CN108018014A - A kind of preparation method of novel nano silver conductive adhesive - Google Patents
A kind of preparation method of novel nano silver conductive adhesive Download PDFInfo
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- CN108018014A CN108018014A CN201810032612.7A CN201810032612A CN108018014A CN 108018014 A CN108018014 A CN 108018014A CN 201810032612 A CN201810032612 A CN 201810032612A CN 108018014 A CN108018014 A CN 108018014A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of preparation method of novel nano silver conductive adhesive, its preparation process is：A) nano silver linkage nano carbon tubes powder is prepared；B) nano-silver conductive glue is prepared；C) curing of nano-silver conductive glue.The advantage of the invention is that：The present invention is using modified carbon nano-tube as bearing substrate, nano-Ag particles are deposited using liquid phase reduction on the carbon nanotubes, since carbon nanotubes have passed through soda acid combined processing, there are a large amount of unsaturated bonds on its surface, surface tension substantially reduces, and carbon nanotubes pipe range is shorter, nano silver particles is largely uniformly attached to carbon nano tube surface, and cause carbon nanotubes and conducting resinl in micron silver strip between interracial contact effectively strengthen, improve the conductivity of conducting resinl；Meanwhile the addition of modified carbon nano-tube also effectively enhances the shock resistance and anti-shear performance of conducting resinl.
Description
Technical field
The present invention relates to conducting resinl technical field, and in particular to a kind of preparation method of nano-silver conductive glue.
Background technology
Connecting material is to influence the key factor of package technique linear resolution and bonding strength, connecting material anti-aging property
Quality directly affect the performance and application value of electronic product.At the same time with the development of society, the environmental consciousness of people
Gradually step up, the requirement it is also proposed that new is developed to connecting material, research and develop low, the environmental-friendly new material of energy consumption to substitute
High energy consumption, environmentally harmful traditional material have caused the great attention of people.Conducting resinl has solidification temperature low, differentiates
Rate is high, and thermomechanical property is good, technique it is simple and with material wetability it is good the advantages that, conducting resinl replace traditional Pb/Sn solders and
Solder is into development trend.
Silver is one of most widely used conductive adhesive filler, but there are valency to pick up height for silver conductive adhesive, and bonding strength is not
The shortcomings of high, and the silver-colored transport phenomena of generation is swallowed under DC electric field and moist conditions, electric conductivity is reduced, it is influenced and uses the longevity
Life.
For the conductive filler of presently commercially available silver conductive adhesive mainly based on micro-silver powder, its volume resistivity is bigger than normal, have impact on
In the particularly fine manufacturing application of many aspects.The size and pattern of nano silver directly influence its macroscopic property, pass through
The size and pattern for controlling nano-Ag particles can make its physics and chemical characteristic adjustable controllable, thus for nano-Ag particles ruler
The very little and pattern great researching value of control, currently has more and more researchers that the nano silver of special appearance is added to conduction
Glue improves its electric conductivity.
The patent of invention that granted patent number is ZL201019050027.0, notification number is 101781541 B of CN discloses one
The in-situ preparation method of kind nano silver/epoxy conductive adhesive, is prepared in situ nano silver first：By epoxy resin, curing agent, accelerating agent
Dissolving in a solvent, adds reducing agent, presoma is added after stirring, and vacuum distillation removing solvent, is further continued for reacting, obtains after reaction
The nano silver/epoxy resin complexes being uniformly dispersed in nano silver in epoxy resin-base.Above-mentioned preparation nano silver/
In epoxy resin composite, silver strip is added, stirring, prepares nano silver/epoxy conductive adhesive.Nano silver/ring prepared by the invention
Oxygen conducting resinl can be cured with high temperature, and the preferable high-performance conducting resin of electric conductivity is obtained by the low-temperature sintering of nano silver, and
In-situ preparation nano silver in epoxy resin-base, improves nano-particle in a polymer matrix scattered.The shortcomings that technology
In the more difficult removal completely of the component such as residual solvent in epoxy resin-base, cause intensity and the shock resistance of epoxide resin conductive adhesive
Performance etc. is decreased obviously, and have impact on conducting resinl service life and effect.
