CN108517517B - A method of titanium phosphate zinc chemical conversion film is prepared on titanium surface - Google Patents
A method of titanium phosphate zinc chemical conversion film is prepared on titanium surface Download PDFInfo
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- CN108517517B CN108517517B CN201810336553.2A CN201810336553A CN108517517B CN 108517517 B CN108517517 B CN 108517517B CN 201810336553 A CN201810336553 A CN 201810336553A CN 108517517 B CN108517517 B CN 108517517B
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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
- C23C22/06—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 aqueous acidic solutions with pH less than 6
- C23C22/07—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 aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
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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
- C23C22/78—Pretreatment of the material to be coated
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Abstract
The invention discloses a kind of methods for preparing titanium phosphate zinc chemical conversion film on titanium surface, include the following steps: first to pre-process Titanium base using strong base solution, the mixed liquor of phosphoric acid zinc, phosphoric acid and nitric acid is prepared again, pretreated Titanium base is placed in 2~10h of reaction in the mixed liquor, finally the Titanium base after reaction is heat-treated.Remarkable advantage of the invention is that the preparation method can realize that titanium ion participates in the growth course of conversion film under the reaction condition of more mild fluoride-free; it can significantly improve the combination between conversion film and matrix; and the conversion film homogeneous grain size generated; arrangement is close; it is not limited by base shape, there is good protective effect；Meanwhile it is easy to operate, using conventional equipment, no higher safety guarantee requirement, process cycle is short, is suitble to production application.
Description
Technical field
The invention belongs to the preparation fields of chemical composition coating, more particularly to one kind to prepare titanium phosphate zinc chemical on titanium surface and turn
Change the method for film.
Background technique
Phposphate film is the process for treating surface of the ceramic layer of metal surface growth in situ, in carbon steel, aluminium, magnesium, zinc etc.
Processing, coating and anticorrosion of metal base product etc. are widely applied.Recently, phposphate film in part is found to have
There is good biocompatibility, Metal Substrate implant can be improved in the intracorporal synosteosis of people and corrosion resistance, presented
Good biomedical applications prospect.The advantages that pure titanium has density small, and elasticity modulus is low, and chemical stability is strong is aviation, boat
Sea and the common metal material of implanted medical device industry, it is low that however, there are also hardness, wears no resistance, in human body slowly
The problem of discharging titanium ion.In view of the good characteristic of phposphate film, numerous researchers wish by preparing on titanium
Phposphate film further improves titanium surface property.But titanium is because there is fine and close oxidation film in surface, so that titanium
Category cannot be sufficiently dissolved into reaction solution, and which has limited the preparations and application of titanium-based phposphate film.
Currently, still few to the report of titanium-based surface phposphate film both at home and abroad.For the barrier for breaking oxidation film,
Valanezhad A. etc. utilizes hydrothermal synthesis method, to surface in 200 DEG C or so of phosphoric acid, nitric acid, zinc oxide mixed solution
The pure titanium of metallurgical polishing is handled, and phposphate film is prepared for, and energy consumption is high for the method, large-scale device cannot be handled, to surface
Smoothness requirements are high, cannot handle the device of complex topography, and pure titanium reacts 10h or more under strong acid, high temperature, easily suction hydrogen
Cause hydrogen embrittlement, there is apparent limitation (document 1.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&Coatings Technology, 2012,206 (8-9): 2207-
2212.)。
(document 2.Zhao X, Xiao G, Zhang X, the et al.Ultrasonic Induced such as Zhao Xingchuan, Lv Yupeng
Rapid Formation and Crystal Refinement of Chemical Conversed Hopeite Coating
On Titanium [J] .Journal of Physical Chemistry C, 2014,118 (4): 1910-1918. document, 3. Lyu
Space roc, Zhao Xingchuan, Xiao Gui bravely wait a kind of method for preparing hot-dipping galvanized coating on titanium surface of, CN103952745A [P]
.2014.) by preparing phosphoric acid zinc coating on pretreated titanium sample by the way of additional ultrasonic wave or electric field.
