CN109295442A - The method of electrocuprol activated carbon fiber and step preparation chemical plating copper-nickel bimetal layer - Google Patents
The method of electrocuprol activated carbon fiber and step preparation chemical plating copper-nickel bimetal layer Download PDFInfo
- Publication number
- CN109295442A CN109295442A CN201811198943.4A CN201811198943A CN109295442A CN 109295442 A CN109295442 A CN 109295442A CN 201811198943 A CN201811198943 A CN 201811198943A CN 109295442 A CN109295442 A CN 109295442A
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- solution
- copper
- nickel
- sodium
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
The present invention is a kind of electrocuprol activated carbon fiber and the method that a step prepares chemical plating copper-nickel bimetal layer.The electrocuprol activation method that this method uses, replaces traditional palladium, the composite deposite uniformly continuous formed when the activating solution stability using cheap material copper sulphate, and after optimization is good, reactivity is strong, subsequent chemistry is plated；And the method for one-step method chemical plating copper-nickel bimetal layer, for the two-step method compared with nickel plating after first copper facing, the dosage of copper sulphate and nickel sulfate is reduced, and one-step method is faster, more efficient；Make reducing agent with sodium hypophosphite substitution formaldehyde, reduces environmental pollution and harm to the human body.
Description
Technical field
The invention belongs to field of compound material, it is related to a kind of electrocuprol activated carbon fiber and a step prepares electroless copper-nickel
The method of double-metal layer.
Background technique
A kind of special fibre that carbon fiber (carbon fiber, abbreviation Cf) is made of carbon, the small, matter with density
Amount is light, intensity is big, thermal expansion coefficient is small, coefficient of friction is small, lubricity is good, good conductivity, good corrosion resistance, with other materials phase
The advantages that capacitive is good, flexibility is good, designability is strong is often selected as ideal composite material reinforcement body and is widely used in composite wood
The preparation of material.The excellent properties of the comprehensive fibre reinforced phase of carbon fiber reinforced aluminum matrix composite and aluminum substrate have in one
The advantage for all various aspects such as anti-oxidant, high temperature resistant, Flouride-resistani acid phesphatase and anti-flaming, non-hygroscopic not aging of not deflating, electrical and thermal conductivity be good, at
For one of most potential composite material.Its application field also from aerospace, military industry field to civilian auto industry,
The fields such as electronics, sports goods, building are gradually expanded, and huge potentiality are shown.
Carbon fiber reinforced aluminum matrix composite generally uses liquid cast method to prepare, and the limited wetting characteristics of Cf and Al cause
The interface compatibility of Cf and Al is poor in composite material, and Cf, which is reacted with Al in interface, under high temperature generates brittlement phase Al4C3Make composite wood
The performance of material is declined.Carbon fiber is modified, single metal layer (Ni or Cu) is coated on the surface Cf, Cf and Al can be improved
Wetability, inhibit the generation of interfacial reaction.Rams studies have shown that the Ni-Al-P that Ni coating is generated in the interface Cf/Al gold
Compound can improve the wetability of 6061 aluminium alloys and carbon fiber between category, but Al3Ni phase is irregularly deposited on the interface Cf-Al
It above or is dispersed in matrix alloy, the bearing capacity of composite material may be made to be deteriorated and be easy disconnected as potential formation of crack
It splits, while diffusion of the Ni to fiber can promote the graphitization of fiber and damage carbon fiber.Urena studies have shown that Cu in Cf/Al circle
Al is generated at face2Cu phase, prevent fiber and aluminium directly contact and Al4C3Generation, improve wetability, and plate Cu carbon fiber exist
There is preferable strength retention, but the interface Cf-Cu, there is no chemical reaction and diffusion reaction, interface is a kind of under high temperature
Physical bond based on mechanical bond, there are holes for interface, and compactness is poor, and interface binding power is poor.Therefore Ni coating and Cu are applied
Layer is not optimal coating as single coating.And the bis- coating modified carbon fibers of Cu-Ni are after heat treatment, composite deposite with
Carbon fiber forms the strong diffusion bond of binding force, and Cu layer as middle layer to Ni to the inhibition that is diffused with of C, decrease is to fibre
The damage of dimension.
Zou Hao person of outstanding talent is composite metal coated using two-step method chemical plating (carbon fiber surface elder generation copper facing nickel plating again) preparation Cu-Ni,
The dosage of nickel sulfate needed for chemical plating single layer Ni and single layer Cu and copper sulphate is respectively 20-25g/L and 25-30g/L, and this patent
Dosage using nickel sulfate needed for the double coating of one-step method Electroless Cu Plating-Ni and copper sulphate is only 2g/L and 10g/L, drug dosage
Less, experimental procedure is simple and direct, and conventional efficient is higher；And reducing agent used in one-step method chemical plating is sodium hypophosphite, substitution passes
Formaldehyde when system electroless copper, reduces the harm to human body.
Using traditional Metal Palladium activation method, (Metal Palladium activation is to make matrix surface forms one layer of your discrete gold to Zhang Ning
Metal particles, make matrix surface have catalysis restore ability, so that electroless plating reaction is gone on smoothly in matrix surface) to carbon fiber into
Row is activated, Metal Palladium it is expensive, cost of drugs is high, and waste liquid easily causes environmental pollution；Xinghua is relied to use traditional glue
The member method of body is activated ABS plastic, and the stability of traditional colloid copper activating liquid is poor, and reactivity is weak, at activation
There are plating leakage phenomenons and being difficult to form the coat of metal of continuous uniform when chemical plating after reason, and after traditional electrocuprol activation processing
It can only carry out chemical plating single metal layer.
