CN105887054A - High-conductivity biomass and nanometal flexible composite film and preparation method thereof - Google Patents
High-conductivity biomass and nanometal flexible composite film and preparation method thereof Download PDFInfo
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- CN105887054A CN105887054A CN201610414363.9A CN201610414363A CN105887054A CN 105887054 A CN105887054 A CN 105887054A CN 201610414363 A CN201610414363 A CN 201610414363A CN 105887054 A CN105887054 A CN 105887054A
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- 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
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
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- 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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
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- 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
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
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Abstract
The invention discloses a high-conductivity biomass and nanometal flexible composite film and a preparation method thereof. The method comprises the following steps that 1, a biomass substrate is impregnated into a dopamine buffer solution, continuous stirring is conducted, an obtained film is washed multiple times with deionized water, and a composite film of which the surface is covered with polydopamine is obtained; 2, the composite film is impregnated into an aqueous solution of (NH4)2PdCl4, stirring is conducted, and a catalyst is fixed on the surface of the substrate; 3, the composite film obtained in the second step is washed multiple times with deionized water and impregnated into a plating solution of copper or silver or gold or nickel for at least 5 min at room temperature, an obtained film is washed to be clean with deionized water, and finally the biomass and nanometal composite film of which the surface has metal luster is obtained after drying is conducted. According to the high-conductivity biomass and nanometal flexible composite film and the preparation method thereof, operation is easy, consumed time is short, and the cost is low; the obtained biomass and nanometal composite film has high conductivity or high reflectivity.
Description
Technical field
The invention belongs to chemical deposition metal, Optical Electro-Chemistry field, be specifically related to a kind of biomass/nanometer gold
Belong to laminated film and preparation method thereof.
Background technology
Portable and developing rapidly of wearable electronic devices field causes people to high connductivity, the need of flexible material
Ask and rise rapidly.The conductive material of polymer base because of its outstanding pliability, low cost, multifunction and quilt
It is widely used in this.Conductive flexible thin film or fabric can be by conducting polymer or flexible polymer preparations
Become, such as PET, paper, rubber etc..Due to the exhaustion of ore resource and increasing the weight of of environmental problem, biological high score
Son is increasingly becoming the important sources of petroleum replacing sill.Compared with petroleum based material, biopolymer has it
Unique advantage, such as biodegradability, biocompatibility, environmentally friendly, low cost, renewable etc..
Wherein, cellulose has been widely used in the fields such as packaging as nature rich in natural resources, the heaviest
Want is because of its stronger mechanical strength, and inherent pliability makes cellulose in compliant conductive, energy storage etc.
There are huge potentiality in field.
There is substantial amounts of research that the conductive material such as Graphene, CNT and cellulose are compounded to form conduction
Fexible film, but the preparation of these conduction products generally requires the operating process of complexity and is added costliness
Filler often add application cost, limit it and extensively apply.From conductivity, cost angularly for,
Metal is still and manufactures being preferably selected of conductive material.
The method of metal current spraying plating mainly includes physical vapour deposition (PVD), and chemical gaseous phase deposits, electrochemical deposition
Metal, and chemical deposition metal.Wherein chemical deposition metal is that one can be at base flexible, stretchable
The method preparing high-test metal structure, this method need not high-temperature process, sets without expensive at the end
Standby and conductive substrates, therefore cost is relatively low.Chemical deposition process includes two steps: (1) substrate surface anchor layer
Metallic catalyst is fixed；(2) growth of metal in plating solution.Wherein anchor layer is most important, because its
Not only determining the fixed efficiency of catalyst, thus affect follow-up redox reaction, anchor layer should simultaneously
The metal plated there is good adhesion effect.Therefore need to be in substrate surface graft polymers molecular brush as anchor
Though layer, its grafting method is complicated, required expensive equipment, relatively costly.
Summary of the invention
High connductivity biomass/the nano metal that the invention provides a kind of poly-dopamine auxiliary electroless deposition is flexible
The preparation method of composite membrane, the method using simple dipping, with biological material as substrate, poly-dopamine is
Anchor Agent, effectively fixes metallic catalyst, thus at the surface of biological material generation redox reaction
Deposition metal.Solve existing surface metalization techniques complex operation, the longest, poorly conductive, surface gold
Belong to a caducous difficult problem, the most applicable simultaneously for the variously-shaped material made by various biomass materials.
