CN101041873A - High-strength copper alloy for thin-belt continuous casting crystallization roller and method for manufacturing same - Google Patents
High-strength copper alloy for thin-belt continuous casting crystallization roller and method for manufacturing same Download PDFInfo
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Abstract
The invention discloses a high-strength and high-conductive copper alloy of continuous casting thin-belt crystal roll, which comprises the following parts: 1-2.5% Ni, 0.05-0.2% Si,0.05-0.2% Zr, 0.2-0.4% Cr, 0.05-0.1% Sn, one or more of Fe, Co and Mg with total quantity less than 0.15% and Cu, wherein the rate of Ni and Si is more than 8: 1. The making method comprises the following steps: adding Ni, Zr, Co and Sn to exert alloy element action; heating; obtaining the copper alloy material without beryllium.
Description
Technical field
The present invention relates to the thin band continuous casting crystallization roller alloy.
Background technology
Thin strap continuous casting is exactly the crystallization roller of molten steel through high speed rotating, and is frozen into the 1-5mm Cast Strip under the effect of rolling load.Overheated and the crystallization latent heat of molten steel will be taken away heat through water-cooled crystallization roller, solidifies on the crystallization roller, and two solidified shell are located to merge and the formation Cast Strip " point coincide ".Crystallization roller one side contacts with molten steel; Another side water-cooled face stands renting of rolling load simultaneously.This requires crystallization roller material to have: 1) good thermal conductivity; 2) high strength and hardness; 3) emergency heat and cooling property resistance chilling performance; 4) fatigue property of heat-resisting alternation.
For the contradiction that exists between copper alloy intensity and heat conduction, electroconductibility.According to the alloying theory, alloying level is high more, and the intensity of alloy is just high, but heat conduction and poorly conductive; Otherwise specific conductivity raises, and intensity then reduces.Be widely applied to alloy series intensity HBS120-135Mpa such as the Cu-Ag alloy of continuous cast mold and Cr-Zr-Cu, can not satisfy the requirement of strength of thin band continuous casting crystallization roller far away.
Reinforcement for copper alloy has two kinds of thinkings: the one, and introduce alloying element and strengthen the copper matrix and form alloy; The secondth, introduce second strengthening phase and form matrix material.Beraloy is an ageing strengthening effect highly significant, and also the hardest copper alloy is as QBe
2, QBe
1.9, QBe
1.7Deng Be content 1.5-2.8% copper alloy series.This series copper alloy has high strength, and HBS can reach 350-400MPa, because the atomic radius of Be much smaller than copper atom, therefore adds more Be, has reduced thermal conductivity and electroconductibility.
U.S. Pat 6,083, the alloys of 328 inventions are thin strap continuous castings with crystallization roller copper alloy material, Be content 0.1-0.45%, Ni (or Co) content 1-2.6%, add the Zr of 0.05-0.25% simultaneously, Ce, Cr, ta, a kind of element such as ha, its intensity reaches HBS200, electric conductivity＞60%IACS.U.S. Pat 6,059,905, US5,074,922, US4,792,365, US4,657,601, US4,533,412, US4,421,570, US4,377,424 US4,179,314 grades and Chinese patent 85107530,89105212,90103861 all is to contain on the Be:0.05-2% basis, adds Ni or Co or Ni+Co (0.6-5%), and add＜0.5% Zr according to separately application target, Cr, Fe, elements or wherein a kind of such as Pb, improve over-all properties, and by corresponding solid solution, aging thermal treating process obtains the beryllium copper of high-strength high conductivity and heat conductivility.
Chinese patent 86102885, US5846346, US5846346 are a kind of copper alloys of Ni-Si-Cu series, U.S. Pat 5370840; US4872048; English Patent 1353430 and Chinese patent 93114361 etc. are the copper alloys of Cr-Zr-Cu series, and it is mainly used in lead frame and junctor etc. this alloy, therefore resist relaxed stress, and bending property etc. have requirement.And thin strap continuous casting requires good thermal conductivity with crystallization roller Cu alloy material; High strength and hardness and emergency heat and cooling property resistance chilling performance.The antagonism relaxed stress, bending property etc. do not require.
