CN102392279B - Nickel electroplating method of ceramic metalized layer - Google Patents
Nickel electroplating method of ceramic metalized layer Download PDFInfo
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Abstract
The invention discloses a novel nickel electroplating method of a ceramic metalized layer, comprising the following steps of: treatment before the plating: activating the ceramic metalized surface layer by using an anode electrolysis method in acid solution with pH of 0-3 for 1-10min, then taking out and washing by water; alkali soaking: soaking by using alkali solution for 1-8min, controlling the pH within 9-12, taking out and washing by water; acid soaking: soaking by using acid solution for 1-12min, controlling the pH within 0-4, taking and washing by water; nickel pre-plating: carrying out nickel plating in mixed solution of nickel chloride and hydrochloric acid for 1-20min, taking out and washing by water; and nickel plating: carrying out nickel plating is a nickel plating system for8-40min, taking out, washing by water and drying. The nick electroplating method provided by the invention is obviously superior to the traditional nickel plating methods and has wide application prospect.
Description
Technical field
The present invention relates to a kind of method for electroplating nickel of ceramic metallized layer, belong to chemical field.
Background technology
After pottery is once metallized, generally be to be difficult to directly weld with scolder commonly used, need to carry out second metallization (electronickelling or coating nickel and sintrered nickel) to it, and the selection of most of producers all is the method for electronickelling, improve scolder at the free-running property of metalized surface, prevent simultaneously scolder to the erosion action of metal layer, and can cover the MoMn metal layer, avoid causing sealing-in failure or gas leakage after the ceramic-metal sealing-in.
The quality of porcelain piece metallization top layer electronickelling directly has influence on the sealing-in quality of metallized ceramic and metal parts, and existing mode of electroplating comprises electronickelling and chemical nickel plating.Liu Huiqing, " nickel chemical plating technology of ceramic-metal sealing-in ", the vacuum electronic technology, the 2nd phase in 2006 the 55th～58 page of common process and relative merits thereof of having set forth existing electronickelling and chemical nickel plating, the technical process that the document discloses existing electronickelling is: 1. clean metal porcelain piece; 2. dilute hydrochloric acid soaks; 3. wash down; 4. immerse plating bath; 5. regulating electric current electroplates; 6. in plating bath, take out; 7. wash down; 8. deionization poach; 9. oven dry, the nickel plating system is the single nickel salt system, the character of the nickel dam of preparation only is 4.23 μ m such as table thickness, covering power and degree of depth ability, general and its disposable electronickelling thickness of resistance to air loss, wear resistance and solidity to corrosion also only can reach 4.23 μ m, has greatly limited the application of electronickelling technique.
Summary of the invention
In order to address the above problem, the invention provides a kind of method of electronickelling on ceramic MoMn metal surface newly.
At first, a kind of method for electroplating nickel of ceramic metallized layer, it comprises the steps:
(1) plating pre-treatment: in pH is 0～3 acid solution, adopt the method for anode electrolysis that activation treatment is carried out on the ceramic metallization top layer, the time is 1min～10min, takes out, and water washes down;
(2) caustic dip: use aqueous slkali soaking, control pH is 9～12, and the time is 1min～8min, takes out, and water washes down;
(3) pickling: soak with acid solution, control pH is 0～4, and time 1min～12min takes out, and water washes down;
(4) nickel preplating: nickel plating 1min～20min in the mixing solutions of nickelous chloride and hydrochloric acid, take out, water washes down;
(5) nickel plating: nickel plating in the nickel plating system, the time is 8min～40min, takes out, water washes down, oven dry.
Activation treatment namely be before electroplating by the specific solution-treated such as acid solution or alkali lye, with removals such as the oxide compound of piece surface, fouls, make piece surface clean and can reach a kind of plating pre-treating process that improves the electrolytic coating bonding force.
Wherein, the described acid solution of step (1) is sulphuric acid soln, and its concentration is 30%～60% (v/v).
Wherein, the described time of step (1) is 3～5min.
Wherein, the described alkaline solution of step (2) is sodium hydroxide solution, and its concentration is 7%～30% (m/m).
