CN102773632A - Low-temperature copper-based brazing filler metal for high-temperature resistance clean steel and preparation method thereof - Google Patents
Low-temperature copper-based brazing filler metal for high-temperature resistance clean steel and preparation method thereof Download PDFInfo
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Abstract
The invention provides a low-temperature copper-based brazing filler metal for high-temperature resistance clean steel and a preparation method thereof. The low-temperature copper-based brazing filler metal is prepared by raw materials in percentage by weight as follows: 4-10% of Ni, 10-30% of Mn, 0.2-1.8% of Zr, 0.2-3.5% of Hf, 0-1% of W, 0-1% of Co, 0.1-0.25% of Ti, 0.02-0.2% of B, 0.8-2.0% of Ge, 0-0.5% of Li and a residual amount of Cu. According to the low-temperature copper-based brazing filler metal provided by the invention, various trace elements are added in copper, so that the using property of the brazing filler metal is improved; a melting process is protected by using gas, a high-temperature resistant quartz glass tube is inserted into molten brazing filler metal alloy after being vacuumized to be in a negative pressure state, so that filament welding strips with different diameters can be directly obtained; techniques of later-stage squeezing, drawing in a reducing manner and the like can be cancelled; the introduction amount of impurities in a production process of the brazing filler metal can be reduced; the cleanliness of the brazing filler metal is improved; the brazing filler metal does not contain an easily-volatile element Zn and can be applicable to vacuum brazing; the brazing filler metal does not contain silver and does not contain any toxic elements; and the brazing filler metal has the advantages of low cost, no pollution, good brazing property and the like.
Description
Technical field
The present invention relates to a kind of high temperature resistant clean steel soldering with can be made into low temperature copper base solder constituent of thread or sheet and preparation method thereof.
Background technology
Impurity in the steel is very big to the production and the serviceability influence of steel, so the research of clean steel is significant.Now, clean steel has been widely used in the materials used under the harsh conditions.Research and develop and produce the high-quality clean steel with good production and serviceability is becoming current wlding industrial development with brazing material a important directions.
Steel soldering in use at present connects used solder has tinbase, money base, copper base, manganese base, Ni-based etc., and the tin-based solder fusing point is lower, but intensity is also lower; Silver-base solder contains noble metal silver, and price comparison is expensive, and elevated temperature strength and creep strength are lower, but temperature is above after 400 ℃, and the intensity of soldered fitting sharply descends; Manganese base and nickel-based solder strength ratio are higher, but fusion temperature is higher, cause the steel grain coarsening easily, influence the serviceability of steel matrix, so the most suitable with copper base solder.The copper base solder of the existing high temperature service condition that does not contain Volatile Elements zinc is following:
But the solder one of production technology production at present is an ordinary copper base solder brazing temperature drift, is prone to the mother metal tissue is affected; The 2nd, impurity content wherein is generally higher, can not satisfy the instructions for use of clean steel soldering.
Summary of the invention
The object of the invention provides a kind of high temperature resistant clean steel with low temperature copper base solder and preparation method thereof to existing weak point in the above-mentioned prior art just.
The object of the invention can be realized through following technique measures:
High temperature resistant condition copper base solder of the present invention is processed by following weight percentages: Ni4-10%, Mn10-30%, Zr0.2～1.8%, Hf0.2-3.5%, W0%-1%, Co0%-1%, Ti0.1～0.25%, B0.02%-0.2%, Ge0.8～2.0%, Li0%-0.5%, surplus is Cu.
