CN110079266A - A kind of nano silver is carbon nano-tube modified to prepare high heat-conductivity conducting glue and preparation method thereof - Google Patents
A kind of nano silver is carbon nano-tube modified to prepare high heat-conductivity conducting glue and preparation method thereof Download PDFInfo
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- CN110079266A CN110079266A CN201910231594.XA CN201910231594A CN110079266A CN 110079266 A CN110079266 A CN 110079266A CN 201910231594 A CN201910231594 A CN 201910231594A CN 110079266 A CN110079266 A CN 110079266A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 89
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 89
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000003292 glue Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 10
- -1 carbon nano-tube modified nano silver Chemical class 0.000 claims abstract description 6
- 239000011268 mixed slurry Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- RRKGBEPNZRCDAP-UHFFFAOYSA-N [C].[Ag] Chemical compound [C].[Ag] RRKGBEPNZRCDAP-UHFFFAOYSA-N 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 11
- 229910052709 silver Inorganic materials 0.000 abstract description 10
- 239000004332 silver Substances 0.000 abstract description 10
- 238000005245 sintering Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000005036 potential barrier Methods 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 7
- 101100272976 Panax ginseng CYP716A53v2 gene Proteins 0.000 description 6
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013036 cure process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
-
- 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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- 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
-
- 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
- C08K2201/001—Conductive additives
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
- Powder Metallurgy (AREA)
Abstract
High heat-conductivity conducting glue and preparation method thereof is prepared the present invention relates to a kind of nano silver is carbon nano-tube modified, belongs to technical field of composite preparation.The carbon nano-tube modified high heat-conductivity conducting glue for preparing of the nano silver is made of the preparation of following raw material: 20~35 parts of resin carrier, 65~80 parts of silver powder, carbon nano-tube modified 1~5 part of nano silver.Resin carrier, the silver powder that partial size is 5 μm are sufficiently mixed using the dispersion of three-high mill grinder, carbon nano-tube modified nano silver, dispersing agent and defoaming agent is added and obtains mixed slurry, is then mixed using centrifuge, high heat-conductivity conducting glue is prepared.The carbon nanotube that this method passes through the addition nanometer modified by silver in elargol, heat-conductive bridges connection is formed between Argent grain in the micron-scale, carbon nano tube surface nano silver and Argent grain sintering are connected, it establishes a large amount of thermal conducting path and reduces carrier transport potential barrier between filler, the efficiency of transmission of phonon between filler interface, electronics is greatly improved.
Description
Technical field
High heat-conductivity conducting glue and preparation method thereof is prepared the present invention relates to a kind of nano silver is carbon nano-tube modified, is belonged to compound
Technical field of material.
Background technique
High heat-conductivity conducting glue is widely used in ultra high-speed computer chip, function as a kind of thermal interfacial material haveing excellent performance
In rate semiconductor devices and high-brightness LED, can be realized by low-temperature setting mode chip and it is heat sink between mechanical connection,
Electrical connection and the requirement for being thermally connected and being able to satisfy under hot environment.Due to metallic silver and carbon nanotube have it is high thermally conductive
Rate is studied extensively as electric slurry heat filling, and simple nanotube-filled polymers resin heating conduction is not high, and
It is not easy to disperse；High silver additive amount is although can be improved thermal conductivity, and the impressionability that will cause slurry is deteriorated and Gao Yin
There are brittleness high expensives for the thermal conductivity glue of content.
Improve the moisture dispersibility of carbon nanotube in the polymer by modifying nano silver in carbon nano tube surface, drops simultaneously
The nano silver of the thermal contact resistance and surface of low-carbon nano pipe and carrier interface forms additional thermal conducting path and further increases electronics
Slurry heating conduction.The carbon nanotube of nanometer modified by silver and silver powder collocation are bonded by low-temperature sintering and construct three dimentional heat conduction structure,
Reduce the phon scattering between interface, realize chip and it is heat sink between efficient heat transfer, show than single filler more
Add excellent heating conduction, and then effectively improves the thermal conductivity of electric slurry.
