CN105887054B - A kind of highly conductive biomass/nano metal flexible compound film and preparation method thereof - Google Patents

A kind of highly conductive biomass/nano metal flexible compound film and preparation method thereof Download PDF

Info

Publication number
CN105887054B
CN105887054B CN201610414363.9A CN201610414363A CN105887054B CN 105887054 B CN105887054 B CN 105887054B CN 201610414363 A CN201610414363 A CN 201610414363A CN 105887054 B CN105887054 B CN 105887054B
Authority
CN
China
Prior art keywords
biomass
preparation
plating solution
laminated film
nano metal
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.)
Active
Application number
CN201610414363.9A
Other languages
Chinese (zh)
Other versions
CN105887054A (en
Inventor
王小慧
杨洋
孙润仓
张楚
于朝阳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201610414363.9A priority Critical patent/CN105887054B/en
Publication of CN105887054A publication Critical patent/CN105887054A/en
Application granted granted Critical
Publication of CN105887054B publication Critical patent/CN105887054B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C23C18/18—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
    • 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
    • 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
    • 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

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)
  • Chemically Coating (AREA)

Abstract

The invention discloses a kind of highly conductive biomass/nano metal flexible compound films and preparation method thereof, include the following steps: that biomass-based bottom is impregnated in dopamine buffer solution by (1), it continuously stirs, gained film is repeatedly rinsed with deionized water, obtains to surface and is covered with the laminated film of poly-dopamine；(2) above-mentioned laminated film is impregnated in (NH4)2PdCl4Aqueous solution in, stirring, so that the fixed upper catalyst of substrate surface；(3) after laminated film obtained by step (2) repeatedly being rinsed with deionized water, it is impregnated at least 5min in the plating solution of copper or silver or gold or nickel at room temperature, gained film is washed with deionized completely, the biomass/nano metal/nano metal laminated film for most having metallic luster through being dried to obtain surface afterwards.Operation of the present invention is simple, and time-consuming shorter, cost is relatively low；Obtained biomass/nano metal laminated film has high conductivity or high reflectance.

