CN101787552B - Cu-W-Ni copper matrix composite used for liner, electroforming method and electroforming solution thereof - Google Patents
Cu-W-Ni copper matrix composite used for liner, electroforming method and electroforming solution thereof Download PDFInfo
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- CN101787552B CN101787552B CN2010103004877A CN201010300487A CN101787552B CN 101787552 B CN101787552 B CN 101787552B CN 2010103004877 A CN2010103004877 A CN 2010103004877A CN 201010300487 A CN201010300487 A CN 201010300487A CN 101787552 B CN101787552 B CN 101787552B
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- electroforming
- cavity liner
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- liner
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Abstract
The invention discloses a Cu-W-Ni copper matrix composite used for a liner, an electroforming method and an electroforming solution thereof, belonging to the electroforming field. The electroforming solution comprises the following components by proportion: 200-250g/L of NiSO4.7H2O, 60-90g/L of Na2WO4.2H2O, 6-10g/L of CuSO4.5H2O, 1-3g/L of CuCl2.2H2O, 270-320g/L of Na3C6H5O7.H2O, 0.3-0.5g/L of C12H25SO4Na, 1.0-1.5g/L of saccharin and 0.25-1mL/L of 1,4-butynediol. The electroforming condition comprises: the pH value of 10% of dilute sulphuric acid is regulated at 5.5-7.0, the temperature is 50-70 DEG C, the current density is 5-15A/dm2, the mechanical stirring is adopted, and a phosphorus-copper plate with 99.9% of Cu and 0.02-0.06% of P is used as an anode. The Cu-W-Ni copper matrix composite prepared in the invention has fine grains and homogeneous structure, and the Cu-W-Ni copper matrix composite liner is easily thickened through electroforming and has no defect on the surface and stable process.
Description
Technical field
The invention belongs to the electroforming preparation field, be specifically related to Cu-W-Ni Cu-base composites and electrocasting method and electroforming solution that a kind of cavity liner is used.
Background technology
The monometallic cavity liner exists great defective, promptly increase effusive length and just must strengthen the effusive velocity slope, and the very big raising of jet speed gradient is solved with the monometallic cavity liner than difficult.If use heavy metals tungsten etc. is done the cavity liner material,, manufacture difficulty and cost or the like have also been increased simultaneously greatly though improved density.
Up to the present, the method for various countries' machining composite material cavity liner mainly contains three kinds of powder metallurgy, flow forming and molding process and electroforming.Compare electroforming cover crystal grain carefully much smaller (≤1 μ m) with traditional powder metallurgy and flow forming and molding process; Have tangible silk weaving structure to exist, crystal grain has preferred orientation along the cover thickness direction; And the silk weaving structure is influenced by the core rotating speed, increases with the core rotating speed, and the texture degree also increases.Employing electroforming method for processing can obtain the cavity liner of superfine crystal particle, and the internal stress of cavity liner is less, wall thickness is even.And, can effectively control the heterogeneous microstructure of cavity liner, thereby improve shaped charge action by control electroforming process parameter.Therefore, the matrix material cavity liner of electroforming processing all has bigger superiority than the cavity liner of spinning processing etc. at aspects such as structure property, broken first effects.The report for preparing existing relevant patent of fine copper, pure nickel cavity liner and application thereof with galvanoplastics both at home and abroad; But the patent application and the mandate that do not have electrocasting to prepare copper-tungsten or copper base composite liner do not have corresponding open source literature report yet.
Summary of the invention
The object of the present invention is to provide a kind of new cavity liner Cu-W-Ni Cu-base composites, the cavity liner of preparation, and supporting electrocasting method and electroforming solution.This method can be relatively low at the technology cost, and under the not high situation of service temperature, it is even to prepare tissue distribution, the Cu-W-Ni Cu-base composites of ultra fine grain size.