In conclusion in current techniques, there is more than the dosage of Metal Palladium in Metal Palladium activation method and palladium is expensive, give up
Liquid seriously pollutes the deficiencies of environment；Traditional colloid copper activating liquid stability is poor, reactivity is weak, exists when chemical plating after activation processing
Plating leakage phenomenon and it is difficult to the deficiencies of forming the coat of metal of continuous uniform；And two-step method chemistry in current composite electroless plating layer
The deficiencies of plating more raw material dosage and complex steps.
Summary of the invention
It is an object of the invention to provide a kind of electrocuprol activation carbon fiber of optimization for deficiency present in current techniques
The method for tieing up simultaneously step preparation chemical plating copper-nickel bimetal layer.The electrocuprol activation method that this method uses, replaces traditional palladium,
Activating solution stability using cheap material copper sulphate, and after optimizing is good, reactivity is strong, subsequent chemistry plating when formed it is compound
Coating uniformly continuous；And the method for one-step method chemical plating copper-nickel bimetal layer, compared with nickel plating after first copper facing two-step method and
The dosage of speech, copper sulphate and nickel sulfate is reduced, and one-step method is faster, more efficient；It is restored with sodium hypophosphite substitution formaldehyde
Agent, reduces environmental pollution and harm to the human body.
The technical solution of the present invention is as follows:
A kind of electrocuprol activated carbon fiber method that simultaneously a step prepares chemical plating copper-nickel bimetal layer, comprising the following steps:
Step 1: carbon fiber surface pre-processes
(1) it removes photoresist: carbon fiber is placed in tube furnace argon atmosphere, 20~40min is kept at 380~420 DEG C, it is complete
At removing photoresist；
(2) disperse: the carbon fiber after removing photoresist is put into polyethylene glycol dispersing agent, and at room temperature ultrasonic treatment 5~
15min；
(3) oil removing: will be dispersed that treated that carbon fiber is put into degreaser, and impregnate at 45~55 DEG C 30~
40min；Wherein, degreaser be the sodium hydroxide containing 50g/L, the sodium carbonate of 15g/L, 30g/L sodium phosphate aqueous solution；
(4) it is roughened: the carbon fiber after oil removal treatment is put into coarsening solution, 20~40min is impregnated at 30~40 DEG C；Its
In, coarsening solution is the aqueous solution of the ammonium sulfate containing 200g/L, 100mL/L sulfuric acid；
(5) neutralize: the carbon fiber for being roughened processing is submerged into 10% sodium hydroxide solution, is ultrasonically treated 2-4min；
(6) it activates: the carbon fiber after roughening treatment is immersed in 3~8min in activating solution at 50-55 DEG C；Wherein, living
Change liquid is every liter of gelatin containing 10g, 25g copper sulphate, 8g sodium borohydride, 20mL n-butanol, 2mL dilute sulfuric acid, and pH value is 8-9
Aqueous solution；
(7) dispergation: the carbon fiber after activation processing is submerged into 5% sodium hydroxide solution, is ultrasonically treated 2min at room temperature；
In above-mentioned preprocessing process after the completion of each step, it will be rinsed 2-3 times with deionized water.
Step 2: one-step method carbon fiber surface chemical plating copper-nickel bimetal layer
Pretreated carbon fiber is put into plating solution, keeps the temperature 55-65min at 60-70 DEG C, coated copper-nickel can be obtained
The modified carbon fiber of double-metal layer；The plating solution is the lemon of every liter of cupric sulfate pentahydrate containing 10g, the nickel sulfate of 2g, 25g
Sour sodium, the boric acid of 30g, the sodium hypophosphite of 30g, the 2.2 '-bipyridyls of 10mg, the benzene sulfinic acid sodium salt of 50mg, 6.5mg methyl
Orange, and pH value is the aqueous solution of 8-9；Wherein, copper sulphate is Cu as mantoquita2+Source of supply；2.2 '-bipyridyls, benzenesulfinic acid
Sodium, methyl orange are effective additive in this chemical plating system, reduce Electroless Deposition Rate to a certain extent, plating solution is more stable；
The Ni that sodium hypophosphite is formed as reducing agent, nickel sulfate+Make reactivator, the two guarantees the lasting progress of electroless plating reaction；
Citric acid is received and adjusts bath pH value as buffer, keeps plating solution more stable；Borate complex buffer is as pH adjusting agent.
The carbon fiber is polyacrylonitrile (PAN) base carbon fibre.
In the step one in (6) step activating solution the preparation method comprises the following steps:
A, the gelatin for weighing 10g is dissolved in 700mL deionized water, and solution temperature is maintained at 60 DEG C, obtains solution A；
B, it by above-mentioned solution dilute sulfuric acid adjusting pH value to 1.8, weighs 25g copper sulphate and is added in solution A, be allowed to dissolve,
Obtain B solution；
C, it weighs 8g sodium borohydride to be dissolved in B solution, obtains C solution；
D, 20ml n-butanol is added into C solution and makees defoaming agent, obtain solution D；
E, after being cooled to room temperature, by solution D plus deionized water to 1L, it is 8.5 that ammonium hydroxide, which adjusts activating solution pH value, activation temperature
50 DEG C of degree, activation time 5min.
Plating solution in the step two the preparation method comprises the following steps:
(1) the cupric sulfate pentahydrate 900mL deionized water dissolving of 10g is weighed, is stirred；
(2) 2.2 '-bipyridyls, the 50mg of the nickel sulfate of 2g, the sodium citrate of 25g, the boric acid of 30g, 10mg are successively weighed
Benzene sulfinic acid sodium salt, 6.5mg methyl orange be added in above-mentioned solution, stirring；
(3) sodium hypophosphite for weighing 30g is added in above-mentioned solution after completely dissolution with 100mL deionized water, stirring；
It (4) is 8-9 with the pH value that ammonium hydroxide adjusts above-mentioned mixed solution；
(5) pretreated carbon fiber is put into above-mentioned plating solution, keeps the temperature 55-65min at 60-70 DEG C in insulating box.
