CN105750759A - Copper-based solder as well as preparation method and application thereof - Google Patents
Copper-based solder as well as preparation method and application thereof Download PDFInfo
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- CN105750759A CN105750759A CN201610185840.9A CN201610185840A CN105750759A CN 105750759 A CN105750759 A CN 105750759A CN 201610185840 A CN201610185840 A CN 201610185840A CN 105750759 A CN105750759 A CN 105750759A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/302—Cu as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
Abstract
The invention discloses a copper-based solder which is of a flaky structure of 0.1-0.3 mm and comprises the following components in parts by weight: 8-12 parts of manganese, 7-11 parts of nickel, 2-4 parts of chromium, 1-3 parts of silicon and 70-82 parts of copper, wherein the total weight parts are 100. The invention further discloses a preparation method and application of the copper-based solder in vacuum brazing soldering. Due to addition of elements of nickel, manganese, chromium and silicon in the copper-based solder, the wettability, the strength and the corrosion resistance of the copper-based solder are improved, the melting point of the copper-based solder is increased, the connecting strength of the copper-based solder is thus improved, and by adoption of the copper-based solder, reliable connection of Ti(C, N)-based metal ceramic with steel is achieved, the maximum shearing strength of a connector is up to 301.5 MPa, the average shearing strength is up to 276.8 MPa, and the shearing strength of the copper-based solder is improved by about 30% as compared with that in the prior art.
Description
Technical field
The invention belongs to the preparation field of hard solder, more particularly, to a kind of copper base solder and preparation method thereof and application.
Background technology
Along with industrial development is more and more higher to the requirement of material property, metal material can not meet demand under many circumstances.Pottery can obtain, with being reliably connected of metal, the composite component having pottery concurrently with metal material each excellent properties so that it is having broad application prospects, vacuum brazing can effectively solve this problem.Wherein, copper base solder has wettability and filling capacity is good, and cost, than silver-base solder low cost and other advantages, is therefore widely used in the welding procedure of Ti (C, N) based ceramic metal and metal.
But, copper base solder of the prior art usually contains Ag, Zn element, and Ag, due to price, improves the cost of solder, and the saturated vapour pressure of Zn is big, volatile during vacuum brazing, causes that the composition of solder changes, worsens the mechanical property of joint.Such as document " Ti (C, N) based ceramic metal and the stainless vacuum brazing of 3Cr13 " a kind of copper base solder disclosed in (Sichuan University's journal (engineering science version) " S1 phase in 2012), the composition of this solder is Cu, Ag, Zn and Ni, its peak shear strength is 154Mpa.But this solder is on the one hand at Ti (C, N) based ceramic metal and Cu base solder side are formed without reliable metallurgical bonding interface, the Ag wherein contained on the other hand causes that solder is softer, intensity is not high, therefore its strength of joint is inadequate, quality of connection is unstable, thus being difficult in many instances meet instructions for use.
Summary of the invention
For disadvantages described above or the Improvement requirement of prior art, the invention provides a kind of copper base solder and preparation method thereof and application, its object is to the composition by improving copper base solder, thus improving its strength of joint and quality.
For achieving the above object, according to one aspect of the present invention, it is provided that a kind of copper base solder, count with gross mass for 100 parts, by the manganese of 8 parts～12 parts, the nickel of 7 parts～11 parts, the chromium of 2 parts～4 parts, the copper composition of the silicon of 1 part～3 parts and 70 parts～82 parts.
Preferably, described copper base solder is the laminated structure of thickness 0.1mm～0.3mm.
It is another aspect of this invention to provide that the preparation method providing above-mentioned copper base solder, comprise the following steps:
(1) in mass fraction, by the manganese powder of 8 parts～12 parts, the nikel powder of 7 parts～11 parts, the chromium powder of 2 parts～4 parts, the metal dust Homogeneous phase mixing of the copper powder composition of the silica flour of 1 part～3 parts and 70 parts～82 parts；
(2) metal dust of the mixing obtained in described step (1) is compressed to pressed compact sheet；
(3) the pressed compact sheet sintering that will obtain in described step (2)；
(4) by the solder thin slice that pressed compact sheet Anneal Roll is thickness 0.1mm～0.3mm of the sintering of acquisition in described step (3).
