CN103614751A - Copper-plate nickel-manganese-alloy electroplated layer of continuous-casting crystallizer and preparation process thereof - Google Patents
Copper-plate nickel-manganese-alloy electroplated layer of continuous-casting crystallizer and preparation process thereof Download PDFInfo
- Publication number
- CN103614751A CN103614751A CN201310590112.2A CN201310590112A CN103614751A CN 103614751 A CN103614751 A CN 103614751A CN 201310590112 A CN201310590112 A CN 201310590112A CN 103614751 A CN103614751 A CN 103614751A
- Authority
- CN
- China
- Prior art keywords
- nickel
- coating
- manganese
- magno
- copper plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Continuous Casting (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a copper-plate nickel-manganese-alloy electroplated layer of a continuous-casting crystallizer and a preparation process thereof. The electroplated layer contains the following ingredients in percentage by mass: 88 to 99.8 percent of nickel and 0.2 to 12 percent of manganese, the thickness of the electroplated layer is 0.2mm to 4.0mm, and the electroplating liquid consists of the following ingredients: 250g/L to 600g/L nickel aminosulfonate, 5g/L to 20g/L nickel chloride, 3g/L to 50g/L manganese ammonium sulfate, 22g/L to 38g/L boracic acid, 1g/L to 5g/L saccharin sodium, 0.5g/L to 3g/L sodium allysulfonate and 0.1g/L to 1g/L lauryl sodium sulfate. An electroplating liquid system is stable in property and simple and convenient to maintain, the micro-hardness of the electroplated layer is 500HV to 850HV, the abrasion-resisting property is good, the thermal expanding coefficient is about (13.9-14.2)*10<-6>/DEG C, and the bonding strength is high; the internal stress is 124 to 173 MPa, and the thermal crack-resisting property is good; the heat conductivity is about four fifth of the electroplated nickel layer, the heat conduction in the crystallizer can be effectively slowed down, and the quality of the casting blank can be improved.
Description
Technical field
The invention belongs to technical field of surface, particularly a kind of continuous casting crystallizer copper plate Magno electrolytic coating and preparation technology.
Background technology
Develop rapidly along with Iron And Steel Industry, the performance of continuous cast mold is towards high pulling rate, high mechanical strength, thermal conductive resin, high rigidity, high-wearing feature and corrosion proof future development, copper crucible is second largest metallurgical consumptive material, copper and copper alloy again resource are nervous, adopting process for treating surface to improve wear resistance and the thermotolerance on copper plate of crystallizer surface, is one of essential measure of increasing economic efficiency with production efficiency.
In existing many crystallizer surface treatment technologies, technical maturity, facility investment is few, productive expense is low, raw material availability is high is still electroplating technology, wherein, electroplate monometallic as the pure Ni coating of routine, though good with basal body binding force, but coating hardness is low, not wear-resisting, affect work-ing life of crystallizer.In electroplating binary alloy, though improved wear resistance as Ni-Fe alloy layer, fragility is larger, and internal stress is larger, good not with the bonding force of matrix, is prone to high temperature thermal crack; Ni-Co coating work-ing life is only 2 times of left and right of pure Ni, but because Co content is high, cost is expensive, and alloy fragility is large, internal stress is larger, alternating thermal stress resisting poor performance, and corrodibility is bad, and production process is various, applies limited.Other,, as electroplated the technology such as ternary alloy and composite deposite, although excellent performance all rests on conceptual phase mostly, cannot carry out large-scale production and application.So, still need to develop new base binary alloy plating, make up the deficiency of existing base binary alloy plating, compare with the technology such as ternary alloy and composite deposite, in large-scale production application, have more feasibility.
Mn is as a kind of effective strengthening element of nickelalloy, low price, but be applied to the data in continuous cast mold about Magno, substantially do not have.Because although Mn energy refinement electrolytic coating crystal grain improves intensity and the hardness of coating, and can reduce the impurity S content in Ni; But manganese too high levels, electrolytic coating internal stress can significantly raise, and internal stress is high can increase coating hardness, makes within the specific limits the wear resistance of coating improve, but surpasses after certain value, and coating is easy to crack; At the position of stress mutation, easily produce the corrosion of stress concentration; In nano-deposit is manufactured, easily cause processing component distortion.
