CN102925876A - Pretreatment method suitable for phenolic resin composite material chemical plating - Google Patents
Pretreatment method suitable for phenolic resin composite material chemical plating Download PDFInfo
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- CN102925876A CN102925876A CN2012104455632A CN201210445563A CN102925876A CN 102925876 A CN102925876 A CN 102925876A CN 2012104455632 A CN2012104455632 A CN 2012104455632A CN 201210445563 A CN201210445563 A CN 201210445563A CN 102925876 A CN102925876 A CN 102925876A
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Abstract
The invention discloses a pretreatment method suitable for phenolic resin composite material chemical plating. Glucose, formaldehyde, acetaldehyde and sodium hypophosphite serve as sensitizing agents, and chemical plating pretreatment of phenolic resin composite materials is achieved according to the following method: a phenolic resin composite material element is treated roughly to enable the surface of the element to have good hydrophilicity and have catalytic activity sequentially through reduction and activation. The pretreated element can be directly used for chemical copper plating, chemical silver plating and chemical nickel plating. The method is characterized in that a reducing agent is used, so stability is good and the treated element can keep good surface property for a long time to facilitate the follow-up chemical plating. Besides, by means of silver salt activation solution, cost is low and stability is good. The method is not influenced by tin ions, so adhesion between chemical plating layers and a matrix is good. Reagents used are low in cost and environment-friendly, so cost during a chemical plating pretreatment and environment pollution is lowered.
Description
Technical field
The present invention relates to the method for electroless plating in a kind of non-metal material surface metallization, particularly a kind of pre-treating process that is applicable to the phenolic resin-base composite electroless plating.
Background technology
Macromolecular material be through can having the performance of macromolecular material and metal behind the surface metalation concurrently, such as good mechanical property, heat-resisting, lightweight, easy-formation, conduction, heat conduction with have metalluster etc., can be widely used in communication, automobile and the industry such as electric.Resol is a class thermosetting resin of developing early, and raw material is easy to get, and is synthetic convenient, has good mechanical property, resistance toheat and high temperature resistant ablation property.Can improve the performance of resol and matrix material thereof behind the surface metalation, expand its range of application.
The method of surface metalation that can be used for non-metallic material is numerous, such as electroless plating, chemical vapour deposition, vacuum evaporation and metal sputtering etc.In numerous non-metal material surface method for metallising, chemical plating method because of with low cost, equipment is simple, coating all even coating be subjected to substrate performance to affect the little industrial circle that is widely used in.
Electroless plating is a kind of energising that do not need, and relies on oxidation-reduction reaction to form the method for densified metal layer at matrix surface.In order to guarantee that chemical reaction only occurs on the product surface in the electroless plating process, need to carry out pre-treatment to matrix surface, make matrix surface have catalytic activity.The electroless plating pre-treatment has not only guaranteed carrying out smoothly of electroless plating process, and all influential to the apparent and sticking power of chemical plating.
The electroless plating pre-treating technology is in continuous development.First-generation pre-treating technology is sensitization activation two-step approach, namely uses first the tin protochloride sensitization, goes out palladium with the palladium chloride solution activating and reducing after the hydrolysis.Although the preparation of activation solution is easy, treatment effect is good, and pretreatment process is complicated, and treatment solution is shorter work-ing life.S-generation pre-treating technology is sensitization activation single stage method or colloidal palladium activation method, and tin protochloride and Palladous chloride are mixed with colloid, through dispergation the stannous ion around the palladium grain is sloughed and is exposed active palladium.Succeeding in developing of single stage method is a significant improvement on the electroless plating front activating treatment process, is widely used in present non-metal electroplating, printed board hole metallization production.But it is huge that the colloidal palladium activating process consumes when scale operation, causes the high expensive of activation; In addition, the existence of tin ion can affect homogeneity and the sticking power of chemical plating.In recent years, Germany and Japan release third generation pre-treating technology, i.e. ionic palladium activation method on the basis of colloidal palladium.The ionic palladium catalytic solution is a kind of aqueous solution of title complex of palladium in essence, the coordination ion of palladium is after matrix surface absorption reaches balance, be reduced into the metal particle with catalytic activity, it is applicable to the metallization in electroless copper, chemical nickel plating and the PCB hole of plastic part.Although ionic palladium activation method excellent performance, technique is immature, and the more high deficiency of bullion content has limited this pre-treating technology in the application of industrial circle.
