CN103320822A - Method for electroplating titanium on surface of metal - Google Patents
Method for electroplating titanium on surface of metal Download PDFInfo
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- CN103320822A CN103320822A CN2013102619100A CN201310261910A CN103320822A CN 103320822 A CN103320822 A CN 103320822A CN 2013102619100 A CN2013102619100 A CN 2013102619100A CN 201310261910 A CN201310261910 A CN 201310261910A CN 103320822 A CN103320822 A CN 103320822A
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Abstract
The invention relates to a method for electroplating titanium on the surface of metal. The method is characterized in that TiOxCy is taken as a positive pole, metal to be electroplated is taken as a negative pole and molten salt is taken as an electrolyte in the titanium electroplating process. By the method provided by the invention, the aim of corrosion resistance can be achieved through electroplating titanium on the surface of metal with the melting point of 800 DEG C, such as carbon steel, stainless steel, foamy copper and foamy nickel, and other matrixes, the use cost of a titanium material can be greatly reduced, the application field of the titanium metal is widened, and the titanium is not only taken as precious space metal. The electro-deposition on general metal can be realized with least reaction steps and cheapest raw materials; the titanium electroplating is directly finished from the step of electrolyzing the raw materials of titanium, so that the step for preparing the titanium through electrolysis is omitted, the loss of the raw materials and energy sources is reduced, the efficiency of electrolytic current and the utilization ratio of the raw materials are improved, and the titanium electroplating cost is reduced.
Description
Technical field
The present invention relates to the method for a kind of metallic surface Titanium Electroplating.
Background technology
Titanium is a kind of light metal of high specific strength high corrosion resistance, so because expensive use is restricted, generally can only be used in expensive aircraft, on the aviation aircraft, therefore is also referred to as on " space metal ".Titanium Electroplating then technology can reach erosion-resisting effect at common metal top layer plating one deck titanium film, can greatly reduce use cost, and titanium more is used in corrosive environment such as the ocean.
Since the discharge potential of titanium very negative (its standard potential is about-1.75V), the deposition of titanium is not easy very much, the electroplating technology of titanium is imperfection very also, mainly be to carry out titanium by dual mode to electroplate at present, the most frequently used method be metal titanium in vacuum or rare gas element, utilize electric arc be ionized into titanium ion then bombarding cathode electroplate, also have a kind of mode to be called as second-level titanizing, mainly be on matrix, to plate first one deck active metal such as magnesium, then clean with titanium tetrachloride solution, by magnesium metal titanium is cemented out, be plated on the matrix.On the whole, the main aspect that carbon oxygen titanium electrochemical plating are different from the various titanium electro-plating methods of existing widespread use is: the electrolysis raw material no longer is the higher simple substance titanium of price, but more stable titanium dioxide and the graphite of less expensive is smelted and two processes of titanium plating with a process implementation titanium.
Traditional electrical titanizing reaction Ti-ne--Tin+
Tin+?—?Ti?+?ne-
Adopt electric arc ionization plating mode, need to do raw material with metal titanium, cost is high, and processing step is many, and energy consumption is large, and process is simply complicated, and operation easier is large.
Adopt second-level titanizing to comprise the step of plating magnesium, the electropotential of magnesium is also relatively born, and electroplates also difficult the realization, therefore can simplify the operation, and reduces cost.(2) need not use titanium tetrachloride to replace, because the titanium tetrachloride water breakthrough very easily decomposes, also hydrolysis generation hydrochloric acid is therefore abnormally dangerous to discharge a large amount of heat, and the use that has reduced titanium tetrachloride can increase production safety.
Summary of the invention
Purpose of the present invention is exactly the deficiency that exists for above-mentioned prior art, provides that a kind of efficient is high, cost is low, can greatly reduce the use cost of titanium material, widens the use field of titanium metal, and step is simple, the method for easy to operate metallic surface Titanium Electroplating.
The objective of the invention is to be achieved through the following technical solutions.
