CN103320838B - The method of the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ - Google Patents
The method of the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ Download PDFInfo
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Abstract
A method for the yellow ceramic film of TC4 titanium alloy surface growth in situ, it relates to a kind of method of titanium alloy surface growth in situ ceramic film.The present invention will solve existing differential arc oxidation method electrolytic solution in the method for TC4 titanium alloy surface growth in situ ceramic film to contain heavy metal element, and cost is higher, seriously polluted, is not suitable for the technical problem of the industrial production shortcoming of greenization.The inventive method is as follows: one, surface treatment; Two, electrolytic solution is prepared; Three, differential arc oxidation process; Four, rinsing, drying can at the yellow ceramic film of TC4 titanium alloy surface growth in situ.The present invention is mainly used at the yellow ceramic film of TC4 titanium alloy surface growth in situ.
Description
Technical field
The present invention relates to a kind of method of titanium alloy surface growth in situ ceramic film.
Background technology
Titanium alloy has non magnetic, the good characteristic such as fusing point is high, thermal expansivity is little, biologically inert, specific tenacity are high, Resisting fractre, antifatigue.TC4 titanium alloy quality is wherein light, and tensile strength is high, and its performance is even better than high-strength steel, is thus widely used in the national defense industry such as aerospace and weapons.Prepare yellow ceramic film at TC4 titanium alloy surface and can not only play the effect beautified, and can erosion resistance be improved, wear resistance etc., thus play the effect of protection matrix.Particularly at tank armor and the gun shell of desert area use, if at the yellow ceramic film of its surface preparation, yellow very close with the natural color of desert area due to it, good stealth effect can be obtained.
Painted general painted anonizing and the painted processing method of electrical spark of adopting now of titanium alloy surface is carried out.Painted anode oxidation method coloring principle is: titanium is when the electrolysis of oxygen-containing medium Anodic, titanyl compound is formed in anode generation oxidizing reaction, because this material is quite large to the specific refractory power of light, and its film is transparent, therefore thin film of titanium oxide can reflect and refracted ray consumingly, and then interfere effect, namely show various interference color.Dark system (purple, blue, deep pink) present high chroma, light color system (light blue, green) presents low colourity.Compared with bright and clean surface, what the low voltage anodic oxidation of sand blasted surface obtained is low colourity.Osaka, Japan stand industrial technology synthetic study the clear moral of increasing well and south carried out the painted research of the painted and titanium alloy spark discharge of titanium alloy Linear cut electric discharge for a long time.Its coloring principle is the electrolytic action utilizing Linear cut to discharge, transparent oxidation titanium film is formed at titanium alloy, due to the interference of light, the oxidation titanium film of different thickness will obtain the interference light of different colours, just can carry out distinct colors painted by the thickness of controlled oxidization titanium film.The painted processing method of electrical spark compares with painted anonizing, and its maximum feature is that technological process is simple.The color of the painted processing method of electric discharge surface can gradually change with the rising of average machining voltage, all distinct colors can be presented within the scope of 60 ~ 110V, oxide thickness increases with the proportional example of rising of average machining voltage, can be easy to obtain required different colours.The painted surface hardness of electrical spark is the highest, weares and teares minimum, has good wear resistance, weathering resistance and erosion resistance.He Yujun, according to the formation basic theory of film in anode oxidation process, adopts constant voltage method to test, and obtains the product that thicknesses of layers and outward appearance can reach specified requirement.But because the coloring principle of above method is all the interference utilizing light, as long as utilize film light interference coloring principle inevitably will there is the thinner problem of film.When rete is thinner, rete bad mechanical property, wears no resistance, and combination rate is low, corrosion-resistant, easily may produce rete and peel off or the phenomenon such as breakage in use procedure.Application number be 200910237073.1 the Chinese invention patent that Chinese invention patent uses phosphoric acid, tartrate, hydrogen peroxide carry out anode oxidation coloration, application number is 200910248899.8 use phosphoric acid and sodium gluconate mixing solutions carry out anode oxidation coloration and application number be 201010172834.2 Chinese invention patent to use the painted rete prepared by novel fluorine-free and environment-friendly technique anode oxidation coloration all to there is combination rate low, corrosion-resistant, the shortcomings such as hardness is little.
