CN108018014B - A kind of preparation method of nano-silver conductive glue - Google Patents
A kind of preparation method of nano-silver conductive glue Download PDFInfo
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- CN108018014B CN108018014B CN201810032612.7A CN201810032612A CN108018014B CN 108018014 B CN108018014 B CN 108018014B CN 201810032612 A CN201810032612 A CN 201810032612A CN 108018014 B CN108018014 B CN 108018014B
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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
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- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K7/00—Use of ingredients characterised by shape
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- C08K7/24—Expanded, porous or hollow particles inorganic
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Abstract
The invention discloses a kind of preparation method of nano-silver conductive glue, preparation process is：A) nano silver linkage nano carbon tubes powder is prepared；B) nano-silver conductive glue is prepared；C) solidification 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 nanotube have passed through soda acid combined processing, there are a large amount of unsaturated bonds on its surface, surface tension substantially reduces, and carbon nanotube pipe range is shorter, and nano silver particles is enable largely uniformly to be attached to carbon nano tube surface, and make carbon nanotube and conducting resinl in micron silver strip between interfacial contact effectively enhance, 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 fields, 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.Simultaneously with the development of society, the environmental consciousness of people
It is gradually increased, the requirement it is also proposed that new that develops to connecting material, the research and development new material that low energy consumption, environmental-friendly is to replace
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, it is simple for process and good with material wetability the advantages that, conducting resinl replace traditional Pb/Sn solders and
Solder is at development trend.
Silver is one of most widely used conductive adhesive filler, but there are valences 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, so that electric conductivity is reduced, influences it and use the longevity
Life.
For the conductive filler of presently commercially available silver conductive adhesive mainly based on micro-silver powder, volume resistivity is bigger than normal, affects
In the especially fine manufacturing application of many aspects.The size and shape of nano silver directly influences its macroscopic property, passes through
The size and shape of control 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, is added reducing agent, presoma is added after stirring, and vacuum distillation removing solvent, is further continued for reacting, obtain 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, nano silver/epoxy conductive adhesive is prepared in stirring.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 the dispersion of nano-particle in a polymer matrix.The shortcomings that technology
It is in epoxy resin-base that the ingredients such as residual solvent are more difficult to completely remove, leads to intensity and the shock resistance of epoxide resin conductive adhesive
Performance etc. is decreased obviously, and affects 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；It, will at 10~25 DEG C
The mixture that epoxy curing agent, accelerating agent form is added drop-wise to the mixed of the high dispersive type nano silver, epoxy resin being kneaded
In being combined point, 3~10 hours are kneaded, high-performance conducting resin is obtained.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
Dispersibility, improve conductivity, and can avoid conductive silver and there are problems that silver migrates during use；Also it solves and works as
There are adhesive strengths and the insufficient defect of shear strength in preceding conducting resinl.But the patent is there are still nano silver mix ratio is higher,
The shortcomings of pre-treatment reaction is difficult to effectively control, limits the use of product.
Application No. is the applications for a patent for invention that 201310181828.7, publication No. is 103265924 A of CN to disclose one kind
By carrying out chemical silvering to carbon nano tube surface silver-plated carbon nanotube is made, so in silver-plated carbon nano tube epoxy resin conducting resinl
It will be introduced into epoxy resin-base afterwards and prepare silver-plated carbon nano tube epoxy resin conducting resinl, availability stabilization, 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 treated carrier of the carbon nanotube as silver particles, is distributed in epoxy resin-base, forms carbon nanometer
Pipe/silver conductive network, still, due to carbon nanotube itself from reunion situation than more serious, in epoxy resin-base be difficult
It is uniformly dispersed, and poor with the intermiscibility of matrix, leverages comprehensive performance and the application of conducting resinl.