Description

A kind of highly conductive biomass/nano metal flexible compound film and preparation method thereof
Technical field
The invention belongs to chemical deposition metals, optical electro-chemistry field, and in particular to a kind of biomass/nano metal THIN COMPOSITE Film and preparation method thereof.
Background technique
It is portable and wearable electronic devices field rapid development cause people to highly conductive, flexible material demand rapidly Rise.The conductive material of polymer matrix is at low cost because of its outstanding flexibility, multifunction and be widely used in this.It is conductive Fexible film or fabric can be prepared by conducting polymer or flexible polymer, such as PET, paper, rubber etc..Due to ore The exhaustion of resource and the exacerbation of environmental problem, boiomacromolecule are increasingly becoming the important sources of substitution petroleum based material.With petroleum Sill is compared, and boiomacromolecule has its unique advantage, such as biodegradability, and biocompatibility is environmentally friendly, it is low at This, it is renewable etc..Wherein, cellulose has been widely used in the fields such as packaging as the most abundant resource of nature, especially It is important that because of its stronger mechanical strength, inherent flexibility has cellulose in fields such as compliant conductive, energy stores Huge potentiality.
There is a large amount of research that the conductive materials such as graphene, carbon nanotube and cellulose are compounded to form conductive flexible thin Film, however the preparation of these conductive products generally requires complicated operating process and the filler of valuableness is added often to increase Application cost limits its extensive use.From conductivity, cost angularly for, metal be still manufacture conductive material it is best Selection.
The method of metallising mainly includes physical vapour deposition (PVD) at present, chemical vapor deposition, electrochemical deposition of metal, with And chemical deposition metal.Wherein chemical deposition metal is that one kind can prepare high-test metal in flexible, stretchable substrate The method of structure, this method do not need high-temperature process, and without expensive equipment and conductive substrates, therefore cost is relatively low.Change Learning deposition process includes two steps: (1) fixation of the substrate surface anchor layer to metallic catalyst；(2) in plating solution metal growth.Its Middle anchor layer is most important, because it not only determines the fixed efficiency of catalyst, so that subsequent redox reaction is influenced, Anchor layer, which copes with plated metal, simultaneously good adhesion effect.It therefore need to be in substrate surface graft polymers molecular brush conduct Anchor layer, but its grafting method is complicated, required expensive equipment, higher cost.
Summary of the invention
The present invention provides a kind of highly conductive biomass/nano metal flexible compound films of poly-dopamine auxiliary electroless deposition Preparation method, using the method simply impregnated, using biological material as substrate, poly-dopamine is Anchor Agent, effectively fixed gold Metal catalyst, so that redox reaction and deposited metal occur on the surface of biological material.Solves existing surface metal Change technical operation is cumbersome, and time-consuming, poorly conductive, the caducous problem of surface metal, simultaneously for various biomass material institutes Manufactured material of various shapes is applicable in.
The present invention is realized especially by following technical scheme:
A kind of highly conductive biomass/nano metal flexible compound film preparation method of poly-dopamine auxiliary electroless deposition, Include the following steps:
(1) biomass-based bottom is impregnated in dopamine buffer solution, and is continuously stirred under 100-500rpm revolving speed Gained film is repeatedly rinsed with deionized water, obtains to surface and be covered with the laminated film of poly-dopamine by 0.5-24h；
(2) above-mentioned laminated film is impregnated in (NH4)2PdCl4Aqueous solution in, stir 0.5- under 100-500rpm revolving speed 4h, so that the fixed upper catalyst of substrate surface；
(3) after repeatedly rinsing laminated film obtained by step (2) with deionized water, it is impregnated in copper or silver or gold at room temperature Or at least 5min in the plating solution of nickel, gained film are washed with deionized completely, are most dried to obtain surface afterwards with metal light Biomass/nano metal/nano metal the laminated film in pool.
TrisHCl buffer of the dopamine buffer described in step (1) for dopamine, concentration 0.5-5mg/ml, The pH=6.0-10.0 of TrisHCl buffer.
(NH described in step (2)4)2PdCl4Aqueous solution concentration be 0.1mg/ml-1mg/ml.
Dip time described in step (3) is 10~60min.
Dry to air-dry or being dried in vacuo described in step (3), vacuum drying temperature is 25-60 DEG C.
The biomass-based bottom includes with two dimension made of biomass material or three-dimensional material.
The biomass-based bottom be cellulose paper, cellulose, chitosan, hemicellulose or its be modified transparent membrane, Aeroge, hydrogel, fabric.
The plating solution of the copper is NaOH, CuSO4·5H2O, the mixed solution of sodium potassium tartrate tetrahydrate and reducing agent formaldehyde；The silver Plating solution be [Ag (NH3)2]NO3With the mixed liquor of sodium potassium tartrate tetrahydrate, the plating solution of the nickel is NiSO4·5H2O, sodium citrate, cream The mixed liquor of acid and dimethylamine borane；The plating solution of the gold is HAuCl4, NaOH, NH2OHHCl, Na2HPO4, NaS2O3· 5H2O and Na2SO3Mixed liquor.
The plating solution of the 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 the silver is by 1g/L [Ag (NH3)2]NO3It is formed with 5g/L sodium potassium tartrate tetrahydrate；The plating of the nickel Liquid is by 40g/L NiSO4·5H2O, 20g/L sodium citrate, the lactic acid of 10g/L and the dimethylamine borane of 1g/L are mixed with volume ratio 4:1 It closes, while adjusting pH with ammonium hydroxide is 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 Na2SO3It mixes.
The above method preparation biomass/nano metal laminated film, be formed by metal can secure adhesion in biology In matter substrate.The nitrogen-containing group of poly-dopamine can be firmly combined with catalyst metal ion, while play firm deposited The effect of metal.
