CN109777335A - A kind of carbon nano-tube modified method for preparing high heat-conductivity conducting glue of nano silver - Google Patents
A kind of carbon nano-tube modified method for preparing high heat-conductivity conducting glue of nano silver Download PDFInfo
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- CN109777335A CN109777335A CN201910047685.8A CN201910047685A CN109777335A CN 109777335 A CN109777335 A CN 109777335A CN 201910047685 A CN201910047685 A CN 201910047685A CN 109777335 A CN109777335 A CN 109777335A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 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 100
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 100
- 239000003292 glue Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 31
- 239000004332 silver Substances 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- RRKGBEPNZRCDAP-UHFFFAOYSA-N [C].[Ag] Chemical compound [C].[Ag] RRKGBEPNZRCDAP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000012536 packaging technology Methods 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 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
- 238000003756 stirring Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 229940100890 silver compound Drugs 0.000 claims description 7
- 150000003379 silver compounds Chemical class 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- -1 silver tetrafluoroborate Chemical compound 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 239000004843 novolac epoxy resin Substances 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- OQXSRALAOPBHPM-UHFFFAOYSA-N 2-hydroxypropanoic acid;silver Chemical compound [Ag].CC(O)C(O)=O OQXSRALAOPBHPM-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229940071575 silver citrate Drugs 0.000 claims description 3
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 3
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 229920003180 amino resin Polymers 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000013339 cereals Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 239000000945 filler Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- 238000007711 solidification Methods 0.000 abstract description 5
- 230000008023 solidification Effects 0.000 abstract description 5
- 238000011049 filling Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 230000007812 deficiency Effects 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 description 9
- 238000009766 low-temperature sintering Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 101100272976 Panax ginseng CYP716A53v2 gene Proteins 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005036 potential barrier Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 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 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001272 pressureless sintering Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ZUVCYFMOHFTGDM-UHFFFAOYSA-N hexadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCOP(O)(O)=O ZUVCYFMOHFTGDM-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- AWEMSNRRIVQFLI-UHFFFAOYSA-N sulfonylmethanesulfonic acid Chemical compound S(=O)(=O)=CS(=O)(=O)O AWEMSNRRIVQFLI-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a kind of carbon nano-tube modified method for preparing high heat-conductivity conducting glue of nano silver, realizes that solidification electric slurry obtains high thermal conductivity, be applied to electric slurry packaging technology.The conducting resinl of the carbon nano-tube modified preparation of nano silver of the invention, by resin carrier 19-32wt%, silver powder 65-80wt%, the carbon nano-tube modified 1-5wt% composition of nano silver.Its specific preparation method step includes the preparation of the carbon nano-tube modified preparation and high heat-conductivity conducting glue of (1) nano silver.The present invention designs carbon nanomaterial and silver is complex sintered with preferable economic feasibility and military service performance, higher heating conduction is obtained than single filling carbon material, pass through nano silver-carbon nano tube compound material synthesis and application, single applying filler is made up in the deficiency of electric slurry thermal conductivity and stability, has substantially widened the application space of electric slurry.
Description
Technical field
The invention belongs to field of composite material preparation, be related to nano silver it is carbon nano-tube modified prepare highly conductive glue and its system
Preparation Method.
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 thermal connection, and the requirement being able to satisfy under hot environment.Due to metallic silver and carbon nanotube is with higher leads
Heating 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；Carbon nanotube loaded nano silver low-temperature sintering bonding and interface transfer function are given full play to, understands that enhancing is multiple
The microcosmic mechanism of condensation material heating conduction is effectively reduced between filler the carrier transport potential barrier between substrate interface, makes electric slurry
Heating conduction is greatly improved, and the typical case research of high power density electronic device is supported.
Improve the moisture dispersibility of carbon nanotube in the polymer by modifying nano silver in carbon nano tube surface, drops simultaneously
The thermal contact resistance of low-carbon nano pipe and carrier interface.The carbon nanotube of nanometer modified by silver and silver powder collocation are bonded by low-temperature sintering
Construct three dimentional heat conduction structure, reduce the phon scattering between interface, realize chip and it is heat sink between efficient heat transfer, table
Reveal the heating conduction more excellent than single filler, and then effectively improves the thermal conductivity of electric slurry.
