CN102925876B - 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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- CN102925876B CN102925876B CN201210445563.2A CN201210445563A CN102925876B CN 102925876 B CN102925876 B CN 102925876B CN 201210445563 A CN201210445563 A CN 201210445563A CN 102925876 B CN102925876 B CN 102925876B
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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 phenolic resin-base composite electroless plating.
Background technology
Macromolecular material can have the performance of macromolecular material and metal concurrently after surface metalation, 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, synthetic convenient, has good mechanical property, resistance toheat and high temperature resistant ablation property.After surface metalation, can improve the performance of resol and matrix material thereof, expand its range of application.
The method of surface metalation that can be used for non-metallic material is numerous, 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 with low cost, equipment is simple, coating all even coating be subject to substrate performance to affect the little industrial circle that is widely used in.
Electroless plating is that one does not need energising, relies on oxidation-reduction reaction to form the method for densified metal layer at matrix surface.In order to ensure that in electroless plating process, chemical reaction only occurs on product surface, need to carry out pre-treatment to matrix surface, make matrix surface there is catalytic activity.Electroless plating pre-treatment has not only ensured carrying out smoothly of electroless plating process, and the apparent and sticking power of chemical plating is all had to impact.
Electroless plating pre-treating technology is in continuous development.First-generation pre-treating technology is sensitization activation two-step approach, first uses tin protochloride sensitization, after hydrolysis, goes out palladium with palladium chloride solution activating and reducing.Although the preparation of activation solution is easy, treatment effect is good, pretreatment process complexity, 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 to colloid, through dispergation, palladium grain stannous ion is around sloughed and is exposed active palladium.Succeeding in developing of single stage method is a significant improvement on electroless plating front activating treatment process, is widely used on producing at current non-metal electroplating, printed board hole metallization.But it is huge that colloidal palladium activating process consumes in the time of scale operation, cause 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.Ionic palladium catalytic solution is a kind of aqueous solution of title complex of palladium in essence, the coordination ion of palladium reaches after balance in matrix surface absorption, 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 the application of this pre-treating technology at 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 generating in sensitizing
2(OH)
3cl, Sn (OH)
2with Sn (OH) Cl is all slightly soluble in water, in water, can form spawn, be adsorbed on substrate material surface and form the uniform film of one deck.Product surface after roughening treatment exists a large amount of grooves, and due to capillary effect, gel-film can not contact with matrix surface completely, because contact area is compared with the little sticking power that affects coating.In addition, the product after electroless plating pre-treatment need to, as early as possible for electroless plating, come off and Sn from matrix to prevent that 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 phenolic resin-base composite electroless plating of the metal plating that sticking power is good.
For achieving the above object, the technical solution used in the present invention is:
1) alligatoring:
After phenolic resin-base composite product after oil removing is processed in the coarsening solution of potassium permanganate-sulfuric acid system, rinse phenolic resin-base composite surface with clear water, remove residual coarsening solution;
2) neutralization:
Phenolic resin-base composite product after alligatoring is placed in to the oxalic acid solution that concentration is 10 ~ 30g/L, to neutralize the oxidizing substance that residues in phenolic resin-base composite product surface, then is greater than by mass concentration after 10% hydrochloric acid cleaning, rinse with clear water;
3) reduction:
Adopt the reductant solution that concentration is 0.1 ~ 2.0mol/L to process phenolic resin-base composite part, remove residual reduced liquid by washed with de-ionized water again, described reductive agent is to be easily adsorbed in matrix surface and in normal-temperature water solution, can to keep one or more in stable micromolecular compound glucose, formaldehyde, acetaldehyde and sodium hypophosphite;
4) activation:
The phenolic resin-base composite product that to process through reduction is placed in after silver salt activation solution activation treatment, washes with deionized water.
The detailed process of described oil removing is as follows:
Phenolic resin-base composite product is placed in to alkaline degreasing liquid, at 30 ~ 70 DEG C, ultrasonic power is under the condition of 50 ~ 200W, to process 5 ~ 30min to remove the greasy dirt on phenolic resin-base composite surface, use again clear water flushing 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:
Phenolic resin-base composite product after oil removing is placed in to the coarsening solution of potassium permanganate-sulfuric acid system, at 40 ~ 80 DEG C, 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, after alligatoring, rinse phenolic resin-base composite product surface with clear water, remove residual coarsening solution.