The present invention is using the method that simply impregnates, using poly-dopamine as anchor layer, in cellulose substrate (or other biological matter Raw material is substrate) surface chemistry deposited metal.Prepared biomass/nano metal laminated film has good electric conductivity, The metal of deposition can be firmly attached to substrate surface simultaneously.Operation is simple for the preparation process, can be completed under room temperature. Prepared biomass/nano metal laminated film has very big application potential in fields such as energy storage, electronic equipments.
Compared with existing polymer surfaces metallization processes, the invention has the following advantages that
(1) operation of the present invention is simple, and time-consuming shorter, cost is relatively low；
(2) there is very strong adhesion strength between the metal and substrate on the laminated film surface prepared by the present invention, metal is not easy The metal layer even compact for falling off, and being formed.
(3) biomass material and dopamine (belonging to biomass) used in be all it is environmental-friendly, it is biodegradable and biological The material of compatibility, 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, implantable electronic device, energy storage, military industrial technology etc. are important The application range of biological material has been widened in field significantly.
Detailed description of the invention
Fig. 1 be in 1-4 of the embodiment of the present invention filter paper and cotton with the mass-change curve of copper facing time change.
Fig. 2 is that filter paper and cotton change with the square resistance of copper facing time change in 1-4 of the embodiment of the present invention.
Fig. 3 is that filter paper/Nanometer Copper laminated film SEM schemes (a) and energy spectrum diagram (b) in the embodiment of the present invention 2.
Fig. 4 is that cotton/Nanometer Copper conductive fabric SEM schemes (a) and energy spectrum diagram (b) in the embodiment of the present invention 2.
Fig. 5 is chitosan film/Nanometer Copper conductive composite film SEM figure in the embodiment of the present invention 5.
Fig. 6 is filter paper/Nanometer Copper laminated film resistance stability test chart in the embodiment of the present invention 3.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but not limited to this.
Embodiment 1
Clip a certain size filter paper or cotton be soaked in dopamine/TrisHCl buffer (pH=8.5) of 1mg/ml In, 6h is stirred under 300rpm revolving speed.After the resulting filter paper for being covered with poly-dopamine or cotton deionized water are repeatedly rinsed, leaching Steep (the NH in 0.1mg/ml4)2PdCl4Aqueous solution in, stir 1h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting After the filter paper or cotton of agent are repeatedly washed with deionized water, it is 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 the reaction was completed, surface is coated with metal Filter paper or after cotton rinsed well with deionized water, be placed in 50 DEG C of vacuum ovens dry.Weigh filter paper and cotton reaction The quality of front and back, and its resistance is tested with four probe sheet resistance testers.
Embodiment 2
Clip a certain size filter paper or cotton be soaked in dopamine/TrisHCl buffer (pH=8.5) of 1mg/ml In, 6h is stirred under 300rpm revolving speed.After the resulting filter paper for being covered with poly-dopamine or cotton deionized water are repeatedly rinsed, leaching Steep (the NH in 0.1mg/ml4)2PdCl4Aqueous solution in, stir 1h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting After the filter paper or cotton of agent are repeatedly washed with deionized water, be impregnated in 10min in the plating solution of copper, plating solution by 12g/L NaOH, 13g/L CuSO4·5H2O, 29g/L sodium potassium tartrate tetrahydrate and reducing agent 9.5ml/L formaldehyde composition.After the reaction was completed, surface is coated with After the filter paper or cotton of metal are rinsed well with deionized water, it is placed in 50 DEG C of vacuum ovens dry.Weigh filter paper and cotton The quality of front and back is reacted, and tests its resistance with four probe sheet resistance testers.
Embodiment 3
Clip a certain size filter paper or cotton be soaked in dopamine/TrisHCl buffer (pH=8.5) of 1mg/ml In, 6h is stirred under 300rpm revolving speed.After the resulting filter paper for being covered with poly-dopamine or cotton deionized water are repeatedly rinsed, leaching Steep (the NH in 0.1mg/ml4)2PdCl4Aqueous solution in, stir 1h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting After the filter paper or cotton of agent are repeatedly washed with deionized water, be impregnated in 30min in the plating solution of copper, plating solution by 12g/L NaOH, 13g/L CuSO4·5H2O, 29g/L sodium potassium tartrate tetrahydrate and reducing agent 9.5ml/L formaldehyde composition.After the reaction was completed, surface is coated with After the filter paper or cotton of metal are rinsed well with deionized water, it is placed in 50 DEG C of vacuum ovens dry.Weigh filter paper and cotton The quality of front and back is reacted, and tests its resistance with four probe sheet resistance testers.
Embodiment 4
Clip a certain size filter paper or cotton be soaked in dopamine/TrisHCl buffer (pH=8.5) of 1mg/ml In, 6h is stirred under 300rpm revolving speed.After the resulting filter paper for being covered with poly-dopamine or cotton deionized water are repeatedly rinsed, leaching Steep (the NH in 0.1mg/ml4)2PdCl4Aqueous solution in, stir 1h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting After the filter paper or cotton of agent are repeatedly washed with deionized water, be impregnated in 60min in the plating solution of copper, plating solution by 12g/L NaOH, 13g/L CuSO4·5H2O, 29g/L sodium potassium tartrate tetrahydrate and reducing agent 9.5ml/L formaldehyde composition.After the reaction was completed, surface is coated with After the filter paper or cotton of metal are rinsed well with deionized water, it is placed in 50 DEG C of vacuum ovens dry.Weigh filter paper and cotton The quality of front and back is reacted, and tests its resistance with four probe sheet resistance testers.
Embodiment 5