Invention content
The present invention proposes a kind of preparation method of novel nano-silver conductive glue in view of the above technical problems, 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 method of nano-silver conductive glue, packet
Include following steps：A) nano silver linkage nano carbon tubes powder is prepared：The silver nitrate solution for configuring 0.0lmol/L first, in solution
In be separately added into polyvinylpyrrolidone, absolute ethyl alcohol, the carbon nanotube of surface-modified processing and surfactant, in height
30-60min is stirred in fast dispersion machine, whipping temp is 60 DEG C, and mixed liquor is made to be sufficiently mixed uniformly；Continue to stir and be slowly added dropwise
5% hydrazine hydrate, until precipitation no longer generates, solution becomes clarification；Filtered sediment is washed with deionized water and ethyl alcohol again
Filtered several times to pH value is in neutrality, and constant weight is dried under vacuum at 40 DEG C, obtains nano silver linkage nano carbon tubes powder；B) it prepares
Nano-silver conductive glue：Using epoxy resin as matrix, plasticizer phthalic acid dibutyl ester is added, adds micro-silver powder and step
Prepared nano silver linkage nano carbon tubes powder in rapid a, is put into wandering star type churning deaerator and is stirred with 1440r/min speed
30-60min；Then epoxy resin is pressed：Triethanolamine weight ratio 100：5-10 ratios are added triethanolamine and make curing agent, again
It is put into wandering star type churning deaerator stirring 30-60min, obtains nano-silver conductive glue；C) solidification of nano-silver conductive glue：It will step
Nano-silver conductive glue obtained, 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；
Wherein, accounting of the carbon nanotube in mixed liquor described in step a be 0.1-1.0wt%, the carbon nanotube 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 nanotube includes following step
Suddenly：
1) alkali process：It is 0.1-2.0% with surfactant and mass concentration after carbon nanotube is carried out airflow milling processing
Strong base solution mixed, the mass ratio ranging from 1 of carbon nanotube and surfactant：0.1-2.0, mixed liquor is through ultrasound
High speed dispersor stirring 1-2h is continued through after 30-60min, filtering, filtrate is crushed using airflow milling, then in N2Atmosphere is protected
Under shield, 30-60min is reacted in 600-800 DEG C, product is in N2Under atmosphere after cooling, then is washed and is filtered to neutrality with deionized water,
Constant weight is dried under vacuum at 40 DEG C, for use；
2) by nitric acid and mass concentration that mass concentration is 68% be 98% sulfuric acid with volume ratio 1：3 ratio mixing,
It adds deionized water to be diluted, the addition of deionized water is 0.1-2.0 with the volume ratio of mixed acid amount：1, it is mixed
Acid solution；
3) by the mixed acid solution in the product and step 2 in step 1 according to the ratio of weight/volume 1.0g/100ml
It is mixed, after mixed liquor ultrasound 30-60min, stirring and condensing reflux 3-10h at 60-100 DEG C, filtering, then use deionization
Water washs filtrate repeatedly to neutrality, and constant weight is dried under vacuum at 40 DEG C, crushes to get to by the composite modified processing of soda acid
Carbon nanotube.
By carrying out soda acid combined processing to carbon nanotube, so that the port of carbon nanotube and sidewall surfaces is etched, generate
A large amount of unsaturated bonds make its surface tension be greatly lowered, improve material compatibility；Meanwhile carbon nanotube is truncated into length
Shorter form considerably increases the surface area and dispersibility of carbon nanotube, keeps the distribution of nano silver particles more uniform.And it adopts
With common strong acid treatment method, it is only capable of eroding modification, modified effect to the pipe end of carbon nanotube or the fault location of tube wall
Poor, it is difficult largely uniformly to be deposited on carbon nano tube surface and form bonding to make nano silver particles, to affect conductive mesh
The structure of network.
Optimization, the caliber of the carbon nanotube is 20-50nm, and pipe range is 0.5-100 μm, purity >=95%.
Optimization, which is characterized 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 nanotube have passed through soda acid combined processing, there are a large amount of unsaturated bonds, tables on surface
Face tension substantially reduces, and carbon nanotube pipe range is shorter, and nano silver particles is enable largely uniformly to be attached to carbon nano tube surface,
And make carbon nanotube and conducting resinl in micron silver strip between interfacial contact effectively enhance, 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.