Described step 2) neutralization detailed process as follows:
Phenolic resin-base composite product after alligatoring is placed in to the oxalic acid solution that 10 ~ 40 DEG C of concentration are 10 ~ 30g/L and processes 1 ~ 10min, residue in the oxidizing substance on phenolic resin-base composite product surface with neutralization, be greater than 10% hydrochloric acid cleaning to the settling of removing phenolic resin-base composite product surface completely by mass concentration again, rinse with clear water.
The temperature that described step 3) reduction is processed is 10 ~ 40 DEG C, and the treatment time is 3 ~ 120min.
The AgNO that described step 4) silver salt activation solution comprises 2～10g/L
3nH with 0.02 ~ 0.1mol/L
3h
2o, activating treatment temperature is 10 ~ 40 DEG C, the treatment time is 3 ~ 15min.
Product after pre-treatment of the present invention can be directly used in electroless copper, chemical nickel plating or chemical silvering.
The present invention, in conjunction with the advantage of the first-generation and third generation electroless plating pre-treating technology, adopts ionic activation solution, by reducing and activating two steps, product is carried out to pre-treatment, can obtain the metal plating that sticking power is good.Meanwhile, the good reductive agent of the stability of employing and lower-cost silver salt activation solution replace tin protochloride and Palladous chloride, can reduce the cost of pre-treatment, and environmental pollution are little.Product after treatment can the long period keep surface properties, and the sticking power of chemical plating coating and matrix is good.
The present invention can improve the effect of electroless plating as sensitizing agent with glucose, formaldehyde, acetaldehyde and sodium hypophosphite replacement tin protochloride, strengthen the sticking power of coating.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 therefore obtaining through this method can the long period keep surface properties, can not affect electroless plating process.
Phenolic resin-base composite product of the present invention refers to taking resol as matrix, adds wherein the composite product through mechanically mixing and curing molding after filler.Wherein filler comprises fibrous and/or pulverous weighting material, the cost that is mainly used in improving mechanical property and the dimensional stability of polymer matrix composites and reduces 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 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 ensure that chemical reaction steadily carries out, and strengthens the sticking power of coating, improves the apparent property of coating simultaneously.
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 oxidized go out more hydrophilic radical (as carboxyl and hydroxyl), increase the wetting ability on product surface, improved the roughness on product surface simultaneously.In good wetting ability guarantee pretreatment process, reductive agent and catalyzer are easily adsorbed in product surface, and coarse surface can provide more anchor point, strengthens anchor and turns use 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 silver ions generation chemical reaction in reductive agent and the activation solution of matrix surface, between the metallics (being catalyst particle) restoring and matrix, fully contact, strengthen the sticking power of catalyzer and matrix.
Compared with prior art, the advantage of method involved in the present invention is:
1) adopt 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.Than traditional containing chromium coarsening solution, more environmental protection of coarsing processing method of the present invention.
2) adopt reductive agent involved in the present invention to process phenolic resin-base composite product, make good combination between reductive agent, catalyzer and metal plating energy and body material, be conducive to improve the sticking power of metal level.
3) adopt reductive agent of the present invention to process phenolic resin-base composite product, reduced the consumption of pink salt, reduced the cost of electroless plating pre-treatment.
4) adopt the product of method processing of the present invention, can the long period keep surface properties and not affect electroless plating process.
5) product after electroless plating pre-treatment can be directly used in electroless copper, chemical nickel plating or chemical silvering.
6) method of the present invention is simple to operate, with low cost, easily produces in industrial amplification.
Specific embodiments
Below with reference to effect, good embodiment is described further method of the present invention:
Embodiment 1:
The resol strengthening taking glass fibre and silicon powder is as starting material, realizes electroless plating pre-treatment after being shaped to product through following steps:
1) oil removing:
Phenolic resin-base composite product is placed in and is comprised: the alkaline degreasing liquid of the OP emulsifying agent of the NaOH of 20g/L and 3g/L, at 50 DEG C, ultrasonic power is under the condition of 100W, to process 20min to remove the greasy dirt on phenolic resin-base composite surface, use again clear water flushing material surface, remove residual degreasing fluid, described alkaline degreasing liquid;
2) alligatoring:
Phenolic resin-base composite product after oil removing is placed in to the coarsening solution of potassium permanganate-sulfuric acid system, at 50 DEG C, alligatoring 20min, described potassium permanganate-sulfuric acid system comprises the KMnO of 30g/L
4h with 1mol/L
2sO
4, after alligatoring, rinse phenolic resin-base composite product surface with clear water, remove residual coarsening solution;
3) neutralization:
Phenolic resin-base composite product after alligatoring is placed in to the oxalic acid solution that 25 DEG C of concentration are 20g/L and processes 3min, residue in the oxidizing substance on phenolic resin-base composite product surface with neutralization, the hydrochloric acid cleaning that is 30% by mass concentration is again to the settling of removing phenolic resin-base composite product surface completely, rinses with clear water.
