CN104858447B - Preparation method and equipment for high-conductivity nano silver for PCB - Google Patents
Preparation method and equipment for high-conductivity nano silver for PCB Download PDFInfo
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- CN104858447B CN104858447B CN201510197484.8A CN201510197484A CN104858447B CN 104858447 B CN104858447 B CN 104858447B CN 201510197484 A CN201510197484 A CN 201510197484A CN 104858447 B CN104858447 B CN 104858447B
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Abstract
The invention discloses a preparation method and equipment for high-conductivity nano silver for a PCB. With adoption of the preparation method, high-conductivity nano silver is prepared through adopting silver nitrate or silver perchlorate as a silver source and adopting the liquid phase reduction method. The prepared nano silver is excellent in conductivity, has an electrical resistivity of 2* 10＜-3＞ omega. cm-6.5* 10＜-3＞ omega. cm, and can be used for the PCB. The equipment comprises a dissolution kettle I, a dissolution kettle II, a silver salt compound purifying column, a reducing agent purifying column, a silver salt compound dissolution kettle, a reducing agent dissolution kettle, a silver salt compound liquid storage tank, a reducing agent liquid storage tank, a temperature control anti-corrosion reaction still, a high-efficient feeding device, a centrifugal separator, a silver recycling device, a temperature control forced air drying box, a tail gas collection treatment device, an effluent treatment device and a water ion exchange device. The preparation method is simple and fewer in working procedures; the equipment is simple in structure, requires less for large-scale production equipment, and facilitates industrialization.
Description
Technical field
The invention belongs to nano material synthesis technical field is and in particular to a kind of preparation method of high connductivity Nano Silver and setting
Standby.
Background technology
Printed electronics are new technologies manufacturing electronic device based on traditional printing methods, can be widely used in big
Area, flexibility and inexpensive various electronics or photovoltaic." 13 " science and technology that the 2014 Nian8Yue Ministry of Science and Technology promulgate
In development prediction, printed electronic material and technology list one of prediction field first in.China in 2002 replaces the U.S. becomes the world
The third-largest wiring board producing country, China's production in 2003 and export amount all reach 6,000,000,000 U.S. dollars, and 2007-2011 annual growth reaches
9.6%, reach 22,000,000,000 U.S. dollars more than the 2.5% of the world, 2012 annual value of production, China is further at aspects such as technology, management within 2013
Improve it is contemplated that 2015 annual value of production reach 27,900,000,000 U.S. dollars, growth rate is stablized 5% thereafter.Existing 3000 many enterprises in the whole nation are carried out
Printed substrate（PCB）Make, larger enterprise focuses mostly in coastal area, and Shenzhen is more, the enterprise of maximum-norm is deep
Southern circuit Co., Ltd, its profit reaches 2,600,000,000 yuan.Traditional etch process, equipment investment is high, production process up to 26 step, waste liquid
Discharge is big, and acidic etching waste liquid discharge capacity is about 2,560,000 tons/year, production high cost serious to environment, if
Standby floor space is big, low production efficiency, and the printed substrate obtaining only plays support in the electronic device and connects electronics unit
The effect of device, i.e. conducting wire plate.Electric PC board is that modern enterprise adopts advanced printing technology of preparing, its base
Electronic component is contained on material（As multi-layer sheet embedded set resistance, electric capacity, and embedding IC device etc.）And connection line, can direct shape
The electronic circuit of functional, is that the miniaturization of electronic equipment is implemented as possibility, at present, domestic and international electric PC board grinds
Send out key technology, be advanced printed electronics and nano material production technology combines and produces, but due to key technology not
Can be grasped by existing enterprise, therefore printed electronics fail to find broad application.
At present, the method preparing nano-silver powder has a lot, generally speaking can be divided into Physical, such as comminuting method, mechanical ball mill,
It is evaporated in vacuo the methods such as condensation；The method such as bioanalysis, such as microorganism, plant tissue reduction；Chemical method, if any liquid phase chemical also
The former, method such as phonochemistry method, microemulsion；The Physical cycle is long, and equipment requirement is high, and investment is big；Bioanalysis has high demands to condition；Liquid
Phase chemical reduction method cycle is short, low cost, industrialization is relatively easy to.
Patent currently, with respect to the preparation method of nano-silver powder has a lot, but existing patent is simply simply related to make
Preparation Method, without reference to complete technological process, equipment and the process to waste liquid, waste gas.The application is related to the system of nano-silver powder
Preparation Method, technological process, equipment and the process to waste liquid, waste gas.Existing closely related with nano-silver powder preparation method
Patent has：Yue Hongqin et al. discloses《The preparation method of nano-silver powder》（201110095156.9）, this patent is with silver nitrite
Prepare nano-silver powder for presoma, silver nitrate, PVA, natrium nitrosum etc. are initiation material, prepare silver nitrite presoma, then
It is thermally decomposed at 180 DEG C～250 DEG C and prepares high-purity nano silver powder, simultaneously in waste water produced by preparation process
Silver is reclaimed it is achieved that the recycling of silver.This inventive method raw material is easy to get, the high conversion rate of silver, preparation technology are simpler
Single, small investment, production cost is relatively low, and silver powder purity is high；The nano-silver powder of the method preparation can be widely applied to health care, electricity
The fields such as sub- industry, effective catalyst；Gao Lingfan et al. discloses《The preparation method of nano-silver powder》（200810230927.9）,
The method is:AgNO3, polyvinyl alcohol, the mixing of emulsifying agent, react 30 minutes after adding qs glycerin, plus deionized water, with true
Empty pumping filter washing, is then dehydrated, and is finally dried the nano-silver powder of available 50～100nm.
Li Zhongchun discloses《The preparation method of flaky nanometer silver powder》（201210500911.1）, a kind of flaky nanometer silver powder
Preparation method, it is by containing surfactant（Polyvinylpyrrolidone, lauryl sodium sulfate etc.）Silver salt solution with sub-
Iron salt solutions react at a temperature of 0～100 DEG C and obtain.The flaky nanometer silver powder pattern being obtained using the method is single, purity
High.Reaction time is short, efficiency high, reaction condition are gentle, Processes and apparatus is simple, low production cost, easy and simple to handle, green no dirty
The advantages of dye, it is suitable for industrialization large-scale production；Liu Fusheng discloses《A kind of preparation method of modified Nano silver powder》
（201410058076.X ）, the method is with mercaptan, containing the silane coupler of sulfydryl, cationic surfactant, corrosion inhibiter with have
Machine solvent is raw material, carries out surface modification to nano-silver powder, prepares modified Nano silver powder, solves nano-silver powder and easily roll into a ball
Problem poly- and that other materials compound tense intermiscibility is poor.It is easy that this preparation method has a simple production process, equipment investment
Little, energy consumption is low, non-environmental-pollution, modified Nano silver powder applied range, is conducive to popularization and application, before having wide application
Scape；《A kind of preparation method of spherical nano-silver powder》（200810046690.9）, history dawn is bright etc. to disclose a kind of spherical nano-silver
The preparation method of powder.The preparation process of this spherical nano-silver powder is 1) spray pyrolysis, 2) preparation of spherical nano-silver powder, this system
Preparation Method is simple, easy to control, pollution-free, low cost, is suitable for industrial-scale production, and prepared spherical nano-silver powder is to receive
Not, powder diameter is evenly distributed meter level, pattern rule, high income；《A kind of nano-silver powder and its manufacture method and its application》
(200910241459.X), Chen Qiao etc. discloses a kind of nano-silver powder for DC electrode slurry and low temperature bonding nanometer silver paste
And its manufacture method, this nano-silver powder adopts chemical reduction method, using hydrazine hydrate, glycerine or triethanolamine at 90～92 DEG C
Reduction silver compound processing technology preparation；The nano-silver powder producing in this way is applied to enter at a temperature of 800 DEG C
The DC electrode slurry of row sintering；It is applied to the nanometer silver paste of the chip such as bonding SiC or GaN at 260 DEG C～270 DEG C, electrode has
The advantages of solderability is good, electric conductivity is high, electric performance stablity and adhesion strength are big, reliability is high；Liu Fusheng discloses《A kind of sticky Jie
The method preparing nano-silver powder in matter》（201110278418.5）, the method is with surfactant, thickener, silver salt, reducing agent
Deng for raw material, prepared with surfactant, thickener, complexing agent, defoamer, antioxidant and deionized water and obtain sticky Jie
Matter, adds silver salt to stir, reduces its viscosity, obtain nano-silver powder through press filtration, washing and vacuum drying；The method has former
Material is easy to get, production technology is brief, production efficiency is high, low production cost, energy consumption are low, powder is difficult reunion, powder dispersity is good, suitable
Together in large-scale production, solve the problems, such as the oxidizable and easy reunion that the existing chemical preparation process of nano-silver powder exists.
The materials such as silver powder, to environment, even result in human body poisoning, and the therefore process to waste liquid is particularly important.Change
Learning traditional method for governing pollution has chemical precipitation method, flocculent precipitation, electrolysis etc.；It is to utilize that chemical precipitation method disposes waste liquid
Silver ion and some chemical reagent occur chemical reaction to generate the solid matter of indissoluble, are then peeled off removing one kind side of silver ion
Method；Silver ion is removed frequently with sodium chloride, effect is preferable, applied widely, low cost, but the chlorination of excess in practical operation
Sodium can make process waste water increase, and such as value has gas to release again when reducing, and liquid waste processing silver environmental protection needs strict control to add
Amount, flocculent precipitation adds ferrous sulfate, caustic soda after certain pretreatment, forms larger particles using flocculation and precipitation
Alumen ustum, separate after remove silver ion, this technique need substantial amounts of chemical reagent, increased treatment cost of waste liquor, available stone
Ash saves the consumption of caustic soda, but produced sludge quantity is larger and is difficult by, and easily produces secondary pollution, needs into one
Step is processed, and electrolysis with the silver ion in Recycling of waste liquid, substantially can realize the recycling of silver, but in electrolytic process
In can produce a large amount of chlorine, lead to etch the losing and pollute environment of liquid chlorine, absorb chlorine using solution and can avoid environment
Pollution.The method is simple to operate, technical feasibility, but produces a large amount of ammonias, still suffers from secondary dirt after adverse condition, and liquid waste processing
Dye problem.Produce substantial amounts of mud, waste liquid, waste residue during administering method traditionally not only to pollute environment but also cause resource
Waste, products obtained therefrom purity is low simultaneously, recycle value and economic worth not high it is difficult to solve the environmental pollution that waste liquid is brought
Problem does not enable to treat both principal and secondary aspect of disease.
A kind of Nano Silver preparation method for PCB high connductivity and equipment, involved simple production process, produce into
This is low, and equipment investment is few, process is easily controlled, yield high, and prepared Nano Silver purity is high, can obtain very high economic valency
Value, avoids waste liquid to enter environment simultaneously, has reached the unification of economic, society and environmental benefit.
