CN1098362C - Copper-base alloy and its prepn. technology - Google Patents

Copper-base alloy and its prepn. technology Download PDF

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CN1098362C
CN1098362C CN98112673A CN98112673A CN1098362C CN 1098362 C CN1098362 C CN 1098362C CN 98112673 A CN98112673 A CN 98112673A CN 98112673 A CN98112673 A CN 98112673A CN 1098362 C CN1098362 C CN 1098362C
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copper
alloy
chromium
base alloy
zirconium
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CN1250816A (en
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陈丕文
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陈丕文
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Abstract

The present invention relates to copper base alloy. The components comprise 0.20 to 0.80% of chromium, 0.06 to 0.28% of zirconium, 0.02 to 0.15% of boron, 0.02 to 0.08% of niobium, 0.02 to 0.08% of rare earth (cerium) and copper as the rest. After the copper base alloy is treated by technology provided by the present invention, the conductivity reaches up to 45 MS/m, the normal temperature hardness HRB reaches up to 84 to 92, and the softening temperature is larger than 620 DEG C. The copper alloy has high yield of mass production, and is suitable for being used as resistance welding electrode materials of light alloy plates, steel plates, coated steel, stainless steel plates and titanium alloy plates. The present invention can replace and is superior to resistance welding electrode materials, such as chromium copper, chromium aluminium magnesium copper, chromium zirconium copper, cadmium copper, beryllium cobalt copper (low beryllium copper alloy), etc., and the cadmium copper and the beryllium cobalt copper contain harmful elements.