High temperature resistant condition low temperature copper base solder preparation method according to the invention is realized by following step:
A, high-melting-point element Ni, Zr, Hf, W, Co are smelted into intermediate alloy A1, A2, A3, A4, A5 with copper respectively; Said intermediate alloy A1 is made up of the Cu:Ni=90:30 of weight ratio; Said intermediate alloy A2 is made up of the Cu:Zr=91:9 of weight ratio; Said intermediate alloy A3 is made up of the Cu:Hf=90:20 of weight ratio; Said intermediate alloy A4 is made up of the Cu:W=98:2 of weight ratio; Said intermediate alloy A5 is made up of the Cu:Co=95:5 of weight ratio;
B, will be prone to oxidation element boron B, Ti, Ge, Li and in vacuum drying oven, be smelted into intermediate alloy B1, B2, B3, B4 with copper respectively; Said intermediate alloy B1 is made up of the Ni:B=86:14 of weight ratio; Said intermediate alloy B2 is made up of the Cu:Ti=80:20 of weight ratio; Said intermediate alloy B3 is made up of the Cu:Ge=88:12 of weight ratio; Said intermediate alloy B4 is the Cu:Li=98:2 by weight ratio;
C, the copper of surplus and intermediate alloy A1 or A1, A4 or A1, A5 or A1, A4, A5 are placed in the induction furnace of argon shield; Be warmed up to 500～600 ℃ with 30 ℃/min speed; Be warmed up to 1100～1300 ℃ with 60 ℃/min again, treat that said copper and intermediate alloy melt fully after, stir, add again Mn and said intermediate alloy B1; Fully the fusing back adds said intermediate alloy A2, A3, treats that it fully merges the back and adds said intermediate alloy B2, B3 or B2, B3, B4;
Behind d, the abundant fusion, left standstill 30 minutes, extract molten metal in the quartz glass tube insertion melt with different-diameter; Obtain different-diameter filament welding rod, said welding rod is rolled gets banded solder.
The present invention adds a spot of Zr, Hf, W, Co, Ti, B, Ge, Li on the basis of Cu, Ni, Mn alloy system.The interpolation of trace Ti can improve the wettability of solder to steel, reduces component segregation, crystal grain thinning, raising plasticity, improves the processing characteristics of solder.The alloy structure of the adding ability refinement solder of Zr element improves its plasticity and toughness and elevated temperature strength.For plasticity and the cleanliness factor that further improves copper base solder added trace elements such as B, Ge in solder; The B element can stop the solder oxidation and can suppress gas and in molten solder, dissolve; Its atomic radius is smaller, in brazing process, can be diffused into the inner bonding strength that improves of matrix fast; The adding of Ge can reduce the fusion temperature of solder significantly, improves the antioxygenic property of solder, and crystal grain thinning improves stream shop performance and wetability, prevents the evaporation of Mn.Pure Hf has plasticity, is prone to good performances such as processing, high-temperature-resistant and anti-corrosion, in solder, adds micro-Hf and can form thermodynamically stable HfC with the carbon in the steel, improves the intensity of brazed seam; Hf can modified MC the type carbide, (Hf) C slows down M for Ti, Ta to form the carbide of rich Hf
23C
6Formation, and control M
23C
6With γ
, In the distribution of crystal boundary, reduce the spreading rate of fatigue crack along crystal boundary; The carbide that contains Hf can increase the corrosion resistance of low-angle boundary, improves fatigue strength; The fusing point of Hf is than higher, and its resistance to elevated temperatures is good especially.W, Co are the strong carbide forming elements, can form the carbide of infusibility, can be used as the core of heterogeneous forming core; Tissue after the refinement soldering; Its existence will improve the mechanical property of solder, eliminate open texture, can obviously improve the hear resistance of solder; When the workpiece after the soldering is worked, can keep higher high temperature strength under higher temperature.Li is a surface reactive material, has very strong reproducibility, and its interpolation can make self fluxing brazing alloy, is applicable to soldering under protective atmosphere or the vacuum condition.
Beneficial effect of the present invention is following:
The present invention adds various trace elements in copper, improve the serviceability of solder; The employing gas shield is smelted; After resistant to elevated temperatures quartz glass tube is pumped into negative pressure; Be inserted in the melted brazing filler metal alloy, directly obtain the filament welding rod of different-diameter, reduce technologies such as later stage extruding, tube reducing drawing; Reduce the solder introducing amount of impurity in process of production, improve the cleanliness factor of solder; This solder does not contain Volatile Elements Zn, can be applicable to vacuum brazing; Said solder is argentiferous not, does not also contain any poisonous element, has characteristics such as cost is low, pollution-free, brazing property is good.