Nano silver is carbon nano-tube modified to be used as compound heat filling with Argent grain collocation, facilitates through sintering structure knot
It is insufficient in electric slurry heating conduction that structure modulation makes up single applying filler.The machinery that the introducing of carbon nanotube enhances system is strong
Degree and thermal stability, while carbon nano tube surface nano silver and Argent grain sintering connection reduce carrier transport gesture between filler
It builds, the efficiency of transmission of phonon between filler interface, electronics is greatly improved, electric slurry heating conduction is made to be largely increased simultaneously
It can adapt under heating condition Argent grain in composite construction and ductile deformation occur, form seamless contact between metal-metal, establish
A large amount of thermal conducting path, realizes composite system high thermal conductivity, while the introducing of carbon nanotube enhances system
Mechanical strength and thermal stability and the roughening for preventing nano silver in sintering process, and link forms heat conduction network and mentions between particle
High heat transmission.
Summary of the invention
It is only simple overlapped the way of contact that the present invention, which solves in traditional elargol functional stuffing, and the thermal resistance between filler is huge
Greatly, the present invention provides that a kind of nano silver is carbon nano-tube modified to prepare high heat-conductivity conducting glue and preparation method thereof.This method by
The carbon nanotube of nanometer modified by silver is added in elargol, heat-conductive bridges connection is formed between Argent grain in the micron-scale, by carbon nanotube table
Face nano silver and Argent grain sintering connect, and establish a large amount of thermal conducting path and reduce carrier transport potential barrier between filler, greatly
Amplitude improves the efficiency of transmission of phonon between filler interface, electronics.The invention is realized by the following technical scheme.
A kind of nano silver is carbon nano-tube modified to prepare high heat-conductivity conducting glue, is made of the preparation of following raw material: resin carrier 20
~35 parts, 65~80 parts of silver powder, carbon nano-tube modified 1~5 part of nano silver.
A kind of carbon nano-tube modified preparation method for preparing high heat-conductivity conducting glue of nano silver, the specific steps of which are as follows:
The carbon nano-tube modified preparation of step 1, nano silver:
Be that 10~20 parts of carbon nanotubes are added in ethanol solutions by mass parts, under condition of ice bath with ultrasonic echography dispersion 20~
30 minutes, it was 10~20 parts, 1mol/L sodium dodecyl sulfate solution that mass parts, which are then added, continues 1~2h of excusing from death dispersion and obtains
To carbon nano tube suspension, activation modification carbon nanotube is prepared in carbon nano tube suspension centrifuge separation, washing；
It is 50~60 parts, in the silver nitrate solution of 1mol/L that obtained activation modification carbon nanotube, which is added to mass parts, magnetic force
12h is stirred, the formalin of 2mol/L is added, reacts 10~15min, obtains nanometer for 24 hours in vacuum drying with after ethanol washing
Modified by silver carbon nanotube；
The preparation of step 2, resin carrier: resin is dissolved in organic solvent, 70 DEG C of stirring in water bath of constant temperature, completely rear drop to be dissolved
To room temperature, curing agent is added, resin carrier is made in dispersion 40min under high revolving speed (3000r/min)；
The preparation of step 3, conductive silver glue: premixing 3min first with multifrequency blender for resin carrier, the silver powder that partial size is 5 μm,
The dispersion of three-high mill grinder is recycled to be sufficiently mixed, until slurry granularity is 7 μm hereinafter, preparing conducting resinl；
The preparation of step 4, high heat-conductivity conducting glue: carbon nano-tube modified nano silver, dispersing agent and defoaming agent are added into conducting resinl
Mixed slurry is obtained, is then mixed using centrifuge, high heat-conductivity conducting glue is prepared.
Resin is epoxy resin, phenolic resin, polyurethane, acrylic resin, one in organic siliconresin in the step 2
Kind or any several scalemic thereofs.
