CN107629544A - A kind of preparation method of multi-element compounds nanoelectronic ink combined type - Google Patents
A kind of preparation method of multi-element compounds nanoelectronic ink combined type Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of multi-element compounds nanoelectronic ink combined type, using the nanometer silver alloy lysate after modified Nano copper and organic selenization as function phase, the graphitic carbon black that deep oxidation is crossed does cladding, it is connector to add ether-containing key modified epoxy, adjuvant and solvent, copper silver carbon graphite is participated in liquid and solid phase reaction and produce nucleus coordination chemistry, form multiple element combination and dispersed 1 splendid 100nm carbon coating silver-bearing copper ink；Its component and weight/mass percentage composition：Copper powder 5 90%, silver powder 5 80%, graphite 0.1% 95%, carbon black 0.1% 95%, resin 0.1% 30%, auxiliary agent 0.1% 30.0%, solvent 3.0% 99%；Antioxidant：Ma2MoO4：C6H5N3：CIO2=3：3：1 PAM solution：High relative molecular mass PAM=3：2 PP：Talcum powder=1.75 1.20: 1.
Description
Technical field
The present invention relates to multi-element compounds preparing technical field, more particularly to a kind of electron ink microcapsule and its preparation
Method, belong to electron ink microcapsule technology.
Background technology
Nanoelectronic ink is suitable for micro- spray of " piezoelectric type " inkjet printing, " laser is directly write " micro- straight connect prints conduction
The doping of circuit and functional material, its tool have been widely used.For example, its can be applied to 3D printing material, PV solar cells,
TP touch-screens, RFID radio frequency recognizing electronic labels, automotive electronics, Electronic Paper, LED, TR, IC, PCB, FPC, CSP, FC, VFD,
ITO, EL cold light film, CMOS modules, LCM modules, PFD flat-panel monitors, LCD liquid crystal displays, PDP plasmas are shown, OLED has
Organic electro luminescent is shown, thin film switch, keyboard, sensor, photoelectric device, communication electronics, microwave communication, medical electronics, passive
The fields such as device, thick film circuit, piezo-electric crystal, integrated circuit.But resistance, conductor and Jie of current China nano materials research
Chylema material poor compatibility, it is few to be related to nanometer research contents of mainstream technology high, precision and frontier, and particularly some have important application
The technical research of prospect is weaker, it is impossible to meets industrial demand.Meanwhile existing technique during ink generally to dividing
Dissipate and granularity viscosity sintering temperature can not be grasped well, HIC is with using Au slurries with spacer medium without compatible product；Grain
Footpath is failed, and distribution is wide, crystallization is incomplete, and activity height is not suitable for some industry.
What foreign study was most now is high-end elemental silver Ag nano inks, but as argent Ag prices persistently rise,
It is difficult to produce on a large scale as noble metal, there is an urgent need to find a kind of low cost, the former material of high conductivity in printed electronic market
Expect to replace noble silver Ag, the multifunctional performance of the cost of conductive ink and raising conductive ink slurry is reduced with this；Copper
Price be silver-colored price 1/50-1/80, resistivity be 1.72 × 10-8 Ω cm, with silver-colored resistivity 1.59 × 10-8 Ω cm
Closely.And also such as copper Cu bases ink, electric conductivity are just fine for graphite and carbon black, Cu belongs to base metal, but its surface
Activity is larger, and particle is easy to reunite, and heat surface is easily oxidized to Cu2O, but, by our continuous research experiments for many years
It was found that can significantly be delayed using three-step approach or prevent oxidization of copper powder, copper powder is placed in corrosion inhibiter sodium molybdate Ma2MoO4 by the first step
Soaked with BTA C6H5N3 proportionings in CIO2 medium solutions, metal surface is formed completely stable passivation against corrosion
Film, contacts of the micro CI of CIO2 with metallic matrix is effectively prevented, avoids the generation of spot corrosion；Second step uses vitamin C (Vc)
Vitamin C bolt is that reducing agent can prevent related copper ion from producing oxygen radical, it is not oxidized easily in atmosphere and is lost gold
The characteristic of category；Inherently the superconduction carbon black graphite with fine electric action mixes (CB) filler to the addition of 3rd step, passes through modification
Ag nano-particles are added afterwards and carry out ball milling, and silver particles are coated by copper and carbon particle, form tri- kinds of a cladding base Ag+Cu+CB
Composition particles are blended in element, and oxidization of copper powder can be further prevented with this moditied processing method（Will also use in 3rd step silver from
Sub- water is put into modified copper powder by the way that liquid phase reduction is primary into the AgNO3 particles for making its uniform ingredients, adding assistant solvent
And Na2Se selenium sources react, and uniformly have children outside the state plan scattered classification final product Organic Selenium Na in 18 megaohms of water by stirring at low speed2Se's
Compound Cu+Ag alloy solutions participate in modified graphitic carbon black ball milling altogether）Matched by suitable surfactant, selection
Hyper-dispersant, self-control effect exceed the thickener of ethyl cellulose, by scattered and purifies and separates, can make every in composite
Individual particle all possesses monodispersity, seldom reunites, improves aerial stability and the affinity with organic material.