The patent of invention that granted patent number is ZL 201110066153.2, notification number is 102199407 B of CN discloses
A kind of high dispersive type nano silver and a kind of high-performance conducting resin.A kind of high-performance conducting resin is prepared by following methods：By ring
Oxygen resin curing agent is uniformly mixed with accelerating agent；High dispersive type nano silver is uniformly mixed with epoxy resin；, will at 10~25 DEG C
Epoxy curing agent, the mixture of accelerating agent composition be added drop-wise to the high dispersive type nano silver being kneaded, epoxy resin it is mixed
In being combined point, 3~10 hours are kneaded, obtain high-performance conducting resin.The nano silver of the invention is by surface modification and modification, i.e.,
Synthesize in nanometer silver surface that sulfydryl is contained in a kind of one end, other end contains by atom transfer radical polymerization (ATRP) technology
The macromolecule of amido, makes nano silver particles and epoxy resin have good intermiscibility, and has in the epoxy good
Dispersiveness, improve conductivity, and can avoid the problem that conductive silver during use exist silver migration；Also solve and work as
There are the defects of adhesive strength and insufficient shear strength in preceding conducting resinl.But it is higher that the patent still suffers from nano silver mix ratio,
The shortcomings of pre-treatment reaction is difficult to effectively control, limit the use of product.
Application No. 201310181828.7, the application for a patent for invention that publication No. is 103265924 A of CN disclose one kind
Silver-plated carbon nano tube epoxy resin conducting resinl, by carrying out chemical silvering to carbon nano tube surface, is made silver-plated carbon nanotubes, so
After be introduced into epoxy resin-base and prepare silver-plated carbon nano tube epoxy resin conducting resinl, availability is stable, dispersion performance
Well, the excellent epoxide resin conductive adhesive of electric conductivity, and preparation process is simple, it is easily operated.The invention is utilized through peracid
Property solution modification processing after carrier of the carbon nanotubes as silver particles, be distributed in epoxy resin-base, form carbon nanometer
Pipe/silver conductive network, still, due to carbon nanotubes in itself from reunion situation than more serious, in epoxy resin-base be difficult
It is uniformly dispersed, and it is poor with the intermiscibility of matrix, leverage comprehensive performance and the application of conducting resinl.
The content of the invention
The present invention proposes a kind of preparation method of new nano-silver conductive glue for above-mentioned technical problem, using liquid phase
Reduction method prepares carbon nano-tube modification composite Nano silver powder, and modified Nano silver powder is added in micro-silver powder, is changed with this
Electric conductivity, switching performance and the stability of kind silver conductive adhesive.
The present invention solves above-mentioned technical problem using following technical scheme：A kind of preparation side of novel nano silver conductive adhesive
Method, includes the following steps：A) nano silver linkage nano carbon tubes powder is prepared：The silver nitrate solution of 0.0lmol/L is configured first,
Polyvinylpyrrolidone, absolute ethyl alcohol, the carbon nanotubes and surface-active of surface-modified processing are separately added into the solution
Agent, stirs 30-60min in high speed dispersor, and whipping temp is 60 DEG C, mixed liquor is sufficiently mixed uniformly；Continue stirring simultaneously
5% hydrazine hydrate is slowly added dropwise, until precipitation no longer produces, solution becomes clarification；Again by the sediment deionized water after filtering and
Ethanol washing and filtering is in neutrality to pH value for several times, and constant weight is dried under vacuum at 40 DEG C, obtains nano silver linkage nano carbon tubes powder
End；B) nano-silver conductive glue is prepared：Using epoxy resin as matrix, plasticizer phthalic acid dibutyl ester is added, is added micro-
Prepared nano silver linkage nano carbon tubes powder, is put into wandering star type churning deaerator with 1440r/ in rice silver powder and step a
Min speed stirs 30-60min；Then epoxy resin is pressed：Triethanolamine part by weight 100：5-10 ratios add triethanolamine and make
Curing agent, is placed again into wandering star type churning deaerator stirring 30-60min, obtains nano-silver conductive glue；C) nano-silver conductive glue
Curing：Obtained nano-silver conductive glue in step b is stored at room temperature 6h makes its precuring, is then placed in 80 DEG C of perseverances in drying box
Temperature places 4h, it is fully cured；
Wherein, accounting of the carbon nanotubes in mixed liquor described in step a is 0.1-1.0wt%, the carbon nanotubes with
The mass ratio of surfactant is 1：0.1-2.0, the carbon nano tube surface pass through the composite modified processing of soda acid；
In step b, the epoxy resin, dibutyl phthalate, micro-silver powder and nano silver linkage nano carbon tubes
The weight ratio of powder is respectively 100：1-5：10-20：5-10.