In the Ni-Mn Alloy Electroforming of document < < jet pipe and the research > > of problem of Cracking thereof, once mentioned the electroforming solution about Magno, the cracking of document proof electroformed layer is because manganese too high levels (having surpassed 0.5%) causes, as long as guarantee anode material zinc impurities content, can select the nickel block that purity is higher or use cleaner; Electroplate the same with electroforming ultimate principle, so electroplating technology is still had to certain reference significance.But electroplate the object with electroforming, and the component content of electrolytic solution, the aspects such as additive level are all different, Magno is mainly used in drilling the unify thrust chamber outer wall of airspace engine of the diamond head of use and micro-electro-mechanical systems at present, how can mass-producing be applied to continuous cast mold field, realize the span in two onrelevant fields, and how to control electroplating technical conditions and solution composition, from numerous solution additives, select suitable additive, maximize the internal stress that reduces plating solution impurity and reduce Magno, avoid the cracking of coating, obtain tiny densification, the Magno coating of high corrosion resistance, obtain economic benefit and realize mass-producing application, it is all problem demanding prompt solution.
Summary of the invention
The object of the invention is in order to make up above-mentioned deficiency, a kind of continuous casting crystallizer copper plate Magno electrolytic coating and preparation technology are provided, this Magno electrolytic coating has that internal stress is low, porosity is low, hardness compared with high, large with substrate combinating strength, high temperature abrasion resistance is superior, thermal conductivity is low, can improve greatly the work-ing life of continuous casting crystallizer copper plate, improve the quality of continuous casting steel billet.
Continuous casting crystallizer copper plate Magno electrolytic coating and a preparation technology, the nickel that described Magno coating contains quality of coating 88～99.8% and 0.2～12% manganese, thickness is 0.2～4.0mm, plated state microhardness 500～850 HV;
Described preparation technology comprises the following steps:
1. matrix pre-electroplating treatment: continuous casting crystallizer copper plate matrix carries out chemical degreasing oil removing, mechanical sandblast, electrolytic degreasing oil removing, the fixing auxiliary mould of electroplating, hydrochloric acid spray activation treatment;
2. configure electroplate liquid: the composite plating solution that preparation contains Magno material in plating tank, described composite plating solution consists of:
Nickel sulfamic acid 250～600g/L,
Thionamic acid manganese 3～50 g/L,
Nickelous chloride 5～20g/L,
Boric acid 22～38g/L,
Soluble saccharin 1～5g/L,
Sodium allyl sulfonate 0.5～3g/L,
Sodium lauryl sulphate: 0.1～1g/L;
3. electroplated Ni-Mn alloy layer: regulating electroplate liquid pH value with thionamic acid is 3.0～5.0, and temperature of electroplating solution is controlled at 40～65 ℃; Using copper plate of crystallizer as negative electrode, cathode current density is controlled at 1～15A/dm
2, anode material is for containing S 0.015%～0.06%(quality) nickel cake, alr mode is that recycle pump or pressurized air stir; Be electroplated to after described Ni-Mn alloy layer thickness reaches setting thickness and automatically stop electroplating.
The interpolation of described thionamic acid manganese, adopts electromagnetic dosing pump by the specified amount continuous adding of every kiloampere electric current;
The interpolation of described soluble saccharin, sodium allyl sulfonate, adopts electromagnetic dosing pump by the specified amount continuous adding of every kiloampere electric current, after regularly detecting, supplements and adds again;
The interpolation of described sodium lauryl sulphate, adopts and first before plating, detects after the surface tension of electroplate liquid, and the result disposable sodium lauryl sulphate of adding before plating detecting according to surface tension, makes the surface tension of electroplate liquid be controlled at 25～32mN/m.
The present invention is first by chemical degreasing oil removing, mechanical sandblast, electrolytic degreasing oil removing, hydrochloric acid spray activation treatment, matrix is carried out to thorough oil removing and activation, prevent that matrix from making electrolytic coating surface seedy because pre-treatment is bad, effectively reduced the probability that the peeling of electrolytic coating comes off.