Preferably, in described step (1), the particle diameter of metal dust is 100 order～200 orders.
Preferably, described step (1) particularly as follows: add metal dust, abrading-ball and can cover the ethanol of metal dust and abrading-ball in ball grinder, and abundant ball milling also obtains the metal dust of mixing after drying.
As it is further preferred that in described step (1) rotating speed of ball milling be 200rpm～220rpm, the time is 180min～240min.
Preferably, in described step (2), the pressure of compacting is 300MPa～400Mpa.
Preferably, in described step (3), the temperature of sintering is 810 DEG C～830 DEG C, and the time is 20min～30min.
It is another aspect of this invention to provide that additionally provide the application in vacuum brazing of the described copper base solder.
Preferably, described copper base solder is used for soldering Ti based ceramic metal and steel.
Preferably, the brazing temperature of described copper base solder is 1050 DEG C～1070 DEG C, and the holding time is 25min～35min.
In general, by the above technical scheme that the present invention is contemplated, compared with prior art there is following beneficial effect:
1, the present invention with the addition of nickel element in copper base solder, for improving resistance to elevated temperatures and the decay resistance of solder；With the addition of manganese element, for improving wettability and the spreadability of solder；With the addition of chromium element, for improving intensity and the corrosion resistance of solder, reduce the fusing point of solder simultaneously；With the addition of element silicon, be used for preventing manganese element from aoxidizing, improve the mobility of solder simultaneously；Thus entirety improves the wettability of solder, intensity, fusing point and corrosion resistance；
2, copper base solder prepared by the present invention is utilized, being successfully realized Ti (C, N) based ceramic metal to be reliably connected with steel, the peak shear strength of joint reaches 301.5MPa, average shear strength reaches 276.8Mpa, and the shear strength obtained than prior art improves about 30%.
Accompanying drawing explanation
Fig. 1 is the soldering processes curve chart of the embodiment of the present invention 8.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.As long as just can be mutually combined additionally, technical characteristic involved in each embodiment of invention described below does not constitute conflict each other.
The invention provides a kind of copper base solder, described copper base solder is the laminated structure of 0.1mm～0.3mm, and its gross mass is 100 parts of meters, and by the manganese of 8 parts～12 parts, the nickel of 7 parts～11 parts, the chromium of 2 parts～4 parts, the copper of the silicon of 1 part～3 parts and 70 parts～82 parts forms.
Wherein, nickel element is for improving resistance to elevated temperatures and the decay resistance of solder, but the nickel element of too high levels easily raises the fusing point of solder；Manganese element is for improving wettability and the spreadability of solder, but the plasticity that the manganese element of too high levels can make solder is deteriorated；With the addition of chromium element, for improving intensity and the corrosion resistance of solder, reduce the fusing point of solder simultaneously, make brazing temperature be in the temperature range of applicable soldering Ti (C, N) based ceramic metal and steel；Element silicon is used for preventing manganese element from aoxidizing, and improves the mobility of solder simultaneously.
The preparation method that present invention also offers above-mentioned copper base solder, comprises the following steps:
(1) in ball grinder, add metal dust, abrading-ball and the ethanol of metal dust and abrading-ball can be covered, abundant ball milling also obtains the metal dust of mixing after drying, wherein, metal dust poor fluidity at least crossed by ethanol, and metal dust mixed effect is not good at most excessively；The particle diameter of described metal dust is 100 order～200 orders, and its quality is in number, by the manganese powder of 8 parts～12 parts, and the nikel powder of 7 parts～11 parts, the chromium powder of 2 parts～4 parts, the copper powder composition of the silica flour of 1 part～3 parts and 70 parts～82 parts；The rotating speed of ball milling is 200rpm～220rpm, and the time is 180min～240min, and ratio of grinding media to material is 5:1～9:1；
(2) with the pressure of 300MPa～400Mpa, the metal dust of the mixing obtained in described step (1) being compressed to pressed compact sheet, pressure is too small, compact strength is not high, copper base solder intensity after heat treatment is not high, and pressure is excessive, and copper base solder can be made to produce elastic after effect；
(3) pressed compact sheet 810 DEG C～830 DEG C sintering 20min～30min that will obtain in described step (2), so that increasing the intensity of pressed compact sheet；
(4) by the solder thin slice that pressed compact sheet Anneal Roll is 0.1mm～0.3mm of the sintering of acquisition in described step (3).