A certain size chitosan film of clip is soaked in dopamine/TrisHCl buffer (pH=8.5) of 2mg/ml In, 12h is stirred under 300rpm revolving speed.After the resulting chitosan film for being covered with poly-dopamine is repeatedly rinsed with deionized water, leaching Steep (the NH in 0.5mg/ml4)2PdCl4Aqueous solution in, stir 3h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting After the chitosan film of agent is repeatedly washed with deionized water, it is 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 the reaction was completed, surface is coated with metal After chitosan film is rinsed well with deionized water, it is placed in 50 DEG C of vacuum ovens dry.It is tested with four probe sheet resistance testers Its resistance.
Embodiment 6
A certain size chitosan film of clip is soaked in dopamine/TrisHCl buffer (pH=8.5) of 2mg/ml In, 12h is stirred under 300rpm revolving speed.After the resulting chitosan film for being covered with poly-dopamine is repeatedly rinsed with deionized water, leaching Steep (the NH in 0.5mg/ml4)2PdCl4Aqueous solution in, stir 3h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting After the chitosan film of agent is repeatedly washed with deionized water, it is impregnated in 10min in the plating solution of nickel.After the reaction was completed, surface is coated with After the chitosan film of metal is rinsed well with deionized water, its resistance is tested with four probe sheet resistance testers after drying at room temperature.
Embodiment 7
A certain size chitosan film of clip is soaked in dopamine/TrisHCl buffer (pH=8.5) of 2mg/ml In, 12h is stirred under 300rpm revolving speed.After the resulting chitosan film for being covered with poly-dopamine is repeatedly rinsed with deionized water, leaching Steep (the NH in 0.5mg/ml4)2PdCl4Aqueous solution in, stir 3h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting After the chitosan film of agent is repeatedly washed with deionized water, first it is impregnated in the plating solution for being impregnated in silver in the plating solution of copper after several seconds again 30min.After the reaction was completed, after the chitosan film that surface is coated with metal being rinsed well with deionized water, with four after drying at room temperature Probe sheet resistance tester tests its resistance.
Embodiment 8
A certain size chitosan film of clip is soaked in dopamine/TrisHCl buffer (pH=8.5) of 2mg/ml In, 12h is stirred under 300rpm revolving speed.After the resulting chitosan film for being covered with poly-dopamine is repeatedly rinsed with deionized water, leaching Steep (the NH in 0.5mg/ml4)2PdCl4Aqueous solution in, stir 3h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting After the chitosan film of agent is repeatedly washed with deionized water, first it is impregnated in the plating solution for being impregnated in gold in the plating solution of copper after several seconds again 30min.After the reaction was completed, after the chitosan film that surface is coated with metal being rinsed well with deionized water, with four after drying at room temperature Probe sheet resistance tester tests its resistance.
Fig. 1 is the mass-change curve of filter paper and cotton with copper facing time change.As seen from the figure, with biomass-based bottom The tenor of the extension of time in the plating solution, substrate surface plating is higher and higher.Illustrate that substrate surface can successfully adhere to gold Metal catalyst, so as to successfully plate metal.
Fig. 2 filter paper and cotton change with the square resistance of copper facing time change.It can be seen from the figure that either filter paper is also Cotton, with the extension of its time in metal plating liquid, square resistance is gradually reduced, the variance of surface square resistance by It is decrescence small, illustrate that coating is more and more uniform.In conjunction with Fig. 1, illustrate to increase with the time, coat of metal progressive additive and gradually It is even, cause resistance to be gradually reduced.It can reach 0.13 Ω/ when especially filter paper impregnates 10min in the plating solution, show that it is preferably led Electrically.
Fig. 3 filter paper/Nanometer Copper laminated film SEM figure and energy spectrum diagram.It can be seen from the figure that the inner fiber of filter paper is equal Metal nanoparticle is plated, illustrating filter paper, dipping is abundant when impregnating dopamine and subsequent metallic catalyst, to make Subsequent surface metalation it is also abundant, this is the superior reason of its electric conductivity.And coating is uniform, this is surface resistive square The lesser reason of difference.The surface known to energy spectrum diagram has plated one layer of copper particle.
Fig. 4 cotton/Nanometer Copper conductive fabric SEM figure and energy spectrum diagram.It can be seen from the figure that the inner fiber of filter paper is equal Metal nanoparticle is plated, illustrating filter paper, dipping is abundant when impregnating dopamine and subsequent metallic catalyst, to make Subsequent surface metalation it is also abundant, this is the superior reason of its electric conductivity.By the SEM of cotton and filter paper scheme comparison it is found that The hole of cotton is more, fine and close not as good as filter paper, therefore to enter the time required inside cotton longer for plating solution.So to reach phase Same electric conductivity, cotton are longer than the time needed for filter paper.
Fig. 5 chitosan film/Nanometer Copper conductive composite film SEM figure.As seen from the figure, the surface of chitosan film is equal It is even to plate one layer of copper nano particles, and copper nano particles are uniform in size, arrangement is fine and close.Compared to filter paper and cotton, chitosan is thin Film surface is more smooth, therefore the coating formed is also more smooth.
Fig. 6 filter paper/Nanometer Copper laminated film resistance stability test chart.As seen from the figure, conductive filter paper is in bending degree Resistance hardly changes in the case where difference, and it is stronger to show that conductive layer is bonded with filter paper, conductive in curved situation Layer will not fall off to will not influence its resistance variations.However in the case where multiple fold, because the folding strength of paper is limited, After folding 50 times or more, paper has been broken, and discontinuous so as to cause conductive layer, resistance greatly improves.
The resistance value of conductive composite film in 1 embodiment 5-8 of table
As shown in Table 1, the resistance of the film of copper is minimum in deposition, may be comparatively fast related with the deposition velocity of copper.Therefore thin Film needs the longer time to can be only achieved smaller resistance when depositing nickel, gold, silver.