Silver powder is one or both of sheet, spherical silver powder arbitrary proportion composition in the step 3.The model of flake silver powder
Enclose 2.4 ~ 4.0g/cm of tap density3, 4.0 ~ 6.1 μm of average grain diameter, scaling loss < 1%, 1.2 ~ 2.5m of specific surface area2/g.Spherical silver powder
4.5 ~ 5.0g/cm of range tap density3, 1.5 ~ 2.4 μm of average grain diameter, scaling loss < 1%, 0.5 ~ 1.3m of specific surface area2/g。
Three-high mill (rolling the distance between two rollers of pulp grinder is 2.0~3.0 μm) grinder dispersion is pre- in the step 3
It is 2 times mixed, it tightly rolls 3 times or more, until pulp particle is 7 μm or less.
Dispersing agent is one of BYK111, BYK110, BYK182, BYK180 or several any ratios in the step 4
Example mixed dispersant；The defoaming agent is one of BYK052, BYK052N or two kinds of arbitrary proportion mixture foam killers.
3~4min of centrifuge mixing centrifugation in the step 4.
The beneficial effects of the present invention are:
(1) nano silver of carbon nano tube surface is seamless between foring metal-metal with bulky grain silver powder contacts, and establishes a large amount of
Thermal conducting path simultaneously reduces carrier transport potential barrier between filler, and the transmission effect of phonon between filler interface, electronics is greatly improved
Rate.
(2) carbon nanotube for adding nanometer modified by silver improves the performances such as electric slurry viscosity, thixotropy, and promotes carbon nanometer
Pipe and silver powder dispersion performance in the slurry and wellability.
(3) method provided by the invention is easy to operate, simple process, does not introduce the bad body of thermal conductivity.
Detailed description of the invention
Fig. 1 is the carbon nano-tube modified TEM figure of nano silver that the embodiment of the present invention 1 is prepared；
Fig. 2 is the high heat-conductivity conducting glue SEM figure A that the embodiment of the present invention 1 is prepared；
Fig. 3 is the high heat-conductivity conducting glue SEM figure B that the embodiment of the present invention 1 is prepared.
Specific embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
The nano silver is carbon nano-tube modified to prepare high heat-conductivity conducting glue, is made of the preparation of following raw material: resin carrier 20g, silver powder
65g, the carbon nano-tube modified 1g of nano silver.
The carbon nano-tube modified preparation method for preparing high heat-conductivity conducting glue of the nano silver, the specific steps of which are as follows:
The carbon nano-tube modified preparation of step 1, nano silver:
By 10g carbon nanotube be added 50mL ethanol solution in, under condition of ice bath with ultrasonic echography disperse 20 minutes, then plus
Enter 10g, 1mol/L sodium dodecyl sulfate solution, continues excusing from death dispersion 1h and obtain carbon nano tube suspension, carbon nanotube is hanged
Activation modification carbon nanotube is prepared in supernatant liquid centrifuge separation, washing；
Obtained activation modification carbon nanotube is added in the silver nitrate solution of 50g, 1mol/L, magnetic agitation 12h, is added
The formalin of 30mL, 2mol/L react 10min, obtain nano silver modified carbon nanometer for 24 hours in vacuum drying with after ethanol washing
Pipe；The carbon nano-tube modified TEM figure of the nano silver being prepared is as shown in Figure 1；
The preparation of step 2, resin carrier: by 6g resin (the modified obtained epoxy novolac of the dissaving polymer that mass ratio is 1:2
Resin and organic siliconresin) be dissolved in 30mLDBE organic solvent, 70 DEG C of stirring in water bath of constant temperature, it is to be dissolved completely after be down to room temperature,
The dicy-curing agent (PPTS content is 80%) that 3g contains a small amount of catalyst PPTS is added, is dispersed under high revolving speed (3000r/min)
Resin carrier is made in 40min；
The preparation of step 3, conductive silver glue: being that (silver powder is sheet, the range of flake silver powder for 5 μm of silver powder by resin carrier, partial size
2.4 ~ 4.0g/cm of tap density3, 4.0 ~ 6.1 μm of average grain diameter, scaling loss < 1%, 1.2 ~ 2.5m of specific surface area2/ g) first with multifrequency
Blender premixes 3min, and the dispersion of three-high mill grinder is recycled to be sufficiently mixed, until slurry granularity is 7 μm hereinafter, preparation is led
Electric glue；Three-high mill (rolling the distance between two rollers of pulp grinder is 2.0~3.0 μm) grinder dispersion premix 2 times, tightly rolls 3 times
More than, until pulp particle is 7 μm or less；
The preparation of step 4, high heat-conductivity conducting glue: it is added that nano silver is carbon nano-tube modified, 2g dispersing agent (BYK180 into conducting resinl
Dispersing agent) and 4g defoaming agent (BYK052 defoaming agent) obtain mixed slurry, then use centrifuge mixing 3min, height is prepared
Thermal conductivity glue.