A kind of cavity liner electroforming preparation electroforming solution of Cu-W-Ni Cu-base composites, composition and proportioning are as follows:
NiSO
4·7H
2O 200-250g/L；
Na
2WO
4·H
2O 60-90g/L；
CuSO
4·5H
2O 6-10g/L；
CuCl
2·2H
2O 1-3g/L；
Na
3C
6H
5O
7·2H
2O 270-320g/L；
C
12H
25SO
4Na 0.3-0.5g/L；
Asccharin 1.0-1.5g/L;
1,4 butynediol 0.25-1mL/L.
Optimum ratio is: NiSO
47H
2O:210g/L; Na
2WO
42H
2O:80g/L; CuSO
45H
2O:6g/L; CuCl
22H
2O:1.5g/L; Na
3C
6H
5O
72H
2O:290g/L; C
12H
25SO
4Na:0.4g/L; Asccharin: 1.0-1.5g/L; 1,4 butynediol: 0.25-1mL/L.
Adopt the electrocasting method of above-mentioned electroforming solution as follows: the dilute sulphuric acid with 10% is regulated pH=5.5-7.0; Temperature is controlled at 50-70 ℃; Current density is 5-15A/dm
2Adopt mechanical stirring; Phosphorus copper plate is done anode and is carried out electroforming.
The cavity liner that utilizes electroforming solution of the present invention and electrocasting method to obtain is the matrix material that electroforming contains 89-83.2wt% copper, 6.2-9.6wt% nickel and 4.8-7.2wt% tungsten on copper coin with the Cu-W-Ni Cu-base composites.The matrix material that preferably contains 85.6wt% copper, 8.4wt% nickel and 6wt% tungsten.
Because the thickness of electroforming cavity liner reaches 2-5mm, the stress of coating increases, and the additive asccharin can reduce the coating internal stress, the refinement particle, and the effect that improves the cathodic polarization ability can be eliminated or reduce coating and crack; Additive 1,4 butynediol has good leveling and light effect.A spot of CuCl
22H
2O is the anode activator, the anode that electroforming Cu-W-Ni Cu-base composites is selected for use mainly is a copper coin, if chloride ion-containing not in the plating bath, the easy passivation of copper anode, bath voltage is raise, and electric current descends, and adds a spot of chlorion copper anode is normally dissolved, alleviate passivation phenomenon, keep the stable of processing condition.By regulating the Na in the electroforming solution
2WO
42H
2The content of O or current density, the tungstenic amount in the may command product.Tungsten adds a certain amount of tungsten and can obtain high penetration ability and jet speed because the moderate velocity of sound, higher density, high-melting-point are arranged in the cavity liner material.
The present invention is directed to conventional metals based composites preparation method's limitation, a kind of new Cu-W-Ni Cu-base composites that is used to prepare cavity liner is provided, and electrocasting method and electroforming solution, key of the present invention has been to provide the formulation of electroforming solution that is used for electroforming, it is meticulously preferred multiple electroplating bath components, and find out one through a large amount of experiments and overlap most preferred proportioning, make that electroforming process cost of the present invention is relatively low, service temperature is not high, and it is even to prepare tissue distribution, crystalline grains ultra, can cast the Cu-W-N Cu-base composites and the cavity liner thereof of thick excellent performance easily continuously.
Description of drawings
Fig. 1 uses the SEM figure of Cu-W-Ni Cu-base composites for the cavity liner of the present invention's preparation;
Fig. 2 can spectrogram with the Cu-W-Ni Cu-base composites for the cavity liner of the present invention's preparation.
Embodiment
Following examples are intended to further specify the present invention, rather than restriction the present invention.