In electroplate liquid primary structure, the solubleness of sulfamate in the aqueous solution is large, during plating, can under high electric current, operate, plating solution sedimentation velocity is fast, dispersive ability is good, and electroplate liquid good stability, is easy to production management, and the coating obtaining is even, careful, internal stress is low, the thick requirement of the fine satisfied plating of energy; The content of nickel salt can change in a big way, but content is when too low, can slow down sedimentation velocity, but the dispersive ability of electrolytic solution is good, and coating crystallization is careful, is easy to polishing; During too high levels, dispersive ability variation, but allow the current density of use high, sedimentation velocity is fast; Be controlled at 250～600g/L, can guarantee to obtain required coating, then coordinate additive and electroplating technological parameter, little on electrolytic solution dispersive ability and sedimentation velocity impact.Alloy manganese element adopts the form of thionamic acid manganese to introduce, increase electroplate liquid good stability, chlorion is one of plating solution main component and influence factor, the easy passivation of anode when chloride ion content is not enough, too much can increase the internal stress of nickel coating, control its content when 5～20g/L, depolarize is remarkable, can guarantee continuously and effectively to have promoted the normal dissolving of anode; The electrolytic coating internal stress that adopts this electroplate liquid basal component to prepare is low, and the bonding force of electrolytic coating and matrix is good.
Suitable additive can be adsorbed in the room in lattice, reduces dislocation, reduces internal stress; If but additive types and add-on are too much, the impurity that can produce or bring into, and plating solution impurity is to affect the factor that coating internal stress is the most complicated, these impurity can deposit or be mixed on crystal boundary together with coated metal, impurity metal lattice is around distorted, increases internal stress.The present invention is after composite test, analysis and research, and additive combination mode adopts the soluble saccharin of 1～5g/L, the sodium lauryl sulphate of the sodium allyl sulfonate of 0.5～3g/L, 0.1～1g/L.Soluble saccharin can effectively reduce the internal stress that mn ion brings, consumption is crossed at most can introduce more sodium ion, make coating embrittlement, internal stress is high, associativity is poor, adopt electromagnetic dosing pump by the specified amount continuous adding of every kiloampere electric current, after regularly detecting, supplement and add again, can effectively control the content of sodium; The interpolation of sodium lauryl sulphate, according to surface tension disposable adding before plating, is generally 0.1-1g/L, makes the surface tension of electroplate liquid be controlled at 25～32mN/m; Sodium allyl sulfonate, as auxiliary brightener, is characterized in containing the C-S group of elementary brightening agent, contains again the G=G group of second-class brightener, can assist soluble saccharin and sodium lauryl sulphate, makes coating obtain good bright property.After three kinds of additive combinations, can effectively improve current efficiency, impel grain refining, align, accelerate bright dipping and leveling speed, effectively reduce internal stress, reduce pin hole.
Electroplating technological parameter of the present invention is: pH value 3.0～5.0, and temperature of electroplating solution is controlled at 40～65 ℃, and cathode current density is controlled at 1～15A/dm
2; In these parameters, pH value is very large on electroplating quality impact, and when pH value is too high, the nickel hydroxide particulate of generation is mingled with in coating, when pH value is too low, and a large amount of liberations of hydrogen in cathodic area, pH value changes fast, also can affect quality of coating; And sulfamate electronickelling solution is through use after a while, pH value generally can raise gradually, and the nickel coating on part easily produces pin hole, and this is because electroplated component region can produce Ni (OH)
2colloid, H
2easily rest on piece surface, make nickel coating produce pin hole; The present invention is higher according to sulfamic acid nickel current efficiency, and the boric acid consumption of adding 22～38g/L can play effective shock absorption, and pH value changes slow, effectively reduces the regulating frequency of plating solution pH, has improved quality of coating; And for regulating the added a small amount of thionamic acid of PH can convert nickel sulfamic acid to, for the wide nickel sulfamic acid of the large content range of consumption without impact.Improve bath temperature and can improve the current density of plating, accelerate sedimentation speed, improve nickel coating luminance brightness; But excess Temperature nickel sulfamic acid facile hydrolysis.The performance that current density affects coating by the manganese content in change alloy and particle size, within the specific limits, current density increases, can reduce crystal grain, put forward heavy alloyed hardness and intensity, make alloy form the crystal habit of tiny densification, improve the deposition distribution of electrodeposit layer.Control current density and temperature, make coating there is less internal stress.The consumption that regulates size and the wetting agent sodium lauryl sulphate of pH value, reduces pin hole and occurs probability, adopts recycle pump or pressurized air to stir, and the microbubble that piece surface is produced is overflowed in time, also can avoid producing pin hole.By regulating current density size and coating time to regulate thickness of coating, be 0.2～4.0mm, and the crystal size on refinement electrolytic coating surface.
Electroplate liquid system of the present invention stable performance, safeguard simple and convenient, long processing period, the current density of electroplate to allow using is high; The electronickelling manganese alloy coating of preparing by the present invention, porosity is low, compact structure, chemical property is good, stability is high, plated state microhardness can be adjusted within the scope of 500～850 HV, wear resistance is about the twice of nickel cobalt (alloy), and wear resisting property is more superior, can in high-speed continuous casting machine continuous casting, be widely used; Internal stress 124～173MPa, heat crack resistance is good, can guarantee that coating is not easy to crack; Thermal expansivity is about (13.9～14.2) * 10
-6/ ℃, high with substrate combinating strength; The thermal conductivity of Magno is lower, is about 61～68W/ (m.K), and thermal conductivity is about 4/5 of electronickelling alloy, effectively slows down the especially thermal conduction at meniscus place of crystallizer inside, improves slab quality.At copper plate working surface of continuously casting crystallizer electronickelling manganese alloy electrolytic coating, there is resistance to erosion under hot conditions, extended the work-ing life of continuous casting crystallizer copper plate, improve the operating rate of continuous-casting steel-making, reduce the ton steel production cost of continuous-casting steel-making.
Embodiment
Embodiment
Below will from six groups test the present invention will be further described.
In six groups of tests, each continuous casting crystallizer copper plate Magno Coating composition and thickness are as shown in the table:
| Group time | 1 | 2 | 3 | 4 | 5 | 6 |
| Ni（%） | 99.8 | 97.5 | 95 | 92.5 | 90 | 88 |
| Mn（%） | 0.2 | 2.5 | 5 | 7.5 | 10 | 12 |
| Thickness (mm) | 0.2 | 1.0 | 1.8 | 2.6 | 3.2 | 4.0 |
The preparation technology of above-mentioned continuous casting crystallizer copper plate Magno electrolytic coating, comprises the following steps:
1. matrix pre-electroplating treatment: continuous casting crystallizer copper plate matrix carries out chemical degreasing oil removing, mechanical sandblast, electrolytic degreasing oil removing, hydrochloric acid spray activation treatment, the fixing auxiliary mould of electroplating; Chemical degreasing oil removing can be selected acetone, and 9～16 order hard quartz sands are selected in mechanical sandblast;
2. configure electroplate liquid: the composite plating solution that preparation contains Ni-Mn alloy material in plating tank, described composite plating solution consists of as shown in the table:
| Component (g/L) | 1 | 2 | 3 | 4 | 5 | 6 |
| Nickel sulfamic acid | 250 | 320 | 390 | 460 | 530 | 600 |
| Thionamic acid manganese | 3 | 12 | 21 | 31 | 41 | 50 |
| Nickelous chloride | 5 | 8 | 11 | 14 | 17 | 20 |
| Boric acid | 22 | 25 | 28 | 32 | 35 | 38 |
| Soluble saccharin | 1.0 | 1.8 | 2.6 | 3.4 | 4.2 | 5.0 |
| Sodium allyl sulfonate | 0. 5 | 1.0 | 1.5 | 2.0 | 2.5 | 3.0 |
| Sodium lauryl sulphate | 0.1 | 0.2 | 0.4 | 0.6 | 0.8 | 1.0 |
Before plating, detect after the surface tension of electroplate liquid, according to detected result disposable sodium lauryl sulphate of adding before plating, make the surface tension of electroplate liquid be controlled at 25～32mN/m; Adopt electromagnetic dosing pump by the specified amount continuous adding thionamic acid manganese of every kiloampere electric current; Adopt electromagnetic dosing pump by specified amount continuous adding soluble saccharin and the sodium allyl sulfonate of every kiloampere electric current, after regularly detecting, supplement and add again;
3. electroplated Ni-Mn alloy layer: regulate electroplate liquid to regulate pH value with thionamic acid, temperature of electroplating solution is controlled at 40～65 ℃; Using copper plate of crystallizer as negative electrode, cathode current density is controlled at 1～15A/dm
2, anode material is for containing S 0.015%～0.06%(quality) nickel cake, alr mode is that recycle pump or pressurized air stir; Be electroplated to after described Ni-Mn alloy layer thickness reaches setting thickness and automatically stop electroplating; Concrete electroplating technological parameter is as shown in the table:
| Group time | 1 | 2 | 3 | 4 | 5 | 6 |
| PH | 4.8～5.0 | 4.5～4.7 | 4.2～4.4 | 3.8～4.1 | 3.4～3.7 | 3.0～3.3 |
| Temperature (℃) | 40～44 | 44～48 | 48～52 | 52～56 | 56～61 | 61～65 |
| Current density (A/dm 2） | 1 | 4 | 6 | 9 | 12 | 15 |
Test-results:
1. detect microhardness, internal stress, thermal expansivity, the thermal conductivity of coating, as shown in the table by statistics:
| Group time | 1 | 2 | 3 | 4 | 5 | 6 |
| Microhardness (HV) | 500 | 623 | 748 | 850 | 714 | 567 |
| Internal stress (MPa) | 165 | 139 | 124 | 131 | 148 | 173 |
| Thermal expansivity (* 10 -6/℃） | 14.1 | 14.1 | 13.9 | 14.0 | 14.1 | 14.2 |
| Thermal conductivity W/ (m.K) | 66 | 64 | 61 | 62 | 65 | 68 |
As seen from the above table, the Magno galvanization coating obtaining by electroplating preparation technology of the present invention, plated state microhardness can be adjusted within the scope of 500～850 HV, and wear resistance is about the twice of nickel cobalt (alloy), coating performance is more superior, can in high-speed continuous casting machine continuous casting, be widely used; Internal stress 124～173MPa, can guarantee that coating is not easy to crack; Thermal expansivity is about (13.9～14.2) * 10
-6/ ℃, roughly the same with nickel, guaranteed between coating and copper coin, to there is good associativity; The thermal conductivity of Magno is lower, is about 61～68W/ (m.K), and thermal conductivity is about 4/5 of electronickelling alloy, effectively slows down the especially thermal conduction at meniscus place of crystallizer inside, improves slab quality.
2. oxidation-resistance: nickel manganese coating is in 700 ℃, 800 ℃ and 900 ℃ of High Temperature Furnaces Heating Apparatuss respectively after continuous calcination 1h, and coating has higher oxidation-resistance without decortication, de-slag and weightening finish phenomenon, explanation nickel manganese coating.
3. heat-resistant anti-fatigue drag: after plating, through 15s, from room temperature, be heated to 800 ℃, insulation l0s, water-cooled is below 10s to 100 ℃, and 15s reheats 800 ℃, and so cold cycling is 235 weeks, and sample is not all found any crackle, illustrates that the thermal fatigue resistance of this coating is high.
Production practice:
3 the high pulling rate casting machine of medium thin slab crystallizers of certain steel mill, ladleful 150t, size of plate blank is 900mm * 135mm, continuous caster radius is 5m, metallurgical length 24.2m, and design pulling rate is 1.8～2.6m/min, copper coin surface temperature is 160～180 ℃, and crystallizer heat flow density is 1.95～2.25Mw/m
2, this high pulling rate casting machine crystallizer mean lifetime is 270 stoves.
This copper plate of crystallizer is used after the coating of the technical program design, and copper plate temperature is 120 ~ 125 ℃, and crystallizer heat flow density is 1.25～1.30Mw/m
2effectively weakened because heat flow density is high, the heat distortion amount of the high copper coin causing of steel plate working temperature and coating is large, slowed down that coating be full of cracks, coating come off, the generation of copper coin defects i.e.cracks, this high pulling rate casting machine crystallizer mean lifetime is extended for 353 stoves, has improved the life-span of continuous casting of middle-thin slabs crystallizer.
Claims (3)
1. a continuous casting crystallizer copper plate Magno electrolytic coating, is characterized in that: the nickel that described Magno coating contains quality of coating 88～99.8% and 0.2～12% manganese, thickness is 0.2～4.0mm, plated state microhardness 500～850 HV.
2. a technique of preparing continuous casting crystallizer copper plate Magno electrolytic coating as claimed in claim 1, is characterized in that, described preparation technology comprises the following steps:
1. matrix pre-electroplating treatment: continuous casting crystallizer copper plate matrix carries out chemical degreasing oil removing, mechanical sandblast, electrolytic degreasing oil removing, the fixing auxiliary mould of electroplating, hydrochloric acid spray activation treatment;
2. configure electroplate liquid: the composite plating solution that preparation contains Magno material in plating tank, described composite plating solution consists of:
Nickel sulfamic acid 250～600g/L,
Thionamic acid manganese 3～50 g/L,
Nickelous chloride 5～20g/L,
Boric acid 22～38g/L,
Soluble saccharin 1～5g/L,
Sodium allyl sulfonate 0.5～3g/L,
Sodium lauryl sulphate 0.1～1g/L;
3. electroplated Ni-Mn alloy layer: regulating electroplate liquid pH value with thionamic acid is 3.0～5.0, and temperature of electroplating solution is controlled at 40～65 ℃; Using copper plate of crystallizer as negative electrode, cathode current density is controlled at 1～15A/dm
2, anode material is for containing S 0.015%～0.06%(quality) nickel cake, alr mode is that recycle pump or pressurized air stir; Be electroplated to after described Ni-Mn alloy layer thickness reaches setting thickness and automatically stop electroplating.
3. the preparation technology of a kind of continuous casting crystallizer copper plate Magno electrolytic coating as claimed in claim 2, is characterized in that:
The interpolation of described thionamic acid manganese, adopts electromagnetic dosing pump by the specified amount continuous adding of every kiloampere electric current;
The interpolation of described soluble saccharin, sodium allyl sulfonate, adopts electromagnetic dosing pump by the specified amount continuous adding of every kiloampere electric current, after regularly detecting, supplements and adds again;
The interpolation of described sodium lauryl sulphate, adopts and first before plating, detects after the surface tension of electroplate liquid, and the result disposable sodium lauryl sulphate of adding before plating detecting according to surface tension, makes the surface tension of electroplate liquid be controlled at 25～32mN/m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310590112.2A CN103614751A (en) | 2013-11-22 | 2013-11-22 | Copper-plate nickel-manganese-alloy electroplated layer of continuous-casting crystallizer and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310590112.2A CN103614751A (en) | 2013-11-22 | 2013-11-22 | Copper-plate nickel-manganese-alloy electroplated layer of continuous-casting crystallizer and preparation process thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103614751A true CN103614751A (en) | 2014-03-05 |
Family
