CN109536772A - A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof - Google Patents

A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof Download PDF

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Publication number
CN109536772A
CN109536772A CN201811611386.4A CN201811611386A CN109536772A CN 109536772 A CN109536772 A CN 109536772A CN 201811611386 A CN201811611386 A CN 201811611386A CN 109536772 A CN109536772 A CN 109536772A
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lead
preparation
copper
brass alloy
alloy
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袁志聪
李福明
张荣金
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Huaiji Dong Guo Copper Products Manufacturing Co Ltd
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Huaiji Dong Guo Copper Products Manufacturing Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B22D11/004—Copper alloys
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

The invention discloses a kind of materials recycling LEAD-FREE BRASS ALLOY sticks and preparation method thereof, using metals such as copper, tin, aluminium, chromium, zinc, copper water after it will melt carries out horizontal casting, the ingot casting heated carries out decortication extruding, extruded stock carries out disk and draws plane skin, disk draws the line base after plane skin to stretch by even drawing continuous annealing unit, and online annealing belongs to the annealing of continuous spreading formula, and line base is through combining the LEAD-FREE BRASS ALLOY bar drawn out；The LEAD-FREE BRASS ALLOY stick has good anti-corrosive properties.

Description

A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof
Technical field
The present invention relates to a kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof more particularly to a kind of corrosion resistants Materials recycling LEAD-FREE BRASS ALLOY stick of erosion and preparation method thereof.
Background technique
The maximum feature of copper is that have very high conductive, heating conduction and good corrosion resistance.But industrial pure copper Intensity it is not high (about 200MPa), thus limit it as the use of structural material.In order to improve the intensity of copper, and assign spy Different performance adds the suitable alloying element of people, to obtain copper alloy in copper.It is copper alloy intensity, toughness with higher, resistance to Mill property and good conductive, heating conduction, it is especially corrosion-resistant in air.Therefore, in industry such as electric power, instrument, ships In be widely used.Some desired strengths are high, heat-resisting, pressure-resistant and anti-corrosion axis class, flange class and valve body and similar parts all It is manufactured with steel alloy forging.
Leather industry generates a large amount of chrome leather scrap every year, and in leather industry, chrome leather scrap is in the quilt on the 31st of August in 2016 It is set to danger wastes, therefore chrome leather scrap has influenced the development of leather industry, and other elements is added by base of chromium and form Alloy, belong to refractory alloy.Compared with metallic nickel, crome metal fusing point is high (1860 DEG C), and specific strength is big (the ratio between intensity and density), With good antioxygenic property and anti-high-sulfur, diesel fuel, seawater corrosion performance.Therefore process hides chromed leather wastes are used to give up In the working process of material regeneration LEAD-FREE BRASS ALLOY, the anti-corrosion of brass is provided using chromium, is had significant innovative.
201410809376.7 disclose a kind of side that Cr (III) adsorbent material is prepared using discarded chrome leather scrap as raw material Method, its main feature is that discarded chrome leather scrap is cleaned, is dry；100 parts of discarded chrome leather scrap is taken, 0.1~1.0mol/L is added 500~2000 parts of NaOH solution, under stiring, 50~80 DEG C of 20~60min of reaction of Yu Wendu obtain hydrolysate；It is protected in N2 Under, then using hydrolysate as base-material, the acrylic monomers that degree of neutralization is 50%~80% is added, discard chrome leather scrap and acrylic acid The mass ratio of monomer is 1: 1~6, and initiator amount is the 1.0%~4.0% of monomer mass, and dosage of crosslinking agent is monomer mass 0.5%~6.0%, Yu Wendu, 40~90 DEG C of 10~60min of reaction, be cooled to room temperature, polymerizate soaked with dehydrated alcohol Bubble 1~3h of sedimentation, filtering, then be washed with distilled water, filter, dry, be ground into particle, it obtains containing to discard chrome leather scrap and be Raw material prepares Cr (III) adsorbent material；The removing containing chromium in Cr (III) waste water that the adsorbent material is generated for process hides factory.
Summary of the invention
The present invention is to utilize the modified materials recycling LEAD-FREE BRASS ALLOY stick of process hides chrome leather scrap, it is therefore intended that improves brass Corrosion resistance, it is raw materials used to be easy to get, a kind of new approach, core of the invention point are provided for process hides chrome leather scrap resource utilization It is to solve the resource utilization of generated secondary pollution in the process hides chromed leather wastes resource utilization stage.