Above-mentioned copper base solder can be applicable to vacuum brazing, especially the soldering between Ti based ceramic metal and steel, and its concrete steps include:
(1) cleaning-drying after the first matrix material to be welded, the second matrix material and copper base solder being polished so that it is surface becomes coarse；
(2) it is sequentially placed the first matrix material, copper base solder and the second matrix material, and makes to be fully contacted between three and relative position is fixed；
(3) less than 10-2Under the vacuum of Pa, with 1050～1070 DEG C of soldering 25～35min, namely completing vacuum brazing after cooling, when brazing temperature is 1060 DEG C, soldering strength is best.
Embodiment 1
(1) by mass percentage: Cu powder 76%, Mn powder 10%, Ni powder 9%, Cr powder 3%, Si powder 2%, its granularity respectively 100 order, 100 orders, 100 orders, 100 orders, 100 orders, carry out ball milling in comprehensive planetary ball mill, and ball-milling medium is the ethanol that metal dust and abrading-ball are completely covered, ratio of grinding media to material is 7:1, rotational speed of ball-mill 210rpm, and Ball-milling Time is 210min, vacuum drying oven is dried, obtains the alloy powder of 50g；(2) alloy powder adopts the two-way compacting of mode of compression molding, and pressing pressure is 350MPa, and the dwell time is 60 seconds；(3) putting in vacuum sintering furnace by the alloy pressed compact of compacting, sintering temperature is 820 DEG C, and temperature retention time is 25min；(4) the block Anneal Roll of sintering being become thickness is 200 μm, and area is 48mm2Solder paillon foil.
Embodiment 2
(1) by mass percentage: Cu powder 82%, Mn powder 8%, Ni powder 7%, Cr powder 2%, Si powder 1%, its granularity respectively 200 order, 200 orders, 200 orders, 200 orders, 200 orders, carry out ball milling in comprehensive planetary ball mill, and ball-milling medium is the ethanol that metal dust and abrading-ball are completely covered, ratio of grinding media to material is 7:1, rotational speed of ball-mill 200rpm, and Ball-milling Time is 180min, vacuum drying oven is dried, obtains the alloy powder of 50g；(2) alloy powder adopts the two-way compacting of mode of compression molding, and pressing pressure is 300MPa, and the dwell time is 60 seconds；(3) putting in vacuum sintering furnace by the alloy pressed compact of compacting, sintering temperature is 810 DEG C, and temperature retention time is 20min；(4) the block Anneal Roll of sintering being become thickness is 300 μm, and area is 48mm2Solder paillon foil.
Embodiment 3
(1) by mass percentage: Cu powder 70%, Mn powder 12%, Ni powder 11%, Cr powder 4%, Si powder 3%, its granularity respectively 100 order, 100 orders, 100 orders, 100 orders, 100 orders, carry out ball milling in comprehensive planetary ball mill, and ball-milling medium is the ethanol that metal dust and abrading-ball are completely covered, ratio of grinding media to material is 7:1, rotational speed of ball-mill 220rpm, and Ball-milling Time is 240min, vacuum drying oven is dried, obtains the alloy powder of 50g；(2) alloy powder adopts the two-way compacting of mode of compression molding, and pressing pressure is 400MPa, and the dwell time is 60 seconds；(3) putting in vacuum sintering furnace by the alloy pressed compact of compacting, sintering temperature is 830 DEG C, and temperature retention time is 30min；(4) the block Anneal Roll of sintering being become thickness is 100 μm, and area is 48mm2Solder paillon foil.
Embodiment 4
Repeating embodiment 1 with described same steps, be distinctive in that, in described step (1), the particle diameter of Cu powder, Mn powder, Ni powder, Cr powder and Si powder is 150 orders, and ratio of grinding media to material is 9:1.
