CN1789493A - Ceramic metal oxide composite anode for cathodic protection - Google Patents
Ceramic metal oxide composite anode for cathodic protection Download PDFInfo
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- CN1789493A CN1789493A CN 200410075561 CN200410075561A CN1789493A CN 1789493 A CN1789493 A CN 1789493A CN 200410075561 CN200410075561 CN 200410075561 CN 200410075561 A CN200410075561 A CN 200410075561A CN 1789493 A CN1789493 A CN 1789493A
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- metal oxide
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- iridium
- cathodic protection
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Abstract
The invention relates ceramal oxidate composite anode used for cathodic protection, comprising base body, intermediate layer and surface layer. The base body adopts metallic titanium or niobium; intermediate layer adopts ceramal oxidate IrO2-Ta2O5 in which the proportion of Ir and Ta is (50-90):(10-50); the surface layer is RuO2-IrO2-TiO2 in which the proportion of Ru,Ir and Ti is (15-25):(5-15):(60-70). The composite anode possesses not only the good electrochemistry activity, but also the high stability and low consumption rate. The method suits for impressed current cathodic protection system and other electrochemistry industry.
Description
Technical field:
The present invention relates to a kind of ceramic metal oxide composite anode for cathodic protection; be mainly used in impressed current cathodic protection system; be used for preventing the galvanic corrosion of seawater, slightly salty, fresh water and soil metallic structures, also can be used for electrochemical industries such as clorox generating unit, plating, sewage disposal.Belong to electrochemistry
Technical field.
Technical background:
Galvanic protection can prevent the corrosion of metallic structures in ionogen such as water medium and soil such as iron and steel effectively.Mode difference according to cathodic protection current is provided can be divided into two kinds of methods of sacrificial anode and impressed current.Sacrificial anode is that the dissolving consumption by electronegative anode material self produces cathodic protection current; And being direct supply by the outside, the impressed current cathodic protection method provides required protective current; be characterized in that driving voltage height, outward current are big; and the size that can regulate outward current automatically with the variation of outer work condition condition; make protected metallic structures be in best guard mode, this technology has been widely used in the corrosion prevention and the control of metallic structures such as oceangoing vessel, naval vessel, oil platform, underground pipeline, harbor work's facility always.
Supplementary anode is the important component part in the impressed current cathodic protection system, and its effect is that the protective current that power unit provides is delivered to protected metallic surface via medium.Supplementary anode should have little rate of consumption, satisfactory stability and the work-ing life of length and good electric conductivity and electrochemical activity, also should have the good and economic and the high ratio of performance to price simultaneously.Chang Yong galvanic protection auxiliary anode material mainly contained iron and steel scrap, graphite, high silicon cast iron, pb-ag alloy and platinum anode etc. in the past.The iron and steel scrap anode consumption rate is big, is approximately 9kg/Aa, and work-ing life is shorter, is generally used for provisional protection.Graphite and high silicon cast-iron anode also have bigger rate of consumption, and rate of consumption is approximately 0.5～1kg/Aa, obtain the long life-span, must use large-sized anode, and its mechanical property are relatively poor, are easy to generate brittle rupture in processes such as transportation and installation.The pb-ag alloy anode belongs to the microsolubility anode, but than great, heaviness, be not easy to install, only be applicable in the medium of chloride ion-containing usually, and lead has toxicity, environment is had pollution, and the use in actual engineering is just fewer and feweri, is replaced by the better anode material of performance gradually.The platinum composite anode is with plating, fused salt plating, ion plating and metallurgical drawing or the compound one deck platinum layer of method such as rolling and constitute on the inert metal matrix, has good electrochemical and long work-ing life, but its preparation technology is comparatively complicated, price is expensive, is extensive use of thereby limited this anodic.
