CN107299249A - A kind of unleaded bell metal of old material regeneration and preparation method thereof - Google Patents
A kind of unleaded bell metal of old material regeneration and preparation method thereof Download PDFInfo
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- CN107299249A CN107299249A CN201710711000.6A CN201710711000A CN107299249A CN 107299249 A CN107299249 A CN 107299249A CN 201710711000 A CN201710711000 A CN 201710711000A CN 107299249 A CN107299249 A CN 107299249A
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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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- 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
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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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
- C22C9/02—Alloys based on copper with tin as the next major constituent
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Abstract
The invention provides a kind of unleaded bell metal of old material regeneration, belong to unleaded bell metal field.The manufacturing cost of the unleaded bell metal of old material regeneration of the present invention is the 80% of newborn resource alloyage, and with excellent casting character, Cutting free, decay resistance, and meet the requirement of International Environmental Protection health and safety standard, it is adapted to extensive low pressure, gravity foundry technology, available for part of the long period of soaking in water environment, especially decay resistance, cavitation-corrosion-resistant ability are more prominent in acid or alkaline aquatic environment.The as shown by data of embodiment, the tensile strength of the unleaded bell metal of old material regeneration of the present invention improves 25%, elongation percentage improves 45%, the perfect recrystallization temperature of alloy brings up to more than 500 DEG C, the resistance to corrosion fatigue limit can improve more than 18%, resistance to corrosion fatigue intensity improves 30%, and aluminium alloy mobility improves 30~40%, and cavitation-corrosion-resistant performance improves 50%.
Description
Technical field
The present invention relates to unleaded bell metal field, more particularly to a kind of unleaded bell metal of old material regeneration and its preparation
Method.
Background technology
Leaded bronze alloy is widely used in machine-building, electrical instrumentation, architectural hardware and potable water system tap, valve
The fields such as water pump pipe fitting, the harm to the mankind and environment increasingly shows, it has also become the social concern of people's common concern.Each international politics
The use limitation order to copper alloy containing lead is successively put into effect in mansion.The U.S. provides that lead leaching content in drinking water is less than 0.001mg/L,
Japan is less than 0.01mg/L, and the Chinese government is also made laws,《Electronics and IT products prevention and cure of pollution management method》Etc. mandatory
Regulation.Electronics and IT products lead tolerance is necessarily less than 0.1%.
At present, successively research and development both at home and abroad is unleaded bell metal, and the unleaded bell metal C89325 in such as U.S. is stanniferous
10%th, bismuth 3.2%, C89835 stanniferous 6.7%, bismuth 2.0%, C89833 stanniferous 5%, bismuth 2.0%；The unleaded bell metal of Japan
CAC903C, CAC902C and CAC911C are containing 6% tin, 3~3.5% bismuth；The unleaded bell metal ZQSn10-1 of China with
And ZQSn10-2 contains 9~11% tin.Above-mentioned alloy uses substantial amounts of noble metal refined tin and refined bismuth, not only expensive, and
Immersion corrosion resistance is poor in acid, alkaline aquatic environment.
The content of the invention
In view of this, it is an object of the invention to provide unleaded bell metal of a kind of old material regeneration and preparation method thereof.
The present invention utilizes the unleaded bell metal of old material regeneration, not only reduces cost, and obtained old material regeneration is closed without Allen's metal
Golden excellent anti-corrosion performance.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
A kind of unleaded bell metal of old material regeneration, includes the element of following mass percent：
Tin 2.1~5.1%, zinc 4.1~11%, bismuth 0.5~2.8%, selenium≤0.15%, nickel≤1.2%, boron 0.01~
0.1%, titanium 0.01~0.1%, zirconium 0.01~0.1%, mischmetal 0.005~0.05%, lead≤0.03%, iron≤
0.25%, phosphorus≤0.04%, silicon≤0.0015%, aluminium≤0.0015%, the copper of surplus；
The mischmetal includes the component of following mass percent：Lanthanum 40~50%, cerium 50~55%, praseodymium 4~10%,
Neodymium≤1.0%.
Preferably, the unleaded bell metal of the old material regeneration, includes the element of following mass percent：
Tin 2.7~4.6%, zinc 5.1~9.5%, bismuth 1.0~2.0%, selenium≤0.1%, nickel≤1.0%, boron 0.05~
0.07%, titanium 0.03~0.04%, zirconium 0.03~0.08%, mischmetal 0.01~0.015%, lead≤0.02%, iron≤
0.2%, phosphorus≤0.02%, silicon≤0.0013%, aluminium≤0.0012%, the copper of surplus.
Preferably, the unleaded bell metal of the old material regeneration, includes the element of following mass percent：
Tin 3.6~4.2%, zinc 6.5~7.5%, bismuth 1.5~1.7%, selenium≤0.08%, nickel≤0.8%, boron 0.03~
0.04%, titanium 0.03~0.04%, zirconium 0.04~0.05%, mischmetal 0.01~0.015%, lead≤0.01%, iron≤
0.15%, phosphorus≤0.01%, silicon≤0.001%, aluminium≤0.001%, the copper of surplus.