Traditional electroless plating pre-treating technology will adopt tin protochloride, the chemical reaction below tin protochloride can occur in pretreatment process:
SnCl
2+H
2O→Sn(OH)Cl↓+HCl
SnCl
2+2H
2O→Sn(OH)
2↓+2HCl
Sn(OH)Cl+Sn(OH)
2→Sn2
(OH)
3Cl↓
The Sn that generates in the sensitizing
2(OH)
3Cl, Sn (OH)
2And Sn (OH) Cl all is slightly soluble in water, can form spawn in water, is adsorbed on substrate material surface and forms the uniform film of one deck.Exist a large amount of grooves through the product surface after the roughening treatment, because capillary effect, gel-film can not contact with matrix surface fully, affects the sticking power of coating because contact area is less.In addition, need to be used for as early as possible electroless plating through the product after the electroless plating pre-treatment, come off and Sn from matrix to prevent that the gel-film dehydration from breaking
2+Oxidized and lose reductibility.
Summary of the invention
The object of the present invention is to provide that a kind of chemical plating quality is high, with low cost, environmental friendliness and obtain the pre-treating process that is applicable to the phenolic resin-base composite electroless plating of the good metal plating of sticking power.
For achieving the above object, the technical solution used in the present invention is:
1) alligatoring:
Phenolic resin-base composite product after the oil removing is processed the rear flushing with clean water phenolic resin-base composite surface of using in the coarsening solution of potassium permanganate-sulfuric acid system, remove residual coarsening solution;
2) neutralization:
It is the oxalic acid solution of 10 ~ 30g/L that phenolic resin-base composite product after the alligatoring is placed concentration, residues in the oxidizing substance on phenolic resin-base composite product surface with neutralization, use again mass concentration greater than 10% hydrochloric acid cleaning after, use flushing with clean water;
3) reduction:
Employing concentration is that the reductant solution of 0.1 ~ 2.0mol/L is processed phenolic resin-base composite spare, remove residual reduced liquid with washed with de-ionized water again, described reductive agent is for easily being adsorbed in matrix surface and can keeping in stable micromolecular compound glucose, formaldehyde, acetaldehyde and the sodium hypophosphite one or more in normal-temperature water solution;
4) activation:
After will placing silver salt activation solution activation treatment through the phenolic resin-base composite product that reduction is processed, wash with deionized water.
The detailed process of described oil removing is as follows:
The phenolic resin-base composite product is placed alkaline degreasing liquid, at 30 ~ 70 ℃, ultrasonic power is to process 5 ~ 30min under the condition of 50 ~ 200W to remove the greasy dirt on phenolic resin-base composite surface, use again the flushing with clean water material surface, remove residual degreasing fluid, described alkaline degreasing liquid comprises: the OP emulsifying agent of the NaOH of 10 ~ 30g/L and 1 ~ 3g/L.
The detailed process of described step 1) alligatoring is as follows:
To place through the phenolic resin-base composite product after the oil removing coarsening solution of potassium permanganate-sulfuric acid system, at 40 ~ 80 ℃, alligatoring 5 ~ 60min, described potassium permanganate-sulfuric acid system comprises the KMnO of 20 ~ 50g/L
4H with 0.3 ~ 2.0mol/L
2SO
4, with flushing with clean water phenolic resin-base composite product surface, remove residual coarsening solution after the alligatoring.