For the more excellent auxiliary anode material of obtained performance, the ceramic metal oxide of some conductions begins to be used for impressed current cathodic protection.U.S. Pat Pat.No.3,850,701 have introduced a kind of ceramic metal oxide anode, and it is to adopt chemical conversion process to form the martial ethiops of one deck conduction on titanium or tantalum matrix, promptly elder generation's galvanic deposit one deck iron on matrix carries out chemical treatment then and makes it be converted into ferric oxide.The kind electrode thickness of coating is thinner, and is lower with basal body binding force, is not used widely in practice.U.S. Pat Pat.No.4,445,989 have introduced a kind of galvanic protection ceramic anode material, and it is the ceramic metal oxide that adopts plasma spraying technology deposition one deck conduction on titanium or niobium matrix, and this oxide compound is mainly by Fe
3O
4, NiFe
2O
4, CoFe
2O
4, LiFe
2O
4Etc. formation.Because this ceramic oxide still has higher rate of consumption, is approximately 0.5～3g/Aa, therefore must have enough thick coating to obtain long work-ing life, and too thick coating will influence the bonding force between ceramic oxide coating and the matrix.Yan Yumin, Zhu Zufang, A.V.Timonine have introduced the Fe with the plasma spray coating process preparation
2O
3The oxide coating anode (galvanic protection ferric oxide coating titanium anode, corrosion science and guard technology, Vol.6 (1994), No.2, pp.192-194.), this anode is similar to the anode material that above-mentioned United States Patent (USP) is introduced, and also has same shortcoming.Peng Qiao, Yin Zhengan, Liu Xuehong have introduced titanium base RuO
2-TiO
2The electrochemical behavior of oxide anode in the seawater galvanic protection (applied research of titanium ruthenium anode in galvanic protection, Rare Metals Materials and engineering, Vol.24 (1995), No.3, pp.64-67.).This anode is the dimensional stability anode of being used widely in chlorine industry.Although in the seawater galvanic protection, have good electrochemical activity, owing to be easy to generate passivation when under high current density, working or under aerobic is separated out condition, working, thus influence its stability and work-ing life.Ji Mingtang, Ma Shide, Yang Fangying etc. are by adding a spot of iridium oxide and manganese oxide to improve ruthenium titanium oxide anodic stability (galvanic protection ruthenium-iridium-tantalum manganese coated anode in oxide coating; China's corrosion and protection journal; Vol.6 (1986); No.3; pp.211-215.); but because the iridium oxide that adds is less, therefore the improvement to stability is very limited.Forward, yellow Yongchang, Jiang Xuewen etc. have been introduced a kind of metal oxide anode (research of titanium base iridium dioxide electrode in galvanic protection is used that is used for the fresh water galvanic protection; corrosion science and guard technology; Vol.10 (1998); No.2; pp.109-113.), its activated coating is made of iridium tin-oxide or the iridium tin-oxide of mixing palladium.The anode of this employing iridium oxide has stronger solidity to corrosion than ruthenium oxide anode, but its electrochemical activity does not contain the oxide anode height of ruthenium oxide.In addition, the iridium tin-oxide also is not the best oxide compound of stability, can not provide sufficient protection to the titanium matrix, and under the condition that high current density or aerobic are separated out, the titanium matrix it under still forms passive film easily and causes the anode inefficacy.
Summary of the invention:
The objective of the invention is to overcome the deficiencies in the prior art; a kind of good electrochemical activity that has is provided; and ceramic metal oxide composite anode for cathodic protection with extremely low rate of consumption and advantages of higher stability; this anode can prevent the matrix passivation effectively, even still have very long work-ing life under high current density or other harsh working conditions.
In order to realize the foregoing invention purpose; the agent structure of ceramic metal oxide composite anode for cathodic protection of the present invention is made of matrix, middle layer and upper layer; every part plays a different role, and matrix, middle layer, upper layer are made the integral type clad structure through thermal decomposition method from inside to outside.
Matrix adopting metal titanium or niobium, its purity should be greater than 99%.When passing to anodic current, its surface can form fine and close passive film, and matrix is protected, and avoids producing spot corrosion, and anodic current can not be discharged in the position of generation passive film in ionogen.When the surface recombination of titanium or niobium matrix has the activated coating of conduction, anodic current will be discharged from activated coating.Matrix is to select titanium or niobium depends on concrete working condition, selects titanium to make matrix under the lower condition of operating potential; Select niobium to make matrix when operating potential is very high, this is because niobium has higher corrosion resistance nature than titanium.Usually the spot corrosion disruptive potential of titanium in muriatic medium is arranged is approximately 9～14V, and the spot corrosion disruptive potential of niobium can reach more than the 40V, can satisfy the requirement of galvanic protection under some special conditions.
