CN103320011B - A kind of carbon fiber enhancement resin base composite material Electroless copper pre-treatment coating used and technique - Google Patents
A kind of carbon fiber enhancement resin base composite material Electroless copper pre-treatment coating used and technique Download PDFInfo
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Abstract
A kind of carbon fiber enhancement resin base composite material Electroless copper pre-treatment coating used and technique, relate to a kind of carbon fiber enhancement resin base composite material surface treatment coating used and utilize it to carry out surface-treated method.Described coating is by 15 ~ 40wt% solvent type resin, 35 ~ 50wt% copper powder, 0.1 ~ 1wt% defoamer, 0.5 ~ 1wt% wetting dispersing agent and 20 ~ 40wt% solvent composition.Its treatment process comprise the steps: carbon fiber enhancement resin base composite material electrochemical deoiling, coating dope layer, alligatoring, activation.The advantage of this technique electroless copper again after being to utilize this technique to process, the bonding force of gained coating and carbon fiber enhancement resin base composite material is good; Dope layer is little on coating performance impact; Can directly plating and do not need palladium to activate in chemical copper plating solution, be suitable as the pre-treatment step of carbon fiber enhancement resin base composite material electroplating of low-stress thick metal layers.
Description
Technical field
The present invention relates to a kind of carbon fiber enhancement resin base composite material surface treatment coating used and utilize it to carry out surface-treated method, particularly relate to a kind of carbon fiber enhancement resin base composite material Electroless copper pre-treatment coating used and utilize it to carry out the technique of electroless copper pre-treatment.
Background technology
Carbon fiber enhancement resin base composite material has the advantages such as specific tenacity is high, specific modulus is large, anti-fatigue performance is good, is used widely in the high-tech area such as aviation, precision manufactureing.If deposit layer of metal layer in its surface, then greatly expand its use range.Carbon fiber enhancement resin base composite material metalized, the normal technological process adopted is: oil removing → alligatoring → sensitization → activation → electroless copper or chemical nickel plating → electroplating other metals.Obtain the metal level of bonding force excellence, key is the effect of alligatoring.For carbon fiber enhancement resin base composite material, such as fibre reinforced polyimide material, carbon-fibre reinforced epoxy resin material etc., due to material surface resin everywhere from fibre fractionation than different, portion is easy crosses alligatoring, portion alligatoring is inadequate, causes the bonding force of metal plating and non-metallic material bad.
CN101082119A describes a kind of pulse arc ion plate coating technique that utilizes and prepares the technology of aluminium film at carbon-fibre composite.The adhesion of coating film that this method obtains is high, and thickness is even, but equipment is complicated, and implements in vacuum apparatus due to needs, and workpiece size is restricted.
Also someone adopts and first in non-metallic material, is coated with conductive coating, then the method for Direct Electroplating realizes metallization.On the one hand, because be coated with conductive coating thickness is too large, 40 ~ 200 μm of scopes of being everlasting, produce material impact to the machinery of material, mechanics and thermal property, are not suitable for being applied in the strict occasion of effects on surface layer thickness requirement; On the other hand, in electroplating process, because electrically conducting coating resistance be can not ignore, be easy to occur with hanger conductive contact point apart from far away, the situation that thickness of coating is thinner, is unfavorable for obtaining the uniform metal plating of thickness.
At some special dimensions, as space flight, precision instrument etc., need on carbon fiber enhancement resin base composite material, to electroplate thick metal layers (thickness G reatT.GreaT.GT200 μm), as nickel dam, and require coating and basal body binding force by force, the course of processing of high strength can be stood.At this moment, adopt conventional roughening process and be coated with conductive coating directly electroplating technology, being difficult to obtain desired result.
Present chemical plating of non-metal material copper process is generally alligatoring → sensitization → activation, and sensitization activation the inside contains palladium activation.This process, complex process, the activation solution life-span is short, and cost is high, not easy care.
