High-strength wear-resistant brass alloy and preparation method thereof
阅读说明：本技术 一种高强耐磨黄铜合金及其制备方法 (High-strength wear-resistant brass alloy and preparation method thereof ) 是由 王世民 王明军 杨标 刘合力 吴明英 于 2020-12-08 设计创作，主要内容包括：本发明涉及金属合金材料技术领域,特别是关于一种高强耐磨黄铜合金及其制备方法,提供按照不同比例添加Cu、Mn、Co、Si、Pb、AL、Ni、Fe、Zn等元素,形成的一种具有优异耐磨性能、较强强度和硬度的黄铜合金；其制备方法包括：称取各组分、第一熔炼、第二熔炼、除气脱氧、精炼、第三熔炼、调整成分、扒渣、浇注铸锭、均匀化处理热轧、铣面、时效处理、拉伸、低温退火即得。(The invention relates to the technical field of metal alloy materials, in particular to a high-strength wear-resistant brass alloy and a preparation method thereof, and provides a brass alloy which is formed by adding elements such as Cu, Mn, Co, Si, Pb, AL, Ni, Fe, Zn and the like according to different proportions and has excellent wear resistance, stronger strength and hardness; the preparation method comprises the following steps: weighing the components, performing first smelting, performing second smelting, degassing and deoxidizing, refining, performing third smelting, adjusting components, slagging off, casting ingots, performing homogenization treatment and hot rolling, milling surfaces, performing aging treatment, stretching and performing low-temperature annealing to obtain the alloy.)
1. A high-strength wear-resistant brass alloy, characterized by comprising:
Cu 55～60%；
Mn 2.0～4.0%；
Co 0.5～1.5%；
Si 2.0～4.0%；
Al 3.0～5.0%；
Ni 2.0～5.0%；
Fe 1.0～2.0%；
Pb 0.05～0.15%；
zn and the balance of inevitable impurities; and is
The mass percentages of Mn and Co have the following definitions: f is not less than 3.051≤3.55，f1=PMn/PCoWherein
PMnIs the mass percent of Mn, PCoIs the mass percentage of Co.
2. A high strength, wear resistant brass alloy as claimed in claim 1, wherein: the mass percentage of Si to Al has the following definitions: f is more than or equal to 80%2≤100%，f2=4×PSi/28+3×PAl/27 wherein PSiIs the molar amount of Si, PAlIs the mass percentage of Al.
3. A high strength wear resistant brass alloy as claimed in claim 1 or 2, wherein: the mass percentages of Ni and Fe are defined as follows: f is not less than 0.36 ‰3≤0.65‰，f3=PNi×PFeIn which P isNiIs the mass percent of Ni, PFeIs the mass percentage of Fe.
4. A process for the preparation of a brass alloy as claimed in any one of claims 1 to 3, which comprises:
1) weighing copper powder, copper-manganese intermediate alloy, cobalt powder, pure silicon, aluminum powder, nickel powder, iron powder, lead powder and zinc powder according to the proportion;
2) smelting copper powder and copper-manganese intermediate alloy, heating, sequentially adding the components according to the melting points from high to low, and carrying out first smelting to obtain first alloy liquid;
3) adding zinc powder and aluminum powder into the first alloy liquid to perform second smelting to obtain a second alloy liquid;
4) adding a phosphorus-copper deoxidizer into the second alloy liquid to perform degassing and deoxidation to obtain a third alloy liquid;
5) adding a refining agent into the third alloy liquid, and carrying out alloying refining to obtain a fourth alloy liquid;
6) and performing third smelting on the fourth alloy liquid, adjusting the component proportion, slagging off, standing, pouring an ingot, homogenizing, and performing hot rolling, face milling, aging treatment, stretching and low-temperature annealing to obtain the brass alloy material.
5. The method of claim 4, wherein: the refining agent is industrial-grade rosin, salt and silica sand in a weight ratio of 1: 2-5: 8-10, and the addition amount of the refining agent is 0.1-1 per mill of the weight of the third alloy liquid.
6. The method according to claim 4 or 5, characterized in that: the aging treatment temperature is controlled to be 580 ℃ + f3The temperature is multiplied by 300000 ℃, is not higher than the hot rolling temperature of 835-880 ℃, and the time is 60-150 min.
7. The method according to any one of claims 4 to 6, wherein: the stretching control temperature is 605 ℃ + f3At a temperature of 180000 ℃, the stretching rate is 1-1.5 mm/min.
8. The method according to any one of claims 4 to 7, wherein: the low-temperature annealing temperature is controlled to be 220℃ + f3At the temperature of 150000 ℃ for 45-180 min, and then the temperature is reduced at a constant speed within 2.5 h.
9. Use of a brass alloy as claimed in any one of claims 1 to 8, including but not limited to:
1) the water pipe is applied to appliances for tap water pipes; and/or
2) Applied to industrial piping parts; and/or
3) For use in appliances that come into contact with liquids; and/or
4) Application in pressure vessels and fittings; and/or
5) The method is applied to components for automobiles; and/or
6) The method is applied to the electric product assembly.
Technical Field
The invention relates to the technical field of metal alloy materials, in particular to a high-strength wear-resistant brass alloy and a preparation method thereof.
Background
The copper alloy is formed by adding one or more other elements into pure copper serving as a matrix, and has good electrical conductivity, thermal conductivity, ductility and corrosion resistance. Commonly used copper alloys include brass, bronze, cupronickel. The brass is a copper alloy taking zinc as a main additive element, the high-strength brass alloy is widely applied in the world, and the high-strength brass alloy in the prior art has fewer types, such as ZHAL63-6-3-3 and ZHAL62-4-3-3 in China, 4-6% of aluminum, 3-4% of iron and 3% of manganese; american C86200 and C86300 contain 5-6% of aluminum, 3% of iron and 3% of manganese. The brass alloy has high aluminum and iron contents, and has poor mechanical property, corrosion resistance and high-temperature heat cracking resistance. Moreover, the brass alloys have the outstanding problems that the corrosion resistance is sharply reduced in the polluted environments such as atmosphere, steam, seawater and fresh water, the corrosion speed is high, the brass alloys are very sensitive to the corrosive environments such as atmosphere, steam, seawater and fresh water, and the service life of parts is greatly shortened.