The matrix that the middle layer should commute produces passivation shields, and good electrical conductivity is arranged simultaneously again, and and matrix and upper layer between should have good bonding force.The present invention adopts the IrO with high solidity to corrosion and stability
2-Ta
2O
5The hybrid ceramic metal oxide is as the middle layer, and it forms Ir: Ta (mol ratio) is (50～90): (10～50).At IrO
2-Ta
2O
5In the hybrid ceramic metal oxide middle layer, iridium oxide has simultaneously very high stability again for the conduction constituent element, and its solidity to corrosion is than high many of ruthenium oxide.Tantalum pentoxide is the inertia constituent element, has amorphous structure, can form mixed metal oxide with iridium oxide, plays function of stabilizer, and can provide protection to matrix.When iridium content was lower than 50%, this middle layer did not have high solidity to corrosion, and the resistivity of coating can increase along with the reduction of iridium content.When iridium content greater than 90% the time owing to can not form the good mixing metal oxide, its solidity to corrosion will reduce.Can select the thickness and the bullion content in middle layer according to working conditions, in order to obtain the good protection effect to matrix, the content range of iridium is 0.5～10g/m
2
Upper layer should have good electrochemical activity, should have lower rate of consumption simultaneously.The upper layer of composite anode of the present invention is RuO
2-IrO
2-TiO
2Mixed metal oxide, it forms Ru: Ir: Ti (mol ratio) is (15～25): (5～15): (60～70), the content of noble ruthenium and iridium is not less than 5g/m
2Owing to contain ruthenium oxide in the coating, therefore have better electrochemical activation.By the iridium oxide of adding high stability in the surfactivity layer, and form the solid solution structure of forming by ruthenium oxide, iridium oxide and titanium oxide mixed metal oxide, make this anodic upper layer also have corrosion resisting property preferably simultaneously.
Ceramic metal oxide composite anode for cathodic protection of the present invention adopts conventional thermolysis process preparation; (1), removes the oxide film on surface and form uniform uneven surface with anode substrate etch in oxalic acid solution or hydrochloric acid soln; (2) chloro-iridic acid and tantalum chloride are dissolved in Virahol or butanols formation masking liquid by proportion of composing, brushing is on the matrix of treated mistake, with after the infrared lamp oven dry,, repeat said process repeatedly to obtain required coating bullion content 450 ℃～600 ℃ sintering 10～15 minutes; (3) ruthenium trichloride, chloro-iridic acid and butyl (tetra) titanate are mixed with masking liquid according to the composition of surfactivity layer, brushing is at the anode surface in existing middle layer, after the oven dry,, repeat said process repeatedly to obtain required coating bullion content 350 ℃～500 ℃ sintering 10～15 minutes.Last sintering time is approximately 1～2 hour.
Product of the present invention is compared with prior art; have higher solidity to corrosion, lower rate of consumption and the electrochemical activity of Geng Gao; thereby not only have good electrochemical, and have very long work-ing life, can under the galvanic protection condition of high current density or harshness, work reliably.Its rate of consumption is about 1～4mg/Aa, and is more much lower than the rate of consumption of high silicon cast iron, pb-ag alloy, titanium base ferric oxide ceramic anode, also littler than the rate of consumption (approximately 6mg/Aa) of platinum composite anode.Its intensified electrolysis life-span is improved several times than conventional ruthenium titanium oxide or ruthenium-iridium-tantalum oxide anode.It is the anode of active component with the iridium oxide that its polarized potential also is lower than simple in platinum composite anode or the coating.
Product of the present invention has following outstanding advantage: (1) adopts titanium or niobium as anode substrate, has the favorable mechanical performance, and is easy to be processed into various required shapes; (2) anode is in light weight, and the high silicon cast iron of alternative heaviness and pb-ag alloy anode are convenient to carrying and installation; (3) adopted the metal oxide compound coating, made this anode have high stability and very low rate of consumption, thereby can have long work-ing life; (4) have high electrochemical activity, can adopt bigger working current density and lower electric power output voltage, thereby have higher efficient; (5) price is cheap than platinum anode, can save the precious metal resource.
