EP0792941B1 - Verwendung einer Kupfer-Aluminium-(Zink)-Legierung als korrosionsbeständiger Werkstoff - Google Patents
Verwendung einer Kupfer-Aluminium-(Zink)-Legierung als korrosionsbeständiger Werkstoff Download PDFInfo
- Publication number
- EP0792941B1 EP0792941B1 EP97102019A EP97102019A EP0792941B1 EP 0792941 B1 EP0792941 B1 EP 0792941B1 EP 97102019 A EP97102019 A EP 97102019A EP 97102019 A EP97102019 A EP 97102019A EP 0792941 B1 EP0792941 B1 EP 0792941B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copper
- alloy
- corrosion
- zinc
- aluminium
- 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.)
- Expired - Lifetime
Links
- 230000007797 corrosion Effects 0.000 title claims description 20
- 238000005260 corrosion Methods 0.000 title claims description 20
- 239000000463 material Substances 0.000 title claims description 10
- 239000000956 alloy Substances 0.000 title description 13
- 229910045601 alloy Inorganic materials 0.000 title description 11
- -1 copper-aluminium-(zinc) Chemical compound 0.000 title description 5
- 239000010949 copper Substances 0.000 claims description 27
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003651 drinking water Substances 0.000 claims description 5
- 235000020188 drinking water Nutrition 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 2
- 230000010287 polarization Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 230000029142 excretion Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 241001136792 Alle Species 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910016943 AlZn Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910017777 Cu—Al—Zn Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
Definitions
- the invention relates to the use of a copper-aluminum-zinc alloy as a corrosion-resistant material for Pipes in the installation and sanitary engineering and on the Drinking water sector.
- Pipes for the purpose mentioned are widely used made of oxygen-free copper (SF-Cu). Through special Manufacturing process can be an oxidic on the inner surface of the pipe Protective layer are generated.
- An alternative is an alloyed material that can be used under operating conditions automatically forms an oxidic, protective cover layer.
- the invention is therefore based on the object of being corrosion-resistant Specify material for which none There is a risk of pitting and in which the copper solubility and the mass loss can be reduced.
- the object is achieved by the use of a copper-aluminum-zinc alloy which consists of 1.01 to 8.8% aluminum; 2 to 38% zinc; optionally one or more of the elements silicon, tin, niobium up to a maximum content of 12% in total; optionally up to a maximum of 0.04% phosphorus; The rest is copper and usual impurities (the percentages refer to the weight).
- composition of a copper alloy of the type mentioned is known for example from DE-OS 2,429,754, there however, there is no indication of the intended use.
- DE-OS 4,423,635 describes a copper alloy based on aluminum-zinc described.
- Compulsory components prescribed nickel and / or chrome the increase the strength, but in return also the formability significantly affect.
- solubility of chrome in copper is very small. At the specified The solubility limit is exceeded, and excretion particles form. With such Structural inhomogeneities, resulting in potential differences can result in the smallest areas is the danger of local corrosion attacks cannot be excluded.
- JP-OS 3 / 229,836 relates to the use of a copper alloy with 0.1 - 2.5% Al and 0.01 - 2.5% Sn as corrosion resistant Material for water. There is no indication of the use of zinc.
- a copper alloy with 1.01 to 5% aluminum; 2nd up to 5% zinc used It is also recommended to use a copper alloy that additionally one or several of the elements silicon, tin, niobium in a quantity, the maximum of that of the respective solubility limit of Mixed crystal corresponds, contains.
- the solubility limit excretions should not be exceeded preferred points of attack for corrosion as inhomogeneities can be avoided. This must be taken into account be that the excretion behavior by appropriate Cooling rate can be influenced within certain limits can, d. H.
- Eliminations can occur with rapid cooling be suppressed, or that the solubility limits are exceeded no longer matters at temperatures ⁇ 300 ° C plays, because of the diffusion inertia here in the Systems in question no undesired elimination processes expire more. Copper alloys are preferred with the compositions according to claims 3 to 6 used.
- 15 x 1 mm tubes were produced from SF-Cu, CuAl0.3Zn0.3 and an alloy according to the invention with the composition according to the following table: SF-Cu CuAl0.3Zn0.3 CuAl3Zn2
- FIG. 1 current density-potential curves (FIG. 1) and the electrochemical polarization resistance (R p ) or polarization conductance (R p -1 ) according to FIGS. 3) determined.