Specific implementation mode
Embodiment 1
Processing is modified to carbon nanotube first, processing procedure includes the following steps：
1) alkali process：After carbon nanotube is carried out airflow milling processing, the hydrogen for being 0.1% with deoxysodium cholate and mass concentration
Sodium hydroxide solution is mixed, the mass ratio ranging from 1 of carbon nanotube and deoxysodium cholate：0.5, 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 600
DEG C reaction 60min, product is in N2Under atmosphere it is cooling after, then filtered to neutrality with deionized water washing, be dried under vacuum at 40 DEG C
Constant weight, for use；
2) by nitric acid and mass concentration that mass concentration is 68% be 98% sulfuric acid with volume ratio 1：3 ratio mixing,
It adds 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) by the mixed acid solution in the product and step 2 in step 1 according to the ratio of weight/volume 1.0g/100ml
It is mixed, after mixed liquor ultrasound 30min, stirring and condensing reflux 8h at 100 DEG C, filtering, then with deionized water to filtering
Object is washed repeatedly to neutrality, is dried under vacuum to constant weight at 40 DEG C, is crushed to get to the carbon nanometer Jing Guo the composite modified processing of soda acid
Pipe.
The preparation method for preparing nano-silver conductive glue, includes the following steps：A) nano silver linkage nano carbon tubes powder is prepared：
The silver nitrate solution 250ml for configuring 0.0lmol/L first, it is anhydrous to be separately added into 5ml polyvinylpyrrolidones, 10ml in the solution
Ethyl alcohol, the carbon nanotube 2.5g of surface-modified processing and deoxysodium cholate 2.5g, stir 30min in high speed dispersor,
Whipping temp is 60 DEG C, and mixed liquor is made to be sufficiently mixed uniformly；Continue to stir and be slowly added dropwise 5% hydrazine hydrate, until precipitation is no longer
It generates, solution becomes clarification；Filtered sediment deionized water and ethyl alcohol filtered several times to pH value is washed again to be in neutrality,
It is dried under vacuum to constant weight at 40 DEG C, obtains nano silver linkage nano carbon tubes powder；B) nano-silver conductive glue is prepared：With epoxy resin
As matrix, according to weight ratio 100：5：20：Plasticizer phthalic acid dibutyl ester, micro-silver powder and step a is added in 10 ratios
In prepared nano silver linkage nano carbon tubes powder, be put into wandering star type churning deaerator and stirred with 1440r/min speed
60min；Then epoxy resin is pressed：Triethanolamine weight ratio 100：10 ratios are added triethanolamine and make curing agent, are placed again into
Wandering star type churning deaerator stirs 60min, obtains nano-silver conductive glue；C) solidification of nano-silver conductive glue：It will be made in step b
The nano-silver conductive glue obtained, which is stored at room temperature 6h, makes its precuring, is then placed in 80 DEG C of constant temperature in drying box and places 4h, makes it completely
Solidification, obtains final nano-silver conductive glue product.
Embodiment 2
Processing is modified to carbon nanotube first, processing procedure includes the following steps：
1) alkali process：After carbon nanotube is carried out airflow milling processing, the hydrogen for being 0.5% with deoxysodium cholate and mass concentration
Sodium hydroxide solution is mixed, the mass ratio ranging from 1 of carbon nanotube and deoxysodium cholate：1, mixed liquor is after ultrasonic 30min
High speed dispersor stirring 1h is continued through, filtering, filtrate is crushed using airflow milling, then in N2Under atmosphere protection, in 700 DEG C
60min is reacted, product is in N2Under atmosphere it is cooling after, then filtered to neutrality with deionized water washing, perseverance be dried under vacuum at 40 DEG C
Weight, for use；
2) by nitric acid and mass concentration that mass concentration is 68% be 98% sulfuric acid with volume ratio 1：3 ratio mixing,
It adds 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) by the mixed acid solution in the product and step 2 in step 1 according to the ratio of weight/volume 1.0g/100ml
It is mixed, after mixed liquor ultrasound 30min, stirring and condensing reflux 10h at 80 DEG C, filtering, then with deionized water to filtering
Object is washed repeatedly to neutrality, is dried under vacuum to constant weight at 40 DEG C, is crushed to get to the carbon nanometer Jing Guo the composite modified processing of soda acid
Pipe.