Embodiment 1
The electroforming solution preparation: the volume according to electrotyping bath, multiply by NiSO with volume
47H
2O; Na
2WO
42H
2O; CuSO
45H
2O; CuCl
22H
2O; Na
3C
6H
5O
7H
2O; C
12H
25SO
4Na; Asccharin; The concentration of 1,4 butynediol obtains required drug weight and volume respectively, and electrotyping bath adds needed deionized water then, is heated to 50-70 ℃.Earlier with Na
2WO
42H
2O is dissolved in the deionized water, adds Na then
3C
6H
5O
7H
2O; C
12H
25SO
4Na, and stir for some time, NiSO added again respectively
47H
2O, CuSO
45H
2O and CuCl
22H
2O.Respectively asccharin and 1,4 butynediol are added in the electrotyping bath at last, keep constant temperature and fully stirring.
The pre-treatment of negative electrode, anode material: used negative electrode core is the aluminium core, uses coated abrasive working earlier before using, and rinses well with deionized water, puts into concentrated nitric acid and carries out surface passivation in 10 minutes, and then wash with deionized water, and is dry then.The homemade phosphorus copper plate surface cleaning of anode is clean, homemade phosphorus copper plate is put into made its surface active in hydrochloric acid 2-3 minute then, use washed with de-ionized water then.
Electroforming: the sulphuric acid soln with 5% is regulated electroforming solution pH=5.5-7.0, and the homemade phosphorus copper plate of anode is put into anode and connected circuit, and the adjusting current density is 5-15A/dm
2The time, the holding current density constant, the electroforming 24-72h that do not cut off the power supply, during an amount of supplemented by additives.
The demoulding: take out negative electrode and on stripper apparatus, rap and carry out the demoulding with hammer, to gained electroforming Cu-W-Ni Cu-base composites cavity liner sample clean, drying and sand papering.
Embodiment 2
The electroforming solution of preparation preparation Cu-W-Ni Cu-base composites in electrotyping bath, its composition is:
NiSO
47H
2O:210g/L; Na
2WO
42H
2O:80g/L; CuSO
45H
2O:6g/L; CuCl
22H
2O:1.5g/L; Na
3C
6H
5O
7H
2O:290g/L; C
12H
25SO
4Na:0.4g/L; Asccharin: 1.0-1.5g/L; 1,4 butynediol: 0.25-1mL/L.
Anode material is homemade phosphorus copper plate (Cu is 99.9%, and P is 0.02-0.06%), and thickness is that the metal copper plate of 1mm is as negative electrode;
Processing condition are: pH=6.0; 55 ℃ of temperature; Current density=15A/dm
2Alr mode: mechanical stirring; The electroforming time: 2-4h.
Copper content is that 85.6% (weight percent), nickel content are 8.4%, W content is 6% in the Cu-W-Ni Cu-base composites of gained, and material structure is evenly distributed, and crystalline grains ultra is seen Fig. 1 and Fig. 2.
Claims (6)
1. a cavity liner is used electroforming solution with the electroforming preparation of Cu-W-Ni Cu-base composites, it is characterized in that, described electroforming solution composition and proportioning are as follows:
NiSO
4·7H
2O 200-250g/L；
Na
2WO
4·2H
2O 60-90g/L；
CuSO
4·5H
2O 6-10g/L；
CuCl
2·2H
2O 1-3g/L；
Na
3C
6H
5O
7·2H
2O?270-320g/L；
C
12H
25SO
4Na 0.3-0.5g/L；
Asccharin 1.0-1.5g/L;
1,4 butynediol 0.25-1mL/L.
2. electroforming solution according to claim 1 is characterized in that, described electroforming solution is formed and proportioning is: NiSO
47H
2O:210g/L; Na
2WO
42H
2O:80g/L; CuSO
45H
2O:6g/L; CuCl
22H
2O:1.5g/L; Na
3C
6H
5O
72H
2O:290g/L; C
12H
25SO
4Na:0.4g/L; Asccharin: 1.0-1.5g/L; 1,4 butynediol: 0.25-1mL/L.