The high heat-conductivity conducting glue SEM figure that the present embodiment is prepared is as shown in Figures 2 and 3.Nano silver can be seen from Fig. 1
It is dispersed in carbon nano tube surface, size integrated distribution is in 10 nm or so.As can be seen from Figure 2 carbon nano tube surface
Nano silver possesses low-temperature sintering activity can be with silver powder sinter molding, and as can be seen from Figure 3 modified by silver carbon nanotube is in silver powder
Between the conduction path that constructs, improve sample electrical and thermal conductivity.
Embodiment 2
The nano silver is carbon nano-tube modified to prepare high heat-conductivity conducting glue, is made of the preparation of following raw material: resin carrier 35g, silver powder
80g, the carbon nano-tube modified 5g of nano silver.
The carbon nano-tube modified preparation method for preparing high heat-conductivity conducting glue of the nano silver, the specific steps of which are as follows:
The carbon nano-tube modified preparation of step 1, nano silver:
By 15g carbon nanotube be added 100 mL ethanol solutions in, under condition of ice bath with ultrasonic echography disperse 25 minutes, then
15g, 1mol/L sodium dodecyl sulfate solution is added, continues excusing from death dispersion 2h and obtains carbon nano tube suspension, by carbon nanotube
Activation modification carbon nanotube is prepared in suspension centrifuge separation, washing；
Obtained activation modification carbon nanotube is added in the silver nitrate solution of 55g, 1mol/L, magnetic agitation 12h, is added
The formalin of 50mL, 2mol/L react 12min, obtain nano silver modified carbon nanometer for 24 hours in vacuum drying with after ethanol washing
Pipe；The carbon nano-tube modified TEM figure of the nano silver being prepared is as shown in Figure 1；
The preparation of step 2, resin carrier: by 6g resin (the modified obtained epoxy novolac of the dissaving polymer that mass ratio is 2:1
Resin and organic siliconresin) be dissolved in 50mLDBE organic solvent, 70 DEG C of stirring in water bath of constant temperature, it is to be dissolved completely after be down to room temperature,
The dicy-curing agent (PPTS content is 85%) that 3g contains a small amount of catalyst PPTS is added, is dispersed under high revolving speed (3000r/min)
Resin carrier is made in 40min；
The preparation of step 3, conductive silver glue: being that (silver powder is sheet, the range of flake silver powder for 5 μm of silver powder by resin carrier, partial size
2.4 ~ 4.0g/cm of tap density3, 4.0 ~ 6.1 μm of average grain diameter, scaling loss < 1%, 1.2 ~ 2.5m of specific surface area2/ g) first with multifrequency
Blender premixes 3min, and the dispersion of three-high mill grinder is recycled to be sufficiently mixed, until slurry granularity is 7 μm hereinafter, preparation is led
Electric glue；Three-high mill (rolling the distance between two rollers of pulp grinder is 2.0~3.0 μm) grinder dispersion premix 2 times, tightly rolls 3 times
More than, until pulp particle is 7 μm or less；
The preparation of step 4, high heat-conductivity conducting glue: it is added that nano silver is carbon nano-tube modified, 2g dispersing agent (BYK180 into conducting resinl
Dispersing agent) and 4g defoaming agent (BYK052 defoaming agent) obtain mixed slurry, then use centrifuge mixing 3min, height is prepared
Thermal conductivity glue.