A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof, composition are:
Copper 56.5%-66%, tin 0.3%-1.0%, aluminium 0.4%-0.6%, silicon 0.4%-1.7%, arsenic 0.005%- 0.04%, bismuth 0.2%-1.7%, boron 0.005%-0.04%, iron≤0.2%, nickel≤0.4%, phosphorus≤0.04%, antimony≤ 0.03%, cadmium≤0.003%, chromium 0.5~0.9%, selenium≤0.1%, calcium≤0.001%, barium≤0.001%, surplus is zinc.
A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof, includes the following steps:
(a) waste and old copper material is sorted to obtain lead-free reflow waste material, electric induction furnace then is added in lead-free reflow waste material, simultaneously The covering of destructive distillation charcoal is added, heats up and carries out melting, 1000 DEG C -1200 DEG C of smelting temperature；
(b) temperature adjustment to addition refining agent after 995 DEG C -1075 DEG C and is stirred, and removes waste and old copper material electroplating surface by slag making Layer and objectionable impurities；
(c) stokehold sampling analysis confirms chemical component；
(d) suitable by the requirement addition of silicon 0.4%-1.7%, arsenic 0.005%-0.04%, boron 0.005%-0.04% In the 0.005%-0.04% copper arsenic of mass percent containing arsenic intermediate alloy, boracic mass percent 0.005%-0.04% copper boron Between the copper silicon intermediate alloy of alloy and siliceous mass percent 0.4%-1.7%, stir evenly；
(e) addition process hides hydrolytic residue is added to furnace, adjusts chromium 0.5~0.9%, calcium≤0.001% meets in the alloy Aforementioned proportion；
(f) it is sufficiently stirred, sampling carries out chemical composition analysis, composition of alloy adjusting component according to claim 1 Ratio, then in 1000 DEG C of -1100 DEG C of heat preservations standing 15min；
(g) copper water after fusing is carried out horizontal casting, ingot casting by temperature control to 1050 DEG C -1120 DEG C, scarfing cinder, tapping casting Specification is 80~Φ of Φ 120mm；Ingot casting is in 500~600 DEG C of 1~2h of induction heating；The ingot casting heated carries out decortication extruding, squeezes Pressure pressure is 5~25MN, 4~6mm of extruded stock specification limit Φ: extruded stock carries out disk and draws plane skin, and working modulus is controlled 2~8%； Disk draws the line base after plane skin to stretch by even drawing continuous annealing unit, inlet wire specification 4~6mm of Φ, outlet specification Φ 2.2~Φ 4.0mm, Online annealing belongs to the annealing of continuous spreading formula, and annealing speed line is 100~200m/min, and annealing correction factor is 3.0~3.5； 2.2~Φ of Φ 6.5mm line base after even drawing continuous annealing draws out the LEAD-FREE BRASS ALLOY bar of 2.0~Φ of Φ 3.0mm through combining；And LEAD-FREE BRASS ALLOY Surface of Rod Bar is handled with organotitanium polymer, product inspection, packaging, storage；
Refining agent mass percentage composition is fluorite 21%, ice crystal 16%, borax 28%, silica sand 12%, copper oxide 21%, barite 2%.
The preparation method of organotitanium polymer is to sequentially add glycerine 4.3g, lemon into the drying three-necked flask of 250mL Lemon acid 21.2g, butyl titanate 16g, diethylene adipate 0.4g, adjust pH=4~5, and control temperature is raised slowly to 70~80 DEG C, it is stirred to react 1~2h, adds 0.4~0.5g of ortho-methylnitrobenzene, is stirred to react 1~2h at 75 DEG C, is obtained faint yellow Transparency liquid, as organotitanium polymer.
The process of organotitanium polymer processing brass alloys LEAD-FREE BRASS ALLOY stick are as follows: to gained LEAD-FREE BRASS ALLOY stick The surface 1kg sprays the mixture of 0.03g organotitanium polymer and styrene-acrylic latex coating 0.2g, and heats under 150 degrees Celsius.
Present invention has an advantage that
The present invention is to utilize the modified materials recycling LEAD-FREE BRASS ALLOY stick of process hides chrome leather scrap, it is therefore intended that improves brass Corrosion resistance, it is raw materials used to be easy to get, a kind of new approach, core of the invention point are provided for process hides chrome leather scrap resource utilization It is produced by solving in process hides chromed leather wastes resource utilization stage (especially as foliar fertilizer, albumen powder, gelatin etc.) Secondary pollution resource utilization.
