CN102330076B - Device and method for preparing stannopailadinite colloid activating agent - Google Patents
Device and method for preparing stannopailadinite colloid activating agent Download PDFInfo
- Publication number
- CN102330076B CN102330076B CN 201110251212 CN201110251212A CN102330076B CN 102330076 B CN102330076 B CN 102330076B CN 201110251212 CN201110251212 CN 201110251212 CN 201110251212 A CN201110251212 A CN 201110251212A CN 102330076 B CN102330076 B CN 102330076B
- Authority
- CN
- China
- Prior art keywords
- palladium
- colloid
- tin
- stannous chloride
- chloride solution
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Colloid Chemistry (AREA)
- Catalysts (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a device for preparing a stannopailadinite colloid activating agent, which comprises a tank, an ultrasonic oscillation device and dispersion plate, wherein a discharge port is formed on the lateral wall of the tank; the ultrasonic oscillation device is arranged on the outer wall of the bottom of the tank; and a plurality of through holes are formed on the thickness direction. Correspondingly, the invention also provides a method for preparing the stannopailadinite colloid activating agent, by utilizing the device. In order to lead stannous chloride solution to uniformly flow into an inorganic acid solution of palladium, the dispersion plate with the plurality of through holes in the thickness direction is adopted, and the stannous chloride solution flows into the inorganic acid solution of palladium via the plurality of through holes in the process of preparing the activating agent, so that uniform mixing of the stannous chloride solution and the inorganic acidsolution of palladium is realized. Meanwhile, stannopailadinite atoms uniformly impact and react by utilizing micro-mixing power of ultrasonic oscillation, so that stannopailadinite colloid in the prepared stannopailadinite colloid activating agent has small grain diameter and uniform dispersion.
Description
Technical field
The present invention relates to the activator technical field, more particularly, relate to a kind of apparatus and method for the preparation of tin palladium colloid activator.
Background technology
At present, along with the fast development of global electronic information technology and the communication technology, printed wiring (PCB) industry becomes the manufacturing maximum pillar of electronic component at world wide.The preparation printed circuit board mainly may further comprise the steps: the boring of multilayer non-metal board is removed the glue slag (Smear) that boring produces by the de-smear flow process, clean processing such as whole hole, microetch, preimpregnation, activation, speedization and electroless copper then, make the non-metallic material metallization in the printed circuit board hole wall, thus electrically conducting between the layer of realization printed circuit board and the layer.
Activation treatment is the important step of making in the printed circuit board process, its objective is at a certain amount of active center of non metallic substrate absorption, in order to bring out electroless plating, detailed process is: the non metallic substrate after the preimpregnation is immersed in the tin palladium colloid activator, tin palladium colloid activator is adsorbed in the non-metal substrate surface, make the non-metal base basal surface generate the precious metal tin palladium nano-particles that one deck has the discontinuity of catalytic reduction chemical copper ability, carry out smoothly at substrate surface thereby be conducive to electroless copper.
The major ingredient of tin palladium colloid activator comprises Palladous chloride, hydrochloric acid, sulfuric acid, tin protochloride and sodium-chlor etc.Tin palladium colloidal particle in the tin palladium colloid activator also is insoluble in the solution medium, but it is little of when as long as the heat energy that provides of solution medium just is enough to overcome the gravity of colloid at particle, this colloid just can suspend and be dispersed in the solution, forms the pedesis (Brown motion) of colloidal particle.Though can colloidal particle be suspended by improving solution-operated temperature mode, but, the size of colloidal particle is still the important factor that influences pedesis, when the colloidal particle particle diameter is big (for example 200nm), even under higher service temperature, the bigger phenomenon of the gap of inevasible generation liquid level colloidal particle number and bottom land colloidal particle number still, this gap will make the active inhomogeneous of the interior each point of activated bath, the excessive easy generation of colloidal particle size simultaneously is Jiao Ji each other, cause the sedimentation of colloid, the activity of activator descends, and therefore, how to prepare the less and finely dispersed tin palladium of particle diameter colloidal solution and has great importance.