Application No. is 201710480391.5, a kind of entitled " system of titanium surface bioactivity conversion film of phosphate containing strontium
Preparation Method " disclosure of the invention pickling is carried out to titanium-based surface using hydrofluoric acid after, titanium-based surface is carried out using colloidal solution
Surface active, but in above two processing mode has no titanium elements presence in the coating finally prepared, and matrix has neither part nor lot in reaction.
Therefore in essence, the above method preparation coating belong to chemical deposition rather than chemical composition coating, and no matter ultrasound field
Or electric field can all cause film forming uneven because of the shielding action of device.
Wang S etc. breaks the protection of titanium surface compact oxidation film using fluorine ion, promotes the dissolution of titanium, therefore most
Phosphate solution closely is added into prepare surface of metal titanium conversion film, but very due to the binding force of fluorine ion and titanium ion
By force, conversion film object is mutually made of fluorine titaniferous compound and titanium dioxide substantially, such as Na3TiF6And Na3TiOF5, and do not contain chemical property
Sufficiently stable phosphoric acid titanium compound, therefore this conversion film quality is loose, part salt belong to water solubility, and the combination of matrix is strong
Degree is not high, and limited (document 4.Wang S, Liu X, Wang L, the et al.Formation mechanism and of protective effect
properties of fluoride–phosphate conversion coating on titanium alloy[J].Rsc
Advances, 2017,7 (26): 16078-16086；Document 5. Chen Tingyi, Li Xinming, Lv Yuansheng .TC4Titanium alloy is in Na3PO4-
The preparation of conversion film and its performance study [J] Metallic Functional Materials, 2014 (2): 16-20. in KF-HF solution system).
In conclusion a kind of titanium participation reaction enabled in matrix is now needed, so that conversion film can be in situ
Growth, significantly improves the method for preparing titanium phosphate zinc chemical conversion film on titanium surface of binding force between conversion film and base member.
Summary of the invention
Goal of the invention: the object of the present invention is to provide a kind of titaniums enabled in matrix to participate in reaction, so that turning
Change film can growth in situ, significantly improve binding force between conversion film and base member prepares the conversion of titanium phosphate zinc chemical on titanium surface
The method of film.
Technical solution: the method that the present invention prepares titanium phosphate zinc chemical conversion film on titanium surface includes the following steps:
(1) Titanium base is pre-processed using strong base solution；
(2) mixed liquor for preparing phosphoric acid zinc, phosphoric acid and nitric acid, pretreated Titanium base is placed in the mixed liquor instead
Answer 2~10h, wherein phosphoric acid zinc concentration is 0.05~0.25mol/L in the mixed liquor, the concentration of phosphoric acid is 0.2~
1.0mol/L, the concentration of nitric acid are 0.3~1.2mol/L；
(3) Titanium base after reaction is heat-treated.
The present invention is handled Titanium base by using strong base solution, has broken Titanium base surface and has existed under natural conditions
Fine and close oxidation film, form one layer of new sodium titanate gel layer.The gel layer has activity well, acid molten being immersed in
Titanium ion can be made to be released after liquid, generate conversion film to react with phosphate radical.Due to the generation in phposphate film
Cheng Zhong, the titanium metal ions from matrix take part in reaction, so that conversion film can have between growth in situ, with matrix
Good gradient transition, and nitric acid is added in the present invention, further promotes the growth of phosphating coat.
Furtherly, in step (1), highly basic preferably can be NaOH or KOH, and concentration is 5~10mol/L, using concentration
Higher strong base solution handles Titanium base, and it is existing fine and close under natural conditions can effectively to have broken Titanium base surface
Oxidation film forms one layer of new sodium titanate gel layer.Pretreatment is that Titanium base is placed in strong base solution, in 60~90 DEG C of conditions
12~36h of lower reaction.