Embodiment 3
The nano silver is carbon nano-tube modified to prepare high heat-conductivity conducting glue, is made of the preparation of following raw material: resin carrier 25g, silver powder
75g, the carbon nano-tube modified 4g of nano silver.
The carbon nano-tube modified preparation method for preparing high heat-conductivity conducting glue of the nano silver, the specific steps of which are as follows:
The carbon nano-tube modified preparation of step 1, nano silver:
By 20g carbon nanotube be added 50mL ethanol solution in, under condition of ice bath with ultrasonic echography disperse 30 minutes, then plus
Enter 20g, 1mol/L sodium dodecyl sulfate solution, continues excusing from death dispersion 1.5h and obtain carbon nano tube suspension, by carbon nanotube
Activation modification carbon nanotube is prepared in suspension centrifuge separation, washing；
Obtained activation modification carbon nanotube is added in the silver nitrate solution of 60g, 1mol/L, magnetic agitation 12h, is added
The formalin of 100mL, 2mol/L react 15min, are received with nano silver modified carbon is obtained for 24 hours in vacuum drying after ethanol washing
Mitron；The carbon nano-tube modified TEM figure of the nano silver being prepared is as shown in Figure 1；
The preparation of step 2, resin carrier: by 6g resin (the modified obtained epoxy novolac of the dissaving polymer that mass ratio is 2:1
Resin and organic siliconresin) be dissolved in 100mLDBE organic solvent, 70 DEG C of stirring in water bath of constant temperature, it is to be dissolved completely after be down to room
Temperature, addition 6g contain the dicy-curing agent (PPTS content be 85%) of a small amount of catalyst PPTS, under high revolving speed (3000r/min)
Resin carrier is made in dispersion 40min；
The preparation of step 3, conductive silver glue: by resin carrier, silver powder that partial size is 5 μm (flake silver powder that silver powder is quality 1:1 and
Spherical silver powder, 2.4 ~ 4.0g/cm of range tap density of flake silver powder3, 4.0 ~ 6.1 μm of average grain diameter, scaling loss < 1%, specific surface
1.2 ~ 2.5m of product2/g；4.5 ~ 5.0g/cm of range tap density of spherical silver powder3, 1.5 ~ 2.4 μm of average grain diameter, scaling loss < 1%, than
0.5 ~ 1.3m of surface area2/ g) first with multifrequency blender premix 3min, recycle the dispersion of three-high mill grinder to be sufficiently mixed,
Until slurry granularity is 7 μm hereinafter, preparing conducting resinl；(roll the distance between two rollers of pulp grinder is 2.0~3.0 μ to three-high mill
M) grinder dispersion premix 2 times, tightly roll 3 times or more, until pulp particle is 7 μm or less；
The preparation of step 4, high heat-conductivity conducting glue: it is added that nano silver is carbon nano-tube modified, 2g dispersing agent (mass ratio into conducting resinl
For BYK180 the and BYK182 mixed dispersant of 1:1) and (BYK052 and the BYK052N defoaming that mass ratio is 1:1 of 4g defoaming agent
Agent) mixed slurry is obtained, centrifuge mixing 3min is then used, high heat-conductivity conducting glue is prepared.
High heat-conductivity conducting glue prepared in the above embodiments is tested for the property, the specific test method is as follows.
(1) heating conduction is tested
Electrically and thermally conductive adhesive after solidification is milled into the disc-shaped of upper and lower surface smooth parallel, diameter is in 11.8 mm or so, thickness
Then about 1mm is sprayed carbon shading in sample surfaces, the heat transfer of electrically and thermally conductive adhesive is measured using 447 thermal conductivity instrument of model Netch LFA
Performance.
(2) electric performance test
On the PET film that ethanol is crossed, by 300 mesh expanded sheet metals, conductive film layer is printed, is put into baking oven, 175 ~ 200 DEG C solid
Change 1 ~ 2h, while in electrically and thermally conductive adhesive both ends extraction electrode, and connects the electrodes to progress in-situ monitoring slurry on low resistance systems
Solidifying and the resistance variations in post cure processes.
Test result is as shown in table 1
Table 1
1 electrical and thermal conductivity performance of embodiment is best as can be seen from Table 1: thermal conductivity improves 38%, and resistivity has dropped 24%,.
Sintering can occur with Argent grain in electric slurry for the nano silver of carbon nano tube surface appendix sintering activity with higher one
It rises, forms seamless contact between metal-metal, realize that carbon nanotube establishes a large amount of conducting path between flake silver powder, improve
The electrical and thermal conductivity performance of composite system.
In conjunction with attached drawing, the embodiment of the present invention is explained in detail above, but the present invention is not limited to above-mentioned
Embodiment within the knowledge of a person skilled in the art can also be before not departing from present inventive concept
Put that various changes can be made.
Claims (9)
1. a kind of nano silver is carbon nano-tube modified to prepare high heat-conductivity conducting glue, it is characterised in that: be made of the preparation of following raw material: tree
20~35 parts of rouge carrier, 65~80 parts of silver powder, carbon nano-tube modified 1~5 part of nano silver.
2. a kind of carbon nano-tube modified preparation method for preparing high heat-conductivity conducting glue of nano silver according to claim 1,
It is characterized in that specific step is as follows:
Resin carrier, the silver powder that partial size is 5 μm are sufficiently mixed using the dispersion of three-high mill grinder, nano silver modified carbon is added
Nanotube, dispersing agent and defoaming agent obtain mixed slurry, are then mixed using centrifuge, high heat-conductivity conducting glue is prepared.
3. the carbon nano-tube modified preparation method for preparing high heat-conductivity conducting glue of nano silver according to claim 2, feature
Be: the resin carrier the preparation method comprises the following steps: resin is dissolved in organic solvent, 70 DEG C of stirring in water bath of constant temperature are to be dissolved complete
It is down to room temperature after complete, adds curing agent, resin carrier is made in dispersion 40min under high revolving speed.
4. the carbon nano-tube modified preparation method for preparing high heat-conductivity conducting glue of nano silver according to claim 3, feature
Be: the resin is one of epoxy resin, phenolic resin, polyurethane, acrylic resin, organic siliconresin or any several
Kind scalemic thereof.
5. the carbon nano-tube modified preparation method for preparing high heat-conductivity conducting glue of nano silver according to claim 2, feature
Be: the silver powder is one or both of sheet, spherical silver powder arbitrary proportion composition.
6. the carbon nano-tube modified preparation method for preparing high heat-conductivity conducting glue of nano silver according to claim 2, feature
Be: three-high mill grinder dispersion premix 2 times is tightly rolled 3 times or more, until pulp particle is 7 μm or less.
7. the carbon nano-tube modified preparation method for preparing high heat-conductivity conducting glue of nano silver according to claim 2, feature
Be: the nano silver it is carbon nano-tube modified the preparation method comprises the following steps:
Be that 10~20 parts of carbon nanotubes are added in ethanol solutions by mass parts, under condition of ice bath with ultrasonic echography dispersion 20~
30 minutes, it was 10~20 parts, 1mol/L sodium dodecyl sulfate solution that mass parts, which are then added, continues 1~2h of excusing from death dispersion and obtains
To carbon nano tube suspension, activation modification carbon nanotube is prepared in carbon nano tube suspension centrifuge separation, washing；
It is 50~60 parts, in the silver nitrate solution of 1mol/L that obtained activation modification carbon nanotube, which is added to mass parts, magnetic force
12h is stirred, the formalin of 2mol/L is added, reacts 10~15min, obtains nanometer for 24 hours in vacuum drying with after ethanol washing
Modified by silver carbon nanotube.
