US20160340759A1 - Brass with improved dezincification resistance and machinability - Google Patents
Brass with improved dezincification resistance and machinability Download PDFInfo
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- US20160340759A1 US20160340759A1 US15/115,084 US201515115084A US2016340759A1 US 20160340759 A1 US20160340759 A1 US 20160340759A1 US 201515115084 A US201515115084 A US 201515115084A US 2016340759 A1 US2016340759 A1 US 2016340759A1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/002—Castings of light metals
- B22D21/005—Castings of light metals with high melting point, e.g. Be 1280 degrees C, Ti 1725 degrees C
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
Definitions
- the present invention concerns an essentially arsenic-free brass alloy with improved dezincification resistance, protection against intergranular grain boundary corrosion, and machinability.
- Brass is a material the basic components of which are copper (Cu) and zinc (Zn).
- alloying materials such as lead (Pb), iron (Fe), aluminium (Al), nickel (Ni), manganese (Mn), silicon (Si)
- the brass can be given unique properties, and there are many different brass alloys adapted to different types of processing and final products.
- the brass will consist of different so-called phases, which are microstructure components.
- the usual phases of brass are the ⁇ -phase, which is rich in copper and the (3-phase, which is rich in zinc. Often, brass consists of a mixture of these two phases.
- a solid solution having a uniform brass composition is formed when up to about 35% by weight of zinc is added to copper.
- a further increase of the content of zinc gives a mixture of the original solid solution (the ⁇ -phase) and a new solid solution having a higher content of zinc (the ⁇ -phase).
- Brass containing between 35-45% by weight of zinc consists of mixtures of these two phases and is called ⁇ - ⁇ -brass or duplex brass, the relationship between the ⁇ -phase to the ⁇ -phase depending primarily on the content of zinc.
- the presence of ⁇ -phase in ⁇ - ⁇ -brass gives a decreased cold ductility but a considerably increased susceptibility to hot working by extrusion or punching and casting without thermal cracks, also when lead is present.
- ⁇ - ⁇ -alloys have better mechanical properties and, since they contain a higher share of zinc, they are in certain cases more inexpensive than ⁇ -brass.
- ⁇ - ⁇ -brass alloys have a higher sensitivity to dezincification. Thereby, there is a need of producing ⁇ - ⁇ -brass alloys with dezincification resistance.
- Dezincification is a type of corrosion where zinc selectively is attacked and leaves a porous copper structure.
- Dezincification resistant brass has a relatively high Cu content, above 60%, and contains an inhibitor such arsenic (As), antimony (Sb), or phosphorus (P), which makes the ⁇ -phase of the brass resistant to dezincification. Since only the ⁇ -phase can be stabilized, it is important to minimize the content of ⁇ -phase by a higher content of copper.
- Brass alloys may in addition to dezincification be subjected to intergranular grain boundary corrosion, which is a form of corrosion taking place along the grain boundaries.
- intergranular grain boundary corrosion is a form of corrosion taking place along the grain boundaries.
- the content of zinc is higher at the grain boundaries of brass alloys and intergranular grain boundary corrosion attacks just at the zinc present along the grain boundaries. Thereby, there is also a need of protecting brass alloys against intergranular grain boundary corrosion.
- the American Academy of Sciences has estimated the lifetime risk of cancer to 1-3 cases per 1000 individuals at a daily intake of 1 l of drinking water having arsenic contents at the threshold level of 10 ⁇ g/l, which exceeds the low-risk level (approx. one case per 100 000 exposed) that could be considered to be an acceptable risk of an individual environmental factor [3]. As with other carcinogenic substances, the risk of health effects decreases at decreased exposure.
- the threshold for arsenic in drinking water is 10 ⁇ g/l within the EU.
- the threshold for arsenic in drinking water in Sweden 10 ⁇ g/l, is based on the cancer risk [3].
- Lifetime risk of the genesis of cancer at a daily intake of arsenic corresponding to the threshold in drinking water (10-20 ⁇ g arsenic per day depending on age, climate and physical activity), has been estimated to 1-3 per 1 000 individuals (0.1-0.3%). Thereby, it is desirable to limit the intake of arsenic as far as possible. This applies particularly to children, since experimental studies show that fetuses and small children are more sensible than adults.
- the object of the present invention is to provide an essentially arsenic-free ⁇ - ⁇ -brass alloy.
- the object is furthermore that the brass alloy has improved dezincification resistance than brass alloys with arsenic or solely arsenic.
- the object is furthermore to provide a brass alloy having similar or better protection against intergranular grain boundary corrosion than brass alloys with arsenic or solely arsenic.
- the object is furthermore that the lead content of the brass alloy should be ⁇ 1.0% by weight, preferably ⁇ 0.10% by weight of Pb.
- the object is furthermore that the content of the ⁇ -phase is ⁇ 5%, preferably ⁇ 1%.
- the invention concerns an essentially arsenic-free ⁇ - ⁇ -brass alloy with improved (i) dezincification resistance, (ii) machinability, and (iii) protection against intergranular grain boundary corrosion.
- the essentially arsenic-free brass alloy comprises 62-68% by weight of Cu, 0.02-1.00% by weight of Pb, ⁇ 0.02% by weight of As, and/or 0.01-0.06% by weight of P and/or 0.01-0.06% by weight of Sb (antimony), and balance Zn.
- Said brass alloy is characterized in that it comprises ⁇ 5% of ⁇ -phase, preferably ⁇ 1%. Since only the ⁇ -phase can be stabilized, it is important to minimize the content of ⁇ -phase to ⁇ 5% of ⁇ -phase, preferably ⁇ 1%, with the purpose of counteracting dezincification and intergranular grain boundary corrosion.
- the essentially arsenic-free brass alloy comprises 62-68% by weight of Cu, 0.02-1.00% by weight of Pb, ⁇ 0.02% by weight of As, and/or 0.01-0.06% by weight of P and/or 0.01-0.06% by weight of Sb, and balance Zn, the brass alloy being produced by means of a method comprising the steps of:
- the essentially arsenic-free brass alloy has been characterized by the method of producing it (product-by-process) in combination with other determinations of the alloy since it is difficult to define the technical features of the alloy in another way, i.e., it is partly thanks to heat treatment that the alloy obtains improved (i) dezincification resistance and (ii) protection against intergranular grain boundary corrosion.
- the essentially arsenic-free brass alloy comprises 63.0-64.0% by weight of Cu, 0.02-1.00% by weight of Pb, and/or 0.02-0.06% by weight of P, 0.02-0.06% by weight of Sb, and balance Zn.
- Pb palladium
- Pb palladium
- Sb silver
- balance Zn zinc
- the somewhat higher amount of Pb gives a certain improved machinability.
- the essentially arsenic-free brass alloy comprises 63.0-64.0% by weight of Cu, 0.80-1.00% by weight of Pb, 0.02-0.06% by weight of P, 0.02-0.06% by weight of Sb, and balance Zn.
- Pb palladium
- Pb palladium
- Sb silver
- balance Zn zinc
- the somewhat higher amount of Pb gives a certain improved machinability.
- the essentially arsenic-free brass alloy comprises also 0.07-0.12% by weight of Fe and 0-0.05% by weight or 0.45-0.70% by weight of Al.
- the presence of Fe and Al in the brass alloy entails a certain increased hardness, strength, and tensile strength.
- the essentially arsenic-free brass alloy comprises 63.5% by weight of Cu, 35.0% by weight of Zn, 0.9% by weight of Pb, 0.10% by weight of Fe, 0.50% by weight of Al, 0.02-0.06% by weight of P, 0.02-0.06% by weight of Sb. Alloying additives such as Fe and Al improve strength, hardness, and tensile strength. The content of P and Sb of 0.02-0.06% by weight each gives protection against dezincification and intergranular grain boundary corrosion.
- the essentially arsenic-free brass alloy comprises 63.5% by weight of Cu, 35.0% by weight of Zn, 0.9% by weight of Pb, 0.10% by weight of Fe, 0.50% by weight of Al, 0.03% by weight of P, and 0.03% by weight of Sb.
- the content of P and Sb of 0.03% by weight each gives better protection against dezincification and intergranular grain boundary corrosion and approx. 10% lower cutting forces.
- the essentially arsenic-free brass alloy comprises 0-0.200% by weight of Ni, 0-0.100% by weight of Mn, 0-0.02% by weight of Si, 0-0.002% by weight of As and/or 0.0004-0.0006% by weight of B (boron), preferably 0.0005% by weight of B.
- Nickel improves corrosion resistance, hardness, and tensile strength without significant effect on ductility, which gives improved properties at elevated temperatures.
- Mn entails a certain increased hardness, strength, and tensile strength.
- Si increases the strength, workability, and the resistance to wear.
- the content of As and B is acceptable contents of inevitable impurities in the alloy.
- the brass alloy comprises 62-68% by weight of Cu, 0.02-1.00% by weight of Pb, 0.01% by weight of As, 0.02% by weight of Sb, and balance Zn.
- the brass alloy comprises 62-68% by weight of Cu, 0.02-1.00% by weight of Pb, 0.01% by weight of As, 0.02% by weight of Sb, 0.015% by weight of P, and balance Zn.
- the essentially arsenic-free brass alloy according to the present application is produced by the steps of:
- the essentially arsenic-free brass alloy is produced by heat treating at 550° C. for 2 h, which lowers the amount of ⁇ -phase to ⁇ 5%, preferably %, as well as that the alloying additive P lowers the cutting forces to approx. 10% lower cutting forces.
- FIG. 1 The microstructure of both cast and heat-treated test alloy 10 is illustrated. All pictures are taken using optical light microscopy. The first row is with 200 ⁇ magnification and the second row is 500 ⁇ magnification.
- FIG. 2 Cross-sections from test plates, which show the degree of corrosion attack for representative test alloys are illustrated.
- the present invention concerns an essentially arsenic-free brass alloy with improved (i) dezincification resistance, (ii) machinability, and (iii) protection against intergranular grain boundary corrosion, wherein said brass alloy comprises 62-68% by weight of Cu, 0.02-1.00% by weight of Pb, ⁇ 0.02% by weight of As, 0.01-0.06% by weight of P and/or 0.01-0.06% by weight of Sb, and balance Zn, and the brass alloy being characterized by it comprising ⁇ 5% of ⁇ -phase, preferably ⁇ 1%.
- the brass alloy according to the present invention may also comprise alloying additives such as Fe, Al, Ni, Mn, and Si with the purpose of improving strength, wear resistance, and/or tensile strength.
- alloying additives such as Fe, Al, Ni, Mn, and Si with the purpose of improving strength, wear resistance, and/or tensile strength.
- the presence of Fe, Mn, and Al in the brass alloy entails a certain increased hardness, strength, and tensile strength.
- Si increases the strength and the resistance to wear of the brass alloy.
- Nickel improves hardness and tensile strength without significant effect on ductility, which gives improved properties at elevated temperatures.
- Other elements such as B, Bi, Mg, Cr, and As may also be present in the brass alloy as inevitable impurities.
- the brass alloy according to the present application comprises ⁇ 0.02% by weight of As.
- the brass alloy comprises ⁇ 0.02% by weight of As, i.e., that As is present as an inevitable impurity.
- the brass alloy according to the present invention is produced by a method comprising the steps of
- a brass alloy comprising ⁇ 5% of ⁇ -phase, preferably % of ⁇ -phase, which gives improved dezincification resistance and protection against intergranular grain boundary corrosion.
- the present invention indicates furthermore that in the presence of Al or Fe, P does not act as inhibitor against dezincification but instead P results in lower cutting forces, which is an unexpected technical effect (see Example 1).
- Sb and the heat treatment at 550° C. for 2 h promotes that the n-zones are not continuous, which in turn promotes protection against intergranular grain boundary corrosion.
- the following examples are there to illustrate a preferred embodiment and do not thereby exclude other brass alloys with both ⁇ - and ⁇ -phases falling within the scope of protection of the claims according to the present invention.
- the example also comprises comparative experiments (with the purpose of demonstrating technical effect) between brass alloys containing different combinations of As, Sb, and/or P.
- Test alloys 1-11 which were tested in the present application, were produced by using a base alloy having the prototype name 752 wherein the content of As, Sb, and P is as close to zero as possible.
- the chemical composition of 752 is given in Table 1 in % by weight wherein “NBG standard value” indicates the chemical composition of the base alloy desired to be achieved while “Min” and “Max” gives the tolerances.
- the measured composition of the base alloy is also given.
- test alloys were produced in the form of ingots of 2 kg by adding As, Sb, and/or P to the base alloy in a furnace (Leybold) where the alloys were melted in a melting-pot (Morgan crucible), which had been placed in an inductance coil. The alloys were melted in the presence of air by means of ventilation above the furnace and the smelt was then poured into a mould by tipping the melting-pot together with the coil. The dimension of the mould was 40 ⁇ 40 mm (height, 300 mm).
- Test alloys with different combinations of As, Sb, and/or P tested are given in Table 2.
- test alloys 1-11 are exposed to corrosion in the form of both cast and heat-treated sample plates. Said heat treatment was made at 550° C. for 2 h, and after removal from the furnace, the samples were quickly quenched in water (with a delay of up to 5 min). As has been indicated previously, the purpose of the heat treatment is to reduce the ⁇ -phase in the test alloys.
- the heat treatment was made at 550° C. for 2 h since comparative experiments with other temperatures and time intervals (such as 460° C. to 550° C. for 30 min-8 h) indicate that improved dezincification resistance and protection against intergranular grain boundary corrosion are obtained upon heat treatment at 550° C. for 2 h. Moreover, experiments have shown that heat treatment at 550° C. for 2 h also promotes that the (3-zones are not continuous, which in turn promotes protection against IGA.
- test alloys 1-11 were exposed to corrosion in accordance with ISO 6509 “Copper and copper alloys—brass—Determination of dezincification”, in 1% CuCl 2 solution for 24 h at 75 ⁇ 2° C.
- Characterizing of structures before corrosion exposure was made in the same way on etched cross-sections. Quantification was made by counting a fraction of the intersection points (mesh-intersection) of the grid which superseded 200 points; i.e., a grid is laid over the picture, then the number of points of ⁇ - and ⁇ -phase, respectively, are counted and translated into %.
- the comparative experiments show that the heat treatment considerably decreased the amount of ⁇ -phase in all test alloys.
- the results indicate that a value below 5% of ⁇ -phase entailed that there unlikely was formed a continuous network, while a content above 10% of ⁇ -phase entailed that continuous networks were formed. This is evidently indicated in FIG. 1 where the microstructure of both cast and heat-treated test alloy 10 is illustrated.
- the results from the tests emphasize that heat treatment is necessary to decrease the ⁇ -phase as much as possible.
- FIG. 2 illustrates cross-sections from test plates showing the degree of corrosion attack for representative test alloys.
- test alloy 7, 9, 10 and 11 which all comprise Sb ⁇ 0.02% by weight or a combination of As and Sb ⁇ 0.02% by weight.
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Abstract
The present invention concerns an essentially arsenic-free brass alloy with improved (i) dezincification resistance, (ii) machinability, and (iii) protection against intergranular grain boundary corrosion, wherein said brass alloy comprises 62-68% by weight of Cu, 0.02-1.00% by weight of Pb, 0.2-0.6% by weight of P, 0.02-0.06% by weight of Sb, and balance Zn, and the brass alloy being characterized in that it comprises <5% of β-phase, preferably <1%. In addition, the invention concerns a method for the production of said brass alloy.
Description
- The present invention concerns an essentially arsenic-free brass alloy with improved dezincification resistance, protection against intergranular grain boundary corrosion, and machinability.
- Brass is a material the basic components of which are copper (Cu) and zinc (Zn). By the addition of different alloying materials such as lead (Pb), iron (Fe), aluminium (Al), nickel (Ni), manganese (Mn), silicon (Si), the brass can be given unique properties, and there are many different brass alloys adapted to different types of processing and final products. Depending on composition and manufacture, the brass will consist of different so-called phases, which are microstructure components. The usual phases of brass are the α-phase, which is rich in copper and the (3-phase, which is rich in zinc. Often, brass consists of a mixture of these two phases.
- A solid solution having a uniform brass composition is formed when up to about 35% by weight of zinc is added to copper. A further increase of the content of zinc gives a mixture of the original solid solution (the α-phase) and a new solid solution having a higher content of zinc (the β-phase). Brass containing between 35-45% by weight of zinc consists of mixtures of these two phases and is called α-β-brass or duplex brass, the relationship between the α-phase to the β-phase depending primarily on the content of zinc. The presence of β-phase in α-β-brass gives a decreased cold ductility but a considerably increased susceptibility to hot working by extrusion or punching and casting without thermal cracks, also when lead is present. In addition, α-β-alloys have better mechanical properties and, since they contain a higher share of zinc, they are in certain cases more inexpensive than α-brass. However, α-β-brass alloys have a higher sensitivity to dezincification. Thereby, there is a need of producing α-β-brass alloys with dezincification resistance.
- In certain environments, special alloys have to be used. Such an example is building services fittings in the form of mixer taps, valves, couplings, etc., when dezincification resistance is required. Dezincification is a type of corrosion where zinc selectively is attacked and leaves a porous copper structure. Dezincification resistant brass has a relatively high Cu content, above 60%, and contains an inhibitor such arsenic (As), antimony (Sb), or phosphorus (P), which makes the α-phase of the brass resistant to dezincification. Since only the α-phase can be stabilized, it is important to minimize the content of β-phase by a higher content of copper. However, it has turned out that there remains β-phase even if arsenic and a high content of copper of above 60% have been used. Thereby, there is a need of minimizing the β-phase of α-β-brass alloys (comprising ≧60% by weight of Cu) in an alternative way.
- It is known by U.S. Pat. No. 3,963,526 that a brass alloy with 5-20% of β-phase can be obtained by means of addition to the alloy of at least 0.02% by weight of dezincification inhibiting alloying elements such as As, Sb, or P. The continuous network of β-phase naturally being present in the alloy may be broken up by the cast brass alloy being heat-treated at a temperature between 400-600° C. for a suitable period of time.
- Brass alloys may in addition to dezincification be subjected to intergranular grain boundary corrosion, which is a form of corrosion taking place along the grain boundaries. The content of zinc is higher at the grain boundaries of brass alloys and intergranular grain boundary corrosion attacks just at the zinc present along the grain boundaries. Thereby, there is also a need of protecting brass alloys against intergranular grain boundary corrosion.
- People are exposed most often to inorganic arsenic via drinking water and certain food, and to various organic arsenic compounds via, above all, fish and shellfish [1-3]. As seen globally, several million people use drinking water having such high arsenic content that there is risk of serious health effects. Worst hit are Bangladesh, India, Taiwan, as well as parts of South America and China [3]. Thereby, there is a need for lowering the contents of arsenic in drinking water by using as little arsenic as possible in alloys of brass that are in contact with drinking water.
- The American Academy of Sciences has estimated the lifetime risk of cancer to 1-3 cases per 1000 individuals at a daily intake of 1 l of drinking water having arsenic contents at the threshold level of 10 μg/l, which exceeds the low-risk level (approx. one case per 100 000 exposed) that could be considered to be an acceptable risk of an individual environmental factor [3]. As with other carcinogenic substances, the risk of health effects decreases at decreased exposure. The threshold for arsenic in drinking water is 10 μg/l within the EU.
- The threshold for arsenic in drinking water in Sweden, 10 μg/l, is based on the cancer risk [3]. Lifetime risk of the genesis of cancer, at a daily intake of arsenic corresponding to the threshold in drinking water (10-20 μg arsenic per day depending on age, climate and physical activity), has been estimated to 1-3 per 1 000 individuals (0.1-0.3%). Thereby, it is desirable to limit the intake of arsenic as far as possible. This applies particularly to children, since experimental studies show that fetuses and small children are more sensible than adults.
- In countries where lead is relatively common in the water work system, lead in drinking water has contributed to high exposure. Lead may damage the nervous system already at very low doses [3.4]. The immature nervous system is particularly sensitive. The lead content of blood may be set in relation to the health risk. At blood lead contents around 100 μg/l and higher, symptoms as degraded intellectual capacity, delayed development, and behaviour disorders have been possible to be demonstrated in children who have been exposed during the fetal stage and the infant ages. Thereby, there is a need for lowering the contents of lead in drinking water by using lower contents of lead in alloys of brass in contact with drinking water.
- The object of the present invention is to provide an essentially arsenic-free α-β-brass alloy.
- The object is furthermore that the brass alloy has improved dezincification resistance than brass alloys with arsenic or solely arsenic.
- The object is furthermore to provide a brass alloy having similar or better protection against intergranular grain boundary corrosion than brass alloys with arsenic or solely arsenic.
- The object is furthermore that the lead content of the brass alloy should be ≦1.0% by weight, preferably ≦0.10% by weight of Pb.
- The object is furthermore that the content of the β-phase is <5%, preferably ≦1%.
- By the present invention, as it is seen in the independent claims, the above-mentioned objects are met. Suitable embodiments of the invention are defined in the dependent claims.
- The invention concerns an essentially arsenic-free α-β-brass alloy with improved (i) dezincification resistance, (ii) machinability, and (iii) protection against intergranular grain boundary corrosion.
- According to a preferred embodiment, the essentially arsenic-free brass alloy comprises 62-68% by weight of Cu, 0.02-1.00% by weight of Pb, <0.02% by weight of As, and/or 0.01-0.06% by weight of P and/or 0.01-0.06% by weight of Sb (antimony), and balance Zn. Said brass alloy is characterized in that it comprises <5% of β-phase, preferably ≦1%. Since only the α-phase can be stabilized, it is important to minimize the content of β-phase to <5% of β-phase, preferably ≦1%, with the purpose of counteracting dezincification and intergranular grain boundary corrosion.
- According to a preferred embodiment, the essentially arsenic-free brass alloy comprises 62-68% by weight of Cu, 0.02-1.00% by weight of Pb, <0.02% by weight of As, and/or 0.01-0.06% by weight of P and/or 0.01-0.06% by weight of Sb, and balance Zn, the brass alloy being produced by means of a method comprising the steps of:
-
- a. adding Sb and P to a base alloy in a furnace,
- b. the smelt being poured into a mould,
- c. the cast brass alloy being heat-treated at 500° C. to 550° C. for 1-2 h
- Since only the α-phase can be stabilized, it is important to minimize the content of β-phase with the purpose of counteracting dezincification and intergranular grain boundary corrosion. The heat treatment in combination with the inhibitor Sb lowers the amount of β-phase as well as that the alloying additive P lowers the cutting forces.
- In this preferred embodiment, the essentially arsenic-free brass alloy has been characterized by the method of producing it (product-by-process) in combination with other determinations of the alloy since it is difficult to define the technical features of the alloy in another way, i.e., it is partly thanks to heat treatment that the alloy obtains improved (i) dezincification resistance and (ii) protection against intergranular grain boundary corrosion.
- According to a preferred embodiment, the essentially arsenic-free brass alloy comprises 63.0-64.0% by weight of Cu, 0.02-1.00% by weight of Pb, and/or 0.02-0.06% by weight of P, 0.02-0.06% by weight of Sb, and balance Zn. The somewhat higher amount of Pb gives a certain improved machinability.
- According to a preferred embodiment, the essentially arsenic-free brass alloy comprises 63.0-64.0% by weight of Cu, 0.80-1.00% by weight of Pb, 0.02-0.06% by weight of P, 0.02-0.06% by weight of Sb, and balance Zn. The somewhat higher amount of Pb gives a certain improved machinability.
- According to a preferred embodiment, the essentially arsenic-free brass alloy comprises also 0.07-0.12% by weight of Fe and 0-0.05% by weight or 0.45-0.70% by weight of Al. The presence of Fe and Al in the brass alloy entails a certain increased hardness, strength, and tensile strength.
- According to a preferred embodiment, the essentially arsenic-free brass alloy comprises 63.5% by weight of Cu, 35.0% by weight of Zn, 0.9% by weight of Pb, 0.10% by weight of Fe, 0.50% by weight of Al, 0.02-0.06% by weight of P, 0.02-0.06% by weight of Sb. Alloying additives such as Fe and Al improve strength, hardness, and tensile strength. The content of P and Sb of 0.02-0.06% by weight each gives protection against dezincification and intergranular grain boundary corrosion.
- According to a preferred embodiment, the essentially arsenic-free brass alloy comprises 63.5% by weight of Cu, 35.0% by weight of Zn, 0.9% by weight of Pb, 0.10% by weight of Fe, 0.50% by weight of Al, 0.03% by weight of P, and 0.03% by weight of Sb. The content of P and Sb of 0.03% by weight each gives better protection against dezincification and intergranular grain boundary corrosion and approx. 10% lower cutting forces.
- According to a preferred embodiment, the essentially arsenic-free brass alloy comprises 0-0.200% by weight of Ni, 0-0.100% by weight of Mn, 0-0.02% by weight of Si, 0-0.002% by weight of As and/or 0.0004-0.0006% by weight of B (boron), preferably 0.0005% by weight of B. Nickel improves corrosion resistance, hardness, and tensile strength without significant effect on ductility, which gives improved properties at elevated temperatures. The presence of Mn entails a certain increased hardness, strength, and tensile strength. Si increases the strength, workability, and the resistance to wear. The content of As and B is acceptable contents of inevitable impurities in the alloy.
- According to a preferred embodiment, the brass alloy comprises 62-68% by weight of Cu, 0.02-1.00% by weight of Pb, 0.01% by weight of As, 0.02% by weight of Sb, and balance Zn.
- According to a preferred embodiment, the brass alloy comprises 62-68% by weight of Cu, 0.02-1.00% by weight of Pb, 0.01% by weight of As, 0.02% by weight of Sb, 0.015% by weight of P, and balance Zn.
- According to a preferred embodiment, the essentially arsenic-free brass alloy according to the present application is produced by the steps of:
-
- a. adding Sb and P to a base alloy in a furnace,
- b. the smelt being poured into a mould,
- c. the cast brass alloy being heat-treated at 500° C. to 550° C. for 1-2 h.
- The heat treatment in combination with the inhibitors Sb and/or As lowers the amount of β-phase as well as that the alloying additive P lowers the cutting forces.
- According to a preferred embodiment, the essentially arsenic-free brass alloy is produced by heat treating at 550° C. for 2 h, which lowers the amount of β-phase to <5%, preferably %, as well as that the alloying additive P lowers the cutting forces to approx. 10% lower cutting forces.
-
FIG. 1 The microstructure of both cast and heat-treatedtest alloy 10 is illustrated. All pictures are taken using optical light microscopy. The first row is with 200× magnification and the second row is 500× magnification. -
FIG. 2 Cross-sections from test plates, which show the degree of corrosion attack for representative test alloys are illustrated. - The present invention concerns an essentially arsenic-free brass alloy with improved (i) dezincification resistance, (ii) machinability, and (iii) protection against intergranular grain boundary corrosion, wherein said brass alloy comprises 62-68% by weight of Cu, 0.02-1.00% by weight of Pb, <0.02% by weight of As, 0.01-0.06% by weight of P and/or 0.01-0.06% by weight of Sb, and balance Zn, and the brass alloy being characterized by it comprising <5% of β-phase, preferably ≦1%.
- The brass alloy according to the present invention may also comprise alloying additives such as Fe, Al, Ni, Mn, and Si with the purpose of improving strength, wear resistance, and/or tensile strength. The presence of Fe, Mn, and Al in the brass alloy entails a certain increased hardness, strength, and tensile strength. Si increases the strength and the resistance to wear of the brass alloy. Nickel improves hardness and tensile strength without significant effect on ductility, which gives improved properties at elevated temperatures. Other elements such as B, Bi, Mg, Cr, and As may also be present in the brass alloy as inevitable impurities.
- With the definition “arsenic-free”, it is meant that the brass alloy according to the present application comprises <0.02% by weight of As. Preferably, the brass alloy comprises ≦0.02% by weight of As, i.e., that As is present as an inevitable impurity.
- The brass alloy according to the present invention is produced by a method comprising the steps of
-
- a. adding Sb and P to a base alloy in a furnace, the base alloy comprising the quantity of Cu, Zn, Pb, and possibly other alloying additives, such as Fe and Al, which should be included in the brass alloy,
- b. the smelt being poured into a mould,
- c. the cast brass alloy being heat-treated at 500° C. to 550° C. for 1-2 h, the heat treatment preferably taking place at 550° C. for 2 h.
- By adding the inhibitor Sb and heat treatment, a brass alloy is obtained comprising <5% of β-phase, preferably % of β-phase, which gives improved dezincification resistance and protection against intergranular grain boundary corrosion. The present invention indicates furthermore that in the presence of Al or Fe, P does not act as inhibitor against dezincification but instead P results in lower cutting forces, which is an unexpected technical effect (see Example 1). Moreover, Sb and the heat treatment at 550° C. for 2 h promotes that the n-zones are not continuous, which in turn promotes protection against intergranular grain boundary corrosion.
- The following examples are there to illustrate a preferred embodiment and do not thereby exclude other brass alloys with both α- and β-phases falling within the scope of protection of the claims according to the present invention. The example also comprises comparative experiments (with the purpose of demonstrating technical effect) between brass alloys containing different combinations of As, Sb, and/or P.
- Test alloys 1-11, which were tested in the present application, were produced by using a base alloy having the prototype name 752 wherein the content of As, Sb, and P is as close to zero as possible. The chemical composition of 752 is given in Table 1 in % by weight wherein “NBG standard value” indicates the chemical composition of the base alloy desired to be achieved while “Min” and “Max” gives the tolerances. Moreover, the measured composition of the base alloy is also given.
-
TABLE 1 Minimum, maximum, and standard values for 752 and chemical analysis of the base alloy 752, which was used for the production of the test alloys 1-11. Chemical composition % Analysis of the base alloy that was used to Min Max NBG std. value produce test alloy 1-11 Cu 63.0 64.0 63.5 63.25 Zn Balance 35.0 35.23 Pb 0.80 1.00 0.90 0.896 Sn 0.016 Fe 0.07 0.12 0.10 0.070 Al 0.45 0.70 0.500 0.504 Ni 0.200 0.013 Mn 0.100 0.003 Si 0.02 0.015 As 0.002 0.002 Sb <0.001 Bi 0.001 P <0.001 B 0.0004 0.0006 0.0005 0.0006 Mg 0.001 Cr 0.002 As + Sb + P 0.005 0.002 - Test Alloy 1-11
- The test alloys were produced in the form of ingots of 2 kg by adding As, Sb, and/or P to the base alloy in a furnace (Leybold) where the alloys were melted in a melting-pot (Morgan crucible), which had been placed in an inductance coil. The alloys were melted in the presence of air by means of ventilation above the furnace and the smelt was then poured into a mould by tipping the melting-pot together with the coil. The dimension of the mould was 40×40 mm (height, 300 mm).
- Test alloys with different combinations of As, Sb, and/or P tested are given in Table 2.
-
TABLE 2 The content of As, P, and Sb of the test alloys 1-11 indicated in % by weight. The “Analysed” contents indicate the measured % by weight while the “Planned” contents indicate the contents desired to achieve in the test alloys. Planned Analysed As P Sb As P Sb (% w) (% w) (% w) (% w) (% w) (% w) Alloy 1— — — 0.002 0.000 0.000 (base alloy) Alloy 20.02 — — 0.020 0.000 0.000 Alloy 3 0.06 — — 0.066 0.000 0.001 Alloy 4 — 0.02 — 0.002 0.018 0.000 Alloy 5— 0.06 — 0.002 0.066 0.000 Alloy 6 — — 0.02 0.002 0.000 0.019 Alloy 7— — 0.06 0.002 0.000 0.062 Alloy 8 0.03 0.03 — 0.029 0.030 0.000 Alloy 9 0.03 0.03 0.030 0.000 0.030 Alloy 100.03 0.03 0.002 0.029 0.029 Alloy 110.02 0.02 0.02 0.021 0.022 0.022 - The chemical composition of the test alloys is presented in Table 3 wherein also inevitable impurities such as B, Bi, Mg, and Cr have been included in the table.
-
TABLE 3 The chemical composition of the test alloys in % by weight. Cu Zn Pb Sn Fe Al Ni Mn Si As Sb B Bi P Mg Cr min 63 0.8 .07 .45 max 64 bal. 0.9 .12 0.7 0.2 0.1 0.02 .002 NBG 63.5 35 1 .10 0.5 std 1 63.1 35.4 .88 .017 .09 .49 .014 .004 .016 .002 0 .001 .001 0 .001 .002 2 63.2 35.2 .88 .014 .11 .49 .013 .004 .016 .020 0 .001 .001 0 .001 .002 3 63.3 35.1 .89 .016 .09 .50 .013 .004 .016 .066 .001 .001 .001 0 .001 .002 4 63.3 35.1 .89 .016 .08 .50 .013 .004 .015 .002 0 .001 .001 .018 .001 .002 5 63.4 35.0 .91 .018 .09 .49 .014 .004 .016 .002 0 .001 .001 .066 .001 .002 6 63.3 35.2 .89 .016 .08 .48 .013 .004 .017 .002 .019 .001 .001 0 .001 .002 7 63.4 35.0 .89 .016 .09 .49 .013 .004 .016 .002 .062 .001 .001 0 .001 .002 8 63.5 34.9 .89 .013 .10 .49 .013 .004 .016 .029 0 .001 .001 .030 .001 .002 9 63.2 35.2 .91 .018 .09 .50 .014 .004 .016 .030 .030 .001 .001 0 .001 .002 10 63.6 34.8 .89 .016 .10 .48 .013 .004 .017 .002 .029 .001 .001 .028 .001 .002 11 63.5 34.9 .89 .015 .10 .49 .013 .004 .016 .020 .022 .001 .001 .022 .001 .002 - Corrosion Tests
- The test alloys 1-11 are exposed to corrosion in the form of both cast and heat-treated sample plates. Said heat treatment was made at 550° C. for 2 h, and after removal from the furnace, the samples were quickly quenched in water (with a delay of up to 5 min). As has been indicated previously, the purpose of the heat treatment is to reduce the β-phase in the test alloys.
- The heat treatment was made at 550° C. for 2 h since comparative experiments with other temperatures and time intervals (such as 460° C. to 550° C. for 30 min-8 h) indicate that improved dezincification resistance and protection against intergranular grain boundary corrosion are obtained upon heat treatment at 550° C. for 2 h. Moreover, experiments have shown that heat treatment at 550° C. for 2 h also promotes that the (3-zones are not continuous, which in turn promotes protection against IGA.
- Testing of dezincification and intergranular grain boundary corrosion was made by cutting out sample plates from the middle of the ingot. The plates were obtained by the fact that samples were cut out from the ingot and the exposed surfaces were ground using 600 mesh paper. Next, said sample plates were partly masked using nail-varnish to create unexposed reference surfaces, which were used to determine the depth of corrosion attack.
- The test alloys 1-11 were exposed to corrosion in accordance with ISO 6509 “Copper and copper alloys—brass—Determination of dezincification”, in 1% CuCl2 solution for 24 h at 75±2° C.
- After the corrosion tests, cross-sections were prepared perpendicular to the nail-varnish masking for metallographic examination by grinding and polishing of the sample plates. Corrosion attack was determined by light optical microscopy by measuring using 200× and 500× magnifications.
- Characterizing of structures before corrosion exposure was made in the same way on etched cross-sections. Quantification was made by counting a fraction of the intersection points (mesh-intersection) of the grid which superseded 200 points; i.e., a grid is laid over the picture, then the number of points of α- and β-phase, respectively, are counted and translated into %.
- Results—Quantification of the β-Phase of the Test Alloys
- The amount of β-phase of the etched cross-sections was determined and the results are presented in Table 4.
- The comparative experiments show that the heat treatment considerably decreased the amount of β-phase in all test alloys. The results indicate that a value below 5% of β-phase entailed that there unlikely was formed a continuous network, while a content above 10% of β-phase entailed that continuous networks were formed. This is evidently indicated in
FIG. 1 where the microstructure of both cast and heat-treatedtest alloy 10 is illustrated. The results from the tests emphasize that heat treatment is necessary to decrease the β-phase as much as possible. -
TABLE 4 The amount of β-phase (%) in cast and heat-treated test alloys 1-11 (measured by using grids having intersection points (mesh-intersection), 13 × 19, with 200× or 500× magnification for low and high, respectively, values) As (% w) P (% w) Sb (% w) Cast Heat treated Alloy 1— — — 13 2 Alloy 20.02 — — 16 4 Alloy 3 0.06 — — 13 2 Alloy 4 — 0.02 — 11 1 Alloy 5— 0.06 — 15 2 Alloy 6 — — 0.02 10 4 Alloy 7— — 0.06 15 2 Alloy 8 0.03 0.03 — 16 1 Alloy 9 0.03 0.03 13 1 Alloy 100.03 0.03 11 1 Alloy 110.02 0.02 0.02 15 1 - Results—Dezincification Resistance
- The results from the CuCl2 exposure of test alloy 1-11 are presented in Table 5 where it is seen if corrosion has occurred in the α- and/or β-phase and how deep (μm) the dezincification (AD—dezincification depth) is present.
FIG. 2 illustrates cross-sections from test plates showing the degree of corrosion attack for representative test alloys. - The tests from the preceding sections indicated that heat treatment considerably decreases β-phase contents for all alloys (see Table 4). The comparative experiments in Table 5 show evidently that decreased quantity of β-phase contents considerably decreases the dezincification depth for all alloys containing As and Sb. When test alloy 1 (base alloy 752) is compared with
test alloy 2, 3, 6-10. it is in addition possible to conclude that As and Sb inhibit dezincification of the α-phase. - The results also show that P does not act to inhibit corrosion in the α-phase. On the contrary, the dezincification of the α-phase seems to become more serious after the reduction of β-phase by the heat treatment (compare the “max” values for the alloy 5). This indicates the need of an optimum relationship between α-phase and β-phase to achieve the best corrosion protection. It is also interesting to compare the brass alloys containing As without Sb and the brass alloys containing Sb without As, and the results indicate that the presence of As promotes intergranular grain boundary corrosion while Sb only results in small general corrosion. The examinations have demonstrated a somewhat increased content of Sb at grain boundaries, which gives a better protection just at the grain boundaries, which is seen in Table 5. The brass alloys containing Sb in the absence of As have not demonstrated any grain boundary attacks in contrast to the brass alloys containing As in the absence of Sb (see Table 5). It has furthermore been demonstrated that a combination of Sb and As, also at very low contents, protects from both general and grain boundary attacks in a synergetic way.
- Moreover, there seems to be a difference between the lowest and highest concentration of Sb, 0.02% by weight and 0.06% by weight of Sb, respectively, which may indicate that a higher concentration than 0.02% by weight is needed for full effect in the use of Sb. A concentration of 0.03% by weight as in
alloy 10 seems to work well as inhibitor of dezincification, - The best results were obtained for
test alloy - To sum up, the results suggest that (i) heat treatment, and (ii) presence of As or Sb, are necessary to obtain dezincification resistance and to counteract intergranular grain boundary corrosion.
-
TABLE 5 Dezincification depth (AD) after CuCl2 exposure and identification of coexistent corrosion mechanisms such as intergranular grain boundary corrosion (IGA) and general. “?” indicates that it was difficult to determine type of corrosion, i.e., it may be α or β. Type of corrosion Type of corrosion Cast AD depth Heat-treated AD depth As P Sb Other max mean Other max mean % w % w % w AD type attack (μm) (μm) AD type attack (μm) (μm) Alloy 1— — — α and β 353 134 α 270 84 Alloy 20.02 — — β IGA 325 57 β IGA 36 10 Alloy 3 0.06 — — β IGA 282 52 β IGA 89 40 Alloy 4 — 0.02 — α and β 402 319 α 211 73 Alloy 5— 0.06 — α and β IGA 203 100 α 328 76 Alloy 6 — — 0.02 α and β IGA 402 155 α general 106 9 Alloy 7— — 0.06 α and β general 165 57 β general 38 0 Alloy 8 0.03 0.03 — β 178 110 β IGA 92 17 Alloy 9 0.03 0.03 β general 209 84 ? general 42 7 Alloy 100.03 0.03 α and β 113 48 α general 35 0 Alloy 110.02 0.02 0.02 β 193 87 ? general 40 0 - Results—Cutting Forces
- Analyses that were made of the cutting forces of the test alloys showed an unexpected technique of
alloy 10. which had good machining and also 10% lower cutting forces thanalloy 1. - It is more advantageous with lower cutting forces since high cutting forces result in problems in low-power machines, which are usual in this context and in the operations in which the chip width is large. Examples of such operations are turning using profile tools, slotting and parting, drilling, and threading. Precision and accuracy are also affected negatively with greater cutting forces.
- The embodiments according to the present invention have been described in detail with reference to the above specific example. The example is, however, intended to be illustrative only and thereby does not limit the scope of protection of the present invention. Thereby, it should be appreciated that changes and amendments to the above example may be made without deviating from the scope of protection of the invention. Therefore, the scope of protection of the present invention may not be embraced only by the above example but rather by the claims.
-
- 1) IARC MONOGRAPHS—100C, ARSENIC AND ARSENIC COMPOUNDS, http://monographs.iarc.fr/ENG/Monohgraphs/vol100C/mono100C-6.pdf
- 2) Sveriges geologiska undersökning, Mineralmarknaden Tema: Arsenik, pp. 70-74 http://www.sgu.se/dokument/service_sgu_publ/perpubl_2005-4.pdf
- 3) Socialstyrelsen, Miljöhälsorapport 2005, Ch. 16—Metaller, pp. 185-187 for arsenic and pp. 190-192 for lead http://www.imm.ki.se/PDF/MHR2005.pdf
- 4) WORLD HEALTH ORGANIZATION, IARC Monographs on the Evaluation of Carcinogenic Risks to Humans, VOLUME 87—Inorganic and Organic Lead Compounds, pp. 127-139
- http://monographs.iarc.fr/ENG/Monographs/vol87/mono87.pdf
Claims (23)
1-17. (canceled)
18. A brass alloy comprising:
a. 62-68% by weight of Cu,
b. 0.02-1.00% by weight of Pb,
c. % by weight of As,
d. 0.01-0.06% by weight of P and/or 0.01-0.06% by weight of Sb,
e. balance Zn and unavoidable impurities,
wherein the brass alloy comprises <5% of β-phase.
19. The brass alloy according to claim 18 , further comprising:
c. 0% by weight of As, and
d. 0.02-0.06% by weight of P and 0.02-0.06% by weight of Sb.
20. The brass alloy according to claim 19 , further comprising:
a. 63.0-64.0% by weight of Cu.
