CN109126757A - A kind of preparation method of in-situ self-grown black oxidation titanium coating - Google Patents
A kind of preparation method of in-situ self-grown black oxidation titanium coating Download PDFInfo
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- CN109126757A CN109126757A CN201810992602.8A CN201810992602A CN109126757A CN 109126757 A CN109126757 A CN 109126757A CN 201810992602 A CN201810992602 A CN 201810992602A CN 109126757 A CN109126757 A CN 109126757A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 97
- 239000010936 titanium Substances 0.000 title claims abstract description 97
- 230000003647 oxidation Effects 0.000 title claims abstract description 36
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 36
- 238000000576 coating method Methods 0.000 title claims abstract description 35
- 239000011248 coating agent Substances 0.000 title claims abstract description 34
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000008246 gaseous mixture Substances 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 5
- 238000005273 aeration Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- KRQUFUKTQHISJB-YYADALCUSA-N 2-[(E)-N-[2-(4-chlorophenoxy)propoxy]-C-propylcarbonimidoyl]-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one Chemical compound CCC\C(=N/OCC(C)OC1=CC=C(Cl)C=C1)C1=C(O)CC(CC1=O)C1CCCSC1 KRQUFUKTQHISJB-YYADALCUSA-N 0.000 claims description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 claims 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 238000006056 electrooxidation reaction Methods 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 239000012535 impurity Substances 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- NICYNNGYHJJJMJ-UHFFFAOYSA-N propan-2-one;titanium Chemical compound [Ti].CC(C)=O NICYNNGYHJJJMJ-UHFFFAOYSA-N 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 229910052911 sodium silicate Inorganic materials 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 20
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000010919 dye waste Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 239000010242 baoji Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000010892 electric spark Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004886 process control Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013034 coating degradation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a kind of in-situ self-grown black oxidation titanium coating and preparation method thereof, this method is made using general industry Titanium board material as template by differential arc oxidation, plasma hydrogenization two-step method.It is well combined between obtained coating and matrix, and thickness distribution is uniform.Compared to common titania coating, color is black, has stronger assimilation effect in visible range, and show good degradating organic dye ability under visible light.Substrate used in the present invention is industrially pure titanium plate, cheap and easy to get, and used equipment is mature, performance is stablized, and process is simple, is easily industrialized.Obtained coating also shows good bactericidal effect except that can be degraded in addition to low concentration organic dye waste water under visible light in low concentration biological wastewater.
Description
Technical field
The invention belongs to material chemistry technical fields, are related to a kind of preparation side of in-situ self-grown black oxidation titanium coating
Method.
Background technique
Titanium oxide has many advantages, such as that biological nontoxic, chemical property are stable, without secondary pollution, in photocatalysis treatment field of sewage
It is widely studied.But titanium oxide greater band gap (>=3.0eV), corresponding light absorption wavelength range is narrow, can only absorbing wavelength
Ultraviolet light less than 387nm, and the visible light part for accounting for sunlight about 50% cannot be utilized；Titanium oxide excites after absorbing sunlight
The photo-generate electron-hole of generation is compound to being easy in body phase, causes its photocatalysis efficiency lower.Black oxidation titanium is in recent years
A kind of more self-doping type photochemical catalyst is studied, kernel is the titanium oxide of crystallization, and shell is to include a large amount of Ti3+And Vo 2-'s
Non crystalline structure, wherein amorphous shell can make white oxide titanium become the functional area of black, cause to be up to the absorption of sunlight
85%, under the conditions of visible light exposure, four times of ordinary white titanium oxide can be reached to the degradation rate of organic pollutant.It is good
Wide-spectrum absorption effect, stable physicochemical properties and lower electron-hole pair recombination rate, meet black oxidation titanium
Efficiently utilize the requirement of solar energy.However, titanium oxide is usually to exist in solution to be reacted with suspended particulate, this can be very big
Ground influences Titanium particles to the radiation depth of absorption and the illumination of light, and suspended particulate is easy to coagulate in aqueous solution
It is poly-, difficulty is recycled after reaction, these unfavorable factors seriously limit the application of titanium oxide suspension system in practice.
Summary of the invention
In view of the above-mentioned problems, the present invention proposes a kind of preparation method of in-situ self-grown black oxidation titanium coating, the present invention
Using general industry Titanium board material as substrate, by preparing in conjunction with matrix with differential arc oxidation, plasma hydrogenization two-step process
The black oxidation titanium coating well and with high visible responded.The coating both has good degradation to have under visible light
Engine dyeing material ability, in addition also shows good bactericidal effect in low concentration biological wastewater.
