CN101671783A - Copper-zinc-nickel-cobalt-indium alloy and preparation method thereof - Google Patents
Copper-zinc-nickel-cobalt-indium alloy and preparation method thereof Download PDFInfo
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- CN101671783A CN101671783A CN200910172414A CN200910172414A CN101671783A CN 101671783 A CN101671783 A CN 101671783A CN 200910172414 A CN200910172414 A CN 200910172414A CN 200910172414 A CN200910172414 A CN 200910172414A CN 101671783 A CN101671783 A CN 101671783A
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Abstract
The invention relates to a copper-zinc-nickel-cobalt-indium alloy and a preparation method thereof. The alloy comprises the following raw materials by weight percent: 43-65% of Cu, 28-45% of Zn, 1-15%of Ni, 0.3-4% of Co, 0.1-2% of In, 0.08-4% of Mn, 0.05-0.3% of Si, 0-2% of Sn, 0-2% of Ag and 0.03-0.07% of Re containing Ce and La in a weight ratio of 2:3. The preparation method comprises the following steps: smelting high melting point metals -- Ni, Co, and Cu to obtain an intermediate alloy A, smelting deoxidizing elements -- Si, Mn and Cu to obtain an intermediate alloy B, smelting oxidablemetals -- Ce, La and Cu in a vacuum furnace to obtain an intermediate alloy C, melting Cu in a medium frequency furnace, adding the intermediate alloy A in the medium frequency furnace to fully fuse,covering the obtained product with a mixture of cullet and cryolite, fully fusing, adding the intermediate alloy B, then adding metal Ag, Zn, Sn and In, adding the intermediate alloy C to perform full deoxidation and fusion, standing for 50min and performing continuous casting to form copper-zinc-nickel-cobalt-indium alloy ingots.
Description
Technical field
The present invention relates to a kind of welding material, relate to a kind of copper-zinc-nickel-cobalt-indium alloy and manufacture method thereof that Wimet is welded of being specially adapted to specifically.
Background technology
The application of Wimet in industrial production and social life is increasingly extensive, because its hardness height, red hardness is good, wear resistance is good, wearability is good, price is low, cost performance is superior, Wimet has an irreplaceable critical positions in the modern industry material.Obtained application widely at aspects such as cutting tool, boring tool, exploration instrument, digging instrument, powder metallurgy.
Wimet links into an integrated entity with the cast setting form or with soldering form and steel matrix in Application Areas.The widespread use of Wimet depends on the development of soldering tech and braze material to a great extent.China is used for nearly 5000 tons of the brazing spelter of soldering Wimet, 400,000,000 yuan of the output values every year.When the soldering Wimet, use maximum simple brass at present, maximum with H60, H62, H68, the general copper of this class alloy source mill all can produce, and the cost of material is low, obtain conveniently.
In order to improve the wettability of market brass to Wimet, adopt the one-ton brass soldering, typical alloying constituent is Cu60Zn39Sn1.In order to prevent the dezincify when the soldering of this class solder to form pore, adopt one-ton brass to add silicon and form new alloy HS221, the composition of alloy HS221 is Cu60Zn38.5Sn1.2Si0.3.In order to reduce the solder fusing point, Zhengzhou Research Institute of Mechanical Engineering has developed Cu53Zn28Mn17SnSi in nineteen ninety, but the manganese content of this solder is too high, can only be used for salt-bath dip brazing.
In order to improve the intensity of brazed seam, adopt the manganese brass soldering, typical solder composition is Cu58Zn38Mn (claiming HL105 or L105 in the industry).On the basis of L105, add cobalt in order to prevent Wimet to take off cobalt, form novel alloy Cu58Zn38Co2Mn2.
Above-mentioned three classes contain the manganese solder when flame brazing and furnace brazing, easily form welding slag at the brazed seam place.For this reason, offshore company has developed the Cu62Zn34Ni3Mn1 solder, and the temperature of fusion of this solder is higher, can cause the oxidation of Wimet and thermal stresses remaining during soldering.
What above-mentioned solder had can solve the brazed seam strength problem but the brazing temperature height; What have can reduce brazing temperature, but brazed seam intensity is low; What have can solve brazed seam intensity and brazing temperature problem, but causes Wimet to take off cobalt easily.Thereby to research and develop a kind of high strength, high-ductility, low-melting copper base solder be the key that solves a carbide quartz welding difficult problem.