Embodiment 5
Repeating embodiment 1 with described same steps, be distinctive in that, in described step (1), the particle diameter of Cu powder and Mn powder is 100 orders, and the particle diameter of Ni powder, Cr powder and Si powder is 150 orders, and ratio of grinding media to material is 5:1.
Embodiment 6
(1) adopt the method for Wire EDM respectively by Ti (C, N) based ceramic metal and mild steel are cut into long 24mm, wide 8mm, the block of high 6mm, before vacuum brazing, by matrix material and embodiment 1 solder paillon foil metallographic liquid honing, then placing it in and carry out ultrasonic waves for cleaning in acetone soln, remove impurity and greasy dirt, the time is 30min, temperature is 30 DEG C, finally with alcohol rinse and dry up.
(2) Ti (C, N) based ceramic metal, solder paillon foil and mild steel are overlapped successively placement, and in order to keep treating that weldment is fully in contact with, placement～200g briquetting on the sample assembled.
(3) vacuum brazing furnace starts to warm up from room temperature, and first paragraph heating rate is 8 DEG C/min, is heated to 580 DEG C of insulation 20min；Second segment heating rate is 4 DEG C/min, is heated to 900 DEG C of insulation 15min；3rd section of heating rate is 4 DEG C/min, is heated to brazing temperature 1050 DEG C, and temperature retention time is 25min；Rate of temperature fall is 5 DEG C/min, cools to 400 DEG C of insulation 20min, and then natural stove is cooled to room temperature and comes out of the stove.The shear strength value obtained under these process conditions is 263.8MPa.
(4), in Process of Vacuum Brazing, vacuum maintains 10-2Pa。
Embodiment 7
(1) adopt the method for Wire EDM respectively by Ti (C, N) based ceramic metal and mild steel are cut into long 24mm, wide 8mm, the block of high 6mm, before vacuum brazing, by the solder paillon foil metallographic liquid honing of matrix material and embodiment 2, then placing it in and carry out ultrasonic waves for cleaning in acetone soln, remove impurity and greasy dirt, the time is 30min, temperature is 30 DEG C, finally with alcohol rinse and dry up.
(2) Ti (C, N) based ceramic metal, solder paillon foil and mild steel are overlapped successively placement, and in order to keep treating that weldment is fully in contact with, placement～200g briquetting on the sample assembled.
(3) vacuum brazing furnace starts to warm up from room temperature, and first paragraph heating rate is 12 DEG C/min, is heated to 620 DEG C of insulation 30min；Second segment heating rate is 7 DEG C/min, is heated to 900 DEG C of insulation 25min；3rd section of heating rate is 7 DEG C/min, is heated to brazing temperature 1070 DEG C, and temperature retention time is 35min；Rate of temperature fall is 7 DEG C/min, cools to 450 DEG C of insulation 30min, and then natural stove is cooled to room temperature and comes out of the stove.The shear strength value obtained under these process conditions is 265.1MPa.
(4), in Process of Vacuum Brazing, vacuum maintains 10-2Pa。
Embodiment 8
(1) adopt the method for Wire EDM respectively by Ti (C, N) based ceramic metal and mild steel are cut into long 24mm, wide 8mm, the block of high 6mm, before vacuum brazing, by the solder paillon foil metallographic liquid honing prepared by matrix material and embodiment 3, then placing it in and carry out ultrasonic waves for cleaning in acetone soln, remove impurity and greasy dirt, the time is 30min, temperature is 30 DEG C, finally with alcohol rinse and dry up.
(2) Ti (C, N) based ceramic metal, solder paillon foil and mild steel are overlapped successively placement, and in order to keep treating that weldment is fully in contact with, placement～200g briquetting on the sample assembled.
(3) vacuum brazing furnace starts to warm up from room temperature, and first paragraph heating rate is 10 DEG C/min, is heated to 600 DEG C of insulation 25min；Second segment heating rate is 6 DEG C/min, is heated to 910 DEG C of insulation 17min；3rd section of heating rate is 6 DEG C/min, is heated to brazing temperature 1060 DEG C, and temperature retention time is 30min；Rate of temperature fall is 6 DEG C/min, cools to 425 DEG C of insulation 25min, and then natural stove is cooled to room temperature and comes out of the stove, and its temperature curve is as shown in Figure 1.The shear strength value obtained under these process conditions is 301.5MPa.
