CN102862003A - Silver-free copper based solder and preparation method thereof - Google Patents
Silver-free copper based solder and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a silver-free copper based solder and a preparation method thereof, particularly to the silver-free copper based solder for soldering of compressor case covers and copper tubes. The silver-free copper based solder comprises, by weight, 56-68% of Cu, 29-38% of Zn, 0.5-8% of Sn, 0.5-8% of Mn, 0.1-2% of In and other microelements. The preparation method includes fully melting the Cu, the Sn, the Mn, the In and the other microelements to obtain a master alloy; adding Zn into the cooled master alloy with full stirring; taking the alloy out of a furnace; preparing an ingot through pouring; and preparing the ingot into solder wires through extrusion and drawing. The silver-free copper based solder and the preparation method thereof have the advantages that the soldering temperature is 815-865 DEG C and satisfies the process requirement, high silver based solders can be replaced, the cost is low, and the metallographic grain size after welding is low.
Description
Technical field
The present invention relates to a kind of silverless Cu-base soldering material for soldering and preparation method thereof, particularly a kind of silverless Cu-base soldering material for compressor cap and copper pipe soldering.
Background technology
In recent years, heterogenous metal brazing is used increasingly extensive.But, because the different materials physicochemical properties differ greatly, the difference of their thermal coefficient of expansion particularly, in the cooling procedure after welding, the amount of contraction of different materials is inconsistent and produce deformational stress.If weld strength is not enough to overcome deformational stress, will make weld cracking, cause compressor leakage.
Particularly compress the welding of cabinet cover and copper pipe for air-conditioning, refrigerator etc., high pressure is born in inside when using in view of compressor, and is higher to the quality requirement of welding.For solving compressor cap and copper pipe different-metal material welding problem, mainly adopt at present high cored solder such as BIn40CuZn, the BIn45CuZn etc. of silver content to carry out soldering to the soldering of compressor cap and copper pipe, because silver-base solder is expensive, causes welding cost higher.
Although it is low that silver content 40% and above high silver solder thereof have welding temperature, good to the mother metal wetability, the weld strength high can be applicable to the soldering of of the same race in various metals or the alloy or heterogeneous material, such as copper and copper alloy, carbon steel, stainless steel, carbide alloy etc.But, because silver-base solder is expensive, according to domestic only compressor year producing 100,000,000 calculating, the about 6.3 yuan/platform of expense that high silver solder consumes * 100,000,000=6.3 hundred million yuan, and the silver price is always constantly high in recent years, causes manufacturing cost high.
Summary of the invention
The object of the present invention is to provide 815～865 ℃ of a kind of brazing temperatures, low-cost silverless Cu-base soldering material of alternative high silver-base solder and preparation method thereof has welding temperature and satisfies technological requirement, the low effect of metallographic grain size number after the welding.
Technical scheme of the present invention is as follows:
Silverless Cu-base soldering material prescription option A:
A kind of silverless Cu-base soldering material and preparation method thereof, it is characterized in that: described silverless Cu-base soldering material elemental composition by weight percentage comprises: copper (Cu) 56～68%, zinc (Zn) 29～38%, tin (Sn) 0.5～8%, manganese (Mn) 0.5～8%, indium (In) 0.1%～2%.
Further, described silverless Cu-base soldering material elemental composition by weight percentage comprises: copper (Cu) 60～64%, zinc (Zn) 30～34%, tin (Sn) 1～3%, manganese (Mn) 1～3%, indium (In) 0.5%～1.5%.
Another further scheme is that described silverless Cu-base soldering material elemental composition by weight percentage comprises: copper (Cu) 62～65%, zinc (Zn) 31～33%, tin (Sn) 1.5～2.5%, manganese (Mn) 1.5～2.5%, indium (In) 0.1%～0.3%.
A nearlyer step, described silverless Cu-base soldering material elemental composition by weight percentage comprises: copper (Cu) 61～63%, zinc (Zn) 31～33%, tin (Sn) 1.5～2.5%, manganese (Mn) 1.5～2.5%, indium (In) 0.5%～1%.
More preferably scheme is that silverless Cu-base soldering material elemental composition by weight percentage comprises: copper (Cu) 62%, zinc (Zn) 32%, tin (Sn) 2%, manganese (Mn) 2%, indium (In) 1%.
Silverless Cu-base soldering material prescription option b:
A kind of silverless Cu-base soldering material and preparation method thereof, it is characterized in that: described silverless Cu-base soldering material elemental composition by weight percentage comprises: copper (Cu) 56～68%, zinc (Zn) 29～35%, tin (Sn) 0.5～8%, manganese (Mn) 0.5～8%, indium (In) 0.1%～2% also contains rare earth element (RE) 0.001～1.5%.