4) reduction:
At 30 DEG C, to adopt concentration be 0.25mol/L that Reduction of Glucose agent solution is processed 30min to phenolic resin-base composite product, then remove residual reduced liquid by washed with de-ionized water; Described reductive agent is to be easily adsorbed in matrix surface and can to keep stable micromolecular compound in normal-temperature water solution;
5) activation:
At 30 DEG C, the phenolic resin-base composite product that will process through reduction is placed in after silver salt activation solution activation treatment 5min, washes the AgNO that described silver salt activation solution comprises 5g/L with deionized water
3nH with 0.05mol/L
3h
2o.
Product after treatment, for electroless copper, has obtained the good metal copper layer of surface property after plating 60min, adopt the sticking power of frame method test coating, and coating is without obscission (with reference to ASTM B 571-97).
Embodiment 2:
Taking carbon fiber (or cloth) as the resol that strengthens is as starting material, realize surface metalation through following steps after being shaped to product:
1) oil removing:
Phenolic resin-base composite product is placed in and is comprised: the alkaline degreasing liquid of the OP emulsifying agent of the NaOH of 10g/L and 3g/L, at 30 DEG C, ultrasonic power is under the condition of 150W, to process 30min to remove the greasy dirt on phenolic resin-base composite surface, use again clear water flushing material surface, remove residual degreasing fluid, described alkaline degreasing liquid;
2) alligatoring:
Phenolic resin-base composite product after oil removing is placed in to the coarsening solution of potassium permanganate-sulfuric acid system, at 70 DEG C, alligatoring 50min, described potassium permanganate-sulfuric acid system comprises the KMnO of 20g/L
4h with 2.0mol/L
2sO
4, after alligatoring, rinse phenolic resin-base composite product surface with clear water, remove residual coarsening solution;
3) neutralization:
Phenolic resin-base composite product after alligatoring is placed in to the oxalic acid solution that 10 DEG C of concentration are 10g/L and processes 10min, residue in the oxidizing substance on phenolic resin-base composite product surface with neutralization, the hydrochloric acid cleaning that is 30% by mass concentration is again to the settling of removing phenolic resin-base composite product surface completely, rinses with clear water.
4) reduction:
At 20 DEG C, to adopt concentration be 0.5mol/L that formaldehyde reducer solution is processed 10min to phenolic resin-base composite product, then remove residual reduced liquid by washed with de-ionized water; Described reductive agent is to be easily adsorbed in matrix surface and can to keep stable micromolecular compound in normal-temperature water solution;
5) activation:
At 30 DEG C, the phenolic resin-base composite product that will process through reduction is placed in after silver salt activation solution activation treatment 15min, washes the AgNO that described silver salt activation solution comprises 2g/L with deionized water
3nH with 0.02mol/L
3h
2o.
Product after reduction, for chemical nickel plating, has obtained the good metal nickel dam of surface property after plating 50min, adopt the sticking power of frame method test coating, and coating is without obscission.
Embodiment 3:
The resol strengthening taking glass fibre (or cloth), as starting material, is realized surface metalation through following steps after being shaped to product:
1) oil removing:
Phenolic resin-base composite product is placed in and is comprised: the alkaline degreasing liquid of the OP emulsifying agent of the NaOH of 30g/L and 2g/L, at 70 DEG C, ultrasonic power is under the condition of 50W, to process 30min to remove the greasy dirt on phenolic resin-base composite surface, use again clear water flushing material surface, remove residual degreasing fluid, described alkaline degreasing liquid;
2) alligatoring:
Phenolic resin-base composite product after oil removing is placed in to the coarsening solution of potassium permanganate-sulfuric acid system, at 60 DEG C, alligatoring 60min, described potassium permanganate-sulfuric acid system comprises the KMnO of 20g/L
4h with 0.3mol/L
2sO
4, after alligatoring, rinse phenolic resin-base composite product surface with clear water, remove residual coarsening solution;
3) neutralization:
Phenolic resin-base composite product after alligatoring is placed in to the oxalic acid solution that 40 DEG C of concentration are 30g/L and processes 1min, residue in the oxidizing substance on phenolic resin-base composite product surface with neutralization, the hydrochloric acid cleaning that is 25% by mass concentration is again to the settling of removing phenolic resin-base composite product surface completely, rinses with clear water.