Present invention design reduces initial configuration defect using micron flakes silver powder as " frame " and stable sintering structure, silver are repaired
Decorations carbon nanotube establishes the heat transfer path between flake silver powder " isolated island " by low-temperature pressureless sintering bonding.Give full play to carbon nanometer
The bonding of pipe loading nano silvery low-temperature sintering and interface transfer function, are effectively reduced between filler the carrier transport gesture between substrate interface
It builds, greatly improves electric slurry heating conduction；Improve slurry viscosity, touching using carbon nanotube as auxiliary packing simultaneously
The comprehensive performances such as denaturation, have substantially widened the application space of electric slurry.
Summary of the invention
Carbon nanomaterial itself has very high heating conduction, can be used as heat filling and prepares electric slurry, still
A large amount of gaps are generated since it is easy aggregation in organic carrier, and mutually overlap joint generates a large amount of interface resistance, greatly
Inhibit the performance of its excellent heat conducting characteristic.The present invention is lived by the carbon nanotube of the addition nanometer modified by silver in elargol using height
Property carbon nano tube surface silver nanoparticle low-temperature sintering realize carbon nanotube and the connection that is bonded between silver powder, formed between silver powder particles
Heat-conductive bridges connection, constructs the Heat transmission approach of efficient Yin-silver.
To achieve the goals above, according to one aspect of the present invention, a kind of carbon nano-tube modified preparation of nano silver is provided
The method of high heat-conductivity conducting glue, which is characterized in that be made of the following each raw material of mass percentage: resin carrier 19-
32wt%, silver powder 65-80wt%, the carbon nano-tube modified 1-5wt% of nano silver.
Preferably, the silver powder is one or both of sheet, spherical silver powder composition, wherein the range vibration of flake silver powder
4.0~6.5g/cm of real density3, 2.5~8.0 μm of average grain diameter, scaling loss < 1%, 0.4~1.5m of specific surface area2/g；Spherical silver powder
4.3~5.6g/cm of range tap density3, 0.7~2.5 μm of average grain diameter, scaling loss < 1%, 0.5~1.3m of specific surface area2/g。
Preferably, the carbon nano-tube modified synthesis condition of nano silver is characterized in that: 1mol/L silver compound solution, 1mol/L table
Face activator solution, 5-15 μm of carbon nanotube of length, by chemical reduction method synthetic composite material, used in reducing agent be boron
One of sodium hydride, hydrazine hydrate, formaldehyde, dimethylformamide, citric acid, oxalic acid, glucose or multiple combinations.
Preferably, the silver compound be silver nitrate, silver oxalate, silver orthophosphate, actol, silver citrate, silver tetrafluoroborate,
The one or more of acetylacetone,2,4-pentanedione silver.
Preferably, the surfactant is anionic surfactant carboxylate, sulfonate, sulfuric acid or phosphate
Salt is a kind of, arrange in pairs or groups nonionic surfactant or inorganic assistant.
It is another aspect of this invention to provide that a kind of carbon nano-tube modified method for preparing high heat-conductivity conducting glue of nano silver,
It is characterized in that including the following steps:
(1) the carbon nano-tube modified preparation of nano silver:
Carbon nanotube is added in ethanol solution in proportion, ultrasonic disperse 20-30 minutes, surfactant is added, carbon is received
Mitron is modified dispersion, and carbon nano tube suspension is centrifugated and washs precipitating repeatedly with ethyl alcohol to get work is arrived by ultrasonic 1-2h
Carbon nanotube after change；
Modified carbon nanotube is added to the silver-colored source solution of 1mol/L, 2mol/L is added under condition of ice bath after stirring 12h
Reducing solution, 10-15min is reacted, with dry for 24 hours to get to nanometer modified by silver in a vacuum drying oven after ethanol washing
Carbon nanotube.
(2) preparation of high heat-conductivity conducting glue:
Hyperbranched novolac epoxy resin or organic siliconresin resin are dissolved in 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, add amino resin curing agents, organic carrier is made in dispersion under high revolving speed.By silver powder and resin
Mixing, disperses silver powder using three-high mill, and the carbon nanotube of nanometer modified by silver is added later, and mixing dispersion is made high thermal conductivity and leads
Electric glue.