The preparation method for preparing nano-silver conductive glue, includes the following steps：A) nano silver linkage nano carbon tubes powder is prepared：
First configure 0.0lmol/L silver nitrate solution 250ml, be separately added into the solution 10ml polyvinylpyrrolidones, 10ml without
Water-ethanol, the carbon nanotube 1.0g of surface-modified processing and deoxysodium cholate 2.0g, are stirred in high speed dispersor
60min, whipping temp are 60 DEG C, and mixed liquor is made to be sufficiently mixed uniformly；Continue to stir and be slowly added dropwise 5% hydrazine hydrate, until heavy
Shallow lake no longer generates, and solution becomes clarification；Filtered sediment deionized water and ethyl alcohol, which are washed filtered several times to pH value, again is in
Neutrality is dried under vacuum to constant weight 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 100：10：30：Plasticizer phthalic acid dibutyl ester, micron silver is added in 10 ratios
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
Degree stirring 30min；Then epoxy resin is pressed：Triethanolamine weight ratio 100：5 ratios are added triethanolamine and make curing agent, again
It is put into wandering star type churning deaerator stirring 60min, obtains nano-silver conductive glue；C) solidification of nano-silver conductive glue：By step b
In nano-silver conductive glue obtained be stored at room temperature 6h and make its precuring, be then placed in 80 DEG C of constant temperature in drying box and place 4h, make it
It is fully cured, obtains final nano-silver conductive glue product.
Embodiment 3
Processing is modified to carbon nanotube first, processing procedure includes the following steps：
1) alkali process：After carbon nanotube is carried out airflow milling processing, the hydrogen for being 0.1% with deoxysodium cholate and mass concentration
Sodium hydroxide solution is mixed, the mass ratio ranging from 1 of carbon nanotube and deoxysodium cholate：1.5, mixed liquor is through ultrasonic 60min
After continue through high speed dispersor stirring 1h, filtering, filtrate using airflow milling crushing, then in N2Under atmosphere protection, in 800
DEG C reaction 30min, product is in N2Under atmosphere it is cooling after, then filtered to neutrality with deionized water washing, be dried under vacuum at 40 DEG C
Constant weight, for use；
2) by nitric acid and mass concentration that mass concentration is 68% be 98% sulfuric acid with volume ratio 1：3 ratio mixing,
It adds 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) by the mixed acid solution in the product and step 2 in step 1 according to the ratio of weight/volume 1.0g/100ml
It is mixed, after mixed liquor ultrasound 30min, stirring and condensing reflux 5h at 100 DEG C, filtering, then with deionized water to filtering
Object is washed repeatedly to neutrality, is dried under vacuum to constant weight at 40 DEG C, is crushed to get to the carbon nanometer Jing Guo the composite modified processing of soda acid
Pipe.
The preparation method for preparing nano-silver conductive glue, includes the following steps：A) nano silver linkage nano carbon tubes powder is prepared：
The silver nitrate solution 250ml for configuring 0.0lmol/L first, it is anhydrous to be separately added into 8ml polyvinylpyrrolidones, 8ml in the solution
Ethyl alcohol, the carbon nanotube 5.0g of surface-modified processing and deoxysodium cholate 2.5g, stir 60min in high speed dispersor,
Whipping temp is 60 DEG C, and mixed liquor is made to be sufficiently mixed uniformly；Continue to stir and be slowly added dropwise 5% hydrazine hydrate, until precipitation is no longer
It generates, solution becomes clarification；Filtered sediment deionized water and ethyl alcohol filtered several times to pH value is washed again to be in neutrality,
It is dried under vacuum to constant weight at 40 DEG C, obtains nano silver linkage nano carbon tubes powder；B) nano-silver conductive glue is prepared：With epoxy resin
As matrix, according to weight ratio 100：10：20：Plasticizer phthalic acid dibutyl ester, micro-silver powder and step a is added in 10 ratios
In prepared nano silver linkage nano carbon tubes powder, be put into wandering star type churning deaerator and stirred with 1440r/min speed
60min；Then epoxy resin is pressed：Triethanolamine weight ratio 100：10 ratios are added triethanolamine and make curing agent, are placed again into
Wandering star type churning deaerator stirs 60min, obtains nano-silver conductive glue；C) solidification of nano-silver conductive glue：It will be made in step b
The nano-silver conductive glue obtained, which is stored at room temperature 6h, makes its precuring, is then placed in 80 DEG C of constant temperature in drying box and places 4h, makes it completely
Solidification, obtains final nano-silver conductive glue product.
Embodiment 4
Processing is modified to carbon nanotube first, processing procedure includes the following steps：
1) alkali process：After carbon nanotube is carried out airflow milling processing, the hydrogen for being 1.0% with deoxysodium cholate and mass concentration
Sodium hydroxide solution is mixed, the mass ratio ranging from 1 of carbon nanotube and deoxysodium cholate：2, mixed liquor is after ultrasonic 40min
High speed dispersor stirring 1h is continued through, filtering, filtrate is crushed using airflow milling, then in N2Under atmosphere protection, in 700 DEG C
50min is reacted, product is in N2Under atmosphere it is cooling after, then filtered to neutrality with deionized water washing, perseverance be dried under vacuum at 40 DEG C
Weight, for use；
2) by nitric acid and mass concentration that mass concentration is 68% be 98% sulfuric acid with volume ratio 1：3 ratio mixing,
It adds 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) by the mixed acid solution in the product and step 2 in step 1 according to the ratio of weight/volume 1.0g/100ml
It is mixed, after mixed liquor ultrasound 40min, stirring and condensing reflux 5h at 90 DEG C, filtering, then with deionized water to filtrate
It is washed repeatedly to neutrality, is dried under vacuum to constant weight at 40 DEG C, crushed to get to the carbon nanometer Jing Guo the composite modified processing of soda acid
Pipe.
The preparation method for preparing nano-silver conductive glue, includes the following steps：A) nano silver linkage nano carbon tubes powder is prepared：
The silver nitrate solution 250ml for configuring 0.0lmol/L first, it is anhydrous to be separately added into 8ml polyvinylpyrrolidones, 10ml in the solution
Ethyl alcohol, the carbon nanotube 5.0g of surface-modified processing and deoxysodium cholate 7.5g, stir 60min in high speed dispersor,
Whipping temp is 60 DEG C, and mixed liquor is made to be sufficiently mixed uniformly；Continue to stir and be slowly added dropwise 5% hydrazine hydrate, until precipitation is no longer
It generates, solution becomes clarification；Filtered sediment deionized water and ethyl alcohol filtered several times to pH value is washed again to be in neutrality,
It is dried under vacuum to constant weight at 40 DEG C, obtains nano silver linkage nano carbon tubes powder；B) nano-silver conductive glue is prepared：With epoxy resin
As matrix, according to weight ratio 100：10：15：Plasticizer phthalic acid dibutyl ester, micro-silver powder and step a is added in 10 ratios
In prepared nano silver linkage nano carbon tubes powder, be put into wandering star type churning deaerator and stirred with 1440r/min speed
60min；Then epoxy resin is pressed：Triethanolamine weight ratio 100：8 ratios are added triethanolamine and make curing agent, are placed again into trip
Planetary churning deaerator stirs 60min, obtains nano-silver conductive glue；C) solidification of nano-silver conductive glue：It will be made in step b
Nano-silver conductive glue be stored at room temperature 6h and make its precuring, be then placed in 80 DEG C of constant temperature in drying box and place 4h, keep it completely solid
Change, obtains final nano-silver conductive glue product.
