manner, the reaction of the method for preparing the zinc phosphate conversion coating on the surface of titanium can be finished at a relatively low temperature, and the obtained product is high in degree of crystallinity and good in electrochemical performance; the method is low in pollution, low in cost and simple in process, and thus suitable for large-scale production and application; the zinc phosphate conversion coatings more excellent in mechanical properties can be obtained by use of the methods of solution optimization, current intensity change, time control and the like.
Description
Technical field
The present invention relates to biomedical metallic material field, particularly relate to a kind of method of preparing zinc phosphate conversion film on titanium surface.
Background technology
Four water zinc phosphate (Zn
3(PO4)
24H
2o) because thering is good solidity to corrosion and protective, be widely used in metallic surface anticorrosion, improve the aspects such as application bonding force and surface lubrication.Recent four water zinc phosphates are found to have good biocompatibility and can be converted into hydroxyapatite (HA) under certain condition, can be used as a kind of potential bio-medical material.Titanium is lightweight because having, intensity is large and the good characteristic such as good corrosion resistance is widely used in the industrial circles such as national defence aerospace, shipbuilding.Meanwhile, because titanium and the near feature such as Young's modulus, good biocompatibility of bone photo are also widely used clinically.Prepare one deck zinc phosphate conversion film on titanium surface, both can improve its surfacecti proteon performance, be applied to the fields such as industry military affairs, also can be used as biological metal implant material surface modification and be applied to medical field.But titanium surface is because the preparation that has stable oxide film to be difficult to carry out conversion film has limited its application.
The research of preparing for titanium surface phosphoric acid zinc both at home and abroad at present rarely has report, as document " Valanezhad A, Tsuru K, Maruta M, et al. A new biocompatible coating layer applied on titanium substrates using a modified zinc phosphatizing method[J]. Surface and Coatings Technology, 2012, 206 (8): 2207-2212. " reported a kind of method of utilizing high-temperature water thermal synthesis to prepare zinc phosphate on titanium surface, the method only has pure titanium is placed in acid solution (0.36 molL is housed at 250 DEG C
1znO, 0.58 molL
1h
3pO
4with 0.63 molL
1hNO
3) closed reactor in synthetic 10h, could there is at titanium Surface Creation one deck the phosphoric acid zinc coating of biocompatibility, reduce the rete that temperature of reaction and reaction times all can not generate superperformance.This technique is extremely complicated, and preparation process is loaded down with trivial details, consuming time, power consumption and reaction process are difficult to control, and is unfavorable for scale operation.Document " Xingchuan Zhao; Yupeng Lu; et al. Ultrasonic Induced Rapid Formation and Crystal Refinement of Chemical Conversed Hopeite Coating on Titanium; J. Phys. Chem. C; 2014; 118 (4): 1910 – 1918. " has been reported a kind of ultrasonic enhancing titanium surface phosphoric acid zinc grain refining and preparation method thereof, although this method is simple to operate, reaction times is shorter and temperature is lower, but the shape and size that are limited by workpiece, are not easy to suitability for industrialized production.
On electrode, there is redox reaction by there is electron exchange in electrolytic solution in current field, it can change the various actions such as the arrangement, orientation, migration, growth of reactive ion and product molecule, and forming core, growth and orientation process to crystal in solution have special effects.Than additive method, this technology has advantages of and can in the substrate of complex-shaped and porous, prepare uniform coating.About current field, the research of titanium surface phosphoric acid zinc impregnation conversion aspect is not yet reported both at home and abroad at present.
Summary of the invention
The technical problem that the present invention mainly solves is to provide a kind of method of preparing zinc phosphate conversion film on titanium surface, the conversion film homogeneous microstructure obtaining, have certain patterned features, chemical property is good, preparation method's environmental friendliness, technique is simple, cost is low, be applicable to suitability for industrialized production.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of method of preparing zinc phosphate conversion film on titanium surface is provided, comprises that step is:
(1) P contained compound, zinc compound, calcium containing compound and promotor are hybridly prepared into chemical conversion base soln, wherein the mol ratio of zine ion, phosphonium ion and calcium ion is 0.6:1.0:0.3;
(2) pure titanium matrix is carried out to activation treatment and surface adjustment;
(3) described pure titanium matrix after treatment is put in described chemical conversion base soln, applied current field, wherein said pure titanium matrix is negative electrode, and platinum is anode, at 50 ~ 70 DEG C, after chemical conversion 5-30 minute, obtains zinc phosphate conversion film on titanium surface.