The content of the invention
In view of this, the invention provides a kind of preparation method of multi-element compounds nanoelectronic ink combined type.
To achieve these goals, the preparation method of a kind of multi-element compounds nanoelectronic ink combined type of the invention,
It comprises the following steps：
1. a kind of preparation method of multi-element compounds nanoelectronic ink combined type, it is characterised in that the preparation method includes
Following steps：
S1. first by sodium molybdate Ma2MoO4 and BTA C6H5N3 solution according to mass fraction 1：1 ratio allotment；
CIO2 media and corrosion inhibiter total amount are 1：Solution is formed in 3 mass fraction, loads container after its impregnation of corrosion inhibition rate 82.1%
In A；
S2. it is presoma Cu solions to be added into dispersing agent C TAB cetyl trimethylammonium bromides and protective agent PVP, with one
In the low plus appropriate reducing agent L- Vitamin C bolts of fixed low price speed, treat that solution is changed into light yellow from colourless, when finally taking on a red color
Stop being added dropwise；The mass fraction of copper and L- Vitamin C bolts is 1：1.3-1.9 aids reduction, copper ion concentration 0.13-
0.20mol/L, time 2.5-3h, temperature are 25-35 DEG C, are added：Degussa hyper-dispersant, in reaction terminating pH value 12-
14th, in reaction temperature and L- Vitamin C bolts rate of addition 5 drip/min~10 drops/min rate control condition under form kind of a Cu powder
Solution, reacted suspension filters separation to filtrate and clarified, and is cleaned 3 times with deionized water, vacuum drying temperature 55-
70 °, product is<100nm copper powder particles；
S3. solvent 20-100nm copper powders particle made from step S2 added in the A containers that mass fraction is 1-3% stirs again
Mix and be uniformly dissolved, then with 25% ammoniacal liquor, by 1：1 volume ratio adds water and is dissolved into weak base ammoniacal liquor wash particle 3 times, Ran Houyong
Deionized water and washes of absolute alcohol 3 times, are dried at a temperature of 60-80 DEG C, add 18 megaohms of water and dispersant, magnetic agitation are equal
It is even obtain it is pretreated<100nm copper particle solution is placed in clean container B；
S4. silver ionized water is held by the way that liquid phase reduction is primary into the AgNO3 particles for making its uniform ingredients, adding assistant solvent input
In device B material stirring dissolving after and Na2Se selenium sources are reacted, and scattered classification is uniformly had children outside the state plan in 18 megaohms of water by stirring at low speed
Final product Organic Selenium Na2Se compound Cu+Ag alloy solutions, are placed in clean container C；S5. particle diameter 1-100um is surpassed
Carbon black and particle diameter 1-100um acetylene carbon blacks are led by 3：2 percentage by weight PWC, addition concentration are 20% ~ 60% mass fraction
HNO3, HNO3Solution is 3 with the percentage by weight PWC of acetylene carbon black and superconduction carbon black mixed powder:1 to 6:1, at 65-90 DEG C
Oxidation reaction 1-8h, filtering, water washing is added to not having-NO3Untill；Then, after then being dried under 60 DEG C of vacuum, it is placed in clean
Container D in；
S6. material in nanomaterial in container C and container D is added into modified epoxy and is placed in ball mill planet rolling wet bulb
Mill, 1 ~ 100 nanometer of granulated carbon coated with silver copper solution is obtained, is respectively placed in clean container E and F；
S7. according to 3：PAM solution and high relative molecular mass PAM solution are uniformly dissolved by 2 ratios, and mixed liquor is diluted to and contained admittedly
The solution for 0.5-1.0% is measured, observes high concentration and high viscosity in suspension, can be further by the aqueous solution, dilution turns into
0.1 ‰, in mass ratio 1.75-1.20: 1 adds PP μ-talcum powder, and the material added in container E and F is with 100-800r/min speed
Degree continues to stir 5-20min；
S8. in E and F material in homogenizer, reactive diluent, dispersant, fire retardant, vertical stream are separately added into successively
Suspending agent, 5-15min is stirred under conditions of mixer 200-500r/min；Mixing temperature is 70-120 DEG C, adds ultra-pure water,
Through it is fully dispersed uniformly after, recycle ultrasonic wave disperse 25min, 1-20nm and 80-100nm granule materials are classified out, with difference
The centrifuge 60min and 30min of rotating speed, are fitted into container in G；
S9. by finely dispersed material, take a small sample to carry out XRD x ray diffractions and test its purity, Span 80 is used in remaining part
Dispersant is added in VC and PVP solution to be disperseed again, is cleaned by ultrasonic and is removed impurity, preferred 1-20nm after water-soluble dilution agent
Argent Ag+ copper Cu+ carbon blacks of particle diameter+graphite C B combination lysate, and go down bubble removing in 60 DEG C of vacuum conditions；
S10. the test of the observational technique and impressing pattern of electrically conductive ink particle crystallization degree component.