The preparation of tin palladium colloid activator mainly comprises two steps: at first tin protochloride and palladium-hydrochloric acid soln collision are stirred the nucleation that realizes colloid; Then the inferior tin of excess chlorination is mixed with the tin Pd nano particle, this step is the growth step of colloid.Wherein, the control of nucleus size is the key in the tin palladium colloid for preparing process in the nucleation step, particle growth speed is far above the formation speed of core if the one-tenth nuclear control is improper, huge Van der Waals force magnetism will be greater than the power that pushes away each other, thereby make tin palladium colloid aggregation, colloidal solid becomes big even produces precipitation.In the prior art, the preparation method of tin palladium colloid activator commonly used is: a large amount of stannous chloride solutions is directly mixed stirring with palladium-hydrochloric acid soln, because this method is mixed a large amount of tin protochlorides too early with the palladium of nucleation not, a large amount of Bivalent Tin and chlorion form highly stable complex compound, palladium can't be reduced into palladium metal, thereby activator non-activity or the activity of preparation are lower.In addition, activator is the preparation method also comprise: adopt stirrer slowly to stir palladium-hydrochloric acid soln, adopt the mode of slowly pouring into a fixed point to add stannous chloride solution then.Because this alr mode easily forms inertia and stirs, can not make tin palladium atom fully and collision equably, therefore bigger the and big small particle size distribution of nucleation particle diameter that forms is wider.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of apparatus and method for the preparation of tin palladium colloid activator, and tin palladium colloidal particle size is less and be uniformly dispersed in the tin palladium colloid activator of this method preparation.
In order to solve above technical problem, the invention provides a kind of device for the preparation of tin palladium colloid activator, comprising:
Sidewall is provided with the cell body of discharge port;
Be arranged at the ultrasound rocking equipment of described cell body bottom outer wall;
The breaker plate that has the through hole of a plurality of perforations at thickness direction.
Preferably, described cell body inwall is polypropylene material, polyvinyl chloride material or tetrafluoroethylene material; Described breaker plate is polypropylene material, polyvinyl chloride material or tetrafluoroethylene material.
Preferably, the aperture of described through hole is 1～5mm.
Preferably, also comprise:
The ultrasound producer that links to each other with described ultrasound rocking equipment.
Accordingly, the present invention also provides a kind of method of utilizing said apparatus to prepare tin palladium colloid activator, comprising:
The a plurality of through holes of first stannous chloride solution through breaker plate are flowed in the inorganic acid solution of palladium, and the ultrasound concussion obtains first mixing solutions;
Described first mixing solutions, second stannous chloride solution are mixed with mineral acid, and heated and stirred obtains tin palladium colloid activator.
Preferably, the oscillation frequency of described ultrasound concussion is 10～70KHz.
Preferably, the oscillation frequency of described ultrasound concussion is 24KHz.
Preferably, the power of described ultrasound concussion is 100～175W.
Preferably, the power of described ultrasound concussion is 125～150W.
Preferably, the inlet time of described first stannous chloride solution is 30～50 seconds.
The invention provides a kind of device for the preparation of tin palladium colloid activator, comprising: sidewall is provided with the cell body of discharge port; Be arranged at the ultrasound rocking equipment of described cell body bottom outer wall; The breaker plate that has the through hole of a plurality of perforations at thickness direction.And the present invention also provides a kind of method of utilizing said apparatus to prepare tin palladium colloid activator, comprising: a plurality of through holes of first stannous chloride solution through breaker plate are flowed in the inorganic acid solution of palladium, and the ultrasound concussion obtains first mixing solutions; Described first mixing solutions, second stannous chloride solution are mixed with mineral acid, and heated and stirred obtains tin palladium colloid activator.In order to make stannous chloride solution can evenly flow in the inorganic acid solution of palladium, the present invention has adopted the breaker plate that has the through hole of a plurality of perforations at thickness direction, in the preparation process of activator, stannous chloride solution flows in the inorganic acid solution of palladium through a plurality of through holes, thereby has realized that stannous chloride solution mixes with the even of inorganic acid solution of palladium.Simultaneously, also utilize little whipping force of ultrasound concussion to make the collision uniformly of tin palladium atom and reaction, thereby make tin palladium colloidal particle size in the tin palladium colloid activator of preparation less and be uniformly dispersed.