Embodiment 5
Processing is modified to carbon nanotube first, processing procedure includes the following steps：
1) alkali process：After carbon nanotube is carried out airflow milling processing, the hydrogen for being 2.0% with deoxysodium cholate and mass concentration
Sodium hydroxide solution is mixed, the mass ratio ranging from 1 of carbon nanotube and deoxysodium cholate：2, mixed liquor is after ultrasonic 50min
High speed dispersor stirring 1h is continued through, filtering, filtrate is crushed using airflow milling, then in N2Under atmosphere protection, in 750 DEG C
30min is reacted, product is in N2Under atmosphere it is cooling after, then filtered to neutrality with deionized water washing, perseverance be dried under vacuum at 40 DEG C
Weight, for use；
2) by nitric acid and mass concentration that mass concentration is 68% be 98% sulfuric acid with volume ratio 1：3 ratio mixing,
It adds 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) by the mixed acid solution in the product and step 2 in step 1 according to the ratio of weight/volume 1.0g/100ml
It is mixed, after mixed liquor ultrasound 50min, stirring and condensing reflux 5h at 90 DEG C, filtering, then with deionized water to filtrate
It is washed repeatedly to neutrality, is dried under vacuum to constant weight at 40 DEG C, crushed to get to the carbon nanometer Jing Guo the composite modified processing of soda acid
Pipe.
The preparation method for preparing nano-silver conductive glue, includes the following steps：A) nano silver linkage nano carbon tubes powder is prepared：
The silver nitrate solution 250ml for configuring 0.0lmol/L first, it is anhydrous to be separately added into 10ml polyvinylpyrrolidones, 8ml in the solution
Ethyl alcohol, the carbon nanotube 5.0g of surface-modified processing and deoxysodium cholate 5.0g, stir 60min in high speed dispersor,
Whipping temp is 60 DEG C, and mixed liquor is made to be sufficiently mixed uniformly；Continue to stir and be slowly added dropwise 5% hydrazine hydrate, until precipitation is no longer
It generates, solution becomes clarification；Filtered sediment deionized water and ethyl alcohol filtered several times to pH value is washed again to be in neutrality,
It is dried under vacuum to constant weight at 40 DEG C, obtains nano silver linkage nano carbon tubes powder；B) nano-silver conductive glue is prepared：With epoxy resin
As matrix, according to weight ratio 100：10：15：Plasticizer phthalic acid dibutyl ester, micro-silver powder and step a is added in 5 ratios
In prepared nano silver linkage nano carbon tubes powder, be put into wandering star type churning deaerator and stirred with 1440r/min speed
60min；Then epoxy resin is pressed：Triethanolamine weight ratio 100：10 ratios are added triethanolamine and make curing agent, are placed again into
Wandering star type churning deaerator stirs 60min, obtains nano-silver conductive glue；C) solidification of nano-silver conductive glue：It will be made in step b
The nano-silver conductive glue obtained, which is stored at room temperature 6h, makes its precuring, is then placed in 80 DEG C of constant temperature in drying box and places 4h, makes it completely
Solidification, obtains final nano-silver conductive glue product.
Silver conductive adhesive electric conductivity is tested
Nano-silver conductive glue electric conductivity obtained test is with the following method in above-described embodiment：5 are carved in glass plate
Length is respectively the groove of 5O, 1O and 5mm, by silver conductive adhesive solidification 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, Ω cm in formula；A is that two contact point of resistance meter is asked away from m；B is groove width, m；C is slot
Height, 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 uses microcomputer universal material to test at room temperature
Machine carries out, and fixture movement speed is 50mm/min, is clamping between experimental machine and sample, each conducting resinl sample makees 5 connections
Strength test takes its average value, calculation formula to see (2)：
In formula：б is bonding strength, MPa；Pulling force when f is failure, N；S is connection area, mm2.
Meanwhile synchronism detection has been carried out to commercially available silver filling epoxide resin conductive adhesive, 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 in comprehensive performance；Moreover, filler addition content is relatively low,
Also there is some superiority in cost.
Above example is only to illustrate the technical solution of the utility model, rather than its limitations；Although with reference to aforementioned reality
Example is applied the utility model is described in detail, it will be understood by those of ordinary skill in the art that：It still can be to preceding
The technical solution recorded in each embodiment is stated to modify or equivalent replacement of some of the technical features；And these
Modification or replacement, the spirit and model of various embodiments of the utility model technical solution that it does not separate the essence of the corresponding technical solution
It encloses.