Summary of the invention
Purpose of the present invention is just at a kind of copper-zinc-nickel-cobalt-indium alloy and manufacture method thereof with high strength, high-ductility, low-melting characteristics of existing weak point research and development in the above-mentioned prior art.
Purpose of the present invention can realize by following technique measures:
Copper-zinc-nickel-cobalt-indium alloy of the present invention comprises following weight percentages: copper Cu:43～65%, zinc Zn:28～45%, nickel: 1～15%, cobalt Co:0.3～4%, indium In:0.1～2%, manganese Mn:0.08～4%, silicon Si:0.05～0.3%, tin Sn:0～2%, silver-colored Ag:0～2% and Re:0.03～0.07% that formed with 2: 3 mixed of weight ratio by cerium Ce and lanthanum La.
Manufacture method of the present invention comprises the steps:
A, refractory metal nickel, cobalt Co are smelted into master alloy A1, A2 with copper Cu respectively; Described master alloy A1 is by the Cu50 of weight ratio: Ni50 forms; Described master alloy A2 is by the Cu70 of weight ratio: Co30 forms;
B, deoxidant element silicon Si, manganese Mn are smelted into master alloy B1, B2 with copper Cu respectively in vacuum oven; Described master alloy B1 is by the Cu83 of weight ratio: Si17 forms; Described master alloy B2 is by the Cu70 of weight ratio: Mn30 forms;
C, easy oxidation metal Re and copper Cu are smelted into master alloy C in vacuum oven; The weight ratio of described copper Cu and Re is 80: 20;
D, the copper Cu of residual content melted in intermediate frequency furnace after, after copper liquid temperature rises to 1450K in the stove, add any or all of among master alloy A1, the A2, fully merge the back with the mixture covering of glass cullet with sodium aluminum fluoride; Molten metal is continued heating, the molten metal temperature rises to the foundry returns CuZnNiCoIn that adds this alloy behind 1500K～1550K again, and (foundry returns is the scrap stock of this alloy, its composition is same with alloy phase to be refined), after fully merging furnace temperature dropped to 1350K～1450K and add any or all of among master alloy B1, the B2, add argent, zinc, tin and indium more successively, treat that furnace temperature drops to 1250K～1350K and adds master alloy C again, fully deoxidation is merged and was left standstill 50 minutes.
E, furnace temperature is risen to 1370K～1450K flame degasification, adopt continuous casting to form the copper-zinc-nickel-cobalt-indium alloy ingot casting.
The weight ratio of glass cullet described in the present invention and sodium aluminum fluoride 1: 1.Described copper-zinc-nickel-cobalt-indium alloy ingot casting cross section has two kinds of forms, and a kind of is the rod of 12 millimeters of diameters, and a kind of is the square billet of 100 * 10 millimeters of cross sections.
Bar-shaped alloy described in the present invention becomes filament through rolling, drawing tube reducing; Described square billet shape alloy is through being rolled into strip.Rolling or pickling of drawing intermediate demand and annealing.Pickle solution adopts 15～20% sulphuric acid soln of normal temperature.Annealing temperature 900K～800K, annealing time 90min; Every time reduces annealing temperature 10K～20K, and finished product after annealing temperature is 650K～600K, annealing time 50min.
Copper-zinc-nickel-cobalt-indium alloy of the present invention is to introduce Co, raising Ni, reduction Mn on the alloy system basis of soldering field existing C u, Zn, Ni, Mn.Co is the most excellent in all metals to the wettability of Wimet, and the introducing of Co can prevent soldering the time Wimet take off cobalt; Raising Ni, reduction Mn replace Mn with Ni exactly, and consequently intensity and plasticity all have raising, but the solder fusing point also increases.Introduce In and can reduce fusing point; Fell fusing point in the past in the copper solder and generally added Sn, but Sn add the plasticity that affiliation reduces rapidly solder, and In to the plasticity influence of copper solder less than tin.
Beneficial effect of the present invention is as follows:
Copper-zinc-nickel-cobalt-indium alloy of the present invention compare with copper solder of the same type have the intensity height, plasticity height, low-melting characteristics, when being used for the soldering Wimet, have brazed seam intensity height as solder, plasticity is good, fatigability is good, brazing temperature is low, prevent that Wimet from taking off characteristics such as cobalt.
When alloy of the present invention is made the copperwelding rod welding rod and is used for flame brazing, has easy to operate, characteristic of strong applicability.When this alloy is made the arrowband and is used for automatic induction brazing, can enhance productivity greatly.When this alloy deep processing is used for carbamide tool soldering such as pick when becoming disk or rectangular sheet, can improve brazed seam intensity greatly, improve tool life.