Description of drawings
Fig. 1 is the device synoptic diagram for the preparation of tin palladium colloid activator disclosed by the invention;
Fig. 2 is breaker plate synoptic diagram disclosed by the invention;
Fig. 3 is the tunnel like electron microscope picture of the tin palladium colloid of embodiment of the invention preparation;
Fig. 4 is the tunnel like electron microscope picture of the tin palladium colloid of embodiment of the invention preparation.。
Embodiment
Below the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
The invention discloses a kind of device for the preparation of tin palladium colloid activator, as shown in Figure 1 and Figure 2, comprising: sidewall is provided with the cell body 12 of discharge port 13; Be arranged at the ultrasound rocking equipment 16 of cell body 12 bottom outer wall; The breaker plate 11 that has the through hole 111 of a plurality of perforations at thickness direction.
The part that the inwall of cell body 12 namely contacts with tin palladium colloid activator, the present invention preferably adopts polypropylene material, polyvinyl chloride material or tetrafluoroethylene material, polypropylene material more preferably, and for the outer wall material of cell body 12, can adopt material well known to those skilled in the art, there is no particular restriction to this present invention.Compare with metal cell body commonly used, inwall is the ionic soil that the cell body of polypropylene material can effectively be avoided the tin palladium colloid activator that the metal stripping causes, and can also avoid metallic palladium is produced unnecessary redox reaction.The volume of cell body 12 is preferably 25～35 liters, more preferably 30～35 liters.The sidewall of cell body 12 is provided with discharge port 13, and discharge port 13 can be controlled its open and close by opening-closing valve.
In addition, the present invention also preferably includes dividing plate 15, and dividing plate 15 surrounds the dividing plate space with cell body 12 bottoms.And the ultrasound rocking equipment 16 that is arranged at cell body 12 bottom outer wall is preferably ultrasound concussion, and ultrasound concussion can be 1 or a plurality of.Ultrasound vibration 16 preferably is positioned in the dividing plate space, and ultrasound vibration is fixed on the cell body below.Also preferably be equipped with sending out the hot fan 14 in the dividing plate space, be used for the heat that ultrasound vibration produces is expelled to beyond the dividing plate space, to increase the work-ing life of ultrasound vibration 16.Ultrasound vibration 16 is preferred to be connected 17 by the high frequency lead and links to each other with ultrasound producer 18, and ultrasound producer 18 be independently to control casing, has power switch and electric power conductor.Be provided with the oscillation frequency pointer gauge 181 of demonstration oscillation frequency in the ultrasound producer 18 and adjust button 182 for the oscillation frequency of adjusting output frequency.
For stannous chloride solution can evenly be flowed in the inorganic acid solution of palladium, comprise breaker plate 11 in the device provided by the invention.When preparation tin palladium colloid activator, breaker plate is set up in the cell body top.Breaker plate 11 is preferably polypropylene material, polyvinyl chloride material or tetrafluoroethylene material, more preferably polypropylene material.The breaker plate that has the through hole of a plurality of perforations on this thickness direction preferably is prepared as follows: utilizing diameter is that the drill bit of 1～2mm is that polyacrylic sheet material is evenly holed with material, boring size and quantity are to be as the criterion in the inorganic acid solution that satisfies stannous chloride solution flow into palladium in 30～50 seconds, and the time was preferably for 40～45 seconds.Wherein, the aperture of the through hole of breaker plate 11 is preferably 1～5mm, more preferably 2～4mm.
Accordingly, the present invention also provides a kind of method of utilizing said apparatus to prepare tin palladium colloid activator, comprising:
The a plurality of through holes of first stannous chloride solution through breaker plate are flowed in the inorganic acid solution of palladium, and the ultrasound concussion obtains first mixing solutions;
Described first mixing solutions, second stannous chloride solution are mixed with mineral acid, and heated and stirred obtains tin palladium colloid activator.
For tin palladium colloid activator, its major ingredient comprises Palladous chloride, hydrochloric acid, sulfuric acid, tin protochloride and sodium-chlor etc.Wherein, the main effect of tin protochloride is as reductive agent palladium ion to be reduced into nanometer palladium nuclear; in this reduction process; remain excessive tin protochloride and can form the adsorption layer (adsorbed layer) that a kind of stannic acid colloid (stannicacid colloids) is centered around the peripheral formation of nanometer palladium nuclear protective colloid; chlorion forms opposition ion district (counter ion region) around colloid, above-mentioned adsorption layer forms electrical double layer jointly with opposition ion district.When the ionic concn in the solution increases, when the diffusibility of ion district in solution that cause opposing weakens gradually, adsorption layer just can further with opposition ion district, just electrical double layer can dwindle, and distance is each other reduced, when the electrical double layer between colloid and the colloid begins when overlapping, electric charge identical down, just begin to occur the effect of pushing away between colloid, just can make colloid present stable dissemination this moment in solution, and can not produce the sedimentation of glue collection each other.