The present invention adopts the following technical scheme:
(1) the industrially pure titanium plate of δ 3mm is cut into electric spark wire cutting machineRound titanium
Piece, then polished step by step with 240-1500# abrasive paper for metallograph and mechanically polish processing, most it is cleaned by ultrasonic afterwards through acetone, it is clear obtains surface
Clean titanium sheet.
(2) Na of 90g is added in the stainless steel Water-cooled electric tank that volume is 8L3PO4, the deionized water of 6L is reinjected, is passed through
After stirring and dissolving, it is made into the electrolyte of 15g/L.
(3) by 1) prepared by titanium sheet use titanium alloy hanger to fix and as anode plate, in addition with 80mm × 100mm ×
Yin, yang two-plate is then completely immersed in electrolyte by the stainless steel plate of 3mm as cathode plate, and parallel in the form of face-to-face
It arranges, distance 50mm or so between two-plate.
(4) start mao power source and control voltage in 350V, current density 10A/dm2, continued oxidation processing
After 30min, closes power supply, takes out sample.The titanium that surface is white oxide titanium coating is obtained after acetone ultrasonic cleaning, drying
Piece.
(5) by 4) prepared by titanium sheet be fixed on the heating zone middle front part of rotary PECVD furnace, by its surface perpendicular to gas
Body flow direction, subsequent closed furnace, starting motor and adjusting burner hearth revolving speed is 20rpm.
(6) hydrogen and argon gas gaseous mixture are passed through into burner hearth by the volume ratio of 2:1, Continuous aeration 10min is to exclude burner hearth
Interior foreign gas.After exhaust, opens radio-frequency power supply and regulation power is to 450W, after aura is stablized, with 6 DEG C/min heating
Rate is slowly heated furnace body and keeps the temperature 5h again to 450 DEG C, and whole process remains at 160Pa by end valve control furnace pressure.
(7) after keeping the temperature, radio-frequency power supply is closed, but maintain gas flow constant, is cooled to room temperature to fire box temperature, closed
It holds one's breath source, opens end valve, and take out black oxidation titanium coating titanium sheet.
In step (1), the sand paper of the preferred five variable grain degree of 240#, 600#, 800#, 1000#, 1500# of abrasive paper for metallograph.
In step (1) and (4), acetone ultrasonic cleaning technique is preferably cleaned by ultrasonic 3 times, each 5min.
In step (2), micro-arc oxidation process electrolyte temperature preferably remains in 35 DEG C.
In step (4), it is preferable to use vacuum oven drying for titania coating stoving process.
In step (6), radio-frequency power supply power increases preferred 200W, 300W, 400W, 450W gradient of technique and increases mode.
Substrate used in the present invention is industrially pure titanium plate, cheap and easy to get, and used equipment is mature, performance is stablized,
Process is simple, is easily industrialized.Obtained coating is except the low concentration organic dye waste water that can degrade under visible light
Outside, good bactericidal effect is also shown in low concentration biological wastewater.
Detailed description of the invention
Fig. 1 (a) is the surface photomacrograph of the untreated titanium sheet of embodiment 1；
Fig. 1 (b) is the surface photomacrograph of 1 micro-arc oxidation treatment titanium sheet of embodiment；
Fig. 1 (c) be differential arc oxidation plasma hydrogenization processing titanium sheet surface photomacrograph；
Fig. 2 (a) is the surface scan Electronic Speculum observation photo of the untreated titanium sheet of embodiment 1；
Fig. 2 (b) is the surface scan Electronic Speculum observation photo of 1 micro-arc oxidation treatment titanium sheet of embodiment；
Fig. 2 (c) be 1 differential arc oxidation of embodiment plasma hydrogenization processing titanium sheet surface scan Electronic Speculum observation photo；
Fig. 3 (a) is the cross-sectional scans Electronic Speculum observation photo of the untreated titanium sheet of embodiment 1；
Fig. 3 (b) is the cross-sectional scans Electronic Speculum observation photo of 1 micro-arc oxidation treatment titanium sheet of embodiment；
Fig. 3 (c) be 1 differential arc oxidation of embodiment plasma hydrogenization processing titanium sheet cross-sectional scans Electronic Speculum observation photo；
Fig. 4 is in-situ self-grown black oxidation titanium coating X-ray diffractogram obtained by embodiment 1；
Fig. 5 is in-situ self-grown black oxidation titanium coating UV-vis DRS figure obtained by embodiment 1；
Fig. 6 is in-situ self-grown black oxidation titanium coating degradation rhodamine B solution curve graph obtained by embodiment 1.
Specific embodiment
Combined with specific embodiments below to the present invention be how to realize do further in detail, be fully described by.
Embodiment 1
Industrially pure titanium (TA2) plate for the δ 3mm that Shaanxi Baoji Titanium Industry Co., Ltd. produces is cut with electric spark wire cutting machine
AtThe round titanium sheet of × 3mm, then step by step using 240,600,800,1000,1500# abrasive paper for metallograph polishes titanium sheet step by step
Surface simultaneously carries out mechanical polishing processing, most afterwards after acetone is cleaned by ultrasonic, obtains the titanium sheet of surface cleaning；It is homemade in laboratory
The Na of 90g is added in electrolytic cell3PO4, suitable deionized water is reinjected, after agitated dissolution, is made into the electrolyte of 15g/L；It will
The titanium sheet of surface cleaning uses hanger to fix and use as anode plate, in addition using stainless steel plate as cathode plate, then by yin, yang
Two-plate is completely immersed in electrolyte；The DSM-30 type mao power source of starting Shenyang Di Si Science and Technology Ltd. production is simultaneously controlled
Voltage processed is in 350V, current density 10A/dm2, after continued oxidation handles 30min, closes power supply, takes out sample, it is super through acetone
The titanium sheet that surface is white oxide titanium coating is obtained after sound cleaning, drying；Prepared titanium sheet is fixed on Hefei section crystalline substance material
The heating zone middle front part of the rotary PECVD furnace of II type of OTF-1200X-4-R- of Technology Co., Ltd.'s production, its surface is vertical
In gas flow direction, subsequent closed furnace, starting motor and adjusting burner hearth revolving speed is 20rpm；By the volume ratio of 2:1 to burner hearth
It is inside passed through hydrogen and argon gas gaseous mixture, Continuous aeration 10min is to exclude foreign gas in burner hearth.After exhaust, radio frequency is opened
Power supply and regulation power are to 450W, after aura is stablized, are slowly heated furnace body with 6 DEG C/min heating rate and are kept the temperature again to 450 DEG C
5h, whole process control furnace pressure by end valve and remain at 160Pa；After heat preservation, radio-frequency power supply is closed, but maintain
Gas flow is constant, is cooled to room temperature to fire box temperature, closes gas source, opens end valve, and take out black oxidation titanium coating titanium sheet.
Embodiment 2
Titanium alloy (TC4) plate for the δ 1.5mm that Shaanxi Baoji Titanium Industry Co., Ltd. produces is cut with electric spark wire cutting machine
AtThe round titanium sheet of × 3mm, then step by step using 240,600,800,1000,1500# abrasive paper for metallograph polishes titanium sheet step by step
Surface simultaneously carries out mechanical polishing processing, most afterwards after acetone is cleaned by ultrasonic, obtains the titanium sheet of surface cleaning；It is homemade in laboratory
The Na of 180g is added in electrolytic cell2SiO3, suitable deionized water is reinjected, after agitated dissolution, is made into the electrolyte of 30g/L；
Use hanger to fix and use as anode plate the titanium sheet of surface cleaning, in addition using stainless steel plate as cathode plate, then by yin,
Positive two-plate is completely immersed in electrolyte；Start the DSM-30 type mao power source of Shenyang Di Si Science and Technology Ltd. production simultaneously
Voltage is controlled in 400V, current density 12A/dm2, after continued oxidation handles 20min, close power supply, take out sample, through acetone
The titanium sheet that surface is white oxide titanium coating is obtained after ultrasonic cleaning, drying；Prepared titanium sheet is fixed on Hefei section crystalline substance material
Expect the positive middle part in heating zone of the OTF-1200X-60HG type high pressure hydrogen tube furnace of Technology Co., Ltd.'s production, its surface is parallel
In gas flow direction, subsequent closed furnace is passed through hydrogen and argon gas gaseous mixture into burner hearth by the volume ratio of 4:1, persistently leads to
Gas 10min is to exclude foreign gas in burner hearth.After exhaust, adjusting furnace pressure by pressure controller is 2.0MPa, then
Burner hearth is slowly heated with 6 DEG C/min heating rate and keeps the temperature 10h again to 450 DEG C, and entire insulating process passes through pressure controller control
Furnace pressure remains at 2.0MPa；After insulating process, heating device is closed, but maintain furnace pressure constant, to furnace
Bore temperature is cooled to room temperature, and closes gas source, opens end valve, after pressure in the burner hearth is restored to atmosphere, is taken out black oxidation titanium and is applied
Layer titanium sheet.