The method of a kind of metallic surface Titanium Electroplating is characterized in that its titanizing process is with TiO
xC
yAs anode,, as ionogen, electroplate with fused salt as negative electrode with the metal of electroplated.
The method of a kind of metallic surface of the present invention Titanium Electroplating is characterized in that its TiO
xC
y0＜X＜2,0＜Y≤1.
The method of a kind of metallic surface of the present invention Titanium Electroplating, the electric current that it is characterized in that its electroplating process are the one or more combination in galvanic current, rectangular wave current, triangular current, the pulsed current.
The method of a kind of metallic surface of the present invention Titanium Electroplating is characterized in that its electroplating process adopts the inert environments that is of plating tank, and plating tank is sealing and is provided with air inlet/outlet, by the rare gas element of air inlet/outlet by flowing.
The method of a kind of metallic surface of the present invention Titanium Electroplating is characterized in that its fused salt is one or several the combination in sodium-chlor, Repone K, Sodium Fluoride and the Potassium monofluoride.
The method of a kind of metallic surface of the present invention Titanium Electroplating is characterized in that adding massfraction in its molten salt electrolyte is the potassium fluotitanate of 1%-30%.
The method of a kind of metallic surface of the present invention Titanium Electroplating is characterized in that adding massfraction in its molten salt electrolyte is 1%-30% Ti
3+, Ti
2+Ion is as additive.
The method of a kind of metallic surface of the present invention Titanium Electroplating is characterized in that the fusing point of its plating metal is higher than 600 ℃, and its structure is the foamed metal of solid metal or hollow.
The method of a kind of metallic surface of the present invention Titanium Electroplating, the foam aperture that it is characterized in that the foamed metal of its hollow is 0.1mm-10mm, 5 ~ 120ppi, porosity: 50% ~ 98%, through-hole rate:＞=98%, volume density:＞0.1g/cm
2
The method of a kind of metallic surface of the present invention Titanium Electroplating is with TiO
xC
yAs anode, carry out proportioning with one or several combinations in sodium-chlor, Repone K, Sodium Fluoride and the Potassium monofluoride, and add potassium fluotitanate or the Ti of certain component
3+, Ti
2+As ionogen, as negative electrode titanizing is carried out on its surface with high-melting-point solid metal or hollow foam metal and reached the rot-resistant purpose.
Its electrochemical plating reaction is: TiO2+C-Ti+CO2
With respect to electric arc ionization plating mode, present method has following advantage: (1) does not need to do raw material with metal titanium, has reduced cost.(2) carbon oxygen titanium is ionized into titanium and titanium and is ionized into titanium ion and electroplates and combine, omitted step, saved the energy.(3) utilize common KCl and NaCl as ionogen, process is simple, and is easy to operate.With respect to second-level titanizing, the advantage of present method is: (1) has omitted the step of plating magnesium, and the electropotential of magnesium is also relatively born, and electroplates also difficult the realization, therefore can simplify the operation, and reduces cost.(2) need not use titanium tetrachloride to replace, because the titanium tetrachloride water breakthrough very easily decomposes, also hydrolysis generation hydrochloric acid is therefore abnormally dangerous to discharge a large amount of heat, and the use that has reduced titanium tetrachloride can increase production safety.
The method of a kind of metallic surface of the present invention Titanium Electroplating, because carbon oxygen titanium electrochemical plating step is simple, cost of material is cheap, and is easy to operate, makes its scale operation make the titanizing material be applied in widely the field possibility that becomes.Can reach etch-proof purpose in refractory metal surface titanizing, the enough minimum reactions steps of energy, the most cheap raw material is realized the lip-deep galvanic deposit of common metal, directly finish the plating of titanium from the starting material of electrolytic titanium, crossed over this step of electrolysis titanium processed, reduce the loss of raw material and the energy, improved Faradaic current efficient and raw material rate of utilization, reduced the Titanium Electroplating cost.