The specific embodiment
To combine embodiment to further describe below the present invention:
Embodiment 1
A, get by weight percentage: Cu84.68%, Ni4%, Mn10%, Zr0.2%, Hf0.2%, B0.02%, Ti0.1%, Ge0.8%;
B, high-melting-point element Ni, Zr, Hf are smelted into intermediate alloy A1, A2, A3 with copper respectively; Said intermediate alloy A1 is made up of the Cu:Ni=90:30 of weight ratio; Said intermediate alloy A2 is made up of the Cu:Zr=91:9 of weight ratio; Said intermediate alloy A3 is made up of the Cu:Hf=90:20 of weight ratio;
C, will be prone to oxidation element boron B, Ti, Ge and in vacuum drying oven, be smelted into intermediate alloy B1, B2, B3 with copper respectively; Said intermediate alloy B1 is made up of the Ni:B=86:14 of weight ratio; Said intermediate alloy B2 is made up of the Cu:Ti=80:20 of weight ratio; Said intermediate alloy B3 is made up of the Cu:Ge=88:12 of weight ratio;
D, the copper and the intermediate alloy A1 of surplus is placed in the induction furnace of argon shield; Be warmed up to 500～600 ℃ with 30 ℃/min speed; Be warmed up to 1100～1300 ℃ with 60 ℃/min again, treat that said copper and intermediate alloy melt fully after, stir, add again Mn and said intermediate alloy B1; Fully the fusing back adds said intermediate alloy A2, A3, treats that it fully merges the back and adds said intermediate alloy B2, B3;
E, fully leaving standstill 30 minutes after merging, is that the quartz glass tube of 2mm inserts in the melt and extracts molten metal with diameter, obtains diameter 2mm welding rod.
Embodiment 2
A, get by weight percentage: Cu52.25%, Ni10%, Mn30%, Zr1.8%, Hf3.5%, B0.2%, Ti0.25%, Ge2.0%;
B, high-melting-point element Ni, Zr, Hf are smelted into intermediate alloy A1, A2, A3 with copper respectively; Said intermediate alloy A1 is made up of the Cu:Ni=90:30 of weight ratio; Said intermediate alloy A2 is made up of the Cu:Zr=91:9 of weight ratio; Said intermediate alloy A3 is made up of the Cu:Hf=90:20 of weight ratio;
C, will be prone to oxidation element boron B, Ti, Ge and in vacuum drying oven, be smelted into intermediate alloy B1, B2, B3 with copper respectively; Said intermediate alloy B1 is made up of the Ni:B=86:14 of weight ratio; Said intermediate alloy B2 is made up of the Cu:Ti=80:20 of weight ratio; Said intermediate alloy B3 is made up of the Cu:Ge=88:12 of weight ratio;
D, the copper and the intermediate alloy A1 of surplus is placed in the induction furnace of argon shield; Be warmed up to 500～600 ℃ with 30 ℃/min speed; Be warmed up to 1100～1300 ℃ with 60 ℃/min again, treat that said copper and intermediate alloy melt fully after, stir, add again Mn and said intermediate alloy B1; Fully the fusing back adds said intermediate alloy A2, A3, treats that it fully merges the back and adds said intermediate alloy B2, B3;
E, fully leaving standstill 30 minutes after merging, is that the quartz glass tube of 2mm inserts in the melt and extracts molten metal with diameter, obtains diameter 2mm welding rod.
Embodiment 3
A, get by weight percentage: Cu72.48, Ni5%, Mn20%, Zr0.5%, Hf 0.2%, W0.2%, Co0.5%, Ti 0.2%, B0.02%, Ge0.8%, Li0.1%;
B, high-melting-point element Ni, Zr, Hf, W, Co are smelted into intermediate alloy A1, A2, A3, A4, A5 with copper respectively; Said intermediate alloy A1 is made up of the Cu:Ni=90:30 of weight ratio; Said intermediate alloy A2 is made up of the Cu:Zr=91:9 of weight ratio; Said intermediate alloy A3 is made up of the Cu:Hf=90:20 of weight ratio; Said intermediate alloy A4 is made up of the Cu:W=98:2 of weight ratio; Said intermediate alloy A5 is made up of the Cu:Co=95:5 of weight ratio;
B, will be prone to oxidation element boron B, Ti, Ge, Li and in vacuum drying oven, be smelted into intermediate alloy B1, B2, B3, B4 with copper respectively; Said intermediate alloy B1 is made up of the Ni:B=86:14 of weight ratio; Said intermediate alloy B2 is made up of the Cu:Ti=80:20 of weight ratio; Said intermediate alloy B3 is made up of the Cu:Ge=88:12 of weight ratio; Said intermediate alloy B4 is the Cu:Li=98:2 by weight ratio;
C, copper and intermediate alloy A1, A4, the A5 of surplus is placed in the induction furnace of argon shield; Be warmed up to 500～600 ℃ with 30 ℃/min speed; Be warmed up to 1100～1300 ℃ with 60 ℃/min again, treat that said copper and intermediate alloy melt fully after, stir, add again Mn and said intermediate alloy B1; Fully the fusing back adds said intermediate alloy A2, A3, treats that it fully merges the back and adds said intermediate alloy B2, B3, B4;
Behind d, the abundant fusion, left standstill 30 minutes, extract molten metal in the quartz glass tube insertion melt with diameter 2mm; Obtain diameter 2mm welding rod, this welding rod can be used for vacuum brazing.