Described step 2) detailed process of neutralization is as follows:
Phenolic resin-base composite product after the alligatoring oxalic acid solution that to place 10 ~ 40 ℃ of concentration be 10 ~ 30g/L is processed 1 ~ 10min, residue in the oxidizing substance on phenolic resin-base composite product surface with neutralization, extremely remove the settling on phenolic resin-base composite product surface with mass concentration fully greater than 10% hydrochloric acid cleaning again, use flushing with clean water.
The temperature that described step 3) reduction is processed is 10 ~ 40 ℃, and the treatment time is 3 ~ 120min.
Described step 4) silver salt activation solution comprises the AgNO of 2～10g/L
3NH with 0.02 ~ 0.1mol/L
3H
2O, activating treatment temperature are 10 ~ 40 ℃, and the treatment time is 3 ~ 15min.
Can be directly used in electroless copper, chemical nickel plating or chemical silvering through the product after the pre-treatment of the present invention.
The present invention is in conjunction with the advantage of the first-generation and third generation electroless plating pre-treating technology, adopts the ionic activation solution by reduction and activates for two steps product is carried out pre-treatment, can obtain the good metal plating of sticking power.Simultaneously, the stability of employing is reductive agent and lower-cost silver salt activation solution replacement tin protochloride and Palladous chloride preferably, can reduce the cost of pre-treatment, and environmental pollution is little.But the product long period after treatment keeps surface properties, and the sticking power of chemical plating coating and matrix is good.
The present invention replaces tin protochloride to be used as the effect that sensitizing agent can improve electroless plating with glucose, formaldehyde, acetaldehyde and sodium hypophosphite, strengthens the sticking power of coating.At first, these reductive agents can not form gel-film at matrix surface, and reductive agent is combined with matrix closely; Secondly, the good stability of above-mentioned several reductive agents is difficult for losing activity.The product of the electroless plating pre-treatment that therefore obtains through this method can the long period keep surface properties, can not affect the electroless plating process.
Phenolic resin-base composite product of the present invention refers to take resol as matrix, to wherein adding the composite product of filler by mechanically mixing and curing molding.Wherein filler comprises fibrous and/or pulverous weighting material, is mainly used in improving the mechanical property of polymer matrix composites and the cost of dimensional stability and reduction matrix material.
The present invention is by adopting non-tin protochloride class reductive agent to replace tin protochloride to process product, make good combination between reductive agent and the body material, absorption has the product of reductive agent to restore catalyzer in the process of activation, and catalyzer is good in the distribution of product surface uniform and sticking power.The adhesion condition of catalyzer and matrix has material impact to the performance of coating, and even and well attached catalyst particle can guarantee that chemical reaction steadily carries out, and strengthens the sticking power of coating, improves simultaneously the apparent property of coating.
Phenolic resin-base composite of the present invention is by phenolic resin as matrix resin and media assemblage, in the coarsening solution of strong oxidizing property, product surface is oxidized to go out more hydrophilic radical (such as carboxyl and hydroxyl), has increased the wetting ability on product surface, has improved simultaneously the roughness on product surface.Reductive agent and catalyzer easily are adsorbed in the product surface in the good wetting ability assurance pretreatment process, and coarse surface can provide more anchor point, strengthens anchor and turns usefulness into, improves the sticking power of coating and matrix.
In reduction process of the present invention, glucose, formaldehyde, acetaldehyde and sodium hypophosphite all can be adsorbed on matrix surface, in reactivation process, be adsorbed in the reductive agent of matrix surface and the silver ions generation chemical reaction in the activation solution, fully contact between the metallics that restores (being catalyst particle) and the matrix, strengthen the sticking power of catalyzer and matrix.
Compared with prior art, the advantage of method involved in the present invention is:
1) adopts the coarsening solution roughening treatment phenolic resin-base composite product of potassium permanganate-sulfuric acid system, effectively improved surface hydrophilicity and the roughness of phenolic resin-base composite.Contain chromium coarsening solution, more environmental protection of coarsing processing method of the present invention than traditional.