Optimization, in the preparation method of above-mentioned nano-silver conductive glue, the modification of the carbon nanotubes includes following step
Suddenly：
1) alkali process：It is 0.1- with surfactant and mass concentration after carbon nanotubes is carried out airflow milling processing
2.0% strong base solution is mixed, and the quality of carbon nanotubes and surfactant is 1 than scope：0.1-2.0, mixed liquor warp
High speed dispersor stirring 1-2h is continued through after ultrasonic 30-60min, filtering, filtrate is crushed using airflow milling, then in N2Gas
Under atmosphere protection, 30-60min is reacted in 600-800 DEG C, product is in N2After being cooled down under atmosphere, then with deionized water washing suction filtration extremely
Neutrality, is dried under vacuum to constant weight at 40 DEG C, stand-by；
2) by nitric acid and mass concentration that mass concentration is 68% be 98% sulfuric acid with volume ratio 1：3 ratio mixing,
Add deionized water to be diluted, the addition of deionized water and the volume ratio of mixed acid amount are 0.1-2.0：1, mixed
Acid solution；
3) ratio by the mixed acid solution in the product in step 1 and step 2 according to weight/volume 1.0g/100ml
Example mixed, after mixed liquor ultrasound 30-60min, at 60-100 DEG C stirring and condensing reflux 3-10h, filtering, then spend from
Sub- water washs to neutrality filtrate repeatedly, and constant weight is dried under vacuum at 40 DEG C, crushes, that is, obtains by the composite modified place of soda acid
The carbon nanotubes of reason.
By carrying out soda acid combined processing to carbon nanotubes, the port and sidewall surfaces for making carbon nanotubes are etched, and are produced
A large amount of unsaturated bonds, are greatly lowered its surface tension, improve material compatibility；Meanwhile carbon nanotubes is truncated into length
Shorter form, considerably increases the surface area and dispersiveness of carbon nanotubes, makes the distribution of nano silver particles more uniform.And adopt
With common strong acid treatment method, modification, modified effect are eroded at the defects of being only capable of the pipe end or tube wall to carbon nanotubes
Poor, it is difficult largely uniformly to be deposited on carbon nano tube surface and form bonding to make nano silver particles, so as to have impact on conductive mesh
The structure of network.
Optimization, the caliber of the carbon nanotubes is 20-50nm, and pipe range is 0.5-100 μm, purity >=95%.
Optimization, it is characterised in that the surfactant is deoxysodium cholate, dodecyl sodium sulfate, fatty acid acyl
Amine, C12-13At least one of alcohol polyoxyethylene ether, poly-methyl acrylate and cetyl trimethylammonium bromide.
Optimization, the highly basic is sodium hydroxide or potassium hydroxide.
The advantage of the invention is that：The present invention is received using modified carbon nano-tube as bearing substrate using liquid phase reduction in carbon
Nano-Ag particles are deposited on mitron, since carbon nanotubes have passed through soda acid combined processing, there are a large amount of unsaturated bonds, table on its surface
Face tension force substantially reduces, and carbon nanotubes pipe range is shorter, nano silver particles is largely uniformly attached to carbon nano tube surface,
And cause carbon nanotubes and conducting resinl in micron silver strip between interracial contact effectively strengthen, improve the conduction of conducting resinl
Rate；Meanwhile the addition of modified carbon nano-tube also effectively enhances the shock resistance and anti-shear performance of conducting resinl.
Embodiment
Embodiment 1
Processing is modified to carbon nanotubes first, processing procedure includes the following steps：
1) alkali process：It is 0.1% with deoxysodium cholate and mass concentration after carbon nanotubes is carried out airflow milling processing
Sodium hydroxide solution is mixed, and the quality of carbon nanotubes and deoxysodium cholate is 1 than scope：0.5, mixed liquor is through ultrasound
High speed dispersor stirring 1h is continued through after 30min, filtering, filtrate is crushed using airflow milling, then in N2Under atmosphere protection,
60min is reacted in 600 DEG C, product is in N2After being cooled down under atmosphere, then filtered to neutrality with deionized water washing, vacuum is done at 40 DEG C
It is dry to constant weight, it is stand-by；
2) by nitric acid and mass concentration that mass concentration is 68% be 98% sulfuric acid with volume ratio 1：3 ratio mixing,
Add deionized water to be diluted, the addition of deionized water is 1 with the volume ratio of mixed acid amount：1, it is molten to obtain mixed acid
Liquid；
3) ratio by the mixed acid solution in the product in step 1 and step 2 according to weight/volume 1.0g/100ml
Example is mixed, after mixed liquor ultrasound 30min, stirring and condensing reflux 8h at 100 DEG C, and filtering, then with deionized water to mistake
Screening is washed to neutrality repeatedly, and constant weight is dried under vacuum at 40 DEG C, is crushed, that is, is obtained the carbon by the composite modified processing of soda acid and receive
Mitron.