The present invention realizes especially by techniques below scheme:
A kind of preparation of the high connductivity biomass/nano metal flexible compound film of poly-dopamine auxiliary electroless deposition
Method, comprises the steps:
(1) the biomass-based end, be impregnated in dopamine buffer solution, and connect under 100-500rpm rotating speed
Continuous stirring 0.5-24h, repeatedly rinses gained thin film deionized water, must arrive surface and be coated with poly-dopamine
Laminated film；
(2) above-mentioned laminated film be impregnated in (NH4)2PdCl4Aqueous solution in, under 100-500rpm rotating speed
Stirring 0.5-4h so that the fixing upper catalyst of substrate surface；
(3), after step (2) gained laminated film deionized water repeatedly being rinsed, at room temperature impregnated in
Copper is silver-colored or golden or at least 5min in the plating solution of nickel, and gained thin film is washed with deionized totally, after warp
It is dried to obtain surface and there is the biomass/nano metal/nano metal laminated film of metallic luster.
Dopamine buffer described in step (1) is the Tris HCl buffer of dopamine, and concentration is
The pH=6.0-10.0 of 0.5-5mg/ml, Tris HCl buffer.
(NH described in step (2)4)2PdCl4The concentration of aqueous solution be 0.1mg/ml-1mg/ml.
Described in step (3), dip time is 10～60min.
Being dried described in step (3) as air-drying or vacuum drying, vacuum drying temperature is 25-60 DEG C.
The described biomass-based end, comprises the two dimension or three-dimensional material made with biomass material.
The described biomass-based end is cellulose paper, cellulose, chitosan, hemicellulose or its modification saturating
Bright thin film, aeroge, hydrogel, fabric.
The plating solution of described copper is NaOH, CuSO4·5H2O, sodium potassium tartrate tetrahydrate and the mixing of reducing agent formaldehyde
Solution；The plating solution of described silver is [Ag (NH3)2]NO3With the mixed liquor of sodium potassium tartrate tetrahydrate, the plating solution of described nickel
For NiSO4·5H2The mixed liquor of O, sodium citrate, lactic acid and dimethylamine borane；The plating solution of described gold is
HAuCl4, NaOH, NH2OH HCl, Na2HPO4, NaS2O3·5H2O and Na2SO3Mixed liquor.
The plating solution of described copper is by 12g/L NaOH, 13g/L CuSO4·5H2O, 29g/L sodium potassium tartrate tetrahydrate and
Reducing agent 9.5ml/L formaldehyde forms；The plating solution of described silver is by 1g/L [Ag (NH3)2]NO3With 5g/L winestone
Acid potassium sodium composition；The plating solution of described nickel is by 40g/L NiSO4·5H2O, 20g/L sodium citrate, 10g/L
Lactic acid and the dimethylamine borane of 1g/L mix with volume ratio 4:1, with ammonia regulation pH be simultaneously
8；The plating solution of gold is 3.3g/L HAuCl4, 0.4g/L NaOH, 6.95g/L NH2OH HCl, 11g/L
Na2HPO4, 16g/L NaS2O3·5H2O and 40g/L Na2SO3Mix.
Biomass prepared by said method/nano metal laminated film, the metal formed can secure adhesion
On the biomass-based end.The nitrogen-containing group of poly-dopamine can be with catalyst metal ion strong bonded, simultaneously
Play the effect of firm deposited metal.
The present invention uses the method for simple dipping, with poly-dopamine as anchor layer, at the bottom of cellulose base (or its
Allogenic material raw material is substrate) surface chemistry deposition metal.Prepared biomass/nano metal THIN COMPOSITE
Film has good electric conductivity, and the metal simultaneously deposited can be firmly attached to substrate surface.This preparation process is grasped
Make simple, can complete under room temperature condition.Prepared biomass/nano metal laminated film is at energy
There is the biggest application potential in the fields such as source storage, electronic equipment.
Compared with existing polymer surfaces metallization processes, the invention have the advantages that
(1) present invention is simple to operate, the shortest, and cost is relatively low；
(2) there is the strongest adhesion between metal and the substrate on the laminated film surface prepared by the present invention,
Metal difficult drop-off, and the metal level even compact formed.