Summary of the invention
The object of the invention is the novel method providing a kind of electroless copper on carbon fiber enhancement resin base composite material, after the method carries out surface treatment to carbon fiber enhancement resin base composite material, bonding force excellence, layers of copper that internal stress is low can be obtained, can be used as the bottom of further plating thick metal level in non-metallic material.
The novel process of carbon fiber enhancement resin base composite material Electroless copper of the present invention pre-treatment, comprises the steps:
1) carbon fiber enhancement resin base composite material surface processes 3 ~ 6min in the electrochemical deoiling liquid of 60 ~ 80 DEG C;
Described carbon fiber enhancement resin base composite material, refers to organic polymer to be the carbon fibre reinforcement of matrix, such as carbon-fibre reinforced epoxy resin composite material, fibre reinforced polyimide resin composite material.
Described electrochemical deoiling liquid consists of: sodium hydroxide 40 ~ 60g/L, sodium carbonate 25 ~ 35g/L, tertiary sodium phosphate 25 ~ 35g/L.
2) apply one deck dope layer on the surface at carbon fiber enhancement resin base composite material, coat-thickness is 10 ~ 30 μm, and then dry;
Described coating is by 15 ~ 40wt% solvent type resin, 35 ~ 50wt% copper powder, 0.1 ~ 1wt% defoamer, 0.5 ~ 1wt% wetting dispersing agent and 20 ~ 40wt% solvent composition.Its preparation method concrete steps are as follows:
A, solvent is put into container, add wetting dispersing agent afterwards, the defoamer of 2/3 component, then add copper powder and stir 12h, make it be uniformly dispersed.
B, under agitation, solvent type resin to be added in said vesse, then add the defoamer of residue 1/3 component, stir 12h, mix for subsequent use.
Solvent type resin should meet in performance strong in carbon fiber enhancement resin base composite material surface wettability, surface tension is low, the requirement of good leveling property, can select polyester modified organic silicon resin, acrylic resin, urethane resin etc.If carbon fiber enhancement resin base composite material thermotolerance is bad, then should select easily dry resin, as acrylic resin, urethane resin.
Copper powder size is between 800 ~ 20000 orders.
Defoamer can be one or more in organic silicon type defoamer, polyether type defoamer.
Wetting dispersing agent can select common coating wetting dispersing agent, as polyacrylate dispersion agent, organic silicon type dispersion agent.
Solvent can select in N-BUTYL ACETATE, butanols or amyl acetate-n one or more.
Described drying conditions is: temperature 110 ~ 160 DEG C, time 20 ~ 40min.
3) roughening treatment is carried out to coating:
Described coarsening solution consists of: 98% sulfuric acid 180 ~ 240mL/L, chromic trioxide 120 ~ 180g/L.
Described treatment condition are: temperature 20 ~ 40 DEG C, etching time 10 ~ 20min.
4) activation treatment is carried out to dope layer:
Described activation solution consists of the nitric acid of volume fraction 5 ~ 15%;
Activation temperature is room temperature, and soak time is 20 ~ 40s.
The advantage of this technique electroless copper again after being to utilize this technique to process, the bonding force of gained coating and carbon fiber enhancement resin base composite material is good; Dope layer is little on coating performance impact; Can directly plating and do not need palladium to activate in chemical copper plating solution, be suitable as the pre-treatment step of carbon fiber enhancement resin base composite material electroplating of low-stress thick metal layers.Be in particular in following some:
1, bonding force is good: after adopting this technique to carry out pre-treatment to carbon fiber enhancement resin base composite material, then electroless copper, and coating and basal body binding force are very high.100 ~ 180 DEG C (25min, this temperature is selected according to material temperature capability), 0 DEG C of (in frozen water 5min) thermal shock test 10 times, coating without foaming, crackle, obscission.
2, coating is activated coating (resistivity is high), and non-conductive coating layer, object is for electroless copper provides active site.
3, the copper-plated palladium activation step of conventional chemical can be replaced.