It further says, in step (2), the concentration of zinc phosphate solution preferably can be 0.1~0.2mol/L.Phosphoric acid solution
Concentration preferably can be 0.5~1.0mol/L.The concentration of nitric acid solution preferably can be 0.5~1mol/L.The temperature of reaction be 60~
90℃。
Furtherly, in step (3), the heat treatment is 1~2h of reaction under the conditions of 600~800 DEG C.
The utility model has the advantages that compared with prior art, remarkable advantage of the invention are as follows: the preparation method can be in more mild nothing
Realize that titanium ion participates in the growth course of conversion film, can significantly improve between conversion film and matrix under the reaction condition of fluorine ion
In conjunction with, and the conversion film homogeneous grain size generated, arrangement is close, is not limited by base shape, there is good protective effect；Together
When, easy to operate, using conventional equipment, no higher safety guarantee requirement, process cycle is short, is suitble to production application.
Detailed description of the invention
Fig. 1 is the surface scan electron microscope of titanium phosphate zinc conversion film prepared by the embodiment of the present invention 1；
Fig. 2 is the X-ray energy spectrogram of titanium phosphate zinc conversion film prepared by the embodiment of the present invention 1；
Fig. 3 is the XRD diagram of 1 Titanium base of the embodiment of the present invention and prepared titanium phosphate zinc conversion film；
Fig. 4 is the surface scan electron microscope of titanium phosphate zinc conversion film prepared by the embodiment of the present invention 2；
Fig. 5 is the surface scan electron microscope of titanium phosphate zinc conversion film prepared by the embodiment of the present invention 3.
Specific embodiment
Further details of the technical solution of the present invention with reference to the accompanying drawings and embodiments.
Embodiment 1
The present invention includes the following steps: in the method that titanium surface prepares titanium phosphate zinc chemical conversion film
(1) a certain amount of deionized water is injected in alkaline-resisting beaker, load weighted NaOH is slowly added to, is stirred continuously, and is made
The solution that standby concentration is 5mol/L；The solution is transferred in sealable resistance to alkali container, polishing, cleaned titanium sheet are immersed
Wherein, it avoids laminating；Sealing container puts it into 60 DEG C of electric heating blast dry oven and keeps the temperature for 24 hours, to complete to pre-process.
(2) deionized water is used, is separately added into trbasic zinc phosphate, phosphoric acid and nitric acid, compound concentration is respectively the phosphorus of 0.05mol/L
The nitric acid mixed solution of sour zinc, the phosphoric acid of 0.71mol/L and 0.94mol/L is transferred in sealable acid-resistant container, will be located in advance
It is transferred in the mixed solution after the titanium sheet of reason deionized water cleaning down, avoids laminating；Sealing container puts it into 60 DEG C
Electric heating blast dry oven in keep the temperature 6h, to complete conversion reaction.
(3) the above-mentioned titanium sheet of deionized water cleaning down is used, is dried in air.
(4) titanium sheet is placed in Muffle furnace, is warming up to 600 DEG C with furnace and keeps the temperature 1h, then furnace cooling is made greyish black
Colour band coating titanium sheet.
Using scanning electron microscope (SEM), X-ray energy spectrometer (EDS) and X-ray diffractometer (XRD) to the embodiment
The titanium plate surface of preparation is characterized, and the result of acquisition is as shown in Figure 1 to Figure 3.As shown in Figure 1, the coating of this method preparation
Homogeneous grain size, arrangement is close, and coating is complete, and crystallinity is high, matrix is completely covered；As shown in Figure 2, film layer mainly by P,
Zn and Ti element composition, it was demonstrated that from the growth that the Ti ion released in matrix successfully participates in coating；It can by Fig. 3
To know, conversion film generated is similar with barbosalite (Lipscombite), there is tetragonal structure crystalline state substance, and
Diffraction maximum is sharp, and crystallinity is higher.