Specific embodiment
Embodiment 1
A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof, composition are:
Copper 56.5%, tin 0.3%, aluminium 0.4%, silicon 0.4%, arsenic 0.005%, bismuth 0.2%, boron 0.005%, iron≤ 0.2%, nickel≤0.4%, phosphorus≤0.04%, antimony≤0.03%, cadmium≤0.003%, chromium 0.5%, selenium≤0.1%, calcium≤ 0.001%, barium≤0.001%, surplus is zinc.
A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof, includes the following steps:
(a) waste and old copper material is sorted to obtain lead-free reflow waste material, electric induction furnace then is added in lead-free reflow waste material, simultaneously The covering of destructive distillation charcoal is added, heats up and carries out melting, 1000 DEG C of smelting temperature；
(b) temperature adjustment to addition refining agent after 995 DEG C and is stirred, and removes waste and old copper material electroplating surface layer and nocuousness by slag making Impurity；
(c) stokehold sampling analysis confirms chemical component；
(d) suitable mass percent containing arsenic is added by the requirement of silicon 0.4%, arsenic 0.005%, boron 0.005% 0.005% bronze medal arsenic intermediate alloy, 0.005% bronze medal boron intermediate alloy of boracic mass percent and siliceous mass percent 0.4% Copper silicon intermediate alloy, stir evenly；
(e) addition process hides hydrolytic residue is added to furnace, adjusts chromium 0.5%, and calcium≤0.001% meets above-mentioned ratio in the alloy Example；
(f) it is sufficiently stirred, sampling carries out chemical composition analysis, composition of alloy adjusting component according to claim 1 Ratio, then in 1000 DEG C of heat preservations standing 15min, (the metallic element ratio as needed for not up to, adds this field conventional material to carry out Adjusting, similarly hereinafter)；
(g) copper water after fusing is carried out horizontal casting by temperature control to 1050 DEG C, scarfing cinder, tapping casting, and ingot casting specification is Φ 80mm；Ingot casting is in 500 DEG C of induction heating 1h；The ingot casting heated carries out decortication extruding, squeeze pressure 5MN, extruded stock specification Range Φ 4mm: extruded stock carries out disk and draws plane skin, and working modulus is controlled 2%；Disk draws the line base after plane skin to draw continuous annealing machine by connecting Group stretches, inlet wire specification Φ 4mm, outlet specification Φ 2.2mm, and online annealing belongs to the annealing of continuous spreading formula, and annealing speed line is 100m/min, annealing correction factor are 3.0；Even draw continuous annealing after Φ 2.2mm line base through combine draw out Φ 2.0mm without lead and yellow-collation Copper alloy bar；And LEAD-FREE BRASS ALLOY Surface of Rod Bar is handled with organotitanium polymer, product inspection, packaging, storage；
Refining agent mass percentage composition is fluorite 21%, ice crystal 16%, borax 28%, silica sand 12%, copper oxide 21%, barite 2%.
The preparation process of process hides hydrolytic residue are as follows: 1kg chrome leather scrap is added in 5kg water, addition calcium hydroxide 60g, Aminomethyl propanol 1g, citric acid 1g and pentaerythrite 0.6g, add at 95 DEG C and hydrolyze 3h, and it is residual that plate compression obtains process hides hydrolysis Slag.
The preparation method of organotitanium polymer is to sequentially add glycerine 4.3g, lemon into the drying three-necked flask of 250mL Lemon acid 21.2g, butyl titanate 16g, diethylene adipate 0.4g, adjust pH=4~5, and control temperature is raised slowly to 70 DEG C, stirs Reaction 1h is mixed, ortho-methylnitrobenzene 0.4g is added, is stirred to react 1h at 75 DEG C, obtain light yellow transparent liquid, it is as organic Titanium polymer.
The process of organotitanium polymer processing brass alloys LEAD-FREE BRASS ALLOY stick are as follows: to gained LEAD-FREE BRASS ALLOY stick The surface 1kg sprays the mixture of 0.03g organotitanium polymer and styrene-acrylic latex coating 0.2g, and heats under 150 degrees Celsius.
Embodiment 2
A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof, composition are:
Copper 66%, tin 1.0%, aluminium 0.6%, silicon 1.7%, arsenic 0.04%, bismuth 1.7%, boron 0.04%, iron≤0.2%, nickel ≤ 0.4%, phosphorus≤0.04%, antimony≤0.03%, cadmium≤0.003%, chromium 0.9%, selenium≤0.1%, calcium≤0.001%, barium≤ 0.001%, surplus is zinc.