2) adopt reductive agent involved in the present invention to process the phenolic resin-base composite product, so that good combination between reductive agent, catalyzer and metal plating energy and the body material, be conducive to improve the sticking power of metal level.
3) adopt reductive agent of the present invention to process the phenolic resin-base composite product, reduced the consumption of pink salt, reduced the cost of electroless plating pre-treatment.
4) product that adopts method of the present invention to process can the long period keep surface properties and not affect the electroless plating process.
5) can be directly used in electroless copper, chemical nickel plating or chemical silvering through the product after the electroless plating pre-treatment.
6) method of the present invention is simple to operate, and is with low cost, easily in industrial amplification production.
Specific embodiments
Below with reference to effect preferably embodiment method of the present invention is described further:
Embodiment 1:
The resol that strengthens take glass fibre and silicon powder is shaped to product and realizes the electroless plating pre-treatment by following steps as starting material:
1) oil removing:
The phenolic resin-base composite product placed comprise: the alkaline degreasing liquid of the OP emulsifying agent of the NaOH of 20g/L and 3g/L, at 50 ℃, ultrasonic power is to process 20min under the condition of 100W to remove the greasy dirt on phenolic resin-base composite surface, use again the flushing with clean water material surface, remove residual degreasing fluid, described alkaline degreasing liquid;
2) alligatoring:
To place through the phenolic resin-base composite product after the oil removing coarsening solution of potassium permanganate-sulfuric acid system, at 50 ℃, alligatoring 20min, described potassium permanganate-sulfuric acid system comprises the KMnO of 30g/L
4H with 1mol/L
2SO
4, with flushing with clean water phenolic resin-base composite product surface, remove residual coarsening solution after the alligatoring;
3) neutralization:
Phenolic resin-base composite product after the alligatoring oxalic acid solution that to place 25 ℃ of concentration be 20g/L is processed 3min, residue in the oxidizing substance on phenolic resin-base composite product surface with neutralization, again with mass concentration be 30% hydrochloric acid cleaning to the settling of removing phenolic resin-base composite product surface fully, use flushing with clean water.
4) reduction:
At the Reduction of Glucose agent solution that 30 ℃ of employing concentration are 0.25mol/L the phenolic resin-base composite product is processed 30min, remove residual reduced liquid with washed with de-ionized water again; Described reductive agent is for easily being adsorbed in matrix surface and can keeping stable micromolecular compound in normal-temperature water solution;
5) activation:
At 30 ℃, will place silver salt activation solution activation treatment 5min through the phenolic resin-base composite product that reduction is processed after, wash with deionized water, described silver salt activation solution comprises the AgNO of 5g/L
3NH with 0.05mol/L
3H
2O.
Product after treatment is used for electroless copper, has obtained the good metal copper layer of surface property behind the plating 60min, adopts the sticking power of frame method test coating, and coating is without obscission (with reference to ASTM B 571-97).
Embodiment 2:
Resol take carbon fiber (or cloth) as enhancing is shaped to product and realizes surface metalation by following steps as starting material:
1) oil removing:
The phenolic resin-base composite product placed comprise: the alkaline degreasing liquid of the OP emulsifying agent of the NaOH of 10g/L and 3g/L, at 30 ℃, ultrasonic power is to process 30min under the condition of 150W to remove the greasy dirt on phenolic resin-base composite surface, use again the flushing with clean water material surface, remove residual degreasing fluid, described alkaline degreasing liquid;
2) alligatoring:
To place through the phenolic resin-base composite product after the oil removing coarsening solution of potassium permanganate-sulfuric acid system, at 70 ℃, alligatoring 50min, described potassium permanganate-sulfuric acid system comprises the KMnO of 20g/L
4H with 2.0mol/L
2SO
4, with flushing with clean water phenolic resin-base composite product surface, remove residual coarsening solution after the alligatoring;
3) neutralization:
Phenolic resin-base composite product after the alligatoring oxalic acid solution that to place 10 ℃ of concentration be 10g/L is processed 10min, residue in the oxidizing substance on phenolic resin-base composite product surface with neutralization, again with mass concentration be 30% hydrochloric acid cleaning to the settling of removing phenolic resin-base composite product surface fully, use flushing with clean water.