Chinese patent ZL2004100158365 discloses a lead-free-cutting antimony brass alloy, which is a copper-zinc-antimony alloy, and because the alloy contains antimony, although the cutting performance and the corrosion resistance can be improved, the cold working performance of the alloy is not ideal, and the subsequent processing performance of the alloy is influenced. The relevant standards of drinking water have strict standards on the release amount of metals such As Sb, Pb, Cd, As and the like in water, for example, the maximum release amount of Sb is 0.6 mu g/L As specified in the US NSF/ANSI61-2007 drinking water standard. When the Sb content in the alloy is more than or equal to 0.2wt%, the leaching amount of the Sb exceeds 0.6 mu g/L, which is the biggest challenge of applying the antimony brass alloy to parts such as a water tap of a drinking water supply system and the like.
The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.
Disclosure of Invention
Objects of the invention
The invention aims to solve at least one technical problem mentioned in the background technology, and provides a brass alloy with excellent wear resistance, strong strength and hardness, which is formed by adding Cu, Mn, Co, Si, Pb, Al, Ni, Fe, Zn and other elements according to different proportions.
(II) technical scheme
In order to solve the above technical problems or to achieve the above technical object, the present invention provides the following technical solutions.
[1] A high strength, wear resistant brass alloy comprising:
Cu 55～60%；
Mn 2.0～4.0%；
Co 0.5～1.5%；
Si 2.0～4.0%；
Al 3.0～5.0%；
Ni 2.0～5.0%；
Fe 1.0～2.0%；
Pb 0.05～0.15%；
zn and the balance of inevitable impurities.
Preferably, the mass percentages of Mn and Co have the following definitions: f is not less than 3.051≤3.55，f1=PMn/PCoIn which P isMnIs the mass percent of Mn (Percentage by Weight), PCoIs the mass percentage of Co.
Preferably, the mass percentage of Si to Al has the following definitions: f is more than or equal to 80%2≤100%，f2=4×PSi/28+3×PAl/27 wherein PSiIs the molar amount of Si, PAlIs the mass percentage of Al.
Preferably, the mass percentages of Ni and Fe are defined as follows: f is not less than 0.36 ‰3≤0.65‰，f3=PNi×PFeIn which P isNiIs the mass percent of Ni, PFeIs the mass percentage of Fe.
General description of the inventionThrough deep experimental research, Mn, Co, Si, Pb, Al, Ni, Fe, Zn and other elements with different weight contents are added into copper to prepare the brass alloy with excellent wear resistance, strong strength and hardness, specifically, Mn is added, Co is cooperatively added, and P is controlled to be more than or equal to 3.05Mn/PCoLess than or equal to 3.55, wherein P isMn、PCoThe brass alloy is respectively the mass percentages of Mn and Co, and endows the brass alloy with certain ductility and stress corrosion resistance; the simultaneous addition and control of the mass percentages of Si and Al have the following limitations: 20.52 percent to 4 XPSi+3×PAlLess than or equal to 32.24 percent, wherein P isSi、PAlThe mass percentages of Si and Al are respectively, and the inventor researches show that when the mass percentages of Si and Al are defined as above, the obtained brass alloy has extremely excellent stress corrosion resistance, probably because the Si and Al respectively form compact and proper amount of oxidation films so as to remarkably improve the stress corrosion resistance and oxidation resistance of the alloy; in addition, the research finds that the mass percentage of Ni and Fe is limited to 0.36 per mill and less than or equal to PNi×PFeLess than or equal to 0.65%, wherein P isNi、PFeThe brass alloy has the characteristics of excellent wear resistance, strength and hardness according to the mass percentages of Ni and Fe respectively. According to the technical scheme, the brass alloy with excellent wear resistance, strong strength and hardness is obtained by limiting the contents of Mn, Co, Si, Pb, Al, Ni, Fe, Zn and other elements in the brass alloy, and meanwhile, the brass alloy also has certain stress corrosion resistance.
[2] A method for producing a brass alloy as recited in item [1], comprising:
1) weighing copper powder, copper-manganese intermediate alloy, cobalt powder, pure silicon, aluminum powder, nickel powder, iron powder, lead powder and zinc powder according to the proportion;
2) smelting copper powder and copper-manganese intermediate alloy, heating, sequentially adding the components according to the melting points from high to low, and carrying out first smelting to obtain first alloy liquid;
3) adding zinc powder and aluminum powder into the first alloy liquid to perform second smelting to obtain a second alloy liquid;
4) adding a phosphorus-copper deoxidizer into the second alloy liquid to perform degassing and deoxidation to obtain a third alloy liquid;
5) adding a refining agent into the third alloy liquid, and carrying out alloying refining to obtain a fourth alloy liquid;
6) and performing third smelting on the fourth alloy liquid, adjusting the component proportion, slagging off, standing, pouring an ingot, homogenizing, and performing hot rolling, face milling, aging treatment, stretching and low-temperature annealing to obtain the brass alloy material.
Preferably, the temperature of the first smelting is 1220-1240 ℃ and the time is 15-30 min.
Preferably, the temperature of the second smelting is 1125-1160 ℃ and the time is 10-20 min.
Preferably, the phosphorus-copper deoxidizer is CuP14 and phosphorus impurities, and the addition amount of the phosphorus-copper deoxidizer is 0.12-0.15 per mill of the weight of the second alloy liquid.
Preferably, the degassing and deoxidation temperature is 1125-1160 ℃ and the time is 2-10 min.
Preferably, the refining agent is industrial-grade rosin, salt and silica sand in a weight ratio of 1: 2-5: 8-10, and the addition amount of the refining agent is 0.1-1 per mill of the weight of the third alloy liquid.
Preferably, the temperature of alloying refining is 1150-1180 ℃ and the time is 2-5 min.
Preferably, the temperature of the third smelting is 1150-1180 ℃ and the time is 5-10 min.
Preferably, the chemical components are analyzed by a direct-reading spectrometer while adjusting the component ratios, and the component ratios are adjusted according to the analysis results.
Preferably, the casting temperature is 950-1050 ℃.
Preferably, the temperature of the homogenization treatment is 835-880 ℃, and the time is 30-45 min.
Preferably, the hot rolling temperature is 840-860 ℃.