Beneficial effects of the present invention:
(1) surfactant carries out non-covalent modification to carbon nanotube, avoids functional method to carbon nanotube
The destruction of body construction, the reduction of fault of construction can be greatly reduced interface phonon scattering, improve structure heat transfer efficiency；
(2) present invention improves the performances such as electric slurry viscosity, thixotropy by the carbon nanotube of addition nanometer modified by silver, and
Promote wellability and dispersibility of the carbon nanotube in slurry organic carrier；
(3) by carrying out nanometer modified by silver to carbon nano tube surface, the model ylid bloom action between carbon nanotube is on the one hand reduced
Power realizes the depolymerization to agglomeration nano pipe；On the other hand, the special surface texture of carbon pipe inhibits poly- between loading nano silvery
Collection, realizes the stable dispersion of nano-Ag particles, reduces the usage amount of covering to greatest extent, meanwhile, what carbon nanotube had
Bigger serface enhances the load capacity of silver nano-grain, it is ensured that the high sintering activity of loading nano silvery；
(4) nano silver of carbon nano tube surface load reduces the thermal resistance between carbon nanotube and polymer interface and promotes sound
Son transmission is conducive to improve interface heat exchanger effectiveness；The low-temperature sintering activity of nano silver realizes carbon nanotube between flake silver powder
Good thermal conducting path is constructed, carrier concentration and carrier mobility are promoted；The introducing of carbon nanotube enhances institutional framework
Mechanical strength and thermal stability, avoid the brittle generation of high silver content system；
(5) method provided by the invention is easy to operate, simple process, does not introduce the bad system of thermal conductivity.
The present invention is made up single applying filler and is starched in electronics by nano silver-carbon nano tube compound material synthesis and application
The deficiency for expecting thermal conductivity and stability gives full play to carbon nanotube loaded nano silver low-temperature sintering bonding and interface transfer function,
It is guiding with high carrier mobility, the efficiency of transmission of phonon between filler interface, electronics is greatly improved, realizes composite wood
Material system high thermal conductivity, while the introducing of carbon nanotube enhances the mechanical strength of system and thermal stability and prevents sintered
The roughening of nano silver in journey, is effectively reduced between filler the carrier transport potential barrier between substrate interface, and carbon nanotube loaded
Nano silver facilitates organic carrier to the wetting and dispersing of carbon nanotube, and the introducing of carbon nanotube can be realized again to slurry rheological property energy
Regulation, meet the requirement of electronic-packaging processes.
The carbon nano-tube modified method for preparing high heat-conductivity conducting glue of nano silver of the invention realizes that solidification electric slurry obtains
High thermal conductivity.Present invention design reduces initial configuration defect and stable sintering structure using micron flakes silver powder as " frame ",
Modified by silver carbon nanotube establishes the heat transfer path between flake silver powder " isolated island " by low-temperature pressureless sintering bonding.Carbon nanomaterial
It is complex sintered with preferable economic feasibility and military service performance with silver, higher thermal conductivity is obtained than single filling carbon material
Can, it is synthesized by nano silver-carbon nano tube compound material and application, makes up single applying filler in electric slurry thermal conductivity and steady
It is qualitatively insufficient, carbon nanotube loaded nano silver low-temperature sintering bonding and interface transfer function are given full play to, filler is effectively reduced
Between between substrate interface carrier transport potential barrier, greatly improve electric slurry heating conduction；Carbon nanotube is utilized simultaneously
Improve the comprehensive performances such as slurry viscosity, thixotropy as auxiliary packing, substantially widens the application space of electric slurry.
Detailed description of the invention
Fig. 1 is the carbon nanotube transmission electron microscope picture that nanometer modified by silver is made in the embodiment of the present invention 1；
Fig. 2 is the carbon nanotube transmission electron microscope picture that nanometer modified by silver is made in the embodiment of the present invention 2；
Fig. 3 is the carbon nanotube transmission electron microscope picture that nanometer modified by silver is made in the embodiment of the present invention 3.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with three specific implementations
Example further illustrates a kind of carbon nano-tube modified method for preparing high heat-conductivity conducting glue of nano silver provided by the present invention, illustrates logical
The high heat-conductivity conducting glue that preparation method provided by the present invention obtains is crossed, the advantage in thermally conductive and comprehensive performance.And to attached drawing
And embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to solve
The present invention is released, is not intended to limit the present invention.In addition, skill involved in the various embodiments of the present invention described below
Art feature can be combined with each other as long as they do not conflict with each other.