Specific embodiments:
Embodiment 1:
Being higher than 99.5% titanium plate with purity is matrix, etch in oxalic acid solution, and the oxide film of removing the surface forms uniform uneven surface; With chloro-iridic acid and tantalum chloride by Ir: the Ta mol ratio is to dissolve in the masking liquid that Virahol constitutes at 70: 30, and brushing after the infrared lamp oven dry, 450 ℃～600 ℃ sintering 10～15 minutes, repeats aforesaid operations on the matrix of treated mistake, brush preparation IrO altogether 6 times
2-Ta
2O
5The anti-corrosion middle layer of ceramic oxide; With ruthenium trichloride, chloro-iridic acid and butyl (tetra) titanate by Ru: Ir: the Ti mol ratio is the masking liquid brushing that is made at 20: 10: 70 anode surface in existing middle layer, after the oven dry, 350 ℃～500 ℃ sintering 10～15 minutes, repeat said process, brush altogether 9 times, last sintering time is approximately 1.5 hours, preparation RuO
2-IrO
2-TiO
2Mixed metal oxide surfactivity layer promptly makes ceramic metal oxide composite anode for cathodic protection sample of the present invention.
On the titanium matrix of treated mistake, adopt thermolysis process to prepare RuO the masking liquid brushing of the upper layer composition of embodiment 1
2-IrO
2-TiO
2The mixed metal oxide layer is brushed 15 times, as a comparison sample altogether.Carried out the test of intensified electrolysis life-span and polarized potential.The intensified electrolysis test is at 1mol/dm
3Sulphuric acid soln in carry out, current density is 2A/cm
2Polarized potential is tested in seawater, and reference electrode is saturated calomel electrode (SCE), and polarized current density is 1000A/m
2Test-results is as shown in table 1.The result shows; the intensified electrolysis life-span of the ceramic metal oxide composite anode for cathodic protection in employing high anti-corrosion iridium tantalum pentoxide of the present invention middle layer is more than 10 times of ruthenium-iridium-tantalum oxide anode of anticorrosion layer in the middle of not containing, and both polarized potentials are suitable.Show that the composite anode of anticorrosion layer has much higher solidity to corrosion and stability in the middle of adopting.
The comparison of table 1 ceramic metal oxide composite anode performance
| Anode material | Intensified electrolysis life-span/hrs | Polarized potential/V |
| Titanium matrix/iridium tantalum pentoxide middle layer/ruthenium-iridium-tantalum oxide surface layer | 550 | 1.3 |
| Titanium matrix/ruthenium-iridium-tantalum oxide surface layer (contrast sample) | 51 | 1.3 |
Embodiment 2:
Adopt method similarly to Example 1 to prepare the ceramic metal oxide composite anode for cathodic protection that contains the middle layer of the present invention.Make the contrast sample with platinum titanium composite anode.Anodic rate of consumption and the polarized potential in seawater have been tested.The tested media of oxide anode rate of consumption is a seawater, and anodic current density is 1000A/m
2Platinum titanium anodic rate of consumption is taken from document.The test condition of polarized potential is with embodiment 1.The results are shown in Table 2.Anode of the present invention has lower polarized potential and rate of consumption than platinum titanium anode, shows that it has higher stability and electrochemical activity.
Table 2 oxide anode and the platinum titanium anode chemical property in seawater relatively
| Anode material | Rate of consumption/mg/Aa | Polarized potential/V |
| Ceramic metal oxide composite anode for cathodic protection | 2.2 | 1.3 |
| Platinum titanium anode | 6 | 1.9 |
Claims (3)
1, a kind of ceramic metal oxide composite anode for cathodic protection; the agent structure that it is characterized in that composite anode is made of matrix, middle layer and upper layer; matrix, middle layer, upper layer are made the integral type clad structure through thermal decomposition method from inside to outside; matrix adopting metal titanium or niobium; iridium tantalum hybrid ceramic metal oxide is adopted in the middle layer, and upper layer is the ruthenium-iridium-tantalum mixed metal oxide.