As a further improvement on the present invention, multi-element compounds composite electronic ink, its multi-element compounds element include：
One kind, the optional Cu of copper Cu compound in AgNO3, AgBF4, AgPF6, Ag2O, CH3COOAg, AgCF3SO3, Ag-CIO4
（NO3）2nd, CuCl 2H O, preferably CuCO3, CuSO4 one of which, Cu（NO3）2 and AgNO3；
As a further improvement on the present invention, the cladding used in multi-element compounds element include graphene, graphite, carbon black,
Activated carbon, CNT, high structure abrasion resistant carbon black, conductive mica powder, conductive titanate dioxide, conductive barium sulfate, conductive barite
One of powder, conductive ATO powder, electrically conductive polyaniline, electrically conductive graphite powder, conductive carbon fibre are planted, preferably superconduction carbon black+acetylene
The modified dissolving compositions of carbon black；
As a further improvement on the present invention, the Organic Selenium source compound sodium selenide [Na used2Se], dimethyl-selenide [(CH3)2Se], diethyl selenide [(C2H5)2Se], di-t-butyl selenium [(C4H9)2Se], allyl methyl selenium [being represented with X], diallyl selenium
[C6H10Se], tert-butyl group pi-allyl selenium [being represented with H], chalcogen Se/S one of which, preferably sodium selenide [Na2Se]；
As a further improvement on the present invention, ammoniacal liquor of the fraction as 5-10% will be measured using diethanol amine reducing agent and adjusts reaction system
PH value 7-10, restore silver powder, copper solution and silver powder in the container B after modification be separately added into and organic selenium source and helped
Agent, dispersant, form Na2Se/Cu and Na2Se/Ag solution, stirring at low speed 10-30min, two kinds of solution mixed dissolution low speed again
Stirring obtains Na2Se/（Cu+Ag）Alloy solution；
As a further improvement on the present invention, the micron material in container C in nanomaterial and container D is according to 5-60%:20-95%
Mass fraction grinds 24-120 hours；Appropriate gasoline liquid medium, 4 grinding pots and ￠ 1mm--- are added every 2-4 hours
￠ 30mm alloying pellets, gasoline are 5 with powder ratio：100 ；Ratio of grinding media to material is 50：1 ；Milling time 70-90h；Rotational velocity
600-800rpm ；Revolution speed 1000rpm.2000rpm is centrifuged, it is more than 10nm particles can on adjustment centrifuge from
The heart, the particle less than 10nm particles centrifuge in ultracentrifuge；
1-5nm particle diameters：50-85min is centrifuged with 40000r/min；
5-10nm particles centrifuge 40-80min with 25000r/min；
8-15nm particles centrifuge 30-75min with 25000r/min；
18-40nm particles centrifuge 20-60min with 15000r/min；
40-80nm particles centrifuge 15-45min with 15000r/min；
80-100nm particles centrifuge 10-40min with 10000r/min;
As a further improvement on the present invention, modified epoxy, be the isocyanate terminated polyurethane using 3-10% as toughener,
Terminal isocyanate group is reacted with the secondary hydroxyl on epoxy resin, and flexible ehter bond is introduced on epoxy resin and is formed；Polyurethane
The mass ratio of modified epoxy IPN and mixture is 1：4-10；Oleyl amine and toluene in material mixture liquid described in step S6
Volume ratio is 5:100, the weight ratio of ball milling powder and mixed solution is 60:100, it is classified out 1 ~ 20 nanometer of particle and 80 ~ 100
Nano-solution；Polymeric hyperdispersants dispersiveness reaches 99.9% in S7, and stabilization is deposited>More than 55h, dosage 0.5-10%；
As a further improvement on the present invention, technological parameter is：PH value 6-13, solids content 10-95%, silver content 5-78%, glue
Degree 3.0 ~ 20.0（MPa.S), particle diameter about 1-16nm particles, average grain diameter<2-12nm；The ink of injection is that the picoliters of 1 picoliters -2 can
Conductor spacing is made and is less than 50um, thickness is less than 8um, and sheet resistance reaches 2.5-5m Ω/mouth, the ∧ 7s/ of electrical conductivity 2.32 × 10
m；
As a further improvement on the present invention, with Japanese JEM-2010F TEM Flied emissions super-resolution transmission electron microscope
（HRTEM）Desk-top transmission：In advance with diluent and absolute ethyl alcohol dilution 1：900, temperature 20C, ultrasonic disperse 20min, then
Nanoparticle suspension is dropped on Electronic Speculum copper mesh, after waiting suspension volatilization, observation is put into sample Cu, Ag, CB atom group
Situations such as dividing crystal structure, crystallinity, phase group；
As a further improvement on the present invention, the ink of five kinds of different Elements Atom proportionings of A, B, C, D, E can be used during detection
TURBO pattern jet speeds 4-300mm2/min carries out chip electrode graphic-print, and 1-18min is sintered through 70-140 DEG C of temperature
Afterwards, tested by microscope, ink can improve coffee toroidal effect nonuniform deposition phenomenon to caused by suspension in liquid, display
Distribution of particles in whole wire line figure is uniform.
Compared with prior art, the beneficial effects of the invention are as follows：The present invention is a kind of multi-element compounds nanoelectronic ink
The preparation method of combined type, by adjusting the pH value of metallic ink slurry, slurry viscosity, temperature, slurry metal particle diameter fineness, show
Writing strengthens resistance to moisture and resistance to corrosion.Part noble silver Ag is substituted using cheap copper Cu and carbon CB, forms Ag+Cu+CB groups
Compound, adulterate 10-15%（Quality）Activation can improve during Ag5-6Again, it is remarkably improved the efficiency of device.Using materialization synthetic method
Graphitization technique is induced with Composite, indigenous graphite is induced in the presence of reactive diluent and initiator, convenient can be produced excellent
The graphite electrode of matter.Cladding base compound particle is formed using three-step approach, can effectively suppress copper oxidation, self-control dispersive property is more preferable
Dispersant, ink can be used for RFID, PCB, and FPCB product particle mean sizes 2-12nm nanometer silver ink coordinates super printer, system
The wire of 1 μm ~ 5 μm of line width/spacing is obtained, nearly 95% effect is reduced compared with conventional screen printing.
The present invention is that a kind of preparation method of multi-element compounds nanoelectronic ink combined type improves material resistance stabilization
The flux creep of rate and conductive path and conductive network activation energy, and sintering temperature can be reduced to 70 ~ 140 DEG C because particle diameter is small
Between, can not only be deposited on PI, more can fast deposition is cheap in cost and Tg is relatively low plastics, on flexible substrate, as FPCB,
PET, paper etc..The solution dispersion stabilization improved in microelectric technique material therefor that is portable at present and becoming more meticulous is poor,
Base material adhesive force is weak, and sheet resistance is big after high temperature sintering, and resolution ratio electric conductivity is low, effectively the porous of coordination electrode can not lack
Fall into.Efficiently solve electrolyte catalytic oxidation composition granule and the technologies such as preheating copper ion postponement oxidation or oxidizing component are smaller are difficult
Point；The more dense structure of multi objective is realized, is advantageous to seepage flow threshold values and NTC phenomenons.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments described in invention, for those of ordinary skill in the art, on the premise of not paying creative work,
Other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is a kind of embodiment of preparation method one of multi-element compounds nanoelectronic ink combined type of the present invention
Method flow schematic diagram.
Embodiment
The present invention discloses a kind of preparation method of multi-element compounds nanoelectronic ink combined type, and it comprises the following steps,
A kind of method that showering nano metal ink prepares film, it comprises the following steps：
1. a kind of preparation method of multi-element compounds nanoelectronic ink combined type, it is characterised in that the preparation method includes
Following steps：
S1. first by sodium molybdate Ma2MoO4 and BTA C6H5N3 solution according to mass fraction 1：1 ratio allotment；
CIO2 media and corrosion inhibiter total amount are 1：Solution is formed in 3 mass fraction, loads container after its impregnation of corrosion inhibition rate 82.1%
In A；
S2. it is presoma Cu solions to be added into dispersing agent C TAB cetyl trimethylammonium bromides and protective agent PVP, with one
In the low plus appropriate reducing agent L- Vitamin C bolts of fixed low price speed, treat that solution is changed into light yellow from colourless, when finally taking on a red color
Stop being added dropwise；The mass fraction of copper and L- Vitamin C bolts is 1：1.3-1.9 aids reduction, copper ion concentration 0.13-
0.20mol/L, time 2.5-3h, temperature are 25-35 DEG C, are added：Degussa hyper-dispersant, in reaction terminating pH value 12-
14th, in reaction temperature and L- Vitamin C bolts rate of addition 5 drip/min~10 drops/min rate control condition under form kind of a Cu powder
Solution, reacted suspension filters separation to filtrate and clarified, and is cleaned 3 times with deionized water, vacuum drying temperature 55-
70 °, product is<100nm copper powder particles；
S3. solvent 20-100nm copper powders particle made from step S2 added in the A containers that mass fraction is 1-3% stirs again
Mix and be uniformly dissolved, then with 25% ammoniacal liquor, by 1：1 volume ratio adds water and is dissolved into weak base ammoniacal liquor wash particle 3 times, Ran Houyong
Deionized water and washes of absolute alcohol 3 times, are dried at a temperature of 60-80 DEG C, add 18 megaohms of water and dispersant, magnetic agitation are equal
It is even obtain it is pretreated<100nm copper particle solution is placed in clean container B；
S4. silver ionized water is held by the way that liquid phase reduction is primary into the AgNO3 particles for making its uniform ingredients, adding assistant solvent input
In device B material stirring dissolving after and Na2Se selenium sources are reacted, and scattered classification is uniformly had children outside the state plan in 18 megaohms of water by stirring at low speed
Final product Organic Selenium Na2Se compound Cu+Ag alloy solutions, are placed in clean container C；
Further, added with silver nitrate in deionized water according to 2：3-5 mass fractions make its dissolving under magnetic stirring, will
Mass fraction is that the pH value 7-10 of regulation reaction system is added dropwise in 5-10% ammoniacal liquor；Diethanol amine and deionized water are according to 1：3-5 matter
Measure fraction dissolving, two kinds of solution are mixed evenly, by copper solution in the container B after modification add again organic selenium source and
Auxiliary agent, dispersant, form Na2Se/Cu and Na2Se/Ag solution, stirring at low speed 10-30min, mixed dissolution is low again for two kinds of solution
Speed stirring obtains Na2Se/（Cu+Ag）Alloy solution.