Further, described silverless Cu-base soldering material elemental composition by weight percentage: copper (Cu) 61～63%, zinc (Zn) 31～33%, tin (Sn) 1.5～2.5%, manganese (Mn) 1.5～2.5%, indium (In) 0.5%～1%, rare earth element (RE) 0.001～1%.
More preferably scheme is silverless Cu-base soldering material elemental composition by weight percentage: copper (Cu) 62%, zinc (Zn) 32%, tin (Sn) 2%, manganese (Mn) 2%, indium (In) 1%, rare earth element (RE) 1%.
Another purpose of the present invention provides the preparation method of above-mentioned solder, and silverless Cu-base soldering material prescription option A comprises following processing step::
At first, with the fully melting of Sn, Mn, In and other trace elements, smelting temperature is 1300～1600 ℃, gets intermediate alloy with Cu;
Secondly: above-mentioned intermediate alloy is cooled to 1050～1120 ℃, Zn is added in the above-mentioned alloy solution, come out of the stove after fully stirring, be cast on the steel grinding tool, naturally cool off and make ingot casting and get final product;
The the 3rd: the ingot casting of making is passed through extruding, drawing, namely obtain needed solder wire material.
Silverless Cu-base soldering material prescription option b comprises following processing step::
At first, with the RE melting, smelting temperature is 1280～1350 ℃ with Cu, gets the Cu-RE intermediate alloy;
Secondly: get a certain amount of Cu-RE intermediate alloy, the Zn in composition of raw materials, Sn, Mn, indium (In) and Cu melting, smelting temperature is 1050～1120 ℃, comes out of the stove after fully stirring, and is cast on the steel grinding tool, naturally cools off to make ingot casting and get final product;
The the 3rd: the ingot casting of making is passed through extruding, drawing, namely obtain needed solder wire material.
In silverless Cu-base soldering material of the present invention, the Zn element of interpolation 29～35% can reduce the fusing point of solder, and improves solder to the wettability of hot rolled plate (particularly compressor cap and copper pipe junction).
Add the fusing point that 0.5～8% Sn element can further reduce solder, still, actual test Sn content is greater than 8% the time, and the plasticity variation of solder causes preparation technology's difficulty, and solder Sn content of the present invention is chosen in 0.5～8% scope for this reason.
Interfacial reaction particularly occurs with surfaces such as iron, ferroalloy, hot rolled plate, copper in the main and base material of the adding of Mn element, strengthens Interface adhesive strength, is conducive to increase the hard and toughness of weld part.Definite through testing, the addition of Mn is 0.5～8% to be advisable, and it is not obvious to cross low effect, and the too high molten solder wettability that then can make reduces, and is unfavorable for that solder flows and sprawls.
If in above-mentioned solder, add 0.001～1.5% RE element, the tissue of energy refinement brazing filler metal alloy, the mechanical property of raising solder, when RE content was less than 0.001%, its effect was not obvious; When yet RE content surpassed 1.5%, the easy segregation of RE caused the brazing filler metal alloy mechanical property relatively poor in crystal boundary.
The invention has the beneficial effects as follows: prior art mainly adopts the high silver solder of argentiferous 40～45% such as BIn40CuZn, BIn45CuZn etc. to carry out soldering to the soldering of compressor cap and copper pipe on year-on-year basis, and silverless Cu-base soldering material of the present invention has been saved precious metal element silver.
Simultaneously, obtain through the solder performance Measurement and Computation to different proportionings, the silverless Cu-base soldering material mechanical property is good, compression case is stamped good wetting and spreading performance, and, the solder heating and temperature control can effectively reduce external heat to the compressor cap at 800～890 ℃ (major control is at 815～865 ℃) during use.The metallographic grain size number reaches 0.09mm～0.11mm after the welding, satisfies compressor cap soldering requirement fully.
By in Cu, Zn matrix, adding an amount of Sn, Mn, and a small amount of In and other trace elements, realize that solder welding temperature scope is 800～890 ℃ (major control is at 815～865 ℃), can effectively reduce external heat to the impact of compressor cap performance.The solder mechanical property is good simultaneously, good wetting and spreading and higher weld strength are all arranged on iron, ferroalloy, copper, through the solder performance test proof to different proportionings, hot rolled plate after the welding and the metallographic grain size number between the copper pipe guarantee＜below the 0.16mm, can reach 0.09mm～0.11mm, the weld seam oil resistant is pressed in pressure 21 MPas/cm
2Kept 1 minute under the state, workpiece does not leak without distortion, and weld appearance is smooth full, is evenly distributed, and the welding copper pipe overcomes not burning, without the defective of distortion, can reach the technical standard of UL and CSA.
