EP0083571A1 - Procédé pour réduire la corrosion de pièces en aluminium - Google Patents
Procédé pour réduire la corrosion de pièces en aluminium Download PDFInfo
- Publication number
- EP0083571A1 EP0083571A1 EP83300018A EP83300018A EP0083571A1 EP 0083571 A1 EP0083571 A1 EP 0083571A1 EP 83300018 A EP83300018 A EP 83300018A EP 83300018 A EP83300018 A EP 83300018A EP 0083571 A1 EP0083571 A1 EP 0083571A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- magnetite
- aluminium
- circulating water
- water
- corrosion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 27
- 230000007797 corrosion Effects 0.000 title claims abstract description 27
- 239000004411 aluminium Substances 0.000 title claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000010949 copper Substances 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 8
- 229910000838 Al alloy Inorganic materials 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 7
- 239000002775 capsule Substances 0.000 claims description 4
- 239000011241 protective layer Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims 1
- 229910001369 Brass Inorganic materials 0.000 abstract description 3
- 239000010951 brass Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910001680 bayerite Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- KRXFTOUYGXMRRU-UHFFFAOYSA-N 3h-1,3-benzothiazole-2-thione;sodium Chemical compound [Na].C1=CC=C2SC(=S)NC2=C1 KRXFTOUYGXMRRU-UHFFFAOYSA-N 0.000 description 1
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000012206 bottled water Nutrition 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000013383 initial experiment Methods 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910021338 magnesium silicide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
Definitions
- the present invention relates to the inhibition of corrosion in circulating water systems which include aluminium or aluminium alloy components; it is particularly advantageous when used in the operation of heating systems employing hot water radiators made of aluminium alloys.
- Aluminium and its alloys have a number of attractions as materials for the construction of hot water radiators, for example their light weight and good heat emissivity characteristics.
- Such radiators may be manufactured in various ways, for example by casting methods, by fabrication from sheet or plate, or by assembly of suitable extruded sections.
- the alloy used is generally an aluminium-silicon alloy, for example Al-11% Si.
- commercially pure aluminium (99.5%) can be used but its mechanical strengths and other properties are generally inadequate and alloys of aluminium are preferred.
- alloys of the aluminium-magnesium silicide group such as AA 6063 are much preferred.
- aluminium and its alloys may undergo pitting corrosion when in contact with potable water drawn from domestic supplies and subjected to the temperature cycles normally encountered in radiators; in particular such pitting corrosion is liable to occur when the system includes copper-containing components so as to provide a source of copper ions in the water.
- British Patent Specification 2013168A describes a method of inhibiting corrosion of a body of e.g. aluminium in the presence of water by adding to the water ferrous sulphate and an organic polymer, preferably in the presence of a reducing or chelating agent, so as to dep-osit an even layer of ferric hydroxide on the body.
- magentite particles were of a size less than 0.1 ⁇ m, i.e.of colloidal dimensions and presumably originated from some colloidal solution and originated with some chance source of iron in contact with the water.
- Some domestic hot water radiator systems to-day are free of iron components.
- chance sources of iron such as the water heating jacket of the boiler, exist, but may not give rise to colloidal particles of magnetite incorporated into the Bayerite film under the operating conditions.
- a method of reducing corrosion of the surface of an aluminium or aluminium alloy component in contact with circulating water comprises providing on the surface a protective oxide layer containing finely divided particles of magnetite.
- a source of colloidal magnetite is introduced into the circulating water so as to form on the surface of the component the protective film of magnetite.
- colloidal magnetite may be introduced into the circulating water, preferably at a concentration of from 500 ppm to 10000 ppm. Below 500 ppm, the protective film may be developed only slowly or to an insufficient extent. Amounts above 10000 ppm contaminate the circulating water without providing sufficient compensating advantages.
- the method of the invention may be used to pretreat the component before it comes in contact with the circulating water.
- the source of colloidal magnetite is introduced into the circulating water at substantially the same time as the component, whereby there is formed on the surface thereof a protective layer of hydrated alumina containing the finely divided particles of magnetite.
- the most convenient route for applying the treatment to an aluminium radiator in situ in a heating system is to dose the water in the radiator system with a magnetite-bearing material in colloidal form or in at least such a fine state of suspension that it can only remain in a settled out condition when entrapped in the growing layer of Bayerite on the surface of aluminium in contact with the water.
- magnetite of an average particle size of about 0.2 ⁇ m was dispersed in water at a temperature of 70 to 75 0 C and circulated through an aluminium alloy pipe in the presence of a copper gauze. It was found that such magnetite was quickly absorbed into the Bayerite layer on the internal surface of the pipe. It was found that the dark-coloured Bayerite layer was highly protective and after a test under these conditions over a three month period the aluminium surface was found to be essentially free from pitting.
- a surface active agent is also introduced into the circulating water in order to assist dispersion of the colloidal magnetite in the water.
- a surface active agent is also introduced into the circulating water in order to assist dispersion of the colloidal magnetite in the water.
- a supplementary corrosion inhibitor may be included in the circulating water.
- Copper passivators are well known, and can be used in conventional amounts as supplementary corrosion inhibitors. Examples are sodium mercaptobenzthiazole (smbt) and benztriazole.
- colloidal magnetite may be mixed with the surface active agent and/or the supplementary corrosion inhibitor before adding the mixture to the circulating water.