The preparation method of novel nano silver conductive adhesive is prepared, is included the following steps：A) nano silver linkage nano carbon tubes are prepared
Powder：First configure 0.0lmol/L silver nitrate solution 250ml, be separately added into the solution 5ml polyvinylpyrrolidones,
10ml absolute ethyl alcohols, the carbon nanotubes 2.5g and deoxysodium cholate 2.5g of surface-modified processing, are stirred in high speed dispersor
30min is mixed, whipping temp is 60 DEG C, mixed liquor is sufficiently mixed uniformly；Continue to stir and 5% hydrazine hydrate is slowly added dropwise, until
Precipitation no longer produces, and solution becomes clarification；Again by the sediment deionized water after filtering and ethanol washing and filtering for several times to pH value
It is in neutrality, constant weight is dried under vacuum at 40 DEG C, obtains nano silver linkage nano carbon tubes powder；B) nano-silver conductive glue is prepared：
Using epoxy resin as matrix, according to weight ratio 100：5：20：10 ratios add plasticizer phthalic acid dibutyl ester, micron
Prepared nano silver linkage nano carbon tubes powder, is put into wandering star type churning deaerator with 1440r/min in silver powder and step a
Speed stirs 60 min；Then epoxy resin is pressed：Triethanolamine part by weight 100：10 ratios add triethanolamine and make curing agent,
Wandering star type churning deaerator stirring 60min is placed again into, obtains nano-silver conductive glue；C) curing of nano-silver conductive glue：Will
Obtained nano-silver conductive glue, which is stored at room temperature 6h, in step b makes its precuring, is then placed in 80 DEG C of constant temperature in drying box and places 4h,
It is fully cured, obtains final nano-silver conductive glue product.
Embodiment 2
Processing is modified to carbon nanotubes first, processing procedure includes the following steps：
1) alkali process：It is 0.5% with deoxysodium cholate and mass concentration after carbon nanotubes is carried out airflow milling processing
Sodium hydroxide solution is mixed, and the quality of carbon nanotubes and deoxysodium cholate is 1 than scope：1, mixed liquor is through ultrasonic 30min
After continue through high speed dispersor stirring 1h, filtering, filtrate using airflow milling crushing, then in N2Under atmosphere protection, in 700
DEG C reaction 60min, product is in N2After being cooled down under atmosphere, then filtered to neutrality with deionized water washing, be dried under vacuum at 40 DEG C
Constant weight, it is stand-by；
2) by nitric acid and mass concentration that mass concentration is 68% be 98% sulfuric acid with volume ratio 1：3 ratio mixing,
Add deionized water to be diluted, the addition of deionized water is 1 with the volume ratio of mixed acid amount：1, it is molten to obtain mixed acid
Liquid；
3) ratio by the mixed acid solution in the product in step 1 and step 2 according to weight/volume 1.0g/100ml
Example is mixed, after mixed liquor ultrasound 30min, stirring and condensing reflux 10h at 80 DEG C, and filtering, then with deionized water to mistake
Screening is washed to neutrality repeatedly, and constant weight is dried under vacuum at 40 DEG C, is crushed, that is, is obtained the carbon by the composite modified processing of soda acid and receive
Mitron.
The preparation method of novel nano silver conductive adhesive is prepared, is included the following steps：A) nano silver linkage nano carbon tubes are prepared
Powder：First configure 0.0lmol/L silver nitrate solution 250ml, be separately added into the solution 10ml polyvinylpyrrolidones,
10ml absolute ethyl alcohols, the carbon nanotubes 1.0g and deoxysodium cholate 2.0g of surface-modified processing, are stirred in high speed dispersor
60min is mixed, whipping temp is 60 DEG C, mixed liquor is sufficiently mixed uniformly；Continue to stir and 5% hydrazine hydrate is slowly added dropwise, until
Precipitation no longer produces, and solution becomes clarification；Again by the sediment deionized water after filtering and ethanol washing and filtering for several times to pH value
It is in neutrality, constant weight is dried under vacuum at 40 DEG C, obtains nano silver linkage nano carbon tubes powder；B) nano-silver conductive glue is prepared：
Using epoxy resin as matrix, according to weight ratio 100：10：30：10 ratios add plasticizer phthalic acid dibutyl ester, micron
Prepared nano silver linkage nano carbon tubes powder, is put into wandering star type churning deaerator with 1440r/min in silver powder and step a
Speed stirs 30 min；Then epoxy resin is pressed：Triethanolamine part by weight 100：5 ratios add triethanolamine and make curing agent,
Wandering star type churning deaerator stirring 60min is placed again into, obtains nano-silver conductive glue；C) curing of nano-silver conductive glue：Will
Obtained nano-silver conductive glue, which is stored at room temperature 6h, in step b makes its precuring, is then placed in 80 DEG C of constant temperature in drying box and places 4h,
It is fully cured, obtains final nano-silver conductive glue product.