The design of alloy will be according to the behaviour in service and the use properties design of material.As can be seen from the above analysis, present high-strength highly-conductive crystallization roller mainly concentrates on copper alloy and contains beryllium copper.Because beryllium element has severe toxicity, very big to environment and human health damage, therefore, the thin band continuous casting crystallization roller copper alloy of developing no beryllium, environmental protection has great importance.
Summary of the invention
The object of the present invention is to provide a kind of thin band continuous casting crystallization roller copper alloy with high strength and high conductivity and manufacture method thereof, by adding the interactional advantages of element performance alloying element such as Ni, Si, Zr, Co, Sn, and by proper heat treatment technology, obtain the copper alloy material of high strength and high thermal conductivity, particularly do not have beryllium, environmental protection and HUMAN HEALTH are brought huge benefits.
For achieving the above object, technical scheme of the present invention is, the thin band continuous casting crystallization roller copper alloy with high strength and high conductivity, and its composition quality per-cent is: Ni:1-2.5%; Si:0.05-0.2%; Zr:0.05-0.2%; Cr:0.2-0.4%; Sn:0.05-0.1%; Fe, Co, one or more among the Mg, its total amount is less than 0.15%; All the other are Cu; The Ni/Si ratio is＞8: 1.
Further, in its composition, Ni:1.5-2.5%; Si:0.05-0.15%; Zr:0.05-0.15%; Cr:0.2-0.3%; Sn:0.05-0.1%.
The manufacture method of copper alloy with high strength and high conductivity of the present invention comprises the steps:
A) copper alloy of smelting according to the mentioned component scope is cast into ingot casting, ingot casting is incubated 1-8 hour in 800-950 ℃ of process furnace after forge hot, the compression ratio of forge hot is greater than 40%;
B) blank after the forge hot is quenched; And 850-1080 ℃ of solution treatment, the treatment time is 5-10h;
C) blank of solution treatment quenches; Carry out greater than 20% cold deformation then, and at 400-550 ℃, insulation 8-30h carries out ageing treatment.
After above-mentioned steps,
Perhaps, carry out secondary or, and at 400-550 ℃, insulation 8-30h carries out ageing treatment repeatedly greater than 20% cold deformation.
Perhaps, carry out greater than 20% cold deformation.
Perhaps, carry out secondary or repeatedly 400-550 ℃ of insulation 8-30h ageing treatment and greater than 20% cold deformation.
The product performance that obtain by aforesaid method reach: HBS＞200; Softening temperature＞550 ℃; Electric conductivity IACS%:＞50.
For thin band continuous casting crystallization roller copper alloy material, the processing requirement according to using requires the copper alloy material to have high strength, medium conduction (heat conduction) property.For reaching this purpose, by adding Ni, elements such as Si, Zr, Cr, Co, Sn are brought into play the interactional advantage of alloying element, and by proper heat treatment technology, obtain the copper alloy material of high strength and high thermal conductivity.Satisfy thin band continuous casting crystallization roller rapid heat cycle, high strength, hardness and thermal conductivity requirement.
The alloy strengthening general fashion is to add an amount of alloying element to realize solution strengthening, reaches working hardening by flow, separates out or grain refining is further strengthened by timeliness.Single solution strengthening, precipitation strength and working hardening effect are limited, and copper alloy intensity is lower, and electroconductibility is also undesirable.So often several modes are united use,, can improve ageing strengthening copper alloy intensity greatly and less to the specific conductivity influence as solid solution+cold deformation+aging technique.