3. prepare the method for cavity liner with the Cu-W-Ni Cu-base composites with the described electroforming solution of claim 1, it is characterized in that, the dilute sulphuric acid with 10% is regulated electroforming solution pH=5.5-7.0; Temperature is controlled at 50-70 ℃; Current density is 5-15A/dm
2Adopt mechanical stirring; The electroforming time: 2-4h; Phosphorus copper plate is done anode and is carried out electroforming.
4. a cavity liner Cu-W-Ni Cu-base composites is characterized in that, is the matrix material that electroforming contains 89-83.2wt% copper, 6.2-9.6wt% nickel and 4.8-7.2wt% tungsten on copper coin.
5. cavity liner Cu-W-Ni Cu-base composites according to claim 4 is characterized in that, is the matrix material that electroforming contains 85.6wt% copper, 8.4wt% nickel and 6wt% tungsten on copper coin.
6. a cavity liner is characterized in that, described cavity liner is with the Composite Preparation of the described method of claim 3 preparation.
Priority Applications (1)
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| CN2010103004877A CN101787552B (en) | 2010-01-20 | 2010-01-20 | Cu-W-Ni copper matrix composite used for liner, electroforming method and electroforming solution thereof |
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| CN2010103004877A CN101787552B (en) | 2010-01-20 | 2010-01-20 | Cu-W-Ni copper matrix composite used for liner, electroforming method and electroforming solution thereof |
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| CN101787552B true CN101787552B (en) | 2011-06-01 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101669087B1 (en) * | 2011-07-29 | 2016-10-25 | 후루카와 덴키 고교 가부시키가이샤 | Electrolytic copper alloy foil, method for producing same, electrolytic solution used for production of same, negative electrode collector for secondary batteries using same, secondary battery, and electrode of secondary battery |
| CN103643265B (en) * | 2013-12-25 | 2016-05-25 | 昆明理工大学 | Electroplate liquid and the method thereof of electro-deposition Cu-W-Co alloy layer |
| CN103726084B (en) * | 2014-01-22 | 2016-05-25 | 贵州大学 | The method of electro-deposition Cu-Mo-Ni/Co alloy layer |
| CN114293232B (en) * | 2021-12-02 | 2023-03-17 | 北京科技大学 | Method for preparing tungsten dispersion strengthened copper composite material by electroforming |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5033387A (en) * | 1981-11-07 | 1991-07-23 | Rheinmetall Gmbh | Explosive charge facing |
| CN101353807A (en) * | 2008-09-22 | 2009-01-28 | 北京科技大学 | Method for producing nickel shaped charge liner using nickel sulfate electroforming solution |
-
2010
- 2010-01-20 CN CN2010103004877A patent/CN101787552B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5033387A (en) * | 1981-11-07 | 1991-07-23 | Rheinmetall Gmbh | Explosive charge facing |
| CN101353807A (en) * | 2008-09-22 | 2009-01-28 | 北京科技大学 | Method for producing nickel shaped charge liner using nickel sulfate electroforming solution |
Non-Patent Citations (6)
| Title |
|---|
| 李小庆 等.电铸镍药型罩的微观组织及织构分析.《兵器材料科学与工程》.2004,第27卷(第2期),29-32. |
| 李小庆等.电铸镍药型罩的微观组织及织构分析.《兵器材料科学与工程》.2004,第27卷(第2期),29-32. * |
| 胡忠武 等.药型罩材料的发展.《稀有金属材料与工程》.2004,第33卷(第10期),1009-1012. |
| 胡忠武等.药型罩材料的发展.《稀有金属材料与工程》.2004,第33卷(第10期),1009-1012. * |
| 范爱玲 等.电铸铜药型罩高速变形前后微观组织的观察以及变形机理的探讨.《兵器材料科学与工程》.2001,第24卷(第4期),3-9. |
| 范爱玲等.电铸铜药型罩高速变形前后微观组织的观察以及变形机理的探讨.《兵器材料科学与工程》.2001,第24卷(第4期),3-9. * |
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