Embodiment
Below in conjunction with preferred embodiment, explanation is further explained to technical scheme of the present invention; but do not limit protection scope of the present invention; everyly technical solution of the present invention is modified or equivalent to replace; and do not depart from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Example 1
Be the carbon-fibre reinforced epoxy resin composite material of 60% to carbon fiber volume ratio, be cut into area 2 × 2cm
2, thick 0.5cm test piece, through electrochemical deoiling (sodium hydroxide 40g/L, sodium carbonate 25g/L, tertiary sodium phosphate 25g/L, temperature 65 DEG C, time 4min) after process, distilled water cleans, after drying up, be immersed in 2min in the coating that, 0.5wt% silane coupling agent 550 high by 931 by the polyurethane-modified silicone resin of 29wt%, 50wt%1000 order copper powder, the commercially available enlightening of 0.5wt% and 20wt% N-BUTYL ACETATE form, apply dope layer in its surface by the method for dip-coating.Sample is taken out, drains, be placed in the loft drier 20min of 130 DEG C.Use spiral micrometer, measure coat-thickness, repetitive measurement is averaged, and recording thickness is 22 microns.Use volometer, the face of test piece is chosen 2 points of the one side that exists together, apart 1cm, and survey its resistance value, resistance sizes is between 600 ~ 4000 Ω.Test piece is process 10min in the coarsening solution (98% sulfuric acid 180mL/L, chromic trioxide 120g/L) of 25 DEG C.After distilled water cleans up, the nitric acid of volume fraction 8% is used at room temperature to process 30s, distilled water cleaning is placed on chemical bronze plating liquid (the copper sulfate 0.04mol/L of 40 DEG C, Seignette salt 0.2mol/L, sodium hydroxide 0.25mol/L, 37% formaldehyde 10mL/L, MBT 0.2mg/L) in, use pneumatic blending, plating 1h.Coating sedimentation rate is 1-3 μm/h.After distilled water cleaning, dry up, at 800 times of metallography microscope sem observation chemical plating copper layers, find that coating is even, fine and close, flawless, peeling or obscission.Use volometer, the face of test piece is chosen 2 points of the one side that exists together, apart 1cm, and survey its resistance value, resistance is less than 1 Ω.Through 100 DEG C (25min), 0 DEG C of (frozen water 5min) thermal shock test 10 times, coating without foaming, crackle, obscission.
Example 2
Be the fibre reinforced polyimide resin composite material of 60% to carbon fiber volume ratio, be cut into area 2 × 2cm
2, thick 0.5cm test piece, through electrochemical deoiling (sodium hydroxide 40g/L, sodium carbonate 25g/L, tertiary sodium phosphate 25g/L, temperature 65 DEG C, time 4min) process after, distilled water cleans, after drying up, be immersed in 2min in the coating that, 0.5wt% silane coupling agent 550 high by 931 by the polyurethane-modified silicone resin of 30wt%, 40wt%1000 order copper powder, the commercially available enlightening of 0.5wt% and 29wt% N-BUTYL ACETATE form, apply dope layer in its surface by the method for brushing.Sample is taken out, drains, be placed in the loft drier 20min of 130 DEG C.Process 10min in the coarsening solutions of 25 DEG C (98% sulfuric acid 180mL/L, chromic trioxide 120g/L).After distilled water cleans up, the nitric acid of volume fraction 8% is used at room temperature to process 30s.Distilled water cleaning is placed on chemical bronze plating liquid (copper sulfate 0.04mol/L, Seignette salt 0.2mol/L, sodium hydroxide 0.25mol/L, 37% formaldehyde 10mL/L, the MBT 0.2mg/L copper sulfate 0.04mol/L of 40 DEG C, Seignette salt 0.2mol/L, sodium hydroxide 0.25mol/L, 37% formaldehyde 10mL/L, MBT 0.2mg/L) in, use pneumatic blending, plating 1h.After distilled water cleaning, use electrocasting toward the nickel metal layer of thick 200 ~ 300 μm of electroforming in test piece at nickel sulfamic acid electroformed nickel solution.The nickel layer thickness homogeneity obtained is better, and stress is little.Through 100 DEG C (25min), 0 DEG C of (frozen water 5min) thermal shock test 10 times, coating without foaming, crackle, obscission.Use polishing wheel polishing test piece side, expose matrix, coating section, find matrix and the dope layer of section part under 400 power microscopes, dope layer is combined with metal plating well, the equal flawless in junction.