S5. particle diameter 1-100um superconductions carbon black and particle diameter 1-100um acetylene carbon blacks are pressed 3：2 percentage by weight PWC, add concentration
For the HNO of 20% ~ 60% mass fraction3, HNO3Solution and acetylene carbon black and the percentage by weight PWC of superconduction carbon black mixed powder
For 3:1 to 6:1, the oxidation reaction 1-8h at 65-90 DEG C, filtering, water washing are added to not having-NO3Untill；Then, then 60
After being dried under DEG C vacuum, it is placed in clean container D；
S6. material in nanomaterial in container C and container D is added into modified epoxy and is placed in ball mill planet rolling wet bulb
Mill, 1 ~ 100 nanometer of granulated carbon coated with silver copper solution is obtained, is respectively placed in clean container E and F；
Further, epoxy resin is added in mixing plant, then is stirred, is stirred while adding ethylene glycol
Ethyl ether acetate ester（CAC）, until epoxy resin is completely dissolved, then warm 70 DEG C in holding, the polyurethane for adding stoichiometry is pre-
Aggressiveness, epoxy resin：Both performed polymers mass ratio is 9：1, reaction time 2h, finally obtain polyurethane modified epoxy resin
IPN。
Micron material in container C in nanomaterial and container D is according to 5-60%:20-95% mass fractions grind 24-120
Hour；Add appropriate gasoline liquid medium, 4 grinding pots and ￠ 1mm--- ￠ 30mm alloying pellets every 2-4 hours, gasoline with
Powder ratio is 5：100 ；Ratio of grinding media to material is 50：1 ；Milling time 70-90h；Rotational velocity 600-800rpm；Revolution speed
Spend 1000rpm.2000rpm is centrifuged, and more than 10nm particles can be centrifuged on adjustment centrifuge, less than 10nm particles
Particle centrifuges in ultracentrifuge；
1-5nm particle diameters：50-85min is centrifuged with 40000r/min；
5-10nm particles centrifuge 40-80min with 25000r/min；
8-15nm particles centrifuge 30-75min with 25000r/min；
18-40nm particles centrifuge 20-60min with 15000r/min；
40-80nm particles centrifuge 15-45min with 15000r/min；
80-100nm particles centrifuge 10-40min with 10000r/min;
The mass ratio of polyurethane modified epoxy resin IPN and principal goods material is 1：4-10；It is oily in material mixture liquid described in step S6
The volume ratio of amine and toluene is 5:100, the weight ratio of ball milling powder and mixed solution is 60:100, it is classified out 1 ~ 20 nanometer of particle
With 80 ~ 100 nano-solutions；Polymeric hyperdispersants dispersiveness reaches 99.9% in S7, and stabilization is deposited>More than 55h, dosage are
0.5-10%；
S7. according to 3：PAM solution and high relative molecular mass PAM solution are uniformly dissolved by 2 ratios, and mixed liquor is diluted to and contained admittedly
The solution for 0.5-1.0% is measured, observes high concentration and high viscosity in suspension, can be further by the aqueous solution, dilution turns into
0.1 ‰, in mass ratio 1.75-1.20: 1 adds PP μ-talcum powder, and the material added in container E and F is with 100-800r/min speed
Degree continues to stir 5-20min；
S8. in E and F material in homogenizer, reactive diluent, dispersant, fire retardant, vertical stream are separately added into successively
Suspending agent, 5-15min is stirred under conditions of mixer 200-500r/min；Mixing temperature is 70-120 DEG C, adds ultra-pure water,
Through it is fully dispersed uniformly after, recycle ultrasonic wave disperse 25min, 1-20nm and 80-100nm granule materials are classified out, with difference
The centrifuge 60min and 30min of rotating speed, are fitted into container in G；
S9. by finely dispersed material, take a small sample to carry out XRD x ray diffractions and test its purity, Span 80 is used in remaining part
Dispersant is added in VC and PVP solution to be disperseed again, is cleaned by ultrasonic and is removed impurity, preferred 1-20nm after water-soluble dilution agent
Argent Ag+ copper Cu+ carbon blacks of particle diameter+graphite C B combination lysate, and go down bubble removing in 60 DEG C of vacuum conditions；
Preparation method below by test experiments to a kind of multi-element compounds nanoelectronic ink combined type by the present invention
The performance for the metal nanometer thin film prepared is tested.