- Fig. 1 are the current density-potential curves of the alloys CuAl0.3Zn0.3, CuAl3Zn2 and SF-Cu in comparison shown. It can be seen that the alloyed elements significantly expand the area of corrosion resistance. The passive current density is reduced compared to SF-Cu, which speaks for the better top layer quality. The breakthrough potential are shifted towards more positive potentials.
- the polarization resistance R p or the reciprocal, the polarization conductance R p -1 is a measure of the rate of corrosion. The lower the polarization conductance, the greater the resistance to uniform corrosion. 2a to c compare the polarization conductance of the materials CuAl0.3Zn0.3 and CuAl3Zn2 with that of SF-Cu. Unalloyed Cu not only exhibits poorer behavior, but also considerable scatter.
- the Cu casualness is compared to SF-Cu according to FIG. 3 significantly reduced.
- the Cu-AlZn alloy used according to the invention shows a significantly better behavior than SF-Cu. It not only is the top layer quality improved, but also affects the rate of education and above all the potential range of corrosion resistance expanded. This formation of the passive layer makes the Cu solubility significantly reduced.
- the breakthrough potential also shifts so far into positive direction that it is no longer in the area of free corrosion potential, there is an additional Protection against element formation such as B. contact or Ventilation elements.
- element formation such as B. contact or Ventilation elements.
- no risk of pitting can be determined.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Prevention Of Electric Corrosion (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Description
wahlweise einem oder mehreren der Elemente Silizium, Zinn, Niob bis zu einem Maximalgehalt von insgesamt 12 %;
wahlweise bis maximal 0,04 % Phosphor;
Rest Kupfer und üblichen Verunreinigungen besteht (die Prozentangaben beziehen sich dabei auf das Gewicht).
SF-Cu
CuAl0,3Zn0,3
CuAl3Zn2
- Fig. 1
- die Stromdichte-Potential-Kurve der Legierung CuAl3Zn2 im Vergleich zu CuAl0,3Zn0,3 und SF-Cu. Bezugselektrode: gesättigte Kalomelektrode;
- Fig. 2a bis 2 c
- den Polarisationsleitwert Rp -1 als Funktion
der Versuchsdauer.
- (a) SF-Cu
- (b) CuAl0,3Zn0,3
- (c) CuAl3Zn2
- Fig. 3
- die Cu-Lässigkeit im Stagnationstest in einem aggressiven
Trinkwasser, wobei alle 24 h bzw. an Wochenenden
alle 72 h ein Wasseraustausch mit Ermittlung
der Cu-Gehalte im Stagnationswasser erfolgte
und das Prüfwasser folgende mittlere Analysendaten
aufwies:
pH-Wert 7,3 elektr. Leitfähigkeit in µS/cm 524 Säurekapazität KS4,3 in mmol/l 5 Basekapazität KB8,2 in mmol/l 0,3 bis 0,4 Sättigungsindex SI 0 bis 0,2 Karbonathärte in °dH 14 Gesamthärte in °dH 15 Chloridgehalt in mg/l 13 Sulfatgehalt in mg/l 250
Claims (6)
- Verwendung einer Kupfer-Aluminium-Zink-Legierung, bestehend aus 1,01 bis 8,8 % Aluminium; 2 bis 38 % Zink;wahlweise einem oder mehreren der Elemente Silizium, Zinn, Niob bis zu einem Maximalgehalt von insgesamt 12 %;wahlweise bis maximal 0,04 % Phosphor;Rest Kupfer und üblichen Verunreinigungen, als korrosionsbeständiger Werkstoff für Rohre in der Installations- und Sanitärtechnik und auf dem Trinkwassersektor.
- Verwendung einer Kupfer-Legierung nach Anspruch 1 mit 1,01 bis 5 % Aluminium; 2 bis 5 % Zink für den Zweck nach Anspruch 1.
- Verwendung einer Kupfer-Legierung nach Anspruch 1 oder 2 mit maximal 3,8 % Silizium für den Zweck nach Anspruch 1.
- Verwendung einer Kupfer-Legierung nach einem oder mehreren der Ansprüche 1 bis 3 mit maximal 7 % Zinn für den Zweck nach Anspruch 1.
- Verwendung einer Kupfer-Legierung nach einem oder mehreren der Ansprüche 1 bis 4 mit maximal 0,1 % Niob für den Zweck nach Anspruch 1.