Differential arc oxidization technique develops from anodic oxidation, it adopts higher operating voltage, faraday's workspace that common anode is oxidized has been incorporated into micro-arc discharge district, material surface is made to produce micro-arc spark electric discharge spot, in the technology of these material surface in-situ growth of oxide film under thermochemistry, plasma chemistry and electrochemical acting in conjunction.Ceramic film obtained by this technology has the constitutional features of inner compact layer, outer rough porous, and good uniformity, high with substrate combinating strength, there is erosion resistance, wear resistance, and there is decoration function.Differential arc oxidization technique technical process is simple, and also can process the workpiece of complicated shape, the treatment time is short, to working temperature without rigors, is applicable to automatic production.Use differential arc oxidization technique to carry out titanium alloy surface paintedization and process the shortcoming that can overcome anonizing and the existence of electrical spark staining method.Obtained thicknesses of layers is comparatively large and in relative broad range, can regulate and control and occur hardly the change of color, while its mechanical property also can not be greatly affected.Because the ceramic membrane of differential arc oxidation growth is growth in situ ceramic membrane, can avoid between metallic matrix and ceramic film, forming strong heterogeneous bonding, and in the auxiliary lower electrochemical reaction occurred of energetic plasma, metal oxide is made to be deep in ceramic film, strengthen the keying action of ceramic film and metallic matrix, thus obtain stronger combination rate.
But differential arc oxidation method prepares the electrolytic solution that coloured ceramic film uses at present, generally containing heavy metal element, cost is higher, has pollution to environment, does not meet the industrial requirement of greenization.
Summary of the invention
The present invention will solve existing differential arc oxidation method electrolytic solution in the method for the coloured ceramic film of TC4 titanium alloy surface growth in situ to contain heavy metal element, cost is higher, seriously polluted, be not suitable for the technical problem of the industrial production shortcoming of greenization, thus the method for the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ is provided.
The method of the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ of the present invention is carried out according to the following steps:
One, surface treatment: first adopt 600# sand papering TC4 titanium alloy substrate to remove surface film oxide completely, then 1000# sand paper is adopted to carry out polished finish, obtain surface more smooth, without the TC4 titanium alloy substrate of obvious cut, ethanol or acetone is adopted to carry out scouring oil removing to the surface of TC4 titanium alloy substrate after polishing, finally use washed with de-ionized water, after naturally drying, obtain the TC4 titanium alloy substrate after surface treatment;
Two, prepare electrolytic solution: be first dissolved in deionized water by main membrane-forming agent, then add secondary film formers and additive, Homogeneous phase mixing preparation obtains electrolytic solution; The quality of described main membrane-forming agent and the volume ratio of deionized water are (1.3g ~ 7.9g): 1L; The quality of described secondary film formers and the volume ratio of deionized water are (0.5g ~ 1.5g): 1L; The quality of described additive and the volume ratio of deionized water are (2g ~ 6g): 1L; Wherein said main membrane-forming agent is that 5:1 mixes by Sodium hexametaphosphate 99 and sodium polyphosphate by the mass ratio of Sodium hexametaphosphate 99 and sodium polyphosphate, and wherein said additive is sodium hydroxide, and wherein said secondary film formers is sodium aluminate;
Three, differential arc oxidation process: the electrolytic solution first step 2 obtained loads in stainless steel trough body, and then the TC4 titanium alloy substrate after surface treatment step one to be obtained is fixed in stainless steel trough body, and the TC4 titanium alloy substrate after guarantee surface treatment wants the part of growth in situ ceramic film to be immersed in completely in electrolytic solution, then with the TC4 titanium alloy substrate after surface treatment for anode, stainless steel trough body is negative electrode, adopt unidirectional pulse power supply, 5min ~ 20min is oxidized under be 350V ~ 420V and frequency being the condition of 50Hz ~ 2000Hz at constant voltage, obtain TC4 titanium alloy sheet after differential arc oxidation process,
Four, clean, dry: the TC4 titanium alloy sheet after differential arc oxidation process step 3 obtained takes out, and first uses deionized water rinsing, then seasoning or electricity consumption dry up, and namely complete TC4 titanium alloy surface growth in situ yellow ceramic film.
The yellow ceramic film of the growth in situ that the method for the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ of the present invention generates is thicker, color even, attractive in appearance and high with titanium alloy combination rate; TC4 titanium alloy after present method process has excellent erosion resistance.Achieve the performance of ornamental and structural coating integration.