Embodiment 2
The present invention includes the following steps: in the method that titanium surface prepares titanium phosphate zinc chemical conversion film
(1) a certain amount of deionized water is injected in alkaline-resisting beaker, load weighted NaOH is slowly added to, is stirred continuously, and is made
The solution that standby concentration is 10mol/L；The solution is transferred in sealable resistance to alkali container, polishing, cleaned titanium sheet are soaked
Enter wherein, avoids laminating；Sealing container puts it into 90 DEG C of electric heating blast dry oven and keeps the temperature for 24 hours, to complete pre- place
Reason.
(2) trbasic zinc phosphate, phosphoric acid and nitric acid are separately added into using deionized water, compound concentration is respectively the phosphorus of 0.25mol/L
Sour zinc, the phosphoric acid of 0.85mol/L and the nitric acid mixed solution of 0.469mol/L, are transferred in sealable acid-resistant container, will be upper
It is transferred in the mixed solution after stating pretreated titanium sheet deionized water cleaning down, avoids laminating；Sealing container is put
Enter in 90 DEG C of electric heating blast dry oven and keep the temperature 6h, to complete conversion reaction.
(3) the above-mentioned titanium sheet of deionized water cleaning down is used, is dried in air.
(4) titanium sheet is placed in Muffle furnace, is warming up to 800 DEG C with furnace and keeps the temperature 2h, then furnace cooling is made greyish black
Colour band coating titanium sheet.
Performance characterization is carried out to the titanium plate surface of embodiment preparation, the result of acquisition is as shown in Figure 4.As shown in Figure 4,
Coated grains are uniform, and arrangement is close, and coating is complete, and crystallinity is high, and matrix is completely covered.Film layer is mainly by P, Zn, Ti element group
Be at, conversion film generated it is similar with barbosalite (Lipscombite), there is tetragonal structure crystalline state substance,
And diffraction maximum is sharp, crystallinity is higher.
Embodiment 3
(1) a certain amount of deionized water is injected in alkaline-resisting beaker, load weighted NaOH is slowly added to, is stirred continuously, and is made
The solution that standby concentration is 8mol/L；The solution is transferred in sealable resistance to alkali container, polishing, cleaned titanium sheet are immersed
Wherein, it avoids laminating；Sealing container puts it into 75 DEG C of electric heating blast dry oven and keeps the temperature for 24 hours, to complete to pre-process.
(2) trbasic zinc phosphate, phosphoric acid and nitric acid being separately added into using deionized water, compound concentration is the trbasic zinc phosphate of 0.15mol/L,
The phosphoric acid of 0.51mol/L and the nitric acid mixed solution of 0.581mol/L, are transferred in sealable acid-resistant container, by above-mentioned pre- place
It is transferred in the mixed solution after the titanium sheet of reason deionized water cleaning down, avoids laminating；Sealing container puts it into 75 DEG C
Electric heating blast dry oven in keep the temperature 6h, to complete conversion reaction.
(3) deionized water cleaning down said sample is used, is dried in air.
(4) titanium sheet is placed in Muffle furnace, is warming up to 700 DEG C with furnace and keeps the temperature 1.5h, ash is made in then furnace cooling
Black bands coating titanium sheet.
Performance characterization is carried out to the titanium plate surface of embodiment preparation, the result of acquisition is as shown in Figure 5.As shown in Figure 5,
Coated grains are uniform, and arrangement is close, and coating is complete, and crystallinity is high, and matrix is completely covered.Film layer is mainly by P, Zn, Ti element group
At.Conversion film generated be it is similar with barbosalite (Lipscombite), have tetragonal structure crystalline state substance,
And diffraction maximum is sharp, crystallinity is higher.
Comparative example 1
Basic step and embodiment 1 are basic, the difference is that not pre-processing to titanium sheet first.Specific step is as follows:
(1) trbasic zinc phosphate, phosphoric acid and nitric acid are separately added into using deionized water, compound concentration is respectively the phosphorus of 0.05mol/L
Sour zinc, the phosphoric acid of 0.71mol/L and the nitric acid mixed solution of 0.94mol/L, are transferred in sealable acid-resistant container, by titanium sheet
It is placed in the mixed solution, avoids laminating；Sealing container puts it into 60 DEG C of electric heating blast dry oven and keeps the temperature 6h, with
Complete conversion reaction.
(2) the above-mentioned titanium sheet of deionized water cleaning down is used, is dried in air.
(4) titanium sheet is placed in Muffle furnace, is warming up to 600 DEG C with furnace and keeps the temperature 1h, then furnace cooling
Titanium sheet prepared by the comparative example is subjected to performance characterization it is found that titanium plate surface does not find that coating or particle are raw
It is long.It follows that being the basis that phposphate film is grown using NaOH solution pretreatment, such as without pretreatment, Titanium base exists
Stable chemical state is kept in conversion reaction solution, will not be reacted.
Comparative example 2
Basic step and embodiment 1 are basic, the difference is that being pre-processed using acid solution to titanium sheet.Specific step
It is rapid as follows:
(1) a certain amount of deionized water is injected in acidproof beaker, is slowly added to the concentrated sulfuric acid measured, is stirred continuously,
Prepare the solution that concentration is 5mol/L；The solution is transferred in sealable resistance to alkali container, polishing, cleaned titanium sheet are soaked
Enter wherein, avoids laminating；Sealing container puts it into 60 DEG C of electric heating blast dry oven and keeps the temperature for 24 hours, to complete pre- place
Reason.
(2) trbasic zinc phosphate, phosphoric acid and nitric acid are separately added into using deionized water, compound concentration is respectively 0.05mol/L phosphoric acid
The nitric acid mixed solution of zinc, the phosphoric acid of 0.71mol/L and 0.94mol/L, is transferred in sealable acid-resistant container, will be above-mentioned pre-
It is transferred in the mixed solution after the titanium sheet of processing deionized water cleaning down, avoids laminating；Sealing container puts it into 60
DEG C electric heating blast dry oven in keep the temperature 6h, to complete conversion reaction.
(3) the above-mentioned titanium sheet of deionized water cleaning down is used, is dried in air.
(4) titanium sheet is placed in Muffle furnace, is warming up to 600 DEG C with furnace and keeps the temperature 1h, then furnace cooling.
Titanium sheet prepared by the comparative example carries out performance characterization it is found that a large amount of etch pits occurs in specimen surface, but does not have
Any deposit.
Comparative example 3
Basic step is substantially the same manner as Example 1, the difference is that the NaOH solution concentration difference prepared when pretreatment
For 2mol/L and 12mol/L.
Titanium sheet prepared by the comparative example carries out performance characterization it is found that the titanium sheet table prepared using the NaOH solution of 2mol/L
Face only generates the particle of dispersion, not can be connected to uniform coating；And the titanium sheet table for using the NaOH solution of 12mol/L to prepare
Finishing coat pattern is compared with Example 1 without significant change.
Embodiment 4
6 groups of parallel tests are designed, basic step is same as Example 1, the difference is that phosphoric acid zinc concentration, specially
0.04mol/L、0.05mol/L、0.1mol/L、0.2mol/L、0.25mol/L、0.3mol/L。
Titanium plate surface prepared by the comparative example is observed, the result of acquisition is as shown in table 1 below.
The coating morphology table of comparisons of the different phosphoric acid zinc concentration preparation of table 1
| Serial number | Concentration/mol/L | Pattern |
| 1 | 0.04 | Surface covering particle is smaller, and there are crackle in coating, coating is relatively thin |
| 2 | 0.05 | Even particle size, arrangement are close, and coating is complete, and crystallinity is high |
| 3 | 0.1 | Even particle size, arrangement are close, and coating is complete, and crystallinity is high |
| 4 | 0.2 | Even particle size, arrangement are close, and coating is complete, and crystallinity is high |
| 5 | 0.25 | Even particle size, arrangement are close, and coating is complete, and crystallinity is high |
| 6 | 0.3 | Even particle size, arrangement are close, and coating is complete, and crystallinity is high |
Embodiment 5
5 groups of parallel tests are designed, basic step is same as Example 1, the difference is that the concentration of phosphoric acid, specially
0.1mol/L、0.2mol/L、0.5mol/L、1mol/L、1.1mol/L。
Titanium plate surface prepared by the comparative example is observed, the result of acquisition is as shown in table 2 below.
The coating morphology table of comparisons of the different phosphoric acid concentration preparation of table 2
| Serial number | Concentration/mol/L | Pattern |
| 1 | 0.1 | Surface covering particle is smaller, and there are crackle in coating, coating is relatively thin |
| 2 | 0.2 | Even particle size, arrangement are close, and coating is complete, and crystallinity is high |
| 3 | 0.5 | Even particle size, arrangement are close, and coating is complete, and crystallinity is high |
| 4 | 1 | Even particle size, arrangement are close, and coating is complete, and crystallinity is high |
| 5 | 1.1 | Even particle size, arrangement are close, and coating is complete, and crystallinity is high |
Embodiment 6
6 groups of parallel tests are designed, basic step is same as Example 1, the difference is that the concentration of nitric acid, specially
0.2mol/L、0.3mol/L、0.5mol/L、1mol/L、1.2mol/L、1.3mol/L。
Titanium plate surface prepared by the comparative example is observed, the result of acquisition is as shown in table 3 below.
The coating morphology table of comparisons of the different concentration of nitric acid preparation of table 3
| Serial number | Concentration/mol/L | Pattern |
| 1 | 0.2 | Surface covering particle is smaller, and there are crackle in coating, coating is relatively thin |
| 2 | 0.3 | Even particle size, arrangement are close, and coating is complete, and crystallinity is high |
| 3 | 0.5 | Even particle size, arrangement are close, and coating is complete, and crystallinity is high |
| 4 | 1 | Even particle size, arrangement are close, and coating is complete, and crystallinity is high |
| 5 | 1.2 | Even particle size, arrangement are close, and coating is complete, and crystallinity is high |
| 6 | 1.3 | Even particle size, arrangement are close, and coating is complete, and crystallinity is high |
By table 1 to table 3 it is found that the concentration of conversion reaction solution has apparent influence to the growth of phposphate film,
Then prevent phposphate film from sufficiently growing when concentration is too low, leads to its thickness low LCL, coating is relatively thin, occurs in heat treatment
Crackle reduces protective effect；And when solution concentration is excessively high, the influence to the performance of coating is smaller, this is because solution cannot
When with substrate contact, conversion reaction stops, and will cause reagent waste instead.
Embodiment 7
Basic step is substantially the same manner as Example 1, the difference is that step (4) in be heat-treated temperature and heat preservation when
Between, shown in table 4 specific as follows.
The different heat treatment temperature of table 4 and the coating and the titanium sheet matrix pattern table of comparisons of soaking time preparation
By table 4 it is found that heat treatment temperature is particularly significant for the performance for improving coating, temperature is too low cannot to promote coating
The fusion of middle crystal grain, temperature is excessively high, seriously affects the microscopic structure of Titanium base；And the too short coated grains of soaking time can not
Fusion, and soaking time is too long, matrix grain can be caused to grow up.
Embodiment 8
Basic step is same as Example 1, the difference is that carrying out pretreatment 12h using KOH, then mix in step (1)
Close in solution and react 2h, the conversion film which is prepared carry out performance characterization it is found that the two coating and indifference.
Embodiment 9
Basic step is same as Example 1, the difference is that carrying out pretreatment 36h using KOH, then mix in step (1)
It closes in solution and reacts 10h under the conditions of 90 DEG C, be warming up to 800 DEG C with furnace and keep the temperature 2h, the conversion film which is prepared carries out
Performance characterization it is found that the two coating and indifference.