Wherein, the described acid solution of step (3) is sulphuric acid soln, and its concentration is 10%～35% (v/v).
Wherein, in the step (4), contain in every liter of mixing solutions: nickelous chloride 200～500g, density is 0.36g/cm
3Hydrochloric acid 10～80ml.
Wherein, the current density of step (4) nickel preplating is 6～40A/dm
2
Wherein, the described nickel plating system of step (5) is the nickel sulfamic acid system.
Preferably, contain in every liter of nickel sulfamic acid system: nickel sulfamic acid 500～700g, nickelous chloride 10～90g and boric acid 30～75g.
Wherein, the current density of step (5) nickel plating is 1～20A/dm
2, temperature is 30～70 ℃, pH is 4～6.
Method provided by the invention can be on the MoMn metal layer once property electroless nickel layer thickness reach 6～10 μ m, tensile strength is large, resistance to air loss and sophistication are good, and yield rate is high, obviously are better than traditional electronickelling system, have broad application prospects.
Obviously, according to foregoing of the present invention, according to ordinary skill knowledge and the customary means of this area, not breaking away under the above-mentioned basic fundamental thought of the present invention prerequisite, can also make modification, replacement or the change of other various ways.
The embodiment of form is described in further detail foregoing of the present invention again by the following examples.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Embodiment
The nickel plating on ceramic metallized layer of embodiment 1 usefulness method provided by the invention
1, the method for electroplating nickel of ceramic metallized layer:
Flow process: plating pre-treatment → caustic dip → pickling → nickel preplating → electronickelling
Detailed step:
(1) plating pre-treatment: at 30%～70% (v/v) sulphuric acid soln, (density is as 1.84g/cm take the vitriol oil
3) and the water preparation, pH is 0～3, adopts the method for anode electrolysis that activation treatment is carried out on the MoMn metallization top layer of pottery, the time is 1min～10min; Temperature: 10～50 ℃, take out, water washes down.
(2) caustic dip: soak with 7%～30% (m/m) sodium hydroxide solution, pH is 9～12, and the time is 2min～8min; Temperature: 10～60 ℃, take out, water washes down.
(3) pickling: with 10%～35% (v/v) sulphuric acid soln, (density is as 1.84g/cm take the vitriol oil
3) and the water preparation, soaking, pH is 0～4, time 2min～12min; Temperature: 10～50 ℃, take out, water washes down.
(4) nickel preplating: carry out nickel preplating in following condition, take out, water washes down;
Nickel plating system (L
-1): (density is 0.36g/cm for nickelous chloride 200～500g, hydrochloric acid
3) 10～80ml
Current density: 6～40A/dm
2
Temperature: 5～50 ℃
(5) nickel plating: carry out under the following conditions nickel plating, take out, water washes down, oven dry.
Nickel plating system (L
-1): nickel sulfamic acid 300～800g, nickelous chloride 10～90g, boric acid 30～75g
Current density: 1～20A/dm
2
Temperature: 20～70 ℃
pH：4～6
2, parameter choice experiment
(1) plating pre-treatment was screened prescription and time that electrolysis is used, and the result is as shown in table 1:
Prescription and the time the selection result of table 1 plating pre-treatment
| Numbering | The sulfuric acid of different concns | Electrolysis time (min) | Experimental phenomena |
| 1 | 10% sulfuric acid | 1～2 | Almost reactionless |
| 2 | 10% sulfuric acid | 3～5 | The same |
| 3 | 20% sulfuric acid | 1～2 | Reaction is slow, and the surface is not any change |
| 4 | 20% sulfuric acid | 3～5 | The same |
| 5 | 30% sulfuric acid | 1～2 | There is minor response on the surface |
| 6 | 30% sulfuric acid | 3～5 | There is minor response on the surface |
| 7 | 40% sulfuric acid | 1～2 | The surface responds, and is not obvious |
| 8 | 40% sulfuric acid | 3～5 | The surface responds, and is not obvious |
| 9 | 50% sulfuric acid | 1～2 | Reaction is violent than 40% sulfuric acid |
| 10 | 50% sulfuric acid | 3～5 | Violent with concentration |
| 7 | 60% sulfuric acid | 1～2 | Surface reaction is obvious |
| 8 | 60% sulfuric acid | 3～5 | React more obvious with concentration |
| 9 | 80% sulfuric acid | 1～2 | Reaction is fast |
| 10 | 80% sulfuric acid | 3～5 | Reaction is fast |
The loss amount of metal layer under the different proportioning acidity of table 2
| Test number | Sulfuric acid concentration | Time (min) | Loss MoMn metallization layer thickness (μ m) |
| 1 | 10% sulfuric acid | 3 | 0.75 |
| 2 | 20% sulfuric acid | 3 | 1.5 |
| 3 | 30% sulfuric acid | 3 | 2.24 |
| 4 | 40% sulfuric acid | 3 | 3.6 |
| 5 | 50% sulfuric acid | 3 | 4.12 |
| 6 | 60% sulfuric acid | 3 | 4.52 |
| 7 | 70% sulfuric acid | 3 | 5.25 |
As shown in table 1, sulfuric acid concentration is greater than 30% the time, and metal layer just can be activated.