A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof, includes the following steps:
(a) waste and old copper material is sorted to obtain lead-free reflow waste material, electric induction furnace then is added in lead-free reflow waste material, simultaneously The covering of destructive distillation charcoal is added, heats up and carries out melting, 1200 DEG C of smelting temperature；
(b) temperature adjustment to addition refining agent after 1075 DEG C and is stirred, and removes waste and old copper material electroplating surface layer by slag making and has Evil impurity；
(c) stokehold sampling analysis confirms chemical component；
(d) suitable 0.04% bronze medal of mass percent containing arsenic is added by the requirement of silicon 1.7%, arsenic 0.04%, boron 0.04% Among the copper silicon of arsenic intermediate alloy, 0.04% bronze medal boron intermediate alloy of boracic mass percent and siliceous mass percent 1.7% Alloy stirs evenly；
(e) addition process hides hydrolytic residue is added to furnace, adjusts chromium 0.9%, and calcium≤0.001% meets above-mentioned ratio in the alloy Example；
(f) it is sufficiently stirred, sampling carries out chemical composition analysis, composition of alloy adjusting component according to claim 1 Ratio, then in 1100 DEG C of heat preservations standing 15min；
(g) copper water after fusing is carried out horizontal casting by temperature control to 1120 DEG C, scarfing cinder, tapping casting, and ingot casting specification is Φ 120mm；Ingot casting is in 600 DEG C of induction heating 2h；The ingot casting heated carries out decortication extruding, squeeze pressure 25MN, extruded stock rule Lattice range Φ 6mm: extruded stock carries out disk and draws plane skin, and working modulus is controlled 8%；Disk draws the line base after plane skin to draw continuous annealing by connecting Unit stretches, inlet wire specification Φ 6mm, outlet specification Φ 4.0mm, and online annealing belongs to the annealing of continuous spreading formula, annealing speed line For 200m/min, correction factor of annealing is 3.5；Even the Φ 6.5mm line base after continuous annealing is drawn to draw out the unleaded of Φ 3.0mm through combining Brass alloys bar；And LEAD-FREE BRASS ALLOY Surface of Rod Bar is handled with organotitanium polymer, product inspection packs, enters Library；
Refining agent mass percentage composition is fluorite 21%, ice crystal 16%, borax 28%, silica sand 12%, copper oxide 21%, barite 2%.
The preparation process of process hides hydrolytic residue are as follows: 1kg chrome leather scrap is added in 5kg water, addition calcium hydroxide 80g, Aminomethyl propanol 3g, citric acid 1.2g and pentaerythrite 2.4g, add at 95 DEG C and hydrolyze 5h, and plate compression obtains process hides water Solve residue.
The preparation method of organotitanium polymer is to sequentially add glycerine 4.3g, lemon into the drying three-necked flask of 250mL Lemon acid 21.2g, butyl titanate 16g, diethylene adipate 0.4g, adjust pH=4~5, and control temperature is raised slowly to 80 DEG C, stirs Reaction 2h is mixed, ortho-methylnitrobenzene 0.5g is added, is stirred to react 2h at 75 DEG C, obtain light yellow transparent liquid, it is as organic Titanium polymer.
The process of organotitanium polymer processing brass alloys LEAD-FREE BRASS ALLOY stick are as follows: to gained LEAD-FREE BRASS ALLOY stick The mixture of 1kg, surface spraying 0.03g organotitanium polymer and styrene-acrylic latex coating 0.2g (market can be bought), and taken the photograph 150 Heat under family name's degree.
Embodiment 3
A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof, composition are:
Copper 61%, tin 0.65%, aluminium 0.5%, silicon 1.05%, arsenic 0.02%, bismuth 0.85%, boron 0.02%, iron≤ 0.2%, nickel≤0.4%, phosphorus≤0.04%, antimony≤0.03%, cadmium≤0.003%, chromium 0.7%, selenium≤0.1%, calcium≤ 0.001%, barium≤0.001%, surplus is zinc.