4) reduction:
At 40 DEG C, to adopt concentration be 0.1mol/L that sodium hypophosphite reductant solution is processed 120min to phenolic resin-base composite product, then remove residual reduced liquid by washed with de-ionized water; Described reductive agent is to be easily adsorbed in matrix surface and can to keep stable micromolecular compound in normal-temperature water solution;
5) activation:
At 20 DEG C, the phenolic resin-base composite product that will process through reduction is placed in after silver salt activation solution activation treatment 3min, washes the AgNO that described silver salt activation solution comprises 10g/L with deionized water
3nH with 0.1mol/L
3h
2o.
Product after reduction, for chemical silvering, has obtained complete metallic silver layer after plating 30min, adopt the sticking power of frame method test coating, and coating is without obscission.
Embodiment 4:
The resol strengthening taking glass fibre and silicon powder is as starting material, realizes electroless plating pre-treatment after being shaped to product through following steps:
1) oil removing:
Phenolic resin-base composite product is placed in and is comprised: the alkaline degreasing liquid of the OP emulsifying agent of the NaOH of 20g/L and 2g/L, at 60 DEG C, ultrasonic power is under the condition of 150W, to process 20min to remove the greasy dirt on phenolic resin-base composite surface, use again clear water flushing material surface, remove residual degreasing fluid, described alkaline degreasing liquid;
2) alligatoring:
Phenolic resin-base composite product after oil removing is placed in to the coarsening solution of potassium permanganate-sulfuric acid system, at 80 DEG C, alligatoring 5min, described potassium permanganate-sulfuric acid system comprises the KMnO of 20g/L
4h with 1mol/L
2sO
4, after alligatoring, rinse phenolic resin-base composite product surface with clear water, remove residual coarsening solution;
3) neutralization:
Phenolic resin-base composite product after alligatoring is placed in to the oxalic acid solution that 30 DEG C of concentration are 10g/L and processes 10min, residue in the oxidizing substance on phenolic resin-base composite product surface with neutralization, the hydrochloric acid cleaning that is 30% by mass concentration is again to the settling of removing phenolic resin-base composite product surface completely, rinses with clear water.
4) reduction:
At 10 DEG C, to adopt concentration be 2mol/L that Reduction of Glucose agent solution is processed 60min to phenolic resin-base composite product, then remove residual reduced liquid by washed with de-ionized water; Described reductive agent is to be easily adsorbed in matrix surface and can to keep stable micromolecular compound in normal-temperature water solution;
5) activation:
At 40 DEG C, the phenolic resin-base composite product that will process through reduction is placed in after silver salt activation solution activation treatment 5min, washes the AgNO that described silver salt activation solution comprises 5g/L with deionized water
3nH with 0.05mol/L
3h
2o.
Product after reduction, for chemical silvering, has obtained complete metallic silver layer after plating 30min, adopt the sticking power of frame method test coating, and coating is without obscission.
Embodiment 5:
The resol that glasscloth strengthens is starting material, realizes surface metalation after being shaped to product through following steps:
1) oil removing:
Phenolic resin-base composite product is placed in and is comprised: the alkaline degreasing liquid of the OP emulsifying agent of the NaOH of 10g/L and 1g/L, at 70 DEG C, ultrasonic power is under the condition of 200W, to process 5min to remove the greasy dirt on phenolic resin-base composite surface, use again clear water flushing material surface, remove residual degreasing fluid, described alkaline degreasing liquid;
2) alligatoring:
Phenolic resin-base composite product after oil removing is placed in to the coarsening solution of potassium permanganate-sulfuric acid system, at 40 DEG C, alligatoring 30min, described potassium permanganate-sulfuric acid system comprises the KMnO of 50g/L
4h with 2.0mol/L
2sO
4, after alligatoring, rinse phenolic resin-base composite product surface with clear water, remove residual coarsening solution;
3) neutralization:
Phenolic resin-base composite product after alligatoring is placed in to the oxalic acid solution that 15 DEG C of concentration are 10g/L and processes 10min, residue in the oxidizing substance on phenolic resin-base composite product surface with neutralization, the hydrochloric acid cleaning that is 30% by mass concentration is again to the settling of removing phenolic resin-base composite product surface completely, rinses with clear water.