As shown in Table 2, electrolytic process has damage to the MoMn metal layer, and the loss amount of metal layer increases and increases along with sulphuric acid soln concentration, the vitriol oil is easily emitted heat in layoutprocedure, its concentration is larger, temperature is higher, and manually-operated danger and cost all increase, and sulfuric acid concentration should be not too high.
Consider when sulfuric acid concentration is 30%～60%, the resistance to air loss of the nickel dam of preparation and sealing strength optimum, and yield rate is also relatively high.
Therefore, the concentration of preferably sulfuric acid solution is 30%～60%.
(2) nickel plating
At first the electroplating solution of single nickel salt system is tested, under the basic components condition of traditional nickel plating, strengthen gradually in proportion the proportioning of each composition, but experimental result is all undesirable, its major defect is that the scorch region area is excessive, because the restriction of single nickel salt system self prescription condition is bad with integrated artistic suitability of the present invention.
Grope experiment with nickel sulfamic acid solution.Wherein, concentration to main salt nickel sulfamic acid is screened, other additional salt content do not change, require the 1. pre-treatment of print during the experiment beginning, be consistent 2. for the 250ml Hull Cell in the situations such as temperature and the actual production, specimen size is 100mm*65mm and the latten(-tin) that carries out polishing experiments, and thickness is about 0.5mm, and anode is selected the nickel plate.
The selection result of table 3 thionamic acid nickel concentration
The concentration of nickel sulfamic acid could satisfy following the requirement in the electroplating process when 500～700g/L: 1. the bonding force side between metal layer and the nickel can reach best, and its internal stress is also minimum; 2. could effectively prevent anode passivation in the electrolytic process, accelerate the diffusion of nickel ion in the aqueous solution; 3. the pH value is kept stable for a long time; 4. current density control is relatively simple, and the product thickness after the plating is more even; 5. product is fine and smooth by the crystallization of naked-eye observation top layer, and texture also reaches preferably level.Therefore, the thionamic acid nickel concentration is being preferably 500～700g/L.
Under the proportioning of above-mentioned preferred concentration, the nickel plating temperature is carried out preferably:
Table 4 temperature the selection result
In the middle of the sintering process that once metallizes, temperature is inconsistent up and down because body of heater may exist, perhaps because of the impact of atmosphere in the sintering process, cause the oxidation of MoMn metal layer, the nickel layer thickness of traditional electrical nickel plating system maintains 3～4 μ m, can't cover some flaws in its sintering process fully, thereby causes a delivery-check qualified rate relatively low, for improving the one-pass finished rate, thicken nickel layer thickness and seem particularly important.Generally speaking, the nickel layer thickness of 5～11 μ m can satisfy high this requirement of yield rate.As shown in Table 4, when temperature was 30-70 ℃, the nickel layer thickness of electronickelling of the present invention can reach requirement.