The high heat-conductivity conducting glue for preparing of the embodiment of the present invention is made of the following each raw material of mass percentage: resin carrier
19-32wt%, silver powder 65-80wt%, the carbon nano-tube modified 1-5wt% of nano silver.
Wherein, the thermally conductive phase of the main body of the conducting resinl is metallic silver powder, and the carbon nanotube of nanometer modified by silver adds as supplement
Enter.4.0~6.5g/cm of range tap density of flake silver powder3, 2.5~8.0 μm of average grain diameter, the range jolt ramming of spherical silver powder
4.3~5.6g/cm of density3, 0.7~2.5 μm of average grain diameter.Nano silver is carbon nano-tube modified living by silver compound solution, surface
Property agent solution and carbon nanotube, by chemical reduction method synthetic composite material, used in reducing agent be sodium borohydride, hydration
One of hydrazine, formaldehyde, dimethylformamide, citric acid, oxalic acid, glucose or multiple combinations.Silver compound is silver nitrate, grass
The one or more of sour silver, silver orthophosphate, actol, silver citrate, silver tetrafluoroborate, acetylacetone,2,4-pentanedione silver.Surfactant is
Anionic surfactant carboxylate, sulfonate, sulfuric acid or phosphate ester salt are a kind of, arrange in pairs or groups nonionic surfactant or nothing
Machine aided agent.
Specific embodiment is described further the present invention, but protection scope of the present invention is not limited to the content.
Embodiment 1
It is a kind of to utilize high heat-conductivity conducting glue preparation method, specifically includes the following steps:
(1) the carbon nano-tube modified preparation of nano silver: 5 μm of carbon nanotubes of 1g average length are added in ethanol solution, are surpassed
Sound disperses 20 minutes, and alkylphosphonate and Tween 80 is added and disperses to carbon nano-tube modification, ultrasonic 1h hangs carbon nanotube
Supernatant liquid centrifuge separation can add a small amount of sodium nitrate or sodium citrate and promote flocculation separation, and repeatedly wash with ethyl alcohol precipitate to get
Carbon nanotube after to activation；
Modified carbon nanotube is added to the silver nitrate solution of 1mol/L, 2mol/ is added under condition of ice bath after stirring 12h
The sodium borohydride solution of L reacts 10min, with after ethanol washing in vacuum drying oven it is dry for 24 hours to get to nanometer modified by silver
Carbon nanotube.
(2) preparation of organic carrier: hyperbranched novolac epoxy resin or organic siliconresin are dissolved in organic solvent, according to
(W:W=1:2) be dissolved in DBE organic solvent, the stirring of 70 DEG C of constant temperature water baths, it is to be dissolved completely after be down to room temperature, addition is containing few
The amino curing agent of catalyst PPTS is measured, organic carrier is made in dispersion 40min under high revolving speed.
(3) preparation of high heat-conductivity conducting elargol: 19wt% organic carrier, 80wt% flake silver powder tap density in proportion
6.5g/cm3, 2.5 μm of average grain diameter, scaling loss < 1%, specific surface area 0.4m2/ g keeps carrier abundant with silver powder using three-high mill
Mixing, is added the carbon nanotube of 1wt% nanometers of modified by silver, and high heat-conductivity conducting glue is made in mixing dispersion.
Embodiment 2
(1) the carbon nano-tube modified preparation of nano silver: 15 μm of carbon nanotubes of 1g average length are added in ethanol solution, are surpassed
Sound disperses 25 minutes, and alkyl polyoxyethylene sulfates and sodium chloride is added and disperses to carbon nano-tube modification, ultrasonic 1.5h receives carbon
The centrifuge separation of mitron suspension, can add a small amount of sodium nitrate or sodium citrate promotes flocculation separation, and is repeatedly washed and sunk with ethyl alcohol
It forms sediment to get the carbon nanotube to after activating；
Modified carbon nanotube is added to the silver oxalate solution of 1mol/L, body is being added under condition of ice bath after stirring 12h
Product is the oxalic acid and hydrazine hydrate solution that concentration is 2mol/L, reacts 15min, with after ethanol washing in vacuum drying oven it is dry for 24 hours,
Obtain the carbon nanotube of nano silver modification.