（1）Adhesive force：3M600# adhesive tapes are bonded on cured good printed sample lines, the long 10cm of conductive line,
Wide 0.9mm, 3 μm of thickness, ensure that adhesive tape long side is parallel with conductive line direction, flat, 1 point of placement is firmly wiped with advanced drawing rubber
Zhong Hou, it is firmly vertical to pull adhesive tape rapidly, observe whether adhesive tape and sample lines have film layer to pull, and survey lines electricity before and after adhesion
Changing value is hindered, every kind of conductive line is surveyed 5 parallel values, averaged.
（2）Coating it is wear-resisting pencil hardness test, using vibrating abrasion wear test machine, by by product put into color pebble and
In the special liquid of liquid medicine mixing, vibration friction, the scratch-resistant performance of test product are carried out.Test result is as follows：The present invention's
Metal nanometer thin film meets ASTM D 3363-74 standards and the standard of ASTM D 3363-00 coating pencil hardness, reaches 5H.
（3）Salt fog burn-in test：Using salt spray test chamber, in standard-GB/T 10125, GB/T 12000, ASTM (35
± 2) DEG C, humidity is more than 95%, and amount of fog is that 1~2mL/80cm*h nozzle exit pressures are 78.5~137.3kPa (0.8~1.4kgf/
Cm2 under the conditions of), in salt spray test chamber, spraying will be passed through containing (5 scholar 0.5) % sodium chloride, the salt solution that pH value is 6.5~7.2
Device is sprayed, and allows salt fog to be deposited on part to be test, by certain time it was observed that metal nanometer thin film surface is corrosion-free
State.
（4）Curing action：Differential scanning calorimeter is carried out with PerkinElmerDSC-7 types thermal analyzer（DSC）, atmosphere
For still air, elevated cure, DSC heating rate is 10 DEG C/min, and temperature range is 35~180 DEG C.
（5）Flexible PCB bending resistance, with open up this up to TOS-817 types wave experimental machine test modified epoxy base lead
The bending resistance of electric ink printed wire.The long 2.4cm of conductive line, wide 0.9mm, 3 μm of thickness are determined, 5 parallel values is surveyed, is averaged
Value.Experiment parameter is as follows：Swing angle：180°；Sway velocity：60 min-1；Wave number：10000 times；Temperature：28
DEG C, relative humidity：80%.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.Any reference in claim should not be considered as to the involved claim of limitation.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that those skilled in the art should for clarity
Using specification as an entirety, the technical scheme in each embodiment can also close through appropriate, and forming those skilled in the art can
With the other embodiment of understanding.
Claims (10)
1. a kind of preparation method of multi-element compounds nanoelectronic ink combined type, it is characterised in that the preparation method includes
Following steps：
S1. first by sodium molybdate Ma2MoO4 and BTA C6H5N3 solution according to mass fraction 1：1 ratio allotment；
CIO2 media and corrosion inhibiter total amount are 1：Solution is formed in 3 mass fraction, loads container after its impregnation of corrosion inhibition rate 82.1%
In A；
S2. it is presoma Cu solions to be added into dispersing agent C TAB cetyl trimethylammonium bromides and protective agent PVP, with one
In the low plus appropriate reducing agent L- Vitamin C bolts of fixed low price speed, treat that solution is changed into light yellow from colourless, when finally taking on a red color
Stop being added dropwise；The mass fraction of copper and L- Vitamin C bolts is 1：1.3-1.9 aids reduction, copper ion concentration 0.13-
0.20mol/L, time 2.5-3h, temperature are 25-35 DEG C, are added：Degussa hyper-dispersant, in reaction terminating pH value 12-
14th, in reaction temperature and L- Vitamin C bolts rate of addition 5 drip/min~10 drops/min rate control condition under form kind of a Cu powder
Solution, reacted suspension filters separation to filtrate and clarified, and is cleaned 3 times with deionized water, vacuum drying temperature 55-
70 °, product is<100nm copper powder particles；
S3. solvent 20-100nm copper powders particle made from step S2 added in the A containers that mass fraction is 1-3% stirs again
Mix and be uniformly dissolved, then with 25% ammoniacal liquor, by 1：1 volume ratio adds water and is dissolved into weak base ammoniacal liquor wash particle 3 times, Ran Houyong
Deionized water and washes of absolute alcohol 3 times, are dried at a temperature of 60-80 DEG C, add 18 megaohms of water and dispersant, magnetic agitation are equal
It is even obtain it is pretreated<100nm copper particle solution is placed in clean container B；
S4. silver ionized water is held by the way that liquid phase reduction is primary into the AgNO3 particles for making its uniform ingredients, adding assistant solvent input
In device B material stirring dissolving after and Na2Se selenium sources are reacted, and scattered classification is uniformly had children outside the state plan in 18 megaohms of water by stirring at low speed
Final product Organic Selenium Na2Se compound Cu+Ag alloy solutions, are placed in clean container C；S5. particle diameter 1-100um is surpassed
Carbon black and particle diameter 1-100um acetylene carbon blacks are led by 3：2 percentage by weight PWC, addition concentration are 20% ~ 60% mass fraction