Embodiment 4
A, get by weight percentage: Cu61.78, Ni8%, Mn28%, Zr0.5%, Hf 0.2%, W0.5%, Ti 0.2%, B0.02%, Ge0.8%;
B, with high-melting-point element Ni, Zr, Hf, W respectively with copper be smelted into intermediate alloy A1, A2, A3, A4; Said intermediate alloy A1 is made up of the Cu:Ni=90:30 of weight ratio; Said intermediate alloy A2 is made up of the Cu:Zr=91:9 of weight ratio; Said intermediate alloy A3 is made up of the Cu:Hf=90:20 of weight ratio; Said intermediate alloy A4 is made up of the Cu:W=98:2 of weight ratio;
B, will be prone to oxidation element boron B, Ti, Ge and in vacuum drying oven, be smelted into intermediate alloy B1, B2, B3 with copper respectively; Said intermediate alloy B1 is made up of the Ni:B=86:14 of weight ratio; Said intermediate alloy B2 is made up of the Cu:Ti=80:20 of weight ratio; Said intermediate alloy B3 is made up of the Cu:Ge=88:12 of weight ratio;
C, copper and intermediate alloy A1, the A4 of surplus is placed in the induction furnace of argon shield; Be warmed up to 500～600 ℃ with 30 ℃/min speed; Be warmed up to 1100～1300 ℃ with 60 ℃/min again, treat that said copper and intermediate alloy melt fully after, stir, add again Mn and said intermediate alloy B1; Fully the fusing back adds said intermediate alloy A2, A3, treats that it fully merges the back and adds said intermediate alloy B2, B3;
Behind d, the abundant fusion, left standstill 30 minutes, extract molten metal in the quartz glass tube insertion melt with diameter 2mm; Obtain diameter 2mm welding rod, make weld tabs being rolled after the drawing of said welding rod tube reducing, shearing.
Embodiment 5
A, get by weight percentage: Cu70.28, Ni5%, Mn20%, Zr0.5%, Hf 2%, Co1%, Ti 0.2%, B0.02%, Ge1%;
B, high-melting-point element Ni, Zr, Hf, Co are smelted into intermediate alloy A1, A2, A3, A5 with copper respectively; Said intermediate alloy A1 is made up of the Cu:Ni=90:30 of weight ratio; Said intermediate alloy A2 is made up of the Cu:Zr=91:9 of weight ratio; Said intermediate alloy A3 is made up of the Cu:Hf=90:20 of weight ratio; Said intermediate alloy A5 is made up of the Cu:Co=95:5 of weight ratio;
B, will be prone to oxidation element boron B, Ti, Ge and in vacuum drying oven, be smelted into intermediate alloy B1, B2, B3 with copper respectively; Said intermediate alloy B1 is made up of the Ni:B=86:14 of weight ratio; Said intermediate alloy B2 is made up of the Cu:Ti=80:20 of weight ratio; Said intermediate alloy B3 is made up of the Cu:Ge=88:12 of weight ratio;
C, copper and intermediate alloy A1, the A5 of surplus is placed in the induction furnace of argon shield; Be warmed up to 500～600 ℃ with 30 ℃/min speed; Be warmed up to 1100～1300 ℃ with 60 ℃/min again, treat that said copper and intermediate alloy melt fully after, stir, add again Mn and said intermediate alloy B1; Fully the fusing back adds said intermediate alloy A2, A3, treats that it fully merges the back and adds said intermediate alloy B2, B3;
Behind d, the abundant fusion, left standstill 30 minutes, extract molten metal in the quartz glass tube insertion melt with diameter 2mm; Obtain diameter 2mm welding rod.