Substantive distinguishing features of the invention are as follows:
The present invention uses copper that precious metal palladium is replaced to carry out nonmetallic plating front activating processing as active component, does not have to noble metal
Palladium reduces cost, reduces environmental pollution, and matter caused by when the precious metal sensitizings such as palladium, platinum, gold is used when reducing conventional activation
Amount loss, catalytic performance is excellent, and the coverage rate through chemical plating after activation is made to have reached nearly 100%；After activation processing, using a step
Method prepares chemical plating copper-nickel bimetal layer, replaces traditional two-step method chemical plating (nickel plating after first copper facing), copper sulphate and nickel sulfate
Dosage reduce；And one-step method chemical plating makees reducing agent using sodium hypophosphite, formaldehyde when instead of traditional chemical copper facing is reduced
Environmental pollution and harm to the human body；One-step method chemical plating saves experimental procedure, reduces drug dosage, improves conventional efficient.
Beneficial effects of the present invention:
(1) carbon fiber is activated using electrocuprol activation method, eliminates the pre-treatment step of sensitization, reduction,
Drug dosage is reduced, it is more efficient；It uses copper to replace precious metal palladium, silver as active component, reduces cost；Reduce precious metal palladium pair
Environmental pollution reduces harm to the human body；Colloid copper activating liquid stability after optimization is good, reactivity is strong, catalytic performance is excellent, after
The coverage rate for the coat of metal that continuous chemical plating is formed is higher and coating continuous uniform；
(2) chemical plating is carried out to carbon fiber, is not necessarily to external dc power supply, transmission facility and auxiliary electrode, simple process；Phase
For plating, cost is relatively low for chemical plating, and environmental pollution is small, and discharging of waste liquid is few；The more uniform densification of chemical deposit, coverage rate
More preferably, the appearance of " black core " phenomenon when avoiding being electroplated；
(3) one-step method can be directlyed adopt after electrocuprol is activated in carbon fiber surface chemical plating copper-compound gold of nickel
Belong to layer, compared to for two-step method chemical plating (nickel plating after first copper facing), the dosage of copper sulphate and nickel sulfate is respectively from 25g/L and 20g/
L is reduced to 10g/L and 2g/L, reduces drug dosage, saves experimental procedure, improves conventional efficient；It is replaced using sodium hypophosphite
Make reducing agent with formaldehyde when electroless copper, reduces the harm to human body；The bath stability of one-step method chemical plating is good, and coating is uniform
It is smooth.After heat treatment, the strong diffusion bond of interface binding power is formed between carbon fiber and copper-nickel composite metal coating.
Detailed description of the invention
Fig. 1 is that carbon fiber surface obtained in embodiment 1 plates copper-nickel bimetal layer SEM figure
Fig. 2 is that carbon fiber surface obtained in embodiment 1 plates copper-nickel bimetal layer EDS figure
Fig. 3 is that carbon fiber surface obtained in embodiment 2 coats layers of copper-nickel particle SEM figure
Fig. 4 is the figure of carbon fiber surface copper-nickel bimetal layer cellular content protrusion SEM obtained in embodiment 3
Fig. 5 is the low SEM figure of carbon fiber surface layers of copper coverage rate obtained in embodiment 4
Fig. 6 is the figure of carbon fiber surface rustic SEM obtained in embodiment 5
Fig. 7 is that carbon fiber surface obtained in embodiment 6 covers copper particle SEM figure
Fig. 8 is the figure of carbon fiber surface copper-nickel bimetal layer cellular content protrusion SEM obtained in embodiment 7
Fig. 9 is the low SEM figure of carbon fiber surface layers of copper coverage rate obtained in embodiment 8
Figure 10 is that the carbon fiber surface that embodiment 9 obtains plates copper-nickel bimetal layer SEM figure
Figure 11 is the low SEM figure of carbon fiber surface layers of copper coverage rate that embodiment 10 obtains
Figure 12 is that the carbon fiber surface that embodiment 11 obtains covers copper particle SEM figure
Specific embodiment
The carbon fiber is polyacrylonitrile (PAN) base carbon fibre, and length 2-3mm, diameter 6.9um, density is
1.76g.cm-3。
The method of a kind of electrocuprol activated carbon fiber proposed by the present invention and step preparation chemical plating copper-nickel bimetal layer.
Embodiment 1
The present embodiment is a kind of electrocuprol activated carbon fiber method that simultaneously a step prepares chemical plating copper-nickel bimetal layer.
The specific implementation step of the present embodiment are as follows:
Step 1: carbon fiber surface pre-processes
1, it removes photoresist: carbon fiber being placed in tube furnace argon atmosphere high temperature at 400 DEG C, 30min is kept to carry out place of removing photoresist
Reason；
2, disperse: the carbon fiber after removing photoresist being submerged into polyethylene glycol dispersing agent, and is ultrasonically treated at room temperature
10min；
3, oil removing: prepare the sodium hydroxide containing 50g/L, the sodium carbonate of 15g/L, 30g/L sodium phosphate aqueous solution make
Degreaser, will be dispersed that treated that carbon fiber is submerged into degreaser, and impregnate 35min at 50 DEG C；
4, be roughened: the sulfuric acid solution of the ammonium sulfate, 100mL/L of preparing 200g/L makees coarsening solution, by the carbon after oil removal treatment
Fiber, which is submerged into coarsening solution, impregnates 30min at 35 DEG C；
5, it neutralizes: the carbon fiber of roughening treatment being submerged into 10% sodium hydroxide solution and is ultrasonically treated 3min；
6, it activates: the preparation sequence of activating solution are as follows:
A, the gelatin for weighing 10g is dissolved in 700mL deionized water, and solution temperature is maintained at 60 DEG C, obtains solution A；
B, above-mentioned solution dilute sulfuric acid is adjusted into pH value to 1.8, weighs 25g copper sulphate and be added in solution A, is allowed to completely molten
Solution, obtains B solution；
C, it weighs 8g sodium borohydride to be dissolved in B solution, obtains C solution；
D, 20mL n-butanol is added into C and makees defoaming agent, obtain solution D；
E, after being cooled to room temperature, by solution D plus deionized water to 1L, it is 8.5 that ammonium hydroxide, which adjusts activating solution pH value, activation temperature
50 DEG C of degree, activation time 5min；
7, dispergation: the carbon fiber after activation processing is submerged into 5% sodium hydroxide solution, is ultrasonically treated 2min at room temperature；
In above-mentioned preprocessing process after the completion of each step, product will be rinsed 2-3 times with deionized water.