In a preferred embodiment of the present invention, the feed composition of described chemical conversion base soln is: phosphoric acid 30 ~ 40g/L, zinc oxide 9 ~ 12g/L, zinc nitrate 23 ~ 30g/L, nitrocalcite 23 ~ 30g/L, promotor 3 ~ 4g/L.
In a preferred embodiment of the present invention, described promotor is one or more in sodium polyphosphate, nickelous nitrate, citric acid, sodium chlorate.
In a preferred embodiment of the present invention, the pH value of described chemical conversion base soln is 2.6, and the pH value of the described chemical conversion base soln of maintenance is 2.6 in step (3).
In a preferred embodiment of the present invention, activation treatment described in step (2) is to carry out activation treatment with the hydrofluoric acid of 2wt%, and wherein said activating treatment temperature is room temperature, and soak time is 30s-1min.
In a preferred embodiment of the present invention, described in step (2), surface adjustment is to carry out with phosphoric acid glue titanium, between table timing, is 30s.
In a preferred embodiment of the present invention, in step (3), current density used is 20 ~ 40 mA/cm
2, chemical conversion temperature is 60 DEG C.
The invention has the beneficial effects as follows: the method for preparing zinc phosphate conversion film on titanium surface of the present invention; the method can complete reaction at a lower temperature; the product degree of crystallinity that obtains is high, chemical property is excellent; and pollution less, cost is low, technique is simple, production efficiency is high; be applicable to large-scale production and application; by methods such as solution optimization, strength of current variation and time controls, can obtain the titanium base zinc phosphate conversion film that surface tissue and mechanical property are more excellent.
Brief description of the drawings
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing of required use during embodiment is described is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing, wherein:
Fig. 1 is XRD diffraction analysis and the contrast collection of illustrative plates of surface that the present invention the obtains titanium matrix that contains zinc phosphate conversion film;
Fig. 2 is the scanning electron microscope image of surface that the present invention the obtains titanium matrix that contains zinc phosphate conversion film.
Embodiment
To the technical scheme in the embodiment of the present invention be clearly and completely described below, obviously, described embodiment is only a part of embodiment of the present invention, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making all other embodiment that obtain under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment mono-:
A kind of method of preparing zinc phosphate conversion film on titanium surface is provided, comprises that step is:
(1) first in acidproof beaker, inject the water of 1/3 volume, the disposable H that adds
3pO
4, more Powdered ZnO is slowly poured into, stir 10 ~ 20min after fully reacting, add successively Zn (NO
3)
26H
2o and Ca (NO
3)
24H
2o.The content of Essential Chemistry raw material used is respectively H
3pO
4: 30g/L, ZnO:9g/L, Zn (NO
3)
26H
2o:23g/L, Ca (NO
3)
24H
2o:23g/L, keeping proportioning is mol ratio Zn:P:Ca=0.6:1:0.3, finally adds respectively dissimilar promotor 3 g/L.Deng being stirred to enough time, add H
3pO
4regulating pH value with ZnO is 2.6.
(2) by alkaline degreasing liquid (NaOH:15g, the Na of 60 DEG C of the pure titanium sample immersions of having polished
2cO
3: 30g, Na
3pO
4: 70g, Na
2siO
3: 10g) middle 20 min that process, thoroughly clean with tap water and deionized water respectively.Under room temperature, the sample of rinsing well is put into 2% HF solution and carried out activation treatment, object is to remove the zone of oxidation of the titanium spontaneous formation in surface.After activation, repeatedly rinse with clear water and deionization at once, then put into phosphoric acid glue titanium table and adjust solution table to adjust 30s, finally directly sample is put into conversion fluid and carried out subsequent current field conversion processing.
(3) in conversion fluid, add current field, adopt noble electrode Pt to do anode, Ti does negative electrode.Current density used is respectively 20mA/cm
2, temperature is 60 DEG C, the reaction times is 30min.
(4) by the product washing of step (3) gained, dry, obtain black gray expandable titanium base phosphoric acid zinc coating.
Embodiment bis-:
A kind of method of preparing zinc phosphate conversion film on titanium surface is provided, comprises that step is:
By 30g/L H
3pO
4, 9g/L ZnO, 23g/L Zn (NO
3)
26H
2o, 23g/L Ca (NO
3)
24H
2o and 3g/L promotor are mixed, and fully stir, and add H
3pO
4regulating pH value with ZnO is 2.6, is mixed with chemical conversion base soln; In chemical conversion base soln, add current field, adopt noble electrode Pt to do anode, the pure Ti after 2% HF activation phosphoric acid glue titanium table is adjusted does negative electrode.Current density used is respectively 40 mA/cm
2, temperature is 60 DEG C, reacting treatment time is 30min.