4) reduction:
At the formaldehyde reducer solution that 20 ℃ of employing concentration are 0.5mol/L the phenolic resin-base composite product is processed 10min, remove residual reduced liquid with washed with de-ionized water again; Described reductive agent is for easily being adsorbed in matrix surface and can keeping stable micromolecular compound in normal-temperature water solution;
5) activation:
At 30 ℃, will place silver salt activation solution activation treatment 15min through the phenolic resin-base composite product that reduction is processed after, wash with deionized water, described silver salt activation solution comprises the AgNO of 2g/L
3NH with 0.02mol/L
3H
2O.
Be used for chemical nickel plating through the product after the reduction, obtained the good metal nickel dam of surface property behind the plating 50min, adopt the sticking power of frame method test coating, coating is without obscission.
Embodiment 3:
The resol that strengthens take glass fibre (or cloth) is shaped to product and realizes surface metalation by following steps as starting material:
1) oil removing:
The phenolic resin-base composite product placed comprise: the alkaline degreasing liquid of the OP emulsifying agent of the NaOH of 30g/L and 2g/L, at 70 ℃, ultrasonic power is to process 30min under the condition of 50W to remove the greasy dirt on phenolic resin-base composite surface, use again the flushing with clean water material surface, remove residual degreasing fluid, described alkaline degreasing liquid;
2) alligatoring:
To place through the phenolic resin-base composite product after the oil removing coarsening solution of potassium permanganate-sulfuric acid system, at 60 ℃, alligatoring 60min, described potassium permanganate-sulfuric acid system comprises the KMnO of 20g/L
4H with 0.3mol/L
2SO
4, with flushing with clean water phenolic resin-base composite product surface, remove residual coarsening solution after the alligatoring;
3) neutralization:
Phenolic resin-base composite product after the alligatoring oxalic acid solution that to place 40 ℃ of concentration be 30g/L is processed 1min, residue in the oxidizing substance on phenolic resin-base composite product surface with neutralization, again with mass concentration be 25% hydrochloric acid cleaning to the settling of removing phenolic resin-base composite product surface fully, use flushing with clean water.
4) reduction:
At the sodium hypophosphite reductant solution that 40 ℃ of employing concentration are 0.1mol/L the phenolic resin-base composite product is processed 120min, remove residual reduced liquid with washed with de-ionized water again; Described reductive agent is for easily being adsorbed in matrix surface and can keeping stable micromolecular compound in normal-temperature water solution;
5) activation:
At 20 ℃, will place silver salt activation solution activation treatment 3min through the phenolic resin-base composite product that reduction is processed after, wash with deionized water, described silver salt activation solution comprises the AgNO of 10g/L
3NH with 0.1mol/L
3H
2O.
Be used for chemical silvering through the product after the reduction, obtained complete metallic silver layer behind the plating 30min, adopt the sticking power of frame method test coating, coating is without obscission.
Embodiment 4:
The resol that strengthens take glass fibre and silicon powder is shaped to product and realizes the electroless plating pre-treatment by following steps as starting material:
1) oil removing:
The phenolic resin-base composite product placed comprise: the alkaline degreasing liquid of the OP emulsifying agent of the NaOH of 20g/L and 2g/L, at 60 ℃, ultrasonic power is to process 20min under the condition of 150W to remove the greasy dirt on phenolic resin-base composite surface, use again the flushing with clean water material surface, remove residual degreasing fluid, described alkaline degreasing liquid;
2) alligatoring:
To place through the phenolic resin-base composite product after the oil removing coarsening solution of potassium permanganate-sulfuric acid system, at 80 ℃, alligatoring 5min, described potassium permanganate-sulfuric acid system comprises the KMnO of 20g/L
4H with 1mol/L
2SO
4, with flushing with clean water phenolic resin-base composite product surface, remove residual coarsening solution after the alligatoring;
3) neutralization:
Phenolic resin-base composite product after the alligatoring oxalic acid solution that to place 30 ℃ of concentration be 10g/L is processed 10min, residue in the oxidizing substance on phenolic resin-base composite product surface with neutralization, again with mass concentration be 30% hydrochloric acid cleaning to the settling of removing phenolic resin-base composite product surface fully, use flushing with clean water.