(2) preparation of organic carrier: hyperbranched novolac epoxy resin or organic siliconresin are dissolved in organic solvent, according to
(W:W=1:2) be dissolved in DBE organic solvent, the stirring of 70 DEG C of constant temperature water baths, it is to be dissolved completely after be down to room temperature, addition is containing few
The amino curing agent of catalyst PPTS is measured, organic carrier is made in dispersion 40min under high revolving speed.
(3) preparation of high heat-conductivity conducting elargol: the range jolt ramming of 32wt% organic carrier, 65wt% flake silver powder in proportion
Density 4.1g/cm3, 8.0 μm of average grain diameter, scaling loss < 1%, specific surface area 1.5m2/ g makes carrier and silver powder using three-high mill
It is sufficiently mixed, the carbon nanotube of 3wt% nanometers of modified by silver is added, high heat-conductivity conducting glue is made in mixing dispersion.
Embodiment 3
(1) the carbon nano-tube modified preparation of nano silver: 10 μm of carbon nanotubes of 1g average length are added in ethanol solution, are surpassed
Sound disperses 30 minutes, and sulfonylmethyl sulfonate and cetyl phosphate is added and disperses to carbon nano-tube modification, ultrasonic 2h, by carbon
Nanotube suspension centrifuge separation, can add a small amount of sodium nitrate or sodium citrate promotes flocculation separation, and repeatedly be washed with ethyl alcohol
It precipitates to get the carbon nanotube to after activating；
Modified carbon nanotube is added to the silver nitrate and silver orthophosphate solution of 1mol/L, stirs after 12h and is volume is added
Concentration is the hydrazine hydrate solution of 2mol/L, reacts 15min, with after ethanol washing in vacuum drying oven it is dry for 24 hours to get arriving nanometer
The carbon nanotube of modified by silver.
(2) preparation of organic carrier: hyperbranched novolac epoxy resin or organic siliconresin resin are dissolved in organic solvent,
Be dissolved in DBE organic solvent according to (W:W=1:2), the stirring of 70 DEG C of constant temperature water baths, it is to be dissolved completely after be down to room temperature, addition contains
There is the amino curing agent of a small amount of catalyst PPTS, organic carrier is made in dispersion 40min under high revolving speed.
(3) preparation of high heat-conductivity conducting elargol: the range jolt ramming of 23wt% organic carrier, 72wt% flake silver powder in proportion
Density 5.2g/cm3, 4.3 μm of average grain diameter, scaling loss < 1%, specific surface area 1.1m2/g；The range tap density of spherical silver powder
4.8g/cm3, 1.2 μm of average grain diameter, scaling loss < 1%, specific surface area 0.9m2/g.Keep carrier abundant with silver powder using three-high mill
Mixing, is added the carbon nanotube of 5wt% nanometers of modified by silver, and high heat-conductivity conducting glue is made in mixing dispersion.
Electrically and thermally conductive adhesive 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 square shape of upper and lower surface smooth parallel, size is on the left side 10 × 10mm
Then the right side, thickness about 1mm spray carbon shading in sample surfaces, measure electrically and thermally conductive adhesive using 447 thermal conductivity instrument of model Netch LFA
Heat transfer property.
(2) electric performance test
On the glass plate that ethanol is crossed, by 300 mesh expanded sheet metals, conductive film layer is printed, is put into baking oven, 175~
200 DEG C of 1~2h of solidification, four probe machine testing coating square resistances utilize Dektak step instrument test features film thickness.
The performance indicator of the electrocondution slurry of 1 Examples 1 to 3 of table preparation
| Performance indicator | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Curing time (min) | 60 | 90 | 120 |
| Solidification temperature (DEG C) | 200 | 185 | 175 |
| Conductivity (S/cm) | <2.0×105 | <3.2×105 | <3.2×105 |
| Thermal conductivity (W/mK) | >70 | >50 | >60 |
| Elasticity modulus | Less than 120% | Less than 120% | Less than 120% |
| Shear strength | >15MPa | >15MPa | >15MPa |
| Slurry thixotropy | 3.6 | 4.8 | 4.1 |
The present invention by carrying out nanometer modified by silver to carbon nano tube surface, make by the Van der Waals on the one hand reduced between carbon nanotube
Firmly, it realizes the depolymerization to agglomeration nano pipe, obtains good thixotropy and moisture dispersibility；On the other hand, carbon pipe is special
Surface texture inhibits the aggregation between loading nano silvery, realizes the stable dispersion of nano-Ag particles, reduces cladding to greatest extent
The usage amount of agent covering, it is ensured that the high sintering activity of loading nano silvery.The nano silver of carbon nano tube surface load reduces carbon and receives
Thermal resistance between mitron and polymer interface promotes phonon transmission, is conducive to improve heat exchanger effectiveness；The low-temperature sintering of nano silver
Activity realizes that carbon nanotube constructs good thermal conducting path between flake silver powder, promotes carrier concentration and carrier mobility；
The introducing of carbon nanotube enhances the mechanical strength and thermal stability of institutional framework, avoids the brittle generation of high silver content system.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as, without departing from the inventive concept of the premise, can also made
Several modifications and improvements, these are all within the scope of protection of the present invention.Therefore, the scope of protection of the patent of the present invention should be with appended power
Subject to benefit requires.