Description

A kind of novel copper base alloy and technology thereof
The invention belongs to a kind of novel copper base alloy and technology thereof, it is by making it reach high softening temperature to the reasonable adjustment of copper base alloy composition and the optimization of processing method, the purpose of high conductivity and high rigidity.
It is existing historical for many years to use chrome zirconium copper alloy in the resistance welding field, and D.5-1% this Albatra metal-contains chromium, zirconium 0.08-0.12%, and it has certain intensity, and electric conductivity also can remain on about 75% (national standard is 75%).But aspect electric conductivity, can not satisfy light alloy fully, the requirement of the particularly spot welding of aluminium alloy and Coated Steel, seam weldering, aspect hardness and softening temperature, it can not adapt to the resistance welding requirement of stainless steel plate, refractory alloy, titanium alloy plate again, therefore is necessary further to improve its performance.For this reason, relating to one after another both at home and abroad is this field, has carried out a large amount of research.For example United States Patent (USP) 4049426 (on September 20th, 1997) discloses the copper base alloy and the processing method thereof that contain chromium 0.05-1.25%, zirconium 0.05-1.00%, niobium 0.05-1.15%, listed performance data shows that the electric conductivity of this copper base alloy increases than before, but mechanical property then still maintains this invention level before.For example English Patent 652997 (on January 28th, 1976) and russian patent 185068 have been illustrated the effect that adds vanadium in chromium zirconium copper again; United States Patent (USP) 4224066 is by adding an amount of iron to increase the controllability of its precipitation hardening process in chromium zirconium copper.Japan good friendly light metals industry company then takes on the basis of fine copper, chromium zirconium copper, the method that adds the vacuum diffusion with extruding, process the electrode that has the aluminum or aluminum alloy diffusion layer in the working end and come (JP58-163586), the advantage that makes it to have long service life and be difficult for taking place molten sticking phenomenon, it is said and be suitable for the spot-wedling electrode that aluminium and Coated Steel are welded in conduct especially, but its complex process, electrode cost of manufacture height, and the raising of electric conductivity is also not obvious.For example Japanese Patent 9-76074 (March 25 1997 day for announcing) has set forth " resistance welding electrode materials and resistance welding combined electrode and manufacture method thereof " again, the composition of this resistance welding material and weight proportion are: chromium 0.3-1.5, zirconium 0.02-0.22%, silver 0.01-0.5%, tungsten 0.1-5.0%, all the other are copper, its manufacture method is: after the powder mixes with above-mentioned materials, put into the deoxidation copper or the copper jar seal, take to vacuumize excluding air is made little base with sealing means sintering method, after sintering is intact, water pushes out with little base, forge hot and cold stretching make it to form core material again, core material is inserted in the groove (having formed after the machining) of embedded electrode body front end position central authorities, make it the combined electrode of becoming one, the complete processing of kind electrode material and electrode is quite complicated, the manufacturing cost height.
The objective of the invention is to produce on the basis of chromium zirconium copper technology again and a kind ofly all obtain the stable copper base alloy that improves in hardness, electric conductivity, softening temperature performance, it had both had higher electric conductivity, also had higher normal temperature hardness and hot mastication temperature.For society provides a kind of fine, multiduty light alloy and the Coated Steel of being common to, the spot welding of stainless steel plate, high temperature steel, titanium alloy sheet and seam welding electrode material, thus replace and be better than chromium-copper, chromium magnalium copper, chromium zirconium copper and contain cadmium copper, Be-Co-Cu beryllium (containing beryllium 0.2-0.7%, cobalt 2-3%) the constant resistance welding electrode material of harmful element.
Another object of the present invention is to be to provide a kind of processing method that above-mentioned copper contains golden finished product of making, and produces the requirement that reduces production costs in enormous quantities to satisfy.
The objective of the invention is to reach, promptly at first adopt polynary, a small amount of, alloying principle, select to add element and their composition weight proportion and processing parameter by following process implementing method.Can from sosoloid, separate out so will at first analyze the element of interpolation, if can from sosoloid, separate out, then will be less than the simple substance element to the detrimentally affect of alloy electric conductivity.Metallic compound makes the electric conductivity fall of alloy little in other words, and the simple substance element makes the electric conductivity fall of alloy big, has once occurred the argumentation of relevant this respect in all kinds of bell metals.
Specific practice of the present invention is to add following element in copper: chromium 0.20-0.80, zirconium 0.06-0.28%, boron 0.02-0.15%, niobium and each 0.02-0.08% of rare earth (cerium).Simultaneously copper alloy technology has been done bigger improvement: 1, melting contains the above copper master alloy of chromium 10-20%, and adds in the copper with the form of master alloy, and chromium fully is dissolved in the copper liquid, and the viscous deformation that improves copper alloy is benefited; 2, casting die reasonable in design, this mould should have following characteristics: vertical-parting, open and close conveniently, be easy to exhaust and heat radiation rapidly, and have rational heat distribution, help filling with die cavity, reduce the ingot casting cold shut; Cavity dimension is up big and down small, helps consecutive solidification from bottom to top, so just can fully improve from feeding capacity, thereby ingot casting smooth surface, pore-free, nothing are mingled with, and has got rid of the quality in kind defective of ingot casting, just can improve lumber recovery about 15%; 3, after the ingot casting forge hot, for the required pond of solution treatment is installed in front portion at the bottom of the box-type furnace, can improve the temperature that workpiece falls into water, its shock chilling medium is that temperature is lower than 3 ℃ cryosel (saliferous 15%) water, so can obtain quick refrigerative effect; 4, afterwards, adopt the classification isothermal aging to add the additional ageing treatment method of (added 500 ℃ * 3 hours in 400 ℃ * 2 hours, and added insulation in 480 ℃ * 3 hours behind the air cooling of coming out of the stove again) in strong plasticity cold deformation (deflection is 55-70%).