Claims (10)

1. a kind of highly conductive biomass/nano metal flexible compound film preparation method, which comprises the steps of:
(1) biomass-based bottom is impregnated in dopamine buffer solution, and continuously stirs 0.5- under 100-500rpm revolving speed For 24 hours, gained film is repeatedly rinsed with deionized water, obtains to surface and is covered with the laminated film of poly-dopamine；
(2) above-mentioned laminated film is impregnated in (NH4)2PdCl4Aqueous solution in, stir 0.5-4h under 100-500rpm revolving speed, make Obtain the fixed upper catalyst of substrate surface；
(3) after repeatedly rinsing laminated film obtained by step (2) with deionized water, it is impregnated in copper or silver or gold or nickel at room temperature Plating solution at least 5min, gained film is washed with deionized completely, most afterwards through being dried to obtain surface with metallic luster Biomass/nano metal laminated film.
2. preparation method according to claim 1, which is characterized in that dopamine buffer described in step (1) is DOPA The TrisHCl buffer of amine, the pH=6.0-10.0 of concentration 0.5-5mg/ml, TrisHCl buffer.
3. preparation method according to claim 1 or 2, which is characterized in that (NH described in step (2)4)2PdCl4It is water-soluble The concentration of liquid is 0.1mg/ml-1mg/ml.
4. preparation method according to claim 1 or 2, which is characterized in that dip time described in step (3) be 10~ 60min。
5. preparation method according to claim 1 or 2, which is characterized in that dry for air-dried or vacuum described in step (3) Dry, vacuum drying temperature is 25-60 DEG C.
6. preparation method according to claim 1 or 2, which is characterized in that the biomass-based bottom includes with biomass original Two dimension or three-dimensional material made of material.
7. preparation method according to claim 6, which is characterized in that the biomass-based bottom is cellulose paper, fiber Element, chitosan, hemicellulose or its transparent membrane being modified, aeroge, hydrogel, fabric.
8. preparation method according to claim 1 or 2, which is characterized in that the plating solution of the copper is NaOH, CuSO4· 5H2O, the mixed solution of sodium potassium tartrate tetrahydrate and reducing agent formaldehyde；The plating solution of the silver is [Ag (NH3)2]NO3And sodium potassium tartrate tetrahydrate Mixed liquor, the plating solution of the nickel is NiSO4·5H2The mixed liquor of O, sodium citrate, lactic acid and dimethylamine borane；The gold Plating solution is HAuCl4, NaOH, NH2OHHCl, Na2HPO4, NaS2O3·5H2O and Na2SO3Mixed liquor.
9. preparation method according to claim 8, which is characterized in that the plating solution of the 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 the silver is by 1g/L [Ag (NH3)2]NO3It is formed with 5g/L sodium potassium tartrate tetrahydrate；The plating solution of the nickel is by 40g/L NiSO4·5H2O, 20g/L sodium citrate, The lactic acid of 10g/L and the dimethylamine borane of 1g/L are mixed with volume ratio 4:1, while adjusting pH with ammonium hydroxide is 8；The plating solution of gold For 3.3g/L HAuCl4, 0.4g/L NaOH, 6.95g/L NH2OHHCl, 11g/L Na2HPO4, 16g/L NaS2O3·5H2O With 40g/L Na2SO3It mixes.
10. biomass/nano metal laminated film of any one of claim 1~9 the method preparation.
CN201610414363.9A 2016-06-13 2016-06-13 A kind of highly conductive biomass/nano metal flexible compound film and preparation method thereof Active CN105887054B (en)