The preparation process of tin palladium colloid activator of the present invention is specially: the inorganic acid solution of palladium is poured in the cell body, the good breaker plate of frame, open ultrasound generating unit power supply, adjust occurrence frequency earlier, lentamente with stannous chloride solution to breaker plate, first stannous chloride solution sees through the through hole of a plurality of perforations of breaker plate, being the spray shape flows in the inorganic acid solution of palladium, simultaneously under the ultrasound concussion, obtain first mixing solutions, then described first mixing solutions, second stannous chloride solution are mixed with mineral acid, heated and stirred obtains tin palladium colloid activator.Among the present invention, described first stannous chloride solution can be identical with described second stannous chloride solution, also can be different, and to this present invention and without particular limitation.In order to make first stannous chloride solution can evenly flow in the inorganic acid solution of palladium, the present invention has adopted the breaker plate that has the through hole of a plurality of perforations at thickness direction, in the preparation process of activator, first stannous chloride solution flows in the inorganic acid solution of palladium through a plurality of through holes, thereby has realized that stannous chloride solution mixes with the even of inorganic acid solution of palladium.Simultaneously, also utilize little whipping force of ultrasound concussion to make the collision uniformly of tin palladium atom and reaction, thereby make tin palladium colloidal particle size in the tin palladium colloid activator of preparation less and be uniformly dispersed.
According to the present invention, the oscillation frequency of described ultrasound concussion is preferably 10～70KHz, more preferably 10～40KHz, more preferably 24KHz.The power of described ultrasound concussion is preferably 100～175W, more preferably 125～150W.The oscillation frequency of the ultrasound concussion that the present invention adopts is preferably no wave band adjustable, and oscillation frequency is adjusted button 182 and adjusted output frequency in the use device, shows present oscillation frequency by oscillation frequency pointer gauge 181.
Therefore, because having adopted at thickness direction, the present invention has the breaker plate of through hole of a plurality of perforations and the method for ultrasound concussion, the tin palladium collision of nucleation stage can be even and complete in the early stage to make the inorganic acid solution of stannous chloride solution and palladium, thereby finally prepare the little and finely dispersed tin palladium of particle diameter colloid activator, significant for the process rate that promotes high aspect ratio deep hole or micro blindness hole workpiece.
In order to further specify technical scheme of the present invention, be described below in conjunction with the preferred embodiment of the invention of embodiment, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
Embodiment
Prepare 100 liters of activators according to following proportioning:
The preparation of A liquid: with 100g Palladous chloride (PdCl
2) add in 20 liter 37% the hydrochloric acid, constantly stirring up to dissolving, liquid presents orange, obtains A liquid.
The preparation of B liquid: with 254g tin protochloride two crystal water (SnCl
22H
2O) be dissolved in 10 liters of pure water, slowly stir up to dissolving, liquid presents transparent haze-free, obtains B liquid.
The preparation of C liquid: 10 liter 37% hydrochloric acid is mixed with 60 premium on currency, add tin protochloride two crystal water (SnCl while stirring
22H
2O), liquid presents transparent haze-free, obtains 70 liters of C liquid.
A liquid is poured in the cell body 12 of Fig. 1, device shown in Figure 2, the good breaker plate 11 of the top shelf of cell body 12 is opened oscillator supply, and the occurrence frequency of vibrator is adjusted to 24KHz;
B liquid is evenly seen through through hole 111 dispersedly be poured onto in the A liquid, remove breaker plate, lid is built, duration of oscillation continues 15 minutes, and with power-off, tin palladium colloid nucleation process finished after vibration finished, and solution presents blackish green;
Vibration is mixed the blackish green liquid of finishing to add in the C liquid at leisure, start whipping appts, slowly stir, and heater, at four hours internal heating to 90 ℃, this mainly is to keep heat even for the aging step of colloid, this whipping process with mixed solution, stirring velocity can not be too fast, and too fast stirring may cause Bivalent Tin to be oxidized to tetravalent tin inclusion of air;
After reaching 90 ℃, the temperature of mixed solution closes well heater, at room temperature still open whipping device, be cooled to below 30 ℃ up to the mixed solution solution temperature, be tin palladium colloid activator stoste, this moment, solution appearance presented brownish black, and solution surface has the distinctive opalescence phenomenon of colloid.