Embodiment 3
Processing is modified to carbon nanotubes first, processing procedure includes the following steps：
1) alkali process：It is 0.1% with deoxysodium cholate and mass concentration after carbon nanotubes is carried out airflow milling processing
Sodium hydroxide solution is mixed, and the quality of carbon nanotubes and deoxysodium cholate is 1 than scope：1.5, mixed liquor is through ultrasound
High speed dispersor stirring 1h is continued through after 60min, filtering, filtrate is crushed using airflow milling, then in N2Under atmosphere protection,
30min is reacted in 800 DEG C, product is in N2After being cooled down under atmosphere, then filtered to neutrality with deionized water washing, vacuum is done at 40 DEG C
It is dry to constant weight, it is stand-by；
2) by nitric acid and mass concentration that mass concentration is 68% be 98% sulfuric acid with volume ratio 1：3 ratio mixing,
Add deionized water to be diluted, the addition of deionized water is 2 with the volume ratio of mixed acid amount：1, it is molten to obtain mixed acid
Liquid；
3) ratio by the mixed acid solution in the product in step 1 and step 2 according to weight/volume 1.0g/100ml
Example is mixed, after mixed liquor ultrasound 30min, stirring and condensing reflux 5h at 100 DEG C, and filtering, then with deionized water to mistake
Screening is washed to neutrality repeatedly, and constant weight is dried under vacuum at 40 DEG C, is crushed, that is, is obtained the carbon by the composite modified processing of soda acid and receive
Mitron.
The preparation method of novel nano silver conductive adhesive is prepared, is included the following steps：A) nano silver linkage nano carbon tubes are prepared
Powder：The silver nitrate solution 250ml of 0.0lmol/L is configured first, is separately added into 8ml polyvinylpyrrolidones, 8ml in the solution
Absolute ethyl alcohol, the carbon nanotubes 5.0g and deoxysodium cholate 2.5g of surface-modified processing, are stirred in high speed dispersor
60min, whipping temp are 60 DEG C, mixed liquor is sufficiently mixed uniformly；Continue to stir and 5% hydrazine hydrate is slowly added dropwise, until heavy
Shallow lake no longer produces, and solution becomes clarification；It is in pH value for several times with deionized water and ethanol washing and filtering by the sediment after filtering again
Neutrality, constant weight is dried under vacuum at 40 DEG C, obtains nano silver linkage nano carbon tubes powder；B) nano-silver conductive glue is prepared：With
Epoxy resin is as matrix, according to weight ratio 100：10：20：10 ratios add plasticizer phthalic acid dibutyl ester, micron silver
Prepared nano silver linkage nano carbon tubes powder in powder and step a, is put into wandering star type churning deaerator with 1440r/min speed
60 min of degree stirring；Then epoxy resin is pressed：Triethanolamine part by weight 100：10 ratios add triethanolamine and make curing agent, then
It is secondary to be put into wandering star type churning deaerator stirring 60min, obtain nano-silver conductive glue；C) curing of nano-silver conductive glue：Will step
Obtained nano-silver conductive glue, which is stored at room temperature 6h, in rapid b makes its precuring, is then placed in 80 DEG C of constant temperature in drying box and places 4h, makes
It is fully cured, and obtains final nano-silver conductive glue product.