Ni and Si are very strong solid solution and ageing strengthening alloys.Add Ni and suppress the crystal boundary reaction, slow down ag(e)ing process, add Si and make that the timeliness precipitate has δ-Ni in the alloy
2The crystalline structure that Si is similar plays strengthening effect, and this Ni-Si timeliness precipitate is in the form of annular discs, has preferred orientation and the alligatoring rate is very little, so Ni-Si can reach very high hardness behind the alloy aging.But it should be noted that the Ni of Ni-Si precipitate and Si atomicity proportioning want rationally, this is because under the low-alloy condition, and when Ni in the alloy and Si atomicity proportioning depart from this ratio, unnecessary strengthening element will exist with the solid solution atomic form.Solid solution Si element is very big to the infringement of copper alloy specific conductivity, and the unnecessary Ni element of solid solution then influences very little to specific conductivity, therefore should guarantee that when design of alloy the Si element is not superfluous after timeliness.
When Ni, Si alloying element enter in the copper matrix,, also reduce the specific conductivity of copper matrix simultaneously to a great extent though can improve the intensity of copper matrix.This is because after alloying element enters the copper matrix, because of its atomic size different with copper, thereby cause lattice distortion.Lattice distortion has the intensive scattering process to electron motion, thereby makes under its specific conductivity.
Cr, Zr are ageing strong alloying elements.The Cr particle that timeliness is separated out has not only been strengthened matrix, and suppresses recrystallize to a certain extent and carry out, and alloy strength is further improved.Simultaneously, tiny precipitation particles disperse is distributed in the high conductivity matrix, and is very little to the specific conductivity influence, so alloy keeps high conductance.Cr that separates out during the Cu-Cr-Zr timeliness and Cu
3The Zr particle weight is many and fine and closely woven, hinder soaring, the slippage and the crystal boundary migration of dislocation, and its solid solubility temperature changes forr a short time than Cu-Cr to the influence of hardness, but the Cu-Cr time hardening is big, is very easy to overaging.But [111] crystal face is separated out thin and thick Cu among the Cu-Zr
3The Zr sheet, the timeliness weak effect.The solubleness of Zr in copper is very little, and electric conductivity reduces minimum, and Cu and Zr form Cu
3The Zr intermetallic compound, the Cu of disperse
3Zr strengthens the copper matrix.Thereby under room temperature and high temperature, have good mechanical performance and an electric conductivity.
In addition, for giving full play to the effect of alloy, according to the service requirements appropriate design thermal treatment process of material.The design main principle of thermal treatment process is according to alloy characteristic, utilize deformation, simultaneously strict control subsequently answer and recrystallization process to obtain small grains tissue, promptly metal and alloy are through the very high structural state of a kind of dislocation desity of formation after the medium and strong cold deformation.The supplementary means of cold-work strengthening Chang Zuowei ageing strengthening is as adopting: 1. solid solution+cold deformation+timeliness, or 2. solid solutions+timeliness+cold deformation.Adopting process 1 when performance requriements laid particular emphasis on specific conductivity, and adopting process 2 when stressing intensity.
Should guarantee alloying element during solution treatment when all dissolving in matrix, avoid that crystal grain Yin Wendu is too high, soaking time is long and growing up unusually of causing.After the solution treatment, the cold plastic deformation of crystal grain experience, size is elongated along deformation direction, after the ageing treatment, though crystal grain has still kept the most of grain properties after the solution treatment changing to some extent in shape.For improving intensity, the crystal grain after the refinement timeliness is a kind of important reinforcement means.Therefore will increase the forge hot operation further improves intensity.Because alloying constituent of the present invention has been added Ni, therefore the alloying element of solution strengthening such as Si must reach the purpose that improves intensity by reasonably controlling solid solubility temperature and time.