Step 2: one-step method carbon fiber surface chemical plating copper-nickel bimetal layer
(1) the cupric sulfate pentahydrate 900mL deionized water dissolving of 10g, electromagnetic agitation 5min are weighed；
(2) 2.2 '-bipyridyls, the 50mg of the nickel sulfate of 2g, the sodium citrate of 25g, the boric acid of 30g, 10mg are successively weighed
Benzene sulfinic acid sodium salt, 6.5mg methyl orange be added in above-mentioned solution, electromagnetic agitation 10min；
(3) it is added in above-mentioned solution after weighing the sodium hypophosphite 100mL deionized water dissolving of 30g, electromagnetic agitation
5min；
It (4) is 8.5 with the pH value that ammonium hydroxide adjusts above-mentioned solution；
(5) pretreated carbon fiber is put into above-mentioned plating solution, keeps the temperature 60min at 70 DEG C in insulating box.
Bright silver is presented in the modified carbon fiber surface that this embodiment obtains, and passes through fiber surface plating known to SEM observation analysis
Layer continuous formation and even compact, internal layer are layers of copper, and outer layer is nickel layer (such as attached drawing 1,2).
Embodiment 2
The present embodiment is a kind of electrocuprol activated carbon fiber method that simultaneously a step prepares chemical plating copper-nickel bimetal layer.
The specific implementation step of the present embodiment are as follows:
Step 1 including removes photoresist, disperses, oil removing, roughening, neutralization, work with the carbon fiber surface preprocessing process of embodiment 1
Change, dispergation.
Step 2: one-step method is in carbon fiber surface chemical plating copper-nickel bimetal layer
(1) the cupric sulfate pentahydrate 900mL deionized water dissolving of 10g, electromagnetic agitation 5min are weighed；
(2) 2.2 '-bipyridyls, the 50mg of the nickel sulfate of 1g, the sodium citrate of 25g, the boric acid of 30g, 10mg are successively weighed
Benzene sulfinic acid sodium salt, 6.5mg methyl orange be added in above-mentioned solution, electromagnetic agitation 10min；
(3) it is added in above-mentioned solution after weighing the sodium hypophosphite 100mL deionized water dissolving of 30g, electromagnetic agitation
5min；
It (4) is 8.5 with the pH value that ammonium hydroxide adjusts above-mentioned solution；
(5) pretreated carbon fiber is put into above-mentioned plating solution, keeps the temperature 60min at 70 DEG C in insulating box.
Dark gray is presented in the modified carbon fiber surface that this embodiment obtains, by internal layer layers of copper uniformly continuous known to SEM, outside
Layer nickel simple substance is attached to layers of copper surface, and not formed complete continuous nickel layer with graininess.Analysis is it is found that when nickel sulfate content is low
When, reaction is difficult to continue progress, cannot complete plating formation copper-nickel bimetal layer (such as attached drawing 3).
Embodiment 3
The present embodiment is a kind of electrocuprol activated carbon fiber method that simultaneously a step prepares chemical plating copper-nickel bimetal layer.
The specific implementation step of the present embodiment are as follows:
Step 1 including removes photoresist, disperses, oil removing, roughening, neutralization, work with the carbon fiber surface preprocessing process of embodiment 1
Change, dispergation.
Step 2: one-step method is in carbon fiber surface chemical plating copper-nickel bimetal layer
(1) the cupric sulfate pentahydrate 900mL deionized water dissolving of 10g, electromagnetic agitation 5min are weighed；
(2) 2.2 '-bipyridyls, the 50mg of the nickel sulfate of 4g, the sodium citrate of 25g, the boric acid of 30g, 10mg are successively weighed
Benzene sulfinic acid sodium salt, 6.5mg methyl orange be added in above-mentioned solution, electromagnetic agitation 10min；
(3) it is added in above-mentioned solution after weighing the sodium hypophosphite 100mL deionized water dissolving of 30g, electromagnetic agitation
5min；
It (4) is 8.5 with the pH value that ammonium hydroxide adjusts above-mentioned solution；
(5) pretreated carbon fiber is put into above-mentioned plating solution, keeps the temperature 60min at 70 DEG C in insulating box.
Dark silver color is presented in modified carbon fiber surface that this embodiment obtains, completely coated by outer layer nickel layer known to SEM in
The layers of copper of layer, but nickel layer rough surface, there is a large amount of cellular content protrusion.Analysis deposits it is found that when the too high levels of nickel sulfate
Rate is too fast, and the coating of formation is loose not fine and close to have cellular content (such as attached drawing 4).
Embodiment 4
The present embodiment is a kind of electrocuprol activated carbon fiber method that simultaneously a step prepares chemical plating copper-nickel bimetal layer.
The specific implementation step of the present embodiment are as follows:
Step 1 including removes photoresist, disperses, oil removing, roughening, neutralization, work with the carbon fiber surface preprocessing process of embodiment 1
Change, dispergation.