(3) biomass material and dopamine (belonging to biomass) used by are all environmental friendliness, can be biological
Degraded and the material of biocompatibility, obtained biomass/nano metal laminated film have high conductivity or
High reflectance, can be used for metallurgy, photoelectric device, wearable electronic, chemical industry, bio-sensing, can plant
Enter the key areas such as electronic device, energy storage, military industrial technology, significantly widen the application of biological material
Scope.
Accompanying drawing explanation
Fig. 1 is the mass-change curve that in embodiment of the present invention 1-4, filter paper and cotton changed with the copper facing time.
Fig. 2 is the square resistance change that in embodiment of the present invention 1-4, filter paper and cotton changed with the copper facing time.
Fig. 3 is SEM figure (a) and the energy spectrogram of filter paper in the embodiment of the present invention 2/Nanometer Copper laminated film
(b)。
Fig. 4 is SEM figure (a) and the energy spectrogram of cotton in the embodiment of the present invention 2/Nanometer Copper conductive fabric
(b)。
Fig. 5 is the SEM figure of the chitosan film in the embodiment of the present invention 5/Nanometer Copper conductive composite film.
Fig. 6 is the resistance stability test figure of the filter paper in the embodiment of the present invention 3/Nanometer Copper laminated film.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, but is not limited to this.
Embodiment 1
Clip a certain size filter paper or cotton be soaked in the dopamine/Tris HCl buffer of 1mg/ml
(pH=8.5), in, 6h under 300rpm rotating speed, is stirred.The filter paper being coated with poly-dopamine of gained or cotton
After repeatedly rinsing with deionized water, it is soaked in (the NH of 0.1mg/ml4)2PdCl4Aqueous solution in, 300rpm
1h is stirred under rotating speed.The filter paper being adsorbed with metallic catalyst or the cotton deionized water of gained are repeatedly washed
After washing, impregnated in 5min in the plating solution of copper, plating solution is by 12g/L NaOH, 13g/L CuSO4·5H2O,
29g/L sodium potassium tartrate tetrahydrate and reducing agent 9.5ml/L formaldehyde composition.After having reacted, surface is coated with metal
Filter paper or after cotton deionized water rinses well, be placed in 50 DEG C of vacuum drying ovens and be dried.Weigh filter
Quality before and after paper and cotton reaction, and test its resistance with four probe sheet resistance testers.
Embodiment 2
Clip a certain size filter paper or cotton be soaked in the dopamine/Tris HCl buffer of 1mg/ml
(pH=8.5), in, 6h under 300rpm rotating speed, is stirred.The filter paper being coated with poly-dopamine of gained or cotton
After repeatedly rinsing with deionized water, it is soaked in (the NH of 0.1mg/ml4)2PdCl4Aqueous solution in, 300rpm
1h is stirred under rotating speed.The filter paper being adsorbed with metallic catalyst or the cotton deionized water of gained are repeatedly washed
After washing, impregnated in 10min in the plating solution of copper, plating solution is by 12g/L NaOH, 13g/L CuSO4·5H2O,
29g/L sodium potassium tartrate tetrahydrate and reducing agent 9.5ml/L formaldehyde composition.After having reacted, surface is coated with metal
Filter paper or after cotton deionized water rinses well, be placed in 50 DEG C of vacuum drying ovens and be dried.Weigh filter
Quality before and after paper and cotton reaction, and test its resistance with four probe sheet resistance testers.
Embodiment 3
Clip a certain size filter paper or cotton be soaked in the dopamine/Tris HCl buffer of 1mg/ml
(pH=8.5), in, 6h under 300rpm rotating speed, is stirred.The filter paper being coated with poly-dopamine of gained or cotton
After repeatedly rinsing with deionized water, it is soaked in (the NH of 0.1mg/ml4)2PdCl4Aqueous solution in, 300rpm
1h is stirred under rotating speed.The filter paper being adsorbed with metallic catalyst or the cotton deionized water of gained are repeatedly washed
After washing, impregnated in 30min in the plating solution of copper, plating solution is by 12g/L NaOH, 13g/L CuSO4·5H2O,
29g/L sodium potassium tartrate tetrahydrate and reducing agent 9.5ml/L formaldehyde composition.After having reacted, surface is coated with metal
Filter paper or after cotton deionized water rinses well, be placed in 50 DEG C of vacuum drying ovens and be dried.Weigh filter
Quality before and after paper and cotton reaction, and test its resistance with four probe sheet resistance testers.