The tin palladium colloid activator stoste palladium concentration of present embodiment preparation is 600ppm, join groove with 8%, the palladium concentration that activated bath is joined groove is 48ppm, and building the 200g/L composition of arranging in pairs or groups when bathing is the pre-preserved material A of sodium-chlor, and the composition of 70ml/L is that the pre-preserved material B of hydrochloric acid, stablizer, antioxidant builds bath.It is pre-preserved material A (sodium-chlor) 200g/L that pre-immersion trough is built the bath mode, and pre-preserved material B (containing hydrochloric acid, stablizer, antioxidant) 70ml/L builds bath.
Press the processing parameter shown in the table 1 and adjust production line overhead traveling crane program time, the soaking the time of putting and drip the time etc. of each operation slot;
The processing parameter that table 1 embodiment adopts
| Operation | Operation slot | Palladium concentration | Soak the time of putting | Drip the time |
| 1 | Pre-immersion trough | 1min | 10sec | |
| 2 | Activated bath (tin palladium colloid) | 48ppm | 4.5min | 15sec |
Test with the yield test panel, test panel is the FR-4 substrate of thickness of slab 2.0mm, and drilling hole amount is 140,000, the aperture is 0.25mm, and the aperture aspect ratio is 8: 1, implements to test 20 altogether in 20 days, after covering the intact chemical copper of plated-through-hole flow process plating, detect in the mode backlight of cutting into slices at microscopically and to be 9.5～10 grades, follow-up all test panels detect porose conduction status in the electrical measurement mode behind plate plating and graphic plating, the phenomenon that the equal atresia of all test panels is broken, percent of pass is 100%.To finish the plating test panel and float the tin experiment, through six times the tin that floats, not find the phenomenon that hole wall bubbles or floats off.
The activated bath stability observing:
By the observation of production line through one month, the hydrolysis phenomenon of color change and gonorrhoea because the instability of colloid causes unusual minimizing, does not take place simultaneously in the palladium concentration of activated bath.
Under the observation of tunnel like electron microscope (TEM), as shown in Figure 3, Figure 4, the size of this tin palladium colloidal solid is about 50nm with tin palladium colloid activator stoste.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments herein.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the wideest scope consistent with principle disclosed herein and features of novelty.
Claims (9)
1. the device for the preparation of tin palladium colloid activator is characterized in that, comprising:
Sidewall is provided with the cell body of discharge port;
Be arranged at ultrasound concussion of described cell body bottom outer wall;
The breaker plate that has the through hole of a plurality of perforations at thickness direction; The aperture of described through hole is 1～5mm.
2. device according to claim 1 is characterized in that, described cell body inwall is polypropylene material, polyvinyl chloride material or tetrafluoroethylene material; Described breaker plate is polypropylene material, polyvinyl chloride material or tetrafluoroethylene material.
3. device according to claim 1 is characterized in that, also comprises:
The ultrasound producer that links to each other with described ultrasound concussion.
4. method of utilizing any described device of claim 1～3 to prepare tin palladium colloid activator comprises:
The a plurality of through holes of first stannous chloride solution through breaker plate are flowed in the inorganic acid solution of palladium, and the ultrasound concussion obtains first mixing solutions;
Described first mixing solutions, second stannous chloride solution are mixed with mineral acid, and heated and stirred obtains tin palladium colloid activator.
5. method according to claim 4 is characterized in that, the oscillation frequency of described ultrasound concussion is 10～70KHz.
6. method according to claim 5 is characterized in that, the oscillation frequency of described ultrasound concussion is 24KHz.
7. method according to claim 4 is characterized in that, the power of described ultrasound concussion is 100～175W.
8. method according to claim 7 is characterized in that, the power of described ultrasound concussion is 125～150W.