The present invention adopts strong alkaline electrolytes system, and phosphoric acid salt and aluminate be energy stable existence all, can not form precipitation, and therefore in oxidising process, electrolytic solution is stablized, energy Reusability; The various salts used are all common medicines, do not reduce 35% ~ 40% containing heavy metal element, cost, cheap environmental protection, be applicable to the industrial production of greenization.In micro-arc oxidation process, by regulating size and the power parameter of each group component in electrolytic solution, the yellow depth of rete is adjustable within the specific limits.
Accompanying drawing explanation
Fig. 1 is the SEM collection of illustrative plates of the ceramic film prepared by test two;
Fig. 2 is the SEM collection of illustrative plates of the ceramic film prepared by test three;
Fig. 3 is XRD figure spectrum, the XRD figure spectrum of the ceramic film of a prepared by test four in figure, the XRD figure spectrum of the ceramic film of b prepared by test two in figure, the XRD figure spectrum of the ceramic film of c prepared by test five in figure, the XRD figure spectrum of the ceramic film of d prepared by test three in figure, the XRD figure spectrum of the ceramic film of e prepared by test six in figure, wherein ■ is the titanium dioxide diffraction peak of anatase phase, ▲ be the titanium dioxide diffraction peak of rutile phase;
Fig. 4 is Tafel curve collection of illustrative plates, in figure, a is the Tafel curve of the yellow ceramic film of TC4 titanium alloy surface growth in situ in test one, in figure, b is the Tafel curve of the yellow ceramic film of TC4 titanium alloy surface growth in situ in test two, and in figure, c is the Tafel curve of the yellow ceramic film of TC4 titanium alloy surface growth in situ in test three.
Fig. 5 is the photo in kind that test two obtains yellow rete, and wherein a region is not through the region of present method process; B region is the part of surface through this method process;
Fig. 6 is the photo in kind that test three obtains yellow rete, and wherein c region is not through the region of present method process; D region is the part of surface through this method process.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: in present embodiment, the method for the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ is carried out according to the following steps:
One, surface treatment: first adopt 600# sand papering TC4 titanium alloy substrate to remove surface film oxide completely, then 1000# sand paper is adopted to carry out polished finish, obtain surface more smooth, without the TC4 titanium alloy substrate of obvious cut, ethanol or acetone is adopted to carry out scouring oil removing to the surface of TC4 titanium alloy substrate after polishing, finally use washed with de-ionized water, after naturally drying, obtain the TC4 titanium alloy substrate after surface treatment;
Two, prepare electrolytic solution: be first dissolved in deionized water by main membrane-forming agent, then add secondary film formers and additive, Homogeneous phase mixing preparation obtains electrolytic solution; The quality of described main membrane-forming agent and the volume ratio of deionized water are (1.3g ~ 7.9g): 1L; The quality of described secondary film formers and the volume ratio of deionized water are (0.5g ~ 1.5g): 1L; The quality of described additive and the volume ratio of deionized water are (2g ~ 6g): 1L; Wherein said main membrane-forming agent is that 5:1 mixes by Sodium hexametaphosphate 99 and sodium polyphosphate by the mass ratio of Sodium hexametaphosphate 99 and sodium polyphosphate, and wherein said additive is sodium hydroxide, and wherein said secondary film formers is sodium aluminate;
Three, differential arc oxidation process: the electrolytic solution first step 2 obtained loads in stainless steel trough body, and then the TC4 titanium alloy substrate after surface treatment step one to be obtained is fixed in stainless steel trough body, and the TC4 titanium alloy substrate after guarantee surface treatment wants the part of growth in situ ceramic film to be immersed in completely in electrolytic solution, then with the TC4 titanium alloy substrate after surface treatment for anode, stainless steel trough body is negative electrode, adopt unidirectional pulse power supply, 5min ~ 20min is oxidized under be 350V ~ 420V and frequency being the condition of 50Hz ~ 2000Hz at constant voltage, obtain TC4 titanium alloy sheet after differential arc oxidation process,
Four, clean, dry: the TC4 titanium alloy sheet after differential arc oxidation process step 3 obtained takes out, and first uses deionized water rinsing, then seasoning or electricity consumption dry up, and namely complete TC4 titanium alloy surface growth in situ yellow ceramic film.
The yellow ceramic film of the growth in situ that the method for the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ of the present invention generates is thicker, color even, attractive in appearance and high with titanium alloy combination rate; TC4 titanium alloy after present method process has excellent erosion resistance.Achieve the performance of ornamental and structural coating integration.