Step 2: one-step method is in carbon fiber surface chemical plating copper-nickel bimetal layer
(1) the cupric sulfate pentahydrate 900mL deionized water dissolving of 10g, electromagnetic agitation 5min are weighed；
(2) 2.2 '-bipyridyls, the 50mg of the nickel sulfate of 2g, the sodium citrate of 25g, the boric acid of 30g, 10mg are successively weighed
Benzene sulfinic acid sodium salt, 6.5mg methyl orange be added in above-mentioned solution, electromagnetic agitation 10min；
(3) it is added in above-mentioned solution after weighing the sodium hypophosphite 100mL deionized water dissolving of 30g, electromagnetic agitation
5min；
It (4) is 8.5 with the pH value that ammonium hydroxide adjusts above-mentioned solution；
(5) pretreated carbon fiber is put into above-mentioned plating solution, keeps the temperature 60min at 50 DEG C in insulating box.
Crineous is presented in the modified carbon fiber surface that this embodiment obtains, and passes through carbon fiber surface layers of copper covering known to SEM
Rate is low, and not formed complete packet copper clad layers.Analysis, cannot be in fiber table it is found that deposition rate is very low when bath temperature is too low
The complete plating in face forms copper metal layer (such as attached drawing 5).
Embodiment 5
The present embodiment is a kind of electrocuprol activated carbon fiber method that simultaneously a step prepares chemical plating copper-nickel bimetal layer.
The specific implementation step of the present embodiment are as follows:
Step 1 including removes photoresist, disperses, oil removing, roughening, neutralization, work with the carbon fiber surface preprocessing process of embodiment 1
Change, dispergation.
Step 2: one-step method is in carbon fiber surface chemical plating copper-nickel bimetal layer
(1) the cupric sulfate pentahydrate 900mL deionized water dissolving of 10g, electromagnetic agitation 5min are weighed；
(2) 2.2 '-bipyridyls, the 50mg of the nickel sulfate of 2g, the sodium citrate of 25g, the boric acid of 30g, 10mg are successively weighed
Benzene sulfinic acid sodium salt, 6.5mg methyl orange be added in above-mentioned solution, electromagnetic agitation 10min；
(3) it is added in above-mentioned solution after weighing the sodium hypophosphite 100mL deionized water dissolving of 30g, electromagnetic agitation
5min；
It (4) is 8.5 with the pH value that ammonium hydroxide adjusts above-mentioned solution；
(5) pretreated carbon fiber is put into above-mentioned plating solution, keeps the temperature 60min at 80 DEG C of insulating box.
Dark silver color is presented in modified carbon fiber surface that this embodiment obtains, completely coated by outer layer nickel layer known to SEM in
The layers of copper of layer, but nickel layer rough surface, there is a large amount of cellular content protrusion.Analysis is it is found that when bath temperature is excessively high, reaction speed
Too fast, deposition rate is promoted, and plating bed roughness obviously increases, and micropore occurs, short texture (such as attached drawing 6).
Embodiment 6
The present embodiment is a kind of electrocuprol activated carbon fiber method that simultaneously a step prepares chemical plating copper-nickel bimetal layer.
The specific implementation step of the present embodiment are as follows:
Step 1 including removes photoresist, disperses, oil removing, roughening, neutralization, work with the carbon fiber surface preprocessing process of embodiment 1
Change, dispergation.
Step 2: one-step method is in carbon fiber surface chemical plating copper-nickel bimetal layer
(1) the cupric sulfate pentahydrate 900mL deionized water dissolving of 10g, electromagnetic agitation 5min are weighed；
(2) 2.2 '-bipyridyls, the 50mg of the nickel sulfate of 2g, the sodium citrate of 25g, the boric acid of 30g, 10mg are successively weighed
Benzene sulfinic acid sodium salt, 6.5mg methyl orange be added in above-mentioned solution, electromagnetic agitation 10min；
(3) it is added in above-mentioned solution after weighing the sodium hypophosphite 100mL deionized water dissolving of 30g, electromagnetic agitation
5min；
It (4) is 7 with the pH value that ammonium hydroxide adjusts above-mentioned solution；
(5) pretreated carbon fiber is put into above-mentioned plating solution, keeps the temperature 60min at 70 DEG C in insulating box.
Crineous is presented in the modified carbon fiber surface that this embodiment obtains, and only adheres to copper by fiber surface known to SEM
Particle, and not formed layers of copper.Analysis it is found that deposition rate is very low when bath pH value is too low, cannot fiber surface plating at
Metal copper layer (such as attached drawing 7).
Embodiment 7
The present embodiment is a kind of electrocuprol activated carbon fiber method that simultaneously a step prepares chemical plating copper-nickel bimetal layer.
The specific implementation step of the present embodiment are as follows:
Step 1 including removes photoresist, disperses, oil removing, roughening, neutralization, work with the carbon fiber surface preprocessing process of embodiment 1
Change, dispergation.
Step 2: one-step method is in carbon fiber surface chemical plating copper-nickel bimetal layer
(1) the cupric sulfate pentahydrate 900mL deionized water dissolving of 10g, electromagnetic agitation 5min are weighed；
(2) 2.2 '-bipyridyls, the 50mg of the nickel sulfate of 2g, the sodium citrate of 25g, the boric acid of 30g, 10mg are successively weighed
Benzene sulfinic acid sodium salt, 6.5mg methyl orange be added in above-mentioned solution, electromagnetic agitation 10min；
(3) it is added in above-mentioned solution after weighing the sodium hypophosphite 100mL deionized water dissolving of 30g, electromagnetic agitation
5min；
It (4) is 10 with the pH value that ammonium hydroxide adjusts above-mentioned solution；
(5) pretreated carbon fiber is put into above-mentioned plating solution, keeps the temperature 60min at 70 DEG C in insulating box.
Dark silver color is presented in the surface for the modified carbon fiber that this embodiment obtains, and is completely coated by outer layer nickel layer known to SEM
The layers of copper of internal layer, but nickel layer rough surface have a large amount of cellular content protrusion.It is found that when bath pH value is excessively high, reaction is fast for analysis
It spends fastly, deposition rate is promoted, and plating bed roughness obviously increases, and micropore occurs, short texture (such as attached drawing 8).