Claims (4)
1. a kind of preparation method of nano-silver conductive glue, which is characterized in that include the following steps：
A) nano silver linkage nano carbon tubes powder is prepared：The silver nitrate solution for configuring 0.0lmol/L first, adds respectively in the solution
Enter polyvinylpyrrolidone, absolute ethyl alcohol, the carbon nanotube of surface-modified processing and surfactant, in high speed dispersor
Middle stirring 30-60min, whipping temp are 60 DEG C, and mixed liquor is made to be sufficiently mixed uniformly；Continue to stir and be slowly added dropwise 5% hydration
Hydrazine, until precipitation no longer generates, solution becomes clarification；Filtered sediment is washed into filtered several times with deionized water and ethyl alcohol again
It is in neutrality to pH values, constant weight is dried under vacuum at 40 DEG C, obtain 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, adds 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 weight ratio 100：5-10 ratios are added triethanolamine and make
Curing agent is placed again into wandering star type churning deaerator stirring 30-60min, obtains nano-silver conductive glue；
C) solidification of nano-silver conductive glue：Nano-silver conductive glue obtained in step b, which 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 made to be fully cured；
Wherein, accounting of the carbon nanotube in mixed liquor described in step a is 0.1-1.0wt%, the carbon nanotube 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；The carbon nanotube
Modification includes the following steps：
1) alkali process：It is the strong of 0.1-2.0% with surfactant and mass concentration after carbon nanotube is carried out airflow milling processing
Aqueous slkali is mixed, the mass ratio ranging from 1 of carbon nanotube and surfactant：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 N2Under atmosphere it is cooling after, then filtered to neutrality with deionized water washing, 40
Constant weight is dried under vacuum at DEG C, for use；
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 is 0.1-2.0 with the volume ratio of mixed acid amount：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 repeatedly to neutrality, is dried under vacuum to constant weight at 40 DEG C, is crushed to get to the carbon Jing Guo the composite modified processing of soda acid
Nanotube；
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.
2. a kind of preparation method of nano-silver conductive glue as described in claim 1, which is characterized in that the pipe of the carbon nanotube
Diameter is 20-50nm, and pipe range is 0.5-100 μm, purity >=95%.
3. a kind of preparation method of nano-silver conductive glue as described in any one of claims 1 or 2, which is characterized in that described
Surfactant is deoxysodium cholate, dodecyl sodium sulfate, fatty acid amide, C12-13Alcohol polyoxyethylene ether, polymethyl
At least one of hydrochlorate and cetyl trimethylammonium bromide.
4. a kind of preparation method of nano-silver conductive glue as claimed in claim 2, which is characterized in that the highly basic is hydroxide
Sodium or potassium hydroxide.
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| CN109777335B (en) * | 2019-01-18 | 2021-05-11 | 昆明贵金属研究所 | Method for preparing high-thermal-conductivity and electric-conductivity adhesive by using nano-silver modified carbon nano-tubes |
| 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 |
| CN111403081B (en) * | 2020-03-19 | 2022-04-15 | 深圳市金百纳纳米科技有限公司 | Carbon nanotube conductive slurry and preparation method thereof |
| CN113201301B (en) * | 2021-04-09 | 2022-04-08 | 北京科技大学 | Modification method of carbon nano tube for copper-clad plate |
| CN113409985B (en) * | 2021-06-21 | 2023-05-23 | 中科检测技术服务(重庆)有限公司 | Preparation and application of nano copper conductive paste |
| 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 |
| CN114806476B (en) * | 2022-06-01 | 2023-09-01 | 山东大福粘合剂股份有限公司 | Epoxy resin conductive adhesive containing composite conductive filler and preparation method thereof |
| CN116275028A (en) * | 2023-03-28 | 2023-06-23 | 哈尔滨工业大学 | Preparation method and interconnection process of carbon nanosphere@Ag core-shell material for low-temperature connection and high-temperature service |
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