Traditional electrical nickel plating is according to the simplest technical process at present: with salt acid soak → electronickelling, namely adopt hydrochloric acid that metal layer is soaked, directly electroplate after the washing, the time is controlled at 30～40 minutes, although this method is simple, its yield rate is not high.The nickel dam of method for electroplating nickel of the present invention and the preparation of traditional electrical nickel plating process is compared, describes beneficial effect of the present invention in detail:
(1) the nickel layer Thickness Ratio
Experimental result is as shown in table 5:
The nickel layer thickness of the nickel plating of table 5 traditional electrical and electronickelling of the present invention relatively
| Method | Electroplating time | Mean thickness/μ m | Average deviation | Maximum value | Minimum value |
| Tradition is electroplated | 20 | 2.30 | 0.37 | 4.02 | 1.78 |
| The present invention electroplates | 20 | 8.6 | 0.22 | 9.36 | 7.57 |
Annotate: the nickel layer maximum thickness of this table and minimum value are the experimental results that measures at the nondestructive thickness measuring instrument in the time of t=50 ℃.
As shown in Table 5, the mean thickness of nickel layer thickness of the present invention is 4 times of traditional nickel layer thickness, is that traditional nickel layer is incomparable.
(2) tensile strength
Tensile test is take the standard tensile members as sample, AgCu
28As scolder, make tensile test behind the high intermediate temperature sealing.Tensile strength is as follows:
The tensile strength of the tensile members of the nickel plating of table 6 traditional electrical and electronickelling of the present invention relatively
| Sample number | Tradition nickel plating (MPa) | Nickel plating of the present invention (MPa) |
| 1 | 102 | 150 |
| 2 | 127 | 343 |
| 3 | 138 | 228 |
| 5 | 139 | 156 |
| 6 | 85 | 257 |
| Mean value | 98.5 | 189 |
As shown in Table 6, the tensile strength of nickel dam of the present invention obviously is better than traditional nickel layer.
(3) resistance to air loss
Thermal shock test
Metallization porcelain piece and metal parts sealing-in that this technique is electroplated are testpieces, and this testpieces is by room temperature---the thermal shocking of 600 ℃ of insulation 30min---room temperatures, and 6 thermal shockings are all air tight by helium mass spectrometer leak, and test-results is qualified.
The bubble-tight yield rate of the sealing-in of the nickel plating of table 7 traditional electrical and electronickelling of the present invention
| Tradition nickel plating | Nickel plating of the present invention | |
| Homogeneous tube sealing-in yield rate | 95％ | 97％ |
| The thermal shocking qualification rate | 100％ | 100％ |
As shown in Table 7, a little higher than traditional nickel plating process of homogeneous tube sealing-in yield rate of nickel dam of the present invention, thermal shock resistance properties is also fabulous, illustrates that the resistance to air loss of nickel dam of the present invention slightly is better than traditional nickel layer.
(4) by relatively the difference of two kinds of nickel plating process properties is as follows comprehensively:
The properties of the nickel plating of table 8 traditional electrical and electronickelling of the present invention relatively
| Performance | Tradition nickel plating | Nickel plating of the present invention |
| Cost | Generally | Higher |
| The technique operability | Simply | Simply |
| Technology stability | Generally | Stable |
| Covering power | Generally | Good |
| Tensile strength (standard tension test part) | ≥90MPa | ≥90MPa |
| Solder wettability | Better | Good |
| Resistance to air loss | Generally | Good |
| Wear resistance | Generally | Good |
| Solidity to corrosion | Generally | Good |
| Internal stress | Greatly | Little |
| Sophistication | Coarse | Fine and smooth |
As shown in Table 8, the performance that the inventive method prepares nickel dam obviously is better than traditional nickel layer, and particularly the sophistication utmost point is better than traditional nickel layer significantly.
In sum, compare with traditional nickel plating process, the properties of the nickel layer of method for electroplating nickel preparation of the present invention is all significantly good, and easy and simple to handle, has good market application foreground.