A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof, includes the following steps:
(a) waste and old copper material is sorted to obtain lead-free reflow waste material, electric induction furnace then is added in lead-free reflow waste material, simultaneously The covering of destructive distillation charcoal is added, heats up and carries out melting, 1100 DEG C of smelting temperature；
(b) temperature adjustment to addition refining agent after 1035 DEG C and is stirred, and removes waste and old copper material electroplating surface layer by slag making and has Evil impurity；
(c) stokehold sampling analysis confirms chemical component；
(d) suitable 0.02% bronze medal of mass percent containing arsenic is added by the requirement of silicon 1.05, arsenic 0.02%, boron 0.02% Among the copper silicon of arsenic intermediate alloy, 0.02% bronze medal boron intermediate alloy of boracic mass percent and siliceous mass percent 1.05% Alloy stirs evenly；
(e) addition process hides hydrolytic residue is added to furnace, adjusts chromium 0.7%, and calcium≤0.001% meets above-mentioned ratio in the alloy Example；
(f) it is sufficiently stirred, sampling carries out chemical composition analysis, composition of alloy adjusting component according to claim 1 Ratio, then in 1050 DEG C of heat preservations standing 15min；
(g) copper water after fusing is carried out horizontal casting by temperature control to 1085 DEG C, scarfing cinder, tapping casting, and ingot casting specification is Φ 100mm；Ingot casting is in 550 DEG C of induction heating 1.5h；The ingot casting heated carries out decortication extruding, squeeze pressure 15MN, extruded stock Specification limit Φ 5mm: extruded stock carries out disk and draws plane skin, and working modulus is controlled 5%；Disk draws the line base after plane skin to pass through Lian Lalian Unit stretching, inlet wire specification Φ 5mm, outlet specification Φ 3.1mm are moved back, online annealing belongs to the annealing of continuous spreading formula, annealing speed Line is 150m/min, and annealing correction factor is 3.0；Φ 4.3mm line base after even drawing continuous annealing draws out the nothing of Φ 2.5mm through combining Lead brass alloy bar；And LEAD-FREE BRASS ALLOY Surface of Rod Bar is handled with organotitanium polymer, product inspection, packaging, Storage；
Refining agent mass percentage composition is fluorite 21%, ice crystal 16%, borax 28%, silica sand 12%, copper oxide 21%, barite 2%.
The preparation process of process hides hydrolytic residue are as follows: 1kg chrome leather scrap is added in 5kg water, addition calcium hydroxide 70g, Aminomethyl propanol 2g, citric acid 1.1g and pentaerythrite 1.5g, add at 95 DEG C and hydrolyze 4h, and plate compression obtains process hides water Solve residue.
The preparation method of organotitanium polymer is to sequentially add glycerine 4.3g, lemon into the drying three-necked flask of 250mL Lemon acid 21.2g, butyl titanate 16g, diethylene adipate 0.4g, adjust pH=4~5, and control temperature is raised slowly to 75 DEG C, stirs Reaction 1.5h is mixed, ortho-methylnitrobenzene 0.45g is added, is stirred to react 1.5h at 75 DEG C, obtain light yellow transparent liquid, as Organotitanium polymer.
The process of organotitanium polymer processing brass alloys LEAD-FREE BRASS ALLOY stick are as follows: to gained LEAD-FREE BRASS ALLOY stick The surface 1kg sprays the mixture of 0.03g organotitanium polymer and styrene-acrylic latex coating 0.2g, and heats under 150 degrees Celsius.
Embodiment 4
A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof, composition are:
Copper 61%, tin 0.8%, aluminium 0.4%, silicon 0.5%, arsenic 0.03%, bismuth 0.6%, boron 0.03%, iron≤0.2%, Nickel≤0.4%, phosphorus≤0.04%, antimony≤0.03%, cadmium≤0.003%, chromium 0.6%, selenium≤0.1%, calcium≤0.001%, barium ≤ 0.001%, surplus is zinc.
A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof, includes the following steps:
(a) waste and old copper material is sorted to obtain lead-free reflow waste material, electric induction furnace then is added in lead-free reflow waste material, simultaneously The covering of destructive distillation charcoal is added, heats up and carries out melting, 1000 DEG C of smelting temperature；
(b) temperature adjustment to addition refining agent after 1000 DEG C and is stirred, and removes waste and old copper material electroplating surface layer by slag making and has Evil impurity；
(c) stokehold sampling analysis confirms chemical component；
(d) suitable 0.03% bronze medal of mass percent containing arsenic is added by the requirement of silicon 0.5%, arsenic 0.03%, boron 0.03% Among the copper silicon of arsenic intermediate alloy, 0.03% bronze medal boron intermediate alloy of boracic mass percent and siliceous mass percent 0.5% Alloy stirs evenly；
(e) addition process hides hydrolytic residue is added to furnace, adjusts chromium 0.6%, and calcium≤0.001% meets above-mentioned ratio in the alloy Example；
(f) it is sufficiently stirred, sampling carries out chemical composition analysis, composition of alloy adjusting component according to claim 1 Ratio, then in 1050 DEG C of heat preservations standing 15min；
(g) copper water after fusing is carried out horizontal casting by temperature control to 1050 DEG C, scarfing cinder, tapping casting, and ingot casting specification is Φ 100mm；Ingot casting is in 550 DEG C of induction heating 1.5h；The ingot casting heated carries out decortication extruding, squeeze pressure 20MN, extruded stock Specification limit Φ 5mm: extruded stock carries out disk and draws plane skin, and working modulus is controlled 5%；Disk draws the line base after plane skin to pass through Lian Lalian Unit stretching, inlet wire specification Φ 5mm, outlet specification Φ 3.0mm are moved back, online annealing belongs to the annealing of continuous spreading formula, annealing speed Line is 150m/min, and annealing correction factor is 3.0；Φ 4.0mm line base after even drawing continuous annealing draws out the nothing of Φ 2.5mm through combining Lead brass alloy bar；And LEAD-FREE BRASS ALLOY Surface of Rod Bar is handled with organotitanium polymer, product inspection, packaging, Storage；
Refining agent mass percentage composition is fluorite 21%, ice crystal 16%, borax 28%, silica sand 12%, copper oxide 21%, barite 2%.