Embodiment 3
Be the fibre reinforced compound polyurethane material of 60% to carbon fiber volume ratio, be cut into area 2 × 2cm
2, thick 0.5cm test piece, through electrochemical deoiling (sodium hydroxide 40g/L, sodium carbonate 25g/L, tertiary sodium phosphate 25g/L, temperature 65 DEG C, time 4min) after process, distilled water cleans, after drying up, be immersed in 2min in the coating that, 0.5wt% silane coupling agent 560 high by 3062 by 29wt% polyester modified organic silicon resin, 50wt%2000 order copper powder, the commercially available enlightening of 0.5wt% and 20wt% N-BUTYL ACETATE form, apply dope layer in its surface by the method for spraying.Sample is taken out, drains, be placed in the loft drier 20min of 160 DEG C.Use spiral micrometer, measure coat-thickness, repetitive measurement is averaged, and recording thickness is 16 microns.Use volometer, the face of test piece is chosen 2 points of the one side that exists together, apart 1cm, and survey its resistance value, resistance sizes is between 2000 ~ 8000 Ω.To test piece process 10min in the coarsening solution (98% sulfuric acid 180mL/L, chromic trioxide 120g/L) of 25 DEG C.After distilled water cleans up, the nitric acid of volume fraction 8% is used at room temperature to process 30s.Distilled water cleaning is placed in the chemical bronze plating liquid (copper sulfate 0.04mol/L, Seignette salt 0.2mol/L, sodium hydroxide 0.25mol/L, 37% formaldehyde 10mL/L, MBT 0.2mg/L) of 40 DEG C, uses pneumatic blending, plating 1h.Coating sedimentation rate is 1-3 μm/h.After distilled water cleaning, dry up, at 800 times of metallography microscope sem observation chemical plating copper layers, find that coating is even, fine and close, flawless, peeling or obscission.Use volometer, the face of test piece is chosen 2 points of the one side that exists together, apart 1cm, and survey its resistance value, resistance is less than 1 Ω.Through 180 DEG C (25min), 0 DEG C of (frozen water 5min) thermal shock test 10 times, coating without foaming, crackle, obscission.
Claims (6)
1. carbon fiber enhancement resin base composite material Electroless copper pre-treatment coating used, it is characterized in that described coating is by 15 ~ 40wt% solvent type resin, 35 ~ 50wt% copper powder, 0.1 ~ 1wt% defoamer, 0.5 ~ 1wt% wetting dispersing agent and 20 ~ 40wt% solvent composition, described solvent type resin is polyester modified organic silicon resin, acrylic resin or urethane resin, defoamer is organic silicon type defoamer, one or both in polyether type defoamer, wetting dispersing agent is polyacrylate dispersion agent or organic silicon type dispersion agent, solvent is N-BUTYL ACETATE, at least one in butanols or amyl acetate-n.
2. carbon fiber enhancement resin base composite material Electroless copper according to claim 1 pre-treatment coating used, is characterized in that described copper powder size is between 800 ~ 20000 orders.
3. a carbon fiber enhancement resin base composite material Electroless copper pre-treating technology, is characterized in that described technological process is:
1) carbon fiber enhancement resin base composite material surface processes 3 ~ 6min in the electrochemical deoiling liquid of 60 ~ 80 DEG C, and described carbon fiber enhancement resin base composite material is carbon-fibre reinforced epoxy resin composite material or fibre reinforced polyimide resin composite material;
2) apply at carbon fiber enhancement resin base composite material the dope layer that a layer thickness is 10 ~ 30 μm on the surface, then at 110 ~ 160 DEG C of drying 20 ~ 40min, described coating is by 15 ~ 40wt% solvent type resin, 35 ~ 50wt% copper powder, 0.1 ~ 1wt% defoamer, 0.5 ~ 1wt% wetting dispersing agent and 20 ~ 40wt% solvent composition;
3) roughening treatment is carried out to coating;
4) activation treatment is carried out to dope layer.