In addition, alloy of the present invention is compared with low-silver solder, and brazed seam intensity height, plasticity is good, cost is low; Compare with common copper solder, have that temperature of fusion is low, pore is few, slag inclusion is few, the weld seam high reliability features.
Embodiment
The present invention is described in further detail below with reference to embodiment:
Embodiment 1
A, get by weight percentage: Cu:46%; Zn:40%; Ni:11%; Co:1%; In:0.8%; Mn:0.6%; Si:0.15%; Sn:0.4%; The Re:0.05% that forms with 2: 3 mixed of weight ratio by cerium Ce and lanthanum La;
B, refractory metal nickel, cobalt Co are smelted into master alloy A1, A2 with copper Cu respectively; Described master alloy A1 is by the Cu50 of weight ratio: Ni50 forms; Described master alloy A2 is by the Cu70 of weight ratio: Co30 forms;
C, deoxidant element silicon Si, manganese Mn are smelted into master alloy B1, B2 with copper Cu respectively in vacuum oven; Described master alloy B1 is by the Cu83 of weight ratio: Si17 forms; Described master alloy B2 is by the Cu70 of weight ratio: Mn30 forms;
D, easy oxidation metal Re and copper Cu are smelted into master alloy C in vacuum oven; The weight ratio of described copper Cu and Re is 80: 20;
E, the copper Cu of residual content melted in intermediate frequency furnace after, after copper liquid temperature rises to 1450K in the stove, add master alloy A, fully merge the back with the mixture covering of glass cullet with sodium aluminum fluoride, the weight ratio of described glass cullet and sodium aluminum fluoride 1: 1; Molten metal is continued heating, the molten metal temperature rises to the foundry returns CuZnNiCoIn that adds this alloy behind 1500K～1550K again, and (foundry returns is the scrap stock of this alloy, its composition is same with alloy phase to be refined), after fully merging furnace temperature is dropped to 1350K～1450K and add master alloy B, add argent, zinc, tin and indium more successively, treat that furnace temperature drops to 1250K～1350K and adds master alloy C again, fully deoxidation is merged and was left standstill 50 minutes.
F, furnace temperature is risen to 1370K～1450K flame degasification, adopt continuous casting to form the copper-zinc-nickel-cobalt-indium alloy ingot casting.
Described copper-zinc-nickel-cobalt-indium alloy ingot casting cross section has two kinds of forms, and a kind of is the rod of 12 millimeters of diameters, and a kind of is the square billet of 100 * 10 millimeters of cross sections.
Bar-shaped alloy described in the present invention becomes filament through rolling, drawing tube reducing; Described square billet shape alloy is through being rolled into strip.Rolling or pickling of drawing intermediate demand and annealing.Pickle solution adopts 15～20% sulphuric acid soln of normal temperature.Annealing temperature 900K～800K, annealing time 90min; Every time reduces annealing temperature 10K～20K, and finished product after annealing temperature is 650K～600K, annealing time 50min.
Following examples 2 in 8 except that step a is different, all the other steps all are same as embodiment 1.
Embodiment 2
Get by weight percentage: Cu:49%; Zn:38%; Ni:10%; Co:1%; In:0.8%; Mn:0.7%; Si:0.15%; Ag:0.3%; The Re:0.05% that forms with 2: 3 mixed of weight ratio by cerium Ce and lanthanum La.
Embodiment 3
Get by weight percentage: Cu:52%; Zn:38%; Ni:8%; Co:0.8%; In:0.3%; Mn:0.2%; Si:0.15%; Sn:0.5%; The Re:0.05% that forms with 2: 3 mixed of weight ratio by cerium Ce and lanthanum La.
Embodiment 4
Get by weight percentage: Cu:54%; Zn:37%; Ni:6%; Co:1%; In:0.5%; Mn:1%; Si:0.1%; Ag:0.35%; The Re:0.05% that forms with 2: 3 mixed of weight ratio by cerium Ce and lanthanum La.
Embodiment 5
Get by weight percentage: Cu:56%; Zn:36%; Ni:5%; Co:0.8%; In:0.35%; Mn:1.2%; Si:0.1%; Sn:0.5%; The Re:0.05% that forms with 2: 3 mixed of weight ratio by cerium Ce and lanthanum La.
Embodiment 6
Get by weight percentage: Cu:56%; Zn:35%; Ni:4%; Co:1.8%; In:0.5%; Mn:2%; Si:0.05%; Sn:0.6%; The Re:0.05% that forms with 2: 3 mixed of weight ratio by cerium Ce and lanthanum La.