8. the carbon nano-tube modified preparation method for preparing high heat-conductivity conducting glue of nano silver according to claim 2, feature
Be: the dispersing agent is one of BYK111, BYK110, BYK182, BYK180 or the mixing dispersion of several arbitrary proportions
Agent；The defoaming agent is one of BYK052, BYK052N or two kinds of arbitrary proportion mixture foam killers.
9. the carbon nano-tube modified preparation method for preparing high heat-conductivity conducting glue of nano silver according to claim 2, feature
It is: 3~4min of the centrifuge mixing centrifugation.
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Cited By (6)
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| CN110549039A (en) * | 2019-09-11 | 2019-12-10 | 桂林电子科技大学 | Carbon nano tube/nano silver soldering paste heat conduction material and preparation method thereof |
| CN110655831A (en) * | 2019-11-15 | 2020-01-07 | 合肥映山红材料科技有限公司 | Preparation method of nano silver carbon nanotube composite conductive ink |
| CN110890169A (en) * | 2019-11-11 | 2020-03-17 | 深圳第三代半导体研究院 | Preparation method of carbon nano tube composite metal paste |
| CN111554445A (en) * | 2020-05-13 | 2020-08-18 | 深圳市先进连接科技有限公司 | Surface-metallized nano-carbon material composite nano-silver paste and preparation method thereof |
| CN113754925A (en) * | 2021-09-28 | 2021-12-07 | 浙江荣泰科技企业有限公司 | Insulating base material-carbon nano tube hybrid material and preparation method and application thereof |
| WO2023083287A1 (en) * | 2021-11-12 | 2023-05-19 | 福建江夏学院 | Low-silver-content high-performance conductive paste and preparation method therefor |
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| CN108018014A (en) * | 2018-01-12 | 2018-05-11 | 深圳名飞远科技有限公司 | A kind of preparation method of novel nano silver conductive adhesive |
| CN108084918A (en) * | 2017-12-18 | 2018-05-29 | 苏州亿拓光电科技有限公司 | Conductive adhesive for LED encapsulation and preparation method thereof |
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| CN108084918A (en) * | 2017-12-18 | 2018-05-29 | 苏州亿拓光电科技有限公司 | Conductive adhesive for LED encapsulation and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110549039A (en) * | 2019-09-11 | 2019-12-10 | 桂林电子科技大学 | Carbon nano tube/nano silver soldering paste heat conduction material and preparation method thereof |
| CN110549039B (en) * | 2019-09-11 | 2021-09-28 | 桂林电子科技大学 | Carbon nano tube/nano silver soldering paste heat conduction material and preparation method thereof |
| CN110890169A (en) * | 2019-11-11 | 2020-03-17 | 深圳第三代半导体研究院 | Preparation method of carbon nano tube composite metal paste |
| CN110655831A (en) * | 2019-11-15 | 2020-01-07 | 合肥映山红材料科技有限公司 | Preparation method of nano silver carbon nanotube composite conductive ink |
| CN111554445A (en) * | 2020-05-13 | 2020-08-18 | 深圳市先进连接科技有限公司 | Surface-metallized nano-carbon material composite nano-silver paste and preparation method thereof |
| CN113754925A (en) * | 2021-09-28 | 2021-12-07 | 浙江荣泰科技企业有限公司 | Insulating base material-carbon nano tube hybrid material and preparation method and application thereof |
| WO2023083287A1 (en) * | 2021-11-12 | 2023-05-19 | 福建江夏学院 | Low-silver-content high-performance conductive paste and preparation method therefor |
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Application publication date: 20190802 |