2, ceramic metal oxide composite anode for cathodic protection according to claim 1 is characterized in that, the purity of matrix titanium or niobium should select titanium to make matrix under the lower condition of operating potential greater than 99%, selects niobium to make matrix when operating potential is very high; Middle layer IrO
2-Ta
2O
5Its mol ratio of forming Ir: Ta of hybrid ceramic metal oxide is (50～90): (10～50), the content range of iridium are 0.5～10g/m
2Upper layer RuO
2-IrO
2-TiO
2Its mol ratio of forming Ru: Ir: Ti of mixed metal oxide is (15～25): (5～15): (60～70), the content of noble ruthenium and iridium is not less than 5g/m
2
3, ceramic metal oxide composite anode for cathodic protection according to claim 1 is characterized in that thermal decomposition method is meant: (1) is removed anode substrate etch in oxalic acid solution or hydrochloric acid soln the oxide film on surface and is formed uniform uneven surface; (2) chloro-iridic acid and tantalum chloride are dissolved in Virahol or butanols formation masking liquid by proportion of composing, brushing is on the matrix of treated mistake, with after the infrared lamp oven dry,, repeat said process repeatedly to obtain required coating bullion content 450 ℃～600 ℃ sintering 10～15 minutes; (3) ruthenium trichloride, chloro-iridic acid and butyl (tetra) titanate are mixed with masking liquid according to the composition of surfactivity layer, brushing is at the anode surface in existing middle layer, after the oven dry,, repeat said process repeatedly to obtain required coating bullion content 350 ℃～500 ℃ sintering 10～15 minutes.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235513B (en) * | 2007-11-14 | 2010-08-18 | 福州大学 | Coating titanium anode |
| WO2014181184A3 (en) * | 2013-05-06 | 2015-04-30 | Saudi Basic Industries Corporation | Cathodic protection anodes |
| CN106590080A (en) * | 2016-12-20 | 2017-04-26 | 中国人民解放军63810部队 | Salt-spray-resistant paint for stainless steel surface, preparation method and salt-spray-resistant stainless steel product |
| CN107937920A (en) * | 2017-11-29 | 2018-04-20 | 青岛双瑞海洋环境工程股份有限公司 | For ocean platform cathodic protection reparation oxide anode material and preparation process |
| CN110904419A (en) * | 2019-12-18 | 2020-03-24 | 厦门佰事兴新材料科技有限公司 | Electrolytic anode plate and preparation method thereof |
| CN113716658A (en) * | 2021-09-27 | 2021-11-30 | 大连理工大学 | Preparation method of ruthenium, iridium and titanium ternary metal mesh electrode containing nano tip structure |
| CN114752971A (en) * | 2022-04-11 | 2022-07-15 | 西安泰金工业电化学技术有限公司 | Preparation method of coated titanium anode with high electrolysis durability |
-
2004
- 2004-12-15 CN CN 200410075561 patent/CN1789493A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235513B (en) * | 2007-11-14 | 2010-08-18 | 福州大学 | Coating titanium anode |
| WO2014181184A3 (en) * | 2013-05-06 | 2015-04-30 | Saudi Basic Industries Corporation | Cathodic protection anodes |
| CN106590080A (en) * | 2016-12-20 | 2017-04-26 | 中国人民解放军63810部队 | Salt-spray-resistant paint for stainless steel surface, preparation method and salt-spray-resistant stainless steel product |
| CN106590080B (en) * | 2016-12-20 | 2019-11-22 | 中国人民解放军63810部队 | A kind of stainless steel product for the coating of stainless steel surface resisting salt fog corrosion, preparation method and resisting salt fog corrosion |
| CN107937920A (en) * | 2017-11-29 | 2018-04-20 | 青岛双瑞海洋环境工程股份有限公司 | For ocean platform cathodic protection reparation oxide anode material and preparation process |
| CN110904419A (en) * | 2019-12-18 | 2020-03-24 | 厦门佰事兴新材料科技有限公司 | Electrolytic anode plate and preparation method thereof |
| CN113716658A (en) * | 2021-09-27 | 2021-11-30 | 大连理工大学 | Preparation method of ruthenium, iridium and titanium ternary metal mesh electrode containing nano tip structure |
| CN114752971A (en) * | 2022-04-11 | 2022-07-15 | 西安泰金工业电化学技术有限公司 | Preparation method of coated titanium anode with high electrolysis durability |
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