Preferably, the milled surface is used for removing oxide skin on the surface of the alloy after hot rolling, and the milled surface is 0.5 mm-1.0 mm on the upper surface and the lower surface of the hot rolled plate.
Preferably, the aging treatment control temperature is 580 ℃ + f3X 300000 ℃, not higher than the hot rolling temperature and 60-150 min; control under the aging treatment conditions of the present application contributes to the formation of Ni and P compounds, and precipitates in the copper matrix in the form of fine particlesPrealloying for high strength and excellent processability; the aging treatment is beneficial to the formation of a silicon-manganese strengthening phase, and the strength and the hardness of the alloy are further improved; if the temperature is too high or the time is too long, precipitates are coarse, the matching of grain size and strengthening phase cannot be realized, otherwise, the precipitation is incomplete, the content of the strengthening phase is low, and the strength and the processing performance cannot be fully improved.
Preferably, the stretching control temperature is 605 ℃ + f3At the temperature of 180000 ℃, the stretching speed is 1-1.5 mm/min; if the stretching temperature is lower than 630 ℃, the thermoplasticity of the alloy is reduced, the alloy can not be extruded smoothly, and the stretching temperature is higher than 680 ℃, the material is over-burnt, the product quality can not be ensured, and under the stretching condition, the cast structure crystal grains are finer and more uniform, and the strength, the plasticity and the processability of the obtained brass alloy material are optimal.
Preferably, the low temperature annealing control temperature is 220 ℃ + f3At the temperature of 150000 ℃ for 45-180 min, and then the temperature is reduced at a constant speed within 2.5 h. Researches find that the low-temperature annealing at the temperature of the application is beneficial to the complete release of residual stress and the adjustment of the orientation of crystal grains; the low-temperature annealing is also beneficial to the improvement of the yield strength and the bending processing performance of the copper alloy; if the annealing temperature is too high, the strength is greatly reduced, and if the annealing temperature is too low, the residual stress cannot be sufficiently released.
[3] Use of a brass alloy according to item [1] or [2], including but not limited to:
1) the water pipe is applied to appliances for tap water pipes; and/or
2) Applied to industrial piping parts; and/or
3) For use in appliances that come into contact with liquids; and/or
4) Application in pressure vessels and fittings; and/or
5) The method is applied to components for automobiles; and/or
6) The method is applied to the electric product assembly.
The above-described preferred conditions may be combined with each other to obtain a specific embodiment, in accordance with common knowledge in the art.
The raw materials or reagents involved in the invention are all common commercial products, and the operations involved are all routine operations in the field unless otherwise specified.
(III) advantageous effects
According to the high-strength wear-resistant brass alloy, elements such as Mn, Co, Si, Pb, Al, Ni, Fe, Zn and the like are added on the basis of common brass, and meanwhile, aging treatment, stretching and low-temperature annealing processes are adopted, so that the microstructure of the brass alloy is greatly changed and is finer and more uniform, the obtained brass alloy is more excellent in wear resistance, higher in strength and hardness, and more outstanding in stress corrosion resistance and processability; concretely, Mn and Co are added in combination, and P is limited to 3.05. ltoreqMn/PCo3.55 or less, imparting excellent ductility and stress corrosion resistance to the brass alloy, adding Si in combination with Al, and limiting the content of 20.52% to 4 XPSi+3×PAl32.24% or less, and the inventors have found that the above-mentioned limitations of the mass percentage of Si to Al are likely to result from the formation of a dense and appropriate oxide film of Si and Al, respectively, to significantly improve the stress corrosion resistance and oxidation resistance of the alloy, and that Ni and Fe are added in combination to a predetermined mass percentage of 0.36% or less and PNi×PFeLess than or equal to 0.65 per mill, and the brass alloy has excellent wear resistance, strength and hardness.
When the high-strength wear-resistant brass alloy is prepared, after the required components are weighed, copper powder and a copper-manganese intermediate alloy are firstly smelted, the components are sequentially added according to the sequence of melting points from high to low after the temperature is raised, the mutual smelting among different melting points is facilitated, the matching balance of all strengthening phases of the alloy is facilitated to be improved, finally, zinc powder and aluminum powder are added and smelted to obtain alloy liquid, a phosphorus-copper deoxidizer is added for degassing and deoxidation, and then, a refining agent is added for alloying refining, so that the industrial-grade rosin, the salt and the silica sand which are specially matched are used as the refining agent of the brass alloy, the refining of ingot casting grains is facilitated, the ingot casting quality is improved, and the wear resistance, the strength and the processability of the brass alloy and; casting ingot after slagging off, and performing special aging treatment, stretching and low-temperature annealing process, specifically, controlling the aging treatment temperature of 580 ℃ + f3X 300000 deg.C, is helpful forThe Ni and P compounds are precipitated in a micro shape in the copper parent phase, so that a silicon-manganese strengthening phase is formed, and the alloy is endowed with higher strength, hardness and excellent processability; controlling the stretching temperature to be 605 ℃ + f3The tensile condition of the temperature of 180000 ℃ and the tensile rate of 1-1.5 mm/min is adopted, the crystal grains of the as-cast structure are finer and more uniform, and the strength, the plasticity and the processability of the obtained brass alloy material are optimal; the low-temperature annealing process control method comprises the following steps: temperature 220 ℃ + f3The temperature is multiplied by 150000 ℃, the time is 45-180 min, the temperature is reduced at a constant speed within 2.5h, and the like, thereby being beneficial to fully and thoroughly releasing the residual stress and adjusting the orientation of crystal grains and improving the mechanical strength of the brass alloy.
The invention adopts the technical scheme for achieving the purpose, makes up the defects of the prior art, and has reasonable design and convenient operation.
Drawings
The foregoing and/or other objects, features, advantages and embodiments of the invention will be more readily understood from the following description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic view of a process for preparing a high strength and wear resistant brass alloy in accordance with the present invention;
FIG. 2 is a metallographic microstructure of a brass alloy according to example 1 of the present invention;
FIG. 3 is an electron micrograph of a brass alloy according to example 1 of the present invention;
fig. 4 is a graph showing the wear resistance test wear amount of the brass alloy of the present invention.