Claims (7)
1. a kind of conducting resinl of the carbon nano-tube modified preparation of nano silver, it is characterised in that: be made of following raw material: resin carrier
19-32wt%, silver powder 65-80wt%, the carbon nano-tube modified 1-5wt% of nano silver.
2. the conducting resinl of the carbon nano-tube modified preparation of a kind of nano silver according to claim 1, it is characterised in that: the silver powder is piece
One or both of shape, spherical silver powder composition, 4.0~6.5g/cm of range tap density of flake silver powder3, average grain diameter 2.5
~8.0 μm, scaling loss < 1%, 0.4~1.5m of specific surface area2/g；4.3~5.6g/cm of range tap density of spherical silver powder3, put down
Equal 0.7~2.5 μm, scaling loss < 1%, 0.5~1.3m of specific surface area of partial size2/g。
3. a kind of conducting resinl of the carbon nano-tube modified preparation of nano silver according to claim 1, it is characterised in that: described to receive
Rice modified by silver carbon nanotube be 1mol/L silver compound solution, 1mol/L surfactant solution, 5-15 μm of carbon nanotube of length,
By chemical reduction method synthetic composite material, used in reducing agent be sodium borohydride, hydrazine hydrate, formaldehyde, dimethylformamide,
One of citric acid, oxalic acid, glucose or multiple combinations.
4. a kind of conducting resinl of the carbon nano-tube modified preparation of nano silver according to claim 3, it is characterised in that: the silver
Compound be silver nitrate, silver oxalate, silver orthophosphate, actol, silver citrate, silver tetrafluoroborate, acetylacetone,2,4-pentanedione silver one kind or
It is a variety of.
5. a kind of conducting resinl of the carbon nano-tube modified preparation of nano silver according to claim 3, it is characterised in that: the table
Face activating agent is one kind of anionic surfactant carboxylate, sulfonate, sulfuric acid or phosphate ester salt, nonionic table of arranging in pairs or groups
Face activating agent or inorganic assistant.
6. the preparation method of conducting resinl prepared by the carbon nanotube of a kind of nanometer of modified by silver described in claim 1, feature exist
Include the following: in specific steps
(1) the carbon nano-tube modified preparation of nano silver:
Carbon nanotube is added in ethanol solution, ultrasonic disperse 20-30 minutes, surfactant is added to carbon nano-tube modification point
It dissipates, ultrasonic 1-2h, carbon nano tube suspension is centrifugated and repeatedly washs precipitating with ethyl alcohol and is received to get to the carbon after activation
Mitron；
Modified carbon nanotube is added to the silver compound solution of 1mol/L, 2mol/L is added under condition of ice bath after stirring 12h
Reducing solution, 10-15min is reacted, with dry for 24 hours to get to nanometer modified by silver in a vacuum drying oven after ethanol washing
Carbon nanotube,
(2) preparation of high heat-conductivity conducting glue:
Hyperbranched novolac epoxy resin or organic siliconresin resin are dissolved in organic solvent, 70 DEG C of stirring in water bath of constant temperature, to molten
It is down to room temperature after solution is complete, adds amino resin curing agents, organic carrier is made in dispersion under high revolving speed, and silver powder and resin are mixed
It closes, keeps silver powder fully dispersed using three-high mill, addition nano silver is carbon nano-tube modified later, and mixing dispersion is made high thermal conductivity and leads
Electric glue.
7. the conducting resinl of the carbon nanotube preparation of described in claim 1 nanometer of modified by silver is applied to electric slurry packaging technology.
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