Content of the invention
Present invention aim at providing a kind of preparation method for PCB high connductivity Nano Silver, the method adopts liquid phase
Learn reducing process and the nano-silver powder of production is incorporated existing advanced electronic circuit printing technology, embody excellent electric conductivity agent
Non-oxidizability, solves the problems, such as micro-silver powder slurry：（1）Consumption is big, high cost；（2）Sintering temperature is high, and base material selects
Narrow range；（3）Serigraphy pitch is wider.
The concrete operations of said method are as follows：
（1）Silver salt compound and reducing agent are dissolved separately in deionized water, are then respectively adding silver salt chemical combination material
The ammoniacal liquor complexing silver ion of amount 0.1～2%, reaches control reaction speed effect, and cupric and ferric ion can be made to sink simultaneously
Form sediment and remove；
（2）Be separately added into dispersant in silver salt compound solution after cleaning and reductant solution, normal pressure, 15 DEG C～
Stir under the conditions of 50 DEG C and oxidation solution dispersion and reducing solution dispersion are obtained, wherein the addition of dispersant is silver salt chemical combination
The 0.5～10% of amount of substance；
（3）Add adjuvant in reducing solution dispersion, process reducing solution dispersion under the conditions of normal pressure, 15 DEG C～50 DEG C
The addition of system, wherein adjuvant is the 1～6% of silver salt compound quality；
（4）Adjust oxidation solution dispersion pH be 1～7 after, by process after reducing solution dispersion pour into wherein,
Normal pressure, reaction 30～45min is obtained nano silver colloid under the conditions of 10 DEG C～80 DEG C, and silver salt compound with the mol ratio of reducing agent is
1:0.5～4；
（5）Regulation nano-silver colloid temperature is 15 DEG C～60 DEG C, pH is 1～5, is enriched with nano silver colloid, the nanometer of enrichment
Silver colloid is through being centrifuged at a high speed and obtaining wet nano-silver powder after deionized water with ethanol cyclic washing；
（6）It is configured to modifying agent with the organic matters such as oleic acid, aliphatic acid and absolute ethyl alcohol, modifying agent is poured directly into wet receiving
Rice silver powder carries out surface modification, and the consumption of oleic acid or aliphatic acid is the 1%～3% of wet nano-silver powder quality, modified centrifugation,
40 DEG C～100 DEG C drying 4～8h obtain Nano Silver product.
Described dispersant is polyvinylpyrrolidone, gum arabic, succinic acid, polyacrylic acid or polyethylene glycol.
Described silver salt compound is silver nitrate or silver perchlorate.
Described reducing agent is hypophosphites such as sodium hypophosphite and potassium hypophosphite, sodium borohydride or hydrazine hydrate.
Described adjuvant is carboxymethylcellulose calcium.
The present invention another object is that a kind of equipment completing the above-mentioned preparation method for PCB high connductivity Nano Silver of offer,
It includes dissolution kettle I 1, dissolution kettle II 2, silver salt compound purifying column 3, reducing agent purifying column 4, silver salt compound dissolution kettle 5, goes back
Former dose of dissolution kettle 6, silver salt Compound Stock solution groove 7, reducing agent reservoir 8, temperature control is anti-corrosion reactor 9, efficient charging device 10, from
Centrifugal separator 11, silver recovery unit 12, temperature control air dry oven 13, exhaust collection processing meanss 14, liquid waste treating apparatus 15, water
Ion-exchange unit 16, dissolution kettle I 1 is connected with silver salt compound purifying column 3 by pump, and silver salt compound purifying column 3 passes through pump
It is connected with silver salt compound dissolution kettle 5, silver salt compound dissolution kettle 5 is connected with silver salt Compound Stock solution groove 7 by pump, silver salt
Compound reservoir 7 is connected by pump reactor 9 anti-corrosion with temperature control, and dissolution kettle II 2 is connected with reducing agent purifying column 4 by pump, also
Former dose of purifying column 4 is connected with reducing agent dissolution kettle 6 by pump, and reducing agent dissolution kettle 6 is connected with reducing agent reservoir 8 by pump,
Reducing agent reservoir 8 is connected by efficient charging device 10 reactor 9 anti-corrosion with temperature control, temperature control is anti-corrosion reactor 9 and centrifugation point
Disembark 11 connections, centrifugal separator 11 1 tunnel is connected with temperature control air dry oven 13, temperature control air dry oven 13 passes through silver recovery
Device 12 is connected with dissolution kettle I 1, another road of centrifugal separator 11 successively with exhaust collection processing meanss 14, liquid waste treating apparatus
15th, water ion switching equipment 16 connects, and water ion switching equipment 16 is connected with dissolution kettle I 1, dissolution kettle II 2 respectively.
When this device uses,（1）Weigh silver salt compound and add in the dissolution kettle I 1 containing stirring with deionized water, normal
Silver salt compound solution is made in pressure temperature control stirring；Weigh reducing agent and add in the dissolution kettle II 2 containing stirring with deionized water,
Reductant solution is prepared in temperature control stirring at ambient pressure；（2）With pump I 17, silver salt compound solution is squeezed into silver salt compound purifying column
Carry out purified treatment in 3；With pump II 18, reductant solution is squeezed into and in reducing agent purifying column 4, carry out purified treatment；（3）With pump III
19th, the silver salt processing compound solution and reductant solution are squeezed into silver salt compound dissolution kettle 5, reducing agent by pump IV 20 respectively
Dissolution kettle 6；（4）Weigh dispersant be separately added into silver salt compound dissolution kettle 5, in reducing agent dissolution kettle 6, normal pressure, 15 DEG C～
Stir under the conditions of 50 DEG C and oxidation solution dispersion and reducing solution dispersion are obtained；（5）Weighing adjuvant, to be added to reducing agent molten
In solution kettle 6, under the conditions of normal pressure, 15 DEG C～50 DEG C, process reducing solution dispersion further；（6）With pump V 21, pump VI 22 will
Oxidation solution dispersion is driven into silver salt Compound Stock solution groove 7, reducing agent liquid storage respectively with the reducing solution dispersion processing
Groove 8；（7）With pump VII 23, the oxidation solution dispersion in silver salt Compound Stock solution groove 7 is squeezed in the anti-corrosion reactor of temperature control 9,
Adjust pH under normal pressure temperature control to be 1～7, stir；Reducing solution dispersion in reducing solution reservoir 8 is passed through efficient charging device
Carry out reaction in the 10 addition anti-corrosion reactors of temperature control 9 and prepare nano silver colloid；After the completion of reaction, adjust nano silver colloid and be 15 DEG C
～60 DEG C, pH be 1～5, make nano-silver powder be aged enrichment, by the nano silver colloid of enrichment be centrifuged machine 11 carry out centrifugation point
From and obtain wet nano-silver powder after deionized water and ethanol cyclic washing；（8）By wet nano-silver powder in the anti-corrosion reaction of temperature control
Carry out surface modification in kettle 9；It is dried putting into temperature control air dry oven 13 after modified nano-silver powder centrifugation；（9）
The nano-silver powder of preparation is detected, if qualified be Nano Silver finished product, it is packed, if unqualified will
Nano Silver puts in silver recovery unit 12 prepares silver nitrate, the silver nitrate of preparation is returned to dissolution kettle I 1 is used for preparing again and receive
Rice silver powder；
（10）To the waste liquid and waste gas producing in nano-silver powder preparation process at exhaust collection processing meanss 14, waste liquid
Reason device 15 is processed；（11）After processing, waste liquid is processed by water ion switching equipment 16, and the water of acquisition is circulated profit
With.
The particle diameter of the nano-silver powder that the present invention prepares is 10nm～100nm, and conductance is 2 × 10-3Ω cm～6.5
×10-3Ω·cm.
Due to developing rapidly of electronics industry, printed electronics are to properties such as the particle diameter of silver powder, pattern and tap densities
Require more and more higher, the electric slurry of micron order silver powder preparation can not meet the demand of printed electronics.Nano-silver powder
Prepare slurry as main functionality, the advantage that it substitutes traditional micro-silver powder has：（1）Particle diameter is little, sintering temperature is low；（2）Electronic seal
The base material range of choice of brush wiring board is wide, cannot be only used for metal base and can be additionally used in non-metallic substrate, reduces to base simultaneously
The resistant to elevated temperatures requirement of material, low cost；（3）The product that printing obtains is finer and smoother, consumption is few, cost reduces by 5%；（4）Operational sequence
Simply, from 26 traditional step operations, it is reduced to above-mentioned operation；（5）Large-scale production equipment requirement is reduced, it is easy to accomplish produce
Industry.
The invention has the characteristics that：（1）Process is simple, equipment requirement are low；（2）Dispersant dosage is less, easily cleans,
Cost-effective；（3）Waste liquid circulation utilizes, pollution-free, cost-effective；（4）The nano-silver powder particle diameter of preparation is little, the low solution of sintering temperature
Determine the problem that micro-silver powder particle diameter is big, sintering temperature is high；（5）The nano-silver powder of application present invention preparation, in printed circuit board (PCB)
Middle consumption is few, finer and smoother, solves micro-silver powder serigraphy pitch width, the problem of high cost；（6）Prepared by the present invention receives
Rice silver powder, in slurry preparation process, sintering temperature is low, solves micro-silver powder sintering temperature height in slurry application, and base material selects
Select the problem of narrow range.Nano Silver purity using present invention preparation is high, and good conductivity can obtain very high economic worth,
Avoid waste liquid to enter environment simultaneously, reach the unification of economic, society and environmental benefit.
Brief description
Fig. 1 is the schematic flow sheet of the inventive method；
Fig. 2 is the structural representation of apparatus of the present invention；
In figure：1- dissolution kettle I；2- dissolution kettle II；3- silver salt compound purifying column；4- reducing agent purifying column；5- silver salt
Compound dissolution kettle；6- reducing agent dissolution kettle；7- silver salt Compound Stock solution groove；8- reducing agent reservoir；9- temperature control is anti-corrosion reactor；
The efficient charging device of 10-；11- centrifugal separator；12- silver recovery unit；13- temperature control air dry oven；14- exhaust collection is processed
Device；15- liquid waste treating apparatus；16- water ion switching equipment；17- pump I；18- pump II；19- pump III；20- pump IV；21- pump
Ⅴ；22- pump VI；23- pump VII.
Specific embodiment
Below by drawings and Examples, the present invention is described in further detail, but the scope of the present invention is not limited to
Described content.
Embodiment 1：This is used for the preparation method of PCB high connductivity Nano Silver, comprises the following steps that：
（1）170g industrial nitric acid silver and 176g sodium hypophosphite are dissolved separately in the deionized water of 1L, add ammoniacal liquor（Nitre
The 0.1% of the silver amount of acid）Complexing silver ion, reaches control reaction speed effect, and cupric and ferric ion can be made to sink simultaneously
Form sediment and remove；
（2）It is separately added into 4.25g dispersant succinic acid, normal in silver nitrate solution after cleaning and sodium hypophosphite solution
Under pressure, 20 DEG C of parts, stirring is obtained silver nitrate dispersion and sodium hypophosphite dispersion；
（3）Add adjuvant carboxymethylcellulose calcium in sodium hypophosphite dispersion, process secondary under the conditions of normal pressure, 20 DEG C
The addition of sodium phosphate dispersion, wherein adjuvant is the 3% of silver nitrate quality；
（4）Adjust silver nitrate dispersion pH be 3 after, by process after sodium hypophosphite dispersion pour into wherein,
Normal pressure, reaction 35min is obtained nano silver colloid under the conditions of 20 DEG C；
（5）Regulation nano-silver colloid temperature is 20 DEG C, pH is 3, is enriched with nano silver colloid, the nano silver colloid of enrichment is through height
Fast centrifugation simultaneously obtains wet nano-silver powder after deionized water with ethanol cyclic washing；
（6）Oleic acid and absolute ethyl alcohol are configured to modifying agent, modifying agent are poured into and carries out surface in wet nano-silver powder and change
Property, the consumption of oleic acid is the 1% of wet nano-silver powder quality, modified centrifugation, drying to obtain nanometer silver products, Nano Silver
Powder be spherical, good dispersion, particle diameter be 40nm, conductance be 4 × 10-3Ω·cm（Fig. 1）.
Realize the equipment of said method, as shown in Fig. 2 it includes dissolution kettle I 1, dissolution kettle II 2, the purification of silver salt compound
Tower 3, reducing agent purifying column 4, silver salt compound dissolution kettle 5, reducing agent dissolution kettle 6, silver salt Compound Stock solution groove 7, reducing agent storage
Liquid bath 8, temperature control is anti-corrosion reactor 9, efficient charging device 10, centrifugal separator 11, silver recovery unit 12, temperature control air dry oven
13rd, exhaust collection processing meanss 14, liquid waste treating apparatus 15, water ion switching equipment 16, dissolution kettle I 1 passes through pump I 17 and silver salt
Compound purifying column 3 connects, and silver salt compound purifying column 3 is connected with silver salt compound dissolution kettle 5 by pump III 19, silver salt chemical combination
Thing dissolution kettle 5 is connected with silver salt Compound Stock solution groove 7 by pump V 21, and silver salt Compound Stock solution groove 7 passes through pump VII 23 and temperature control
Anti-corrosion reactor 9 connects, and dissolution kettle II 2 is connected with reducing agent purifying column 4 by pump II 18, and reducing agent purifying column 4 passes through pump IV
20 are connected with reducing agent dissolution kettle 6, and reducing agent dissolution kettle 6 is connected with reducing agent reservoir 8 by pump VI 22, reducing agent reservoir
8 are connected by efficient charging device 10 reactor 9 anti-corrosion with temperature control, and temperature control is anti-corrosion, and reactor 9 is connected with centrifugal separator 11, from
Centrifugal separator 11 1 tunnel is connected with temperature control air dry oven 13, and temperature control air dry oven 13 passes through silver recovery unit 12 and dissolution kettle
I 1 connections, another road of centrifugal separator 11 exchanges and sets with exhaust collection processing meanss 14, liquid waste treating apparatus 15, water ion successively
Standby 16 connections, water ion switching equipment 16 is connected with dissolution kettle I 1, dissolution kettle II 2 respectively.
When this device uses, molten by being configured to silver nitrate in 170g industrial nitric acid silver, 1L deionized water addition dissolution kettle I 1
Liquid, will be configured to reductant solution in 176g sodium hypophosphite, 1L deionized water addition dissolution kettle II 2；Use pump I 17, pump II respectively
Silver nitrate solution and reductant solution are squeezed into silver salt compound purifying column 3 and are gone back in reducing agent purifying column 4 by 18, add ammoniacal liquor net
Eliminate miscellaneous, for avoiding foreign ion to affect；With pump III 19, pump IV 20 respectively by the silver nitrate solution processing and reductant solution
Be driven into silver salt compound dissolution kettle 5, in reducing agent dissolution kettle 6；Dispersant succinic acid is separately added into the dissolving of silver salt compound
In kettle 5, reducing agent dissolution kettle 6, stir under the conditions of normal pressure, 20 DEG C and oxidation solution dispersion and reducing solution dispersion are obtained；
Weigh adjuvant to be added in reducing agent dissolution kettle 6, under the conditions of normal pressure, 20 DEG C, process reducing solution dispersion further；With
Oxidation solution dispersion is driven into silver salt Compound Stock solution with the reducing solution dispersion processing by pump V 21, pump VI 22 respectively
Groove 7, reducing agent reservoir 8；With pump VII 23, the oxidation solution dispersion in silver salt Compound Stock solution groove 7 is squeezed into temperature control anti-corrosion anti-
Answer in kettle 9, stir under the conditions of normal pressure, 20 DEG C, pH are for 3；Reducing solution dispersion in reducing solution reservoir 8 is passed through efficiently
Carry out reaction 35min in the charging device 10 addition anti-corrosion reactor of temperature control 9 and prepare nano silver colloid；After the completion of reaction, regulation is received
Rice silver colloid is 20 DEG C, pH is 3, makes nano-silver powder be aged enrichment, the nano silver colloid of enrichment is centrifuged machine 11 and carries out
Centrifugation simultaneously obtains wet nano-silver powder after deionized water and ethanol cyclic washing 3 times；Will be resistance in temperature control for wet nano-silver powder
Carry out surface modification in erosion reactor 9；Put into after modified nano-silver powder centrifugation 70 in temperature control air dry oven 13
6h is dried at DEG C and can obtain nano-silver powder；After after testing, to qualified nano-silver powder packaging, underproof utilization silver recovery dress
Put 12 and carry out recovery and prepare silver nitrate, the silver nitrate of preparation is returned to dissolution kettle I 1 and is used for preparing again nano-silver powder；To system
The waste gas producing during standby is processed with waste water utilization exhaust collection processing meanss 14, liquid waste treating apparatus 15；After process
Waste liquid through water ion switch 16 process Posterior circle utilize.
Embodiment 2：This is used for the preparation method of PCB high connductivity Nano Silver, comprises the following steps that：
（1）100kg industrial nitric acid silver and 22.3kg sodium borohydride are dissolved separately in the deionized water of 58.2L and 22.3L
In, add ammoniacal liquor（The 1% of silver nitrate quality）Complexing silver ion, reach control reaction speed effect, can make simultaneously cupric and
Ferric ions precipitation removes；
（2）Add 1kg dispersant gum arabic in silver nitrate solution after cleaning, add in sodium borohydride solution
1kg gum arabic, stirs under the conditions of normal pressure, 30 DEG C and silver nitrate dispersion and sodium borohydride dispersion is obtained；
（3）Add 1kg adjuvant carboxymethylcellulose calcium in sodium borohydride dispersion, locate under the conditions of normal pressure, 30 DEG C
Reason sodium hypophosphite dispersion；
（4）Adjust silver nitrate dispersion pH be 2 after, by process after sodium hypophosphite dispersion pour into wherein,
Normal pressure, reaction 45min is obtained nano silver colloid under the conditions of 30 DEG C；
（5）Regulation nano-silver colloid temperature is 30 DEG C, pH is 2, is enriched with nano silver colloid, the nano silver colloid of enrichment is through height
Fast centrifugation simultaneously obtains wet nano-silver powder after deionized water with ethanol cyclic washing；
（6）Oleic acid and absolute ethyl alcohol are configured to modifying agent, modifying agent are poured into and carries out surface in wet nano-silver powder and change
Property, the consumption of oleic acid is the 2% of wet nano-silver powder quality, modified centrifugation, drying to obtain nanometer silver products, Nano Silver
Powder be spherical, good dispersion, particle diameter be 20nm, 2 × 10-3Ω·cm.
Realize the equipment of said method with embodiment 1, by 100kg industrial nitric acid silver, 58.2L deionized water in dissolution kettle I 1
In be configured to silver nitrate solution, 22.3kg sodium borohydride（NaBH4）, 22.3L deionized water be configured in dissolution kettle II 2 reduce
Agent solution；With pump I 17, pump II 18, silver nitrate solution and reductant solution are squeezed into silver salt compound purifying column 3 respectively and go back
In former dose of purifying column 4, add ammoniacal liquor purification and impurity removal, for avoiding foreign ion to affect；To be processed respectively with pump III 19, pump IV 20
Silver nitrate solution and reductant solution be driven into silver salt compound dissolution kettle 5, in reducing agent dissolution kettle 6；Weigh 1kg Arabic
Natural gum adds reductant solution, weighs 1kg succinic acid and adds silver nitrate solution, stirs oxidation is obtained under the conditions of normal pressure, 30 DEG C
Liquid dispersion and reducing solution dispersion；Weigh adjuvant to be added in reducing agent dissolution kettle 6, under the conditions of normal pressure, 30 DEG C
Process reducing solution dispersion further；With pump V 21, pump VI 22 by oxidation solution dispersion and processed reducing solution dispersion
System is driven into silver salt Compound Stock solution groove 7, reducing agent reservoir 8 respectively；With pump VII 23 by silver salt Compound Stock solution groove 7
Oxidation solution dispersion is squeezed in the anti-corrosion reactor of temperature control 9, and in normal pressure 30, lower regulation pH is 2, stirring；By reducing solution reservoir 8
In reducing solution dispersion by efficient charging device 10 add the anti-corrosion reactor of temperature control 9 in carry out react 45min preparation receive
Rice silver colloid；After the completion of reaction, regulation nano silver colloid is 30 DEG C, pH makes nano-silver powder be aged enrichment for 2, the nanometer that will be enriched with
Silver colloid is centrifuged machine 11 and is centrifuged and obtains wet Nano Silver after deionized water and ethanol cyclic washing 3 times
Powder；Wet nano-silver powder is carried out surface modification with oleic acid in the anti-corrosion reactor of temperature control 9；By modified nano-silver powder centrifugation point
From after put into and 6h is dried at 80 DEG C in temperature control air dry oven 13 can obtain nano-silver powder；After after testing, to qualified nanometer
Silver powder is packed, underproof carry out recovery using silver recovery unit 12 and prepare silver nitrate, the silver nitrate of preparation is returned to dissolving
Kettle I 1 is used for preparing nano-silver powder again；To waste gas and the waste water utilization exhaust collection processing meanss 14 producing in preparation process,
Liquid waste treating apparatus 15 are processed；Waste liquid after process processes Posterior circle through water ion switch 16 and utilizes.
Embodiment 3：This is used for the preparation method of PCB high connductivity Nano Silver, comprises the following steps that：
（1）By 250kg industry silver perchlorate and 60.2L hydrazine hydrate（Mass percent concentration is 50%）Dissolve 603L respectively
In the deionized water of 60.2L, add ammoniacal liquor（The 2% of silver perchlorate quality）Complexing silver ion, reaches control reaction speed effect
Really, cupric and ferric ions precipitation can be made to remove simultaneously；
（2）Add 1.25kg dispersant polyethylene glycol in silver perchlorate solution after cleaning, add in hydrazine hydrate solution
1.25kg polyethylene glycol, stirs under the conditions of normal pressure, 40 DEG C and silver perchlorate dispersion and hydrazine hydrate dispersion is obtained；
（3）Add adjuvant carboxymethylcellulose calcium in hydrazine hydrate dispersion, process hydration under the conditions of normal pressure, 40 DEG C
The addition of hydrazine dispersion, wherein adjuvant is the 4% of silver perchlorate quality
（4）After regulation silver perchlorate dispersion pH is 3, the sodium hypophosphite dispersion after processing is poured into wherein,
Under the conditions of normal pressure, 70 DEG C, reaction 30min is obtained nano silver colloid；
（5）Regulation nano-silver colloid temperature is 40 DEG C, pH is 3, is enriched with nano silver colloid, the nano silver colloid of enrichment is through height
Fast centrifugation simultaneously obtains wet nano-silver powder after deionized water with ethanol cyclic washing；
（6）Aliphatic acid and absolute ethyl alcohol are configured to modifying agent, modifying agent are poured into and in wet nano-silver powder, carries out surface
Modification, the consumption of aliphatic acid is the 3% of wet nano-silver powder quality, modified centrifugation, drying to obtain nanometer silver products, receives
Rice silver powder be spherical, good dispersion, particle diameter be 25nm, conductance be 3. × 10-3Ω·cm.
Realize the equipment of said method with embodiment 1, by 250kg industry silver perchlorate with 603L ionized water in dissolution kettle I 1
In be configured to silver nitrate solution, 60.2L hydrazine hydrate, 60.2L deionized water are configured to reductant solution in dissolution kettle II 2；Point
With pump I 17, pump II 18, silver perchlorate solution and reductant solution are not squeezed into silver salt compound purifying column 3 and reducing agent purifying column
In 4, add ammoniacal liquor purification and impurity removal, for avoiding foreign ion to affect；With pump III 19, pump IV 20 respectively by the silver perchlorate processing
Solution and reductant solution are driven into silver salt compound dissolution kettle 5, in reducing agent dissolution kettle 6；Weigh polyethylene glycol and add reduction
Agent solution, weigh polyethylene glycol add silver perchlorate solution, under the conditions of normal pressure, 40 DEG C stir be obtained oxidation solution dispersion and
Reducing solution dispersion；Weigh adjuvant to be added in reducing agent dissolution kettle 6, process further also under the conditions of normal pressure, 40 DEG C
Stoste dispersion；With pump V 21, pump VI 22, oxidation solution dispersion is squeezed into respectively with the reducing solution dispersion processing
To silver salt Compound Stock solution groove 7, reducing agent reservoir 8；With pump VII 23 by the oxidation solution dispersion in silver salt Compound Stock solution groove 7
System squeezes in the anti-corrosion reactor of temperature control 9, adjust at 40 DEG C of normal pressure pH be 3, stirring；By the reducing solution in reducing solution reservoir 8
Dispersion prepares nano silver colloid by carrying out reaction 30min in the efficient charging device 10 addition anti-corrosion reactor of temperature control 9；Instead
Should after the completion of, adjust nano silver colloid be 40 DEG C, pH be 3, make nano-silver powder be aged enrichment, by enrichment nano silver colloid through from
Centrifugal separator 11 is centrifuged and obtains wet nano-silver powder after deionized water and ethanol cyclic washing 3 times；Receive wet
Rice silver powder is prepared modifying agent with aliphatic acid and ethanol in the anti-corrosion reactor of temperature control 9 and is carried out surface modification, and aliphatic acid quality is wet
The 2% of nano-silver powder quality；Dry at 100 DEG C in temperature control air dry oven 13 by putting into after modified nano-silver powder centrifugation
Dry 6h can obtain nano-silver powder；After after testing, to qualified nano-silver powder packaging, underproof entered using silver recovery unit 12
Silver nitrate is prepared in row recovery, the silver nitrate of preparation is returned to dissolution kettle I 1 and is used for preparing again nano-silver powder；To preparation process
The waste gas of middle generation is processed with waste water utilization exhaust collection processing meanss 14, liquid waste treating apparatus 15；Waste liquid after process
Process Posterior circle through water ion switch 16 to utilize.
Claims (6)
1. a kind of preparation method for PCB high connductivity Nano Silver is it is characterised in that comprise the following steps that：
（1）Silver salt compound and reducing agent are dissolved separately in deionized water, are then respectively adding silver salt compound quality 0.1
～2% ammoniacal liquor complexing silver ion；
（2）Be separately added into dispersant in silver salt compound solution after cleaning and reductant solution, normal pressure, 15 DEG C～50 DEG C
Under the conditions of stirring oxidation solution dispersion and reducing solution dispersion are obtained, the wherein addition of dispersant is silver salt chemical combination material
The 0.5～10% of amount；
（3）Add adjuvant in reducing solution dispersion, process reducing solution dispersion under the conditions of normal pressure, 15 DEG C～50 DEG C
System, the wherein addition of adjuvant are the 1～6% of silver salt compound quality；
（4）After regulation oxidation solution dispersion pH is 1～7, the reducing solution dispersion after processing is poured into wherein, normal
Pressure, reaction 30～45min is obtained nano silver colloid under the conditions of 10 DEG C～80 DEG C, and silver salt compound is 1 with the mol ratio of reducing agent:
0.5～4；
（5）Regulation nano-silver colloid temperature is 15 DEG C～60 DEG C, pH is 1～5, is enriched with nano silver colloid, the nano-silver colloid of enrichment
Body is through being centrifuged at a high speed and obtaining wet nano-silver powder after deionized water with ethanol cyclic washing；
（6）Oleic acid or aliphatic acid are configured to modifying agent with absolute ethyl alcohol, modifying agent are poured into and in wet nano-silver powder, carries out table
Face is modified, and the consumption of oleic acid or aliphatic acid is the 1%～3% of wet nano-silver powder quality, and modified centrifugation, drying to obtain are received
Rice silver products.
2. the preparation method for PCB high connductivity Nano Silver according to claim 1 it is characterised in that：Dispersant is poly-
Vinylpyrrolidone, gum arabic, succinic acid, polyacrylic acid or polyethylene glycol.
3. the preparation method for PCB high connductivity Nano Silver according to claim 1 and 2 it is characterised in that：Silver salt chemical combination
Thing is silver nitrate or silver perchlorate.
4. the preparation method for PCB high connductivity Nano Silver according to claim 3 it is characterised in that：Reducing agent is secondary
Sodium phosphate, potassium hypophosphite, sodium borohydride or hydrazine hydrate.
5. the preparation method for PCB high connductivity Nano Silver according to claim 4 it is characterised in that：Adjuvant is carboxylic
Methylcellulose.
6. complete the equipment of the preparation method for PCB high connductivity Nano Silver described in any one of claim 1-5, its feature exists
In：Including dissolution kettle I（1）, dissolution kettle II（2）, silver salt compound purifying column（3）, reducing agent purifying column（4）, silver salt compound
Dissolution kettle（5）, reducing agent dissolution kettle（6）, silver salt Compound Stock solution groove（7）, reducing agent reservoir（8）, temperature control is anti-corrosion reactor
（9）, efficient charging device（10）, centrifugal separator（11）, silver recovery unit（12）, temperature control air dry oven（13）, tail gas receive
Collection processing meanss（14）, liquid waste treating apparatus（15）, water ion switching equipment（16）, dissolution kettle I（1）By pump and silver salt chemical combination
Thing purifying column（3）Connect, silver salt compound purifying column（3）By pump and silver salt compound dissolution kettle（5）Connect, silver salt compound
Dissolution kettle（5）By pump and silver salt Compound Stock solution groove（7）Connect, silver salt Compound Stock solution groove（7）Anti-corrosion with temperature control by pump
Reactor（9）Connection, dissolution kettle II（2）By pump and reducing agent purifying column（4）Connect, reducing agent purifying column（4）By pump with
Reducing agent dissolution kettle（6）Connect, reducing agent dissolution kettle（6）By pump and reducing agent reservoir（8）Connection, reducing agent reservoir
（8）By efficient charging device（10）The anti-corrosion reactor with temperature control（9）Connection, temperature control is anti-corrosion reactor（9）With centrifugal separator
（11）Connect, centrifugal separator（11）One tunnel and temperature control air dry oven（13）Connect, temperature control air dry oven（13）By silver
Retracting device（12）With dissolution kettle I（1）Connect, centrifugal separator（11）Another road successively with exhaust collection processing meanss（14）、
Liquid waste treating apparatus（15）, water ion switching equipment（16）Connect, water ion switching equipment（16）Respectively with dissolution kettle I（1）, molten
Solution kettle II（2）Connect.
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| CN105562712B (en) * | 2016-01-30 | 2018-10-23 | 北京印刷学院青岛研究院有限公司 | A kind of method of nano-Ag particles in enrichment water |
| CN106513705B (en) * | 2016-12-01 | 2018-03-16 | 上海银波生物科技有限公司 | The method and apparatus that a kind of method of fractional steps prepares ball shape silver powder |
| CN108311713A (en) * | 2018-05-16 | 2018-07-24 | 清远市宝晶新材料有限公司 | A kind of Automatic Control manufactures the method and its equipment of silver powder |
| CN109439268B (en) * | 2018-10-31 | 2021-09-17 | 烟台德邦科技股份有限公司 | Conductive adhesive with low Tg and low silver content for photovoltaic laminated tile assembly |
| CN111360281A (en) * | 2020-05-11 | 2020-07-03 | 河南金渠银通金属材料有限公司 | Excellent conductive silver powder and preparation method thereof |
| CN112404450B (en) * | 2020-11-05 | 2023-04-07 | 成都市天甫金属粉体有限责任公司 | Chemical synthesis method of high-dispersion high-sphericity porous silver powder |
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| CN1266761A (en) * | 2000-03-23 | 2000-09-20 | 南京大学 | Process for preparing nm-class silver powder |
| CN101554664A (en) * | 2009-05-20 | 2009-10-14 | 广东风华高新科技股份有限公司 | Method for preparing nano-scale silver powder |
| CN101972855A (en) * | 2010-11-11 | 2011-02-16 | 肇庆市羚光电子化学品材料科技有限公司 | Method for preparing silver micro-powder for high-temperature sintering silver pastes |
| CN204639140U (en) * | 2015-04-24 | 2015-09-16 | 昆明理工大学 | A kind of equipment preparing PCB high connductivity Nano Silver |
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| JP5633045B2 (en) * | 2012-05-25 | 2014-12-03 | Ｄｏｗａエレクトロニクス株式会社 | Silver powder and method for producing the same |
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| CN1266761A (en) * | 2000-03-23 | 2000-09-20 | 南京大学 | Process for preparing nm-class silver powder |
| CN101554664A (en) * | 2009-05-20 | 2009-10-14 | 广东风华高新科技股份有限公司 | Method for preparing nano-scale silver powder |
| CN101972855A (en) * | 2010-11-11 | 2011-02-16 | 肇庆市羚光电子化学品材料科技有限公司 | Method for preparing silver micro-powder for high-temperature sintering silver pastes |
| CN204639140U (en) * | 2015-04-24 | 2015-09-16 | 昆明理工大学 | A kind of equipment preparing PCB high connductivity Nano Silver |
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