The present invention adopts strong alkaline electrolytes system, and phosphoric acid salt and aluminate be energy stable existence all, can not form precipitation, and therefore in oxidising process, electrolytic solution is stablized, energy Reusability; The various salts used are all common medicines, do not reduce 35% ~ 40% containing heavy metal element, cost, cheap environmental protection, be applicable to the industrial production of greenization.In micro-arc oxidation process, by regulating size and the power parameter of each group component in electrolytic solution, the yellow depth of rete is adjustable within the specific limits.
Embodiment two: present embodiment and embodiment one unlike: the quality of the main membrane-forming agent described in step 2 and the volume ratio of deionized water are (2.3g ~ 6.9g): 1L.Other is identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two unlike: the quality of the secondary film formers described in step 2 and the volume ratio of deionized water are (0.8g ~ 1.2g): 1L.Other is identical with one of embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: the quality of the additive described in step 2 and the volume ratio of deionized water are (3g ~ 5g): 1L.Other is identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: be oxidized 5min ~ 20min under be 370V ~ 400V and frequency being the condition of 50Hz ~ 2000Hz at constant voltage in step 3.Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: be oxidized 5min ~ 20min under be 350V ~ 420V and frequency being the condition of 550Hz ~ 1500Hz at constant voltage in step 3.Other is identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: be oxidized 7min ~ 15min under be 350V ~ 420V and frequency being the condition of 50Hz ~ 2000Hz at constant voltage in step 3.Other is identical with one of embodiment one to six.
By following verification experimental verification beneficial effect of the present invention:
Test one: this test is tested as a comparison, surface treatment: first adopt 600# sand papering TC4 titanium alloy substrate to remove surface film oxide completely, then 1000# sand paper is adopted to carry out polished finish, obtain surface more smooth, without the TC4 titanium alloy substrate of obvious cut, adopt ethanol or acetone to carry out scouring oil removing to the surface of TC4 titanium alloy substrate after polishing, finally use washed with de-ionized water, after naturally drying, obtain the TC4 titanium alloy substrate after surface treatment;
Test two: the method for the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ of this test completes according to the following steps:
One, surface treatment: first adopt 600# sand papering TC4 titanium alloy substrate to remove surface film oxide completely, then 1000# sand paper is adopted to carry out polished finish, obtain surface more smooth, without the TC4 titanium alloy substrate of obvious cut, ethanol or acetone is adopted to carry out scouring oil removing to the surface of TC4 titanium alloy substrate after polishing, finally use washed with de-ionized water, after naturally drying, obtain the TC4 titanium alloy substrate after surface treatment;
Two, prepare electrolytic solution: be first dissolved in deionized water by main membrane-forming agent, then add secondary film formers and additive, Homogeneous phase mixing preparation obtains electrolytic solution; The quality of described main membrane-forming agent and the volume ratio of deionized water are 2.6g:1L; , the quality of described secondary film formers and the volume ratio of deionized water are 1g:1L; The quality of described additive and the volume ratio of deionized water are 4g:1L; Wherein said main membrane-forming agent is that 5:1 mixes by Sodium hexametaphosphate 99 and sodium polyphosphate by the mass ratio of Sodium hexametaphosphate 99 and sodium polyphosphate, and wherein said additive is sodium hydroxide, and wherein said secondary film formers is sodium aluminate;
Three, differential arc oxidation process: the electrolytic solution first step 2 obtained loads in stainless steel trough body, and then the TC4 titanium alloy substrate after surface treatment step one to be obtained is fixed in stainless steel trough body, and the TC4 titanium alloy substrate after guarantee surface treatment wants the part of growth in situ ceramic film to be immersed in completely in electrolytic solution, then with the TC4 titanium alloy substrate after surface treatment for anode, stainless steel trough body is negative electrode, adopt unidirectional pulse power supply, 10min is oxidized under be 380V and frequency being the condition of 1000Hz at constant voltage, obtain TC4 titanium alloy sheet after differential arc oxidation process,
Four, clean, dry: the TC4 titanium alloy sheet after differential arc oxidation process step 3 obtained takes out, and first uses deionized water rinsing, then seasoning or electricity consumption dry up, and namely complete TC4 titanium alloy surface growth in situ yellow ceramic film.