Embodiment tri-:
A kind of method of preparing zinc phosphate conversion film on titanium surface is provided, comprises that step is:
By 40g/L H
3pO
4, 12g/L ZnO, 30g/L Zn (NO
3)
26H
2o, 30g/L Ca (NO
3)
24H
2o and 4g/L promotor are mixed, and fully stir, and add H
3pO
4regulating pH value with ZnO is 2.6, is mixed with chemical conversion base soln; In chemical conversion base soln, add current field, adopt noble electrode Pt to do anode, the pure Ti after 2% HF activation phosphoric acid glue titanium table is adjusted does negative electrode.Current density used is respectively 20 mA/cm
2, temperature is 60 DEG C, reacting treatment time is 30min.
Embodiment tetra-:
A kind of method of preparing zinc phosphate conversion film on titanium surface is provided, comprises that step is:
By 40g/L H
3pO
4, 12g/L ZnO, 30g/L Zn (NO
3)
26H
2o, 30g/L Ca (NO
3)
24H
2o and 4g/L promotor are mixed, and fully stir, and add H
3pO
4regulating pH value with ZnO is 2.6, is mixed with chemical conversion base soln; In chemical conversion base soln, add current field, adopt noble electrode Pt to do anode, the pure Ti after 2% HF activation phosphoric acid glue titanium table is adjusted does negative electrode.Current density used is respectively 40 mA/cm
2, temperature is 60 DEG C, reacting treatment time is 30min.
Utilize in titanium base phosphoric acid zinc coating prepared by the inventive method, zinc phosphate crystal directly generates through reaction in－situ, is formed according to certain mode set by the crystal of lamellar discoid, has certain patterned features.The method can complete reaction at a lower temperature, and the product degree of crystallinity that obtains is high, chemical property is excellent.And pollution less, cost is low, technique is simple, production efficiency is high, thereby be particularly suitable for large-scale production and application.In addition, by methods such as solution optimization, strength of current variation and time controls, can obtain the titanium base phosphoric acid zinc coating that mechanical property is more excellent, patterned surface structure is conducive to the regulation and control to biomedical sector cell behavior.
The foregoing is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or conversion of equivalent flow process that utilizes description of the present invention to do; or be directly or indirectly used in other relevant technical field, be all in like manner included in scope of patent protection of the present invention.
Claims (7)
1. a method of preparing zinc phosphate conversion film on titanium surface, is characterized in that, comprises that step is:
(1) P contained compound, zinc compound, calcium containing compound and promotor are hybridly prepared into chemical conversion base soln, wherein the mol ratio of zine ion, phosphonium ion and calcium ion is 0.6:1.0:0.3;
(2) pure titanium matrix is carried out to activation treatment and surface adjustment;
(3) described pure titanium matrix after treatment is put in described chemical conversion base soln, applied current field, wherein said pure titanium matrix is negative electrode, and platinum is anode, at 50 ~ 70 DEG C, after chemical conversion 5-30 minute, obtains zinc phosphate conversion film on titanium surface.
2. method according to claim 1, is characterized in that, the feed composition of described chemical conversion base soln is: phosphoric acid 30 ~ 40g/L, zinc oxide 9 ~ 12g/L, zinc nitrate 23 ~ 30g/L, nitrocalcite 23 ~ 30g/L, promotor 3 ~ 4g/L.
3. method according to claim 2, is characterized in that, described promotor is one or more in sodium polyphosphate, nickelous nitrate, citric acid, sodium chlorate.
4. method according to claim 1, is characterized in that, the pH value of described chemical conversion base soln is 2.6, and the pH value of the described chemical conversion base soln of maintenance is 2.6 in step (3).
5. method according to claim 1, is characterized in that, activation treatment described in step (2) is to carry out activation treatment with the hydrofluoric acid of 2wt%, and wherein said activating treatment temperature is room temperature, and soak time is 30s-1min.
6. method according to claim 1, is characterized in that, described in step (2), surface adjustment is to carry out with phosphoric acid glue titanium, between table timing, is 30s.
7. method according to claim 1, is characterized in that, in step (3), current density used is 20 ~ 40 mA/cm
2, chemical conversion temperature is 60 DEG C.