Embodiment 7
Get by weight percentage: Cu:56%; Zn:34%; Ni:5%; Co:2%; In:0.7%; Mn:1.8%; Si:0.1%; Ag:0.35%; The Re:0.05% that forms with 2: 3 mixed of weight ratio by cerium Ce and lanthanum La.
Embodiment 8
Get by weight percentage: Cu:58%; Zn:33%; Ni:3%; Co:2%; In:0.7%; Mn:2.6%; Si:0.1%; Sn:0.55%; The Re:0.05% that forms with 2: 3 mixed of weight ratio by cerium Ce and lanthanum La.
Claims (3)
1, a kind of copper-zinc-nickel-cobalt-indium alloy is characterized in that: comprise following weight percentages: copper Cu:43～65%, zinc Zn:28～45%, nickel: 1～15%, cobalt Co:0.3～4%, indium In:0.1～2%, manganese Mn:0.08～4%, silicon Si:0.05～0.3%, tin Sn:0～2%, silver-colored Ag:0～2% and Re:0.03～0.07% that formed with 2: 3 mixed of weight ratio by cerium Ce and lanthanum La.
2, a kind of manufacture method that is used for the described alloy of claim 1, it is characterized in that: this method comprises the steps:
A, refractory metal nickel, cobalt Co are smelted into master alloy A1, A2 with copper Cu respectively; Described master alloy A1 is by the Cu50 of weight ratio: Ni50 forms; Described master alloy A2 is by the Cu70 of weight ratio: Co30 forms;
B, deoxidant element silicon Si, manganese Mn are smelted into master alloy B1, B2 with copper Cu respectively in vacuum oven; Described master alloy B1 is by the Cu83 of weight ratio: Si17 forms; Described master alloy B2 is by the Cu70 of weight ratio: Mn30 forms;
C, easy oxidation metal Re and copper Cu are smelted into master alloy C in vacuum oven; The weight ratio of described copper Cu and Re is 80: 20;
D, the copper Cu of residual content melted in intermediate frequency furnace after, after copper liquid temperature rises to 1450K in the stove, add any or all of among master alloy A1, the A2, fully merge the back with the mixture covering of glass cullet with sodium aluminum fluoride; Molten metal is continued heating, the molten metal temperature rises to the foundry returns CuZnNiCoIn that adds this alloy behind 1500K～1550K again, after fully merging furnace temperature dropped to 1350K～1450K and add any or all of among master alloy B1, the B2, add argent, zinc, tin and indium more successively, treat that furnace temperature drops to 1250K～1350K and adds master alloy C again, fully deoxidation is merged and was left standstill 50 minutes.
E, furnace temperature is risen to 1370K～1450K flame degasification, adopt continuous casting to form the copper-zinc-nickel-cobalt-indium alloy ingot casting.
3, method according to claim 2 is characterized in that: the weight ratio of described glass cullet and sodium aluminum fluoride 1: 1.
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| CN101787463B (en) * | 2010-04-09 | 2012-04-25 | 宁波博威合金材料股份有限公司 | Environmentally-friendly lead-free free-machining zinc white copper and preparation method thereof |
| CN102990241A (en) * | 2012-08-24 | 2013-03-27 | 张�林 | Metal powder welding material special for high-frequency welding machine |
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| CN109434318A (en) * | 2018-11-09 | 2019-03-08 | 路达(厦门)工业有限公司 | A kind of tin-brass alloy solder |
| CN113981269A (en) * | 2021-10-29 | 2022-01-28 | 宁波金田铜业(集团)股份有限公司 | Brass alloy and preparation method thereof |
| WO2023154468A1 (en) * | 2022-02-11 | 2023-08-17 | Oerlikon Metco (Us) Inc. | Silver braze alloys for poly-crystalline diamond cutters |
| CN115418526A (en) * | 2022-10-09 | 2022-12-02 | 日丰企业（佛山）有限公司 | Copper alloy and preparation method thereof |
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Address after: Fengyang Zhengzhou high tech Industrial Development Zone, Henan province Zhengzhou city 450001 Street No. 10 Patentee after: Zhengzhou Machinery Research Institute Co., Ltd. Address before: Fengyang Zhengzhou high tech Industrial Development Zone, Henan province Zhengzhou city 450001 Street No. 10 Patentee before: Zhengzhou Research Institute of Mechanical Engineering |