- the colloidal magnetite optionally in admixture with other ingredients, may be added to the circulating water as a paste, or as capsules or tablets.
- the mixture is in the form of capsules coated with water-soluble gelatin.
- Example 1 The comparative experiments of Example 1 were repeated using a test-rig system which simulates the actual use of an aluminium radiator in a circulating water system containing also ccpper pipes and brass fittings.
- the test-rig experiments confirmed the results of the beaker tests.
- the radiators were examined after one month's exposure in the simulated central heating system; previous experience had been that, after .one month, some galvanic corrosion would have been observable in the absence of a copper passi- vator.
- the radiator which had been exposed to water containing 1 g/litre magnetite and 0.5 g/litre smbt showed no signs of corrosion whatsoever. Furthermore the test sample was covered with a very good black film which was determined to comprise hydrated alumina containing embedded therein the colloidal particles of magnetite.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8200291 | 1982-01-06 | ||
GB8200291 | 1982-01-06 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0083571A1 true EP0083571A1 (fr) | 1983-07-13 |
EP0083571B1 EP0083571B1 (fr) | 1986-04-16 |
Family
ID=10527484
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19830300018 Expired EP0083571B1 (fr) | 1982-01-06 | 1983-01-05 | Procédé pour réduire la corrosion de pièces en aluminium |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0083571B1 (fr) |
DE (1) | DE3362966D1 (fr) |
GB (1) | GB2114113B (fr) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4835072A (en) * | 1985-06-17 | 1989-05-30 | International Fuel Cells Corporation | Apparatus employing an aqueous solution |
US4670357A (en) * | 1985-06-17 | 1987-06-02 | International Fuel Cells Corporation | Fuel cell powerplant employing an aqueous solution |
GB2178220B (en) * | 1985-06-18 | 1989-07-05 | Int Fuel Cells Corp | Fuel cell powerplant employing an aqueous solution |
US4804591A (en) * | 1985-06-18 | 1989-02-14 | International Fuel Cells | Fuel cell powerplant employing an aqueous solution |
US4923767A (en) * | 1985-06-18 | 1990-05-08 | International Fuel Cells | Fuel cell power plants employing an aqueous solution |
NZ223955A (en) * | 1987-03-24 | 1990-06-26 | Alcan Int Ltd | Aqueous heat transfer system containing delayed release inhibitor capsule |
GB8712198D0 (en) * | 1987-05-22 | 1987-06-24 | Alcan Int Ltd | Water treatment |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1087475A (fr) * | 1953-08-03 | 1955-02-24 | Condensation Application Mec | Procédé et dispositif de protection de cuivre et d'alliages de cuivre en contact avec de l'eau salée, en particulier pour les condenseurs tubulaires |
FR1204092A (fr) * | 1957-10-08 | 1960-01-22 | Ca Atomic Energy Ltd | Perfectionnements à la protection des alliages d'aluminium contre la corrosion |
FR2048116A5 (en) * | 1969-06-02 | 1971-03-19 | Borg Service | Protection of copper in salt - water |
US3578508A (en) * | 1967-04-12 | 1971-05-11 | Martin B Pearlman | Treatment of ferrous metal surfaces to prevent corrosion |
DE2225030A1 (de) * | 1971-05-28 | 1972-12-07 | Mitsubishi Heavy Ind Ltd | Verfahren zum Schützen von Kupferoder Kupferlegierungsmaterialien, insbesondere von Kühlleitungen, sowie eine Vorrichtung dazu |
US3968313A (en) * | 1971-05-10 | 1976-07-06 | Pearlman Martin B | Surface treatment |
-
1983
- 1983-01-05 DE DE8383300018T patent/DE3362966D1/de not_active Expired
- 1983-01-05 EP EP19830300018 patent/EP0083571B1/fr not_active Expired
- 1983-01-05 GB GB08300120A patent/GB2114113B/en not_active Expired
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1087475A (fr) * | 1953-08-03 | 1955-02-24 | Condensation Application Mec | Procédé et dispositif de protection de cuivre et d'alliages de cuivre en contact avec de l'eau salée, en particulier pour les condenseurs tubulaires |
FR1204092A (fr) * | 1957-10-08 | 1960-01-22 | Ca Atomic Energy Ltd | Perfectionnements à la protection des alliages d'aluminium contre la corrosion |
US3578508A (en) * | 1967-04-12 | 1971-05-11 | Martin B Pearlman | Treatment of ferrous metal surfaces to prevent corrosion |
FR2048116A5 (en) * | 1969-06-02 | 1971-03-19 | Borg Service | Protection of copper in salt - water |
US3968313A (en) * | 1971-05-10 | 1976-07-06 | Pearlman Martin B | Surface treatment |
DE2225030A1 (de) * | 1971-05-28 | 1972-12-07 | Mitsubishi Heavy Ind Ltd | Verfahren zum Schützen von Kupferoder Kupferlegierungsmaterialien, insbesondere von Kühlleitungen, sowie eine Vorrichtung dazu |
Also Published As
Publication number | Publication date |
---|---|
GB8300120D0 (en) | 1983-02-09 |
GB2114113A (en) | 1983-08-17 |
GB2114113B (en) | 1985-01-09 |
EP0083571B1 (fr) | 1986-04-16 |
DE3362966D1 (en) | 1986-05-22 |
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
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17P | Request for examination filed |
Effective date: 19840113 |
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ITF | It: translation for a ep patent filed | ||
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