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|---|---|---|---|
| CN201410191307.4A CN103952745A (en) | 2014-05-08 | 2014-05-08 | Method for preparing zinc phosphate conversion coating on surface of titanium |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104195531A (en) * | 2014-08-29 | 2014-12-10 | 山东大学 | Method for depositing bionic hydroxyapatite (HA) on zinc phosphate conversion coating surface |
| CN105568272A (en) * | 2015-12-18 | 2016-05-11 | 山东大学 | Method for regulating and controlling physical phases of zinc and calcium conversion films on pure-titanium surfaces by aid of pH (potential of hydrogen) value |
| CN106521466A (en) * | 2016-09-18 | 2017-03-22 | 山东大学 | Preparation method for inducing titanium or titanium alloy surface chemical conversion film by virtue of electric coupling |
| IT201600091766A1 (en) * | 2016-09-12 | 2018-03-12 | Innovaplants Srl | IMPLANTABLE MEDICAL DEVICES HAVING A COATING LAYER WITH ANTIMICROBIAL PROPERTIES BASED ON NANOSTRUCTURED HYDROXYAPATITIS. |
| CN109989054A (en) * | 2019-04-19 | 2019-07-09 | 山东大学 | A kind of titanium surface micronano phosphoric acid zinc strontium chemical composition coating and its controllable method for preparing |
| CN110117784A (en) * | 2019-05-10 | 2019-08-13 | 山东大学 | A kind of preparation method of pure titanium surface hydroxyl apatite conversion film |
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| US4874480A (en) * | 1987-04-20 | 1989-10-17 | Henkel Corporation | Process for treatment of titanium and titanium alloys |
| CN1891865A (en) * | 2005-04-28 | 2007-01-10 | 株式会社电装 | Electrolytic phosphating process |
| CN103769432A (en) * | 2014-01-28 | 2014-05-07 | 威海银兴预应力线材有限公司 | Steel strand production device and electrolysis phosphating technology |
-
2014
- 2014-05-08 CN CN201410191307.4A patent/CN103952745A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4874480A (en) * | 1987-04-20 | 1989-10-17 | Henkel Corporation | Process for treatment of titanium and titanium alloys |
| CN1891865A (en) * | 2005-04-28 | 2007-01-10 | 株式会社电装 | Electrolytic phosphating process |
| CN103769432A (en) * | 2014-01-28 | 2014-05-07 | 威海银兴预应力线材有限公司 | Steel strand production device and electrolysis phosphating technology |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104195531A (en) * | 2014-08-29 | 2014-12-10 | 山东大学 | Method for depositing bionic hydroxyapatite (HA) on zinc phosphate conversion coating surface |
| CN105568272A (en) * | 2015-12-18 | 2016-05-11 | 山东大学 | Method for regulating and controlling physical phases of zinc and calcium conversion films on pure-titanium surfaces by aid of pH (potential of hydrogen) value |
| CN105568272B (en) * | 2015-12-18 | 2018-06-01 | 山东大学 | A kind of method for regulating and controlling pure titanium surface zinc-calcium conversion film object phase using pH value |
| IT201600091766A1 (en) * | 2016-09-12 | 2018-03-12 | Innovaplants Srl | IMPLANTABLE MEDICAL DEVICES HAVING A COATING LAYER WITH ANTIMICROBIAL PROPERTIES BASED ON NANOSTRUCTURED HYDROXYAPATITIS. |
| WO2018047130A1 (en) * | 2016-09-12 | 2018-03-15 | Innovaplants S.R.L. | Implantable medical devices having a coating layer with antimicrobial properties based on nanostructured hydroxyapatite |
| CN106521466A (en) * | 2016-09-18 | 2017-03-22 | 山东大学 | Preparation method for inducing titanium or titanium alloy surface chemical conversion film by virtue of electric coupling |
| CN106521466B (en) * | 2016-09-18 | 2019-06-04 | 山东大学 | The preparation method of titanium or titanium alloy surface chemical composition coating is induced using electric coupling |
| CN109989054A (en) * | 2019-04-19 | 2019-07-09 | 山东大学 | A kind of titanium surface micronano phosphoric acid zinc strontium chemical composition coating and its controllable method for preparing |
| CN109989054B (en) * | 2019-04-19 | 2020-01-17 | 山东大学 | Titanium surface micro-nano strontium zinc phosphate chemical conversion coating and controllable preparation method thereof |
| CN110117784A (en) * | 2019-05-10 | 2019-08-13 | 山东大学 | A kind of preparation method of pure titanium surface hydroxyl apatite conversion film |
| CN110117784B (en) * | 2019-05-10 | 2020-07-14 | 山东大学 | Preparation method of hydroxyapatite conversion film on surface of pure titanium |
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Application publication date: 20140730 |
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