HNO3, HNO3Solution is 3 with the percentage by weight PWC of acetylene carbon black and superconduction carbon black mixed powder:1 to 6:1, at 65-90 DEG C
Oxidation reaction 1-8h, filtering, water washing is added to not having-NO3Untill；Then, after then being dried under 60 DEG C of vacuum, it is placed in clean
Container D in；
S6. material in nanomaterial in container C and container D is added into modified epoxy and is placed in ball mill planet rolling wet bulb
Mill, 1 ~ 100 nanometer of granulated carbon coated with silver copper solution is obtained, is respectively placed in clean container E and F；
S7. according to 3：PAM solution and high relative molecular mass PAM solution are uniformly dissolved by 2 ratios, and mixed liquor is diluted to and contained admittedly
The solution for 0.5-1.0% is measured, observes high concentration and high viscosity in suspension, can be further by the aqueous solution, dilution turns into
0.1 ‰, in mass ratio 1.75-1.20: 1 adds PP μ-talcum powder, and the material added in container E and F is with 100-800r/min speed
Degree continues to stir 5-20min；
S8. in E and F material in homogenizer, reactive diluent, dispersant, fire retardant, vertical stream are separately added into successively
Suspending agent, 5-15min is stirred under conditions of mixer 200-500r/min；Mixing temperature is 70-120 DEG C, adds ultra-pure water,
Through it is fully dispersed uniformly after, recycle ultrasonic wave disperse 25min, 1-20nm and 80-100nm granule materials are classified out, with difference
The centrifuge 60min and 30min of rotating speed, are fitted into container in G；
S9. by finely dispersed material, take a small sample to carry out XRD x ray diffractions and test its purity, Span 80 is used in remaining part
Dispersant is added in VC and PVP solution to be disperseed again, is cleaned by ultrasonic and is removed impurity, preferred 1-20nm after water-soluble dilution agent
Argent Ag+ copper Cu+ carbon blacks of particle diameter+graphite C B combination lysate, and go down bubble removing in 60 DEG C of vacuum conditions；
S10. the test of the observational technique and impressing pattern of electrically conductive ink particle crystallization degree component.
A kind of 2. preparation method of multi-element compounds nanoelectronic ink combined type according to claim 1, it is characterised in that
Multi-element compounds composite electronic ink, its multi-element compounds element include：AgNO3、AgBF4、AgPF6、Ag2O、
One kind, the optional Cu of copper Cu compound in CH3COOAg, AgCF3SO3, Ag-CIO4（NO3）2、CuCl₂·2H₂O、CuCO3、
CuSO4 one of which, preferably Cu（NO3）2 and AgNO3.
A kind of 3. preparation method of multi-element compounds nanoelectronic ink combined type according to claim 1, it is characterised in that
The cladding used in multi-element compounds element includes graphene, graphite, carbon black, activated carbon, CNT, the wear-resisting charcoal of high structure
It is black, conductive mica powder, conductive titanate dioxide, conductive barium sulfate, conductive blanc fixe, conductive ATO powder, electrically conductive polyaniline, conduction
One of graphite powder, conductive carbon fibre is planted, preferably the modified dissolving compositions of superconduction carbon black+acetylene carbon black.
A kind of 4. preparation method of multi-element compounds nanoelectronic ink combined type according to claim 1, it is characterised in that
The Organic Selenium source compound sodium selenide [Na used in the S42Se], dimethyl-selenide [(CH3)2Se], diethyl selenide [(C2H5)2Se], di-t-butyl selenium [(C4H9)2Se], allyl methyl selenium [being represented with X], diallyl selenium [C6H10Se], tert-butyl group allyl
Base selenium [being represented with H], preferably chalcogen Se/S one of which, sodium selenide [Na2Se]。
A kind of 5. preparation method of multi-element compounds nanoelectronic ink combined type according to claim 1, it is characterised in that
In step S4, pH value 7-10 of the fraction as 5-10% ammoniacal liquor regulation reaction system will be measured using diethanol amine reducing agent, restore silver
Powder, copper solution and silver powder in the container B after modification are separately added into organic selenium source and auxiliary agent, dispersant, form Na2Se/
Cu and Na2Se/Ag solution, stirring at low speed 10-30min, mixed dissolution stirring at low speed obtains Na to two kinds of solution again2Se/（Cu+
Ag）Alloy solution.
A kind of 6. preparation method of multi-element compounds nanoelectronic ink combined type according to claim 1, it is characterised in that
Micron material in the step S6 containers C in nanomaterial and container D is according to 5-60%:20-95% mass fractions grind 24-
120 hours；Appropriate gasoline liquid medium, 4 grinding pots and ￠ 1mm--- ￠ 30mm alloying pellets, vapour are added every 2-4 hours
Oil is 5 with powder ratio：100 ；Ratio of grinding media to material is 50：1 ；Milling time 70-90h；Rotational velocity 600-800rpm；It is public
Rotary speed 1000rpm；2000rpm is centrifuged, and more than 10nm particles can be centrifuged on adjustment centrifuge, less than 10nm
The particle of grain centrifuges in ultracentrifuge；
1-5nm particle diameters：50-85min is centrifuged with 40000r/min；
5-10nm particles centrifuge 40-80min with 25000r/min；
8-15nm particles centrifuge 30-75min with 25000r/min；
18-40nm particles centrifuge 20-60min with 15000r/min；
40-80nm particles centrifuge 15-45min with 15000r/min；
80-100nm particles centrifuge 10-40min with 10000r/min.