Detailed Description
Those skilled in the art can appropriately substitute and/or modify the process parameters to implement the present disclosure, but it is specifically noted that all similar substitutes and/or modifications will be apparent to those skilled in the art and are deemed to be included in the present invention. While the products and methods of making described herein have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the products and methods of making described herein may be made and utilized without departing from the spirit and scope of the invention.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The present invention uses the methods and materials described herein; other suitable methods and materials known in the art may be used. The materials, methods, and examples described herein are illustrative only and are not intended to be limiting. All publications, patent applications, patents, provisional applications, database entries, and other references mentioned herein, and the like, are incorporated by reference herein in their entirety. In case of conflict, the present specification, including definitions, will control.
All percentages, parts, ratios, etc., are by weight unless otherwise indicated; additional instructions include, but are not limited to, "wt%" means weight percent, "mol%" means mole percent, "vol%" means volume percent.
When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5(1 to 5)" is described, the described range is understood to include ranges of "1 to 4(1 to 4)", "1 to 3(1 to 3)", "1 to 2(1 to 2) and 4 to 5(4 to 5)", "1 to 3(1 to 3) and 5", and the like. Where numerical ranges are described herein, unless otherwise stated, the ranges are intended to include the endpoints of the ranges, and all integers and fractions within the ranges.
When the term "about" is used to describe a numerical value or an end point value of a range, the disclosure should be understood to include the specific value or end point referred to.
Furthermore, "or" means "or" unless expressly indicated to the contrary, rather than "or" exclusively. For example, condition a "or" B "applies to any of the following conditions: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), and both a and B are true (or present).
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to mean no limitation on the number of occurrences (i.e., occurrences) of the element or component. Thus, "a" or "an" should be understood to include one or at least one and the singular forms of an element or component also include the plural unless the singular is explicitly stated.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation. The use of the phrase "comprising one of the elements does not exclude the presence of other like elements in the process, method, article, or apparatus that comprises the element.
The materials, methods, and examples described herein are illustrative only and not intended to be limiting unless otherwise specified. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.
The present invention is described in detail below.
Example 1:
the embodiment provides a high-strength wear-resistant brass alloy, which comprises:
Cu 58.5%；
Mn 2.7%；
Co 0.8%；
Si 3.2%；
Al 3.6%；
Ni 2.8%；
Fe 1.5%；
Pb 0.1%；
zn and the balance of inevitable impurities.
Wherein the content of the first and second substances,
f1=PMn/PCo=3.375；
f2=4×PSi/28+3×PAl/27=23.6%；
f3=PNi×PFe=0.42‰。
weighing copper powder, copper-manganese intermediate alloy, cobalt powder, pure silicon, aluminum powder, nickel powder, iron powder, lead powder and zinc powder according to the proportion; smelting copper powder and copper-manganese intermediate alloy, heating, sequentially adding the components according to the melting points from high to low, and carrying out first smelting to obtain first alloy liquid; adding zinc powder and aluminum powder into the first alloy liquid to perform second smelting to obtain a second alloy liquid; adding a phosphorus-copper deoxidizer into the second alloy liquid to perform degassing and deoxidation to obtain a third alloy liquid; adding a refining agent into the third alloy liquid, and carrying out alloying refining to obtain a fourth alloy liquid; thirdly smelting the fourth alloy liquid, adjusting the component proportion, slagging off, standing, pouring an ingot, homogenizing, and obtaining the brass alloy material through hot rolling, surface milling, aging treatment, stretching and low-temperature annealing;
wherein the content of the first and second substances,
the temperature of the first melting is 1225 ℃ and the time is 20 min;
the temperature of the second melting is 1150 ℃ and the time is 15 min;
the phosphorus-copper deoxidizer is CuP14, and the addition amount is 0.14 per mill of the weight of the second alloy liquid;
degassing and deoxidizing at 1155 ℃ for 4 min;
the refining agent is industrial grade rosin, salt and silica sand with the weight ratio of 1:5:9, and the addition amount is 0.2 per mill of the weight of the third alloy liquid;
the temperature of alloying refining is 1155 ℃, and the time is 3 min;
the temperature of the third smelting is 1165, and the time is 10 min;
the casting temperature is 980 ℃;
the homogenization temperature is 880 ℃ and the homogenization time is 45 min;
the hot rolling temperature is 850 ℃;
milling surfaces for removing oxide skin on the surface of the alloy after hot rolling, wherein the upper milling surface and the lower milling surface of the hot rolled plate are 0.5 mm;
the aging treatment temperature is controlled to be 580 ℃ + f3X 300000 deg.C =706 deg.C, for 120 min;
the stretching temperature was 605 ℃ + f3X 180000 deg.C =680 deg.C, and the stretching rate is 1 mm/min;
the low temperature annealing temperature is 220 ℃ + f3X 150000 deg.C =283 deg.C for 180min, and then cooling at constant speed within 2.5 h.
The metallographic microstructure of the brass alloy obtained in this example is shown in fig. 1, and it can be seen from fig. 1 that the α phase is needle-like and dendritic, and in addition, many fine complex silicides of silicon and manganese are present in the α phase grain boundaries and crystals; it can be seen from the electron micrograph of fig. 2 that the α phase is the main phase, a small amount of β phase, and regular-shaped silicomanganese phase with different sizes exist, and the single phase rarely connects with α. A fine white rod-like phase of about 0.5 μm was found in the alpha phase matrix, with only two orientations perpendicular to each other. The brass alloy in the embodiment contains extremely low elements such as lead, so the detected precipitation amount of alloy elements in water meets the NSF/ANSI61-2007 standard. It can be seen that the brass alloy of the present example has excellent strength and hardness.
Example 2:
embodiment 2 provides a series of brass alloys, which are marked as 2# to 12 #; the brass alloy of example 1 is marked as # 1, and the detailed mixture ratio content is shown in table 1.
TABLE 1 Brass alloy ratio content
The series of brass alloys described in embodiment # 2 to 12# are all prepared by the same method as embodiment 1, that is, the aging treatment temperature is 706 ℃, and the time is 120 min; the stretching temperature is 680 ℃ and the stretching speed is 1 mm/min; the low temperature annealing temperature was 283 ℃.