Embodiment 4
Processing is modified to carbon nanotubes first, processing procedure includes the following steps：
1) alkali process：It is 1.0% with deoxysodium cholate and mass concentration after carbon nanotubes is carried out airflow milling processing
Sodium hydroxide solution is mixed, and the quality of carbon nanotubes and deoxysodium cholate is 1 than scope：2, mixed liquor is through ultrasonic 40min
After continue through high speed dispersor stirring 1h, filtering, filtrate using airflow milling crushing, then in N2Under atmosphere protection, in 700
DEG C reaction 50min, product is in N2After being cooled down under atmosphere, then filtered to neutrality with deionized water washing, be dried under vacuum at 40 DEG C
Constant weight, it is stand-by；
2) by nitric acid and mass concentration that mass concentration is 68% be 98% sulfuric acid with volume ratio 1：3 ratio mixing,
Add deionized water to be diluted, the addition of deionized water is 1 with the volume ratio of mixed acid amount：1, it is molten to obtain mixed acid
Liquid；
3) ratio by the mixed acid solution in the product in step 1 and step 2 according to weight/volume 1.0g/100ml
Example is mixed, after mixed liquor ultrasound 40min, stirring and condensing reflux 5h at 90 DEG C, and filtering, then with deionized water to filtering
Thing is washed to neutrality repeatedly, and constant weight is dried under vacuum at 40 DEG C, is crushed, that is, is obtained the carbon nanometer by the composite modified processing of soda acid
Pipe.
The preparation method of novel nano silver conductive adhesive is prepared, is included the following steps：A) nano silver linkage nano carbon tubes are prepared
Powder：First configure 0.0lmol/L silver nitrate solution 250ml, be separately added into the solution 8ml polyvinylpyrrolidones,
10ml absolute ethyl alcohols, the carbon nanotubes 5.0g and deoxysodium cholate 7.5g of surface-modified processing, are stirred in high speed dispersor
60min is mixed, whipping temp is 60 DEG C, mixed liquor is sufficiently mixed uniformly；Continue to stir and 5% hydrazine hydrate is slowly added dropwise, until
Precipitation no longer produces, and solution becomes clarification；Again by the sediment deionized water after filtering and ethanol washing and filtering for several times to pH value
It is in neutrality, constant weight is dried under vacuum at 40 DEG C, obtains nano silver linkage nano carbon tubes powder；B) nano-silver conductive glue is prepared：
Using epoxy resin as matrix, according to weight ratio 100：10：15：10 ratios add plasticizer phthalic acid dibutyl ester, micron
Prepared nano silver linkage nano carbon tubes powder, is put into wandering star type churning deaerator with 1440r/min in silver powder and step a
Speed stirs 60 min；Then epoxy resin is pressed：Triethanolamine part by weight 100：8 ratios add triethanolamine and make curing agent,
Wandering star type churning deaerator stirring 60min is placed again into, obtains nano-silver conductive glue；C) curing of nano-silver conductive glue：Will
Obtained nano-silver conductive glue, which is stored at room temperature 6h, in step b makes its precuring, is then placed in 80 DEG C of constant temperature in drying box and places 4h,
It is fully cured, obtains final nano-silver conductive glue product.
Embodiment 5
Processing is modified to carbon nanotubes first, processing procedure includes the following steps：
1) alkali process：It is 2.0% with deoxysodium cholate and mass concentration after carbon nanotubes is carried out airflow milling processing
Sodium hydroxide solution is mixed, and the quality of carbon nanotubes and deoxysodium cholate is 1 than scope：2, mixed liquor is through ultrasonic 50min
After continue through high speed dispersor stirring 1h, filtering, filtrate using airflow milling crushing, then in N2Under atmosphere protection, in 750
DEG C reaction 30min, product is in N2After being cooled down under atmosphere, then filtered to neutrality with deionized water washing, be dried under vacuum at 40 DEG C
Constant weight, it is stand-by；
2) by nitric acid and mass concentration that mass concentration is 68% be 98% sulfuric acid with volume ratio 1：3 ratio mixing,
Add deionized water to be diluted, the addition of deionized water is 0.5 with the volume ratio of mixed acid amount：1, it is molten to obtain mixed acid
Liquid；
3) ratio by the mixed acid solution in the product in step 1 and step 2 according to weight/volume 1.0g/100ml
Example is mixed, after mixed liquor ultrasound 50min, stirring and condensing reflux 5h at 90 DEG C, and filtering, then with deionized water to filtering
Thing is washed to neutrality repeatedly, and constant weight is dried under vacuum at 40 DEG C, is crushed, that is, is obtained the carbon nanometer by the composite modified processing of soda acid
Pipe.
The preparation method of novel nano silver conductive adhesive is prepared, is included the following steps：A) nano silver linkage nano carbon tubes are prepared
Powder：First configure 0.0lmol/L silver nitrate solution 250ml, be separately added into the solution 10ml polyvinylpyrrolidones,
8ml absolute ethyl alcohols, the carbon nanotubes 5.0g and deoxysodium cholate 5.0g of surface-modified processing, are stirred in high speed dispersor
60min is mixed, whipping temp is 60 DEG C, mixed liquor is sufficiently mixed uniformly；Continue to stir and 5% hydrazine hydrate is slowly added dropwise, until
Precipitation no longer produces, and solution becomes clarification；Again by the sediment deionized water after filtering and ethanol washing and filtering for several times to pH value
It is in neutrality, constant weight is dried under vacuum at 40 DEG C, obtains nano silver linkage nano carbon tubes powder；B) nano-silver conductive glue is prepared：
Using epoxy resin as matrix, according to weight ratio 100：10：15：5 ratios add plasticizer phthalic acid dibutyl ester, micron
Prepared nano silver linkage nano carbon tubes powder, is put into wandering star type churning deaerator with 1440r/min in silver powder and step a
Speed stirs 60 min；Then epoxy resin is pressed：Triethanolamine part by weight 100：10 ratios add triethanolamine and make curing agent,
Wandering star type churning deaerator stirring 60min is placed again into, obtains nano-silver conductive glue；C) curing of nano-silver conductive glue：Will
Obtained nano-silver conductive glue, which is stored at room temperature 6h, in step b makes its precuring, is then placed in 80 DEG C of constant temperature in drying box and places 4h,
It is fully cured, obtains final nano-silver conductive glue product.
Silver conductive adhesive electric conductivity is tested
Obtained nano-silver conductive glue electric conductivity is tested with the following method in above-described embodiment：5 are carved in glass plate
Bar length is respectively the groove of 5O, 1O and 5mm, and silver conductive adhesive is cured in groove, is surveyed with intelligent low resistance tester
Determine both ends resistance, volume resistivity is then calculated according to formula, is finally averaged, calculation formula is shown in (1)：
ρ v are volume resistivity in formula, Ω cm；A is asked away from m for two contact point of resistance meter；B is groove width, m；C is
Groove is high, m；V is voltage, V；J is electric current, A.
Silver conductive adhesive bonding strength is tested
Bonding strength test is carried out with reference to national standard GB 7124-86, and experiment is tested using microcomputer universal material at room temperature
Machine carries out, and fixture translational speed is 50mm/min, is clamping between experimental machine and sample, each conducting resinl sample makees 5 connections
Strength test, takes its average value, meter
Formula is calculated to see (2)：
In formula：б is bonding strength, MPa；Pulling force when f is fails, N；S is connection area, mm2.
Meanwhile synchronism detection has been carried out to commercially available silver filling epoxide resin conductive adhesive, its comparing result is as shown in table 1：
Table 1
As known from Table 1, it can effectively improve conducting resinl by adding carbon nano-tube modification nano-silver powder in micro-silver powder
Electric conductivity and switching performance, volume resistivity is up to 1.997*10-4Ω cm, are significantly better than existing conducting resinl product, together
When bonding strength up to 22.9Mpa, the condition of commercial Application is complied fully with comprehensive performance；Moreover, filler addition content is relatively low,
Also there is some superiority in cost.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention is described in detail, it will be understood by those of ordinary skill in the art that：It still can be to foregoing each implementation
Technical solution described in example is modified, or carries out equivalent substitution to which part technical characteristic；And these modification or
Replace, the essence of appropriate technical solution is departed from the spirit and scope of various embodiments of the present invention technical solution.
