EP3225707A1 - Component for media-conducting gas or water lines comprising a copper alloy - Google Patents
Component for media-conducting gas or water lines comprising a copper alloy Download PDFInfo
- Publication number
- EP3225707A1 EP3225707A1 EP17151949.9A EP17151949A EP3225707A1 EP 3225707 A1 EP3225707 A1 EP 3225707A1 EP 17151949 A EP17151949 A EP 17151949A EP 3225707 A1 EP3225707 A1 EP 3225707A1
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- European Patent Office
- Prior art keywords
- alloy
- component according
- lead
- component
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 63
- 239000000956 alloy Substances 0.000 claims abstract description 63
- 239000003651 drinking water Substances 0.000 claims abstract description 22
- 235000020188 drinking water Nutrition 0.000 claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 230000007797 corrosion Effects 0.000 claims description 44
- 238000005260 corrosion Methods 0.000 claims description 44
- 239000002245 particle Substances 0.000 claims description 29
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 239000011701 zinc Substances 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 238000013508 migration Methods 0.000 claims description 10
- 230000005012 migration Effects 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical class S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 42
- 230000015572 biosynthetic process Effects 0.000 description 27
- 239000011133 lead Substances 0.000 description 26
- 239000012071 phase Substances 0.000 description 22
- 230000032683 aging Effects 0.000 description 17
- 238000001816 cooling Methods 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- 238000009826 distribution Methods 0.000 description 11
- 229910001369 Brass Inorganic materials 0.000 description 10
- 239000010951 brass Substances 0.000 description 10
- 150000004763 sulfides Chemical class 0.000 description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000155 melt Substances 0.000 description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 8
- 238000005266 casting Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 238000003754 machining Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 230000001464 adherent effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical class [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 3
- 238000010191 image analysis Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007528 sand casting Methods 0.000 description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 208000036829 Device dislocation Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241001295925 Gegenes Species 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000009827 uniform distribution 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
- C22C9/02—Alloys based on copper with tin as the next major constituent
-
- 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
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03B—INSTALLATIONS OR METHODS FOR OBTAINING, COLLECTING, OR DISTRIBUTING WATER
- E03B7/00—Water main or service pipe systems
Definitions
- the present invention relates to a component for media-carrying gas or water pipes, in particular fitting or fitting for drinking water pipes, wherein the component consists at least partially of a lead-free copper alloy.
- the materials used to protect consumers must comply with very narrow limits, which are regulated by the Drinking Water Ordinance.
- the in the EP 1 798 298 A1 described alloy shows a comparison with a conventional gunmetal improved migration behavior for lead, nickel, copper and zinc ions.
- the alloy can be subjected to a heat treatment after casting in order to achieve a high proportion of ⁇ -mixed crystal and thus a particularly favorable migration behavior of the alloy.
- Lead is practically insoluble in copper and has a low melting point. As a result, it is the last solidifying element in copper-tin alloys.
- This constitutional behavior leads to lead being present in the structure at the end of the solidification in the form of evenly distributed, small, drop-shaped particles between the dendrite arms.
- These fine, teardrop-shaped particles act as chipbreakers without affecting the original properties of the material. This is particularly evident in the corrosion resistance, since the lead particles are present as incoherent phases and thus can not interact with the surrounding matrix. Also, the uniform distribution of small, teardrop-shaped lead particles ensures that similar mechanical characteristics are consistently to be expected over a uniform cross section.
- Patent US 8,470,101 B2 a lead-free alloy is described, which in addition to copper and unavoidable impurities from 0.1 wt .-% to 0.7 wt .-% sulfur, up to 8 wt .-% tin and up to 4 wt .-% zinc, and in the task of the lead over sulfur phases in the form of sulfide particles are fulfilled.
- these sulfides do not have the property of forming themselves inevitably at the end of the solidification in the form of small, distributed phases.
- an unfavorably chosen composition of in Patent US 8,470,101 B2 Alloy described may lead to unfavorable sulfide formation in the structure.
- the object of the present invention is to provide a lead-free copper alloy for the production of components for media-carrying gas or water lines, which in comparison with a conventional gunmetal alloy, such as, for example, CuSn5Zn5Pb2, a corrosion-resistant matrix, good strength properties with good machining properties, high pressure tightness and improved migration behavior.
- a conventional gunmetal alloy such as, for example, CuSn5Zn5Pb2
- the lead-free copper alloy should have a good casting behavior, eg. In sand or continuous casting.
- the lead-free copper alloy shows no dezincification or similar selective corrosion attack. Therefore, the lead-free copper alloy has improved corrosion resistance over the entire frame prescribed by the Drinking Water Ordinance (hereinafter referred to as "TWVO"). Accordingly, the present invention preferably represents a component for media-carrying gas or water pipes, in particular a fitting or a fitting for drinking water pipes, wherein the component consists at least partially of the lead-free copper alloy according to the invention.
- the tin content has an influence on the strength, corrosion resistance and on the phase distribution and, in the claimed range from 3.5% by weight to ⁇ 4.8% by weight, achieves an optimally balanced, economical ratio of the properties described above.
- a tin content of more than 4.8% by weight the strength and corrosion resistance in the matrix continue to increase, but under normal cooling conditions in sand casting, the distribution of the sulfides becomes coarser and the size increases.
- At levels below 3.5% by weight of tin there is insufficient corrosion inhibition.
- a high tensile strength can be achieved at levels above 4.8% by weight of tin, the elongation values of the material are reduced. Contents of well over 4.8 wt .-% tin lead to the formation of a structure which embrittlement and unfavorable effect on the processing.
- the sulfur content of 0.25 wt .-% to 0.65 wt .-% determines the volume fraction of the sulfides with. From 0.25 wt .-% sulfur, an amount of sulfide particles is produced, which ensures sufficient machinability of the alloy. Sulfur content above 0.65 wt% sulfur can lead to the formation of undesirable coarse sulfide particles. In addition, due to the high content of sulfide particles, the load transmitted cross section, i. the cross-section of the component which receives voltages from the outside, reduce so much that it leads to a deterioration of the mechanical characteristics, such. Elongation at break and the like comes.
- the metal sulfides are present in such a sulfur content in the lead-free copper alloy as an incoherent, finely divided, disperse phase in the form of finely divided particles. This offers the advantage that any corrosion occurring only to a small extent locally on these particles and not along contiguous, larger, individual phases of the alloy structure takes place, as is the case for example with standard brass. Due to the small size of the particles no significant corrosive attack takes place.
- the proportion of phosphorus (P) in the lead-free copper alloy according to the invention is 0.015 wt .-% to 0.1 wt .-%. Below 0.015% by weight of phosphorus, there is no sufficient deoxidation of the melt, which has a negative effect on the phase formation of the alloy. On the other hand, if the phosphorus content exceeds 0.1 wt%, the lead-free copper alloy tends to have adverse effects on the mechanical properties such as reduced elongation at break. From these viewpoints, the weight proportion of phosphorus in the lead-free copper alloy is preferably in the range of 0.02 wt% to 0.08 wt%, more preferably in the range of 0.04 wt% to 0.06 wt%. -%.
- the term "lead-free copper alloy” means a copper alloy containing, in particular, lead as an unavoidable impurity in an amount of not more than 0.25 wt%, but preferably 0.09 wt%, more preferably not more than 0 , 05 wt .-% includes.
- the lead content is at most 0.25 wt .-%, preferably at most 0.09 wt .-% and particularly preferably at most less than or equal to 0.05 wt .-%.
- the alloy shows no signs of increased lead delivery in the first few weeks.
- the low lead content in the alloy used in the invention thus leads to a significant reduction of metal ion migration in drinking water, the low lead content has no negative effects on the chip breaking and thus on the machinability of the alloy used in the invention.
- the nickel content in the alloy used in the invention is at most 0.4 wt .-%, preferably, the nickel content is at most 0.3 wt .-%.
- the addition of nickel increases the corrosion resistance of the alloy, without being in conflict with hygienic safety. Similar to lead, the values of nickel migration are far below the legally required limit when tested according to DIN EN 15664-1.
- an antimony content of at most 0.1% by weight with respect to the properties of the drinking water migration is not critical.
- the alloy may furthermore have an iron content of at most 0.3% by weight.
- the lead-free copper alloy may also contain fractions of the elements iron (Fe), zirconium (Zr) and / or boron (B) alone or in a combination of at least two of said elements as grain refiner. It is preferred that iron in a weight fraction of up to 0.3 wt .-%, zirconium in a weight fraction of up to 0.01 wt .-% and / or boron in a weight fraction of up to 0.01 wt. -% are contained in the lead-free copper alloy.
- the grain finers avoid hot cracking and affect the mechanical properties, such as e.g. Tensile strength, material hardness and the like positive.
- the copper content of the lead-free copper alloy is at least 90% by weight, preferably more than 91% by weight.
- the sulfides of the lead-free copper alloy are homogeneously distributed in the structure.
- the number of sulfide particles should be high and their average size should be low in order to ensure uniform mechanical properties, good corrosion resistance, improved machinability and high pressure tightness over the entire microstructure.
- copper sulfide is preferable. because the presence of copper sulphide allows to substitute the volume of lead with a much lower content of sulfur.
- the component according to the invention at least partially has a wall thickness in the range of 0.5 mm to 6.0 mm, since the thin wall thickness leads to suitable for the formation of copper sulfides cooling rates. Furthermore, it is preferred if the entire component according to the invention has a wall thickness within the ranges of 0.5 mm to 4.0 mm, since a wall thickness in this range results in a particularly increased formation of the desired sulfide particles. A wall thickness below 0.5 mm could not have sufficient mechanical strength of the component according to the invention due to the small cross section. From these points of view, it is preferred that the component according to the invention at least in sections has a wall thickness in the range of 1.0 mm to 4.0 mm.
- At a wall thickness of less than 6 mm in the transverse section of the component according to the invention at least a proportion of 1.6 area percent sulfide particles and / or a surface area factor ASP% is less than 1000.
- Such values result in sulfur sulfides being present as an incoherent, finely divided, disperse phase. As a result, deep trough and / or hole-shaped attacks, in particular corrosion attacks, are avoided on the components according to the invention.
- the term "Area Property Code ASP%" is the mathematical description for the measure of the shape and location of a bell curve, which is a plot of the averages of the area classes (abscissa) in combination with the percent distribution of the sulfide particles in those area classes (ordinates ) yields (cf. Fig. 1 ).
- the value of the surface content index ASP% is obtained by measuring the area of the respective particles, for example from an enlarged image of a micrograph, the percentage allocation of the particles detectable in the image in classes, the multiplication of the percentage values of the allocation with the mean of the class and the formation of a large average from the resulting averages of the classes, with the large mean being taken as the "area key figure ASP%".
- the alloy used in the invention has the excellent property of forming a topcoat very rapidly on the inner, water-wetted surface.
- the cover layer has a thickness of preferably at least 2 ⁇ m, more preferably of at least 3 microns, on. This covering layer increases the corrosion resistance and ensures the longevity of the components made of this material, since further corrosion is prevented. Migration from the material to the drinking water can only take place if corrosion processes take place in the material.
- the top layer thus acts as a protective layer and limits the further metal delivery to the drinking water to a minimum.
- the copper content in the described alloy is higher than in conventional gunmetal alloys, such. As CuSnZn5Pb2, only a reduced copper metal release takes place.
- the term "component for media-carrying gas or drinking water pipes” is to be understood in particular as those components which come into contact with a domestic installation pipe system with water, in particular with drinking water, wherein fitting and fittings of such domestic installation pipe systems are preferred according to the invention.
- a fitting is in particular from the EP 2 250 421 A1 to call known connector.
- Fig. 2 shows a Turner diagram for the test waters used in the thermal aging test.
- the carbonate hardness (as a measure of water hardness) is plotted against the chloride ion content of the test water.
- the line labeled "Turner Classic” represents the corrosion characteristic of dezincification developed by Turner (" The Influence of Water Composition on the Dezincification of Duplex Brass Fittings ", 1965 ). According to the usual interpretation of the world of corrosion, there is no dezincification in the area below this line. Above this line, however, there is a very high risk that a damage due to dezincification of the relevant component occurs.
- the points shown give an overview of the different test waters that were used in the described hot swapping test.
- test specimens For the production of test specimens, half cylinders with a wall thickness of 5 mm were cast from the alloys 1 and 2. Thereafter, the test specimens were on the outside by means of a turning to a roughness Rz of max. Machined 25 ⁇ m and on the inside by means of a drilling with a through hole of roughness Rz of max. 40 ⁇ m provided. This special surface treatment is intended to allow comparability of the specimens with real manufactured components.
- test specimens The surface of the specimens was cleaned with acetone. Subsequently, the test specimens were placed freely hanging in a test container. The test containers were then placed in a 90 ° C oven for five months with the test medium changed at seven-day intervals.
- test media were each 21 different test water with different pH values and carbonate hardness (the carbonate hardness (KH) is that proportion of calcium and magnesium ions for which an equivalent concentration of bicarbonate ions is present in the unit volume), in addition, different levels of chloride ions and / or sulfate ions.
- KH carbonate hardness
- Table 2 ⁇ u> Table 2: ⁇ / u> water number PH value Carbonate hardness in ° dH Chloride in mg / l Sulfate in mg / l 1 8th 0.5 10 - 2 8th 0.5 100 - 3 8th 0.5 250 - 4 8th 0.5 1000 - 5 8th 1.5 15 - 6 8th 1.5 60 - 7 8th 1.5 140 - 8th 8th 3.0 30 - 9 8th 3.0 100 - 10 8th 5.5 80 - 11 8th 5.5 120 - 12 8th 5.5 250 - 13 7 9.0 100 - 14 7 9.0 160 - 15 7 14.0 140 - 16 7 18.0 40 - 17 7 18.0 100 - 18 7 18.0 250 - 19 8th 0.5 250 250 20 8th 5.5 250 250 21 7 18.0 250 250 250
- test containers After completion of the five-month test period, the test containers are removed from the oven, cooled to room temperature, taken the test specimens from the respective test containers, dried, cut open and the cut surface is examined by appropriate optical microscopy.
- Alloys 1 and 2 showed over the entire area of the drinking water ordinance tested in hot aging an outstanding formation of a protective, adherent, closed covering layer required for copper alloys which has a thickness of at least 2 ⁇ m in the hot aging test and thus an improved covering layer with respect to a conventional lead-containing copper alloy based on a CuSnZn alloy (eg CuSn5Zn5Pb). Furthermore, this layer is virtually free of defects or defects and thus unfolds their full protection by avoiding a deeper, local corrosion attack (see Fig. 4 and Fig. 6 ).
- Fig. 4 shows the behavior of the cover layer formation of a lead-free copper alloys (alloy 1 and alloy 2) used according to the invention after a five-month hot aging test for the respective test waters. It turns out that it only comes to the formation of a protective topcoat. There is no visible selective corrosion attack.
- the thickness of the formed, adherent, protective cover layer is at least 4 microns.
- FIG. 5 is a photograph of the standard brass (CuZn40Pb2) microstructure as a result of an exemplary corrosive attack after the 5 month hot aging test, based on Turner, with a chloride content of 250 mg / l and a carbonate hardness of 5.5 ° dH.
- a non-uniform, partially disturbed structure of the cover layer and the selective corrosion attack in the form of a dezincification is clearly visible.
- FIG. 6 a photograph of the microstructure of a result of the five-month hot aging test, based on Turner, with a chloride content of 250 mg / l and a carbonate hardness of 5.5 ° dH, on an inventive component of the alloy 2 (Alloy 1 shows an analogous behavior ) was carried out.
- microstructure shows in the component according to the invention after an identical heat aging test no selective corrosion attack, but a uniform, homogeneous structure of a protective, adherent cover layer with a thickness of 4 microns to 23 microns.
- the alloy in the hot aging test carried out here is free from selective corrosion attacks (eg dezincification and stress corrosion cracking) and almost all other corrosion phenomena.
- Fig. 7 represents a thermal analysis in a temperature-time diagram, which can be used to detect thermal effects on metals (for example, release of latent heat), which can occur in solid-to-liquid or phase-to-solid phase transformations.
- Plotted is the cooling temperature of the alloy and the first time derivative of the measurement signal against the time, which is described as the cooling rate.
- a change in the peak in the cooling rate curve corresponds to a thermal effect in the material.
- sulfide formation should be aimed for shortly before the end of solidification at low temperature, since in this way the sulfides, like the lead, are distributed more homogeneously in the microstructure.
- the cooling rate in Fig. 7 corresponds to the typical solidification process of a copper-tin alloy to 5 wt .-% tin in sand casting.
- alloy 3 at about 400 s, an early thermal effect occurs during the course of solidification, which is due to sulfide formation.
- the sulfide formation takes place delayed, shortly before the end of the solidification.
- the fact that both samples have been cooled under identical conditions is underpinned by the further cooling rate profile of the samples, which is identical after phase formation.
- the varying time of phase formation is thus due to the different zinc content in the alloys.
- Early sulfide formation affects the sulfide form and distribution in the microstructure.
- the early formation of sulfide in alloy 3 leads to a heterogeneous, partial phase distribution, which adversely affects the mechanical characteristics such as elongation.
- the material composition is adjusted in a way that avoids premature sulfide formation and promotes homogeneous distribution.
- Des shimmer was recognized that the cooling conditions of the melt to a component according to the invention, have an influence on the sulfide formation.
- a high cooling rate which is preferred for a thin wall, results in a fine-meshed dendritic network with fine residual melt areas, from which a globular formation of the sulfides is supported.
- rapid cooling is preferred according to the invention.
- Fig. 10 and Fig. 11 shows micrographs of components according to the invention of an identical melt which has been cooled under varying conditions. In a rapid cooling, the micrograph in Fig. 11 a structure that leads to higher mechanical characteristics, such as tensile strength, elongation at break and the like.
- the particles were examined and characterized by means of image analysis on microstructures of the test specimens.
- the volume of sulfides and the surface area can be determined by means of this image analysis.
- the alloys used in accordance with the invention can be characterized by a surface area factor ASP% of less than 1000.
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Abstract
Die vorliegende Erfindung bezieht sich auf ein Bauteil für medienführende Gas- oder Wasserleitungen, insbesondere Fitting oder Armatur für Trinkwasserleitungen, wobei das Bauteil zumindest teilweise aus einer bleifreien Kupferlegierung besteht, die die folgenden Legierungskomponenten in Gew.-% aufweist: 3,5 Gew.-% ¤ Sn ¤ 4,8 Gew.-%; 1,5 Gew.-% ¤ Zn ¤ 3,5 Gew.-%; 0,25 Gew.-¤ S ¤ 0,65 Gew.-%; 0,015 Gew.-¤ P ¤ 0,1 Gew.-%; unvermeidbare Verunreinigungen sowie zum Rest Kupfer.The present invention relates to a component for media-carrying gas or water lines, in particular a fitting or fitting for drinking water lines, the component consisting at least partially of a lead-free copper alloy that has the following alloy components in % by weight: 3.5 wt% ¤ Sn ¤ 4.8 wt%; 1.5 wt% ¤ Zn ¤ 3.5 wt%; 0.25 wt. S 0.65 wt.%; 0.015 wt% P 0.1 wt%; unavoidable impurities as well the rest copper.
Description
Die vorliegende Erfindung betrifft ein Bauteil für medienführende Gas- oder Wasserleitungen, insbesondere Fitting oder Armatur für Trinkwasserleitungen, wobei das Bauteil zumindest teilweise aus einer bleifreien Kupferlegierung besteht.The present invention relates to a component for media-carrying gas or water pipes, in particular fitting or fitting for drinking water pipes, wherein the component consists at least partially of a lead-free copper alloy.
An metallische Werkstoffe für den Einsatz in Bauteilen für wasserführende, insbesondere trinkwasserführende Gewerke, wie beispielsweise Fittings, Armaturen, Rohre, Pressverbinder, Dach- oder Ablaufrinnen, sind besondere Anforderungen zu stellen. Insbesondere im Falle von mit Trinkwasser in Kontakt stehenden Bauteilen ist dabei die Korrosionsbeständigkeit zu nennen. Speziell stark kupferhaltige Buntmetall-Legierungen wie Bronze, Messing oder Rotguss enthalten auch einen gewissen Anteil an Blei, weil Blei die Bearbeitbarkeit derartiger Legierungen verbessert. In der Praxis ist in solchen Legierungen auch Nickel vorhanden, um die Festigkeit und Korrosionsbeständigkeit der Legierungen zu erhöhen. Aufgrund der Toxizität dieser Metalle müssen solche Werkstoffe allerdings eine geringe Migrationsneigung von Metallionen in das Medium aufweisen, d.h. eine geringe Abgabe von Ionen der Legierungskomponenten an das Medium. Hierzu sind von den Werkstoffen zum Schutz der Verbraucher sehr enge Grenzen einzuhalten, die durch die Trinkwasserordnung geregelt sind. Dazu ist aus der
Für den Einsatz in der Trinkwasserinstallation findet derzeit die Rotgusslegierung CuSn5Zn5Pb2 mit Gehalten von etwa 5 Gew.-% Zinn und etwa 5 Gew.-% Zink eine breite Anwendung. Diese Kupferlegierung besitzt eine hervorragende Korrosionsbeständigkeit und ist daher in allen Wasserqualitäten innerhalb der Trinkwasserversorgung einsetzbar. Legierungen dieser Art sind üblicherweise im Gefüge einphasig ausgebildet und bieten daher eine hohe plastische Verformbarkeit. Jedoch bereitet gerade diese plastische Verformbarkeit bei der spanabhebenden mechanischen Bearbeitung Probleme. Einphasige Kupferwerkstoffe neigen zu einer Langspanbildung. Diese Spanart hemmt den Arbeitsablauf beim vollautomatisierten Drehen, bzw. Bohren, und führt zu einem starken Verschleiß an den Werkzeugschneiden. Um die Produkte dennoch wirtschaftlich bearbeiten zu können, werden den Legierungen Blei als spanbrechender Zusatz hinzugegeben. Blei ermöglicht eine wirtschaftliche, vollautomatisierte mechanische Bearbeitung.For use in drinking water installations currently finds the gun metal alloy CuSn5Zn5Pb2 with contents of about 5 wt .-% tin and about 5 wt .-% zinc is widely used. This copper alloy has excellent corrosion resistance and can therefore be used in all water qualities within the drinking water supply. Alloys of this type are usually formed in the structure of a single phase and therefore offer a high plastic deformability. However, it is precisely this plastic deformability that causes problems in machining machining. Single-phase copper materials tend to form a long chip. This type of chip inhibits the work flow during fully automated turning or drilling, and leads to heavy wear on the tool cutting edges. In order to be able to process the products nevertheless economically, lead is added to the alloys as a chip-breaking additive. Lead enables economical, fully automated mechanical processing.
Blei ist in Kupfer praktisch unlöslich und besitzt einen niedrigen Schmelzpunkt. Infolgedessen handelt es sich um das zuletzt erstarrende Element in Kupfer-Zinn-Legierungen. Dieses Konstitutionsverhalten führt dazu, dass Blei am Ende der Erstarrung im Gefüge in Form von gleichmäßig verteilten, kleinen, tropfenförmigen Partikeln zwischen den Dendritenarmen vorliegt. Diese feinen, tropfenförmigen Partikel wirken als Spanbrecher, ohne dass die ursprünglichen Eigenschaften des Werkstoffs, beeinflusst werden. Dies ist besonders deutlich an der Korrosionsbeständigkeit erkenntlich, da die Bleipartikel als inkohärente Phasen vorliegen und somit nicht mit der umgebenden Matrix interagieren können. Auch wird durch die gleichmäßige Verteilung kleiner, tropfenförmiger Bleipartikel gewährleistet, dass über einen gleichmäßigen Querschnitt durchgehend ähnliche mechanische Kennwerte zu erwarten sind.Lead is practically insoluble in copper and has a low melting point. As a result, it is the last solidifying element in copper-tin alloys. This constitutional behavior leads to lead being present in the structure at the end of the solidification in the form of evenly distributed, small, drop-shaped particles between the dendrite arms. These fine, teardrop-shaped particles act as chipbreakers without affecting the original properties of the material. This is particularly evident in the corrosion resistance, since the lead particles are present as incoherent phases and thus can not interact with the surrounding matrix. Also, the uniform distribution of small, teardrop-shaped lead particles ensures that similar mechanical characteristics are consistently to be expected over a uniform cross section.
In der
Nickel ist in Kupferlegierungen in der Lage, sowohl die Korrosionsbeständigkeit zu erhöhen als auch die Verteilung von Sulfidphasen im Gefüge zu verbessern. Hohe Nickelgehalte führen aber zu einer hohen Metallionenabgabe ins Trinkwasser und sind daher als hygienisch bedenklich eingestuft. Der vorgegebene Legierungsbereich in der
Vor diesem Hintergrund liegt der vorliegenden Erfindung die Aufgabe zugrunde, eine bleifreie Kupferlegierung zur Herstellung von Bauteilen für medienführende Gas- oder Wasserleitungen anzugeben, die im Vergleich zu einer konventionellen Rotgusslegierung, wie z.B. CuSn5Zn5Pb2, eine korrosionsbeständige Matrix, gute Festigkeitseigenschaften bei gleichzeitig guten Bearbeitungseigenschaften, eine hohe Druckdichtigkeit und ein verbessertes Migrationsverhalten aufweist. Darüber hinaus soll die bleifreie Kupferlegierung ein gutes Gießverhalten, bspw. im Sand- oder Strangguss, besitzen.Against this background, the object of the present invention is to provide a lead-free copper alloy for the production of components for media-carrying gas or water lines, which in comparison with a conventional gunmetal alloy, such as, for example, CuSn5Zn5Pb2, a corrosion-resistant matrix, good strength properties with good machining properties, high pressure tightness and improved migration behavior. In addition, the lead-free copper alloy should have a good casting behavior, eg. In sand or continuous casting.
Diese und andere Aufgaben werden durch ein Bauteil für medienführende Gas- oder Wasserleitungen mit den Merkmalen des Anspruchs 1 gelöst. Bevorzugte Ausführungsformen des erfindungsgemäßen Bauteils sind in den abhängigen Ansprüchen beschrieben.These and other objects are achieved by a component for media-carrying gas or water pipes with the features of
Gemäß der vorliegenden Erfindung wurde überaschenderweise erkannt, dass eine bleifreie Kupferlegierung, die als Legierungskomponenten in Gew.-% neben Kupfer (Cu) und unvermeidbaren Verunreinigungen noch 3,5 Gew.-% ≤ Zinn (Sn) ≤ 4,8 Gew.-%, 1,5 Gew.-% ≤ Zink (Zn) ≤ 3,5 Gew.-%, 0,25 Gew.-% ≤ Schwefel (S) ≤ 0,65 Gew.-% und 0,015 Gew.-% ≤ Phosphor (P) ≤ 0,1 Gew.-% umfasst, bei Kontakt mit Wassern verschiedener Wasserqualitäten eine gegenüber Standardmessing (CuZn40Pb2) und entzinkungsbeständigem Messing (CuZn36Pb2As) verbesserte Deckschichtbildung zeigt, was u.a. durch geeignete Warmauslagerungsversuche belegt wurde. Aufgrund dieser verbesserten Deckschichtbildung, zeigt die bleifreie Kupferlegierung keinerlei Entzinkung oder ähnliche selektive Korrosionsangriffe. Daher verfügt die bleifreie Kupferlegierung über eine verbesserte Korrosionsbeständigkeit über den gesamten, durch die Trinkwasserverordnung (nachstehend als "TWVO" bezeichnet) vorgegebenen Rahmen. Dementsprechend stellt die vorliegende Erfindung bevorzugt ein Bauteil für medienführende Gas- oder Wasserleitungen dar, insbesondere ein Fitting oder eine Armatur für Trinkwasserleitungen, wobei das Bauteil zumindest teilweise aus der erfindungsgemäßen bleifreien Kupferlegierung besteht.Surprisingly, according to the present invention, it has been recognized that a lead-free copper alloy containing as alloy components in wt% besides copper (Cu) and unavoidable impurities still 3.5 wt% ≤ tin (Sn) ≤ 4.8 wt% , 1.5% by weight ≦ zinc (Zn) ≦ 3.5% by weight, 0.25% by weight ≦ sulfur (S) ≦ 0.65% by weight and 0.015% by weight ≦ phosphorus (P) ≤ 0.1 wt .-%, shows on contact with waters of different water qualities compared to standard brass (CuZn40Pb2) and dezincification resistant brass (CuZn36Pb2As) improved top layer formation, which has been proved, inter alia, by suitable hot aging experiments. Because of this improved overcoat, the lead-free copper alloy shows no dezincification or similar selective corrosion attack. Therefore, the lead-free copper alloy has improved corrosion resistance over the entire frame prescribed by the Drinking Water Ordinance (hereinafter referred to as "TWVO"). Accordingly, the present invention preferably represents a component for media-carrying gas or water pipes, in particular a fitting or a fitting for drinking water pipes, wherein the component consists at least partially of the lead-free copper alloy according to the invention.
Es wurde festgestellt, dass sich in der erfindungsgemäß verwendeten Legierung zwei schwefelhaltige Phasen, Kupfersulfid und Zinksulfid, im Gefüge temperaturabhängig und versetzt voneinander ausbilden. Um durch Sulfidpartikel optimale Zerspanungseigenschaften zu erreichen, sollten diese möglichst rund, feinverteilt und klein vorliegen. Dieses Verhalten ist bevorzugt bei der Bildung von Kupfersulfiden zu beobachten. Zinksulfide hingegen neigen zu einer geometrisch ungünstigen Form. Es wurde erkannt, dass der Zeitpunkt der Phasenausbildung, die Art, die Anzahl und die Verteilung der schwefelhaltigen Partikel entscheidend für die Zerspanbarkeit und für die mechanischen Eigenschaften, wie etwa der Dehnung, des Bauteils sind. Die ausgebildeten Sulfide, bevorzugt als Kupfersulfid, bieten ähnlich den Bleipartikeln den Vorteil, als inkohärente Phasen vorzuliegen.It has been found that in the alloy used according to the invention, two sulfur-containing phases, copper sulfide and zinc sulfide, form in the microstructure as a function of the temperature and offset from one another. In order to achieve optimum machining properties through sulfide particles, they should be as round, finely divided and small as possible. This behavior is preferable to observe in the formation of copper sulfides. Zinc sulfides, however, tend to have a geometrically unfavorable shape. It has been recognized that the timing of phase formation, the type, number and distribution of the sulfur-containing particles are critical to machinability and mechanical properties such as elongation of the component. The formed sulfides, preferably as copper sulfide, offer the advantage, similar to the lead particles, of being present as incoherent phases.
Der Zinngehalt nimmt Einfluss auf die Festigkeit, Korrosionsbeständigkeit und auf die Phasenverteilung und erreicht im beanspruchten Bereich von 3,5 Gew.-% bis ≤ 4,8 Gew.-% ein optimal ausgewogenes, wirtschaftliches Verhältnis der davor beschriebenen Eigenschaften. Mit einem Zinngehalt von über 4,8 Gew.-% steigt zwar die Festigkeit und Korrosionsbeständigkeit in der Matrix weiter an, bei üblichen Abkühlungsbedingungen im Sandguss wird die Verteilung der Sulfide aber gröber und die Größe nimmt zu. Bei Gehalten unter 3,5 Gew.-% Zinn liegt keine ausreichende Korrosionsinhibierung vor. Auch werden wegen der schwachen Mischkristallverfestigung die für die Praxis notwendigen Eigenschaften nicht erreicht. Bei Gehalten über 4,8% Gew.-% Zinn kann zwar eine hohe Zugfestigkeit erreicht werden, wohingegen die Dehnungswerte des Materials reduziert werden. Gehalte von weit über 4,8 Gew.-% Zinn führen zur Ausbildung eines Gefüges, welches sich versprödend und ungünstig auf die Bearbeitung auswirkt.The tin content has an influence on the strength, corrosion resistance and on the phase distribution and, in the claimed range from 3.5% by weight to ≦ 4.8% by weight, achieves an optimally balanced, economical ratio of the properties described above. With a tin content of more than 4.8% by weight, the strength and corrosion resistance in the matrix continue to increase, but under normal cooling conditions in sand casting, the distribution of the sulfides becomes coarser and the size increases. At levels below 3.5% by weight of tin, there is insufficient corrosion inhibition. Also, because of the weak solid solution hardening necessary for the practice properties are not achieved. Although a high tensile strength can be achieved at levels above 4.8% by weight of tin, the elongation values of the material are reduced. Contents of well over 4.8 wt .-% tin lead to the formation of a structure which embrittlement and unfavorable effect on the processing.
Es konnte festgestellt werden, dass bei gleichbleibenden Abkühlungsbedingungen mit steigendem Zinkgehalt der Anteil von Kupfersulfid abnimmt und der Anteil von Zinksulfid steigt. Mit einem Zinkgehalt von 1,5 Gew.-% bis 3,5 Gew.-%, besonders bevorzugt mit einem Zinkgehalt im Bereich von 1,8 Gew.-% bis 3,0 Gew.-%, kann gesichert werden, dass in Wänden von bis zu 6 mm eine homogene Verteilung kleinerer Sulfide begünstigt wird. Unter diesem Gesichtspunkt ist ein Zinkgehalt von 2,0 Gew-% bis 2,8 Gew-% besonders bevorzugt. Der Gehalt von max. 3,5 Gew.-% Zink sichert zusätzlich, dass partielle Korrosionserscheinungen vermieden und eine hohe Korrosionsbeständigkeit erreicht werden kann.It was found that with constant cooling conditions with increasing zinc content, the proportion of copper sulfide decreases and the proportion of zinc sulfide increases. With a zinc content of 1.5% by weight to 3.5% by weight, particularly preferably with a zinc content in the range of 1.8% by weight to 3.0% by weight, it can be ensured that Walls of up to 6 mm a homogeneous distribution of smaller sulfides is favored. From this point of view, a zinc content of 2.0% by weight to 2.8% by weight is particularly preferred. The content of max. 3.5% by weight of zinc additionally ensures that partial corrosion phenomena can be avoided and high corrosion resistance can be achieved.