Present invention also offers the preparation method of the unleaded bell metal of old material regeneration described in above-mentioned technical proposal, including with
Lower step：
(1) Pb-free copper-alloy waste material and destructive distillation charcoal are subjected to the first melting, obtain fused materials；
(2) fused materials for obtaining the step (1) are refined after being mixed with refining agent, obtain refining material；
(3) the is carried out after the refining material that obtains the step (2), boron source, titanium source, zirconium source and mischmetal mixing
Two meltings, obtain the unleaded bell metal of old material regeneration.
Preferably, the consumption of destructive distillation charcoal is 2~3cm of covering Pb-free copper-alloy waste material in the step (1).
Preferably, refining agent includes the composition of following mass percent in the step (2)：Fluorite 35~45%, carbonic acid
Sodium 25~35%, ice crystal 10~20%, calcium carbonate 10~20%.
Preferably, the consumption of refining agent is the 0.15~0.4% of fused materials quality in the step (2).
Preferably, the temperature of refining is 1100~1150 DEG C in the step (2), and the time of the refining is 12~24h.
Preferably, also include preheating the boron source, titanium source and zirconium source before step (3) mixing, the boron source, titanium
The preheating temperature in source and zirconium source independently is 140~160 DEG C.
Preferably, also include preheating the mischmetal before the step (3) mixing, the preheating of the mischmetal
Temperature is 110~130 DEG C.
The invention provides a kind of unleaded bell metal of old material regeneration, include the element of following mass percent：Tin 2.1
~5.1%, zinc 4.1~11%, bismuth 0.5~2.8%, selenium≤0.15%, nickel≤1.2%, boron 0.01~0.1%, titanium 0.01~
0.1%, zirconium 0.01~0.1%, mischmetal 0.005~0.05%, lead≤0.03%, iron≤0.25%, phosphorus≤0.04%, silicon
≤ 0.0015%, aluminium≤0.0015%, the copper of surplus；The mischmetal includes the component of following mass percent：Lanthanum 40~
50%th, cerium 50~55%, praseodymium 4~10%, neodymium≤1.0%.The present invention is closed using Pb-free copper-alloy old material regeneration without Allen's metal
Gold, not only reduces cost, and the obtained unleaded bell metal excellent anti-corrosion performance of old material regeneration.In the present invention, tin member
Element can improve the intensity of alloy, and the SnO of densification is formed in cast(ing) surface2Diaphragm, significantly improves Dezincification corrosion resistant performance；Zinc
Element can reduce tin bronze crystallization range, and type and feeding energy are filled so as to improve, and prevent loose tendency；Bismuth element is substituted
Lead element, makes alloy be free of lead element, and a small amount of bismuth and the synergy of trace selenium make alloy obtain the machinability out of anticipation
Energy；Micro nickel element can crystal grain thinning, improve mechanical performance, improve Dezincification corrosion resistant and heat endurance, moreover it is possible to make the matter of bismuth
Point distribution is more uniform, improves wear-resisting and waterproof pressure performance；Trace B, titanium, zirconium have synergy, improve the corrosion-resistant energy of alloy
Power, casting character, cutting ability, tensile strength, elongation percentage, and effectively suppress the dynamic and Static Recrystallization of alloy, improve and close
The perfect recrystallization temperature of gold；Minipool rare earth element can improve the casting character of alloy, mechanical property, cutting ability,
The resistance to corrosion fatigue limit, resistance to corrosion fatigue intensity and cavitation-corrosion-resistant performance, it is to avoid segregation or inverse inclined in alloy graining process
Analysis and chill crack tendency, efficiently solve the problem of tin bronze heat crack resistance is poor, are effectively improved crystallization range, make
Alloy grain is evenly fine and close；Micro ferro element plays the role of crystal grain thinning, can improve alloy rigidity and intensity；Micro P elements
It is excellent degasification deoxidier, casting character can be improved, improves wearability and alloy flowability and mold-filling capacity.
The manufacturing cost of the unleaded bell metal of old material regeneration of the present invention is that newborn resource prepares unleaded bell metal
80%, with excellent casting character, Cutting free, decay resistance, and meet the requirement of International Environmental Protection health and safety standard, be adapted to
Extensive low pressure, gravity foundry technology, available for part of the long period of soaking in water environment, especially in acid or alkaline water quality
Decay resistance, cavitation-corrosion-resistant ability are more prominent in environment.The as shown by data of embodiment, the waste material that the present invention is provided is again
The tensile strength of raw unleaded bell metal improves 25%, and elongation percentage improves 45%, and the perfect recrystallization temperature of alloy is improved
To more than 500 DEG C, the resistance to corrosion fatigue limit can improve more than 18%, and resistance to corrosion fatigue intensity improves 30%, aluminium alloy mobility
30~40% are improved, cavitation-corrosion-resistant performance improves 50%.
Embodiment
The invention provides a kind of unleaded bell metal of old material regeneration, include the element of following mass percent：
Tin 2.1~5.1%, zinc 4.1~11%, bismuth 0.5~2.8%, selenium≤0.15%, nickel≤1.2%, boron 0.01~
0.1%, titanium 0.01~0.1%, zirconium 0.01~0.1%, mischmetal 0.005~0.05%, lead≤0.03%, iron≤
0.25%, phosphorus≤0.04%, silicon≤0.0015%, aluminium≤0.0015%, the copper of surplus；
The mischmetal includes the element of following mass percent：Lanthanum 40~50%, cerium 50~55%, praseodymium 4~10%,
Neodymium≤1.0%.