(4), in Process of Vacuum Brazing, vacuum maintains 10-2Pa。
Embodiment 9
With the method identical with embodiment 8, using embodiment 4-embodiment 5 as solder, carry out Ti (C, N) welding between based ceramic metal with mild steel, also can obtaining the result similar with embodiment 6-embodiment 8, shear strength value is 263.8MPa～301.5Mpa.
Those skilled in the art will readily understand; the foregoing is only presently preferred embodiments of the present invention; not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, should be included within protection scope of the present invention.
Claims (10)
1. a copper base solder, it is characterised in that count for 100 parts with gross mass, by the manganese of 8 parts～12 parts, the nickel of 7 parts～11 parts, the chromium of 2 parts～4 parts, the copper composition of the silicon of 1 part～3 parts and 70 parts～82 parts.
2. copper base solder as claimed in claim 1, it is characterised in that described copper base solder is the laminated structure of thickness 0.1mm～0.3mm.
3. the preparation method of copper base solder as claimed in claim 1 or 2, it is characterised in that comprise the following steps:
(1) in mass fraction, by the manganese powder of 8 parts～12 parts, the nikel powder of 7 parts～11 parts, the chromium powder of 2 parts～4 parts, the metal dust Homogeneous phase mixing of the copper powder composition of the silica flour of 1 part～3 parts and 70 parts～82 parts；
(2) metal dust of the mixing obtained in described step (1) is compressed to pressed compact sheet；
(3) the pressed compact sheet sintering that will obtain in described step (2)；
(4) by the solder thin slice that pressed compact sheet Anneal Roll is 0.1mm～0.3mm of the sintering of acquisition in described step (3).
4. method as stated in claim 3, it is characterised in that described step (1) particularly as follows: add metal dust, abrading-ball and can cover the ethanol of metal dust and abrading-ball in ball grinder, and abundant ball milling also obtains the metal dust of mixing after drying.
5. the method as shown in claim 4, it is characterised in that in described step (1), the rotating speed of ball milling is 200rpm～220rpm, the time is 180min～240min.
6. method as stated in claim 3, it is characterised in that in described step (2), the pressure of compacting is 300MPa～400Mpa.
7. method as stated in claim 3, it is characterised in that in described step (3), the temperature of sintering is 810 DEG C～830 DEG C, and the time is 20min～30min.
8. method as stated in claim 3, it is characterised in that in described step (1), the particle diameter of metal dust is 100 order～200 orders.
9. copper base solder application in vacuum brazing as claimed in claim 1 or 2.
10. apply as claimed in claim 9, it is characterised in that for soldering Ti (C, N) based ceramic metal and steel.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109531457A (en) * | 2018-12-29 | 2019-03-29 | 郑州机械研究所有限公司 | A kind of powdered activated solder of diamond abrasive tool |
| CN114571137A (en) * | 2022-05-09 | 2022-06-03 | 中机智能装备创新研究院(宁波)有限公司 | Copper-based brazing paste, copper-based pre-alloy and preparation method thereof |
| CN114571129A (en) * | 2021-09-30 | 2022-06-03 | 中机智能装备创新研究院(宁波)有限公司 | Copper-based brazing filler metal and preparation method and application thereof |
| CN115041865A (en) * | 2022-04-27 | 2022-09-13 | 西安交通大学 | High-activity, multipurpose and rapid brazing Cu-based brazing filler metal and preparation method thereof |
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| CN109531457A (en) * | 2018-12-29 | 2019-03-29 | 郑州机械研究所有限公司 | A kind of powdered activated solder of diamond abrasive tool |
| CN114571129A (en) * | 2021-09-30 | 2022-06-03 | 中机智能装备创新研究院(宁波)有限公司 | Copper-based brazing filler metal and preparation method and application thereof |
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| CN105750759B (en) | 2018-02-27 |
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