Der Schwefelgehalt von 0,25 Gew.-% bis 0,65 Gew.-% bestimmt den Volumenanteil der Sulfide mit. Ab 0,25 Gew.-% Schwefel wird eine Menge an Sulfidpartikeln erzeugt, welche eine ausreichende Zerspanbarkeit der Legierung gewährleistet. Ein Schwefelgehalt über 0,65 Gew.-% Schwefel kann zur Ausbildung von unerwünschten, groben Sulfidpartikeln führen. Darüber hinaus kann sich durch den hohen Sulfidpartikelanteil der lastübertragene Querschnitt, d.h. der Querschnitt des Bauteiles, welcher Spannungen von außen aufnimmt, so stark reduzieren, dass es zu einer Verschlechterung der mechanischen Kennwerte, wie z.B. Bruchdehnung und dergleichen, kommt. Weiter verbesserte Eigenschaften wurden mit einer Legierung erzielt, deren Schwefelanteil im Bereich von 0,3 Gew.-% bis 0,6 Gew.-%, insbesondere im Bereich von 0,35 Gew.-% bis 0,55 Gew.-% liegt. Aufgrund der erfindungsgemäß verwendeten Legierungszusammensetzung liegen die Metallsulfide bei einem derartigen Schwefelgehalt in der bleifreien Kupferlegierung als inkohärente, fein verteilte, disperse Phase in Form von fein verteilten Partikeln vor. Dies bietet den Vorteil, dass eine eventuell auftretende Korrosion nur in einem geringem Umfang lokal an diesen Partikeln und nicht entlang zusammenhängender, größerer, einzelner Phasen des Legierungsgefüges stattfindet, wie dies beispielsweise bei Standardmessing der Fall ist. Bedingt durch die geringe Größe der Partikel findet kein signifikanter Korrosionsangriff statt.The sulfur content of 0.25 wt .-% to 0.65 wt .-% determines the volume fraction of the sulfides with. From 0.25 wt .-% sulfur, an amount of sulfide particles is produced, which ensures sufficient machinability of the alloy. Sulfur content above 0.65 wt% sulfur can lead to the formation of undesirable coarse sulfide particles. In addition, due to the high content of sulfide particles, the load transmitted cross section, i. the cross-section of the component which receives voltages from the outside, reduce so much that it leads to a deterioration of the mechanical characteristics, such. Elongation at break and the like comes. Further improved properties have been achieved with an alloy whose sulfur content is in the range of 0.3% to 0.6% by weight, in particular in the range of 0.35% to 0.55% by weight , Due to the alloy composition used according to the invention, the metal sulfides are present in such a sulfur content in the lead-free copper alloy as an incoherent, finely divided, disperse phase in the form of finely divided particles. This offers the advantage that any corrosion occurring only to a small extent locally on these particles and not along contiguous, larger, individual phases of the alloy structure takes place, as is the case for example with standard brass. Due to the small size of the particles no significant corrosive attack takes place.
Der Anteil an Phosphor (P) in der bleifreien Kupferlegierung beträgt erfindungsgemäß 0,015 Gew.-% bis 0,1 Gew.-%. Unterhalb von 0,015 Gew.-% Phosphor erfolgt keine ausreichende Desoxidation der Schmelze, was sich auf die Phasenbildung der Legierung negativ auswirkt. Hingegen neigt die bleifreie Kupferlegierung bei einem Phosphoranteil von mehr als 0,1 Gew.-% zu ungünstigen Auswirkungen auf die mechanischen Eigenschaften, wie z.B reduzierter Bruchdehnung. Unter diesen Gesichtspunkten liegt der Gewichtsanteil an Phosphor in der bleifreien Kupferlegierung vorzugsweise im Bereich von 0,02 Gew.-% bis 0,08 Gew.-%, besonders bevorzugt im Bereich von 0,04 Gew.-% bis 0,06 Gew.-%.The proportion of phosphorus (P) in the lead-free copper alloy according to the invention is 0.015 wt .-% to 0.1 wt .-%. Below 0.015% by weight of phosphorus, there is no sufficient deoxidation of the melt, which has a negative effect on the phase formation of the alloy. On the other hand, if the phosphorus content exceeds 0.1 wt%, the lead-free copper alloy tends to have adverse effects on the mechanical properties such as reduced elongation at break. From these viewpoints, the weight proportion of phosphorus in the lead-free copper alloy is preferably in the range of 0.02 wt% to 0.08 wt%, more preferably in the range of 0.04 wt% to 0.06 wt%. -%.
Wie hierin verwendet, bedeutet der Begriff "bleifreie Kupferlegierung" eine Kupferlegierung, die insbesondere Blei als unvermeidbare Verunreinigung in einer Menge von nicht mehr als 0,25 Gew.-% bevorzugt aber 0,09 Gew.-%, besonders bevorzugt nicht mehr als 0,05 Gew.-% umfasst. In der Legierung liegt der Bleianteil bei maximal 0,25 Gew.-%, vorzugsweise bei maximal 0,09 Gew.-% und besonders bevorzugt bei maximal kleiner gleich 0,05 Gew.-%. Bei einer Prüfung der Bleimigration nach Norm DIN EN 15664-1 zeigt die Legierung keine Anzeichen einer erhöhten Bleiabgabe in den ersten Wochen. Stattdessen lässt sich ab der achten Prüfwoche keine nennenswerte Bleimigration mehr ins Trinkwasser ermitteln oder liegt im Bereich der Messgenauigkeit des Verfahrens. Der niedrige Bleigehalt in der erfindungsgemäß verwendeten Legierung, führt somit zu einer deutlichen Reduzierung der Metallionenmigration im Trinkwasser, wobei der niedrige Bleigehalt keine negativen Auswirkungen auf den Spanbruch und somit auf die Zerspanbarkeit der erfindungsgemäß verwendeten Legierung besitzt.As used herein, the term "lead-free copper alloy" means a copper alloy containing, in particular, lead as an unavoidable impurity in an amount of not more than 0.25 wt%, but preferably 0.09 wt%, more preferably not more than 0 , 05 wt .-% includes. In the alloy, the lead content is at most 0.25 wt .-%, preferably at most 0.09 wt .-% and particularly preferably at most less than or equal to 0.05 wt .-%. In a test of lead migration according to standard DIN EN 15664-1, the alloy shows no signs of increased lead delivery in the first few weeks. Instead, it is possible From the eighth week of testing, no significant lead migration is detected in the drinking water or lies within the range of the measuring accuracy of the method. The low lead content in the alloy used in the invention thus leads to a significant reduction of metal ion migration in drinking water, the low lead content has no negative effects on the chip breaking and thus on the machinability of the alloy used in the invention.
Der Nickelanteil in der erfindungsgemäß verwendeten Legierung beträgt maximal 0,4 Gew.-%, bevorzugt beträgt der Nickelanteil maximal 0,3 Gew.-%. Der Nickelzusatz erhöht die Korrosionsbeständigkeit der Legierung, ohne im Widerspruch zur hygienischen Unbedenklichkeit zu stehen. Ähnlich wie beim Blei, befinden sich die Werte der Nickelmigration bei einer Prüfung nach Norm DIN EN 15664-1 weit unter den gesetzlich geforderten Grenzwert.The nickel content in the alloy used in the invention is at most 0.4 wt .-%, preferably, the nickel content is at most 0.3 wt .-%. The addition of nickel increases the corrosion resistance of the alloy, without being in conflict with hygienic safety. Similar to lead, the values of nickel migration are far below the legally required limit when tested according to DIN EN 15664-1.
Des Weiteren konnte festgestellt werden, dass ein Antimongehalt von maximal 0,1 Gew.-% bzgl. der Eigenschaften der Trinkwassermigration unkritisch ist. Die Legierung kann weiterhin einen Eisengehalt von maximal 0,3 Gew.-% aufwiesen.Furthermore, it was found that an antimony content of at most 0.1% by weight with respect to the properties of the drinking water migration is not critical. The alloy may furthermore have an iron content of at most 0.3% by weight.
In bevorzugten Ausführungsformen kann die bleifreie Kupferlegierung auch Anteile der Elemente Eisen (Fe), Zirconium (Zr) und/oder Bor (B) allein oder in einer Kombination von mindestens zwei der genannten Elemente als Kornfeiner enthalten. Dabei ist es bevorzugt, dass Eisen in einem Gewichtsanteil von bis zu 0,3 Gew.-%, Zirconium in einem Gewichtsanteil von bis zu 0,01 Gew.-% und/oder Bor in einem Gewichtsanteil von bis zu 0,01 Gew.-% in der bleifreien Kupferlegierung enthalten sind. Die Kornfeiner vermeiden Warmrissigkeit und beeinflussen die mechanischen Eigenschaften, wie z.B. Zugfestigkeit, Materialhärte und dergleichen positiv.In preferred embodiments, the lead-free copper alloy may also contain fractions of the elements iron (Fe), zirconium (Zr) and / or boron (B) alone or in a combination of at least two of said elements as grain refiner. It is preferred that iron in a weight fraction of up to 0.3 wt .-%, zirconium in a weight fraction of up to 0.01 wt .-% and / or boron in a weight fraction of up to 0.01 wt. -% are contained in the lead-free copper alloy. The grain finers avoid hot cracking and affect the mechanical properties, such as e.g. Tensile strength, material hardness and the like positive.
Vorzugsweise beträgt der Kupfergehalt der bleifreien Kupferlegierung mindestens 90 Gew.-%, vorzugsweise mehr als 91 Gew.-%.Preferably, the copper content of the lead-free copper alloy is at least 90% by weight, preferably more than 91% by weight.
Erfindungsgemäß ist es bevorzugt, wenn die Sulfide der bleifreien Kupferlegierung homogen im Gefüge verteilt vorliegen sind. Die Anzahl der Sulfidpartikel sollte hoch und deren mittlere Größe gering sein, um über das gesamte Gefüge gleichmäßige mechanische Kennwerte, eine gute Korrosionsbeständigkeit, eine verbesserte Spanbarkeit und eine hohe Druckdichtigkeit zu gewährleisten. Als Material der Sulfidpartikel ist Kupfersulfid bevorzugt, da das Auftreten von Kupfersulfid ermöglicht, mit einem deutlich geringeren Gehalt an Schwefel das Volumen von Blei zu substituieren.According to the invention it is preferred if the sulfides of the lead-free copper alloy are homogeneously distributed in the structure. The number of sulfide particles should be high and their average size should be low in order to ensure uniform mechanical properties, good corrosion resistance, improved machinability and high pressure tightness over the entire microstructure. As the material of the sulfide particles, copper sulfide is preferable. because the presence of copper sulphide allows to substitute the volume of lead with a much lower content of sulfur.
Darüber hinaus hat es sich als sehr vorteilhaft erwiesen, wenn das erfindungsgemäße Bauteil zumindest abschnittsweise eine Wandstärke im Bereich von 0,5 mm bis 6,0 mm aufweist, da die dünne Wandstärke zu für die Ausbildung der Kupfersulfide geeigneten Abkühlungsraten führt. Weiterhin ist es bevorzugt, wenn das gesamte erfindungsgemäße Bauteil eine Wandstärke innerhalb der genannten Bereiche von 0,5 mm bis 4,0 mm besitzt, da es bei einer Wandstärke in diesem Bereich zu einer besonders erhöhten Ausbildung der gewünschten Sulfidpartikel kommt. Eine Wandstärke unterhalb von 0,5 mm könnte aufgrund des geringen Querschnitts keine ausreichende mechanische Festigkeit des erfindungsgemäßen Bauteils aufweisen. Unter diesen Gesichtspunkten ist es bevorzugt, dass das erfindungsgemäße Bauteil zumindest abschnittsweise eine Wandstärke im Bereich von 1,0 mm bis 4,0 mm aufweist.In addition, it has proven to be very advantageous if the component according to the invention at least partially has a wall thickness in the range of 0.5 mm to 6.0 mm, since the thin wall thickness leads to suitable for the formation of copper sulfides cooling rates. Furthermore, it is preferred if the entire component according to the invention has a wall thickness within the ranges of 0.5 mm to 4.0 mm, since a wall thickness in this range results in a particularly increased formation of the desired sulfide particles. A wall thickness below 0.5 mm could not have sufficient mechanical strength of the component according to the invention due to the small cross section. From these points of view, it is preferred that the component according to the invention at least in sections has a wall thickness in the range of 1.0 mm to 4.0 mm.
Es kann auch von Vorteil sein, wenn bei einer Wandstärke unter 6 mm im Querschliff des erfindungsgemäßen Bauteiles mindestens ein Anteil von 1,6 Flächenprozent Sulfidpartikeln und/oder eine Flächeninhaltskennzahl ASP % kleiner als 1000 vorliegt. Derartige Werte führen dazu, dass Schwefelsulfide als inkohärente, fein verteilte, disperse Phase vorliegen. Dadurch werden tiefe mulden- und/oder lochförmige Angriffe, insbesondere Korrosionsangriffe, auf die erfindungsgemäßen Bauteile vermieden. Wie hierin verwendet ist der Begriff "Flächeninhaltskennzahl ASP %" die mathematische Beschreibung für das Maß der Form und der Lage einer Glockenkurve, welche sich aus einer Auftragung der Mittelwerte der Flächenklassen (Abszisse) in Kombination mit der prozentualen Verteilung der Sulfidpartikel in diesen Flächenklassen (Ordinate) ergibt (vgl.
Die erfindungsgemäß verwendete Legierung weist die hervorragende Eigenschaft auf, sehr schnell auf der inneren, trinkwasserbenetzten Oberfläche eine Deckschicht zu bilden. Die Deckschicht weist eine Dicke von vorzugsweise mindestens 2 µm, besonders bevorzugt von mindestens 3 µm, auf. Diese Deckschicht erhöht die Korrosionsbeständigkeit und sichert die Langlebigkeit der Bauteile aus diesem Werkstoff, da eine weitere Korrosion verhindert wird. Eine Migration aus dem Werkstoff an das Trinkwasser kann nur stattfinden, wenn Korrosionsvorgänge im Werkstoff ablaufen. Hier fungiert die Deckschicht also als Schutzschicht und begrenzt die weitere Metallabgabe an das Trinkwasser auf ein Minimum. Obwohl der Kupfergehalt in der beschriebenen Legierung höher liegt als in konventionellen Rotgusslegierungen, wie z. B. CuSnZn5Pb2, findet nur eine reduzierte Kupfermetallabgabe statt. Die guten Ergebnisse der Prüfung nach DIN EN 15664-1 beweisen, dass ohne weitgehende Einschränkungen in der Bearbeitbarkeit die Zusammensetzung der erfindungsgemäß verwendeten Legierung über den gesamten beanspruchten Bereich die Qualität des Trinkwassers nicht beeinträchtigt. Dabei weist die erfindungsgemäß verwendete Legierung im Vergleich zu konventionellen Rotguss-Legierungen, wie z.B. CuSnZn5Pb2, gleichzeitig ein verbessertes Migrationsverhalten in Kombination mit einer ausgezeichneten Korrosionsbeständigkeit auf.The alloy used in the invention has the excellent property of forming a topcoat very rapidly on the inner, water-wetted surface. The cover layer has a thickness of preferably at least 2 μm, more preferably of at least 3 microns, on. This covering layer increases the corrosion resistance and ensures the longevity of the components made of this material, since further corrosion is prevented. Migration from the material to the drinking water can only take place if corrosion processes take place in the material. Here, the top layer thus acts as a protective layer and limits the further metal delivery to the drinking water to a minimum. Although the copper content in the described alloy is higher than in conventional gunmetal alloys, such. As CuSnZn5Pb2, only a reduced copper metal release takes place. The good results of the test according to DIN EN 15664-1 prove that the composition of the alloy used according to the invention does not affect the quality of the drinking water over the entire claimed range without extensive restrictions in the workability. At the same time, compared to conventional gunmetal alloys, such as, for example, CuSnZn5Pb2, the alloy used according to the invention simultaneously has improved migration behavior in combination with excellent corrosion resistance.
In Gussversuchen konnte belegt werden, das die erfindungsgemäßen Bauteile für medienführende Gas- oder Wasserleitungen mit den herkömmlichen Gussverfahren, wie Sand-, Kokillen-, oder Stranggussverfahren herstellbar sind. Das durch derartige Gussverfahren hergestellte Gussteil lässt sich gut spanhebend bearbeiten.In casting experiments could be proven that the components of the invention for media-leading gas or water pipes with conventional casting methods, such as sand, mold or continuous casting can be produced. The casting produced by such casting method can be machined well spanhebend.
Hierin verwendet sind unter dem Begriff "Bauteil für medienführende Gas- oder Trinkwasserleitungen" insbesondere solche Bauteile zu verstehen, die einem Hausinstallationsrohrsystem mit Wasser, insbesondere mit Trinkwasser in Verbindung kommen, wobei Fitting und Armaturen derartiger Hausinstallationsrohrsysteme erfindungsgemäß bevorzugt sind. Als Beispiel für ein derartiges Fitting ist insbesondere das aus der
Nachstehend soll die vorliegende Erfindung unter Bezugnahme auf Ausführungsbeispiele und damit durchgeführte Tests sowie beigefügte Zeichnungen näher erläutert werden. Es versteht sich, dass diese Beispiele nicht als die Erfindung in irgendeiner Weise einschränkend zu betrachten sind. Sofern nichts Anderes angegeben ist, sind in der vorliegenden Anmeldung einschließlich der Ansprüche sämtliche Prozentangaben und Anteilsangaben auf das Gewicht bezogen.In the following, the present invention will be explained in more detail with reference to exemplary embodiments and tests carried out therewith as well as attached drawings. It should be understood that these examples are not to be construed as limiting the invention in any way. Unless otherwise specified, all percentages and percentages in the present application including the claims are based on the weight.
In den Zeichnungen zeigen
- Fig. 1
- exemplarische Auftragungen der Flächen der Partikel gegen die prozentuale Verteilung der Partikel in verschiedenen Größenklassen, welche als Basis zur Ermittlung der ASP% dienen ("Glockenkurve");
- Fig. 2
- eine Übersicht der Prüfwässer im Diagramm nach Turner;
- Fig. 3
- ein Diagramm, aus dem die Angriffstiefen der Entzinkung beim Standardmessing im durchgeführten Warmauslagerungstest nach 5 Monaten Auslagerungsdauer hervorgehen;
- Fig. 4
- ein Übersichtsdiagramm, dass die Bildung der Deckschicht bei der erfindungsgemäß verwendeten bleifreien Kupferlegierung im durchgeführten Warmauslagerungstest nach 5 Monaten Auslagerungsdauer zeigt;
- Fig. 5
- eine fotografische Aufnahme, die ein Beispiel eines Korrosionsangriffs von Standardmessing im Warmauslagerungstest (angelehnt an Turner mit
einem Chloridgehalt von 250 mg/l und einerKarbonathärte von - Fig. 6
- eine fotografische Aufnahme der erfindungsgemäß verwendeten Legierung 2, die ein Beispiel einer durchgängigen Deckschicht im Warmauslagerungstest (angelehnt an Turner mit
einem Chloridgehalt von 250 mg/l und einerKarbonathärte von - Fig. 7
- ein Diagramm der thermischen Analyse zweier Schmelzen mit unterschiedlichen Zinkgehalten, die unter gleichen Bedingungen vergossen wurden;
- Fig. 8
- ein Gefügeschliffbild eines Bauteiles aus einer Schmelze, die mit einem Zinkgehalt von ca. 3,9 Gew.-% vergossen wurde;
- Fig. 9
- ein Gefügeschliffbild eines erfindungsgemäßen Bauteiles aus einer Schmelze, die mit einem Zinkgehalt von ca. 2,4 Gew.-% vergossen wurde;
- Fig. 10
- ein Gefügeschliffbild eines erfindungsgemäßen Bauteiles aus einer Schmelze, die langsam abgekühlt wurde; und
- Fig. 11
- ein Gefügeschliffbild eines erfindungsgemäßen Bauteiles aus einer Schmelze, die schnell abgekühlt wurde.
- Fig. 1
- exemplary plots of the areas of the particles versus the percentage distribution of the particles in different size classes, which serve as the basis for determining the ASP% ("bell curve");
- Fig. 2
- an overview of the test waters in the diagram according to Turner;
- Fig. 3
- a diagram from which the depths of attack of the dezincification in the standard brass in the carried out Ausausungsstest after 5 months aging out;
- Fig. 4
- an overview diagram shows that the formation of the cover layer in the lead-free copper alloy used in the invention carried out in the hot aging test after 5 months aging time;
- Fig. 5
- a photograph showing an example of a corrosion attack of standard brass in the hot aging test (based on Turner with a chloride content of 250 mg / l and a carbonate hardness of 5.5 ° dH);
- Fig. 6
- a photograph of the alloy used in the
invention 2, showing an example of a continuous cover layer in the thermal aging test (based on Turner with a chloride content of 250 mg / l and a carbonate hardness of 5.5 ° dH) shows; - Fig. 7
- a diagram of the thermal analysis of two melts with different zinc contents, which were cast under the same conditions;
- Fig. 8
- a Gefügeschliffbild a component of a melt that has been cast with a zinc content of about 3.9 wt .-%;
- Fig. 9
- a Gefügeschliffbild a component according to the invention from a melt which has been cast with a zinc content of about 2.4 wt .-%;
- Fig. 10
- a Gefügeschliffbild a component according to the invention from a melt which has been cooled slowly; and
- Fig. 11
- a Gefügeschliffbild a component of the invention from a melt that has been cooled rapidly.
Zur Beurteilung der Korrosionsbeständigkeit von Kupferlegierungen wurde ein Warmauslagerungstest entwickelt, der das Langzeitkorrosionsverhalten von Legierungen in einem fünfmonatigen Versuchszeitraum simuliert. Aufbau und Durchführung des Tests lehnen sich an die seit Jahrzehnten etablierten Korrosionstest und das darauf basierende Diagramm von
Für die durchgeführten Warmauslagerungstests wurden unter anderem die folgenden bleifreien Kupferlegierungen eingesetzt, wobei die Anteile der Komponenten in nachstehender Tabelle 1 in Gew.-% angegeben sind:
Zur Herstellung von Prüfkörpern wurden, aus den Legierungen 1 und 2 Halbzylinder mit einer Wandstärke von 5 mm gegossen. Danach wurden die Prüfkörper an der Außenseite mittels einer Drehbearbeitung auf eine Rauigkeit Rz von max. 25µm bearbeitet und an der Innenseite mittels einer Bohrbearbeitung mit einer Durchgangsbohrung der Rauigkeit Rz von max. 40 µm versehen. Diese spezielle Oberflächenbehandlung soll eine Vergleichbarkeit der Probekörper mit real gefertigten Bauteilen ermöglichen.For the production of test specimens, half cylinders with a wall thickness of 5 mm were cast from the
Die Oberfläche der Prüfkörper wurde mit Aceton gereinigt. Anschließend wurden die Prüfkörper frei hängend in ein Prüfbehältnis eingebracht. Die Prüfbehältnisse wurden dann für fünf Monate in einen Wärmeschrank bei 90°C eingestellt, wobei das Prüfmedium jeweils in Intervallen von sieben Tagen gewechselt wurde.The surface of the specimens was cleaned with acetone. Subsequently, the test specimens were placed freely hanging in a test container. The test containers were then placed in a 90 ° C oven for five months with the test medium changed at seven-day intervals.
Als Prüfmedien wurden jeweils 21 verschiedene Prüfwasser mit unterschiedlichen pH-Werten und Karbonathärten (Die Karbonathärte (KH) ist jener Anteil an Calcium- und Magnesiumionen, für den in der Volumeneinheit eine äquivalente Konzentration an Hydrogencarbonationen vorliegt) eingestellt, darüber hinaus wurden verschiedene Gehalte an Chloridionen und/oder Sulfationen eingestellt. Die Gehalte können aus Tabelle 2 entnommen werden:
Nach Abschluss des fünfmonatigen Testzeitraums werden die Prüfbehältnisse aus dem Wärmeschrank entnommen, auf Raumtemperatur abgekühlt, die Prüfkörper aus den jeweiligen Prüfbehältnissen entnommen, getrocknet, aufgeschnitten und die Schnittfläche wird jeweils nach entsprechender Aufarbeitung lichtmikroskopisch untersucht.After completion of the five-month test period, the test containers are removed from the oven, cooled to room temperature, taken the test specimens from the respective test containers, dried, cut open and the cut surface is examined by appropriate optical microscopy.
Die Legierungen 1 und 2 zeigten über den gesamten in der Warmauslagerung geprüften Bereich der Trinkwasserverordnung eine herausragende Bildung einer für Kupferlegierungen notwendigen schützenden festhaftenden, geschlossenen Deckschicht, welche im Warmauslagerungstest eine Dicke von mindestens 2 µm besitzt und damit eine verbesserte Deckschicht im Bezug auf eine herkömmliche, bleihaltige Kupferlegierung auf Basis einer CuSnZn-Legierung (z.B. CuSn5Zn5Pb) aufweist. Des Weiteren ist diese Schicht nahezu frei von Störungen bzw. Defekten und entfaltet damit ihren vollständigen Schutz durch die Vermeidung eines tiefergehenden, lokalen Korrosionsangriffes (siehe
Im Diagramm gemäß
In
Im Vergleich dazu zeigt
Im Vergleich zum Standardmessing zeigt sich die Legierung in dem hier durchgeführten Warmauslagerungstest in Anlehnung an Turner frei von selektiven Korrosionsangriffen (z.B. Entzinkung und Spannungsrisskorrosion) und nahezu allen anderen Korrosionserscheinungen.In comparison to the standard brass, the alloy in the hot aging test carried out here, based on Turner, is free from selective corrosion attacks (eg dezincification and stress corrosion cracking) and almost all other corrosion phenomena.
Die Versuche zeigen darüber hinaus, dass Schwefelsulfide als inkohärente, fein verteilte, disperse Phasen einen deutlichen korrosiven Vorteil zeigen. Dies resultiert aus der Vermeidung von tiefen mulden- und/oder lochförmigen Angriffen, welche durch ein mögliches Absinken des pH-Wertes und einer Aufkonzentration der kritischen Inhaltsstoffe des Mediums zu einer deutlich beschleunigten Korrosion führen könnten. Darüber hinaus werden keine korrosionstechnisch ungünstigen unedleren, flächenmäßig sehr großen Phasen gebildet, welche wie oben bereits beschrieben durch Korrosion angegriffen werden könnten und dann zu einem schnellen Ausfall des Bauteiles führen (vgl. β-Phase im Standardmessing).The experiments also show that sulfur sulfides as incoherent, finely divided, disperse phases show a significant corrosive advantage. This results from the avoidance of deep trough and / or hole-shaped attacks, which could lead to a significantly accelerated corrosion by a possible decrease in the pH and a concentration of the critical ingredients of the medium. In addition, no unfavorable corrosion-unfavorable, surface-moderately large phases are formed, which could be attacked as already described above by corrosion and then lead to a rapid failure of the component (see β-phase in standard brass).
Es konnte aus Versuchen ermittelt werden, dass die Legierungszusammensetzung die Verteilung, die Form und den Zeitpunkt der Phasenausbildung entscheidend mitbeeinflusst und ungünstige Gehalte sich negativ auf die Phasen- und Gefügeausbildung auswirken.It could be determined from experiments that the alloy composition decisively influences the distribution, the form and the time of phase formation and that unfavorable contents have a negative effect on the phase and microstructure formation.
Zuerst wurden thermische Versuche durchgeführt, die anschließend mittels Bildanalyse verifiziert worden sind.First, thermal tests were performed, which were subsequently verified by image analysis.
Die Abkühlungsrate in
In
Desweiten wurde erkannt, dass die Abkühlungsbedingungen der Schmelze zu einem erfindungsgemäßen Bauteil, einen Einfluss auf die Sulfidausbildung besitzen. Durch eine hohe Abkühlrate wie sie bei einer dünnen Wand bevorzugt vorliegt entsteht ein feinmaschiges Dendritennetzwerk mit feinen Restschmelzegebieten, aus denen eine globulare Ausbildung der Sulfide unterstützt wird. Insofern ist ein schnelles Abkühlen erfindungsgemäß bevorzugt.
Zur Bestätigung dieser Charakteristik wurden die Partikel mittels Bildanalyse an Gefügeschliffen der Probekörper untersucht und charakterisiert.To confirm this characteristic, the particles were examined and characterized by means of image analysis on microstructures of the test specimens.
Dabei hat sich gezeigt, dass sich bei der Herstellung erfindungsgemäßer Bauteile unter den genannten Abkühlungsbedingungen einer Schmelze, einer erfindungsgemäß zusammengesetzten Legierung, erreicht werden kann, dass zumindest abschnittsweise in einem Gefügeschliff des Gussteiles mindestens 1,8 Flächenprozent der Gesamtfläche als Sulfidpartikel ausgebildet vorliegt.It has been shown that in the production of components according to the invention under the mentioned cooling conditions of a melt, a composite according to the invention Alloy, can be achieved that at least in sections present in a Gefügeschliff the casting at least 1.8 area percent of the total area formed as sulfide particles.
Unter anderem kann das Volumen der Sulfide und die Flächeninhalte mittels dieser Bildanalyse ermittelt werden.Among other things, the volume of sulfides and the surface area can be determined by means of this image analysis.
Zur näheren Bestimmung der Sulfidpartikel werden verschiedene Größenklassen eingeführt (vgl. Tabelle 4). Anschließend werden die Partikel vermessen und den Klassen prozentual zugerechnet. Nun werden die prozentualen Zurechnungen mit dem Mittelwert der Klasse multipliziert. Die sich ergebenden Mittelwerte der Klassen werden zu einem großen Mittelwert zusammengefasst. Der sich ergebende Wert stellt die Flächeninhaltskennzahl Sulfidpartikel ASP% dar.For the further determination of the sulfide particles different size classes are introduced (see Table 4). Subsequently, the particles are measured and assigned to the classes as a percentage. Now the percentages are multiplied by the mean of the class. The resulting mean values of the classes are summarized to a large mean. The resulting value represents the area key figure sulfide particle ASP%.
Die erfindungsgemäß verwendeten Legierungen lassen sich mit einer Flächeninhaltskennzahl ASP% kleiner als 1000 charakterisieren.
Voranstehend wurde die vorliegende Erfindung unter Bezugnahme auf Beispiele und Vergleichsbeispiele beschrieben. Für den Fachmann ist es jedoch ersichtlich, dass die Erfindung nicht auf diese Beispiele eingeschränkt ist, sondern sich der Umfang der vorliegenden Erfindung aus den beiliegenden Ansprüchen ergibt.Hitherto, the present invention has been described with reference to Examples and Comparative Examples. However, it will be apparent to those skilled in the art that the invention is not limited to these examples, but the scope of the present invention from the appended claims.
Claims (14)
zum Rest Kupfer.Component for media-carrying gas or water pipes, in particular fitting or fitting for drinking water pipes, wherein the component consists at least partially of a lead-free copper alloy, which has the following alloy components in wt .-%:
to the rest of copper.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL17151949T PL3225707T3 (en) | 2016-03-29 | 2017-01-18 | Component for media-conducting gas or water lines comprising a copper alloy |
| RU2018137812A RU2712161C1 (en) | 2016-03-29 | 2017-03-28 | Constructive element for heat-conducting gas- or water pipes |
| PCT/EP2017/000374 WO2017167441A2 (en) | 2016-03-29 | 2017-03-28 | Component for media-conducting gas or water lines |
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| Application Number | Priority Date | Filing Date | Title |
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| DE202016101661.4U DE202016101661U1 (en) | 2016-03-29 | 2016-03-29 | Component for media-carrying gas or water pipes |
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| EP3225707A1 true EP3225707A1 (en) | 2017-10-04 |
| EP3225707B1 EP3225707B1 (en) | 2020-12-30 |
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| EP (1) | EP3225707B1 (en) |
| DE (1) | DE202016101661U1 (en) |
| DK (1) | DK3225707T3 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102018004702A1 (en) * | 2018-06-12 | 2019-12-12 | Gebr. Kemper Gmbh + Co. Kg Metallwerke | Moldings made of a corrosion-resistant and machinable copper alloy |
| US20220016693A1 (en) * | 2019-03-11 | 2022-01-20 | Rehau Ag + Co. | Method for producing metal components and metal component produced in this way |
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| AT520560B1 (en) * | 2018-01-29 | 2019-05-15 | Miba Gleitlager Austria Gmbh | Multilayer plain bearing element |
| DE102019106131A1 (en) * | 2019-03-11 | 2020-09-17 | M.G. Meccanica Srl | Process for the production of components for media-carrying gas or water pipes and the component produced thereby |
| AT522440B1 (en) | 2019-05-07 | 2020-11-15 | Miba Gleitlager Austria Gmbh | Multi-layer plain bearing element |
| DE102021106229A1 (en) | 2020-12-17 | 2022-06-23 | REHAU Industries SE & Co. KG | Connecting element system for producing a pipe connection, pipe connection comprising this, and method for producing such a pipe connection |
| DE202020107328U1 (en) | 2020-12-17 | 2022-03-18 | REHAU Industries SE & Co. KG | Pipe connection and connecting element for producing a pipe connection |
| AU2021399776A1 (en) | 2020-12-17 | 2023-07-20 | REHAU Industries SE & Co. KG | Connecting element system for producing a tube connection, tube connection comprising the former, and method for producing a tube connection of this type |
| DE102021110302A1 (en) * | 2021-04-22 | 2022-10-27 | Ks Gleitlager Gmbh | Copper-tin continuously cast alloy |
| DE102023000334A1 (en) | 2023-02-03 | 2024-08-08 | Wieland-Werke Aktiengesellschaft | Copper alloy, semi-finished product and electrical connecting element made of a copper alloy |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102018004702A1 (en) * | 2018-06-12 | 2019-12-12 | Gebr. Kemper Gmbh + Co. Kg Metallwerke | Moldings made of a corrosion-resistant and machinable copper alloy |
| EP3581667A2 (en) | 2018-06-12 | 2019-12-18 | Gebr. Kemper GmbH + Co. KG Metallwerke | Moulded parts made from a corrosion resistant and machinable alloy |
| EP3581667A3 (en) * | 2018-06-12 | 2020-06-17 | Gebr. Kemper GmbH + Co. KG Metallwerke | Moulded parts made from a corrosion resistant and machinable alloy |
| US20220016693A1 (en) * | 2019-03-11 | 2022-01-20 | Rehau Ag + Co. | Method for producing metal components and metal component produced in this way |
Also Published As
| Publication number | Publication date |
|---|---|
| DE202016101661U1 (en) | 2017-06-30 |
| EP3225707B1 (en) | 2020-12-30 |
| DK3225707T3 (en) | 2021-04-06 |
| WO2017167441A2 (en) | 2017-10-05 |
| RU2712161C1 (en) | 2020-01-24 |
| PL3225707T3 (en) | 2021-07-19 |
| WO2017167441A3 (en) | 2018-03-01 |
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