21. The brass alloy according to claim 20 , further comprising:
b. 0.80-1.00% by weight of Pb.
22. The brass alloy according to claim 18 , further comprising:
c. 0% by weight of As, and
d. 0.01% by weight of P and 0.02% by weight of Sb.
23. The brass alloy according to claim 18 , further comprising:
c. 0.01% by weight of As, and
d. 0.02% by weight of Sb.
24. The brass alloy according to claim 18 , further comprising:
c. 0.01% by weight of As, and
d. 0.015% by weight of P and 0.02% by weight of Sb.
25. A brass alloy comprising:
a. 62-68% by weight of Cu,
b. 0.02-1.00% by weight of Pb,
c. ≦0.02% by weight of As,
d. 0.01-0.06% by weight of P and/or 0.01-0.06% by weight of Sb,
e. balance Zn and unavoidable impurities,
f. 0.07-0.12% by weight of Fe, and
g. 0-0.70% by weight of Al,
wherein the brass alloy comprises <5% of β-phase.
26. The brass alloy according to claim 15, further comprising:
a. 63.5% by weight of Cu,
b. 0.9% by weight of Pb,
c. 0% by weight of As,
d. 0.02-0.06% by weight of P and 0.02-0.06% by weight of Sb.
e. 35.0% by weight of Zn and unavoidable impurities,
f. 0.10% by weight of Fe, and
g. 0.50% by weight of Al.
27. The brass alloy according to claim 26 , further comprising:
d. 0.03% by weight of P and 0.03% by weight of Sb.
28. A brass alloy comprising:
a. 62-68% by weight of Cu,
b. 0.02-1.00% by weight of Pb,
c. ≦0.02% by weight of As,
d. 0.01-0.06% by weight of P and/or 0.01-0.06% by weight of Sb,
e. balance Zn and unavoidable impurities
f. optionally 0.07-0.12% by weight of Fe,
g. optionally 0-0.70% by weight of Al,
h. 0-0.200% by weight of Ni,
i. 0-0.100% by weight of Mn,
j. 0-0.02% by weight of Si, and
k. 0.0004-0.0006% by weight of B,
wherein the brass alloy comprises <5% of β-phase.
29. A method for the production of a brass alloy according to claims 18 , comprising the steps of:
a. adding Sb and/or P to a base alloy in a furnace,
b. the smelt obtained in step a being poured into a mould,
c. the cast brass alloy obtained in step b being heat-treated at 500° C. to 550° C. for 1-2 h.
30. A method for the production of a brass alloy according to claim 25 , comprising the steps of:
a. adding Sb and/or P to a base alloy in a furnace,
b. the smelt obtained in step a being poured into a mould,
c. the cast brass alloy obtained in step b being heat-treated at 500° C. to 550° C. for 1-2 h.
31. A method for the production of a brass alloy according to claim 28 , comprising the steps of:
a. adding Sb and/or P to a base alloy in a furnace,
b. the smelt obtained in step a being poured into a mould,
c. the cast brass alloy obtained in step b being heat-treated at 500° C. to 550° C. for 1-2 h.
32. Use of the brass alloy according to claim 18 in environments which contact water.
33. Use of the brass alloy according to claim 25 in environments which contact water.
34. Use of the brass alloy according to claim 28 in environments which contact water.
35. An article which is produced with the use of the brass alloy according to claim 18 .
36. An article which is produced with the use of the brass alloy according to claim 25 .
37. An article which is produced with the use of the brass alloy according to claim 28 .
38. Use of P in order to decrease cutting forces of the brass alloy according to claim 25 in the presence of Al or Fe.
39. Use of P in order to decrease cutting forces of the brass alloy according to claim 28 in the presence of Al or Fe.
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SE1450094-6 | 2014-01-30 | ||
SE1450094A SE1450094A1 (en) | 2014-01-30 | 2014-01-30 | Arsenic-free brass with improved zinc toughness and cutability |
PCT/SE2015/050103 WO2015115989A2 (en) | 2014-01-30 | 2015-01-30 | Brass with improved dezincification resistance and machinability |
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US (1) | US20160340759A1 (en) |
EP (1) | EP3099832B1 (en) |
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KR (1) | KR101802933B1 (en) |
CN (1) | CN106170569A (en) |
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CA (1) | CA2937664A1 (en) |
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RU (1) | RU2016133287A (en) |
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JP6315868B1 (en) * | 2017-11-28 | 2018-04-25 | 日酸Tanaka株式会社 | Gas cutting crater |
CN111235427B (en) * | 2020-01-15 | 2020-12-29 | 宁波博威合金材料股份有限公司 | Free-cutting brass alloy and preparation method and application thereof |
CN112342428A (en) * | 2020-10-23 | 2021-02-09 | 开平大昌铜材有限公司 | DZR copper and preparation method thereof |
CN114672690B (en) * | 2022-03-16 | 2023-02-24 | 宁波金田铜业(集团)股份有限公司 | Easily-colored brass and preparation method thereof |
CN118064759A (en) * | 2024-04-23 | 2024-05-24 | 中铝科学技术研究院有限公司 | Dezincification corrosion-resistant and corrosion-resistant brass alloy, and preparation method and application thereof |
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US10584776B2 (en) * | 2018-08-08 | 2020-03-10 | Dongguan Tomuu Actuator Technology Co., Ltd. | High-efficiency high-thrust electric linear actuator for solar panel |
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EP3099832B1 (en) | 2018-11-14 |
JP2017508073A (en) | 2017-03-23 |
JP6178016B2 (en) | 2017-08-09 |
MX2016009812A (en) | 2017-02-28 |
BR112016017682A2 (en) | 2017-08-08 |
CN106170569A (en) | 2016-11-30 |
RU2016133287A (en) | 2018-03-05 |
SE1450094A1 (en) | 2015-07-31 |
WO2015115989A2 (en) | 2015-08-06 |
AU2015211433A1 (en) | 2016-09-01 |
SG11201605577PA (en) | 2016-08-30 |
EP3099832A2 (en) | 2016-12-07 |
RU2016133287A3 (en) | 2018-10-15 |
WO2015115989A3 (en) | 2015-09-24 |
CA2937664A1 (en) | 2015-08-06 |
KR20170005402A (en) | 2017-01-13 |
KR101802933B1 (en) | 2017-11-29 |
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