Embodiment 6
A, get by weight percentage: Cu54.59%, Ni10%, Mn30%, Zr1%, Hf 2.5%, Ti 0.2%, B0.06%, Ge1.5%, Li0.15%;
B, high-melting-point element Ni, Zr, Hf are smelted into intermediate alloy A1, A2, A3 with copper respectively; Said intermediate alloy A1 is made up of the Cu:Ni=90:30 of weight ratio; Said intermediate alloy A2 is made up of the Cu:Zr=91:9 of weight ratio; Said intermediate alloy A3 is made up of the Cu:Hf=90:20 of weight ratio;
B, will be prone to oxidation element boron B, Ti, Ge, Li and in vacuum drying oven, be smelted into intermediate alloy B1, B2, B3, B4 with copper respectively; Said intermediate alloy B1 is made up of the Ni:B=86:14 of weight ratio; Said intermediate alloy B2 is made up of the Cu:Ti=80:20 of weight ratio; Said intermediate alloy B3 is made up of the Cu:Ge=88:12 of weight ratio; Said intermediate alloy B4 is the Cu:Li=98:2 by weight ratio;
C, the copper and the intermediate alloy A1 of surplus is placed in the induction furnace of argon shield; Be warmed up to 500～600 ℃ with 30 ℃/min speed; Be warmed up to 1100～1300 ℃ with 60 ℃/min again, treat that said copper and intermediate alloy melt fully after, stir, add again Mn and said intermediate alloy B1; Fully the fusing back adds said intermediate alloy A2, A3, treats that it fully merges the back and adds said intermediate alloy B2, B3, B4;
Behind d, the abundant fusion, left standstill 30 minutes, extract molten metal in the quartz glass tube insertion melt with diameter 2mm; Obtain diameter 2mm welding rod, this welding rod can be used for vacuum brazing.
The present invention is under the constant situation of principle, and embodiment and production details can change in certain scope.
Claims (2)
1. a high temperature resistant clean steel is used the low temperature copper base solder; It is characterized in that: it is processed by following weight percentages: Ni4-10%, Mn10-30%, Zr0.2～1.8%, Hf0.2-3.5%, W0%-1%, Co0%-1%, Ti0.1～0.25%, B0.02%-0.2%, Ge0.8～2.0%, Li0%-0.5%, surplus is Cu.
2. one kind is used to prepare the method for the described high temperature resistant clean steel of claim 1 with the low temperature copper base solder, and it is characterized in that: it is realized by following step:
A, high-melting-point element Ni, Zr, Hf, W, Co are smelted into intermediate alloy A1, A2, A3, A4, A5 with copper respectively; Said intermediate alloy A1 is made up of the Cu:Ni=90:30 of weight ratio; Said intermediate alloy A2 is made up of the Cu:Zr=91:9 of weight ratio; Said intermediate alloy A3 is made up of the Cu:Hf=90:20 of weight ratio; Said intermediate alloy A4 is made up of the Cu:W=98:2 of weight ratio; Said intermediate alloy A5 is made up of the Cu:Co=95:5 of weight ratio;
B, will be prone to oxidation element boron B, Ti, Ge, Li and in vacuum drying oven, be smelted into intermediate alloy B1, B2, B3, B4 with copper respectively; Said intermediate alloy B1 is made up of the Ni:B=86:14 of weight ratio; Said intermediate alloy B2 is made up of the Cu:Ti=80:20 of weight ratio; Said intermediate alloy B3 is made up of the Cu:Ge=88:12 of weight ratio; Said intermediate alloy B4 is the Cu:Li=98:2 by weight ratio;
C, the copper of surplus and intermediate alloy A1 or A1, A4 or A1, A5 or A1, A4, A5 are placed in the induction furnace of argon shield; Be warmed up to 500～600 ℃ with 30 ℃/min speed; Be warmed up to 1100～1300 ℃ with 60 ℃/min again, treat that said copper and intermediate alloy melt fully after, stir, add again Mn and said intermediate alloy B1; Fully the fusing back adds said intermediate alloy A2, A3, treats that it fully merges the back and adds said intermediate alloy B2, B3 or B2, B3, B4;
Behind d, the abundant fusion, left standstill 30 minutes, extract molten metal in the quartz glass tube insertion melt with different-diameter; Obtain different-diameter filament welding rod, said welding rod is rolled gets banded solder.
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