Embodiment 4
Clip a certain size filter paper or cotton be soaked in the dopamine/Tris HCl buffer of 1mg/ml
(pH=8.5), in, 6h under 300rpm rotating speed, is stirred.The filter paper being coated with poly-dopamine of gained or cotton
After repeatedly rinsing with deionized water, it is soaked in (the NH of 0.1mg/ml4)2PdCl4Aqueous solution in, 300rpm
1h is stirred under rotating speed.The filter paper being adsorbed with metallic catalyst or the cotton deionized water of gained are repeatedly washed
After washing, impregnated in 60min in the plating solution of copper, plating solution is by 12g/L NaOH, 13g/L CuSO4·5H2O,
29g/L sodium potassium tartrate tetrahydrate and reducing agent 9.5ml/L formaldehyde composition.After having reacted, surface is coated with metal
Filter paper or after cotton deionized water rinses well, be placed in 50 DEG C of vacuum drying ovens and be dried.Weigh filter
Quality before and after paper and cotton reaction, and test its resistance with four probe sheet resistance testers.
Embodiment 5
A certain size chitosan film of clip is soaked in the dopamine/Tris HCl buffer of 2mg/ml
(pH=8.5), in, 12h under 300rpm rotating speed, is stirred.The chitosan film being coated with poly-dopamine of gained
After repeatedly rinsing with deionized water, it is soaked in (the NH of 0.5mg/ml4)2PdCl4Aqueous solution in, 300rpm
3h is stirred under rotating speed.The chitosan film deionized water being adsorbed with metallic catalyst of gained is repeatedly washed
After, impregnated in 5min in the plating solution of copper, plating solution is by 12g/L NaOH, 13g/L CuSO4·5H2O, 29
G/L sodium potassium tartrate tetrahydrate and reducing agent 9.5ml/L formaldehyde composition.After having reacted, surface is coated with metal
After chitosan film deionized water is rinsed well, it is placed in 50 DEG C of vacuum drying ovens and is dried.With four probe sides
Its resistance tested by resistance tester.
Embodiment 6
A certain size chitosan film of clip is soaked in the dopamine/Tris HCl buffer of 2mg/ml
(pH=8.5), in, 12h under 300rpm rotating speed, is stirred.The chitosan film being coated with poly-dopamine of gained
After repeatedly rinsing with deionized water, it is soaked in (the NH of 0.5mg/ml4)2PdCl4Aqueous solution in, 300rpm
3h is stirred under rotating speed.The chitosan film deionized water being adsorbed with metallic catalyst of gained is repeatedly washed
After, impregnated in 10min in the plating solution of nickel.After having reacted, the chitosan film that surface is coated with metal spends
After ionized water is rinsed well, after drying at room temperature, test its resistance with four probe sheet resistance testers.
Embodiment 7
A certain size chitosan film of clip is soaked in the dopamine/Tris HCl buffer of 2mg/ml
(pH=8.5), in, 12h under 300rpm rotating speed, is stirred.The chitosan film being coated with poly-dopamine of gained
After repeatedly rinsing with deionized water, it is soaked in (the NH of 0.5mg/ml4)2PdCl4Aqueous solution in, 300rpm
3h is stirred under rotating speed.The chitosan film deionized water being adsorbed with metallic catalyst of gained is repeatedly washed
After, first impregnated in 30min in the plating solution that impregnated in silver in the plating solution of copper after several seconds again.After having reacted, will
Surface is coated with after the chitosan film deionized water of metal rinses well, surveys by four probe sheet resistances after drying at room temperature
Its resistance tested by examination instrument.
Embodiment 8
A certain size chitosan film of clip is soaked in the dopamine/Tris HCl buffer of 2mg/ml
(pH=8.5), in, 12h under 300rpm rotating speed, is stirred.The chitosan film being coated with poly-dopamine of gained
After repeatedly rinsing with deionized water, it is soaked in (the NH of 0.5mg/ml4)2PdCl4Aqueous solution in, 300rpm
3h is stirred under rotating speed.The chitosan film deionized water being adsorbed with metallic catalyst of gained is repeatedly washed
After, first impregnated in 30min in the plating solution that impregnated in gold in the plating solution of copper after several seconds again.After having reacted, will
Surface is coated with after the chitosan film deionized water of metal rinses well, surveys by four probe sheet resistances after drying at room temperature
Its resistance tested by examination instrument.