Test three: the method for the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ of this test completes according to the following steps:
One, surface treatment: first adopt 600# sand papering TC4 titanium alloy substrate to remove surface film oxide completely, then 1000# sand paper is adopted to carry out polished finish, obtain surface more smooth, without the TC4 titanium alloy substrate of obvious cut, ethanol or acetone is adopted to carry out scouring oil removing to the surface of TC4 titanium alloy substrate after polishing, finally use washed with de-ionized water, after naturally drying, obtain the TC4 titanium alloy substrate after surface treatment;
Two, prepare electrolytic solution: be first dissolved in deionized water by main membrane-forming agent, then add secondary film formers and additive, Homogeneous phase mixing preparation obtains electrolytic solution; The quality of described main membrane-forming agent and the volume ratio of deionized water are 5.2g:1L; , the quality of described secondary film formers and the volume ratio of deionized water are 1g:1L; The quality of described additive and the volume ratio of deionized water are 4g:1L; Wherein said main membrane-forming agent is that 5:1 mixes by Sodium hexametaphosphate 99 and sodium polyphosphate by the mass ratio of Sodium hexametaphosphate 99 and sodium polyphosphate, and wherein said additive is sodium hydroxide, and wherein said secondary film formers is sodium aluminate;
Three, differential arc oxidation process: the electrolytic solution first step 2 obtained loads in stainless steel trough body, and then the TC4 titanium alloy substrate after surface treatment step one to be obtained is fixed in stainless steel trough body, and the TC4 titanium alloy substrate after guarantee surface treatment wants the part of growth in situ ceramic film to be immersed in completely in electrolytic solution, then with the TC4 titanium alloy substrate after surface treatment for anode, stainless steel trough body is negative electrode, adopt unidirectional pulse power supply, 10min is oxidized under be 380V and frequency being the condition of 1000Hz at constant voltage, obtain TC4 titanium alloy sheet after differential arc oxidation process,
Four, clean, dry: the TC4 titanium alloy sheet after differential arc oxidation process step 3 obtained takes out, and first uses deionized water rinsing, then seasoning or electricity consumption dry up, and namely complete TC4 titanium alloy surface growth in situ yellow ceramic film.
Fig. 1 and Fig. 2 is not divided into the SEM figure of the yellow ceramic film of TC4 titanium alloy surface growth in situ in test two and test three, and can find out that its surface is covered with hole, be typical differential arc oxidation coating.And along with the increase of membrane-forming agent concentration main in electrolytic solution, ceramic film surface hole defect increases, and surface becomes more coarse.
TC4 titanium alloy surface in situ in test one, test two and test three being grown to yellow ceramic film adopts electrochemical method to carry out corrosion resistance nature test.After the NaCl solution that three samples are placed in 3.5%wt is soaked 24h, carry out electrochemistry tafel test.The test result obtained is as shown in Fig. 4 Tafel curve, in figure, a is the Tafel curve of the yellow ceramic film of TC4 titanium alloy surface growth in situ in test one, in figure, b is the Tafel curve of the yellow ceramic film of TC4 titanium alloy surface growth in situ in test two, and in figure, c is the Tafel curve of the yellow ceramic film of TC4 titanium alloy surface growth in situ in test three.As can be seen from the figure, after yellow ceramic film growth, TC4 titanium alloy erosion resistance is significantly increased compared to TC4 titanium alloy substrate, and polarized current density reduces, and Linear Polarization Resistance raises, and along with the increase of membrane-forming agent concentration main in electrolytic solution, its erosion resistance also improves thereupon.Table 1 is according to Fig. 4 matching gained related data.It is 8.54 × 10 that existing differential arc oxidation method tests corrosion current at the ceramic film that the method for TC4 titanium alloy surface growth in situ ceramic film is obtained through electrochemistry tafel
-6~ 5.01 × 10
-6the corrosion current of the yellow ceramic film of A, present method TC4 titanium alloy surface growth in situ is also in this underrange, and corrosive nature does not decline.
Table 1. different condition obtains the Electrochemical results of sample
| Sample | Linear Polarization Resistance | Corrosion current (A) |
| Test one | 5199 | 8.323×10 -6 |
| Test two | 6465 | 6.688×10 -6 |
| Test three | 7662 | 5.636×10 -6 |
TT260 cladding thickness measurer, TR-200 type surface roughometer is adopted to carry out thickness, roughness test to the yellow ceramic film sample of TC4 titanium alloy surface growth in situ of test 1, test two and test three respectively.Result is as shown in table 2.Ceramic film thickness is between 11 μm ~ 13 μm, and roughness is between 0.59 μm ~ 1.00 μm, and along with the increase of membrane-forming agent concentration main in electrolytic solution, ceramic film thickness increases further, and roughness becomes large.Existing differential arc oxidation method is 4.0 μm ~ 9.3 μm at the ceramic film thickness that the method for TC4 titanium alloy surface growth in situ ceramic film is obtained, roughness is 1.1 μm ~ 2.0 μm, comparatively speaking, the yellow ceramic film thickness of present method TC4 titanium alloy surface growth in situ increases, roughness declines, and performance increases.
Table 2. different condition obtains thickness and the roughness of sample
| Sample | Thickness (μm) | Roughness (μm) |
| Test one | 0 | 0.387 |
| Test two | 11.7 | 0.597 |
| Test three | 12.5 | 0.950 |
Fig. 5 is the photo in kind that test two obtains yellow rete, and wherein a region is not through the region of present method process; B region is the part of surface through this method process; Fig. 6 is the photo in kind that test three obtains yellow rete, and wherein c region is not through the region of present method process; D region is the part of surface through this method process.Wherein b and d region is the part of surface through this method process, as can be seen from the figure the yellow ceramic film even compact of gained, and ceramic film color is adjustable within the specific limits; A and c region is not through the region of present method process, and still keep primary colors, surface does not have ceramic film to generate.
Test four: the method for the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ of this test completes according to the following steps:
One, surface treatment: first adopt 600# sand papering TC4 titanium alloy substrate to remove surface film oxide completely, then 1000# sand paper is adopted to carry out polished finish, obtain surface more smooth, without the TC4 titanium alloy substrate of obvious cut, ethanol or acetone is adopted to carry out scouring oil removing to the surface of TC4 titanium alloy substrate after polishing, finally use washed with de-ionized water, after naturally drying, obtain the TC4 titanium alloy substrate after surface treatment;
Two, prepare electrolytic solution: be first dissolved in deionized water by main membrane-forming agent, then add secondary film formers and additive, Homogeneous phase mixing preparation obtains electrolytic solution; The quality of described main membrane-forming agent and the volume ratio of deionized water are 1.3g:1L; , the quality of described secondary film formers and the volume ratio of deionized water are 1g:1L; The quality of described additive and the volume ratio of deionized water are 4g:1L; Wherein said main membrane-forming agent is that 5:1 mixes by Sodium hexametaphosphate 99 and sodium polyphosphate by the mass ratio of Sodium hexametaphosphate 99 and sodium polyphosphate, and wherein said additive is sodium hydroxide, and wherein said secondary film formers is sodium aluminate;
Three, differential arc oxidation process: the electrolytic solution first step 2 obtained loads in stainless steel trough body, and then the TC4 titanium alloy substrate after surface treatment step one to be obtained is fixed in stainless steel trough body, and the TC4 titanium alloy substrate after guarantee surface treatment wants the part of growth in situ ceramic film to be immersed in completely in electrolytic solution, then with the TC4 titanium alloy substrate after surface treatment for anode, stainless steel trough body is negative electrode, adopt unidirectional pulse power supply, 10min is oxidized under be 380V and frequency being the condition of 1000Hz at constant voltage, obtain TC4 titanium alloy sheet after differential arc oxidation process,
Four, clean, dry: the TC4 titanium alloy sheet after differential arc oxidation process step 3 obtained takes out, and first uses deionized water rinsing, then seasoning or electricity consumption dry up, and namely complete TC4 titanium alloy surface growth in situ yellow ceramic film.
Test five: the method for the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ of this test completes according to the following steps:
One, surface treatment: first adopt 600# sand papering TC4 titanium alloy substrate to remove surface film oxide completely, then 1000# sand paper is adopted to carry out polished finish, obtain surface more smooth, without the TC4 titanium alloy substrate of obvious cut, ethanol or acetone is adopted to carry out scouring oil removing to the surface of TC4 titanium alloy substrate after polishing, finally use washed with de-ionized water, after naturally drying, obtain the TC4 titanium alloy substrate after surface treatment;
Two, prepare electrolytic solution: be first dissolved in deionized water by main membrane-forming agent, then add secondary film formers and additive, Homogeneous phase mixing preparation obtains electrolytic solution; The quality of described main membrane-forming agent and the volume ratio of deionized water are 3.9g:1L; , the quality of described secondary film formers and the volume ratio of deionized water are 1g:1L; The quality of described additive and the volume ratio of deionized water are 4g:1L; Wherein said main membrane-forming agent is that 5:1 mixes by Sodium hexametaphosphate 99 and sodium polyphosphate by the mass ratio of Sodium hexametaphosphate 99 and sodium polyphosphate, and wherein said additive is sodium hydroxide, and wherein said secondary film formers is sodium aluminate;
Three, differential arc oxidation process: the electrolytic solution first step 2 obtained loads in stainless steel trough body, and then the TC4 titanium alloy substrate after surface treatment step one to be obtained is fixed in stainless steel trough body, and the TC4 titanium alloy substrate after guarantee surface treatment wants the part of growth in situ ceramic film to be immersed in completely in electrolytic solution, then with the TC4 titanium alloy substrate after surface treatment for anode, stainless steel trough body is negative electrode, adopt unidirectional pulse power supply, 10min is oxidized under be 380V and frequency being the condition of 1000Hz at constant voltage, obtain TC4 titanium alloy sheet after differential arc oxidation process,
Four, clean, dry: the TC4 titanium alloy sheet after differential arc oxidation process step 3 obtained takes out, and first uses deionized water rinsing, then seasoning or electricity consumption dry up, and namely complete TC4 titanium alloy surface growth in situ yellow ceramic film.
Test six: the method for the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ of this test completes according to the following steps:
One, surface treatment: first adopt 600# sand papering TC4 titanium alloy substrate to remove surface film oxide completely, then 1000# sand paper is adopted to carry out polished finish, obtain surface more smooth, without the TC4 titanium alloy substrate of obvious cut, ethanol or acetone is adopted to carry out scouring oil removing to the surface of TC4 titanium alloy substrate after polishing, finally use washed with de-ionized water, after naturally drying, obtain the TC4 titanium alloy substrate after surface treatment;
Two, prepare electrolytic solution: be first dissolved in deionized water by main membrane-forming agent, then add secondary film formers and additive, Homogeneous phase mixing preparation obtains electrolytic solution; The quality of described main membrane-forming agent and the volume ratio of deionized water are 7.8g:1L; , the quality of described secondary film formers and the volume ratio of deionized water are 1g:1L; The quality of described additive and the volume ratio of deionized water are 4g:1L; Wherein said main membrane-forming agent is that 5:1 mixes by Sodium hexametaphosphate 99 and sodium polyphosphate by the mass ratio of Sodium hexametaphosphate 99 and sodium polyphosphate, and wherein said additive is sodium hydroxide, and wherein said secondary film formers is sodium aluminate;
Three, differential arc oxidation process: the electrolytic solution first step 2 obtained loads in stainless steel trough body, and then the TC4 titanium alloy substrate after surface treatment step one to be obtained is fixed in stainless steel trough body, and the TC4 titanium alloy substrate after guarantee surface treatment wants the part of growth in situ ceramic film to be immersed in completely in electrolytic solution, then with the TC4 titanium alloy substrate after surface treatment for anode, stainless steel trough body is negative electrode, adopt unidirectional pulse power supply, 10min is oxidized under be 380V and frequency being the condition of 1000Hz at constant voltage, obtain TC4 titanium alloy sheet after differential arc oxidation process,
Four, clean, dry: the TC4 titanium alloy sheet after differential arc oxidation process step 3 obtained takes out, and first uses deionized water rinsing, then seasoning or electricity consumption dry up, and namely complete TC4 titanium alloy surface growth in situ yellow ceramic film.
Fig. 3 is XRD figure spectrum, in figure, a is the XRD figure spectrum of the yellow ceramic film of TC4 titanium alloy surface growth in situ in test four, in figure, b is the XRD figure spectrum of the yellow ceramic film of TC4 titanium alloy surface growth in situ in test two, in figure, c is the XRD figure spectrum of the yellow ceramic film of TC4 titanium alloy surface growth in situ in test five, in figure, d is the XRD figure spectrum of the yellow ceramic film of TC4 titanium alloy surface growth in situ in test three, in figure, e is the XRD figure spectrum of the yellow ceramic film of TC4 titanium alloy surface growth in situ in test six, wherein ■ is the titanium dioxide diffraction peak of anatase phase, ▲ be the titanium dioxide diffraction peak of rutile phase.When therefrom can find out that main membrane-forming agent concentration is less, ceramic film is non-crystalline state, after main membrane-forming agent concentration increases, in anatase phase in ceramic film and the titanium dioxide of rutile phase, and along with the increase of main membrane-forming agent concentration, rutile titanium dioxide exists always, and anatase titanium dioxide just exists when main membrane-forming agent concentration reaches more than about 5.2g/L.
Hardness test is carried out to the yellow ceramic film of the TC4 titanium alloy surface growth in situ in test one to six.At load 100g, during guarantor 15s condition under, the hardness recording rete is 328HV ~ 352HV, and the obtained TC4 titanium alloy surface ceramic film of its hardness and the painted processing method of painted anonizing and electrical spark is compared basically identical.
Claims (6)
1. a method for the yellow ceramic film of TC4 titanium alloy surface growth in situ, its feature is carried out according to the following steps in the method for the yellow ceramic film of TC4 titanium alloy surface growth in situ:
One, surface treatment: first adopt 600# sand papering TC4 titanium alloy substrate to remove surface film oxide completely, then 1000# sand paper is adopted to carry out polished finish, obtain the TC4 titanium alloy substrate after polishing, ethanol or acetone is adopted to carry out scouring oil removing to the surface of TC4 titanium alloy substrate after polishing, finally use washed with de-ionized water, after naturally drying, obtain the TC4 titanium alloy substrate after surface treatment;
Two, prepare electrolytic solution: be first dissolved in deionized water by main membrane-forming agent, then add secondary film formers and additive, Homogeneous phase mixing preparation obtains electrolytic solution; The quality of described main membrane-forming agent and the volume ratio of deionized water are (1.3g ~ 7.9g): 1L; The quality of described secondary film formers and the volume ratio of deionized water are (0.8g ~ 1.2g): 1L; The quality of described additive and the volume ratio of deionized water are (2g ~ 6g): 1L; Wherein said main membrane-forming agent is that 5:1 mixes by Sodium hexametaphosphate 99 and sodium polyphosphate by the mass ratio of Sodium hexametaphosphate 99 and sodium polyphosphate, and wherein said additive is sodium hydroxide, and wherein said secondary film formers is sodium aluminate;
Three, differential arc oxidation process: the electrolytic solution first step 2 obtained loads in stainless steel trough body, and then the TC4 titanium alloy substrate after surface treatment step one to be obtained is fixed in stainless steel trough body, and the TC4 titanium alloy substrate after guarantee surface treatment wants the part of growth in situ ceramic film to be immersed in completely in electrolytic solution, then with the TC4 titanium alloy substrate after surface treatment for anode, stainless steel trough body is negative electrode, adopt unidirectional pulse power supply, 5min ~ 20min is oxidized under be 350V ~ 420V and frequency being the condition of 50Hz ~ 2000Hz at constant voltage, obtain TC4 titanium alloy sheet after differential arc oxidation process,
Four, clean, dry: the TC4 titanium alloy sheet after differential arc oxidation process step 3 obtained takes out, and first uses deionized water rinsing, then seasoning or electricity consumption dry up, and namely complete TC4 titanium alloy surface growth in situ yellow ceramic film.
2. the method for the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ according to claim 1, is characterized in that the quality of the main membrane-forming agent described in step 2 and the volume ratio of deionized water are (2.3g ~ 6.9g): 1L.
3. the method for the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ according to claim 1, is characterized in that the quality of the additive described in step 2 and the volume ratio of deionized water are (3g ~ 5g): 1L.
4. the method for the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ according to claim 1, it is characterized in that be 370V ~ 400V and frequency be the condition of 50Hz ~ 2000Hz at constant voltage in step 3 under be oxidized 5min ~ 20min.
5. the method for the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ according to claim 1, it is characterized in that be 350V ~ 420V and frequency be the condition of 550Hz ~ 1500Hz at constant voltage in step 3 under be oxidized 5min ~ 20min.
6. the method for the yellow ceramic film of a kind of TC4 titanium alloy surface growth in situ according to claim 1, it is characterized in that be 350V ~ 420V and frequency be the condition of 50Hz ~ 2000Hz at constant voltage in step 3 under be oxidized 7min ~ 15min.
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