ID=50165465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310590112.2A Pending CN103614751A (en) | 2013-11-22 | 2013-11-22 | Copper-plate nickel-manganese-alloy electroplated layer of continuous-casting crystallizer and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103614751A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103911637A (en) * | 2014-03-28 | 2014-07-09 | 马鞍山马钢表面工程技术有限公司 | Ni-Co-W alloy electroplating solution for working surface of copper plate of continuous casting crystallizer and preparation method of Ni-Co-W alloy electroplating solution |
| CN104831326A (en) * | 2015-04-21 | 2015-08-12 | 西峡龙成特种材料有限公司 | Electroplating method of continuous casting crystallizer copper plate heterogeneous alloy plating layer |
| CN105568324A (en) * | 2016-02-25 | 2016-05-11 | 南京工业大学 | Preparation method of high-performance surface alloying copper material |
| CN105562636A (en) * | 2015-12-31 | 2016-05-11 | 张颖 | Preparation method for crystallizer copper plate coated with nickel-cobalt-iron alloy layer |
| CN107737892A (en) * | 2017-10-23 | 2018-02-27 | 西峡龙成特种材料有限公司 | Continuous casting crystallizer copper plate electroplates nickel cobalt manganese alloy coating and its preparation technology |
| CN112247487A (en) * | 2020-10-14 | 2021-01-22 | 山东聊城富锋汽车部件有限公司 | Manufacturing method of high-temperature-resistant engine support |
| CN112376091A (en) * | 2020-11-24 | 2021-02-19 | 赵玉平 | Preparation method of electroplating Co-Ni alloy electroplating solution |
| CN112663100A (en) * | 2020-12-30 | 2021-04-16 | 四川轻化工大学 | Method for preparing nickel-copper alloy coating on surface of carbon steel |
| CN112921368A (en) * | 2021-02-01 | 2021-06-08 | 林元霞 | Plate making method of gravure plate roller |
| CN114910114A (en) * | 2021-02-07 | 2022-08-16 | 哈尔滨工业大学 | Online in-situ monitoring device for internal stress of plating layer and pH of plating solution in electroforming process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202008A (en) * | 1997-05-20 | 1998-12-16 | 三星航空产业株式会社 | Lead frame and method for manufacturing the same |
| CN1454735A (en) * | 2003-04-30 | 2003-11-12 | 陈小飞 | Method of manufacturing crystallizer of square or rectangular billet copper tube |
-
2013
- 2013-11-22 CN CN201310590112.2A patent/CN103614751A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202008A (en) * | 1997-05-20 | 1998-12-16 | 三星航空产业株式会社 | Lead frame and method for manufacturing the same |
| CN1454735A (en) * | 2003-04-30 | 2003-11-12 | 陈小飞 | Method of manufacturing crystallizer of square or rectangular billet copper tube |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103911637B (en) * | 2014-03-28 | 2016-08-17 | 马鞍山马钢表面工程技术有限公司 | Copper plate working surface of continuously casting crystallizer Ni-Co-W alloy plating liquid and preparation method thereof |
| CN103911637A (en) * | 2014-03-28 | 2014-07-09 | 马鞍山马钢表面工程技术有限公司 | Ni-Co-W alloy electroplating solution for working surface of copper plate of continuous casting crystallizer and preparation method of Ni-Co-W alloy electroplating solution |
| CN104831326A (en) * | 2015-04-21 | 2015-08-12 | 西峡龙成特种材料有限公司 | Electroplating method of continuous casting crystallizer copper plate heterogeneous alloy plating layer |
| CN105562636B (en) * | 2015-12-31 | 2018-03-23 | 永春琦承茶叶专业合作社 | A kind of preparation method for the copper plate of crystallizer for being plated with permivar layer |
| CN105562636A (en) * | 2015-12-31 | 2016-05-11 | 张颖 | Preparation method for crystallizer copper plate coated with nickel-cobalt-iron alloy layer |
| CN105568324A (en) * | 2016-02-25 | 2016-05-11 | 南京工业大学 | Preparation method of high-performance surface alloying copper material |
| CN105568324B (en) * | 2016-02-25 | 2017-12-15 | 南京工业大学 | A kind of preparation method of high performance surface alloying copper product |
| CN107737892B (en) * | 2017-10-23 | 2019-06-28 | 西峡龙成特种材料有限公司 | Nickel cobalt manganese alloy coating and its preparation process is electroplated in continuous casting crystallizer copper plate |
| CN107737892A (en) * | 2017-10-23 | 2018-02-27 | 西峡龙成特种材料有限公司 | Continuous casting crystallizer copper plate electroplates nickel cobalt manganese alloy coating and its preparation technology |
| CN112247487A (en) * | 2020-10-14 | 2021-01-22 | 山东聊城富锋汽车部件有限公司 | Manufacturing method of high-temperature-resistant engine support |
| CN112376091A (en) * | 2020-11-24 | 2021-02-19 | 赵玉平 | Preparation method of electroplating Co-Ni alloy electroplating solution |
| CN112376091B (en) * | 2020-11-24 | 2023-05-05 | 峨山金峰金属制品有限责任公司 | Preparation method of alloy electroplating solution |
| CN112663100A (en) * | 2020-12-30 | 2021-04-16 | 四川轻化工大学 | Method for preparing nickel-copper alloy coating on surface of carbon steel |
| CN112921368A (en) * | 2021-02-01 | 2021-06-08 | 林元霞 | Plate making method of gravure plate roller |
| CN114910114A (en) * | 2021-02-07 | 2022-08-16 | 哈尔滨工业大学 | Online in-situ monitoring device for internal stress of plating layer and pH of plating solution in electroforming process |
| CN114910114B (en) * | 2021-02-07 | 2023-12-12 | 哈尔滨工业大学 | In-situ monitoring device for internal stress of plating layer and pH of plating solution in electroforming process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103614751A (en) | Copper-plate nickel-manganese-alloy electroplated layer of continuous-casting crystallizer and preparation process thereof | |
| CN103614750B (en) | A kind of preparation technology of continuous casting crystallizer copper plate nickel tungsten electroplating coating | |
| Tian et al. | Microstructure and properties of nanocrystalline nickel coatings prepared by pulse jet electrodeposition | |
| CN1229525C (en) | Gradient composite deposite for continuous casting crystallizer copper plate and production method thereof | |
| CN102773434A (en) | Nanocomposite electroplating layer copper plate of continuous casting crystallizer and preparation process of nanocomposite electroplating layer copper plate | |
| CN101724873B (en) | Functional electroplating process of copperplates of crystallizers | |
| Hashemi et al. | Effect of SiC nanoparticles on microstructure and wear behavior of Cu-Ni-W nanocrystalline coating | |
| CN103614724A (en) | Preparation technique of continuous casting crystallizer copper plate surface cermet coating | |
| CN104790004A (en) | Nickel and/or chromium plated component and manufacturing method thereof | |
| CN102773432A (en) | Ni-P alloy coating continuous casting crystallizer copper plate and preparation process thereof | |
| Karakurkchi et al. | Electrodeposition of iron–molybdenum–tungsten coatings from citrate electrolytes | |
| CN103014794B (en) | Preparation method of composite coating on crystallizer copper plate surface | |
| CN104772946A (en) | Nickel-chromium plating part and manufacturing method thereof | |
| Fan et al. | Effect of jet electrodeposition conditions on microstructure and mechanical properties of Cu–Al 2 O 3 composite coatings | |
| CN107737892B (en) | Nickel cobalt manganese alloy coating and its preparation process is electroplated in continuous casting crystallizer copper plate | |
| US4404232A (en) | Method of depositing metal coating layers containing particles on the walls of chill moulds | |
| CN104195606B (en) | Thick nickel-iron-tungsten ternary alloy plating layer and preparation method thereof | |
| CN106011957B (en) | A kind of method that continuous casting crystallizer copper plate surface prepares ni-b alloy coating | |
| JPH08100273A (en) | Production of chromium-plated product | |
| CN104120461A (en) | Method for preparing gradient alloy plating layer on surface of thin strip continuous casting crystallization roller and plating solution | |
| Mo et al. | Ni/TiC composite electrodeposition on the surface of Ni-based superalloy | |
| CN105780063A (en) | Repairing method of scrapped continuous casting crystallizer copper plate | |
| CN104762644A (en) | Electroplated amorphous-state nickel-tungsten-phosphorous alloy for copper plate of crystallizer for continuous casting and preparation process of amorphous-state nickel-tungsten-phosphorous alloy | |
| CN112371934B (en) | Coating material | |
| RU2437967C1 (en) | Procedure for sedimentation of composite coating nickel-vanadium-phosphorus-boron nitride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140305 |