The mass-change curve that Fig. 1 is filter paper and cotton changed with the copper facing time.As seen from the figure, along with life
The prolongation of material substrate time in the plating solution, the tenor of substrate surface plating is more and more higher.Substrate is described
Surface can success adhesion metal catalyst such that it is able to successfully plate metal.
The square resistance change that Fig. 2 filter paper and cotton changed with the copper facing time.It can be seen that no matter
Being filter paper or cotton, along with the prolongation of its time in metal plating liquid, its square resistance is gradually reduced,
The variance of surface square resistance is gradually reduced, and illustrates that coating is more and more uniform.In conjunction with Fig. 1, illustrate along with time
Between increase, coat of metal progressive additive and gradually uniform, cause resistance to be gradually reduced.Especially filter paper is at plating solution
Can reach 0.13 Ω/ during middle dipping 10min, show its preferable electric conductivity.
The SEM figure of Fig. 3 filter paper/Nanometer Copper laminated film and energy spectrogram.It can be seen that filter paper
Inner fiber plated with gold metal nano-particle the most, illustrates that filter paper is at dipping dopamine and follow-up metallic catalyst
In time, all impregnate fully, so that follow-up surface metalation is also abundant, this is the reason that its electric conductivity is superior.
And coating is uniform, this is the reason that its surface resistance variance is less.Understood its surface by energy spectrogram to plate
One layer of copper granule.
The SEM figure of Fig. 4 cotton/Nanometer Copper conductive fabric and energy spectrogram.It can be seen that filter paper
Inner fiber plated with gold metal nano-particle the most, illustrates that filter paper is at dipping dopamine and follow-up metallic catalyst
In time, all impregnate fully, so that follow-up surface metalation is also abundant, this is the reason that its electric conductivity is superior.
From the SEM figure contrast of cotton with filter paper, the hole of cotton is more, fine and close not as good as filter paper, therefore plates
Time needed for liquid enters cotton inside is longer.So, for reaching identical electric conductivity, cotton is than filter paper institute
The time needed is longer.
The SEM figure of Fig. 5 chitosan film/Nanometer Copper conductive composite film.As seen from the figure, chitosan film
Last layer copper nano particles is the most uniformly plated on surface, and copper nano particles size is uniform, arrangement densification.Compare
In filter paper and cotton, chitosan film surface is more smooth, and the coating therefore formed is the most smooth.
The resistance stability test figure of Fig. 6 filter paper/Nanometer Copper laminated film.As seen from the figure, conduction filter paper exists
In the case of degree of crook difference, resistance changes hardly, shows that conductive layer is stronger with what filter paper bonded,
In the case of bending, conductive layer does not comes off thus does not interferes with its resistance variations.But repeatedly folding
In the case of, because the folding strength of paper is limited, after folding more than 50 times, paper has ruptured, thus leads
Cause conductive layer is discontinuous, and resistance is greatly improved.
The resistance value of the conductive composite film in table 1 embodiment 5-8
As shown in Table 1, in deposition, the resistance of the thin film of copper is minimum, may be the most relevant with the deposition velocity of copper.
Therefore thin film needs the longer time to can be only achieved less resistance when depositing nickel, gold, silver.
Claims (10)
1. the preparation method of high connductivity biomass/nano metal flexible compound film, it is characterised in that bag
Include following steps:
(1) the biomass-based end, be impregnated in dopamine buffer solution, and connect under 100-500rpm rotating speed
Continuous stirring 0.5-24h, repeatedly rinses gained thin film deionized water, must arrive surface and be coated with poly-dopamine
Laminated film；
(2) above-mentioned laminated film be impregnated in (NH4)2PdCl4Aqueous solution in, under 100-500rpm rotating speed
Stirring 0.5-4h so that the fixing upper catalyst of substrate surface；
(3), after step (2) gained laminated film deionized water repeatedly being rinsed, at room temperature impregnated in
Copper is silver-colored or golden or at least 5min in the plating solution of nickel, and gained thin film is washed with deionized totally, after warp
It is dried to obtain surface and there is the biomass/nano metal/nano metal laminated film of metallic luster.