9. method according to claim 4 is characterized in that, the inlet time of described first stannous chloride solution is 30～50 seconds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110251212 CN102330076B (en) | 2011-08-29 | 2011-08-29 | Device and method for preparing stannopailadinite colloid activating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110251212 CN102330076B (en) | 2011-08-29 | 2011-08-29 | Device and method for preparing stannopailadinite colloid activating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102330076A CN102330076A (en) | 2012-01-25 |
| CN102330076B true CN102330076B (en) | 2013-09-04 |
Family
ID=45482034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110251212 Expired - Fee Related CN102330076B (en) | 2011-08-29 | 2011-08-29 | Device and method for preparing stannopailadinite colloid activating agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102330076B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152875A (en) * | 2014-08-25 | 2014-11-19 | 志超科技（遂宁）有限公司 | PCB-PTH (Printed Circuit Board-Plated Through Hole) line hole conditioning and activation ultrasonic device and method |
| TWI826151B (en) * | 2022-11-29 | 2023-12-11 | 實踐大學 | Complex frequency ultrasonic and drum stirrer device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1467304A (en) * | 2002-07-09 | 2004-01-14 | 中鼎化工股份有限公司 | Non-conductor metallization manufacturing process applying ultrasonic equipment to activator containing colloid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090238979A1 (en) * | 2008-03-21 | 2009-09-24 | William Decesare | Method of Applying Catalytic Solution for Use in Electroless Deposition |
-
2011
- 2011-08-29 CN CN 201110251212 patent/CN102330076B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1467304A (en) * | 2002-07-09 | 2004-01-14 | 中鼎化工股份有限公司 | Non-conductor metallization manufacturing process applying ultrasonic equipment to activator containing colloid |
Non-Patent Citations (2)
| Title |
|---|
| 塑料电镀中的敏化活化一步法;孙永泰;《塑料制造》;20090630;第84-87页 * |
| 孙永泰.塑料电镀中的敏化活化一步法.《塑料制造》.2009,第84-87页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102330076A (en) | 2012-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102489717B (en) | Preparation method of nanometer silver particles | |
| CN105555023B (en) | High conducting clear glass base circuit board | |
| CN102303124A (en) | Method for preparing length-diameter-ratio nano-silver wire by pH-value regulation solvothermal method | |
| CN101716685A (en) | Method for preparing spherical superfine silver powder by using chemical reduction method | |
| CN105671515B (en) | The simple method for preparing of monovalence golden nanometer particle/three-dimensional grapheme/nickel foam composite construction | |
| CN103231072A (en) | Preparation method of silicon dioxide/silver core-shell composite powder for high temperature electronic paste | |
| WO2006025485A1 (en) | Electroconductive fine particle and anisotropically electroconductive material | |
| CN102330076B (en) | Device and method for preparing stannopailadinite colloid activating agent | |
| CN211047455U (en) | PCB copper deposition device | |
| CN102321878B (en) | Surface activation method for nonmetal material | |
| CN101569935A (en) | Preparation method for flaky micro-silver powder | |
| CN108907226A (en) | A kind of preparation method for laser ablation electrode circuit super fine silver powder | |
| WO2012067706A1 (en) | Reactor and continuous process for producing silver powders | |
| WO2021243970A1 (en) | Composite catalyst and preparation method therefor | |
| CN105063580A (en) | Preparation method of nickel-coated graphite powder for electroconductive rubber of electromagnetic shielding material | |
| CN104789949A (en) | Compounding method of epoxy resin solution with autocatalysis chemical copper plating activity and chemical copper plating method | |
| CN108672718A (en) | A kind of preparation method of the spherical silver powder of high specific area and its silver powder obtained | |
| CN102199763B (en) | Preparation method for electroless plating activator capable of screen printing, and activating treatment process using same | |
| CN101163562A (en) | Tin powder, process for producing tin powder, and tin powder-containing elctrically conductive paste | |
| CN102554218A (en) | Method for preparing tungsten-copper composite powder by means of electroless copper plating | |
| CN106041123A (en) | High-activity hollow silver powder for front silver of solar cell and preparing method for high-activity hollow silver powder | |
| JP2009206089A (en) | Manufacturing method of electrically conductive fine particle, and electrically conductive fine particle | |
| CN2441817Y (en) | Supersonic plating device | |
| JP2004068072A (en) | Manufacturing method of silver particulate colloid dispersion solution | |
| CN101358050A (en) | Conductive pattern formation ink, conductive pattern and wiring substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130904 |