Adding the purpose of small amount of boron in chromium zirconium copper, is in order to improve hardness of alloy, and when the amount when being lower than 0.02% of boron adds, its alloy rigidity does not reach ideal value, if add-on is above 0.15% o'clock, and just can be to the electric conductivity generation detrimentally affect of alloy.Adding trace niobium in chromium zirconium copper, mainly is to play crystal grain thinning, improves the effect of intensity and resistance to elevated temperatures, has also improved casting and processing characteristics simultaneously.In chromium zirconium copper, add trace rare-earth (cerium) or mix rare on, can impel the refinement of cast alloy product grains.Improve thermoplasticity and thermotolerance, improve the conduction and the heat conductivility of copper.Facts have proved that the optimal components weight proportion of alloy of the present invention is: chromium 0.25-0.50%, zirconium 0.10-0.16%, boron 0.03-0.08%, niobium and rare go up (cerium) respectively contain 0.02-0.06%.
The copper alloy casting chain that will meet alloying element of the presently claimed invention and weight proportion is processed by following technology again: solid solubility temperature is 800 ℃ * 0.5 hour after the forge hot, insulation rises to insulation in 980 ℃ * 2 hours again, come out of the stove fast and drop into Quench in 15% the icy salt solution that temperature is lower than 3 ℃, carry out the strong cold deformation of 55-70% after the Quench, carry out the processing of secondary isothermal aging at last and add additional timeliness (added 500 ℃ * 3 hours and add 480 ℃ * 3 hours additional timeliness behind the air cooling of coming out of the stove again in 400 ℃ * 2 hours) again.Because the speed of cooling of solution treatment also has bigger influence to the strengthening effect of alloy, so when speed of cooling is slow, can reduce vacancy concentration in the sosoloid, even the generation solid solution is decomposed, thereby reduce the effect of ageing strengthening, therefore Quench in being lower than 3 ℃ icy salt solution (saliferous 15%), the solid solution effect is ideal comparatively.Why salt pair water cooling performance produces intense influence, mainly is because the explosive action of salt breaks vapor film rapidly, has shortened the filmwise boiling phase, helps thermal energy transfer, improves hardening capacity and homogeneity, also helps supersaturated solid solution simultaneously and forms; And adopt the classification isothermal aging to handle, to improving and the over-all properties of stable alloy has a significant effect.
Facts have proved, by the moiety weight proportion of copper base alloy provided by the invention and processing method thereof requirement and the copper alloy made, its performance perameter chromium zirconium copper than before has and more significantly improves, and has obtained more satisfactory effect, mainly comprises;
One, Specifeca tion speeification:
1, the HRB75-80 of its normal temperature hardness before by the present invention brings up to MRB84-92, and 2, electric conductivity brings up to 45MS/m by 43MS/m, 3, softening temperature brings up to 620 ℃-650 ℃ by 575 ℃.
Two, adopt the copper master alloy that contains more than the chromium 10-20%, improved the copper alloy viscous deformation; Reasonably casting die has improved again from feeding capacity, has improved the quality in kind of ingot casting significantly, so lumber recovery improves about 15%.
Three, owing to adopt the secondary isothermal aging to add additional ageing treatment, suppressed the discontinuous phenomenon of separating out significantly, and made second become the mutually disperse more, evenly, therefore made the copper alloy over-all properties in high volume production process, obtain effective and stable control.
Four, because copper base alloy moiety weight proportion of the present invention is reasonable, technology advanced person, reliable, the lumber recovery height, thus production cost decrease, good in economic efficiency.
In sum, copper base alloy by the present invention's production, its electric conductivity average out to 45MS/m, normal temperature hardness average out to HRB88, softening temperature is greater than 620 ℃, its lumber recovery obviously improves in batch production process, because its over-all properties obviously is better than chromium zirconium copper, so be suitable for light alloy plate, steel plate, Coated Steel, the resistance welding electrode material of stainless steel plate and titanium alloy sheet.
Be described as follows about embodiments of the invention:
Obtain copper alloy casting ingot with method of the present invention just like listed (3 batches 18 stoves) moiety of embodiment parameter list and weight proportion, promptly contain chromium 0.21-0.71%, zirconium 0.08-0.22%, boron 0.03-0.134%, niobium 0.02-0.08%, cerium 0.02-0.06%, this copper alloy casting ingot is handled through following operation, it is forge hot (forge repeatedly and dial once) → solid solution → strong cold deformation → timeliness → air cooling, resulting copper alloy after testing, has following performance: normal temperature hardness HRB84-92, electric conductivity 43.5-47MS/m, 620 ℃-680 ℃ of softening temperatures.
Embodiment of the invention parameter list
Embodiment Moiety weight (%) proportioning Detected result
Batch (heat (batch) number) Chromium Zirconium Boron Niobium Cerium HRB Electric conductivity (MS/m) Softening temperature (℃)
1 21 0.21 0.13~0.22 0.086~0.134 0.02~0.08 0.02~0.06 84 46 620
22 0.23 0.13~0.22 0.086~0.134 0.02~0.08 0.02~0.06 84.5 46.3 620
23 0.24 0.13~0.22 0.086~0.134 0.02~0.08 0.02~0.06 84.8 46.5 620
24 0.28 0.13~0.22 0.086~0.134 0.02~0.08 0.02~0.06 85 46.7 620
25 0.30 0.13~0.22 0.086~0.134 0.02~0.08 0.02~0.06 86 46.8 620
26 0.32 0.13~0.22 0.086~0.134 0.02~0.08 0.02~0.06 86.2 47 620
2 28 0.35 0.10~0.17 0.05~0.10 0.02~0.08 0.02~0.06 86.4 45 650
29 0.37 0.10~0.17 0.05~0.10 0.02~0.08 0.02~0.06 86.5 45.2 650
30 0.40 0.10~0.17 0.05~0.10 0.02~0.08 0.02~0.06 87 45.5 650
31 0.42 0.10~01.7 0.05~0.10 0.02~0.08 0.02~0.06 87.2 45.6 650
32 0.45 0.10~0.17 0.05~0.10 0.02~0.08 0.02~0.06 87.6 45.8 650
33 0.47 0.10~0.17 0.05~0.10 0.02~0.08 0.02~0.06 88 46 650
3 40 0.52 0.08~0.12 0.03~0.08 0.02~0.08 0.02~0.06 88.5 45 680
41 0.55 0.08~0.12 0.03~0.08 0.02~0.08 0.02~0.06 89 44.8 680
42 0.57 0.08~0.12 0.03~0.08 0.02~0.08 0.02~0.06 90 44.5 680
43 0.60 0.08~0.12 0.03~0.08 0.02~0.08 0.02~0.06 91 44 680
44 0.65 0.0~0.12 0.003~0.08 0.02~0.08 0.02~0.06 91.8 43.8 68O
45 0.71 0.08~0.12 0.03~0.08 0.02~0.08 0.02~0.06 92 43.5 680