In summary, preparation method of the invention can break pure titanium surface compact oxidation film under conditions of more mild
Protection promotes titanium ion to participate in reaction, forms fine and close, uniform coating on pure Titanium base surface, realizes in pure titanium surface system
Standby phposphate film, and it is easy to operate not to be related to high temperature, high pressure and fluorine ion in conversion reaction.
Claims (7)
1. a kind of method for preparing titanium phosphate zinc chemical conversion film on titanium surface, it is characterised in that include the following steps:
(1) concentration is used to pre-process for the strong base solution of 5~10mol/L to Titanium base；
(2) mixed liquor for preparing phosphoric acid zinc, phosphoric acid and nitric acid, pretreated Titanium base is placed in the mixed liquor and reacts 2
~10h, wherein phosphoric acid zinc concentration is 0.05~0.25mol/L in the mixed liquor, and the concentration of phosphoric acid is 0.2~1.0mol/
L, the concentration of nitric acid are 0.3~1.2mol/L；
(3) Titanium base after reaction is heat-treated, which is that the Titanium base after reaction is placed in reacting furnace
In, 600~800 DEG C are warming up to furnace, keeps the temperature 1~2h.
2. the method according to claim 1 for preparing titanium phosphate zinc chemical conversion film on titanium surface, it is characterised in that: step
(1) in, the highly basic is NaOH or KOH.
3. the method according to claim 1 for preparing titanium phosphate zinc chemical conversion film on titanium surface, it is characterised in that: step
(1) in, the pretreatment is that Titanium base is placed in strong base solution, and 12~36h is reacted under the conditions of 60~90 DEG C.
4. the method according to claim 1 for preparing titanium phosphate zinc chemical conversion film on titanium surface, it is characterised in that: step
(2) in, the phosphoric acid zinc concentration is 0.1~0.2mol/L.
5. the method according to claim 1 for preparing titanium phosphate zinc chemical conversion film on titanium surface, it is characterised in that: step
(2) in, the concentration of the phosphoric acid is 0.5~1.0mol/L.
6. the method according to claim 1 for preparing titanium phosphate zinc chemical conversion film on titanium surface, it is characterised in that: step
(2) in, the concentration of the nitric acid is 0.5~1mol/L.
7. the method according to claim 1 for preparing titanium phosphate zinc chemical conversion film on titanium surface, it is characterised in that: step
(2) in, the temperature of the reaction is 60~90 DEG C.
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| CN1475602A (en) * | 2002-08-16 | 2004-02-18 | 中国科学院金属研究所 | Preparation method of magnesium alloy chromeless chemical conversion film and its used film forming solution |
| CN101457354A (en) * | 2009-01-09 | 2009-06-17 | 北京化工大学 | Environment friendly room temperature non-slag colorful chemical conversion solution and process |
| CN105420786A (en) * | 2015-11-19 | 2016-03-23 | 西安交通大学 | Preparation method for nano-sodium silicotitanate/titanium dioxide bio-coatings on titanium surfaces |
| DE102017208802A1 (en) * | 2016-05-25 | 2017-11-30 | Chemetall Gmbh | Process for corrosion-protecting phosphating of a metallic surface with reduced pickling removal |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1475602A (en) * | 2002-08-16 | 2004-02-18 | 中国科学院金属研究所 | Preparation method of magnesium alloy chromeless chemical conversion film and its used film forming solution |
| CN101457354A (en) * | 2009-01-09 | 2009-06-17 | 北京化工大学 | Environment friendly room temperature non-slag colorful chemical conversion solution and process |
| CN105420786A (en) * | 2015-11-19 | 2016-03-23 | 西安交通大学 | Preparation method for nano-sodium silicotitanate/titanium dioxide bio-coatings on titanium surfaces |
| DE102017208802A1 (en) * | 2016-05-25 | 2017-11-30 | Chemetall Gmbh | Process for corrosion-protecting phosphating of a metallic surface with reduced pickling removal |
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