CN110183592A - A kind of Nanometer Copper/silver houghite conducing composite material and preparation method thereof - Google Patents
A kind of Nanometer Copper/silver houghite conducing composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Nanometer Copper/silver houghite conducing composite materials and preparation method thereof, utilize the special structure of houghite, the designability of its layer structure, and the excellent electric conductivity of Nanometer Copper, nano silver, in combination with the easily molded processing advantage of polymer material, make reducing agent using hydrazine hydrate, PVP makees dispersing agent, novel nano-copper/silver, houghite and the compound conductive film material of epoxy acrylate are prepared using liquid phase reduction and co-precipitation one-step method, with excellent conductive performance, it can be used for the fields such as conducting resinl, antistatic coating；And the method prepares simple process, application field is extensive, has preferable economic results in society.
Description
Technical field
The invention belongs to conducing composite material technical fields, and in particular to a kind of Nanometer Copper/silver houghite conduction is compound
Material and preparation method thereof.
Background technique
By the packing material and different types of composite wood of the polymer such as high polymer, rubber material and conductive energy
The composite material for expecting the conductive energy that the technique Jing Guo series of steps is made into, not only has excellent electric conductivity, and have
The advantages of multiplicity is rich in utility value, for example be easy to be processed to different shape, light-weight, superior electric conductivity and machine
Tool performance, it is cheap etc., it is widely applied in chemical industry.
Houghite is a kind of hydrotalcite powder body material, has layered double hydroxide structure, structure and performance
With very big design adjustment space.Houghite is prepared into the special construction of thin-film material, and expansible houghite is in membrane material
Expect super-hydrophobicity, corrosivity, the application field in optical, electromagnetic domain, possesses huge development space.Copper and silver have extraordinary lead
It is electrical, and high stability, excellent performance is embodied in chemical field, physical field, becomes chemistry, physics, biology
With the focus and scientific research emphasis of other field.The fast development of nano material attracts researcher constantly to be visited
Study carefully discovery, property is possessed by the material that nanometer forms, such as the effect of volume, the effect on surface, the effect of the size of quantum,
Macroscopically performance not available for the material in many macro-scopes such as the effect in the tunnel of quantum.Although electric conductivity laminated film
Discussion have many relevant reports, but to the conducing composite material that houghite/nano silver or houghite, Nanometer Copper are formed
Preparation and research not yet report.
Summary of the invention
It is an object of the invention in place of overcome the deficiencies in the prior art, provide a kind of Nanometer Copper/silver houghite to lead
Composite and preparation method thereof prepares novel nano-copper/silver houghite and epoxy acrylic using local reduction way
The conductive material of ester resin compounded can be used for the fields such as conducting resinl, antistatic coating, have a good application prospect.
The technical solution adopted by the present invention to solve the technical problems first is that:
A kind of preparation method of Nanometer Copper/silver houghite conducing composite material, comprising:
1) Cu (NO is added in aqueous solution of sodium stearate3)2Aqueous solution or AgNO3Aqueous solution, after mixing, while to
NaAlO is wherein added dropwise2Solution and MgCl2Solution is uniformly mixed, and adjusting pH value is then old at 75~85 DEG C to 9~10
Change 10~14h；It is separated by solid-liquid separation after ageing, it is 7~8 that solid portion, which is washed to the pH value of cleaning solution, then is soaked with dehydrated alcohol
It is separated by solid-liquid separation after bubble solid portion, obtains copper ions houghite or silver ion houghite；
2) PVP aqueous solution is mixed with the copper ions houghite or silver ion houghite, water, ultrasound is added
After oscillation treatment, dehydrated alcohol is added, hydrazine hydrate is then added dropwise thereto, is stirred to react after being added dropwise to complete, stands, discard supernatant
Liquid, remainder are washed with dehydrated alcohol, are separated by solid-liquid separation, are obtained Nanometer Copper/houghite or nano silver/houghite；
3) Nanometer Copper/houghite or nano silver/class neatly after mixing by acrylic acid, acrylamide, is added
Stone simultaneously makes it completely dissolved, and adds epoxy acrylate, is solidified after mixing, and it is conductive to obtain nano-copper type hydrotalcite
Composite material or nano silver houghite conducing composite material.
In one embodiment: in the nano-copper type hydrotalcite conducing composite material, magnalium match (molar ratio) be 2.5~
3.5:1。
In one embodiment: in the nano silver houghite conducing composite material, magnalium silver match (molar ratio) be 2.5~
3.5:0.8~1.2:2.5~3.5, and nano silver therein/houghite content is 6~8%.
In one embodiment: in the step 2), the total volume of the water of water and addition in PVP aqueous solution and dehydrated alcohol
Volume ratio is 2~4:1~3.
In one embodiment: in the step 2), the concentration of hydrazine hydrate is 38~42%.
In one embodiment: in the step 3), cured mode is ultraviolet lighting solidification, the reaction system of the step 3)
In be additionally added photoinitiator.
In one embodiment: the photoinitiator is 1173.
In one embodiment: in the step 3), epoxy acrylate, acrylic acid, acrylamide and the Nanometer Copper/class water
Talcum or nano silver/houghite mass ratio are 3.1~3.2:0.7~0.8:0.9~1.1:0.045~0.6.
In one embodiment: the Nanometer Copper/houghite is used further to prepare nano-copper type neatly after anti-oxidant treatment
Stone conducing composite material, the anti-oxidant treatment include: by the Nanometer Copper/houghite be added to volume ratio be 0.8~
In the dehydrated alcohol and butyl titanate mixed solution of 1.2:0.8~1.2,3~5h is stirred at 65~75 DEG C, stands 22~26h,
Filtering, washing, it is dry to get.
The technical solution adopted by the present invention to solve the technical problems second is that:
A kind of Nanometer Copper according to prepared by above-mentioned preparation method/silver houghite conducing composite material.
The technical program compared with the background art, it has the following advantages:
The present invention using special structure, the designability of its layer structure and the Nanometer Copper of houghite, nano silver it is excellent
Good electric conductivity makees reducing agent using hydrazine hydrate, PVP work disperses in combination with the easily molded processing advantage of polymer material
It is compound to prepare novel nano-copper/silver, houghite and epoxy acrylate using liquid phase reduction and co-precipitation one-step method for agent
Conductive film material, have excellent conductive performance；And the method prepares simple process, application field is extensive, has preferable society
It can economic benefit.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is the infrared spectroscopy of Nanometer Copper/houghite (a) and houghite (b).
Fig. 2 is nano silver/houghite infrared spectroscopy.
Fig. 3 is nano silver/houghite/EA coating ultraviolet spectra.
Fig. 4 is nano silver/houghite/EA coating fluorescence spectrum.
Fig. 5 is Nanometer Copper/houghite/EA coating resistance value.
Fig. 6 is nano silver/houghite/EA coating resistance value.
Fig. 7 is nano silver/houghite/EA coating resistance value and conducting particles type and content relationship, in figure: a-3:
1:10 (magnesium: aluminium: silver, similarly hereinafter), b-3:1:7, c-3:1:5, d-3:1:1, e-3:1:3.
Specific embodiment
The contents of the present invention are illustrated below by embodiment:
Material involved in following embodiment includes: with equipment
Experimental raw: dehydrated alcohol (C2H5OH), acrylic acid (AA), sodium metaaluminate (NaAlO2), magnesium chloride (MgCl2), it is hard
Resin acid sodium (C17H35COONa), silver nitrate (AgNO3), copper nitrate (Cu (NO3)2), 80% hydrazine hydrate (H6N2O), polyvinyl pyrrole
Alkanone (PVP), acrylamide (AM), butyl titanate (TiOC4H9)4) etc. be AR, be purchased from Tianjin chemical reagent wholesaling firm.
Instrument and equipment: thermostat water bath (Changzhou Guohua Electric Appliance Co., Ltd., HH-1), accurate reinforcement electric mixer
(Changzhou Guohua Electric Appliance Co., Ltd., JJ-1), portable UV curing light source (melt up to Electronics Equipment Co., Ltd, UV- in Baoding
1KW), constant temperature blender with magnetic force (all over the country Industrial Co., Ltd., Shenzhen, HT-3), ultrasonic cleaner (city of Kunshan's ultrasound
Instrument Ltd., KQ218), vacuum oven (Shanghai Boxun Industrial Co., Ltd., DZF-6050), volume, sheet resistance survey
Determine instrument (Beijing Guan Ce laboratory apparatus Co., Ltd, EST121), ultraviolet/visible spectrophotometer (Shimadzu Seisakusho Ltd., UV2250),
U.S.'s Varian sepectrophotofluorometer (Shanghai Shi Yan electric furnace Co., Ltd, SXZ-4-10) etc..
The preparation of 1 nano-copper type hydrotalcite conducing composite material of embodiment
1) preparation of copper ions houghite
Weigh MgCl24.066g is dissolved in 10mL deionized water；Weigh NaAlO20.8197g is dissolved in deionized water, is claimed
Take odium stearate 1.001g that 100mL deionized water stirring and dissolving in 40 DEG C of thermostat water baths is added, preparing mass fraction is 1%
The aqueous solution of sodium stearate of left and right；Weigh Cu (NO3)22.416g is dissolved in 10mL deionized water.Measure 50mL odium stearate water
Solution pours three-necked flask into, and Cu (NO is added3)2Aqueous solution stirs 5min, while by NaAlO2Solution and MgCl2It is added dropwise to hard
In the aqueous solution of resin acid sodium, after being added dropwise to complete, continue to stir 30min.Mixed system pH value is adjusted with sodium hydrate aqueous solution, until
The pH of mixed serum be 9~10, then stop stirring, resulting substance be it is light blue, be finally aged 12h at 80 DEG C.Ageing
After to filter, filter cake is washed with deionized to filtrate pH be 7~8, then with being filtered after a small amount of soaked in absolute ethyl alcohol, contained
Copper ion houghite is directly used without dry.
2) Nanometer Copper/houghite preparation
It weighs 0.01g PVP and is dissolved in 5mL deionized water stirring and dissolving in 30 DEG C of thermostat water baths, by dissolved PVP
The beaker that the 1g copper ions houghite after filtering is housed is added in aqueous solution, and 55mL deionized water is added, and is put into ultrasonic clear
It vibrates 20min in washing machine, dehydrated alcohol 40mL (deionized water and the ratio of dehydrated alcohol be 3:2) is added, the stirring the case where
Lower that 40% hydrazine hydrate of 20mL is slowly added drop-wise in the mixed aqueous solution of copper ions houghite, solution immediately becomes red
Color continues to be stirred to react 1h after being added dropwise to complete, stands 3h, remove supernatant, washed 3 times with dehydrated alcohol, filters, obtain magnalium
Copper molar ratio is Nanometer Copper/houghite of 2:1:1.
Be prepared for magnesium in aforementioned manners: aluminium: the molar ratio of copper is respectively 2:2:1；3:1:1；3:2:1；3:3:1；4:1:1；
4:2:1；5:1:1；Nanometer Copper/houghite of 5:3:1, and prepare a nanometer copper simple substance.
3) Nanometer Copper/houghite anti-oxidant treatment
Configuration volume fraction is the dehydrated alcohol and butyl titanate solution 200mL of 1:1 first, adds it to 10g nanometers
In copper/houghite, the mixed solution is stirred into 4h under 70 DEG C of constant temperature using constant temperature blender with magnetic force, is stood after being sufficiently stirred
24h.Processed Nanometer Copper/houghite is placed in 60 DEG C of vacuum ovens dry 12h after being filtered, washed.
4) nano-copper type hydrotalcite conducing composite material --- Nanometer Copper/houghite/EA coating preparation
It is formulated, takes suitable acrylic acid (AA), suitable acrylamide (AM) is stirred 10min with glass bar by table 1
Afterwards, with supersonic cleaning machine ultrasonic dissolution 20min, proper amount of nano copper/houghite is added, after stirring 5min, is continued with ultrasound
Cleaning machine, which shakes to Nanometer Copper/houghite powder, to be completely dissolved, and is added suitable epoxy acrylate (EA) and is drawn with 1173
Agent is sent out, being persistently stirred in mixed system with glass bar does not have bubble presence.Then product is poured on to smooth square glass plate
On, glass plate must use washes of absolute alcohol, strike off product with the scraper plate that scraper thickness is 85 μm, utilize ultraviolet light irradiation one
The fixed time carries out curing process, obtains nano-copper type hydrotalcite conducing composite material --- and Nanometer Copper/houghite/EA is applied
Layer.Nanometer Copper/houghite Nanometer Copper/houghite/EA coating containing different proportion is prepared respectively, and it is all to measure its
Resistance value measures magnalium optimum ratio.
1 nano silver of table (copper)/houghite/EA UV solidification coating formula
The preparation of 2 nano silver houghite conducing composite material of embodiment
1) preparation of silver ion houghite
Weigh MgCl26.099g is dissolved in 10mL deionized water；Weigh NaAlO20.8197g is dissolved in deionized water；Claim
Take odium stearate 1.001g that 100mL deionized water stirring and dissolving in 40 DEG C of thermostat water baths is added, preparing mass fraction is 1%
The aqueous solution of left and right；Weigh AgNO31.6987g being dissolved in 10mL deionized water.It measures 50mL aqueous solution of sodium stearate and pours three into
Mouth flask, is added AgNO3Aqueous solution, ceaselessly agitating solution 5 minutes, while by NaAlO2Solution and MgCl2It is added dropwise to tristearin
In the aqueous solution of sour sodium, after being added dropwise to complete, continue stirring 30 minutes.Mixed system pH value is adjusted with sodium hydrate aqueous solution, until
The pH of mixed serum be 9~10, then stop stirring, resulting substance be it is light blue, be finally aged 12h at 80 DEG C.Ageing
After to filter, filter cake is washed with deionized to filtrate pH be 7~8, then with being filtered after a small amount of soaked in absolute ethyl alcohol, contained
Silver ion houghite is directly used without dry.
2) nano silver/houghite preparation
It weighs 0.02g PVP and is dissolved in 5mL deionized water stirring and dissolving in 30 DEG C of thermostat water baths, by dissolved PVP
The beaker that the 1g silver ion houghite after filtering is housed is added in aqueous solution, adds 55ml deionized water, is put into ultrasound
It is vibrated 20 minutes in cleaning machine, dehydrated alcohol 40ml (deionized water and the ratio of dehydrated alcohol be 3:2) is added, in stirring
In the case of 40% hydrazine hydrate of 20ml is slowly added drop-wise in the mixed aqueous solution of cupric houghite, solution is become by white
Field gray continues to be stirred to react 1 hour after being added dropwise to complete, stands 3 hours, remove supernatant, washed 3 times with dehydrated alcohol,
It filters, obtains nano silver/houghite, be put into 60 DEG C of vacuum ovens 12 hours dry.
3) nano silver houghite conducing composite material --- nano silver/houghite/EA coating preparation
It is formulated by table 1, weighs suitable nano silver/houghite powder and be added to the acrylic acid of fixed proportion, acryloyl
It is persistently stirred in amine with glass bar, then ultrasonic machine sonic oscillation is dissolved in propylene until nano silver/houghite powder
In sour mixed solution, then suitable epoxy acrylate and 1173 photoinitiators are added, is put into after persistently being stirred with glass bar super
It is no into mixed system with supersonic oscillations in sound cleaning machine to generate bubble.Then product is poured on to smooth square glass plate
On, glass plate must use washes of absolute alcohol, strike off product with the scraper plate that scraper thickness is 85 μm, utilize ultraviolet light irradiation one
The fixed time carries out curing process, obtains nano silver houghite conducing composite material --- and nano silver/houghite/EA is applied
Layer.
The infrared spectrum analysis of 3 Nanometer Copper of embodiment/silver houghite conducing composite material
Using preparing the infrared spectroscopy of product in FT-IR measurement embodiment 1 and embodiment 2, and inquire into its 4000~
500cm-1The situation of change at the flexible peak of vibration, solid powder and potassium bromide are 1:40 according to mass ratio, are pressed into little Bao after grinding
Piece detects it, watches the fluctuation situation at Absorption Characteristics peak, analyzes the synthetic effect of prepared product.
As shown in Figure 1, curve a is in 3447cm-1There are the stretching vibration absworption peak of the m- OH of houghite laminate, 614cm in place-1
There are Mg-OH, Al-OH stretching vibration absworption peak, 1641cm at place-1There are the stretching vibration absorptions of C=O in pyrrolidone group at place
Peak, 1110cm-1For the infrared C=O absorption peak of Nanometer Copper and the PVP hybrid formed, experiment known to the above analysis, which has synthesized, to be received
Rice copper/houghite.Curve b is in 3447cm-1Place is the stretching vibration absworption peak of the m- OH of houghite laminate, 614cm-1It deposits at place
In Mg-OH, Al-OH stretching vibration absworption peak, the above analysis knows that experiment has synthesized magnesia-alumina hydrotalcite.
As shown in Figure 2, in 3447cm-1There are the stretching vibration peak of the m- OH of houghite laminate, 614cm in place-1There are Mg- at place
OH, Al-OH stretching vibration peak, 1673cm-1Place is above there are the infrared C=O absorption peak of nano silver and the PVP hybrid formed
Analysis knows that experiment has synthesized nano silver/houghite.
4 Nanometer Copper of embodiment/silver houghite conducing composite material ultraviolet spectral analysis
With the nano silver/houghite/EA coating being cured in embodiment 2, in wavelength within the scope of 200~800nm, benefit
The detection of uv-vis spectra is carried out with ultraviolet-visible spectrophotometer.
From the figure 3, it may be seen that there are three features in nano silver/houghite/EA coating UV-visible absorption spectrum
Absorption peak, respectively at 207nm, 427nm and 564nm.Wherein emerging absorption peak is that the feature of nano silver is inhaled at 427nm
Peak is received, this shows that there are nano silvers in composite material.
The spectrofluorimetry of 5 Nanometer Copper of embodiment/silver houghite conducing composite material
It is that excitation wavelength changes nano silver/houghite content under conditions of slit width is 5nm in fixed 280nm,
Nano silver/houghite/EA coating fluorescence intensity is detected, the fluorescence spectra of Fig. 4 is obtained.As shown in Figure 4, nano silver/class
Hydrotalcite/EA coating Fluorescent peal is at 348nm.On the whole, the nano silver in coating/houghite content is 10%
Fluorescence intensity is maximum, reduces with its content, and fluorescence intensity gradually decreases.But when content is between 3%, 5% and 7%, nano silver/
Houghite/EA coating fluorescence intensity change is little.When nano silver/houghite content is 1%, nano silver/houghite/
The fluorescence intensity of EA coating is minimum.
The measurement of 6 Nanometer Copper of embodiment/silver houghite conducing composite material resistance value
The coating being cured in embodiment 1 and embodiment 2 is put into volume, measures resistance value in sheet resistance analyzer,
Resulting resistance value characterizes the surface conductivity of laminated film, judges electric conductivity according to resistance value.
The amount of fixed copper nitrate changes magnalium proportion, surveys Nanometer Copper/houghite/EA coating resistance value, as a result such as Fig. 5.
As shown in Figure 5, magnalium has significant impact with Nanometer Copper/houghite/EA coating electric conductivity is compared, and coating resistance value is equal
108~109Within the scope of Ω.With the change that magnalium matches, electric conductivity also changes therewith.When magnalium proportion is 2:1,2:2, nanometer
Copper/houghite/EA coating resistance value is higher, and magnalium proportion be 3:1 when, electric conductivity be it is strongest, resistance value is
0.336×10 8Ω。
The composition of fixed coating, changes nano silver/houghite content, surveys nano silver/houghite/EA coating resistance
Value, as a result such as Fig. 6.It will be appreciated from fig. 6 that nano silver class/hydrotalcite/EA coating resistance value of preparation is 0.26 × 106~1 × 106Ω
In range.Nano silver/houghite/EA coated conductive is better than Nanometer Copper/houghite/EA coating.
The composition of fixed composite coating, changes the type and content of conducting particles, surveys nano silver/houghite/EA coating
Resistance value, as a result such as Fig. 7.As can be seen from Figure 7, the nano silver/houghite surveyed/EA coating resistance value range is all 106~107
Between Ω, magnesium: aluminium: silver-colored proportion is 3:1:3, and nano silver/houghite containing in nano silver/houghite/EA coating
When amount is 7% (mass fraction), resistance value is 0.26 × 106Ω, electric conductivity is best at this time.
The above is only the preferred embodiment of the present invention, the range implemented of the present invention that therefore, it cannot be limited according to, i.e., according to
Equivalent changes and modifications made by the invention patent range and description, should still be within the scope of the present invention.
Claims (10)
1. a kind of Nanometer Copper/silver houghite conducing composite material preparation method, it is characterised in that: include:
1) Cu (NO is added in aqueous solution of sodium stearate3)2Aqueous solution or AgNO3Aqueous solution, after mixing, while thereto
NaAlO is added dropwise2Solution and MgCl2Solution is uniformly mixed, and is adjusted pH value to 9~10, is then aged 10 at 75~85 DEG C
~14h；It is separated by solid-liquid separation after ageing, it is 7~8 that solid portion, which is washed to the pH value of cleaning solution, then solid with soaked in absolute ethyl alcohol
It is separated by solid-liquid separation after body portion, obtains copper ions houghite or silver ion houghite；
2) PVP aqueous solution is mixed with the copper ions houghite or silver ion houghite, water, sonic oscillation is added
After processing, dehydrated alcohol is added, hydrazine hydrate is then added dropwise thereto, is stirred to react after being added dropwise to complete, stands, discard supernatant liquid,
Remainder is washed with dehydrated alcohol, is separated by solid-liquid separation, is obtained Nanometer Copper/houghite or nano silver/houghite；
3) Nanometer Copper/houghite or nano silver/houghite after mixing by acrylic acid, acrylamide, is added simultaneously
It makes it completely dissolved, adds epoxy acrylate, solidified after mixing, it is compound to obtain nano-copper type hydrotalcite conduction
Material or nano silver houghite conducing composite material.
2. Nanometer Copper according to claim 1/silver houghite conducing composite material preparation method, it is characterised in that:
In the nano-copper type hydrotalcite conducing composite material, magnalium proportion is 2.5~3.5:1.
3. Nanometer Copper according to claim 1/silver houghite conducing composite material preparation method, it is characterised in that:
In the nano silver houghite conducing composite material, magnalium silver proportion is 2.5~3.5:0.8~1.2:2.5~3.5, and its
In nano silver/houghite content be 6~8%.
4. Nanometer Copper according to claim 1/silver houghite conducing composite material preparation method, it is characterised in that:
In the step 2), the total volume of the water of water and addition in PVP aqueous solution and the volume ratio of dehydrated alcohol are 2~4:1~3.
5. Nanometer Copper according to claim 1/silver houghite conducing composite material preparation method, it is characterised in that:
In the step 2), the concentration of hydrazine hydrate is 38~42%.
6. Nanometer Copper according to claim 1/silver houghite conducing composite material preparation method, it is characterised in that:
In the step 3), cured mode is ultraviolet lighting solidification, is additionally added photoinitiator in the reaction system of the step 3).
7. Nanometer Copper according to claim 6/silver houghite conducing composite material preparation method, it is characterised in that:
The photoinitiator is 1173.
8. Nanometer Copper according to claim 1/silver houghite conducing composite material preparation method, it is characterised in that:
In the step 3), epoxy acrylate, acrylic acid, acrylamide and the Nanometer Copper/houghite or nano silver/class neatly
The mass ratio of stone is 3.1~3.2:0.7~0.8:0.9~1.1:0.045~0.6.
9. Nanometer Copper according to claim 1/silver houghite conducing composite material preparation method, it is characterised in that:
Nanometer Copper/the houghite is used further to prepare nano-copper type hydrotalcite conducing composite material after anti-oxidant treatment, described
Anti-oxidant treatment includes: the dehydrated alcohol Nanometer Copper/houghite being added to volume ratio for 0.8~1.2:0.8~1.2
In butyl titanate mixed solution, 3~5h is stirred at 65~75 DEG C, stands 22~26h, is filtered, washing, it is dry to get.
10. a kind of Nanometer Copper prepared by preparation method according to any one of claim 1 to 9/silver houghite is led
Composite.
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