The present invention can electroplate for the titanium of realizing high-efficiency and low-cost, can greatly reduce the use cost of titanium material, and the use field of widening titanium metal makes no longer just " the space metal " of costliness of titanium.The enough minimum reactions steps of energy, the most cheap raw material is realized the galvanic deposit on the common metal, directly finish the plating of titanium from the starting material of electrolytic titanium, crossed over this step of electrolysis titanium processed, reduced the loss of raw material and the energy, improve Faradaic current efficient and raw material rate of utilization, reduced the Titanium Electroplating cost.
Description of drawings
Fig. 1 is the coating sectional drawing that obtained in 1 hour with the direct current electrode position of 10A at copper sheet for adopting method of the present invention, and the picture top is the copper sheet matrix, is titanium coating below the picture.
Embodiment
The method of a kind of metallic surface Titanium Electroplating, its titanizing process is with TiO
xC
yAs anode,, as ionogen, electroplate with fused salt as negative electrode with the metal of electroplated; The electric current of its electroplating process is the one or more combination in galvanic current, rectangular wave current, triangular current, the pulsed current; What its electroplating process adopted plating tank is inert environments, and plating tank is sealing and has been provided with air inlet/outlet, by the rare gas element of air inlet/outlet by flowing; Its fused salt is one or several the combination in sodium-chlor, Repone K, Sodium Fluoride and the Potassium monofluoride; Adding massfraction in its molten salt electrolyte is the potassium fluotitanate of 1%-30%; Adding massfraction in its molten salt electrolyte is 1%-30% Ti
3+, Ti
2+Ion is as additive; The fusing point of its plating metal is higher than 600 ℃, and its structure is the foamed metal of solid metal or hollow; The foam aperture of the foamed metal of its hollow is 0.1mm-10mm, 5 ~ 120ppi, and porosity: 50% ~ 98%, through-hole rate:＞=98%, volume density:＞0.1g/cm
2
Embodiment 1
Select TiO
xC
y(x is that 1, y is 1) is basic raw material, adds 10% PVC and mixes and vibratory compaction, carries out high temperature sintering 10 hours under 1500 ℃ of conditions, after the moulding and connect guide rod as galvanic anode, electroplates as negative electrode with carbon steel rod.The taking-up negative electrode is cooled off in direct current plating with 10A after 3 hours, soak in tap water, electroplates the part non-corrosive, proves that titanium plates.
Embodiment 2
Select TiO
xC
y(x is 0.5, y is 0.5) be basic raw material, the PVC of adding 12% mixes and vibratory compaction as binding agent, carries out high temperature sintering 8 hours under 1800 ℃ of conditions, moulding also connects guide rod as galvanic anode, electroplates as negative electrode with the copper mesh connection guide rod of light.Take size as 0A-10A-0A, the cycle electroplates after 2 hours cooling as 30 minutes rectangular wave current and takes out negative electrode, soaks in tap water, the copper mesh of light becomes grey black, proves that titanium plates.
Embodiment 3
Select TiO
xC
y(x is 1, y is 1) be basic raw material, the paraffin of adding 15% mixes and vibratory compaction as binding agent, carries out high temperature sintering 8 hours under 1700 ℃ of conditions, moulding also connects guide rod as galvanic anode, electroplates as negative electrode with the copper sheet connection filamentary silver of light.Electroplate after 2 hours cooling with the circulation rectangular wave current of 1A electric current 10 minutes, 10A electric current 10 minutes and take out negative electrode, in 3% hydrochloric acid, soak, have the grey black material to adhere on the copper sheet of light, prove that titanium plates.
Embodiment 4
Select TiO
xC
y(x is that 0.2, y is 0.8) is basic raw material,, take by weighing TiO
xC
yRaw material 1kg, the paraffin thinner of adding anode material gross weight 25% carries out extrusion molding, form oval blank, carried out high temperature sintering 8 hours under 1800 ℃ of conditions, moulding also connects guide rod as galvanic anode, directly electroplates as negative electrode with the stainless steel guide rod.Take 5A as amplitude, 10A electroplates after 5 hours cooling and takes out negative electrode as maximum, 20 minutes as the sine-wave current of one-period, soak in tap water, the surface has the grey black material to adhere to, and proves that titanium plates.