Claims (5)
1. a kind of preparation method of novel nano silver conductive adhesive, it is characterised in that include the following steps：
A) nano silver linkage nano carbon tubes powder is prepared：The silver nitrate solution of 0.0lmol/L is configured first, is added respectively in the solution
Enter polyvinylpyrrolidone, absolute ethyl alcohol, the carbon nanotubes of surface-modified processing and surfactant, in high speed dispersor
Middle stirring 30-60min, whipping temp are 60 DEG C, mixed liquor is sufficiently mixed uniformly；Continue to stir and 5% hydration is slowly added dropwise
Hydrazine, until precipitation no longer produces, solution becomes clarification；Again by the sediment deionized water after filtering and ethanol washing and filtering for several times
It is in neutrality to pH value, constant weight is dried under vacuum at 40 DEG C, obtains nano silver linkage nano carbon tubes powder；
B) nano-silver conductive glue is prepared：Using epoxy resin as matrix, plasticizer phthalic acid dibutyl ester is added, is added micro-
Prepared nano silver linkage nano carbon tubes powder, is put into wandering star type churning deaerator with 1440r/ in rice silver powder and step a
Min speed stirs 30-60min；Then epoxy resin is pressed：Triethanolamine part by weight 100：5-10 ratios add triethanolamine and make
Curing agent, is placed again into wandering star type churning deaerator stirring 30-60min, obtains nano-silver conductive glue；
C) curing of nano-silver conductive glue：Obtained nano-silver conductive glue in step b is stored at room temperature 6h makes its precuring, then
It is put into 80 DEG C of constant temperature in drying box and places 4h, it is fully cured；
Wherein, accounting of the carbon nanotubes in mixed liquor described in step a is 0.1-1.0wt%, the carbon nanotubes and surface
The mass ratio of activating agent is 1：0.1-2.0, the carbon nano tube surface pass through the composite modified processing of soda acid；
In step b, the epoxy resin, dibutyl phthalate, micro-silver powder and nano silver linkage nano carbon tubes powder
Weight ratio be respectively 100：1-5：10-20：5-10.
A kind of 2. preparation method of novel nano silver conductive adhesive as claimed in claim 1, it is characterised in that the carbon nanotubes
Modification include the following steps：
1) alkali process：It is the strong of 0.1-2.0% with surfactant and mass concentration after carbon nanotubes is carried out airflow milling processing
Aqueous slkali is mixed, and the quality of carbon nanotubes and surfactant is 1 than scope：0.1-2.0, mixed liquor is through ultrasonic 30-
High speed dispersor stirring 1-2h is continued through after 60min, filtering, filtrate is crushed using airflow milling, then in N2Atmosphere protection
Under, 30-60min is reacted in 600-800 DEG C, product is in N2After being cooled down under atmosphere, then filtered to neutrality with deionized water washing, 40
Constant weight is dried under vacuum at DEG C, it is stand-by；
2) by nitric acid and mass concentration that mass concentration is 68% be 98% sulfuric acid with volume ratio 1：3 ratio mixing, then add
Enter deionized water to be diluted, the addition of deionized water and the volume ratio of mixed acid amount are 0.1-2.0：1, it is molten to obtain mixed acid
Liquid；
3) mixed acid solution in the product and step 2 in step 1 is carried out according to the ratio of weight/volume 1.0g/100ml
Mixing, after mixed liquor ultrasound 30-60min, stirring and condensing reflux 3-10h at 60-100 DEG C, filtering, then with deionized water pair
Filtrate is washed to neutrality repeatedly, and constant weight is dried under vacuum at 40 DEG C, is crushed, that is, is obtained the carbon by the composite modified processing of soda acid
Nanotube.
A kind of 3. preparation method of novel nano silver conductive adhesive as claimed in claim 2, it is characterised in that the carbon nanotubes
Caliber be 20-50nm, pipe range is 0.5-100 μm, purity >=95%.
A kind of 4. preparation method of novel nano silver conductive adhesive as any one of claim 1 or 2, it is characterised in that
The surfactant is deoxysodium cholate, dodecyl sodium sulfate, fatty acid amide, C12-13Alcohol polyoxyethylene ether, poly- methyl
At least one of acrylates and cetyl trimethylammonium bromide.
5. a kind of preparation method of novel nano silver conductive adhesive as claimed in claim 2, it is characterised in that the highly basic is hydrogen
Sodium oxide molybdena or potassium hydroxide.
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| CN109777335A (en) * | 2019-01-18 | 2019-05-21 | 昆明贵金属研究所 | A kind of carbon nano-tube modified method for preparing high heat-conductivity conducting glue of nano silver |
| CN110079266A (en) * | 2019-03-26 | 2019-08-02 | 昆明理工大学 | A kind of nano silver is carbon nano-tube modified to prepare high heat-conductivity conducting glue and preparation method thereof |
| CN111403081A (en) * | 2020-03-19 | 2020-07-10 | 深圳市金百纳纳米科技有限公司 | Carbon nanotube conductive slurry and preparation method thereof |
| CN113201301A (en) * | 2021-04-09 | 2021-08-03 | 北京科技大学 | Modification method of carbon nano tube for copper-clad plate |
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| CN113638240A (en) * | 2021-07-19 | 2021-11-12 | 苏州昆盛堂智能科技有限公司 | Method for implanting nano-silver into fabric |
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