The unleaded bell metal of old material regeneration that the present invention is provided includes the tin of 2.1~5.1% mass percents, is preferably
2.7~4.6%, more preferably 3.6~4.2%.In the present invention, the tin element can improve the intensity of alloy, in casting table
Face forms the SnO of densification2Diaphragm, significantly improves Dezincification corrosion resistant performance.
The unleaded bell metal of old material regeneration that the present invention is provided includes the zinc of 4.1~11% mass percents, is preferably
5.1~9.5%, more preferably 3.6~4.2%.In the present invention, the Zn-ef ficiency can reduce tin bronze crystallization range, from
And improve and fill type and feeding energy, prevent loose tendency.
The unleaded bell metal of old material regeneration that the present invention is provided includes the bismuth of 0.5~2.8% mass percent, is preferably
1.0~2.0%, more preferably 1.5~1.7%.In the present invention, the bismuth element substitutes lead element, alloy is free of lead element,
A small amount of bismuth and the synergy of trace selenium make alloy obtain the cutting ability out of anticipation.
The unleaded bell metal of old material regeneration that the present invention is provided includes the selenium of≤0.15% mass percent, be preferably≤
0.1%, more preferably≤0.08%.In the present invention, the synergy of the selenium and bismuth makes alloy obtain the cutting out of anticipation
Performance.
The unleaded bell metal of old material regeneration that the present invention is provided includes the nickel of≤1.2% mass percent, be preferably≤
1.0%, more preferably≤0.8%.In the present invention, the nickel element being capable of crystal grain thinning, raising mechanical performance, the resistance to dezincification of raising
Corrosion and heat endurance, moreover it is possible to make the distribution of particles of bismuth more uniform, improve wear-resisting and waterproof pressure performance.
The unleaded bell metal of old material regeneration that the present invention is provided includes the boron of 0.01~0.1% mass percent, preferably
For 0.05~0.07%, more preferably 0.03~0.04%.
The unleaded bell metal of old material regeneration that the present invention is provided includes the titanium of 0.01~0.1% mass percent, preferably
For 0.03~0.04%.
The unleaded bell metal of old material regeneration that the present invention is provided includes the zirconium of 0.01~0.1% mass percent, preferably
For 0.03~0.08%, more preferably 0.04~0.05%.In the present invention, the boron, titanium, zirconium have synergy, improve and close
Corrosion resistance, casting character, cutting ability, tensile strength, the elongation percentage of gold, and effectively suppress the dynamic and static state of alloy again
Crystallization, improves the perfect recrystallization temperature of alloy.
The mixing that the unleaded bell metal of old material regeneration that the present invention is provided includes 0.005~0.05% mass percent is dilute
Soil, preferably 0.01~0.015%.In the present invention, the mischmetal includes the component of following mass percent：Lanthanum 40~
50%th, cerium 50~55%, praseodymium 4~10%, neodymium≤1.0%.In the present invention, the mischmetal includes 40~50% mass percentages
The lanthanum of ratio, more preferably 45~48%.In the present invention, the mischmetal includes the cerium of 50~55% mass percents, more excellent
Elect 52~53% as.In the present invention, the mischmetal includes the praseodymium of 4~10% mass percents, more preferably 6~8%.This
In invention, the mischmetal includes the neodymium of≤1.0% mass percent, and more preferably≤0.5%.It is described mixed in the present invention
Rare-earth elements can improve the casting character of alloy, mechanical property, cutting ability, the resistance to corrosion fatigue limit, resistance to corrosion fatigue
Intensity and cavitation-corrosion-resistant performance, it is to avoid segregation or inverse segregation and chill crack tendency in alloy graining process, are effectively solved
The problem of tin bronze heat crack resistance is poor, is effectively improved crystallization range, makes alloy grain evenly fine and close.
The unleaded bell metal of old material regeneration that the present invention is provided includes the lead of≤0.02% mass percent, preferably≤
0.01%.
The unleaded bell metal of old material regeneration that the present invention is provided includes the iron of≤0.25% mass percent, be preferably≤
0.2%, more preferably≤0.15%.In the present invention, the ferro element plays the role of crystal grain thinning, can improve alloy rigidity and strong
Degree.
The unleaded bell metal of old material regeneration that the present invention is provided includes the phosphorus of≤0.04% mass percent, be preferably≤
0.02%, more preferably≤0.01%.In the present invention, the P elements are excellent degasification deoxidiers, can improve casting character, carry
High-wearing feature and alloy flowability and mold-filling capacity.
The unleaded bell metal of old material regeneration that the present invention is provided includes the silicon of≤0.0015% mass percent, is preferably
≤ 0.0013%, more preferably≤0.001%.
The unleaded bell metal of old material regeneration that the present invention is provided includes the aluminium of≤0.0015% mass percent, is preferably
≤ 0.0012%, more preferably≤0.0010%.In the present invention, the silicon and aluminium are objectionable impurities elements, oxidizable, are easily formed
The oxide particle SiO of tiny infusibility2And Al2O3, aluminium alloy mobility and compactness are not only reduced, causes casting because of seepage
Scrap, and drop low-alloyed mechanical performance.
Present invention also offers the preparation method of the unleaded bell metal of old material regeneration described in above-mentioned technical proposal, including with
Lower step：
(1) Pb-free copper-alloy waste material and destructive distillation charcoal are subjected to the first melting, obtain fused materials；
(2) fused materials for obtaining the step (1) are refined after being mixed with refining agent, obtain refining material；
(3) the is carried out after the refining material that obtains the step (2), boron source, titanium source, zirconium source and mischmetal mixing
Two meltings, obtain the unleaded bell metal of old material regeneration.
Pb-free copper-alloy waste material and destructive distillation charcoal are carried out the first melting by the present invention, obtain fused materials.In the present invention
In, tin element, Zn-ef ficiency, bismuth element, selenium element and nickel element are contained in the Pb-free copper-alloy waste material.The present invention is to institute
The source of Pb-free copper-alloy waste material is stated without special restriction, it is waste and old using Pb-free copper-alloy well known to those skilled in the art
Material.The present invention utilizes the unleaded bell metal of Pb-free copper-alloy old material regeneration, not only realizes the recycling of waste and old copper material,
And reduce cost.
In the present invention, the consumption of the destructive distillation charcoal is preferably covering Pb-free copper-alloy 2~3cm of waste material, more preferably
For 2.4~2.8cm.In the present invention, the destructive distillation charcoal is a kind of coverture, being capable of starvation, it is to avoid Pb-free copper-alloy gives up
Old material is oxidized.The present invention originates without special restriction to the destructive distillation charcoal, using well known to those skilled in the art
Commercial goods.
In the present invention, the temperature of first melting is preferably 1200~1250 DEG C, more preferably 1230~1240 DEG C,
The present invention does not have special restriction to the time of first melting, can obtain uniform Pb-free copper-alloy waste material fused mass
Material.
Obtain after fused materials, the present invention is refined after the fused materials are mixed with refining agent, obtains raffinate
Material.In the present invention, the refining agent preferably includes the composition of following mass percent：Fluorite 35~45%, sodium carbonate 25~
35%, ice crystal 10~20%, calcium carbonate 10~20%, more preferably fluorite 38~42%, sodium carbonate 28~32%, ice crystal
14~16%, calcium carbonate 14~16%, most preferably fluorite 40%, sodium carbonate 30%, ice crystal 15%, calcium carbonate 15%.This
In invention, the refining agent can remove objectionable impurities, such as SiO2、Al2O3Deng.
In the present invention, the consumption of the refining agent is preferably the 0.15~0.4% of fused materials quality, more preferably
0.2~0.3%.
The present invention does not have special restriction to the charging sequence of the fused materials and refining agent, using people in the art
Feed way known to member, refining agent in embodiments of the present invention, preferably added in fused materials, more preferably melted
Material adds refining agent in the case of stirring.
In the present invention, the temperature of the refining is preferably 1100~1150 DEG C, more preferably 1130~1140 DEG C；It is described
The time of refining is preferably 12~24h, more preferably 18~20h.
Obtain after refining material, after the present invention mixes the refining material, boron source, titanium source, zirconium source and mischmetal
The second melting is carried out, the unleaded bell metal of old material regeneration is obtained.The present invention is to the boron source, titanium source, zirconium source and mixes dilute
The source of soil is without any special restriction, using commercial goods well known to those skilled in the art, specifically, such as copper boron
Intermediate alloy, copper titanium intermediate alloy and copper zirconium intermediate alloy etc..
In the present invention, the boron source, titanium source and zirconium source are preferably entered before the melting of row second is mixed into refining material
Row preheating, the preheating temperature of the boron source, titanium source and zirconium source is preferably independently 140~160 DEG C, more preferably 145~155
DEG C, most preferably 150 DEG C.
In the present invention, the mischmetal is preferably preheated before being mixed into the melting of row second with refining material, described
The preheating temperature of mischmetal is preferably 110~130 DEG C, more preferably 115~125 DEG C, most preferably 120 DEG C.In the present invention
In, the mischmetal is preferably to be mixed again with refining material, boron source, titanium source and zirconium source after each rare earth element is mixed, this hair
The bright hybrid mode to each rare earth element does not have any particular determination, using hybrid mode well known to those skilled in the art
.
The present invention does not have any special to the charging sequence of the refining material, boron source, titanium source, zirconium source and mischmetal
Restriction, using charging sequence well known to those skilled in the art, in embodiments of the present invention, preferably by boron source, titanium source,
Zirconium source and mischmetal are added in refining material simultaneously.The present invention does not have special restriction to the hybrid mode, uses
Hybrid mode well known to those skilled in the art.
In the present invention, the temperature of second melting is preferably 1260~1280 DEG C, more preferably 1270 DEG C；The present invention
There is no special restriction to the time of second melting, homogeneous material can be obtained.