Preparation method the most according to claim 1, it is characterised in that DOPA described in step (1)
Amine buffer is the Tris HCl buffer of dopamine, and concentration is 0.5-5mg/ml, Tris HCl buffer
PH=6.0-10.0.
Preparation method the most according to claim 1 and 2, it is characterised in that described in step (2)
(NH4)2PdCl4The concentration of aqueous solution be 0.1mg/ml-1mg/ml.
Preparation method the most according to claim 1 and 2, it is characterised in that described in step (3)
Dip time is 10～60min.
Preparation method the most according to claim 1 and 2, it is characterised in that described in step (3)
Being dried as air-drying or vacuum drying, vacuum drying temperature is 25-60 DEG C.
Preparation method the most according to claim 1 and 2, it is characterised in that the described biomass-based end
Comprise the two dimension or three-dimensional material made with biomass material.
Preparation method the most according to claim 6, it is characterised in that the described biomass-based end is fine
Dimension element paper, the transparent membrane of cellulose, chitosan, hemicellulose or its modification, aeroge, hydrogel,
Fabric.
Preparation method the most according to claim 1 and 2, it is characterised in that the plating solution of described copper is
NaOH、CuSO4·5H2O, sodium potassium tartrate tetrahydrate and the mixed solution of reducing agent formaldehyde；The plating solution of described silver
For [Ag (NH3)2]NO3With the mixed liquor of sodium potassium tartrate tetrahydrate, the plating solution of described nickel is NiSO4·5H2O, lemon
Lemon acid sodium, lactic acid and the mixed liquor of dimethylamine borane；The plating solution of described gold is HAuCl4, NaOH,
NH2OH HCl, Na2HPO4, NaS2O3·5H2O and Na2SO3Mixed liquor.
Preparation method the most according to claim 8, it is characterised in that the plating solution of described copper is by 12g/L
NaOH, 13g/L CuSO4·5H2O, 29g/L sodium potassium tartrate tetrahydrate and reducing agent 9.5ml/L formaldehyde composition；
The plating solution of described silver is by 1g/L [Ag (NH3)2]NO3Form with 5g/L sodium potassium tartrate tetrahydrate；The plating solution of described nickel
By 40g/L NiSO4·5H2O, 20g/L sodium citrate, the lactic acid of 10g/L and the dimethylamine borane of 1g/L
Alkane mixes with volume ratio 4:1, and regulate pH with ammonia is 8 simultaneously；The plating solution of gold is 3.3g/L
HAuCl4, 0.4g/L NaOH, 6.95g/L NH2OH HCl, 11g/L Na2HPO4, 16g/L
NaS2O3·5H2O and 40g/L Na2SO3Mix.
10. biomass/nano metal laminated film that prepared by method described in any one of claim 1～9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610414363.9A CN105887054B (en) | 2016-06-13 | 2016-06-13 | A kind of highly conductive biomass/nano metal flexible compound film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610414363.9A CN105887054B (en) | 2016-06-13 | 2016-06-13 | A kind of highly conductive biomass/nano metal flexible compound film and preparation method thereof |
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| CN110331391A (en) * | 2019-07-17 | 2019-10-15 | 安徽启明表面技术有限公司 | Nickel-plating liquid used for magnesium alloy and preparation method thereof |
| CN111827000A (en) * | 2020-08-04 | 2020-10-27 | 济南大学 | Copper composite conductive paper prepared based on multi-site catalytic in-situ reduction technology |
| CN113096885A (en) * | 2021-04-07 | 2021-07-09 | 宁波龙圣新材料科技有限公司 | Preparation method of low-resistance high-transparency conductive film |
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| CN111827000A (en) * | 2020-08-04 | 2020-10-27 | 济南大学 | Copper composite conductive paper prepared based on multi-site catalytic in-situ reduction technology |
| CN113096885A (en) * | 2021-04-07 | 2021-07-09 | 宁波龙圣新材料科技有限公司 | Preparation method of low-resistance high-transparency conductive film |
| CN113899895A (en) * | 2021-09-30 | 2022-01-07 | 华中农业大学 | Detection substrate based on macromolecule passivation self-polymerization type thin film coating modification and matched detection method and equipment |
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