A kind of 7. preparation method of multi-element compounds nanoelectronic ink combined type according to claim 1, it is characterised in that
Modified epoxy described in the step S6, be the isocyanate terminated polyurethane using 3-10% as toughener, it is isocyanate terminated
Base is reacted with the secondary hydroxyl on epoxy resin, and flexible ehter bond is introduced on epoxy resin and is formed；Polyurethane modified epoxy tree
The mass ratio of fat IPN and mixture is 1：4-10；The volume ratio of oleyl amine and toluene is 5 in material mixture liquid described in step S6:
100, the weight ratio of ball milling powder and mixed solution is 60:100, it is classified out 1 ~ 20 nanometer of particle and 80 ~ 100 nano-solutions；S7
Middle polymeric hyperdispersants dispersiveness reaches 99.9%, and stabilization is deposited>More than 55h, dosage 0.5-10%.
A kind of 8. preparation method of multi-element compounds nanoelectronic ink combined type according to claim 1, it is characterised in that
Technological parameter is：PH value 6-13, solids content 10-95%, silver content 5-78%, viscosity 3.0 ~ 20.0（MPa.S), particle diameter about 1-
16nm particles, average grain diameter<2-12nm；The ink of injection can be made conductor spacing for the picoliters of 1 picoliters -2 and be less than 50um, and thickness is small
In 8um, sheet resistance reaches 2.5-5m Ω/mouth, the ∧ 7s/m of electrical conductivity 2.32 × 10.
A kind of 9. preparation method of multi-element compounds nanoelectronic ink combined type according to claim 1, it is characterised in that
In step 10, with Japanese JEM-2010F TEM Flied emissions super-resolution transmission electron microscope（HRTEM）Desk-top transmission：In advance
With diluent and absolute ethyl alcohol dilution 1：900, temperature 20C, ultrasonic disperse 20min, then nanoparticle suspension is dropped in
On Electronic Speculum copper mesh, after waiting suspension volatilization, observation is put into sample Cu, Ag, CB atomic composition crystal structure, crystallinity, phase
Situations such as group.
10. a kind of preparation method of multi-element compounds nanoelectronic ink combined type, its feature exist according to claim 1
In in the step 10, the ink of five kinds of different Elements Atoms proportionings of A, B, C, D, E being sprayed using TURBO patterns during detection
Black speed 4-300mm2/min carries out chip electrode graphic-print, after 70-140 DEG C of temperature sinters 1-18min, passes through microscope
Test, ink can improve coffee toroidal effect nonuniform deposition phenomenon to caused by suspension in liquid, show whole wire line
Distribution of particles in figure is uniform.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111299606A (en) * | 2020-03-19 | 2020-06-19 | 中国科学院高能物理研究所 | Preparation method of nano-gold coffee ring and application of nano-gold coffee ring in SERS detection |
| CN113426995A (en) * | 2021-06-07 | 2021-09-24 | 西湖大学 | Combustible 3D direct writing ink and preparation method and application thereof |
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| CN103772723A (en) * | 2014-01-17 | 2014-05-07 | 苏州斯贝孚光伏科技有限公司 | Method for non-vacuum preparation of nano thin film by taking metallic compound as precursor |
| CN104662106A (en) * | 2013-07-19 | 2015-05-27 | Lg化学株式会社 | Ink composition for producing light-absorbing layer comprising metal nanoparticles, and production method for thin film using same |
| KR20160069728A (en) * | 2014-12-09 | 2016-06-17 | 고려대학교 산학협력단 | A cobalt-molybdenum nanoparticles and method of thereof |
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| CN102205423A (en) * | 2010-03-30 | 2011-10-05 | 株式会社东进世美肯 | Metal nanoparticles, method for producing same, and metal ink composition containing same |
| CN104662106A (en) * | 2013-07-19 | 2015-05-27 | Lg化学株式会社 | Ink composition for producing light-absorbing layer comprising metal nanoparticles, and production method for thin film using same |
| CN103772723A (en) * | 2014-01-17 | 2014-05-07 | 苏州斯贝孚光伏科技有限公司 | Method for non-vacuum preparation of nano thin film by taking metallic compound as precursor |
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| CN111299606A (en) * | 2020-03-19 | 2020-06-19 | 中国科学院高能物理研究所 | Preparation method of nano-gold coffee ring and application of nano-gold coffee ring in SERS detection |
| CN113426995A (en) * | 2021-06-07 | 2021-09-24 | 西湖大学 | Combustible 3D direct writing ink and preparation method and application thereof |
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