4) reduction:
At the Reduction of Glucose agent solution that 10 ℃ of employing concentration are 2mol/L the phenolic resin-base composite product is processed 60min, remove residual reduced liquid with washed with de-ionized water again; Described reductive agent is for easily being adsorbed in matrix surface and can keeping stable micromolecular compound in normal-temperature water solution;
5) activation:
At 40 ℃, will place silver salt activation solution activation treatment 5min through the phenolic resin-base composite product that reduction is processed after, wash with deionized water, described silver salt activation solution comprises the AgNO of 5g/L
3NH with 0.05mol/L
3H
2O.
Be used for chemical silvering through the product after the reduction, obtained complete metallic silver layer behind the plating 30min, adopt the sticking power of frame method test coating, coating is without obscission.
Embodiment 5:
The resol that glasscloth strengthens is starting material, is shaped to product and realizes surface metalation by following steps:
1) oil removing:
The phenolic resin-base composite product placed comprise: the alkaline degreasing liquid of the OP emulsifying agent of the NaOH of 10g/L and 1g/L, at 70 ℃, ultrasonic power is to process 5min under the condition of 200W to remove the greasy dirt on phenolic resin-base composite surface, use again the flushing with clean water material surface, remove residual degreasing fluid, described alkaline degreasing liquid;
2) alligatoring:
To place through the phenolic resin-base composite product after the oil removing coarsening solution of potassium permanganate-sulfuric acid system, at 40 ℃, alligatoring 30min, described potassium permanganate-sulfuric acid system comprises the KMnO of 50g/L
4H with 2.0mol/L
2SO
4, with flushing with clean water phenolic resin-base composite product surface, remove residual coarsening solution after the alligatoring;
3) neutralization:
Phenolic resin-base composite product after the alligatoring oxalic acid solution that to place 15 ℃ of concentration be 10g/L is processed 10min, residue in the oxidizing substance on phenolic resin-base composite product surface with neutralization, again with mass concentration be 30% hydrochloric acid cleaning to the settling of removing phenolic resin-base composite product surface fully, use flushing with clean water.
4) reduction:
10 ℃ adopt concentration be the reductant solution made of glucose and the mixture of acetaldehyde of 2mol/L to phenolic resin-base composite product processing 3min, remove residual reduced liquid with washed with de-ionized water again; Described reductive agent is for easily being adsorbed in matrix surface and can keeping stable micromolecular compound in normal-temperature water solution;
5) activation:
At 10 ℃, will place silver salt activation solution activation treatment 10min through the phenolic resin-base composite product that reduction is processed after, wash with deionized water, described silver salt activation solution comprises the AgNO of 5g/L
3NH with 0.05mol/L
3H
2O.
Be used for chemical nickel plating through the product after the reduction, obtained the good metal nickel dam of surface property behind the plating 40min, adopt the frame method to record the sticking power of coating, coating is without obscission.