Embodiment 5
Select TiO
xC
y(x is that 1.7, y is 0.3) is basic raw material, adds the paraffin thinner of anode material gross weight 25%, vibratory compaction forms stock of square, carried out high temperature sintering 8 hours under 1800 ℃ of conditions, moulding also connects guide rod as galvanic anode, electroplates as negative electrode with the foam copper of different pore size.Take 10A as amplitude, 20A electroplates after 2 hours cooling and takes out negative electrode as maximum, 20 minutes as the sine-wave current of one-period, soak in tap water, the surface has the grey black material to adhere to, and proves that titanium plates.
Embodiment 6
Select TiO
xC
y(x is that 1, y is 1) makes anode for basic raw material, electroplates as negative electrode with the nickel foam of different pore size.Take out negative electrode with cooling after electroplating 2 hours every the pulsed current that added 5 minutes 10A electric currents in 5 minutes, in tap water, soak, electroplate the part non-corrosive, prove that titanium plates.
Embodiment 7
Select TiO
xC
y(x is that 1.1, y is 0.9) makes anode for basic raw material,, electroplate as negative electrode with the foam iron of different pore size.Cool off the taking-up negative electrode after 5 hours with the plating of 10A direct current, soak in tap water, the surface has the grey black material to adhere to, and proves that titanium plates.
Claims (9)
1. the method for a metallic surface Titanium Electroplating is characterized in that its titanizing process is with TiO
xC
yAs anode,, as ionogen, electroplate with fused salt as negative electrode with the metal of electroplated.
2. require the method for 1 described a kind of metallic surface Titanium Electroplating according to the authority profit, the electric current that it is characterized in that its electroplating process is the one or more combination in galvanic current, rectangular wave current, triangular current, the pulsed current.
3. require the method for 1 described a kind of metallic surface Titanium Electroplating according to the authority profit, it is characterized in that its electroplating process adopts the inert environments that is of plating tank, plating tank is sealing and is provided with air inlet/outlet, by the rare gas element of air inlet/outlet by flowing.
4. require the method for 1 described a kind of metallic surface Titanium Electroplating according to the authority profit, it is characterized in that its fused salt is one or several the combination in sodium-chlor, Repone K, Sodium Fluoride and the Potassium monofluoride.
5. require the method for 1 described a kind of metallic surface Titanium Electroplating according to the authority profit, it is characterized in that in its molten salt electrolyte adding massfraction and be the potassium fluotitanate of 1%-30% as additive.
6. require the method for 1 described a kind of metallic surface Titanium Electroplating according to the authority profit, it is characterized in that adding massfraction in its molten salt electrolyte is 1%-30% Ti
3+, Ti
2+Ion is as additive.
7. require the method for 1 described a kind of metallic surface Titanium Electroplating according to the authority profit, it is characterized in that the fusing point of its plating metal is higher than 600 ℃, its structure is the foamed metal of solid metal or hollow.
8. require the method for 1 described a kind of metallic surface Titanium Electroplating according to the authority profit, the foam aperture that it is characterized in that the foamed metal of its hollow is 0.1mm-10mm, 5 ~ 120ppi, and porosity: 50% ~ 98%, through-hole rate:＞=98%, volume density:＞0.1g/cm
2
9. require the method for 1 described a kind of metallic surface Titanium Electroplating according to the authority profit, it is characterized in that its TiO
xC
yIn 0＜X＜2,0＜Y≤1.
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| CN2013102619100A CN103320822A (en) | 2013-06-27 | 2013-06-27 | Method for electroplating titanium on surface of metal |
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|---|---|---|---|
| CN2013102619100A CN103320822A (en) | 2013-06-27 | 2013-06-27 | Method for electroplating titanium on surface of metal |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106514039A (en) * | 2016-11-03 | 2017-03-22 | 华北水利水电大学 | Copper-tin-titanium brazing filler metal and preparation method thereof |
| CN106757235A (en) * | 2016-11-19 | 2017-05-31 | 祁阳宏泰铝业有限公司 | A kind of aluminum alloy surface titanizing processing method |
| CN110023544A (en) * | 2016-11-22 | 2019-07-16 | 住友电气工业株式会社 | The preparation method of titanium electroplate liquid and the manufacturing method of plating titanium article |
| CN110536978A (en) * | 2017-05-22 | 2019-12-03 | 住友电气工业株式会社 | The manufacturing method of metal porous body and metal porous body |
| CN113913888A (en) * | 2021-08-16 | 2022-01-11 | 福建威鹏实业有限公司 | Melamine product with sterilization function and manufacturing method thereof |
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| US2722509A (en) * | 1952-11-12 | 1955-11-01 | Horizons Titanium Corp | Production of titanium |
| US2868703A (en) * | 1954-11-08 | 1959-01-13 | Horizons Titanium Corp | Cell feed material for the production of titanium |
| US4121982A (en) * | 1978-02-03 | 1978-10-24 | American Chemical & Refining Company Incorporated | Gold alloy plating bath and method |
| US20050166706A1 (en) * | 2003-08-20 | 2005-08-04 | Withers James C. | Thermal and electrochemical process for metal production |
| CN1712571A (en) * | 2005-05-08 | 2005-12-28 | 北京科技大学 | Pure titanium production from titanium monoxide/titanium carbide soluble solid anode electrolysis |
-
2013
- 2013-06-27 CN CN2013102619100A patent/CN103320822A/en active Pending
Patent Citations (6)
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| US2722509A (en) * | 1952-11-12 | 1955-11-01 | Horizons Titanium Corp | Production of titanium |
| US2868703A (en) * | 1954-11-08 | 1959-01-13 | Horizons Titanium Corp | Cell feed material for the production of titanium |
| US4121982A (en) * | 1978-02-03 | 1978-10-24 | American Chemical & Refining Company Incorporated | Gold alloy plating bath and method |
| US20050166706A1 (en) * | 2003-08-20 | 2005-08-04 | Withers James C. | Thermal and electrochemical process for metal production |
| CN1867702A (en) * | 2003-08-20 | 2006-11-22 | 材料及电气化学研究公司 | Thermal and electrochemical process for metal production |
| CN1712571A (en) * | 2005-05-08 | 2005-12-28 | 北京科技大学 | Pure titanium production from titanium monoxide/titanium carbide soluble solid anode electrolysis |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106514039A (en) * | 2016-11-03 | 2017-03-22 | 华北水利水电大学 | Copper-tin-titanium brazing filler metal and preparation method thereof |
| CN106514039B (en) * | 2016-11-03 | 2019-03-08 | 华北水利水电大学 | A kind of copper and tin titanium solder and preparation method thereof |
| CN106757235A (en) * | 2016-11-19 | 2017-05-31 | 祁阳宏泰铝业有限公司 | A kind of aluminum alloy surface titanizing processing method |
| CN106757235B (en) * | 2016-11-19 | 2018-06-26 | 祁阳宏泰铝业有限公司 | A kind of aluminum alloy surface titanizing processing method |
| CN110023544A (en) * | 2016-11-22 | 2019-07-16 | 住友电气工业株式会社 | The preparation method of titanium electroplate liquid and the manufacturing method of plating titanium article |
| CN110536978A (en) * | 2017-05-22 | 2019-12-03 | 住友电气工业株式会社 | The manufacturing method of metal porous body and metal porous body |
| US11757101B2 (en) | 2017-05-22 | 2023-09-12 | Sumitomo Electric Industries, Ltd. | Metal porous body and method for producing metal porous body |
| CN113913888A (en) * | 2021-08-16 | 2022-01-11 | 福建威鹏实业有限公司 | Melamine product with sterilization function and manufacturing method thereof |
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Application publication date: 20130925 |