After the completion of second melting, the second obtained smelted product is preferably incubated and stood by the present invention, obtains old material regeneration
Unleaded bell metal.In the present invention, the temperature that the insulation is stood is preferably 1100~1150 DEG C, more preferably 1130~
1140℃；The time that the insulation is stood is preferably 10~20min, more preferably 15min.In the present invention, by the second melting
The cooldown rate that temperature is cooled to holding temperature does not have special restriction, is using the type of cooling well known to those skilled in the art
Can, preferably furnace cooling in the present invention.In the present invention, the insulation, which is stood, can make the impurity in the second smelted product,
Such as SiO2、Al2O3Deng floating or sinking, and then impurity can be removed.
Unleaded bell metal of old material regeneration provided with reference to embodiment the present invention and preparation method thereof carries out detailed
Thin explanation, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
A kind of unleaded bell metal of old material regeneration, includes the element of following mass percent：
Tin 2.1%, zinc 4.1%, bismuth 0.5%, selenium 0.15%, nickel 1.2%, boron 0.01%, titanium 0.01%, zirconium 0.01%,
Mischmetal 0.01%, lead 0.03%, iron 0.25%, phosphorus 0.04%, silicon 0.0015%, aluminium 0.0015%, the copper of surplus；
The mischmetal includes the component of following mass percent：Lanthanum 40%, cerium 50%, praseodymium 9%, neodymium 1.0%.
The preparation method of the unleaded bell metal of old material regeneration, comprises the following steps：
The covering of destructive distillation charcoal is higher than Pb-free copper-alloy waste material surface 2cm, in the first melting at 1200 DEG C, melted
Material, fused materials are carried out at 1100 DEG C of refining 24h after being mixed with refining agent, obtain refining the quality of material, wherein refining agent
For the 0.15% of fused materials, refining agent includes the component of mass percent：Fluorite 40%, sodium carbonate 30%, ice crystal 15%,
Calcium carbonate 15%, 140 DEG C are preheated to by copper boron intermediate alloy, copper titanium intermediate alloy and copper zirconium intermediate alloy, by each rare earth member
Mischmetal is obtained after element mixing, then mischmetal is preheated to 110 DEG C, material, boron source, titanium source, zirconium source will be refined and mixed
Close rare earth mixing and obtain the second smelted product after 1260 DEG C of second meltings of progress, then cool to 1100 DEG C of insulation standings with the furnace
20min, obtains the unleaded bell metal of old material regeneration.
Dispensing is carried out using newborn alloy resource unleaded bell metal same as Example 1 is made, be computed, implement
Example 1 prepares 80% or so of alloy by newborn alloy resource of the cost of the unleaded bell metal of old material regeneration.
Embodiment 2
A kind of unleaded bell metal of old material regeneration, includes the element of following mass percent：
Tin 2.7%, zinc 5.1%, bismuth 1.0%, selenium 0.1%, nickel 0.6%, boron 0.05%, titanium 0.04%, zirconium 0.05% is mixed
Close rare earth 0.015%, lead 0.02%, iron 0.2%, phosphorus 0.03%, silicon 0.0013%, aluminium 0.0014%, the copper of surplus；
The mischmetal includes the component of following mass percent：Lanthanum 40%, cerium 55%, praseodymium 4%, neodymium 1.0%.
The covering of destructive distillation charcoal is higher than Pb-free copper-alloy waste material surface 3cm, in the first melting at 1250 DEG C, melted
Material, fused materials are carried out at 1150 DEG C of refining 12h after being mixed with refining agent, obtain refining the quality of material, wherein refining agent
For the 0.4% of fused materials, refining agent includes the component of mass percent：Fluorite 40%, sodium carbonate 30%, ice crystal 15%,
Calcium carbonate 15%, 160 DEG C are preheated to by copper boron intermediate alloy, copper titanium intermediate alloy and copper zirconium intermediate alloy, by each rare earth member
Mischmetal is obtained after element mixing, then mischmetal is preheated to 130 DEG C, material, boron source, titanium source, zirconium source will be refined and mixed
Close rare earth mixing and obtain the second smelted product after 1280 DEG C of second meltings of progress, then cool to 1150 DEG C of insulation standings with the furnace
10min, obtains the unleaded bell metal of old material regeneration.
Embodiment 3
A kind of unleaded bell metal of old material regeneration, includes the element of following mass percent：
Tin 3.6%, zinc 6.5%, bismuth 1.5%, selenium 0.08%, nickel 0.8%, boron 0.03%, titanium 0.04%, zirconium 0.03%,
Mischmetal 0.015%, lead 0.007%, iron 0.15%, phosphorus 0.02%, silicon 0.001%, aluminium 0.0014%, the copper of surplus；
The mischmetal includes the component of following mass percent：Lanthanum 40%, cerium 55%, praseodymium 4%, neodymium 1.0%.