Embodiment 8
The present embodiment is a kind of electrocuprol activated carbon fiber method that simultaneously a step prepares chemical plating copper-nickel bimetal layer.
The specific implementation step of the present embodiment are as follows:
Step 1 including removes photoresist, disperses, oil removing, roughening, neutralization, work with the carbon fiber surface preprocessing process of embodiment 1
Change, dispergation.Wherein activation time is 2min.
One-step method carbon fiber surface chemical plating copper-nickel bimetal layer of the step 2 with embodiment 1.
Chocolate is presented in the surface for the modified carbon fiber that this embodiment obtains, unevenly uneven by layers of copper known to SEM
Whole, there is the place that do not plate in fiber surface, illustrate that activation time 2min is too short, and the catalytic active center of formation is very little, so that plating
The coverage rate of layer is low (such as attached drawing 9).
Embodiment 9
The present embodiment is a kind of electrocuprol activated carbon fiber method that simultaneously a step prepares chemical plating copper-nickel bimetal layer.
The specific implementation step of the present embodiment are as follows:
Step 1 including removes photoresist, disperses, oil removing, roughening, neutralization, work with the carbon fiber surface preprocessing process of embodiment 1
Change, dispergation.Wherein activation time is 10min.
One-step method carbon fiber surface chemical plating copper-nickel bimetal layer of the step 2 with embodiment 1.
Bright silver, fiber surface coating uniform ground, with activation is presented in the surface for the modified carbon fiber that this embodiment obtains
It is no different when 5min, illustrates that activation time is that 5min can form a large amount of catalytic active center in carbon fiber surface, promote subsequent
The absorption of complex metal layer is formed when chemical plating, without extending activation time (such as attached drawing 10).
Embodiment 10
The present embodiment is a kind of electrocuprol activated carbon fiber method that simultaneously a step prepares chemical plating copper-nickel bimetal layer.
The specific implementation step of the present embodiment are as follows:
Step 1 including removes photoresist, disperses, oil removing, roughening, neutralization, work with the carbon fiber surface preprocessing process of embodiment 1
Change, dispergation.Wherein 40 DEG C of activation temperature.
One-step method carbon fiber surface chemical plating copper-nickel bimetal layer of the step 2 with embodiment 1.
Crineous is presented in the surface for the modified carbon fiber that this embodiment obtains, and by fiber surface known to SEM, there are plating leakages
The phenomenon that, and the copper coating of not formed continuous formation, illustrate that activation temperature is too low, is unfavorable for forming catalysis work in carbon fiber surface
Property center, be unfavorable for metal copper layer when chemical plating absorption formed (such as attached drawing 11).
Embodiment 11
The present embodiment is a kind of electrocuprol activated carbon fiber method that simultaneously a step prepares chemical plating copper-nickel bimetal layer.
The specific implementation step of the present embodiment are as follows:
Step 1 including removes photoresist, disperses, oil removing, roughening, neutralization, work with the carbon fiber surface preprocessing process of embodiment 1
Change, dispergation.Wherein 70 DEG C of activation temperature.
One-step method carbon fiber surface chemical plating copper-nickel bimetal layer of the step 2 with embodiment 1.
Crineous is presented in the surface for the modified carbon fiber that this embodiment obtains, and adheres to copper by fiber surface known to SEM
Particle, and the coating of not formed continuous formation, activation temperature known to analysis is excessively high, and activating solution activity reduces, and is unfavorable in carbon fiber
Dimension table face forms catalytic active center, and the absorption for being unfavorable for metal layer when chemical plating forms (such as attached drawing 12).
In summary, when the cupric sulfate pentahydrate of 25g/L, the gelatin of 10g/L, the sodium borohydride of 8g/L, 20mL/L n-butanol,
2mL/L dilution heat of sulfuric acid makees activating solution, and activating solution pH value is 8-9, activation time 5min, living when activation temperature is 50-55 DEG C
After change processing the catalytic activation center that carbon fiber surface is formed more more evenly, be more advantageous to compound during subsequent chemistry plating
Formation of the coat of metal in fiber surface.When the citric acid that plating solution is the cupric sulfate pentahydrate of 10g/L, the nickel sulfate of 2g/L, 25g/L
Sodium, the boric acid of 30g/L, the sodium hypophosphite of 30g/L, the 2.2 '-bipyridyls of 10mg/L, 50mg/L benzene sulfinic acid sodium salt,
When the methyl orange of 6.5mg/L is formulated, and the pH value of plating solution is 8-9, and temperature is 70 DEG C, when plating time is 60min, is formed
Copper-nickel alloy coating it is smooth, even compact.
By above embodiments it is recognised that the colloid copper activating liquid after present invention optimization replaces expensive metal
Palladium, using cheap material, and the activating solution stability after optimization is good, and catalytic performance is excellent, subsequent one-step method electroless copper-nickel
The coverage rate of double-metal layer is higher and coating is more evenly smooth.
Therefore the invention patent carries out activating pretreatment to carbon fiber using the electrocuprol activation method after optimization, and uses one-step method
In fiber surface plating copper-nickel bimetal layer, the bis- coating modified carbon fibers of Cu-Ni are heat-treated, the Ni layer of outer layer passes through
Cu layers of inertia of internal layer are diffused into the surface Cf, play pinning effect by limited chemical reaction and strengthen interface cohesion, i.e. Cf/
The interface cohesion of Cu-Ni is to be strengthened to form the strong diffusion of binding force by chemical reaction mechanism and dissolution flooding mechanism respectively
In conjunction with, so as to improve and improve the performance of composite material.
Unaccomplished matter of the present invention is well-known technique.