Claims (3)

1, a kind of copper base alloy, containing the alloy element component weight proportion is: chromium 0.20-0.80%, zirconium 0.06-0.28%, it is characterized in that it also contains alloying element boron, niobium and cerium, and it contains for boron 0.02-0.15%, niobium and cerium respectively contain 0.02-0.08%, and surplus is a copper.
2, according to the described copper base alloy of claim 1, the weight proportion that it is characterized in that contained alloy is that chromium 0.25-0.50%, zirconium 0.10-0.16%, boron 0.03-0.08%, niobium and cerium respectively contain 0.02-0.06%, and all the other are copper.
3, a kind of processing method that obtains above-mentioned copper base alloy is characterized in that comprising following process: i.e. mould cold deformation → classification isothermal aging by force under copper base alloy ingot casting → forge hot → classification isothermal solid solution → room temperature; Its main technique condition and parameter are: first melting contains the copper master alloy of chromium 10-20%, and adds melting in the copper in the master alloy mode, adopts the vertical-parting mold, and die cavity descends little anti-rising head mould greatly for last; The required pond of solution treatment is installed in front portion at the bottom of the box-type furnace; Shock chilling medium is that temperature is lower than 3 ℃ 15% icy salt solution; The deflection of strong plasticity cold deformation is 55-70%; Adopt the classification isothermal aging to add the method for replenishing ageing treatment: promptly 400 ℃ *Added 500 ℃ in 2 hours *3 hours, add 480 ℃ behind the air cooling of coming out of the stove again *Insulation in 3 hours.
CN98112673A 1998-10-09 1998-10-09 Copper-base alloy and its prepn. technology Expired - Fee Related CN1098362C (en)

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CN101113498B (en) * 2007-07-13 2010-04-14 宁波博威合金材料股份有限公司 High-strength highly-conductive low-calcium boron chromic zirconium copper alloy and method for manufacturing same
CN103710508B (en) * 2013-12-13 2016-05-18 柳城县鼎铭金属制品有限公司 The manufacture method of anti-bacteria stainless steel wire rod
CN105695776B (en) * 2016-02-26 2017-06-06 济南大学 A kind of Graphene strengthens the preparation method of copper-based electrical contact material
CN106001977B (en) * 2016-06-12 2018-04-13 常熟明辉焊接器材有限公司 The preparation method of automobile welding electrode material
CN105908009B (en) * 2016-06-12 2018-10-09 常熟明辉焊接器材有限公司 A kind of aluminium alloy plate welding electrode material and preparation method thereof
CN109913691A (en) * 2019-04-22 2019-06-21 南通科誉德摩尔新材料有限公司 A kind of manufacture craft of high-strength compound chromium-zirconium-copper material
CN110042273B (en) * 2019-05-29 2020-11-06 南京达迈科技实业有限公司 High-strength high-conductivity copper alloy pipe and preparation method thereof
CN110773567B (en) * 2019-10-21 2021-05-04 东莞市大忠电子有限公司 Pin riveting process of vehicle-mounted inductor
CN111471879B (en) * 2020-04-17 2021-05-28 中铝材料应用研究院有限公司 Preparation method of copper alloy for contact wire

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049426A (en) * 1976-10-04 1977-09-20 Olin Corporation Copper-base alloys containing chromium, niobium and zirconium

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049426A (en) * 1976-10-04 1977-09-20 Olin Corporation Copper-base alloys containing chromium, niobium and zirconium

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