4. carbon fiber enhancement resin base composite material Electroless copper pre-treating technology according to claim 3, is characterized in that described electrochemical deoiling liquid consists of: sodium hydroxide 40 ~ 60g/L, sodium carbonate 25 ~ 35g/L, tertiary sodium phosphate 25 ~ 35g/L.
5. carbon fiber enhancement resin base composite material Electroless copper pre-treating technology according to claim 3, is characterized in that in described step 3), coarsening solution consists of: 98% sulfuric acid 180 ~ 240mL/L, chromic trioxide 120 ~ 180g/L; Treatment condition are: temperature 20 ~ 40 DEG C, etching time 10 ~ 20min.
6. carbon fiber enhancement resin base composite material Electroless copper pre-treating technology according to claim 3, is characterized in that, in described step 4), activation solution consists of the nitric acid of volume fraction 5 ~ 15%; Activation temperature is room temperature, and soak time is 20 ~ 40s.
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| CN103866299B (en) * | 2014-03-24 | 2016-08-24 | 大连理工大学 | The pre-treating technology of epoxy resin-base composite material surface chemical plating |
| CN108126880A (en) * | 2017-12-20 | 2018-06-08 | 贺州宝兴新材料有限公司 | Resin matrix substrate release materials and its manufacturing method |
| CN108329776A (en) * | 2018-02-01 | 2018-07-27 | 东莞市佳乾新材料科技有限公司 | A kind of Environment-friendlycarbon carbon fiber/polypropylene acid conductive coating |
| CN111253745A (en) * | 2020-01-20 | 2020-06-09 | 苏州道田新材料科技有限公司 | Polymer composite material and preparation method of filter cavity |
| CN114075344A (en) * | 2020-08-19 | 2022-02-22 | 华为机器有限公司 | Composite base material, electronic device, and method for manufacturing composite base material |
| CN112961385A (en) * | 2021-02-03 | 2021-06-15 | 成都雅印电子科技有限公司 | Method for metalizing surface of three-dimensional non-metal substrate |
| CN113645825A (en) * | 2021-08-11 | 2021-11-12 | 中国电子科技集团公司第十四研究所 | Preparation method of electromagnetic shielding composite film based on non-metallic material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944718A (en) * | 2006-07-17 | 2007-04-11 | 昆明亘宏源科技有限公司 | New process for electroplating non-metal material surface and its special conductive paint |
| CN101967629A (en) * | 2010-09-29 | 2011-02-09 | 北京卫星制造厂 | Method for preparing surface-metalized coating of epoxy resin matrix composite material |
| CN102392234A (en) * | 2011-10-17 | 2012-03-28 | 哈尔滨工程大学 | Chemical plating or electro -brush plating pretreatment method for organic non-conducting base material and resin base conductive paint |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01301882A (en) * | 1988-05-30 | 1989-12-06 | Koei Kogyo Kk | Method for plating electrically nonconductive body with metal |
-
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- 2013-06-17 CN CN201310238580.3A patent/CN103320011B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944718A (en) * | 2006-07-17 | 2007-04-11 | 昆明亘宏源科技有限公司 | New process for electroplating non-metal material surface and its special conductive paint |
| CN101967629A (en) * | 2010-09-29 | 2011-02-09 | 北京卫星制造厂 | Method for preparing surface-metalized coating of epoxy resin matrix composite material |
| CN102392234A (en) * | 2011-10-17 | 2012-03-28 | 哈尔滨工程大学 | Chemical plating or electro -brush plating pretreatment method for organic non-conducting base material and resin base conductive paint |
Non-Patent Citations (2)
| Title |
|---|
| 铜填充导电涂料的研究;佟富强等;《吉林大学自然科学学报》;19931231(第4期);第65页 * |
| 非金属电镀用导电漆的研制;于晓辉等;《电镀与涂饰》;20060815;第25卷(第8期);第28-31页 * |
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