4) reduction:
The reductant solution of making at 10 DEG C of to adopt concentration be 2mol/L glucose and the mixture of acetaldehyde is to phenolic resin-base composite product processing 3min, then removes residual reduced liquid by washed with de-ionized water; Described reductive agent is to be easily adsorbed in matrix surface and can to keep stable micromolecular compound in normal-temperature water solution;
5) activation:
At 10 DEG C, the phenolic resin-base composite product that will process through reduction is placed in after silver salt activation solution activation treatment 10min, washes the AgNO that described silver salt activation solution comprises 5g/L with deionized water
3nH with 0.05mol/L
3h
2o.
Product after reduction, for chemical nickel plating, has obtained the good metal nickel dam of surface property after plating 40min, adopt frame method to record the sticking power of coating, and coating is without obscission.
Claims (4)
1. be applicable to a pre-treating process for phenolic resin-base composite electroless plating, it is characterized in that comprising the following steps:
1) oil removing:
Phenolic resin-base composite product is placed in to alkaline degreasing liquid, at 30～70 DEG C, ultrasonic power is under the condition of 50～200W, to process 5～30min to remove the greasy dirt on phenolic resin-base composite surface, use again clear water flushing 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;
2) alligatoring:
After phenolic resin-base composite product after oil removing is processed in the coarsening solution of potassium permanganate-sulfuric acid system, rinse phenolic resin-base composite surface with clear water, remove residual coarsening solution;
3) neutralization:
Phenolic resin-base composite product after alligatoring is placed in to the oxalic acid solution that 10～40 DEG C of concentration are 10～30g/L and processes 1～10min, residue in the oxidizing substance on phenolic resin-base composite product surface with neutralization, be greater than 10% hydrochloric acid cleaning to the settling of removing phenolic resin-base composite product surface completely by mass concentration again, rinse with clear water;
4) reduction:
Adopt the reductant solution that concentration is 0.1～2.0mol/L to process phenolic resin-base composite part, remove residual reduced liquid by washed with de-ionized water again, described reductive agent is to be easily adsorbed in matrix surface and in normal-temperature water solution, can to keep one or more in stable micromolecular compound glucose, formaldehyde, acetaldehyde and sodium hypophosphite;
5) activation:
The phenolic resin-base composite product that to process through reduction is placed in after silver salt activation solution activation treatment, washes with deionized water.
2. the pre-treating process that is applicable to phenolic resin-base composite electroless plating according to claim 1, is characterized in that: described step 2) detailed process of alligatoring is as follows:
Phenolic resin-base composite product after oil removing is placed in to the coarsening solution of potassium permanganate-sulfuric acid system, at 40～80 DEG C, 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, after alligatoring, rinse phenolic resin-base composite product surface with clear water, remove residual coarsening solution.
3. the pre-treating process that is applicable to 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 DEG C, and the treatment time is 3～120min.
4. the pre-treating process that is applicable to phenolic resin-base composite electroless plating according to claim 1, is characterized in that: the AgNO that described step 4) silver salt activation solution comprises 2～10g/L
3nH with 0.02～0.1mol/L
3h
2o, activating treatment temperature is 10～40 DEG C, the treatment time is 3～15min.
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| CN105369227B (en) * | 2015-12-08 | 2017-08-25 | 丽水学院 | Stabilizer for acid permanganate soln |
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| CN102418090A (en) * | 2011-11-07 | 2012-04-18 | 深圳市欣天科技有限公司 | Method for surface metallization of resin-based composite material compressed by mold |
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| CN102418090A (en) * | 2011-11-07 | 2012-04-18 | 深圳市欣天科技有限公司 | Method for surface metallization of resin-based composite material compressed by mold |
Non-Patent Citations (2)
| Title |
|---|
| 卢健体等.无钯活化化学镀银玻璃纤维的制备.《稀有金属材料与工程》.2010,第39卷(第增刊1期),27-30. * |
| 无钯活化化学镀银玻璃纤维的制备;卢健体等;《稀有金属材料与工程》;20100630;第39卷(第增刊1期);27-30 * |
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