The preparation process of process hides hydrolytic residue are as follows: 1kg chrome leather scrap is added in 5kg water, addition calcium hydroxide 70g, Aminomethyl propanol 2g, citric acid 1.1g and pentaerythrite 1.2g, add at 95 DEG C and hydrolyze 4h, and plate compression obtains process hides water Solve residue.
The preparation method of organotitanium polymer is to sequentially add glycerine 4.3g, lemon into the drying three-necked flask of 250mL Lemon acid 21.2g, butyl titanate 16g, diethylene adipate 0.4g, adjust pH=4~5, and control temperature is raised slowly to 75 DEG C, stirs Reaction 1.5h is mixed, ortho-methylnitrobenzene 0.4g is added, is stirred to react 2h at 75 DEG C, obtain light yellow transparent liquid, as have Machine titanium polymer.
The process of organotitanium polymer processing brass alloys LEAD-FREE BRASS ALLOY stick are as follows: to gained LEAD-FREE BRASS ALLOY stick The surface 1kg sprays the mixture of 0.03g organotitanium polymer and styrene-acrylic latex coating 0.2g, and heats under 150 degrees Celsius.
Embodiment 5
A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof, composition are:
Copper 60%, tin 0.5%, aluminium 0.6%, silicon 0.4%, arsenic 0.01%, bismuth 1.7%, boron 0.04%, iron≤0.2%, nickel ≤ 0.4%, phosphorus≤0.04%, antimony≤0.03%, cadmium≤0.003%, chromium 0.7%, selenium≤0.1%, calcium≤0.001%, barium≤ 0.001%, surplus is zinc.
A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof, includes the following steps:
(a) waste and old copper material is sorted to obtain lead-free reflow waste material, electric induction furnace then is added in lead-free reflow waste material, simultaneously The covering of destructive distillation charcoal is added, heats up and carries out melting, 1100 DEG C of smelting temperature；
(b) temperature adjustment to addition refining agent after 1000 DEG C and is stirred, and removes waste and old copper material electroplating surface layer by slag making and has Evil impurity；
(c) stokehold sampling analysis confirms chemical component；
(d) suitable 0.01% bronze medal of mass percent containing arsenic is added by the requirement of silicon 0.4%, arsenic 0.01%, boron 0.04% Among the copper silicon of arsenic intermediate alloy, 0.04% bronze medal boron intermediate alloy of boracic mass percent and siliceous mass percent 0.4% Alloy stirs evenly；
(e) addition process hides hydrolytic residue is added to furnace, adjusts chromium 0.7%, and calcium≤0.001% meets above-mentioned ratio in the alloy Example；
(f) it is sufficiently stirred, sampling carries out chemical composition analysis, composition of alloy adjusting component according to claim 1 Ratio, then in 1100 DEG C of heat preservations standing 15min；
(g) copper water after fusing is carried out horizontal casting by temperature control to 1100 DEG C, scarfing cinder, tapping casting, and ingot casting specification is Φ 100mm；Ingot casting is in 550 DEG C of induction heating 1.5h；The ingot casting heated carries out decortication extruding, squeeze pressure 20MN, extruded stock Specification limit Φ 5mm: extruded stock carries out disk and draws plane skin, and working modulus is controlled 5%；Disk draws the line base after plane skin to pass through Lian Lalian Unit stretching, inlet wire specification Φ 5mm, outlet specification Φ 3.0mm are moved back, online annealing belongs to the annealing of continuous spreading formula, annealing speed Line is 150m/min, and annealing correction factor is 3.0；Even the Φ 4mm line base after continuous annealing is drawn to draw out the unleaded of Φ 2.5mm through combining Brass alloys bar；And LEAD-FREE BRASS ALLOY Surface of Rod Bar is handled with organotitanium polymer, product inspection packs, enters Library；
Refining agent mass percentage composition is fluorite 21%, ice crystal 16%, borax 28%, silica sand 12%, copper oxide 21%, barite 2%.
The preparation process of process hides hydrolytic residue are as follows: 1kg chrome leather scrap is added in 5kg water, addition calcium hydroxide 70g, Aminomethyl propanol 2g, citric acid 1g and pentaerythrite 2.4g, add at 95 DEG C and hydrolyze 4h, and it is residual that plate compression obtains process hides hydrolysis Slag.
The preparation method of organotitanium polymer is to sequentially add glycerine 4.3g, lemon into the drying three-necked flask of 250mL Lemon acid 21.2g, butyl titanate 16g, diethylene adipate 0.4g, adjust pH=4~5, and control temperature is raised slowly to 75 DEG C, stirs Reaction 1h is mixed, ortho-methylnitrobenzene 0.4g is added, is stirred to react 2h at 75 DEG C, obtain light yellow transparent liquid, it is as organic Titanium polymer.
The process of organotitanium polymer processing brass alloys LEAD-FREE BRASS ALLOY stick are as follows: to gained LEAD-FREE BRASS ALLOY stick The surface 1kg sprays the mixture of 0.03g organotitanium polymer and styrene-acrylic latex coating 0.2g, and heats under 150 degrees Celsius.
The measurement of GB 10119-1988 brass Dezincification corrosion resistant performance is tested, dissolving out capability test is pressed in alloying element water According to GB/T5750-2006 " the drinking water standard method of inspection " carry out test and according to (；B5749-2006 " Drinking Water Sanitary standard " determine
1 performance test of table
As it can be seen from table 1 maximum load, tensile strength, yield strength, Vickers hardness and Dezincification corrosion are strong again by the present invention Degree shows relatively good effect.
2 performance test of table (does not add leather hydrolytic residue)
From table 2 it can be seen that the Dezincification corrosion depth for not adding leather hydrolytic residue significantly improves, display chromium plays wherein Antioxidation.
3 performance test of table (adds leather hydrolytic residue, do not ammoniate methylpropanol)
From table 3 it can be seen that the Dezincification corrosion depth for adding leather hydrolytic residue is decreased obviously, display chromium plays wherein Antioxidation, if the anticorrosive depth for not ammoniating methylpropanol improves, display aminomethyl propanol improves the hydrolysis of leather, promotes The fractions distribution of chromium improves the inoxidizability of chromium.
4 performance test of table (add leather hydrolytic residue, not plus pentaerythrite)
From table 4, it can be seen that the Dezincification corrosion depth for adding leather hydrolytic residue is decreased obviously, display chromium plays wherein Antioxidation, if not plus pentaerythrite anticorrosive depth improve, display pentaerythrite improve leather hydrolysis, improve its in The complexing of chromium plays the antioxidation of chromium.
Similarly it is similar also to play the role of pentaerythrite for citric acid.
5 performance test of table (not plus organotitanium polymer)
As can be seen from Table 5, not plus Dezincification corrosion depth declines.
6 performance test of table (dissolving out capability is tested in alloying element water)
In terms of test index, chromium content meets dissolving out capability index request in alloying element water.

Claims (6)

1. a kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof, composition is:
Copper 56.5%-66%, tin 0.3%-1.0%, aluminium 0.4%-0.6%, silicon 0.4%-1.7%, arsenic 0.005%-0.04%, Bismuth 0.2%-1.7%, boron 0.005%-0.04%, iron≤0.2%, nickel≤0.4%, phosphorus≤0.04%, antimony≤0.03%, cadmium≤ 0.003%, chromium 0.5~0.9%, selenium≤0.1%, calcium≤0.001%, barium≤0.001%, surplus is zinc.
2. a kind of materials recycling LEAD-FREE BRASS ALLOY stick as described in claim 1 and preparation method thereof, includes the following steps:
(a) waste and old copper material is sorted to obtain lead-free reflow waste material, electric induction furnace then is added in lead-free reflow waste material, is added simultaneously The covering of destructive distillation charcoal, heating progress melting, 1000 DEG C -1200 DEG C of smelting temperature；
(b) temperature adjustment is to adding refining agent after 995 DEG C -1075 DEG C and stir, by slag making remove waste and old copper material electroplating surface layer and Objectionable impurities；
(c) stokehold sampling analysis confirms chemical component；
(d) suitable containing arsenic by the requirement addition of silicon 0.4%-1.7%, arsenic 0.005%-0.04%, boron 0.005%-0.04% Mass percent 0.005%-0.04% copper arsenic intermediate alloy, boracic mass percent 0.005%-0.04% copper boron intermediate alloy And the copper silicon intermediate alloy of siliceous mass percent 0.4%-1.7%, it stirs evenly；
(e) addition process hides hydrolytic residue is added to furnace, adjusts chromium 0.5~0.9%, calcium≤0.001% meets above-mentioned in the alloy Ratio；
(f) be sufficiently stirred, sampling carry out chemical composition analysis, composition of alloy adjusting component ratio according to claim 1, Then 15min is stood in 1000 DEG C of -1100 DEG C of heat preservations；
(g) copper water after fusing is carried out horizontal casting, ingot casting specification by temperature control to 1050 DEG C -1120 DEG C, scarfing cinder, tapping casting For 80~Φ of Φ 120mm；Ingot casting is in 500~600 DEG C of 1~2h of induction heating；The ingot casting heated carries out decortication extruding, squeezes pressure Power is 5~25MN, 4~6mm of extruded stock specification limit Φ: extruded stock carries out disk and draws plane skin, and working modulus is controlled 2~8%；Disk is drawn Line base after digging skin is by even drawing continuous annealing unit to stretch, inlet wire specification 4~6mm of Φ, outlet specification Φ 2.2~Φ 4.0mm, online Annealing belongs to the annealing of continuous spreading formula, and annealing speed line is 100~200m/min, and annealing correction factor is 3.0~3.5；Lian La 2.2~Φ of Φ 6.5mm line base after continuous annealing draws out the LEAD-FREE BRASS ALLOY bar of 2.0~Φ of Φ 3.0mm through combining；And to nothing Lead brass alloy Surface of Rod Bar is handled with organotitanium polymer, product inspection, packaging, storage.
3. a kind of materials recycling LEAD-FREE BRASS ALLOY stick as described in right 2 and preparation method thereof；
Refining agent mass percentage composition is fluorite 21%, ice crystal 16%, borax 28%, silica sand 12%, copper oxide 21%, again Spar 2%.
4. a kind of materials recycling LEAD-FREE BRASS ALLOY stick as described in right 2 and preparation method thereof, addition process hides hydrolysis used The preparation process of residue are as follows: 1kg chrome leather scrap is added in 5kg water, calcium hydroxide 60g~80g, aminomethyl propanol 1 is added 0.6~2.4g of~3g, 1~1.2g of citric acid and pentaerythrite adds 3~5h of hydrolysis, plate compression at 95 DEG C and obtains process hides Hydrolytic residue.
5. a kind of materials recycling LEAD-FREE BRASS ALLOY stick as claimed in claim 2 and preparation method thereof, organotitanium polymer Preparation method be sequentially added into the drying three-necked flask of 250mL glycerine 4.3g, citric acid 21.2g, butyl titanate 16g, Diethylene adipate 0.4g, adjusts pH=4~5, and control temperature is raised slowly to 70~80 DEG C, is stirred to react 1~2h, adds 0.4~0.5g of ortho-methylnitrobenzene is stirred to react 1~2h at 75 DEG C, obtains light yellow transparent liquid, and as organic titanium polymerize Object.
6. preparation method according to claim 2, it is characterised in that: organotitanium polymer handles brass alloys lead-free reflow The process of alloy bar are as follows: spray 0.03g organotitanium polymer and styrene-acrylic latex coating to the gained LEAD-FREE BRASS ALLOY surface stick 1kg The mixture of 0.2g, and heat under 150 degrees Celsius.
CN201811611386.4A 2018-12-27 2018-12-27 A kind of materials recycling LEAD-FREE BRASS ALLOY stick and preparation method thereof Pending CN109536772A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110405168A (en) * 2019-07-18 2019-11-05 上海海亮铜业有限公司 Red copper horizontal casting scaling loss removes iron processes
CN111363938A (en) * 2020-03-25 2020-07-03 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
CN113182375A (en) * 2021-04-09 2021-07-30 宁波长振铜业有限公司 Method for producing brass alloy small-size wire and bar products

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110405168A (en) * 2019-07-18 2019-11-05 上海海亮铜业有限公司 Red copper horizontal casting scaling loss removes iron processes
CN111363938A (en) * 2020-03-25 2020-07-03 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
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
CN113182375A (en) * 2021-04-09 2021-07-30 宁波长振铜业有限公司 Method for producing brass alloy small-size wire and bar products

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Application publication date: 20190329