The specific embodiment
For being illustrated more clearly in content of the present invention, be further described below in conjunction with the specific embodiment:
Embodiment 1:
At first, with the Cu of 62Kg In and the fully melting of other micro-1Kg with Mn, the 1Kg of Sn, the 2Kg of 2Kg, smelting temperature is 1500 ℃, is incubated 2 hours, gets intermediate alloy; Secondly, mentioned solution being cooled to 1100 ℃, is that Zn adds in the above-mentioned alloy solution with 32Kg, after fully stirring and be incubated 0.5 and as a child came out of the stove, is cast on the steel grinding tool, naturally cools off to make ingot casting and get final product; At last, the ingot casting of making namely obtains needed solder wire material by extruding, drawing.
Embodiment 2:
At first, with the Cu of the 63Kg fully melting of In with Mn, the 1Kg of Sn, the 2Kg of 2Kg, smelting temperature is 1500 ℃, is incubated 2 hours, gets intermediate alloy; Secondly, mentioned solution being cooled to 1100 ℃, is that Zn adds in the above-mentioned alloy solution with 32Kg, after fully stirring and be incubated 0.5 and as a child came out of the stove, is cast on the steel grinding tool, naturally cools off to make ingot casting and get final product; At last, the ingot casting of making namely obtains needed solder wire material by extruding, drawing.
Embodiment 3:
At first, with the Cu of 56Kg In and the fully melting of other micro-1Kg with Mn, the 1Kg of Sn, the 2Kg of 2Kg, smelting temperature is 1500 ℃, is incubated 2 hours, gets intermediate alloy; Secondly, mentioned solution being cooled to 1100 ℃, is that Zn adds in the above-mentioned alloy solution with 38Kg, after fully stirring and be incubated 0.5 and as a child came out of the stove, is cast on the steel grinding tool, naturally cools off to make ingot casting and get final product; At last, the ingot casting of making namely obtains needed solder wire material by extruding, drawing.
Embodiment 4:
At first, with the Cu of 58Kg In and the fully melting of other micro-1Kg with Mn, the 1Kg of Sn, the 2Kg of 6Kg, smelting temperature is 1500 ℃, is incubated 2 hours, gets intermediate alloy; Secondly, mentioned solution being cooled to 1100 ℃, is that Zn adds in the above-mentioned alloy solution with 32Kg, after fully stirring and be incubated 0.5 and as a child came out of the stove, is cast on the steel grinding tool, naturally cools off to make ingot casting and get final product; At last, the ingot casting of making namely obtains needed solder wire material by extruding, drawing.
Embodiment 5:
At first, with the Cu of 58Kg In and the fully melting of other micro-1Kg with Mn, the 1Kg of Sn, the 6Kg of 2Kg, smelting temperature is 1500 ℃, is incubated 2 hours, gets intermediate alloy; Secondly, mentioned solution being cooled to 1100 ℃, is that Zn adds in the above-mentioned alloy solution with 32Kg, after fully stirring and be incubated 0.5 and as a child came out of the stove, is cast on the steel grinding tool, naturally cools off to make ingot casting and get final product; At last, the ingot casting of making namely obtains needed solder wire material by extruding, drawing.
Embodiment 6:
At first, with the Cu of 61Kg In and the fully melting of other micro-1Kg with Mn, the 2Kg of Sn, the 2Kg of 2Kg, smelting temperature is 1500 ℃, is incubated 2 hours, gets intermediate alloy; Secondly, mentioned solution being cooled to 1100 ℃, is that Zn adds in the above-mentioned alloy solution with 32Kg, after fully stirring and be incubated 0.5 and as a child came out of the stove, is cast on the steel grinding tool, naturally cools off to make ingot casting and get final product; At last, the ingot casting of making namely obtains needed solder wire material by extruding, drawing.
Embodiment 7:
At first, with the Cu of 62.8Kg In and the fully melting of other micro-1Kg with Mn, the 0.2Kg of Sn, the 2Kg of 2Kg, smelting temperature is 1500 ℃, is incubated 2 hours, gets intermediate alloy; Secondly, mentioned solution being cooled to 1100 ℃, is that Zn adds in the above-mentioned alloy solution with 32Kg, after fully stirring and be incubated 0.5 and as a child came out of the stove, is cast on the steel grinding tool, naturally cools off to make ingot casting and get final product; At last, the ingot casting of making namely obtains needed solder wire material by extruding, drawing.
Embodiment 8:
At first, with the Cu of the 90Kg fully melting of RE with 10Kg, smelting temperature is 1300 ℃, is incubated 2 hours, gets the Cu-RE intermediate alloy; Secondly, get above-mentioned Cu-RE intermediate alloy 10Kg, with the In of Mn, the 1Kg of Sn, the 2Kg of Zn, the 2Kg of 32Kg and the Cu melting of 53Kg, smelting temperature is 1100 ℃, after fully stirring and be incubated 0.5 and as a child came out of the stove, be cast on the steel grinding tool, naturally cool off and make ingot casting and get final product; At last, the ingot casting of making namely obtains needed solder wire material by extruding, drawing.
Embodiment 9:
At first, with the Cu of the 99.5Kg fully melting of RE with 0.5Kg, smelting temperature is 1300 ℃, is incubated 2 hours, gets the Cu-RE intermediate alloy; Secondly, get above-mentioned Cu-RE intermediate alloy 10Kg, with the In of Mn, the 1Kg of Sn, the 2Kg of Zn, the 2Kg of 32Kg and the Cu melting of 53Kg, smelting temperature is 1100 ℃, after fully stirring and be incubated 0.5 and as a child came out of the stove, be cast on the steel grinding tool, naturally cool off and make ingot casting and get final product; At last, the ingot casting of making namely obtains needed solder wire material by extruding, drawing.
The composition of embodiment is shown in Table 1:
Table 1: embodiment composition
According to country and industry related standards regulation, the fusion temperature of testing each embodiment, welding post crystallization granularity, test result sees Table 2.
Table 2: embodiment performance test
| Sequence number | The melt temperature scope | Welding temperature | Metallographic grain size number after the welding |
| Embodiment 1 | 800～815℃ | 830～850℃ | 0.10mm～0.11mm |
| Embodiment 2 | 835～855℃ | 865～890℃ | 0.13mm～0.15mm |
| Embodiment 3 | 780～800℃ | 800～830℃ | 0.10mm～0.11mm |
| Embodiment 4 | 780～800℃ | 800～830℃ | 0.10mm～0.11mm |
| Embodiment 5 | 835～855℃ | 865～890℃ | 0.10mm～0.11mm |
| Embodiment 6 | 790～800℃ | 810～830℃ | 0.10mm～0.11m |
| Embodiment 7 | 795～805℃ | 815～835℃ | 0.10mm～0.11mm |
| Embodiment 8 | 780～800℃ | 815～845℃ | 0.09mm～0.10mm |
| Embodiment 9 | 805～820℃ | 835～865℃ | 0.10mm～0.11mm |
As seen from the above table, the application's solder fusing point satisfies the requirement of compressor cap soldering processes at 800～890 ℃; Equipment adopts the high-efficiency copper-iron automatic brazing machine of company's independent research in the welding procedure, welding auxiliary agent elemental composition by weight percentage comprises: trimethyl 65～70%, ethanol 20～25%, acetone 1～5%, surplus is other, the metallographic grain size number can reach 0.09mm～0.11mm after the welding below 0.16mm, and the weld seam oil resistant is pressed in pressure 21 MPas/cm
2Kept 1 minute under the state, workpiece does not leak without distortion, and weld appearance is smooth full, is evenly distributed, and the welding copper pipe overcomes not burning, without the defective of distortion, can reach the technical standard of UL and CSA, and effect is better.
Above-described embodiment can not be thought limiting the scope of the invention; change or improvement that those skilled in the art make based on technical scheme of the present invention or means; as in the rights protection scope, changing the formula rate of specific embodiment, all should fall within the protection domain of claim of the present invention.
Claims (10)
1. silverless Cu-base soldering material and preparation method thereof, it is characterized in that: described silverless Cu-base soldering material elemental composition by weight percentage comprises: Cu56～68%, Zn29～38%, Sn0.5～8%, Mn0.5～8%, In0.1%～2%.
2. a kind of silverless Cu-base soldering material according to claim 1 and preparation method thereof, it is characterized in that: described silverless Cu-base soldering material elemental composition by weight percentage comprises: Cu60～64%, Zn30～34%, Sn1～3%, Mn1～3%, In0.5%～1.5%.
3. a kind of silverless Cu-base soldering material according to claim 2 and preparation method thereof, it is characterized in that: described silverless Cu-base soldering material elemental composition by weight percentage comprises: Cu61～63%, Zn31～33%, Sn1.5～2.5%, Mn1.5～2.5%, In0.5%～1%.
4. a kind of silverless Cu-base soldering material according to claim 3 and preparation method thereof, it is characterized in that: described silverless Cu-base soldering material elemental composition by weight percentage comprises: Cu62%, Zn32%, Sn2%, Mn2%, In1%.
5. a kind of silverless Cu-base soldering material according to claim 1 and preparation method thereof, it is characterized in that: described silverless Cu-base soldering material elemental composition by weight percentage comprises: Cu62～65%, Zn31～33%, Sn1.5～2.5%, Mn1.5～2.5%, In0.1%～0.3%.
6. a kind of silverless Cu-base soldering material according to claim 1 and preparation method thereof, it is characterized in that: described silverless Cu-base soldering material also contains RE0.001～1.5% by weight percentage.
7. according to claim 1 or 6 described a kind of silverless Cu-base soldering materials and preparation method thereof, it is characterized in that: described silverless Cu-base soldering material elemental composition by weight percentage: Cu61～63%, Zn31～33%, Sn1.5～2.5%, Mn1.5～2.5%, In0.5%～1%, RE0.001～1%.
8. a kind of silverless Cu-base soldering material according to claim 7 and preparation method thereof is characterized in that: described silverless Cu-base soldering material elemental composition composition by weight percentage: Cu62%, Zn32%, Sn2%, Mn2%, In1%, RE1%.
9. method of producing the silverless Cu-base soldering material of claim 1 comprises following processing step:
At first, with the fully melting of Sn, Mn, In and other trace elements, smelting temperature is 1300～1600 ℃, gets intermediate alloy with Cu;
Secondly: above-mentioned intermediate alloy is cooled to 1050～1120 ℃, Zn is added in the above-mentioned alloy solution, come out of the stove after fully stirring, be cast on the steel grinding tool, naturally cool off and make ingot casting and get final product;
The the 3rd: the ingot casting of making is passed through extruding, drawing, namely obtain needed solder wire material.
10. method of producing the silverless Cu-base soldering material of claim 6 comprises following processing step:
At first, with the RE melting, smelting temperature is 1280～1350 ℃ with Cu, gets the Cu-RE intermediate alloy;
Secondly: get a certain amount of Cu-RE intermediate alloy, the Zn in composition of raw materials, Sn, Mn, In and Cu melting, smelting temperature is 1050～1120 ℃, comes out of the stove after fully stirring, and is cast on the steel grinding tool, naturally cools off to make ingot casting and get final product;
The the 3rd: the ingot casting of making is passed through extruding, drawing, namely obtain needed solder wire material.
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| CN103480987A (en) * | 2013-09-26 | 2014-01-01 | 郑州机械研究所 | Preparation method for high-fragility copper-zinc welding wires/welding lugs |
| CN103480987B (en) * | 2013-09-26 | 2015-08-19 | 郑州机械研究所 | A kind of preparation method of high fragility copper zinc welding rod/weld tabs |
| CN104275562A (en) * | 2014-06-18 | 2015-01-14 | 黄河科技学院 | Brazing material, polycrystalline diamond composite product and preparing method thereof |
| CN104439749A (en) * | 2014-11-05 | 2015-03-25 | 安徽华众焊业有限公司 | Special silver-free welding rod |
| CN104942476A (en) * | 2015-07-23 | 2015-09-30 | 徐鲁豫 | Self-fluxing brazing filler metal and preparation method thereof |
| CN106270915A (en) * | 2016-08-31 | 2017-01-04 | 安徽众汇制冷有限公司 | A kind of air conditioning liquid reservoir welding protection device and using method thereof |
| CN106270915B (en) * | 2016-08-31 | 2018-08-31 | 安徽众汇制冷有限公司 | A kind of application method of air conditioning liquid reservoir welding protection device |
| CN106695164A (en) * | 2016-11-30 | 2017-05-24 | 安徽华众焊业有限公司 | Spelter solder |
| CN106736010A (en) * | 2016-11-30 | 2017-05-31 | 安徽华众焊业有限公司 | Copper zinc solder paste |
| CN106736015A (en) * | 2016-11-30 | 2017-05-31 | 安徽华众焊业有限公司 | Without silver yellow copper brazing filler metal alloy |
| CN107052614A (en) * | 2016-11-30 | 2017-08-18 | 安徽华众焊业有限公司 | Without silver yellow spelter solder |
| CN106514050A (en) * | 2016-12-29 | 2017-03-22 | 安徽华众焊业有限公司 | Brass solder and preparation method thereof |
| CN107378303A (en) * | 2017-06-09 | 2017-11-24 | 芜湖云邦铜业有限公司 | A kind of high intensity alternating-current resistance welding wire production method |
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