The covering of destructive distillation charcoal is higher than Pb-free copper-alloy waste material surface 2.5cm, in the first melting at 1220 DEG C, melted
Melt material, fused materials are carried out at 1120 DEG C of refining 18h, obtain refining the matter of material, wherein refining agent after being mixed with refining agent
Measure as the 0.2% of fused materials, refining agent includes the component of mass percent：Fluorite 40%, sodium carbonate 30%, ice crystal
15%th, calcium carbonate 15%, 145 DEG C are preheated to by copper boron intermediate alloy, copper titanium intermediate alloy and copper zirconium intermediate alloy, will be each dilute
Obtain mischmetal after earth elements mixing, then mischmetal be preheated to 115 DEG C, will refining material, boron source, titanium source, zirconium source with
And mischmetal mixing carries out the second melting after 1280 DEG C and obtains the second smelted product, then cools to 1130 DEG C of insulations with the furnace
10min is stood, the unleaded bell metal of old material regeneration is obtained.
Embodiment 4
A kind of unleaded bell metal of old material regeneration, includes the element of following mass percent：
Tin 4.2%, zinc 7.5%, bismuth 1.7%, selenium 0.06%, nickel 1.0%, boron 0.04%, titanium 0.03%, zirconium 0.04%,
Mischmetal 0.01%, lead 0.01%, iron 0.1%, phosphorus 0.01%, silicon 0.001%, aluminium 0.001%, the copper of surplus；
The mischmetal includes the component of following mass percent：Lanthanum 40%, cerium 55%, praseodymium 4%, neodymium 1.0%.
The covering of destructive distillation charcoal is higher than Pb-free copper-alloy waste material surface 2.5cm, in the first melting at 1240 DEG C, melted
Melt material, fused materials are carried out at 1130 DEG C of refining 20h, obtain refining the matter of material, wherein refining agent after being mixed with refining agent
Measure as the 0.25% of fused materials, refining agent includes the component of mass percent：Fluorite 40%, sodium carbonate 30%, ice crystal
15%th, calcium carbonate 15%, 155 DEG C are preheated to by copper boron intermediate alloy, copper titanium intermediate alloy and copper zirconium intermediate alloy, will be each dilute
Obtain mischmetal after earth elements mixing, then mischmetal be preheated to 125 DEG C, will refining material, boron source, titanium source, zirconium source with
And mischmetal mixing carries out the second melting after 1270 DEG C and obtains the second smelted product, then cools to 1140 DEG C of insulations with the furnace
15min is stood, the unleaded bell metal of old material regeneration is obtained.
Embodiment 5
A kind of unleaded bell metal of old material regeneration, includes the element of following mass percent：
Tin 4.6%, zinc 9.5%, bismuth 2.0%, selenium 0.03%, nickel 0.4%, boron 0.07%, titanium 0.1%, zirconium 0.08% is mixed
Close rare earth 0.005%, lead 0.008%, iron 0.09%, phosphorus 0.008%, silicon 0.0014%, aluminium 0.0013%, the copper of surplus；
The mischmetal includes the component of following mass percent：Lanthanum 40%, cerium 55%, praseodymium 4%, neodymium 1.0%.
The covering of destructive distillation charcoal is higher than Pb-free copper-alloy waste material surface 2cm, in the first melting at 1240 DEG C, melted
Material, fused materials are carried out at 1130 DEG C of refining 24h after being mixed with refining agent, obtain refining the quality of material, wherein refining agent
For the 0.3% of fused materials, refining agent includes the component of mass percent：Fluorite 40%, sodium carbonate 30%, ice crystal 15%,
Calcium carbonate 15%, 150 DEG C are preheated to by copper boron intermediate alloy, copper titanium intermediate alloy and copper zirconium intermediate alloy, by each rare earth member
Mischmetal is obtained after element mixing, then mischmetal is preheated to 120 DEG C, material, boron source, titanium source, zirconium source will be refined and mixed
Close rare earth mixing and obtain the second smelted product after 1270 DEG C of second meltings of progress, then cool to 1150 DEG C of insulation standings with the furnace
15min, obtains the unleaded bell metal of old material regeneration.
Embodiment 6
A kind of unleaded bell metal of old material regeneration, includes the element of following mass percent：
Tin 5.1%, zinc 11%, bismuth 2.8%, selenium 0.01%, nickel 0.2%, boron 0.1%, titanium 0.041%, zirconium 0.01% is mixed
Close rare earth 0.05%, lead 0.01%, iron 0.05%, phosphorus 0.005%, silicon 0.0012%, aluminium 0.0012%, the copper of surplus；
The mischmetal includes the component of following mass percent：Lanthanum 40%, cerium 55%, praseodymium 4%, neodymium 1.0%.
The covering of destructive distillation charcoal is higher than Pb-free copper-alloy waste material surface 3cm, in the first melting at 1200 DEG C, melted
Material, fused materials are carried out at 1100 DEG C of refining 24h after being mixed with refining agent, obtain refining the quality of material, wherein refining agent
For the 0.35% of fused materials, refining agent includes the component of mass percent：Fluorite 40%, sodium carbonate 30%, ice crystal 15%,
Calcium carbonate 15%, 140 DEG C are preheated to by copper boron intermediate alloy, copper titanium intermediate alloy and copper zirconium intermediate alloy, by each rare earth member
Mischmetal is obtained after element mixing, then mischmetal is preheated to 110 DEG C, material, boron source, titanium source, zirconium source will be refined and mixed
Close rare earth mixing and obtain the second smelted product after 1260 DEG C of second meltings of progress, then cool to 1100 DEG C of insulation standings with the furnace
20min, obtains the unleaded bell metal of old material regeneration.