- Verwendung einer Kupfer-Legierung nach Anspruch 5 mit maximal 0,05 % Niob für den Zweck nach Anspruch 1.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19606162A DE19606162C2 (de) | 1996-02-20 | 1996-02-20 | Verwendung einer Kupfer-Aluminium-Zink-Legierung als korrosionsbeständiger Werkstoff |
DE19606162 | 1996-02-20 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0792941A1 EP0792941A1 (de) | 1997-09-03 |
EP0792941B1 true EP0792941B1 (de) | 2000-05-03 |
Family
ID=7785832
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97102019A Expired - Lifetime EP0792941B1 (de) | 1996-02-20 | 1997-02-08 | Verwendung einer Kupfer-Aluminium-(Zink)-Legierung als korrosionsbeständiger Werkstoff |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0792941B1 (de) |
DE (2) | DE19606162C2 (de) |
DK (1) | DK0792941T3 (de) |
ES (1) | ES2147950T3 (de) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20010032007A (ko) * | 1997-11-11 | 2001-04-16 | 시게후치 마사토시 | 금속재료, 황동 및 이의 제조방법 |
CN102534295B (zh) * | 2011-11-21 | 2016-07-06 | 宁波三旺洁具有限公司 | 一种耐腐蚀硼铜合金 |
EP3045740B1 (de) * | 2015-01-19 | 2021-04-21 | BTS BauTechnischeSysteme GmbH & Co. KG | Befestigungselement zur Befestigung eines Bauteils an einem Wärmedämmverbundsystem |
FR3064280B1 (fr) * | 2017-03-23 | 2022-08-05 | Favi Le Laiton Injecte | Alliage a base de cuivre et de zinc pour une utilisation dans l'industrie alimentaire |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1938172A (en) * | 1933-03-24 | 1933-12-05 | Chase Companies Inc | Copper-base alloys |
US2224095A (en) * | 1940-02-15 | 1940-12-03 | Scovill Manufacturing Co | Tube for heat exchanging apparatus |
DE1127092B (de) * | 1953-04-13 | 1962-04-05 | Osnabruecker Kupfer Und Draht | Verwendung von Kupferlegierungen zur Herstellung von Waschkesseln oder Innenausstattungen von Waschmaschinen |
DK99834C (da) * | 1962-09-19 | 1964-09-21 | Aktieselkabet Nordiske Kabel T | Havvandsbestandig legering af messing eller aluminiummessing egnet for plastisk deformation. |
DE2429754C3 (de) | 1974-06-21 | 1981-12-17 | Olin Corp., 06511 New Haven, Conn. | Verfahren zur Verbesserung der Kriechfestigkeit und Spannungsrelaxation von Federn aus Kupferwerkstoffen |
LU81564A1 (fr) * | 1979-07-31 | 1981-03-24 | Liege Usines Cuivre Zinc | Procede de fabrication de tubes,tubes obtenus par ce procede et leur utilisation dans des condenseurs et des echangeurs de chaleur |
JPS5675541A (en) | 1979-11-22 | 1981-06-22 | Sumitomo Light Metal Ind Ltd | Copper alloy for water or hot water supply piping material and heat exchanger tube material |
JPH03229836A (ja) * | 1990-02-01 | 1991-10-11 | Kobe Steel Ltd | 耐食性銅合金管 |
JPH03291341A (ja) * | 1990-04-06 | 1991-12-20 | Chuetsu Gokin Chuko Kk | 耐摩耗性銅合金 |
DE4213487C1 (de) | 1992-04-24 | 1993-11-18 | Wieland Werke Ag | Verwendung einer Kupfer-Aluminium-Zink-Legierung als korrosionsbeständiger Werkstoff |
DE4324008C2 (de) * | 1993-07-17 | 2003-03-27 | Km Europa Metal Ag | Verwendung einer korrosionsbeständigen Legierung auf Kupferbasis |
DE4423635A1 (de) | 1994-07-06 | 1996-01-11 | Prym William Gmbh & Co Kg | Korrosionsbeständige Kupferlegierung |
-
1996
- 1996-02-20 DE DE19606162A patent/DE19606162C2/de not_active Expired - Fee Related
-
1997
- 1997-02-08 DE DE59701554T patent/DE59701554D1/de not_active Expired - Lifetime
- 1997-02-08 ES ES97102019T patent/ES2147950T3/es not_active Expired - Lifetime
- 1997-02-08 DK DK97102019T patent/DK0792941T3/da active
- 1997-02-08 EP EP97102019A patent/EP0792941B1/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
ES2147950T3 (es) | 2000-10-01 |
DE19606162A1 (de) | 1997-08-21 |
DE19606162C2 (de) | 2003-01-30 |
EP0792941A1 (de) | 1997-09-03 |
DK0792941T3 (da) | 2000-10-02 |
DE59701554D1 (de) | 2000-06-08 |
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