Claims (3)
1. a kind of method of electrocuprol activated carbon fiber and step preparation chemical plating copper-nickel bimetal layer, it is characterized in that this method
The following steps are included:
Step 1: carbon fiber surface pre-processes
(1) it removes photoresist: carbon fiber is placed in tube furnace argon atmosphere, 20~40min is kept at 380~420 DEG C, is completed
Glue；
(2) disperse: the carbon fiber after removing photoresist is put into polyethylene glycol dispersing agent, and be ultrasonically treated 5~15min at room temperature；
(3) oil removing: will be dispersed that treated that carbon fiber is put into degreaser, and 30~40min is impregnated at 45~55 DEG C；Its
In, degreaser be the sodium hydroxide containing 50g/L, the sodium carbonate of 15g/L, 30g/L sodium phosphate aqueous solution；
(4) it is roughened: the carbon fiber after oil removal treatment is put into coarsening solution, 20~40min is impregnated at 30~40 DEG C；Wherein, slightly
Change liquid is the aqueous solution containing 200g/L ammonium sulfate, 100mL/L sulfuric acid；
(5) neutralize: the carbon fiber for being roughened processing is submerged into 10% sodium hydroxide solution, is ultrasonically treated 2-4min；
(6) it activates: the carbon fiber after roughening treatment is immersed in 3~8min in activating solution at 50-55 DEG C；Wherein, activating solution
The water for being 8-9 for every liter of gelatin containing 10g, 25g copper sulphate, 8g sodium borohydride, 20mL n-butanol, 2mL dilute sulfuric acid, and pH value
Solution；
(7) dispergation: the carbon fiber after activation processing is submerged into 5% sodium hydroxide solution, is ultrasonically treated 2min at room temperature；
In above-mentioned preprocessing process after the completion of each step, it will be rinsed 2-3 times with deionized water；
Step 2: one-step method carbon fiber surface chemical plating copper-nickel bimetal layer
Pretreated carbon fiber is put into plating solution, keeps the temperature 55-65min at 60-70 DEG C, the double gold of coated copper-nickel can be obtained
Belong to the modified carbon fiber of layer；The plating solution is the citric acid of every liter of cupric sulfate pentahydrate containing 10g, the nickel sulfate of 2g, 25g
Sodium, the boric acid of 30g, the sodium hypophosphite of 30g, the 2.2 '-bipyridyls of 10mg, the benzene sulfinic acid sodium salt of 50mg, 6.5mg methyl
Orange, and pH value is the aqueous solution of 8-9；
The carbon fiber is polyacrylonitrile (PAN) base carbon fibre.
2. the method for electrocuprol activated carbon fiber as described in claim 1 and step preparation chemical plating copper-nickel bimetal layer,
Feature be the step one in (6) step activating solution the preparation method comprises the following steps:
A, the gelatin for weighing 10g is dissolved in 700mL deionized water, and solution temperature is maintained at 60 DEG C, obtains solution A；
B, above-mentioned solution dilute sulfuric acid is adjusted into pH value to 1.8, weighs 25g copper sulphate and be added in solution A, is allowed to dissolve, obtains B
Solution；
C, it weighs 8g sodium borohydride to be dissolved in B solution, obtains C solution；
D, 20mL n-butanol is added into C solution and makees defoaming agent, obtain solution D；
E, after being cooled to room temperature, by solution D plus deionized water to 1L, it is 8.5 that ammonium hydroxide, which adjusts activating solution pH value, activation temperature 50
DEG C, activation time 5min.
3. the method for electrocuprol activated carbon fiber as described in claim 1 and step preparation chemical plating copper-nickel bimetal layer,
Feature be the step two in plating solution the preparation method comprises the following steps:
(1) the cupric sulfate pentahydrate 900mL deionized water dissolving of 10g is weighed, is stirred；
(2) benzene of the nickel sulfate of 2g, the sodium citrate of 25g, the boric acid of 30g, the 2.2 '-bipyridyls of 10mg, 50mg are successively weighed
Sulfinic acid sodium, 6.5mg methyl orange be added in above-mentioned solution, stirring；
(3) it is added in above-mentioned solution, stirs after weighing the sodium hypophosphite 100mL deionized water dissolving of 30g；
It (4) is 8-9 with the pH value that ammonium hydroxide adjusts above-mentioned mixed solution；
(5) pretreated carbon fiber is put into above-mentioned plating solution, keeps the temperature 55-65min at 60-70 DEG C in insulating box.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811198943.4A CN109295442A (en) | 2018-10-15 | 2018-10-15 | The method of electrocuprol activated carbon fiber and step preparation chemical plating copper-nickel bimetal layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811198943.4A CN109295442A (en) | 2018-10-15 | 2018-10-15 | The method of electrocuprol activated carbon fiber and step preparation chemical plating copper-nickel bimetal layer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109295442A true CN109295442A (en) | 2019-02-01 |
Family
ID=65162550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811198943.4A Pending CN109295442A (en) | 2018-10-15 | 2018-10-15 | The method of electrocuprol activated carbon fiber and step preparation chemical plating copper-nickel bimetal layer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109295442A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109735830A (en) * | 2019-02-19 | 2019-05-10 | 广东工业大学 | A kind of preparation method of activating solution and preparation method and carbon fibre composite |
| CN111549523A (en) * | 2020-06-18 | 2020-08-18 | 大连理工大学 | Modified carbon fiber and preparation method thereof, modified carbon fiber reinforced aluminum matrix composite and preparation method thereof |
| CN113862995A (en) * | 2021-09-29 | 2021-12-31 | 长春工业大学 | Pretreatment method and coating method for metallization of carbon fiber surface |
| WO2022043417A1 (en) | 2020-08-27 | 2022-03-03 | Atotech Deutschland GmbH & Co. KG | A method for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization |
| WO2022223062A1 (en) * | 2021-04-19 | 2022-10-27 | Technicka Univerzita V Liberci | A method of preparing a continuous layer of porous carbon fibers, a continuous layer of porous carbon fibers prepared in this manner, an air filter and personal protective equipment comprising at least one such layer |
| CN115537788A (en) * | 2022-08-29 | 2022-12-30 | 深圳大学 | Chemical plating activator and preparation method and application thereof |
| CN117966136A (en) * | 2024-01-31 | 2024-05-03 | 南京航空航天大学 | Method for preparing fine ceramic circuit board by laser-assisted chemical plating |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06343897A (en) * | 1993-06-02 | 1994-12-20 | Hideo Yoshikawa | Air cleaning device |
| JP2000195998A (en) * | 1998-12-28 | 2000-07-14 | Polymatech Co Ltd | Heat conductive sheet, its manufacture, and semiconductor device |
| CN104357816A (en) * | 2014-11-13 | 2015-02-18 | 南通大学 | Preparation method of copper-nickel conducting fabric |
| CN106498717A (en) * | 2016-11-08 | 2017-03-15 | 长春工业大学 | A kind of method that carbon fiber surface plates multiple layer metal |
-
2018
- 2018-10-15 CN CN201811198943.4A patent/CN109295442A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06343897A (en) * | 1993-06-02 | 1994-12-20 | Hideo Yoshikawa | Air cleaning device |
| JP2000195998A (en) * | 1998-12-28 | 2000-07-14 | Polymatech Co Ltd | Heat conductive sheet, its manufacture, and semiconductor device |
| CN104357816A (en) * | 2014-11-13 | 2015-02-18 | 南通大学 | Preparation method of copper-nickel conducting fabric |
| CN106498717A (en) * | 2016-11-08 | 2017-03-15 | 长春工业大学 | A kind of method that carbon fiber surface plates multiple layer metal |
Non-Patent Citations (1)
| Title |
|---|
| 庄严等: "碳纤维无贵金属化学镀铜一步活化工艺", 《昆明理工大学学报（自然科学版）》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109735830A (en) * | 2019-02-19 | 2019-05-10 | 广东工业大学 | A kind of preparation method of activating solution and preparation method and carbon fibre composite |
| CN111549523A (en) * | 2020-06-18 | 2020-08-18 | 大连理工大学 | Modified carbon fiber and preparation method thereof, modified carbon fiber reinforced aluminum matrix composite and preparation method thereof |
| WO2022043417A1 (en) | 2020-08-27 | 2022-03-03 | Atotech Deutschland GmbH & Co. KG | A method for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization |
| WO2022223062A1 (en) * | 2021-04-19 | 2022-10-27 | Technicka Univerzita V Liberci | A method of preparing a continuous layer of porous carbon fibers, a continuous layer of porous carbon fibers prepared in this manner, an air filter and personal protective equipment comprising at least one such layer |
| CN113862995A (en) * | 2021-09-29 | 2021-12-31 | 长春工业大学 | Pretreatment method and coating method for metallization of carbon fiber surface |
| CN115537788A (en) * | 2022-08-29 | 2022-12-30 | 深圳大学 | Chemical plating activator and preparation method and application thereof |
| CN117966136A (en) * | 2024-01-31 | 2024-05-03 | 南京航空航天大学 | Method for preparing fine ceramic circuit board by laser-assisted chemical plating |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109295442A (en) | The method of electrocuprol activated carbon fiber and step preparation chemical plating copper-nickel bimetal layer | |
| Han et al. | Electromagnetic interference shielding effectiveness of electroless Cu-plated PET fabrics | |
| CN102899890A (en) | Aramid fiber surface metallization treatment method | |
| CN101649477B (en) | Preparation method of metal carbon aerogel composite material | |
| CN109848611B (en) | Preparation method of Sn-based composite solder sheet based on porous Ni/Cu alloy | |
| CN102418090A (en) | Surface metallization preparation method of resin-based composite material capable of being molded by die pressing | |
| CN101215693A (en) | Method for preparing high-performance conductive fiber | |
| CN106498715A (en) | A kind of aromatic polyamide conductive fibers preparation method of the coat of metal | |
| CN111519226A (en) | Polyetherimide chemical roughening electroplating process | |
| CN112126957A (en) | Surface metallization pretreatment method for carbon fiber resin composite material | |
| CN106544656B (en) | Modified carbon fiber and its preparation and application of the one kind containing Ni-P-SiC (titanium diboride) composite deposite | |
| CN114032675B (en) | Conductive fiber and preparation method thereof | |
| CN114210975A (en) | Ag @ Ni core-shell structure powder prepared by chemical plating and preparation method thereof | |
| Pavithran et al. | Copper coating on coir fibres | |
| CN101831645B (en) | Cemented carbide steelwork surface electroless copper plating method | |
| CN115537788B (en) | Electroless plating activator and preparation method and application thereof | |
| CN110029331A (en) | A kind of sensitizing solution and its sensitization technique for chemical plating of non-metal material copper | |
| CN109750283A (en) | A kind of process of SMC material chemical plating nickel-phosphorus alloy on surface | |
| CN203080040U (en) | Nano-porous surface structure of intensifying and boiling metal | |
| CN101768736A (en) | Formula for chemical plating of nickel-copper on calcium magnesium silicate mineral whisker surface and process thereof | |
| CN109735830A (en) | A kind of preparation method of activating solution and preparation method and carbon fibre composite | |
| CN108103507A (en) | A kind of electromagnetic shielding material and preparation method thereof | |
| CN102517616B (en) | Plating solution formula for electroplating tin and bismuth on aluminum material and electroplating method thereof | |
| CN117983810B (en) | Diamond copper high-heat-conductivity powder material and preparation method and application thereof | |
| CN112251739A (en) | Aluminum-induced chemical plating method for pre-plating copper film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190201 |
|
| WD01 | Invention patent application deemed withdrawn after publication |