According to GB/T5750-2006《The drinking water standard method of inspection》To dissolution in the alloying element water of embodiment 1~6
Performance is tested, as a result as shown in table 1, as can be seen from Table 1, and the unleaded bell metal of old material regeneration of the invention is in water
Dissolution concentration meets GB/T5750-2006《The drinking water standard method of inspection》Middle controlled concentration.
Dissolving out capability test result in the alloying element water of 1 embodiment of table 1~6
| Numbering | Copper/mgL | Arsenic/mgL | Lead/mgL | Iron/mgL | Zinc/mgL | Chromium/mgL | Cadmium/mgL |
| Embodiment 1 | ＜ 1.0 | ＜ 0.01 | ＜ 0.01 | ＜ 0.3 | ＜ 0.01 | ＜ 0.005 | ＜ 0.005 |
| Embodiment 2 | ＜ 1.0 | ＜ 0.01 | ＜ 0.01 | ＜ 0.3 | ＜ 0.01 | ＜ 0.005 | ＜ 0.005 |
| Embodiment 3 | ＜ 1.0 | ＜ 0.01 | ＜ 0.01 | ＜ 0.3 | ＜ 0.01 | ＜ 0.005 | ＜ 0.005 |
| Embodiment 4 | ＜ 1.0 | ＜ 0.01 | ＜ 0.01 | ＜ 0.3 | ＜ 0.01 | ＜ 0.005 | ＜ 0.005 |
| Embodiment 5 | ＜ 1.0 | ＜ 0.01 | ＜ 0.01 | ＜ 0.3 | ＜ 0.01 | ＜ 0.005 | ＜ 0.005 |
| Embodiment 6 | ＜ 1.0 | ＜ 0.01 | ＜ 0.01 | ＜ 0.3 | ＜ 0.01 | ＜ 0.005 | ＜ 0.005 |
Comparative example 1
It is identical with the preparation method of embodiment 1, differ only in without mixed rare-earth elements, mixed rare-earth elements are replaced
It is changed to copper.
Comparative example 2
Identical with the preparation method of embodiment 1, the mass percent for differing only in addition mixed rare-earth elements is adjusted to
0.001%.
Comparative example 3
The measured performance parameter of correlation is carried out by comparative example 3 of C83600 alloys.
Conjunction according to JBT4022.2-1999 alloy casting character assay methods to embodiment 1~6 and comparative example 1~3
The casting character of gold is measured, and as a result as shown in table 2, as can be seen from Table 2, comparative example 1 is not added with mischmetal, castability
Can not improve, the mischmetal addition 0.001% of comparative example 2, casting character not be improved significantly, the embodiment of the present invention 1~6
Mischmetal difference addition is 0.005~0.05%, and casting character is significantly improved, it can be seen that mischmetal addition is appropriate,
Casting character can be significantly improved, improves the defect in casting process, yields is significantly improved.The waste material that the present invention is provided is again
Raw unleaded bell metal is not leaded, meets the standard requirement of environment protection health safety, is the leaded tin bronze alloys of currently available technology
Direct substitute.
The casting character test result of the alloy of the embodiment 1~6 of table 2 and comparative example 1~3
Using carrying out cutting ability test with unified lathe tool and turning mode during universal lathe turning.Turning process test-strips
Part：Rotating speed is 960r/min, and feed is 0.1mm/r, and cutting depth 0.5mm, cutter forward leaning angle is 4 °, respectively to the present invention
The unleaded bell metal of old material regeneration made from embodiment 1~6 carries out cutting ability experiment with the alloy of comparative example 1~3 and compared,
Collect 100 chips respectively, measure average length, with the average length of the alloy chip of comparative example 3 respectively divided by embodiment 1~
6th, as a result as shown in table 3 the chip average length of each sample of comparative example 1~2, as can be seen from Table 3, is implemented as evaluation index
Because mischmetal addition is appropriate in example 1~6, cutting ability is significantly better than comparative example 1~2, with the alloy cutting ability of comparative example 3
It is close.