Embodiment 3
Shaanxi Baoji Titanium Industry Co., Ltd. is producedIndustrially pure titanium (TA2) ball carries out Surface Nanocrystalline,
Obtaining surface thickness is 10-15 μm of nano-crystalline layers；It is raw that the nanocrystalline titanium ball of gained is placed in Hefei Ke Jing Materials Technology Ltd.
In the KSL-1800X-S type high temperature box furnace of production, closed furnace door is simultaneously slowly heated furnace body to 550 with the heating rate of 8 DEG C/min
DEG C 5h is kept the temperature again, cool to room temperature with the furnace later, closed power supply, take out sample, obtain surface after acetone ultrasonic cleaning, drying
For the titanium ball of white nano-titanium oxide coating layer；The prepared nano oxidized coated titanium ball of white is placed at Hefei section crystalline substance material skill
The positive middle part in heating zone of the OTF-1200X-60HG type high pressure hydrogen tube furnace of art Co., Ltd production, subsequent closed furnace are pressed
The volume ratio of 8:1 is passed through hydrogen and argon gas gaseous mixture into burner hearth, and Continuous aeration 10min is to exclude foreign gas in burner hearth.Row
After gas, adjusting furnace pressure by pressure controller is 2.0MPa, then extremely with 6 DEG C/min heating rate slow heating burner hearth
550 DEG C keep the temperature 8h again, and entire insulating process controls furnace pressure by pressure controller and remains at 2.0MPa；Insulating process
After, heating device is closed, but maintain furnace pressure constant, be cooled to room temperature to fire box temperature, close gas source, opens tail
Valve takes out black nano titania coating titanium ball after pressure in the burner hearth is restored to atmosphere.
Embodiment 4
Shaanxi Baoji Titanium Industry Co., Ltd. is producedTitanium alloy (TC4) ball carries out Surface Nanocrystalline, obtains
It is 10-15 μm of nano-crystalline layers to surface thickness；The K of 45g is added in the homemade electrolytic cell in laboratory2HPO4, reinject suitable
Deionized water after agitated dissolution, is made into the electrolyte of 20g/L；It is with mesh by nano surface crystalline substance titanium ballTitanium
Alloy network pocket cover is lived, and is used as anode, in addition using stainless steel plate as cathode plate, is then soaked yin, yang two-plate completely
Enter in electrolyte；Start the DSM-30 type mao power source of Shenyang Di Si Science and Technology Ltd. production and control voltage and exists
330V, current density 5A/dm2, after continued oxidation handles 15min, close power supply, take out sample, through acetone ultrasonic cleaning, dry
The titanium ball that surface is white nano-titanium oxide coating layer is obtained after dry；It is limited that prepared titanium ball is placed in Hefei section crystalline substance material technology
The heating zone middle front part of the rotary PECVD furnace of II type of OTF-1200X-4-R- of company's production, subsequent closed furnace；By 2:1's
Volume ratio is passed through hydrogen and argon gas gaseous mixture into burner hearth, and Continuous aeration 10min is to exclude foreign gas in burner hearth.Exhaust terminates
Afterwards, radio-frequency power supply and regulation power are opened to 450W, after aura is stablized, extremely with 6 DEG C/min heating rate slow heating furnace body
450 DEG C keep the temperature 5h again, and whole process controls furnace pressure by end valve and remains at 180Pa；After heat preservation, radio frequency is closed
Power supply, but maintain gas flow constant, it is cooled to room temperature to fire box temperature, closes gas source, open end valve, and take out black oxidation
Titanium coating titanium ball.
Embodiment 5
1. take the quartz curette of two 150ml, after ultrasonic cleaning is clean, be respectively charged into 100ml rhodamine B solution (concentration:
10mg/l), and with ultraviolet-visible spectrophotometer the absorbance C of solution at this time is tested0；
2. weighing raw materialTechnical pure titanium sheet, white oxide titanium coating titanium sheet, black oxidation titanium coating titanium sheet, point
It is not added in three quartz curettes, and marking cup body is A, B, C；
3. three quartz curettes are respectively placed under 30W xenon light etc., start timing, it is molten to draw 20ml rhodamine B every 1h
Liquid, and its absorbance is tested with ultraviolet-visible spectrophotometer, it is recorded as CA1、CA2、…CA5；CB1、CB2、…CB5；CC1、
CC2、…CC5, the sample solution after test, which is all refunded in former quartz curette, every time continues photocatalytic degradation processing；
4. testing absorbance C of the rhodamine B solution after different xenon lamp irradiation timest: CA1、CA2、…CA5；CB1、CB2、…
CB5；CC1、CC2、…CC5, with original solution absorbance C0, further according to formula:It can be calculated
Solution degradation rate to after when the irradiation of different xenon lamps, and drafting pattern 5；
5. as shown in Figure 5, the pure titanium sheet of primary industry does not have degradating organic dye ability under visible light；In-situ self-grown is black
Color titania coating has photocatalytically degradating organic dye ability, and its degradating organic dye ability is same surface area white
2-3 times of titania coating；
The titania coating color prepared as can be seen from Figure 1 through differential arc oxidation, plasma hydrogenization two-step method is black.
In-situ self-grown black oxidation titanium coating surface is covered with honeycomb hole as can be seen from Figure 2.
In-situ self-grown black oxidation titanium coating layer thickness is about at 35 μm or so as can be seen from Figure 3.
It can learn that made in-situ self-grown black oxidation titanium coating main component is titanium oxide and titanium from Fig. 4.
It can learn that made in-situ self-grown black oxidation titanium coating has in visible range from Fig. 5 and relatively absorb energy by force
Power.
Made in-situ self-grown black oxidation titanium coating photocatalytically degradating organic dye ability is that it is same as can be seen from Figure 6
2-3 times of sample area white oxide titanium coating.
Claims (9)
1. a kind of preparation method of in-situ self-grown black oxidation titanium coating, it is characterised in that following steps:
1) the industrially pure titanium plate of δ 3mm is cut into titanium sheet, then grinding machine polishing, is cleaned by ultrasonic to obtain surface cleaning through acetone
Titanium sheet；
2) volume is the Na that 90g is added in the stainless steel Water-cooled electric tank of 8L3PO4, the deionized water of 6L is reinjected, it is agitated molten
Xie Hou is made into the electrolyte of 15g/L；
3) titanium alloy hanger is used to fix the titanium sheet prepared by step 1) and as anode plate, not with 80mm × 100mm × 3mm
Yin, yang two-plate is then completely immersed in the electrolyte that step 2) obtains by rust steel plate as cathode plate, and in the form of face-to-face
Parallel arrangement, distance 50mm or so between two-plate；
4) start mao power source and control voltage in 350V, current density 10A/dm2, after continued oxidation handles 30min,
It closes power supply, take out sample.The titanium sheet that surface is white oxide titanium coating is obtained after acetone ultrasonic cleaning, drying.
5) titanium sheet prepared by step 4) is fixed on to the heating zone middle front part of rotary PECVD furnace, by its surface perpendicular to gas
Body flow direction, burner hearth rotational speed regulation are 20rpm.
6) hydrogen and argon gas gaseous mixture are passed through into burner hearth by the volume ratio of 2:1, Continuous aeration 10min is to exclude impurity in burner hearth
Gas.After exhaust, opens radio-frequency power supply and regulation power is to 450W, it is slow with 6 DEG C/min heating rate after aura is stablized
Slow heating furnace body keeps the temperature 5h to 450 DEG C again, and whole process remains at 160Pa by end valve control furnace pressure.
7) after keeping the temperature, radio-frequency power supply is closed, but maintain gas flow constant, is cooled to room temperature to fire box temperature, close gas
End valve is opened, and takes out black oxidation titanium coating titanium sheet in source.
2. preparation method according to claim 1, it is characterised in that: in step 1), used substrate material is industry
Pure titanium.
3. preparation method according to claim 1 or 2, it is characterised in that: in step 1), used titanium sheet outer dimension
For
4. preparation method according to claim 3, it is characterised in that: in step 1), used titanium sheet shape is circle
Pie.
5. preparation method according to claim 1 or 2, it is characterised in that: in step 2), used electrolyte solute is
Na3PO4、K2HPO4Or Na2SiO3。
6. preparation method according to claim 5, it is characterised in that: in step 4), the micro-arc oxidation process of titanium sheet is electricity
Press 350V, current density 10A/dm2, continued oxidation handle 30min.
7. preparation method according to claim 1 or 5, it is characterised in that: the preparation process of white oxide titanium coating is micro-
Arc oxidation, air calcination, pure oxygen sintering, chemical oxidation, electrochemical oxidation or Surface Oxygen Diffusion.
8. preparation method according to claim 7, it is characterised in that: in step (1) and (4), acetone ultrasonic cleaning technique
It is preferred that ultrasonic cleaning 3 times, each 5min.
9. preparation method described according to claim 1 or 5 or 8, it is characterised in that: in step (2), micro-arc oxidation process electrolysis
Liquid temperature is maintained at 35 DEG C.
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