Claims (6)
1. pre-treating process that is applicable to the phenolic resin-base composite electroless plating is characterized in that may further comprise the steps:
1) alligatoring:
Phenolic resin-base composite product after the oil removing is processed the rear flushing with clean water phenolic resin-base composite surface of using in the coarsening solution of potassium permanganate-sulfuric acid system, remove residual coarsening solution;
2) neutralization:
It is the oxalic acid solution of 10 ~ 30g/L that phenolic resin-base composite product after the alligatoring is placed concentration, residues in the oxidizing substance on phenolic resin-base composite product surface with neutralization, use again mass concentration greater than 10% hydrochloric acid cleaning after, use flushing with clean water;
3) reduction:
Employing concentration is that the reductant solution of 0.1 ~ 2.0mol/L is processed phenolic resin-base composite spare, remove residual reduced liquid with washed with de-ionized water again, described reductive agent is for easily being adsorbed in matrix surface and can keeping in stable micromolecular compound glucose, formaldehyde, acetaldehyde and the sodium hypophosphite one or more in normal-temperature water solution;
4) activation:
After will placing silver salt activation solution activation treatment through the phenolic resin-base composite product that reduction is processed, wash with deionized water.
2. the pre-treating process that is applicable to the phenolic resin-base composite electroless plating according to claim 1, it is characterized in that: the detailed process of described oil removing is as follows:
The phenolic resin-base composite product is placed alkaline degreasing liquid, at 30 ~ 70 ℃, ultrasonic power is to process 5 ~ 30min under the condition of 50 ~ 200W to remove the greasy dirt on phenolic resin-base composite surface, use again the flushing with clean water material surface, remove residual degreasing fluid, described alkaline degreasing liquid comprises: the OP emulsifying agent of the NaOH of 10 ~ 30g/L and 1 ~ 3g/L.
3. the pre-treating process that is applicable to the phenolic resin-base composite electroless plating according to claim 1, it is characterized in that: the detailed process of described step 1) alligatoring is as follows:
To place through the phenolic resin-base composite product after the oil removing coarsening solution of potassium permanganate-sulfuric acid system, at 40 ~ 80 ℃, alligatoring 5 ~ 60min, described potassium permanganate-sulfuric acid system comprises the KMnO of 20 ~ 50g/L
4H with 0.3 ~ 2.0mol/L
2SO
4, with flushing with clean water phenolic resin-base composite product surface, remove residual coarsening solution after the alligatoring.
4. the pre-treating process that is applicable to the phenolic resin-base composite electroless plating according to claim 1 is characterized in that: described step 2) detailed process of neutralization is as follows:
Phenolic resin-base composite product after the alligatoring oxalic acid solution that to place 10 ~ 40 ℃ of concentration be 10 ~ 30g/L is processed 1 ~ 10min, residue in the oxidizing substance on phenolic resin-base composite product surface with neutralization, extremely remove the settling on phenolic resin-base composite product surface with mass concentration fully greater than 10% hydrochloric acid cleaning again, use flushing with clean water.
5. the pre-treating process that is applicable to the phenolic resin-base composite electroless plating according to claim 1 is characterized in that: the temperature that described step 3) reduction is processed is 10 ~ 40 ℃, and the treatment time is 3 ~ 120min.
6. the pre-treating process that is applicable to the phenolic resin-base composite electroless plating according to claim 1, it is characterized in that: described step 4) silver salt activation solution comprises the AgNO of 2～10g/L
3NH with 0.02 ~ 0.1mol/L
3H
2O, activating treatment temperature are 10 ~ 40 ℃, and the treatment time is 3 ~ 15min.
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| CN107841731A (en) * | 2017-10-25 | 2018-03-27 | 昆明理工大学 | A kind of rubber rapid chemical copper coating |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103280567A (en) * | 2013-03-06 | 2013-09-04 | 广州市东力电池实业有限公司 | Li4Ti5O12 having surface chemically plated by metal, and preparation method thereof |
| CN103280567B (en) * | 2013-03-06 | 2016-11-23 | 广东工业大学 | A kind of surface chemical metal plating modifies Li4ti5o12and preparation method thereof |
| CN105369227A (en) * | 2015-12-08 | 2016-03-02 | 丽水学院 | Stabilizer for acid potassium permanganate solution |
| CN107841731A (en) * | 2017-10-25 | 2018-03-27 | 昆明理工大学 | A kind of rubber rapid chemical copper coating |
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