The cutting ability test result of the alloy of the embodiment 1~6 of table 3 and comparative example 1~3
| Numbering | Machinability rating % |
| Embodiment 1 | ＞ 97.2 |
| Embodiment 2 | ＞ 98.1 |
| Embodiment 3 | ＞ 99.2 |
| Embodiment 4 | ＞ 98.5 |
| Embodiment 5 | ＞ 93 |
| Embodiment 6 | ＞ 94 |
| Comparative example 1 | 87 |
| Comparative example 2 | 89 |
| Comparative example 3 | 100 |
The tensile property and decay resistance of embodiment 1~6 and the alloy of comparative example 1~3 are tested.With ten thousand
Energy material pull-test machine carries out normal tensile property test, and decay resistance test condition is：Size of sample is 20mm*
20mm*20mm, 0.1mol/LHCl+0.1mol/LH is used after being handled by grinding and polishing cleaning, drying2O2Mixed liquid dipping sample,
Routine weighing sample, calculates mass loss rate, and the corrosive liquid more renewed, by FeCl3It is cleaned to dry after alcoholic solution corrosion
Dry-cure, determines corrosion depth, and calculate weight-loss ratio under the microscope.Tensile property and decay resistance measurement result such as table
Shown in 4, as can be seen from Table 4, the mechanical property of the alloy of embodiment 1~6 is significantly improved, and is significantly better than comparative example 1~3,
The tensile strength for the unleaded bell metal of old material regeneration that the present invention is provided improves 25%, and elongation percentage improves 45%, this hair
Bright alloy shows directly substitute leaded tin bronze alloys by experiment；The decay resistance of the alloy of embodiment 1~6 is significantly excellent
Mischmetal addition is moderate in comparative example 1~3, the unleaded bell metal of old material regeneration produced by the present invention, can be notable
Corrosion resisting property is improved, and the resistance to corrosion fatigue limit can improve more than 18%, resistance to corrosion fatigue intensity improves 30%, aluminium alloy flowing
Property improve 30~40%, cavitation-corrosion-resistant performance improve 50%.
The tensile property and decay resistance test result of the alloy of the embodiment 1~6 of table 4 and comparative example 1~3
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of unleaded bell metal of old material regeneration, includes the element of following mass percent：
Tin 2.1~5.1%, zinc 4.1~11%, bismuth 0.5~2.8%, selenium≤0.15%, nickel≤1.2%, boron 0.01~0.1%,
Titanium 0.01~0.1%, zirconium 0.01~0.1%, mischmetal 0.005~0.05%, lead≤0.03%, iron≤0.25%, phosphorus≤
0.04%, silicon≤0.0015%, aluminium≤0.0015%, the copper of surplus；
The mischmetal includes the component of following mass percent：Lanthanum 40~50%, cerium 50~55%, praseodymium 4~10%, neodymium≤
1.0%.
2. the unleaded bell metal of old material regeneration according to claim 1, it is characterised in that including following mass percent
Element：
Tin 2.7~4.6%, zinc 5.1~9.5%, bismuth 1.0~2.0%, selenium≤0.1%, nickel≤1.0%, boron 0.05~
0.07%, titanium 0.03~0.04%, zirconium 0.03~0.08%, mischmetal 0.01~0.015%, lead≤0.02%, iron≤
0.2%, phosphorus≤0.02%, silicon≤0.0013%, aluminium≤0.0012%, the copper of surplus.
3. the unleaded bell metal of old material regeneration according to claim 1 or 2, it is characterised in that including following quality hundred
Divide the element of ratio：
Tin 3.6~4.2%, zinc 6.5~7.5%, bismuth 1.5~1.7%, selenium≤0.08%, nickel≤0.8%, boron 0.03~0.04,
Titanium 0.03~0.04%, zirconium 0.04~0.05%, mischmetal 0.01~0.015%, lead≤0.01%, iron≤0.15%, phosphorus
≤ 0.01%, silicon≤0.001%, aluminium≤0.001%, the copper of surplus.
4. the preparation method of the unleaded bell metal of old material regeneration described in claims 1 to 3 any one, comprises the following steps：
(1) unleaded copper alloy waste material and destructive distillation charcoal are subjected to the first melting, obtain fused materials；
(2) fused materials for obtaining the step (1) are refined with refining agent, obtain refining material；
(3) the refining material for obtaining the step (2) carries out second after being mixed with boron source, titanium source, zirconium source and mischmetal
Melting, obtains the unleaded bell metal of old material regeneration.
5. preparation method according to claim 4, it is characterised in that the consumption of destructive distillation charcoal is to cover in the step (1)
2~3cm of lid Pb-free copper-alloy waste material.
6. preparation method according to claim 4, it is characterised in that refining agent includes following quality in the step (2)
The component of percentage：Fluorite 35~45%, sodium carbonate 25~35%, ice crystal 10~20%, calcium carbonate 10~20%.
7. the preparation method according to claim 4 or 6, it is characterised in that the consumption of refining agent is molten in the step (2)
Melt the 0.15~0.4% of quality of material.
8. preparation method according to claim 4, it is characterised in that in the step (2) temperature of refining for 1100~
1150 DEG C, the time of the refining is 12~24h.
9. preparation method according to claim 4, it is characterised in that boron source, titanium source, zirconium source and essence in the step (3)
Also include preheating before refining material mixing, the preheating temperature of the boron source, titanium source and zirconium source independently is 140~160 DEG C.
10. the preparation method according to claim 4 or 9, it is characterised in that mischmetal and refining in the step (3)
Also include preheating before material mixing, the preheating temperature of the mischmetal is 110~130 DEG C.
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| CN111363938B (en) * | 2020-03-25 | 2021-06-25 | 宁波金田铜业(集团)股份有限公司 | Modifier for scrap brass and method for producing brass alloy by using modifier |
| CN115261669A (en) * | 2022-07-27 | 2022-11-01 | 宁波金田铜业(集团)股份有限公司 | Tin-lead bronze bar and preparation method thereof |
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