Example 3:
embodiment 3 provides a high-strength wear-resistant brass alloy, which is marked as # 13:
Cu 58.5%；
Mn 2.7%；
Co 0.8%；
Si 3.2%；
Al 3.6%；
Ni 2.8%；
Fe 1.5%；
Pb 0.1%；
zn and the balance of inevitable impurities.
Wherein the content of the first and second substances,
f1=PMn/PCo=3.375；
f2=4×PSi/28+3×PAl/27=23.6%；
f3=PNi×PFe=0.42‰。
weighing copper powder, copper-manganese intermediate alloy, cobalt powder, pure silicon, aluminum powder, nickel powder, iron powder, lead powder and zinc powder according to the proportion; smelting copper powder and copper-manganese intermediate alloy, heating, sequentially adding the components according to the melting points from high to low, and carrying out first smelting at 1225 ℃ for 20min to obtain first alloy liquid; adding zinc powder and aluminum powder into the first alloy liquid, and carrying out second smelting at 1150 ℃ for 15min to obtain a second alloy liquid; adding a phosphorus-copper deoxidizer CuP14 which is 0.14 per mill of the weight of the second alloy liquid into the second alloy liquid, and degassing and deoxidizing at 1155 ℃ for 4min to obtain a third alloy liquid; adding a refining agent (a mixture of cryolite, fluorite, silica sand, sodium fluoride and borax in a weight ratio of 4:2:1:2: 1) which is 0.2 per mill of the weight of the third alloy liquid into the third alloy liquid, and carrying out alloying refining at 1155 ℃ for 3min to obtain a fourth alloy liquid; performing third smelting on the fourth alloy liquid at 1165 ℃ for 10min, adjusting the component proportion, slagging off, standing, pouring an ingot at 980 ℃, homogenizing at 880 ℃ for 45min, hot rolling at 850 ℃, removing oxide skin on the surface of the alloy after hot rolling by milling 0.5mm on the upper surface and the lower surface of a hot rolled plate, aging at 706 ℃ for 120min, stretching at 680 ℃ at a speed of 1mm/min, annealing at 283 ℃ for 180min, and then uniformly cooling within 2.5h to obtain the brass alloy material.
Example 4:
embodiment 4 provides a high-strength wear-resistant brass alloy, which is marked as # 14, and the mixture ratio of the brass alloy is completely the same as that of embodiment 3, and copper powder, copper-manganese intermediate alloy, cobalt powder, pure silicon, aluminum powder, nickel powder, iron powder, lead powder and zinc powder are weighed according to the mixture ratio; smelting copper powder and copper-manganese intermediate alloy, heating, sequentially adding the components according to the melting points from high to low, and carrying out first smelting at 1225 ℃ for 20min to obtain first alloy liquid; adding zinc powder and aluminum powder into the first alloy liquid, and carrying out second smelting at 1150 ℃ for 15min to obtain a second alloy liquid; adding a phosphorus-copper deoxidizer CuP14 which is 0.14 per mill of the weight of the second alloy liquid into the second alloy liquid, and degassing and deoxidizing at 1155 ℃ for 4min to obtain a third alloy liquid; adding a refining agent (a mixture of salt and silica sand in a weight ratio of 5: 9) which is 0.2 per mill of the weight of the third alloy liquid into the third alloy liquid, and carrying out alloying refining at 1155 ℃ for 3min to obtain a fourth alloy liquid; adding a refining agent (a mixture of industrial grade rosin, salt and silica sand in a weight ratio of 1:5: 9) which is 0.2 per mill of the weight of the third alloy liquid into the fourth alloy liquid, and carrying out alloying refining at 1155 ℃ for 3min to obtain a fourth alloy liquid; performing third smelting on the fourth alloy liquid at 1165 ℃ for 10min, adjusting the component proportion, slagging off, standing, pouring an ingot at 980 ℃, homogenizing at 880 ℃ for 45min, hot rolling at 850 ℃, removing oxide skin on the surface of the alloy after hot rolling by milling 0.5mm on the upper surface and the lower surface of a hot rolled plate, aging at 706 ℃ for 120min, stretching at 680 ℃ at a speed of 1mm/min, annealing at 283 ℃ for 180min, and then uniformly cooling within 2.5h to obtain the brass alloy material.
Example 5:
embodiment 5 provides a high-strength wear-resistant brass alloy, which is marked as # 15, and the mixture ratio of the brass alloy is completely the same as that of embodiment 3, and copper powder, copper-manganese intermediate alloy, cobalt powder, pure silicon, aluminum powder, nickel powder, iron powder, lead powder and zinc powder are weighed according to the mixture ratio; smelting copper powder and copper-manganese intermediate alloy, heating, adding other components except the zinc powder and the aluminum powder, and performing first smelting at 1225 ℃ for 20min to obtain first alloy liquid; adding zinc powder and aluminum powder into the first alloy liquid, and carrying out second smelting at 1150 ℃ for 15min to obtain a second alloy liquid; adding a phosphorus-copper deoxidizer CuP14 which is 0.14 per mill of the weight of the second alloy liquid into the second alloy liquid, and degassing and deoxidizing at 1155 ℃ for 4min to obtain a third alloy liquid; adding a refining agent (a mixture of industrial grade rosin, salt and silica sand in a weight ratio of 1:5: 9) which is 0.2 per mill of the weight of the third alloy liquid into the third alloy liquid, and carrying out alloying refining at 1155 ℃ for 3min to obtain a fourth alloy liquid; performing third smelting on the fourth alloy liquid at 1165 ℃ for 10min, adjusting the component proportion, slagging off, standing, pouring an ingot at 980 ℃, homogenizing at 880 ℃ for 45min, hot rolling at 850 ℃, removing oxide skin on the surface of the alloy after hot rolling by milling 0.5mm on the upper surface and the lower surface of a hot rolled plate, aging at 706 ℃ for 120min, stretching at 680 ℃ at a speed of 1mm/min, annealing at 283 ℃ for 180min, and then uniformly cooling within 2.5h to obtain the brass alloy material.
Example 6:
embodiment 6 provides a high-strength wear-resistant brass alloy, which is denoted by # 16, and the mixture ratio thereof is completely the same as that in embodiment 3, and copper powder, copper-manganese intermediate alloy, cobalt powder, pure silicon, aluminum powder, nickel powder, iron powder, lead powder and zinc powder are weighed according to the mixture ratio; smelting copper powder and copper-manganese intermediate alloy, heating, sequentially adding the components according to the melting points from high to low, and carrying out first smelting at 1225 ℃ for 20min to obtain first alloy liquid; adding zinc powder and aluminum powder into the first alloy liquid, and carrying out second smelting at 1150 ℃ for 15min to obtain a second alloy liquid; adding a phosphorus-copper deoxidizer CuP14 which is 0.14 per mill of the weight of the second alloy liquid into the second alloy liquid, and degassing and deoxidizing at 1155 ℃ for 4min to obtain a third alloy liquid; adding a refining agent (a mixture of industrial grade rosin, salt and silica sand in a weight ratio of 1:5: 9) which is 0.2 per mill of the weight of the third alloy liquid into the third alloy liquid, and carrying out alloying refining at 1155 ℃ for 3min to obtain a fourth alloy liquid; adding a refining agent (a mixture of industrial grade rosin, salt and silica sand in a weight ratio of 1:5: 9) which is 0.2 per mill of the weight of the third alloy liquid into the fourth alloy liquid, and carrying out alloying refining at 1155 ℃ for 3min to obtain a fourth alloy liquid; and thirdly smelting the fourth alloy liquid at 1165 ℃ for 10min, adjusting the component proportion, slagging off, standing, pouring an ingot at 980 ℃, homogenizing at 880 ℃ for 45min, hot rolling at 850 ℃, removing oxide skin on the surface of the alloy after hot rolling by milling 0.5mm on the upper surface and the lower surface of a hot rolled plate, aging at 680 ℃ for 120min, drawing at 680 ℃ at a speed of 1mm/min, annealing at 283 ℃ for 180min, and then uniformly cooling within 2.5h to obtain the brass alloy material.
Example 7:
embodiment 7 provides a high-strength wear-resistant brass alloy, which is denoted as # 17, and the mixture ratio thereof is completely the same as that in embodiment 3, and copper powder, copper-manganese intermediate alloy, cobalt powder, pure silicon, aluminum powder, nickel powder, iron powder, lead powder and zinc powder are weighed according to the mixture ratio; smelting copper powder and copper-manganese intermediate alloy, heating, sequentially adding the components according to the melting points from high to low, and carrying out first smelting at 1225 ℃ for 20min to obtain first alloy liquid; adding zinc powder and aluminum powder into the first alloy liquid, and carrying out second smelting at 1150 ℃ for 15min to obtain a second alloy liquid; adding a phosphorus-copper deoxidizer CuP14 which is 0.14 per mill of the weight of the second alloy liquid into the second alloy liquid, and degassing and deoxidizing at 1155 ℃ for 4min to obtain a third alloy liquid; adding a refining agent (a mixture of industrial grade rosin, salt and silica sand in a weight ratio of 1:5: 9) which is 0.2 per mill of the weight of the third alloy liquid into the third alloy liquid, and carrying out alloying refining at 1155 ℃ for 3min to obtain a fourth alloy liquid; performing third smelting on the fourth alloy liquid at 1165 ℃ for 10min, adjusting the component proportion, slagging off, standing, pouring an ingot at 980 ℃, homogenizing at 880 ℃ for 45min, hot rolling at 850 ℃, removing oxide skin on the surface of the alloy after hot rolling by milling 0.5mm on the upper surface and the lower surface of a hot rolled plate, aging at 706 ℃ for 120min, stretching at 660 ℃ at a speed of 1mm/min, annealing at 283 ℃ for 180min, and then uniformly cooling within 2.5h to obtain the brass alloy material.
Example 8:
embodiment 8 provides a high-strength wear-resistant brass alloy, which is marked as # 18, and the mixture ratio thereof is completely the same as that in embodiment 3, and copper powder, copper-manganese intermediate alloy, cobalt powder, pure silicon, aluminum powder, nickel powder, iron powder, lead powder and zinc powder are weighed according to the mixture ratio; smelting copper powder and copper-manganese intermediate alloy, heating, sequentially adding the components according to the melting points from high to low, and carrying out first smelting at 1225 ℃ for 20min to obtain first alloy liquid; adding zinc powder and aluminum powder into the first alloy liquid, and carrying out second smelting at 1150 ℃ for 15min to obtain a second alloy liquid; adding a phosphorus-copper deoxidizer CuP14 which is 0.14 per mill of the weight of the second alloy liquid into the second alloy liquid, and degassing and deoxidizing at 1155 ℃ for 4min to obtain a third alloy liquid; adding a refining agent (a mixture of industrial grade rosin, salt and silica sand in a weight ratio of 1:5: 9) which is 0.2 per mill of the weight of the third alloy liquid into the third alloy liquid, and carrying out alloying refining at 1155 ℃ for 3min to obtain a fourth alloy liquid; performing third smelting on the fourth alloy liquid at 1165 ℃ for 10min, adjusting the component proportion, slagging off, standing, pouring an ingot at 980 ℃, homogenizing at 880 ℃ for 45min, hot rolling at 850 ℃, removing oxide skin on the surface of the alloy after hot rolling by milling 0.5mm on the upper surface and the lower surface of a hot rolled plate, aging at 706 ℃ for 120min, stretching at 680 ℃ at the speed of 1mm/min, annealing at 303 ℃ for 180min, and then uniformly cooling within 2.5h to obtain the brass alloy material.
Experimental example 1:
the mechanical properties of brass alloy materials 1# to 18# in the embodiments of the present application were tested with the ZHAL63-6-3-3(C) brass alloy as a reference, and the test results are shown in Table 2.
TABLE 2 mechanical properties of the brass alloys
Model number
Tensile Strength/KPa
Elongation/percent
Brinell hardness
Whether NSF/ANSI61-2007 is satisfied
C
457.5
16.8
105
Is that
1#
698.4
26.5
176
Is that
2#
702.1
24.3
169
Is that
3#
694.0
27.2
173
Is that
4#
689.2
26.7
172
Is that
5#
670.5
21.9
165
Is that
6#
662.7
23.9
168
Is that
7#
569.2
21.5
145
Is that
8#
642.0
20.7
160
Is that
9#
508.4
18.2
138
Is that
10#
522.7
18.9
134
Is that
11#
486.1
17.4
126
Is that
12#
690.6
25.5
170
Whether or not
13#
695.2
27.5
178
Is that
14#
671.4
24.9
155
Is that
15#
666.8
26.8
162
Is that
16#
618.5
25.4
167
Is that
17#
624.1
23.3
161
Is that
18#
620.9
27.0
155
Is that
From the statistical results of the mechanical properties of the brass alloys in table 2, the brass alloys 1#, 2#, 3#, 4#, and 13# have excellent strength, hardness and elongation, and 12# has excellent mechanics but does not meet the lead release standard of NSF/ANSI 61-2007; in addition, the proportion of samples 1# and 5# to 11# is combined to show that the contents of Mn, Co, Si, Al, Ni, Fe and other elements and the content relationship between the elements have obvious influence on the mechanical property of the brass alloy, particularly the influence of the mass percent of Ni and Fe is more serious; and the combination of the process conditions of No. 1 and No. 14-18 shows that the selection of the refining agent, the addition sequence of each metal element, the aging treatment, the temperature selection of the stretching and low-temperature annealing process have important relations to the strength, the elongation and the hardness of the brass alloy. Particularly, comparative analysis on No. 1 and No. 14 shows that the refining agent containing the industrial rosin, the salt and the silica sand in special proportions has positive significance for improving the mechanical property of the brass alloy.
Experimental example 2:
the stress corrosion resistance of brass alloy materials 1# to 18# in the embodiments of the present application was tested with ZHAl63-6-3-3(C) brass alloy as reference: the method comprises the steps of dividing brass materials into 1-inch ball valves, assembling products by fastening torque of 90 N.m, dividing the assembled products into a no-load non-connected external pipe and a torque-applied external pipe, applying the torque of 140 N.m, soaking the products in 7% and 14% ammonia water for 48 hours at 25 ℃, taking out the products, washing the products with water, cleaning the surfaces of the products with 5% sulfuric acid solution at room temperature to remove corrosion dirt, washing the products with water, drying the products, observing the surfaces of the products with a magnifier, representing the product with O if no obvious cracks exist on the surfaces of the products, representing the product with delta if the surfaces of the products have the tiny cracks, representing the product with L if the surfaces of the products have the obvious cracks, and displaying statistical results in a table 3.
TABLE 3 stress corrosion resistance
As can be seen from Table 3, the brass alloys 1#, 2#, 3#, 4#, and 13# preferred in the present application have excellent stress corrosion resistance, and comparative analyses of 1#, 5#, and 11# show that the mass relationship between Mn and Co and the mass relationship between Si and Pb have an important influence on the stress corrosion resistance of the brass alloys, and P is 3.05 ≦ PMn/PCoLess than or equal to 3.55 percent and less than or equal to 20.52 percent and less than or equal to 4 XPSi+3×PAlThe limitation of less than or equal to 32.24 percent is beneficial to improving the stress corrosion resistance of the brass alloy. The selection of the refining agent, the addition sequence of each metal element and the aging treatment can be known by combining the process conditions of No. 1 and No. 14 to No. 18The temperature of the drawing, particularly the low-temperature annealing process, is selected to have certain correlation with the stress corrosion resistance of the brass alloy.
Experimental example 3:
the wear resistance of brass alloy materials 1# to 18# in the embodiments of the present application was tested with ZHAl63-6-3-3(C) brass alloy as reference: the test is carried out on an M200 abrasion tester, the test method refers to GB/T12444-2006, and the test result is shown in figure 4. As can be seen from FIG. 4, the brass alloys 1#, 2#, 3#, 4#, and 13# preferred in the present application have excellent wear resistance, and comparative analysis of 5# to 11# brass alloys shows that Ni and Fe are added in combination and the mass percentage of the alloy is limited to 0.36 ‰ PNi×PFeLess than or equal to 0.65 per mill has important significance on the wear resistance of the brass alloy; the comparative analysis of 13# to 18# brass alloy shows that the proper refining agent is selected, and the temperature is 580 ℃ + f3X 300000 ℃ aging treatment temperature, 605 ℃ + f3X 180000 deg.C, especially 220 deg.C + f3The low-temperature annealing temperature of x 150000 ℃ can obviously improve the wear resistance of the brass alloy.
Experimental example 4:
the machinability of brass alloy materials 1# to 18# in the present embodiment was tested with ZHAL63-6-3-3(C) brass alloy as reference according to the method for measuring the casting performance of alloy JBT4022.2-1999, and the results are shown in Table 4.
TABLE 4 processability
As can be seen from Table 4, the brass alloys 1#, 2#, 3#, 4#, 13# preferred in the present invention have excellent processability, the yield can be controlled within 99%, the alloys 11%, 15# -18 # with lower yield can be compared and analyzed, the mutual relationship of the weight contents of metals such as Mn, Co, Si, Al, Ni, Fe and the like and the melting point can be sequentially added from high to low during melting, and the aging treatment temperature is controlled to 580 ℃ + f3X 300000 ℃, and the stretching temperature is controlled to be 605 ℃ + f3X 180000 ℃, low-temperature annealing temperature is controlled to be 220 ℃ + f3The processing performance of the brass alloy is obviously influenced by processes such as multiplied by 150000 ℃ and the like. Therefore, according to the composition ratio of the components of the brass alloy and the process control of the preparation method, the brass alloy with excellent wear resistance, stronger strength and hardness and good processability can be obtained.
In the above embodiments and alternatives, f1=PMn/PCoMay be any one of 3.05, 3.06, 3.07, 3.08, 3.09, 3.10, 3.11, 3.12, 3.13, 3.14, 3.15, 3.16, 3.17, 3.18, 3.19, 3.20, 3.21, 3.22, 3.23, 3.24, 3.25, 3.26, 3.27, 3.28, 3.29, 3.30, 3.31, 3.32, 3.33, 3.34, 3.35, 3.36, 3.37, 3.38, 3.39, 3.40, 3.41, 3.42, 3.43, 3.44, 3.45, 3.46, 3.47, 3.48, 3.49, 3.50, 3.51, 3.52, 3.53, 3.54, 3.55, 3.05, 3.45, 3.55, 3.05, 3.45, 3.55, 3.20, 3.05, 3.55, 3.45, 3.55, 3.20, 3.05, 3.45, 3.55, 3.20, 3.55, 3.20, 3.45, 3.55, 3.05, 3.45, 3.55, 3.20, 3.05, 3.45, 3.20, 3.55, 3.20, 3.05, 3.20, 3.55, 3.20, 3.55, 3.05, 3.55, 3.20, 3.55, 3., 3.05 to 3.35, 3.10 to 3.35, 3.15 to 3.35, 3.20 to 3.35, 3.25 to 3.35, 3.30 to 3.35, 3.05 to 3.30, 3.10 to 3.30, 3.15 to 3.30, 3.20 to 3.30, 3.25 to 3.30, 3.05 to 3.25, 3.10 to 3.25, 3.15 to 3.25, 3.20 to 3.25, 3.05 to 3.20, 3.10 to 3.20, 3.15 to 3.20, 3.05 to 3.15, 3.10 to 3.15, and 3.05 to 3.10.
In the above examples and alternatives, f is 80% ≦ f2Less than or equal to 100 percent can also be any value of 80 percent, 81 percent, 82 percent, 83 percent, 84 percent, 85 percent, 86 percent, 87 percent, 88 percent, 89 percent, 90 percent, 91 percent, 92 percent, 93 percent, 94 percent, 95 percent, 96 percent, 97 percent, 98 percent, 100 percent and any value between any two values, and can also be any value of 80 percent to 100 percent, 82 percent to 100 percent, 84 percent to 100 percent, 86 percent to 100 percent, 88 percent to 100 percent, 90 percent to 100 percent, 92 percent to 100 percent, 94 percent to 100 percent, 96 percent to 100 percent, 98 percent to 100 percent, 80 percent to 98 percent82% -98%, 84% -98%, 86% -98%, 88% -98%, 90% -98%, 92% -98%, 94% -98%, 96% -98%, 80% -96%, 82% -96%, 84% -96%, 86% -96%, 88% -96%, 90% -96%, 92% -96%, 94% -96%, 80% -94%, 82% -94%, 84% -94%, 86% -94%, 88% -94%, 90% -94%, 92% -94%, 80% -92%, 82% -92%, 84% -92%, 86% -92%, 88% -92%, 90% -92%, 80% -90%, 82% -90%, 84% -90%, 86% -90%, 88% -90%, 80% -88%, 82% -88%, 88% -88%, 84% -88%, 86% -88%, 80% -86%, 80% -84%, 82% -48%, Any value in any interval of 80% -82%.
In the above embodiments and alternatives, f3=PNi×PFeMay also be any value or any value between any two values of 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.60, 0.61, 0.62, 0.63, 0.64, 0.65, 0.36-0.65, 0.38-0.65, 0.40-0.65, 0.42-0.65, 0.44-0.65, 0.46-0.65, 0.48-0.65, 0.65-0.64, 0.64-0.64, 0.65, 0.64-0.65, 0.64-0.64, 0.65-0.65, 0.60-0.65, 0.60-0.64, 0.65, 0.60-0.65, 0.60-0.65, 0.60-0.65, 0.60-0.60, 0.65, 0.60-0.60, 0.65, 0.60-0.60, 0.65, 0., 0.36-0.62%, 0.38-0.62%, 0.40-0.62%, 0.42-0.62%, 0.44-0.62%, 0.46-0.62%, 0.48-0.62%, 0.50-0.62%, 0.52-0.62%, 0.54-0.62%, 0.56-0.62%, 0.58-0.62%, 0.60-0.62%, 0.36-0.60%, 0.38-0.60%, 0.40-0.60%, 0.42-0.60%, 0.44-0.60%, 0.36-60%, 0.38-0.60%, 0.40-60%, 0.60-60%, 0.42-0.60%, 0.44-0.60%, 0.60-60.60%, 0.60-60%, 0.60-60.60%, 60-60%, 60.60-60%, 60-60%, 60-60%, 60-60, 60-60, 600.58-0.58, 0.38-0.58, 0.40-0.58, 0.42-0.58, 0.44-0.58, 0.46-0.58, 0.48-0.58, 0.50-0.58, 0.52-0.58, 0.54-0.58, 0.56-0.58, 0.36-0.56, 0.38-0.56, 0.40-0.56, 0.42-0.56, 0.44-0.56, 0.46-0.56, 0.48-0.56, 0.38-0.58, 0.56-0.56, 0.38-0.56, 0.40-0.56, 0.42-0.56, 50-0.56, 0.44-0.52, 54-0.56, 50-0.56, 50-0.56, 0.52-0.56, or, 0.48-0.50%, 0.36-0.48%, 0.38-0.48%, 0.40-0.48%, 0.42-0.48%, 0.44-0.48%, 0.46-0.48%, 0.36-0.46%, 0.38-0.46%, 0.40-0.46%, 0.42-0.44%, 0.44-0.46%, 0.36-0.46%, 0.38-0.44%, 0.40-0.44%, 0.42-0.44%, 0.36-0.42%, 0.38-0.42%, 0.40-0.42%, 0.38-0.42%, 0.42-0.42%, 0.38-0.42%, 0.40-0.40%, 0.42-40.42%, 0.42-40%, and any range of the values of the above.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
In view of the numerous embodiments of the present invention, the experimental data of each embodiment is huge and is not suitable for being listed and explained herein one by one, but the contents to be verified and the final conclusions obtained by each embodiment are close. Therefore, the contents of the verification of the respective examples are not described herein, and the excellent points of the present invention will be described only by examples 1 to 8 and experimental examples 1 to 4.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
While the above detailed description has shown, described, and pointed out novel features as applied to various embodiments, it will be understood that various omissions, substitutions, and changes in the form and details of the device or method illustrated may be made without departing from the spirit of the disclosure. In addition, the various features and methods described above may be used independently of one another, or may be combined in various ways. All possible combinations and sub-combinations are intended to fall within the scope of the present disclosure. Many of the embodiments described above include similar components, and thus, these similar components are interchangeable in different embodiments. While the invention has been disclosed in the context of certain embodiments and examples, it will be understood by those skilled in the art that the invention extends beyond the specifically disclosed embodiments to other alternative embodiments and/or uses and obvious modifications and equivalents thereof. Accordingly, the invention is not intended to be limited by the specific disclosure of preferred embodiments herein.
The invention is not the best known technology.
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