Claims (1)
1. the method for electroplating nickel of a ceramic metallized layer, it is characterized in that: it comprises the steps:
(1) plating pre-treatment: in pH is 0～3 acid solution, adopt the method for anode electrolysis that activation treatment is carried out on the metallization top layer of pottery, the time is 1min～10min, takes out, and water washes down;
(2) caustic dip: use aqueous slkali soaking, control pH is 9～12, and the time is 1min～8min, takes out, and water washes down;
(3) pickling: soak with acid solution, control pH is 0～4, and time 1min～12min takes out, and water washes down;
(4) nickel preplating: nickel plating 1min～20min in the mixing solutions of nickelous chloride and hydrochloric acid, take out, water washes down;
(5) nickel plating: nickel plating in the nickel plating system, the time is 8min～40min, takes out, water washes down, oven dry;
In the step (4), contain in every liter of mixing solutions: nickelous chloride 200～500g, density is 0.36g/cm
3Hydrochloric acid 10～80 ml;
The described nickel plating system of step (5) is the nickel sulfamic acid system; Contain in every liter of nickel sulfamic acid system: nickel sulfamic acid 500～700g, nickelous chloride 10～90g and boric acid 30～75g;
The current density of step (5) nickel plating is 1～20A/dm
2, temperature is 30～70 ℃, the pH of nickel plating system is 4～6.
2, method for electroplating nickel according to claim 1 is characterized in that: the described acid solution of step (1) is sulphuric acid soln, and its concentration is 30%～60%(v/v).
3, method for electroplating nickel according to claim 1 is characterized in that: the described time of step (1) is 3 ~ 5min.
4, method for electroplating nickel according to claim 1 is characterized in that: the described alkaline solution of step (2) is sodium hydroxide solution, and its concentration is 7%～30%(m/m).
5, method for electroplating nickel according to claim 1 is characterized in that: the described acid solution of step (3) is sulphuric acid soln, and its concentration is 10%～35%(v/v).
6, method for electroplating nickel according to claim 1 is characterized in that: the current density of step (4) nickel preplating is 6～40A/dm
2
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| CN105887149B (en) * | 2016-05-27 | 2018-09-25 | 中国电子科技集团公司第五十五研究所 | A kind of metallized ceramic electro-plating method |
| CN106435679B (en) * | 2016-10-24 | 2018-12-11 | 中国工程物理研究院电子工程研究所 | A method of reducing ceramic electroless nickel layer blistering |
| CN111074248A (en) * | 2019-12-27 | 2020-04-28 | 娄底市安地亚斯电子陶瓷有限公司 | Chemical nickel plating solution and ceramic secondary metallization method |
| CN114540801A (en) * | 2020-11-24 | 2022-05-27 | 娄底市安地亚斯电子陶瓷有限公司 | Nickel plating process suitable for ceramic sealing connector |
| CN112647102A (en) * | 2020-12-18 | 2021-04-13 | 成都宏明双新科技股份有限公司 | Method for improving bonding force of nickel plating layer of chip capacitor terminal electrode |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4127709A (en) * | 1977-08-24 | 1978-11-28 | Samuel Ruben | Process for electro-plating nickel on titanium |
| CN1058053A (en) * | 1991-06-01 | 1992-01-22 | 东北工学院 | The method of electroplating bright nickel on Nd-Fe-B alloy |
-
2011
- 2011-10-31 CN CN 201110337891 patent/CN102392279B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4127709A (en) * | 1977-08-24 | 1978-11-28 | Samuel Ruben | Process for electro-plating nickel on titanium |
| CN1058053A (en) * | 1991-06-01 | 1992-01-22 | 东北工学院 | The method of electroplating bright nickel on Nd-Fe-B alloy |
Non-Patent Citations (4)
| Title |
|---|
| 唐敏,洪宇.陶瓷-金属封接中的二次金属化工艺.《真空电子技术》.2002,(第3期), |
| 崔永丽,江利.陶瓷二次金属化镀镍工艺研究.《表面技术》.2002,第31卷(第4期), |
| 陶瓷二次金属化镀镍工艺研究;崔永丽,江利;《表面技术》;20020831;第31卷(第4期);29-31 * |
| 陶瓷-金属封接中的二次金属化工艺;唐敏,洪宇;《真空电子技术》;20021231(第3期);21-23 * |
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