Single solution strengthening is the performance requriements that can't satisfy product, and cold deformation makes alloy still keep higher electric conductivity when improving alloy strength.And cold forging is than the recrystal grain size that affects alloy.Cold forging is than too small, and the storage during lattice distortion can be not enough to cause alloy generation recrystallize for a short time.Cold forging can increase owing to storing than big more, thereby causes recrystallize nucleation rate and coarsening rate all to increase, but the increase of nucleation rate is greater than the increase of coarsening rate, so recrystallize grain refining later on takes place.After cold deformation acquires a certain degree.The recrystal grain size remains unchanged substantially.Therefore controlling rational cold forging ratio is even more important.
Alloy produces a large amount of dislocations later on through cold forging, in moving process, hindered because of the strengthening phase that the matrix diffusion-precipitation distributes, form a large amount of dislocation tangling, caused hardness to rise to peak value in a short period of time, owing to beginning to assemble, the precipitated phase particle grows up and alligatoring gradually afterwards, so cause hardness to begin to descend.Electric conductivity raise with the timeliness time lengthening fast in early stage, and this is because the variation of resistivity mainly is subjected to the influence of solid solution atom precipitation speed in the matrix, and precipitation mainly relies on the migration of solid solution atom, and this again need be by the effect of defectives such as dislocation, room.Because at a certain temperature, the decay index of coincidence in room relation is so at the timeliness initial stage, the electric conductivity of alloy changes very fast.Along with the prolongation with the timeliness time of the increase alloy conductive rate of time slowly raises, this may be because the size of timeliness product be near the conduction electron wavelength at this moment, this size makes the scattering of electronics generation intensive, separate out the alloy conductive rate that causes the dilution of matrix sosoloid and cause with timeliness and improve partial offset, so this moment, electric conductivity rose slowly.The present invention has added the strong Cr of ageing strengthening, Zr, elements such as Sn.Separate out second purpose that reaches reinforcement mutually by timeliness.But must rationally control the time and the temperature of timeliness.
The difference of the present invention and prior art and improvements:
1, U.S. Pat 6,083, the alloy of 328 inventions is thin strap continuous casting crystallization roller copper alloy materials, Be content 0.1-0.45%, Ni (or Co) content 1-2.6%, add the Zr of 0.05-0.25%, Ce, Cr simultaneously, ta, a kind of element such as ha, its intensity reaches HBS200, electric conductivity＞60%IACS.U.S. Pat 6,059,905, US5,074,922, US4,792,365, US4,657,601, US4,533,412, US4,421,570, US4,377,424 US4,179,314 grades all are to contain on the Be:0.05-2% basis, add Ni or Co or Ni+Co (0.6-5%), and add＜0.5% Zr, Cr according to separately application target, Fe, elements or wherein a kind of such as Pb improve over-all properties.
Alloying constituent of the present invention does not contain the Be element.Because the Be element is the element that severe toxicity is arranged, environment and human body are had very big harm, so the present invention is useful to environmental protection.
2, Chinese patent 86102885 and U.S. Pat 5,846,346th, a kind of Cu-Ni-Si series copper alloy.Chinese patent 86102885 is to add Mg to improve its intensity and anti-relaxed stress on the alloy basis.Its alloys range is: Ni:2～4.8%; Si:0.2～1.4%; Mg:0.05～0.45%; Ni/Si:3.5: 1～4.5: 1.U.S. Pat 5,46,346th adds Sn and improves intensity on the alloy basis.Its alloys range is: Ni:0.5～4%; Si:0.1～1%; Sn:0.05～0.8%;
The present invention is different with the composition that above-mentioned patent difference is an alloy, and above-mentioned patent mainly improves intensity by Ni and Si, so constituent content is higher, and the present invention mainly improves intensity by the ageing strengthening of Cr and Zr, can reduce the content of Ni and Si.
3, the composition range of U.S. Pat 4872048 patents is: 0.05～1Cr-0.005～0.3Zr-0.001～0.05Li-0～0.10Si-0～1Ni-(5-60ppmC), and other P, Mg, Al, Zn, a kind of among the Mn.
The difference of the present invention and this patent is that Ni content of the present invention is greater than 1%, not in the scope of this patent.The purpose that the present invention increases Ni content is to improve performance by solution strengthening, and therefore thermal treatment process of the present invention has this process of solution treatment.And this patent is mainly gained in strength by the ageing strengthening of Cr and Zr and other alloying element, so this patent does not have this technological process of solution treatment in an embodiment.
4, the main component of English Patent 1353430 is 0.5Cr-0.13Ti-0.25Sn-0.12Zr, do not contain Ni in its composition, and characteristics of the present invention is to contain Ni, and its composition range is different with it.
Beneficial effect of the present invention
Thin band continuous casting crystallization roller copper alloy with high strength and high conductivity of the present invention, by adding Ni, elements such as Si, Zr, Co, Sn are brought into play the interactional advantage of alloying element, and by proper heat treatment technology, obtain the copper alloy material of high strength and high thermal conductivity, HBS＞200; Softening temperature＞550 ℃; Electric conductivity IACS%:＞50%; Particularly do not have beryllium, environmental protection and HUMAN HEALTH are brought huge benefits.
Embodiment
Embodiment 1
To consist of Ni:1.5%; Si:0.1%; Zr:0.15%; Cr:0.2%; Sn:0.08; Fe+Co+Mg＜0.1%, all the other are the alloy of Cu, are cast in the ingot mold 1100 ℃ temperature, are cast into ingot casting, ingot casting is incubated 2 hours in 880 ℃ of process furnace after forge hot, the compression ratio 45% of forge hot; Blank after the forge hot is quenched; And 950 ℃ of solution treatment; Treatment time is 8h; The blank of solution treatment quenches; Carry out 30% cold deformation then; And at 450 ℃, insulation 24h carries out ageing treatment; Obtain the performance hardness HB:210 of alloy, electric conductivity: 50%.
Embodiment 2
To consist of Ni:2.5%; Si:0.05%; Zr:0.1%; Cr:0.2%; Sn:0.05%; Fe+Co+Mg＜0.1%, all the other are the alloy of Cu, are cast to 1100 ℃ temperature and are cast into ingot casting in the ingot mold, ingot casting is incubated 3 hours in 950 ℃ of process furnace after forge hot, the compression ratio of forge hot is greater than 40%; Blank after the forge hot is quenched; And 1000 ℃ of solution treatment; Treatment time is 5h; The blank of solution treatment quenches; Carry out then greater than 20% cold deformation; At 450 ℃, ageing treatment is carried out in insulation 12 then; Cold deformation greater than 20%; And at 550 ℃, insulation 12h carries out ageing treatment; Obtain the performance hardness HB:212 of alloy, electric conductivity: 54%.
Embodiment 3
To consist of Ni:1%; Si:0.1%; Zr:0.2%; Cr:0.3%; Sn:0.05%; Fe+Co+Mg＜0.1%, all the other are the alloy of Cu, are cast in the ingot mold 1100 ℃ temperature, are cast into ingot casting, ingot casting is incubated 3 hours in 900 ℃ of process furnace after forge hot, the compression ratio of forge hot is greater than 40%; Blank after the forge hot is quenched; And 980 ℃ of solution treatment; Treatment time is 5h; The blank of solution treatment quenches; At 480 ℃, insulation 30h carries out ageing treatment; Carry out then greater than 20% cold deformation; Obtain the performance hardness HB:203 of alloy, electric conductivity: 56%.
Embodiment 4
To consist of Ni:1.5%; Si:0.18%; Zr:0.15%; Cr:0.28%; Sn:0.05%; Fe+Co+Mg＜0.1%, all the other are the alloy of Cu, are cast in the ingot mold 1100 ℃ temperature, are cast into ingot casting, ingot casting is incubated 2 hours in 900 ℃ of process furnace after forge hot, the compression ratio of forge hot is greater than 40%; Blank after the forge hot is quenched; And 980 ℃ of solution treatment; Treatment time is 6h; The blank of solution treatment quenches; At 550 ℃, insulation 12h carries out ageing treatment; Carry out then greater than 20% cold deformation; At 450 ℃, insulation 24h carries out ageing treatment; And then carry out greater than 20% cold deformation; Obtain the performance hardness HB:228 of alloy, electric conductivity: 52%.
Embodiment 5
To consist of Ni:1%; Si:0.05%; Zr:0.05%; Cr:0.4%; Sn:0.1%; Fe+Co+Mg＜0.1%, all the other are the alloy of Cu, are cast in the ingot mold 1100 ℃ temperature, are cast into ingot casting, ingot casting is incubated 5 hours in 950 ℃ of process furnace after forge hot, the compression ratio of forge hot is greater than 40%; Blank after the forge hot is quenched; And 980 ℃ of solution treatment; Treatment time is 8h; The blank of solution treatment quenches; At 550 ℃, insulation 24h carries out ageing treatment; Carry out then greater than 20% cold deformation; At 450 ℃, insulation 24h carries out ageing treatment; And then carry out greater than 20% cold deformation; Obtain the performance hardness HB:206 of alloy, electric conductivity: 50%.
Claims (7)
1. thin band continuous casting crystallization roller copper alloy with high strength and high conductivity, its composition quality per-cent is: Ni:1-2.5%; Si:0.05-0.2%; Zr:0.05-0.2%; Cr:0.2-0.4%; Sn:0.05-0.1%; Fe, Co, one or more among the Mg, its total amount is less than 0.15%; All the other are Cu; The Ni/Si ratio is＞8: 1.
2. thin band continuous casting crystallization roller copper alloy with high strength and high conductivity as claimed in claim 1 is characterized in that, Ni:1.5～2.5%; Si:0.05-0.15%; Zr:0.05-0.15%; Cr:0.2-0.3%; Sn＜0.05%.
3. thin band continuous casting crystallization roller copper alloy with high strength and high conductivity as claimed in claim 1 or 2 is characterized in that, the performance of this copper alloy reaches: HBS＞200; Softening temperature＞550 ℃; Electric conductivity IACS%:＞50%.
4. thin band continuous casting crystallization roller as claimed in claim 1 or 2 comprises the steps: with the manufacture method of copper alloy with high strength and high conductivity
A) copper alloy of smelting according to the mentioned component scope is cast into ingot casting, ingot casting is incubated 1-8 hour in 800-950 ℃ of process furnace after forge hot, the compression ratio of forge hot is greater than 40%;
B) blank after the forge hot is quenched; And 850-1080 ℃ of solution treatment, the treatment time is 5-10h;
C) blank of solution treatment quenches; Carry out greater than 20% cold deformation then, and at 400-550 ℃, insulation 8-30h carries out ageing treatment.
5. thin band continuous casting crystallization roller as claimed in claim 4 is characterized in that with the manufacture method of copper alloy with high strength and high conductivity, after the step c), carry out secondary or repeatedly greater than 20% cold deformation, and at 400-550 ℃, insulation 8-30h carries out ageing treatment.
6. thin band continuous casting crystallization roller as claimed in claim 4 is characterized in that with the manufacture method of copper alloy with high strength and high conductivity, after the step c), carries out greater than 20% cold deformation;
7. thin band continuous casting crystallization roller as claimed in claim 4 is characterized in that with the manufacture method heat of copper alloy with high strength and high conductivity, after the step c), carry out secondary or repeatedly 400-550 ℃ of insulation 8-30h ageing treatment and greater than 20% cold deformation.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102560191A (en) * | 2010-12-09 | 2012-07-11 | 北京有色金属研究总院 | High-performance elastic copper alloy and preparation and processing method thereof |
| CN105478693A (en) * | 2016-01-21 | 2016-04-13 | 张颖 | Preparation method of continuous casting roller type crystallizer |
| CN107739877A (en) * | 2017-11-09 | 2018-02-27 | 河南科技大学 | One Albatra metal roller set and preparation method thereof |
| CN107779660A (en) * | 2017-11-09 | 2018-03-09 | 河南科技大学 | A kind of high-strength high Vulcan metal and preparation method thereof |
| CN109079116A (en) * | 2018-07-10 | 2018-12-25 | 浙江力博实业股份有限公司 | A kind of preparation method of electrode material corson alloy |
| CN110358945A (en) * | 2019-08-27 | 2019-10-22 | 天长市华海电子科技有限公司 | A kind of high hardness alloy forge piece and its preparation process |
| CN110462077A (en) * | 2017-03-30 | 2019-11-15 | 捷客斯金属株式会社 | Cu-Ni-Si series copper alloy strip |
| CN112410611A (en) * | 2020-11-10 | 2021-02-26 | 北京中超伟业信息安全技术股份有限公司 | Copper alloy plate for safety encryption chip lead frame and preparation method thereof |
| CN113046594A (en) * | 2021-03-11 | 2021-06-29 | 郑州大学 | High-strength high-thermal-conductivity copper alloy material roller sleeve and preparation method thereof |
| CN113957286A (en) * | 2021-10-20 | 2022-01-21 | 烟台万隆真空冶金股份有限公司 | Copper alloy for thin strip chilling crystallizer, preparation method thereof and thin strip chilling crystallizer |
| CN116065053A (en) * | 2023-04-03 | 2023-05-05 | 凯美龙精密铜板带（河南）有限公司 | Copper alloy and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102560191A (en) * | 2010-12-09 | 2012-07-11 | 北京有色金属研究总院 | High-performance elastic copper alloy and preparation and processing method thereof |
| CN105478693A (en) * | 2016-01-21 | 2016-04-13 | 张颖 | Preparation method of continuous casting roller type crystallizer |
| CN110462077B (en) * | 2017-03-30 | 2021-08-03 | 捷客斯金属株式会社 | Cu-Ni-Si copper alloy strip |
| CN110462077A (en) * | 2017-03-30 | 2019-11-15 | 捷客斯金属株式会社 | Cu-Ni-Si series copper alloy strip |
| CN107739877A (en) * | 2017-11-09 | 2018-02-27 | 河南科技大学 | One Albatra metal roller set and preparation method thereof |
| CN107779660A (en) * | 2017-11-09 | 2018-03-09 | 河南科技大学 | A kind of high-strength high Vulcan metal and preparation method thereof |
| CN107739877B (en) * | 2017-11-09 | 2019-10-18 | 河南科技大学 | One Albatra metal roller set and preparation method thereof |
| CN109079116A (en) * | 2018-07-10 | 2018-12-25 | 浙江力博实业股份有限公司 | A kind of preparation method of electrode material corson alloy |
| CN110358945A (en) * | 2019-08-27 | 2019-10-22 | 天长市华海电子科技有限公司 | A kind of high hardness alloy forge piece and its preparation process |
| CN112410611A (en) * | 2020-11-10 | 2021-02-26 | 北京中超伟业信息安全技术股份有限公司 | Copper alloy plate for safety encryption chip lead frame and preparation method thereof |
| CN113046594A (en) * | 2021-03-11 | 2021-06-29 | 郑州大学 | High-strength high-thermal-conductivity copper alloy material roller sleeve and preparation method thereof |
| CN113957286A (en) * | 2021-10-20 | 2022-01-21 | 烟台万隆真空冶金股份有限公司 | Copper alloy for thin strip chilling crystallizer, preparation method thereof and thin strip chilling crystallizer |
| CN116065053A (en) * | 2023-04-03 | 2023-05-05 | 凯美龙精密铜板带（河南）有限公司 | Copper alloy and preparation method thereof |
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