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
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

Publications (2)

Publication Number Publication Date
CN105887054A CN105887054A (en) 2016-08-24
CN105887054B true CN105887054B (en) 2019-01-18

Family

ID=56729522

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610414363.9A Active CN105887054B (en) 2016-06-13 2016-06-13 A kind of highly conductive biomass/nano metal flexible compound film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105887054B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN113096885B (en) * 2021-04-07 2022-09-09 佳雅(威海)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

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2737507B1 (en) * 1995-08-04 1997-09-26 Scps COMPOUND POROUS METALLIC OR METALLIC STRUCTURES, PRE-METALLIZED BY DEPOSITION OF A CONDUCTIVE POLYMER
DE19822075C2 (en) * 1998-05-16 2002-03-21 Enthone Gmbh Process for the metallic coating of substrates
CN102228884B (en) * 2011-06-20 2013-04-24 哈尔滨工业大学 Preparation method and application of super-hydrophobic/super-lipophilic material in oil-water separation field
CN103060779A (en) * 2012-12-04 2013-04-24 复旦大学 Preparation method of copper/modal fiber composite material
CN104549499B (en) * 2014-12-25 2017-02-22 华中科技大学 Preparation method and application of fibrous catalyst

Also Published As

Publication number Publication date
CN105887054A (en) 2016-08-24

Similar Documents

Publication Publication Date Title
CN105887054B (en) A kind of highly conductive biomass/nano metal flexible compound film and preparation method thereof
Olivera et al. Plating on acrylonitrile–butadiene–styrene (ABS) plastic: a review
Zhu et al. Mussel‐inspired flexible, durable, and conductive fibers manufacturing for finger‐monitoring sensors
Lu et al. Electromagnetic interference shielding, mechanical properties and water absorption of copper/bamboo fabric (Cu/BF) composites
Liu et al. Electroless nickel plating on APTHS modified wood veneer for EMI shielding
CN109423637B (en) Preparation method of high-conductivity material
CN102121194B (en) Conductive fabric manufacturing method and fabric manufactured by same
Lu et al. Adhesion enhancement between electroless nickel and polyester fabric by a palladium-free process
Zhang et al. Developing a superhydrophobic absorption-dominated electromagnetic shielding material by building clustered Fe3O4 nanoparticles on the copper-coated cellulose paper
Lu et al. Electroless nickel deposition on silane modified bamboo fabric through silver, copper or nickel activation
JP3845823B2 (en) Method for coating natural fibers with carbon nanotubes
CN103114437B (en) Method for chemically plating nickel at textile surface without using palladium
JP7093539B2 (en) Composite surface, its manufacturing method, and the members on which it is formed
CN109957144B (en) Preparation method of conductive filler with silver-plated surface
Sun et al. Electromagnetic interference shielding material from electroless copper plating on birch veneer
Hussain et al. A facile approach to synthesize highly conductive electrospun aramid nanofibers via electroless deposition
Han et al. Fabrication of a flexible and stretchable three-dimensional conductor based on Au–Ni@ graphene coated polyurethane sponge by electroless plating
CN106048564A (en) ABS plastic surface palladium-free activation metallization method
CN111501030B (en) Surface modification system before chemical plating and method for double modifying polymer substrate surface
CN114032675B (en) Conductive fiber and preparation method thereof
Geng et al. Conductive aramid fibers from electroless silver plating of crosslinked HPAMAM-modified PPTA: preparation and properties
Zhao et al. Fabrication of conductive soybean protein fiber for electromagnetic interference shielding through electroless copper plating
Zhang et al. A facile solution-based metallisation method without harsh conditions and expensive activators for paper substrate and its application in flexible supercapacitor
CN104762614B (en) A kind of high heat conduction graphite fibre surface is without palladium chemical-copper-plating process
CN115323790A (en) Electrically conductive textile element and method for producing the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant