CN103614750B - A kind of preparation technology of continuous casting crystallizer copper plate nickel tungsten electroplating coating - Google Patents
A kind of preparation technology of continuous casting crystallizer copper plate nickel tungsten electroplating coating Download PDFInfo
- Publication number
- CN103614750B CN103614750B CN201310590068.5A CN201310590068A CN103614750B CN 103614750 B CN103614750 B CN 103614750B CN 201310590068 A CN201310590068 A CN 201310590068A CN 103614750 B CN103614750 B CN 103614750B
- Authority
- CN
- China
- Prior art keywords
- coating
- continuous casting
- plating
- preparation technology
- 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.)
- Active
Links
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Continuous Casting (AREA)
Abstract
The invention discloses a kind of preparation technology of continuous casting crystallizer copper plate nickel tungsten electroplating coating, described coating contains the tungsten of quality of coating>=44%, and thickness is 0.2 ~ 1.8mm; Described preparation technology's electroplate liquid composition (unit: g/L) is: 50 ~ 75 nickel sulfamic acids, 60 ~ 90 sodium wolframates, 55 ~ 120 Trisodium Citrates, 1 ~ 4.7 soluble saccharin, 0.5 ~ 3 sodium allyl sulfonate, 0.2 ~ 1 sodium lauryl sulphate, current density 0.5 ~ 10A/dm
2, pH? 6.5 ~ 8.0, T? 55 ~ 75 DEG C, insulation 2.5 ~ 3h at 350 ~ 370 DEG C in plating final vacuum heat treatment furnace; Gained coating of the present invention, thermal crack resistant, anti-oxidant, corrosion resistance and good, heat-resistant anti-fatigue drag is high, and under its plated state, microhardness can reach more than 670HV, reaches about 1230HV after thermal treatment, and wear resisting property significantly improves, and can be widely used in high-speed continuous casting machine continuous casting.
Description
Technical field
The invention belongs to continuous casting crystallizer copper plate technical field of surface, be specifically related to a kind of preparation technology of continuous casting crystallizer copper plate nickel tungsten electroplating coating.
Background technology
Continuous cast mold is the nucleus equipment that whole continuous casting is produced, and the quality of its quality directly affects the quality of strand and the operating rate of continuous caster.And crystallizer performance is towards high pulling rate, high mechanical strength, thermal conductive resin, high rigidity, high-wearing feature and corrosion proof future development, crystallizer surface must be treated.
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, plating monometallic coating, as the pure Ni coating of routine, though good with basal body binding force, coating hardness is low, not wear-resisting, affect the work-ing life of crystallizer.In electroplating binary alloy, Ni-Fe alloy layer wear resistance is good, but fragility is comparatively large, and internal stress is comparatively large, easily occurs high-temperature hot crackle; Ni-Co coating long service life, but Co content is high, cost intensive, and alloy fragility is comparatively large, and alternating thermal stress resisting poor performance, erosion resistance is bad, and apply limited, production process is various.Other, as technology such as plating ternary alloy and composite deposite etc., although excellent performance, mostly all rests on conceptual phase, 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, as compared to the technology such as ternary alloy and composite deposite, large-scale production application has more feasibility.
Nickel tungsten alloy electroplating Rotating fields is fine and close, thermotolerance is high, can match in excellence or beauty with pottery, graphite-phase, at high temperature anti-oxidant; corrosion resistance and good, has higher hardness, and due to the existence of tungsten; make between itself and mating plate, to form one deck and stablize the transfer layer shielded, there is excellent wear resistance.Along with the increase of W content in coating, W atom enters Ni lattice, cause lattice swell, there is pincushion distortion, when W content reaches more than 44%, the regularly arranged of nickel-tungsten alloy plating atom is damaged, and X diffractogram spike disappears, become smooth broadening peak, now coating structure is non-crystalline state by crystalline state.W content be the amorphous alloy coating of more than 44% compared with crystal alloy, corrosion speed obviously reduces, excellent anti-corrosion performance.Nickel tungsten alloy electroplating liquid is divided into thionamic acid salt form and sulfate type by nickel salt kind, and electroplate liquid contains nickel salt, tungstate, also containing various different additive and complexing agent as citric acid, tartrate, asccharin etc.
Present stage, nickel-tungsten alloy plating was mainly used in mould and oil engine part workpiece, data for continuous casting crystallizer copper plate does not have substantially, and the ubiquitous weak point of nickel tungsten technique of preparing of mould aspect is that coating is coarse, irregular or containing the defect such as pit.How will originally be mainly used in the alloy of die industry, mass-producing can be applied to continuous cast mold field, realize the span in two onrelevant fields, and how to control electroplating technical conditions and solution composition, suitable additive is selected from numerous solution additive, maximize the performance reducing plating solution impurity and improve nickel tungsten, make up and existingly prepare the ubiquitous weak point of nickel tungsten technique, obtain the continuous cast mold base binary alloy plating that over-all properties is more more excellent than prior art, 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 to make up above-mentioned deficiency, a kind of preparation technology of continuous casting crystallizer copper plate nickel tungsten electroplating coating is provided, the coating microhardness utilizing this technique to prepare is high, heat crack resistance is good, anti-oxidant, corrosion resistance and good, heat-resistant anti-fatigue drag is high, can be widely used in high-speed continuous casting machine continuous casting.
A preparation technology for continuous casting crystallizer copper plate nickel tungsten electroplating coating, described nickel tungsten plating contains the tungsten being more than or equal to quality of coating 44%, and thickness of coating is 0.2 ~ 1.8mm;
The processing step of described preparation technology is: electrochemical deoiling, sandblasting, electrolytic degreasing, clean water, fixing auxiliary mould, acid activation process, plating, vacuum heat treatment;
The electroplate liquid of described plating consists of:
Nickel sulfamic acid 50 ~ 75g/L,
Sodium wolframate 60 ~ 90g/L,
Trisodium Citrate 55 ~ 120g/L,
Soluble saccharin 1 ~ 4.7g/L,
Sodium allyl sulfonate 0.5 ~ 3g/L,
Sodium lauryl sulphate 0.2 ~ 1g/L;
Described electroplating technique parameter is:
D
k0.5～10A/dm
2
pH6.5～8.0
T55～75℃
Agitation condition pressurized air stirs and recycle pump stirs
The interpolation of described sodium wolframate, adopts electromagnetic dosing pump to add continuously by the specified amount of every kiloampere electric current;
The interpolation of described soluble saccharin, sodium allyl sulfonate, adopts electromagnetic dosing pump to add continuously by the specified amount of every kiloampere electric current, supplements again and add after periodic detection;
The interpolation of described sodium lauryl sulphate, adopts after first detecting the surface tension of electroplate liquid before plating, adds sodium lauryl sulphate, make the surface tension transition of electroplate liquid at 27 ~ 34mN/m according to the result of surface tension detection is disposable before plating.
Described vacuum heat treatment is in vacuum tightness≤10
-2carry out in the vacuum heat treatment furnace of Pa, coating is incubated 2.5 ~ 3h at 350 ~ 370 DEG C, then cools with argon gas or nitrogen.
The sulfamate bath system that the present invention selects, hardness less compared to sulfate bath system gained coating internal stress and current efficiency higher, sulfamate solubleness in water is large, and deposition rate of metal is fast, is easy to high current density operation; Adopt Citrate trianion and nickel complexing, make current potential become negative, close with the sedimentation potential of tungsten, thus impel co-precipitation, Trisodium Citrate can improve solution dispersibility and current efficiency, significantly improves coating microhardness; When not having Trisodium Citrate, the existence of sodium wolframate can make current efficiency decline, and when concentration of sodium tungstate is 60 ~ 90g/L, adding Trisodium Citrate 55 ~ 120g/L effectively can improve current efficiency.
One of reason of the defects such as the easy generation of plating is coarse, uneven, pit, main relevant with the foreign matter content in plating solution, and additive types and add-on too much, can produce or bring impurity into, these impurity can deposit or be mixed on crystal boundary together with coated metal, metal lattice around impurity is distorted, increases internal stress.The present invention is after composite test, analysis and research, and additive adopts soluble saccharin, the sodium allyl sulfonate of 0.5 ~ 3g/L, the sodium lauryl sulphate of 0.2 ~ 1g/L of 1 ~ 4.7g/L, to obtain higher luminance brightness and to reduce internal stress as far as possible.Soluble saccharin has destressing, can make coating poor flatness by quantity not sufficient, crosses and causes coating fragility large at most, when concentration controls at 1 ~ 4.7g/L, effectively can improve the bonding force of coating and matrix; Sodium lauryl sulphate is as brightening agent and wetting agent, and concentration controls at 0.2 ~ 1g/L, effectively can reduce the surface tension between plating solution and plating piece, makes hydrogen be difficult to be attached to cathode surface, reduces the probability that pin hole appears in coating; Sodium allyl sulfonate, as auxiliary brightener, can assist soluble saccharin and sodium lauryl sulphate, makes coating obtain good bright property.After three kinds of additive combinations, effectively can improve current efficiency, impel grain refining, align, accelerate bright dipping and leveling speed, effectively reduce internal stress, and reduce pin hole.
PH value and the temperature of electroplate liquid are too high, citrate ions easily decomposes, cause plating solution unstable, the ability of complexing tungsten is more weak, the too low nickel salt of acidity is hydrolyzed, the too low coating blackout of temperature, when pH6.5 ~ 8.0, temperature controls at 55 ~ 75 DEG C, effectively can improve the diffusive migration speed of metal ion and the electrodeposit metals current efficiency at negative electrode, and increase the increase that current density contributes to the comparatively negative deposition rate of metal of current potential, the cathodic polarization of tungsten strengthens, can refinement coating structure, but current density is excessive, have hydrogen to separate out from cathode surface, coating is thin and coarse, in this electroplate liquid, cathode current density D
kat 0.5 ~ 10A/dm
2time, thickness of coating is even, compact structure.
One of reason that plating defects causes is that copper coin process is unreasonable or insufficient, adhere to sand grains during sandblasting or chiltern bad or impure etc., therefore this technique adopts electrochemical deoiling, sandblasting, electrolytic degreasing, clean water, acid activation process, fully processes matrix.In addition, after plating completes, adopt vacuum heat treatment, coating is in vacuum tightness≤10
-2pa, insulation 2.5 ~ 3h at 350 ~ 370 DEG C, degas, promote the effects such as diffusion, eliminate the unrelieved stress produced in electrodeposition process, improve the density of coating, the combination of promotion coating and matrix, reaches maximum precipitation hardening effect.
The present invention is based on sulfamate bath system, adopt 60 ~ 90g/L sodium wolframate and 55 ~ 120g/L Trisodium Citrate proportioning, add the soluble saccharin of 1 ~ 4.7g/L, the sodium allyl sulfonate of 0.5 ~ 3g/L, the sodium lauryl sulphate of 0.2 ~ 1g/L, the stable performance of electroplate liquid system, safeguard simple and convenient, long processing period, effectively overcomes plating defects, improve quality of coating, add conservative control PH, T and D
kgained continuous casting crystallizer copper plate nickel tungsten plating, anti-oxidant, corrosion resistance and good, heat-resistant anti-fatigue drag is high, under its plated state, microhardness can reach more than 670HV, after thermal treatment, hardness can reach about 1230HV, significantly improve the wear resistance of coating, after plating, internal stress is 185 ~ 196MPa, and thermal treatment internal stress reduces to 129 ~ 131MPa, and heat crack resistance is good, ensure that coating is not easy to crack, extend the work-ing life of continuous casting crystallizer copper plate, improve the operating rate of continuous-casting steel-making, can be widely used in high-speed continuous casting machine continuous casting.
Embodiment
Embodiment
Below will from five groups test the present invention will be further described.
Five groups test in, each continuous casting crystallizer copper plate nickel tungsten electroplating Coating composition and thickness as shown in the table
The preparation technology of above-mentioned continuous casting crystallizer copper plate nickel tungsten alloy electroplating layer, comprise the following steps: electrochemical deoiling, sandblasting, electrolytic degreasing, clean water, fixing auxiliary mould, acid activation process, plating, then carry out vacuum heat treatment and eliminate electrolytic coating internal stress, described vacuum heat treatment is in vacuum tightness≤10
-2carry out in the vacuum heat treatment furnace of Pa, coating is incubated 2.5 ~ 3h at 350 ~ 370 DEG C, then cools with argon gas or nitrogen;
The electroplate liquid of described preparation technology consists of:
| Component (g/L) | 1 | 2 | 3 | 4 | 5 |
| Nickel sulfamic acid | 50 | 56 | 62 | 69 | 75 |
| Sodium wolframate | 60 | 67 | 74 | 82 | 90 |
| Trisodium Citrate | 50 | 67 | 85 | 102 | 120 |
| Soluble saccharin | 1.0 | 1.9 | 2.8 | 3.7 | 4.7 |
| Sodium allyl sulfonate | 0. 5 | 1.1 | 1.7 | 2.3 | 3.0 |
| Sodium lauryl sulphate | 0.2 | 0.4 | 0.6 | 0.8 | 1.0 |
The processing parameter of described preparation technology is:
| Group time | 1 | 2 | 3 | 4 | 5 |
| PH | 6.5～6.7 | 6.8～7.0 | 7.1～7.3 | 7.4～7.6 | 7.8～8.0 |
| Current density (A/dm 2） | 0.5 | 4.0 | 6.0 | 9.0 | 10.0 |
| Temperature (DEG C) | 55～59 | 59～63 | 63～67 | 67～71 | 71～75 |
Test-results:
1. microhardness and internal stress: to detect respectively after plating and the microhardness of coating and internal stress after thermal treatment, through adding up as shown in the table;
As seen from the above table, after plating, the plated state microhardness of coating is 670 ~ 689HV, internal stress is 185 ~ 196MPa, wear resistance and heat crack resistance good, after thermal treatment, the microhardness of coating is 1225 ~ 1236HV, internal stress is 129 ~ 131MPa, obviously further increases coating hardness, and reduces the internal stress of coating to a certain extent.
2. oxidation-resistance: nickel tungsten plating in 700 DEG C, 800 DEG C and 900 DEG C of High Temperature Furnaces Heating Apparatuss respectively after continuous calcination 1h, coating without decortication, de-slag and weightening finish phenomenon, illustrate that nickel tungsten plating has higher oxidation-resistance.
3. erosion resistance: nickel tungsten alloy electroplating layer is put into 30 DEG C, the HNO of 1mol/L
3soak 100h in corrosive medium, erosion rate is 0.019 ~ 0.026mm/a, lower than 0.04 ~ 0.10mm/a of similar coating, and this electrolytic coating presents good erosion resistance.
4. heat-resistant anti-fatigue drag: after plating, is heated to 800 DEG C through 15s from room temperature, and l0s, water-cooled 10s are to less than 100 DEG C in insulation, and 15s reheats 800 DEG C, cold cycling like this 250 weeks, and sample does not all find any crackle, illustrates that the thermal fatigue resistance of this coating is high.
Production practice:
Certain steel mill 3 medium thin slab height pulling rate casting machine crystallizers, 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 DEG C, and crystallizer heat flow density is 1.95 ~ 2.25Mw/m
2, this high pulling rate casting machine crystallizer mean lifetime is 270 stoves.
After this copper plate of crystallizer uses the ceramic coating of the technical program design, copper plate temperature is 110 ~ 120 DEG C, and crystallizer heat flow density is 1.15 ~ 1.20Mw/m
2effectively reduce because heat flow density is high, the heat distortion amount of the high copper coin that causes of steel plate working temperature and coating is large, slow down the generation of the defects such as coating chaps, coating comes off, copper coin crackle, this high pulling rate casting machine crystallizer mean lifetime is extended for 400 stoves, has increased substantially the life-span of continuous casting of middle-thin slabs crystallizer.
Claims (2)
1. a preparation technology for continuous casting crystallizer copper plate nickel tungsten electroplating coating, is characterized in that: described nickel tungsten plating contains the tungsten being more than or equal to quality of coating 44%, and thickness of coating is 0.2 ~ 1.8mm;
The processing step of described preparation technology is: electrochemical deoiling, sandblasting, electrolytic degreasing, clean water, fixing auxiliary mould, acid activation process, plating, vacuum heat treatment;
The electroplate liquid of described plating consists of:
Described electroplating technique parameter is:
The interpolation of described sodium wolframate, adopts electromagnetic dosing pump to add continuously by the specified amount of every kiloampere electric current;
The interpolation of described soluble saccharin, sodium allyl sulfonate, adopts electromagnetic dosing pump to add continuously by the specified amount of every kiloampere electric current, supplements again and add after periodic detection;
The interpolation of described sodium lauryl sulphate, adopts after first detecting the surface tension of electroplate liquid before plating, adds sodium lauryl sulphate, make the surface tension transition of electroplate liquid at 27 ~ 34mN/m according to the result of surface tension detection is disposable before plating.
2. the preparation technology of a kind of continuous casting crystallizer copper plate nickel tungsten electroplating coating as claimed in claim 1, is characterized in that: described vacuum heat treatment is in vacuum tightness≤10
-2carry out in the vacuum heat treatment furnace of Pa, coating is incubated 2.5 ~ 3h at 350 ~ 370 DEG C, then cools with argon gas or nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310590068.5A CN103614750B (en) | 2013-11-22 | 2013-11-22 | A kind of preparation technology of continuous casting crystallizer copper plate nickel tungsten electroplating coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310590068.5A CN103614750B (en) | 2013-11-22 | 2013-11-22 | A kind of preparation technology of continuous casting crystallizer copper plate nickel tungsten electroplating coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103614750A CN103614750A (en) | 2014-03-05 |
| CN103614750B true CN103614750B (en) | 2016-03-16 |
Family
ID=50165464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310590068.5A Active CN103614750B (en) | 2013-11-22 | 2013-11-22 | A kind of preparation technology of continuous casting crystallizer copper plate nickel tungsten electroplating coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103614750B (en) |
Families Citing this family (9)
| 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 |
| CN104028716B (en) * | 2014-06-19 | 2016-03-23 | 马鞍山马钢表面工程技术有限公司 | The method of nickel plating fourplatemold narrow boards is repaired with the plating of Ni-Co-W alloy plating liquid |
| CN104762644A (en) * | 2015-04-24 | 2015-07-08 | 西峡龙成特种材料有限公司 | 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 |
| CN104846409A (en) * | 2015-04-30 | 2015-08-19 | 云南民族大学 | High-tungsten-content flawless tungsten-nickel alloy coating layer and electroplating liquid and electroplating process |
| CN106048680B (en) * | 2016-07-22 | 2018-05-22 | 东莞普瑞得五金塑胶制品有限公司 | A kind of corrosion resistant special coating of mobile phone fast charge interface energization |
| CN107958946A (en) * | 2017-11-17 | 2018-04-24 | 扬州乾照光电有限公司 | A kind of light-emitting diode chip for backlight unit for improving current expansion and preparation method thereof |
| CN108330521A (en) * | 2018-02-06 | 2018-07-27 | 营口奥捷专用汽车制造有限公司 | A kind of alloy electrolyte and preparation method instead of chromium |
| CN112267134B (en) * | 2020-11-24 | 2023-05-30 | 中山市康迪斯威科技有限公司 | Alloy electroplating solution |
| CN115182009B (en) * | 2022-07-11 | 2023-05-09 | 余姚市爱迪升电镀科技有限公司 | Bright nickel-tungsten alloy plating solution and preparation process of corrosion-resistant multilayer plating layer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 CN201310590068.5A patent/CN103614750B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454735A (en) * | 2003-04-30 | 2003-11-12 | 陈小飞 | Method of manufacturing crystallizer of square or rectangular billet copper tube |
Non-Patent Citations (1)
| Title |
|---|
| 镍-钨非晶态合金电镀的研究;丁英;《电镀与涂饰》;19900402;第41页镀液成分的选择及其工艺规范 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103614750A (en) | 2014-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103614750B (en) | A kind of preparation technology of continuous casting crystallizer copper plate nickel tungsten electroplating coating | |
| CN103614751A (en) | Copper-plate nickel-manganese-alloy electroplated layer of continuous-casting crystallizer and preparation process thereof | |
| CN103614724B (en) | A kind of preparation technology of continuous casting crystallizer copper plate surface cermet coating | |
| CN100577889C (en) | A kind of thin belt continuous casting crystal roller surface electroplating method and electroplate liquid thereof | |
| CN102773432B (en) | Ni-P alloy coating continuous casting crystallizer copper plate and preparation process thereof | |
| CN1500916A (en) | Gradient composite deposite for continuous casting crystallizer copper plate and production method thereof | |
| CN107604397A (en) | The electro-plating method of continuous casting crystallizer copper plate deposit N i Co B alloy layers | |
| CN106011957B (en) | A kind of method that continuous casting crystallizer copper plate surface prepares ni-b alloy coating | |
| 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 | |
| CN103757667A (en) | Chrome plating additive and electroplating liquid thereof | |
| CN101514469A (en) | Fluid and method for pretreating copper surfaces of continuous casting molds before electroplating | |
| CN104120461A (en) | Method for preparing gradient alloy plating layer on surface of thin strip continuous casting crystallization roller and plating solution | |
| CN109440147A (en) | A kind of electroplating process of copper plate of crystallizer | |
| CN102864453B (en) | Laser Cladding in-situ synthesis boride ceramics coating and preparation method thereof | |
| CN112371934B (en) | Coating material | |
| CN103182489A (en) | Method for electroplating non-uniform performance alloy coating on continuous casting crystallizer | |
| CN112267134B (en) | Alloy electroplating solution | |
| Matsui et al. | Influence of bath composition on tensile ductility in electrodeposited bulk nanocrystalline nickel | |
| CN104831326A (en) | Electroplating method of continuous casting crystallizer copper plate heterogeneous alloy plating layer | |
| CN109628967B (en) | Nickel-cobalt alloy plating solution for crystallizer copper plate and device thereof | |
| CN114016100A (en) | Preparation method of super-hard wear-resistant electroplating coating on surface of MEMS probe | |
| CN103614753B (en) | A kind of continuous casting crystallizer copper plate nickel tungsten alloy electroplating layer thermal treatment process | |
| CN111286768A (en) | Nickel-cobalt-manganese-lanthanum alloy plating solution and preparation method and application thereof | |
| CN114214674B (en) | Chromium plating process of copper continuous casting crystallizer | |
| CN115584404B (en) | Preparation method of high-strength high-conductivity 1-series aluminum alloy cathode plate base material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |