CN106832272A - The preparation method of PANI/Fe3O4/MWCNTs paraffin composites - Google Patents
The preparation method of PANI/Fe3O4/MWCNTs paraffin composites Download PDFInfo
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- CN106832272A CN106832272A CN201710124954.7A CN201710124954A CN106832272A CN 106832272 A CN106832272 A CN 106832272A CN 201710124954 A CN201710124954 A CN 201710124954A CN 106832272 A CN106832272 A CN 106832272A
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- mwcnts
- fe3o4
- pani
- paraffin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention provides a kind of preparation method of PANI/Fe3O4/MWCNTs paraffin composite, including CNT and acid solution are put into there-necked flask, there-necked flask is put into mechanical agitation hour, suction filtration in oil bath pan, in the sample baking oven that will filter out, that is, the MWCNTs suspension being acidified；The CNT of functionalization is added and fills ultrasound in beaker, form the carbon nano tube suspension of stabilization, add 157 mg (0.4mmol) (NH4) 2FeSO4 6H2O and 386 mg (0.8mmol) NH4Fe (SO4) 2 12H2O 20ml to continue ultrasound, that is, obtain Fe3O4/MWCNTs heterojunction structures；Weigh 0.02gFe3O4/MWCNTs and 0.08g paraffin to be put into the beaker of 100ml, add the ether ultrasonic disperse of 20ml, after ether evaporates, be cooled to room temperature, sample is fitted into mould, be pressed into cylinder.Compared to existing technology, the PANI/Fe3O4/MWCNTs paraffin composite material surfaces that the present invention is prepared are evenly coated, and structure is neat, while dielectric properties are also fine.
Description
Technical field
The present invention relates to a kind of preparation method of PANI/Fe3O4/MWCNTs- paraffin composite, belong to nano material system
Standby field.
Background technology
Polymer/inorganic thing nano composite material combines good flexibility, machinability, the height of polymer due to it
The performances such as modulus, thermal conductivity and magnetic-particle unique magnetic property, electrical property, optical property etc., cause electromagnetic shielding microwave and inhale
The concern in receipts field, is widely used in electromagnetic shielding, electrochromic device and nonlinear optical system.Polyaniline is changeable due to its
Structure, special mechanism of doping effect, excellent environmental stability, machinability etc., have potential application in electromagnetic shielding field,
Ferroso-ferric oxide has good magnetic property, electric conductivity, but environmental stability is not good, and CNT is combined into system with Fe3O4
Into Fe3O4/MWCNTs heterojunction structures, then aniline is coated into the surface that expires, the environmental stability of composite can be increased, with reference to
The magnetic of CNT and the good electrical conductance of polyaniline and Fe3O4, is expected to synthesize good environmental stability, lightweight and inhales ripple
The wideband microwave absorbing material of better performances.It is poor all to there is adhesion property in the material for preparing in the prior art, uneven, matter
The relatively low situation of amount fraction.
The content of the invention
In view of above-mentioned the deficiencies in the prior art part, it is an object of the invention to provide a kind of PANI/Fe3O4/MWCNTs-
The preparation method of paraffin composite.
The invention aims to overcome the shortcomings of material prepared by traditional preparation methods, there is provided a kind of PANI/
The preparation method of Fe3O4/MWCNTs- paraffin composites.In order to achieve the above object, this invention takes following technical side
Case：
The invention provides a kind of preparation method of PANI/Fe3O4/MWCNTs- paraffin composite, comprise the following steps：
Step one, 1gCNT and 100ml acid solutions are put into there-necked flask, there-necked flask is put into machinery in 100 DEG C of oil bath pan
Stirring 2 hours, suction filtration is cleaned with substantial amounts of deionized water, until filtrate is close to neutrality, the sample that will filter out is put into 60 DEG C
Dried in baking oven 24 hours to constant weight, that is, the MWCNTs suspension being acidified；
Ultrasound 3 hours, forms in step 2, the beaker of the deionized water that the CNT addition of 0.1g functionalizations is filled into 40ml
The carbon nano tube suspension of stabilization, adds 157 mg (0.4mmol) (NH4) 2FeSO4 6H2O and 386 mg (0.8mmol)
The 12H2O 20ml of NH4Fe (SO4) 2 continue ultrasound 10 minutes, and mixed liquor is poured into four-hole boiling flask, are put into 50 DEG C of silicone oil pot
In, add the ammoniacal liquor that 5ml mass fractions are 25%, solution to become dark brown by black at once, magnetic agitation is reacted 30 minutes, is used
For several times, reacted powder dries 24 hours in being put into 80 DEG C of baking oven, that is, obtain Fe3O4/ for deionized water and washes of absolute alcohol
MWCNTs heterojunction structures；
Step 3, weigh 0.02gFe3O4/MWCNTs and 0.08g paraffin and be put into the beaker of 100ml, add the ether of 20ml to surpass
Sound disperses, and after ether evaporates, is cooled to room temperature, and sample is fitted into mould, is pressed into cylinder.
Preferably, the acid solution in above-mentioned steps one is the concentrated sulfuric acid that mass fraction is 98%.
Preferably, the cylinder external diameter in above-mentioned steps two is that 7.03mm internal diameters are 3.0mm, and thickness is generally 2mm or so.
Preferably, the above-mentioned PANI/Fe3O4/MWCNTs- paraffin composites prepared, mass fraction is 20%.
Compared to existing technology, the preparation method of the PANI/Fe3O4/MWCNTs- paraffin composites that the present invention is provided, work
Skill is simple and convenient, and the PANI/Fe3O4/MWCNTs- paraffin composite material surfaces for preparing are evenly coated, and structure is neat, while
Dielectric properties are also fine.
Brief description of the drawings
Fig. 1 is the preparation method schematic diagram of PANI/Fe3O4/MWCNTs- paraffin composite of the present invention；
Fig. 2 is Fourier's infared spectrum of PANI/Fe3O4/MWCNTs- paraffin heterojunction structure of the present invention；
Fig. 3 is the Raman light collection of illustrative plates of PANI/Fe3O4/MWCNTs- paraffin heterojunction structure of the present invention；
Fig. 4 is the XRD spectrum of PANI/Fe3O4/MWCNTs- paraffin heterojunction structure of the present invention.
Specific embodiment
The present invention provides a kind of preparation method of PANI/Fe3O4/MWCNTs- paraffin composite, to make mesh of the invention
, technical scheme and effect it is clearer, clear and definite, the present invention is described in more detail for the embodiment that develops simultaneously referring to the drawings.
It should be appreciated that specific embodiment described herein is only used to explain the present invention, it is not intended to limit the present invention.
As shown in figure 1, in embodiment, the present embodiment includes that the functionalization of MWCNTs, PANI/Fe3O4/MWCNTs are heterogeneous
The preparation of structure and the preparation of PANI/Fe3O4/MWCNTs- paraffin composites.
Wherein, the functionalization of MWCNTs is as follows：
Although CNT has excellent process based prediction model, because the Van der Waals force between CNT is stronger, very
It is susceptible to reunite, has had a strong impact on the performance of its performance.Oxidisability acid solution treatment must be being carried out before, its tube wall is connect
Upper substantial amounts of functional group (mainly-COOH), usual acid solution has the concentrated sulfuric acid, concentrated nitric acid, nitration mixture, potassium bichromate, permanganic acid
Acid solution of potassium etc., in the present embodiment, ours is the concentrated sulfuric acid that mass fraction is 98%.1gCNT and 100ml mass point
Number is put into there-necked flask for 98% concentrated sulfuric acid, and there-necked flask is put into mechanical agitation 2 hours in 100 DEG C of oil bath pan, is taken out
Filter, is cleaned with substantial amounts of deionized water, until filtrate is close to neutrality, the sample that will filter out dries 24 in being put into 60 DEG C of baking oven
Hour to constant weight, that is, the CNT being acidified.
The preparation process of PANI/Fe3O4/MWCNTs heterojunction structures is as follows：
The deionized water of the MWNTs additions 40ml of 0.1g functionalizations is ultrasonic 3 hours, the suspension of stabilization is formed, it is subsequently adding
0.4mmol (NH4) 2FeSO4 6H2O and 0.8mmmol NH4Fe (SO4) 2 12H2O continues ultrasound 10 minutes, and mixed liquor is fallen
Enter in four-hole boiling flask, be put into 50 DEG C of silicone oil pot, add 5ml, 25% ammoniacal liquor, magnetic agitation is reacted 30 minutes, uses deionization
For several times, 80 DEG C of reacted powder dries 24 hours, that is, obtain Fe3O4/MWCNT heterojunction structures for water and washes of absolute alcohol.Will be upper
State heterojunction structure and be put into ultrasound 3 hours in the deionized water of 20ml, solution is put into flask and is transferred in ice bath pot, add
The aniline of 0.2mlH3PO4 (85wt%) and 0.2ml, magnetic agitation is reacted 10 minutes；0.456g ammonium persulfates are dissolved in 20ml's
In deionized water, be slowly dropped in above-mentioned solution, reaction 6 hours with deionized water and washes of absolute alcohol for several times, 60 DEG C baking
24 hours.
The process of the preparation of PANI/Fe3O4/MWCNTs- paraffin composites is as follows：
Weigh 0.02gPANI/Fe3O4/MWCNTs and 0.08g paraffin to be put into the beaker of 100ml, add the ether ultrasound of 20ml
Dispersion, after ether evaporates, is cooled to room temperature, and sample is fitted into mould, is pressed into external diameter for 7.03mm internal diameters are 3.0mm
Cylinder, thickness is typically in 2mm or so.
It is illustrated in figure 2 the infared spectrum of PANI/Fe3O4/MWCNTs heterojunction structures, PANI and PANI/Fe3O4/
MWCNTs heterojunction structure infared spectrums, in 3400cm-1And 1700cm-1Neighbouring peak is sour in PANI/MWCNTs heterojunction structures
The carbon nano tube surface O-H and C=O washed after oxidation processes.In 1600cm-1And 1430cm-1Peak be respectively quinone ring in polyaniline
C=N and phenyl ring C=C stretching vibration peaks, 3237cm-1The peak at place is the stretching vibration peak of N-H in polyaniline, 1290 cm- 1790cm-1It is respectively the absworption peak of C-H on the stretching vibration peak and phenyl ring of C-N in polyaniline.
The Raman spectrum analysis figure of PANI/Fe3O4/MWCNTs heterojunction structures is illustrated in figure 3, relative to MWCNTs,
D the bands (~ 1320cm of Fe3O4/MWCNTs heterojunction structures-1) and G bands (~ 1590cm-1) position do not change significantly.PANI
After cladding, D is triggered to be moved with slight image height wave number, about ~ 1330 cm-1, and 1168 cm-1, 1252 cm-1, 1380
cm-1, 1450 cm-1Band gap then belongs to polyaniline.
Fig. 4 is shown the XRD spectrum of MWCNTs, and it is the diffraction maximum of MWCNTs that the diffraction maximum at 2 θ=26.5 ° is corresponding,
It can be seen that CNT remains in that original crystal property after pickling processes.According to JCPDS No. 89-
0691 data, 2 θ=30.2 °, 35.7 °, 43.3 °, 53.8 °, 57.3 ° and 62.9 ° respectively with (220), (311), (400),
(422), (511) are corresponding with (440) crystal face.The particle generated in PANI/ Fe3O4/MWCNTs heterojunction structures is pure
Fe3O4 nano particles, PANI cladding after Fe3O4 crystal property it is still fine.In the curve of PANI, 2 θ=15.10,
20.40 and 25.10 it is corresponding be polyaniline peak crystallization, therefore deduce that polyaniline is partially crystallizable.In PANI/
In Fe3O4/MWCNTs heterojunction structures, the diffraction maximum of PANI is weaker than the diffraction maximum of pure PANI a lot, illustrates the knot of doping PANI
Crystal property of the brilliant performance than PANI in PANI/Fe3O4/MWCNTs heterojunction structure is good, reason be due to MWCNT and Fe3O4 it
Between interface, limit the crystallization of PANI.
Compared to existing technology, the preparation method of the PANI/Fe3O4/MWCNTs- paraffin composites that the present invention is provided, work
Skill is simple and convenient, and the PANI/Fe3O4/MWCNTs- paraffin composite material surfaces for preparing are evenly coated, and structure is neat, while
Dielectric properties are also fine.
It is understood that for those of ordinary skills, can be with technology according to the present invention scheme and its invention structure
Think of is subject to equivalent or change, and all these changes or replacement should all belong to the protection model of appended claims of the invention
Enclose.
Claims (4)
1. a kind of preparation method of PANI/Fe3O4/MWCNTs- paraffin composite, it is characterised in that：The preparation method bag
Include following steps：
Step one, CNT and acid solution are put into there-necked flask, there-necked flask is put into mechanical agitation in oil bath pan, suction filtration, with big
The deionized water cleaning of amount, until filtrate is close to neutrality, the sample that will filter out dries to constant weight in being put into baking oven, that is, is acidified
MWCNTs suspension；
Ultrasound 3 hours, forms stabilization in step 2, the beaker of the deionized water that the CNT addition of functionalization is filled into 40ml
Carbon nano tube suspension, add 157 mg (0.4mmol) (NH4) 2FeSO4 6H2O and 386 mg (0.8mmol) NH4Fe
(SO4) 2 12H2O 20ml continue ultrasound 10 minutes, and mixed liquor is poured into four-hole boiling flask, are put into 50 DEG C of silicone oil pot, plus
Enter the ammoniacal liquor that 5ml mass fractions are 25%, solution becomes dark brown by black at once, and magnetic agitation is reacted 30 minutes, uses deionization
For several times, reacted powder dries 24 hours in being put into 80 DEG C of baking oven, that is, obtain Fe3O4/MWCNTs for water and washes of absolute alcohol
Heterojunction structure；
Step 3, weigh 0.02gFe3O4/MWCNTs and 0.08g paraffin and be put into the beaker of 100ml, add the ether of 20ml to surpass
Sound disperses, and after ether evaporates, is cooled to room temperature, and sample is fitted into mould, is pressed into cylinder.
2. the preparation method of PANI/Fe3O4/MWCNTs- paraffin composite as claimed in claim 1, it is characterised in that：Institute
The acid solution in step one is stated for the concentrated sulfuric acid that mass fraction is 98%.
3. the preparation method of PANI/Fe3O4/MWCNTs- paraffin composite as claimed in claim 1, it is characterised in that：Institute
The cylinder external diameter in step 2 is stated for 7.03mm internal diameters are 3.0mm, thickness is generally 2mm or so.
4. the preparation method of the PANI/Fe3O4/MWCNTs- paraffin composites as described in claim 1 or 3, its feature exists
In：The PANI/Fe3O4/MWCNTs- paraffin composites prepared, mass fraction is 20%.
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| CN201710124954.7A CN106832272A (en) | 2017-03-03 | 2017-03-03 | The preparation method of PANI/Fe3O4/MWCNTs paraffin composites |
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| CN201710124954.7A CN106832272A (en) | 2017-03-03 | 2017-03-03 | The preparation method of PANI/Fe3O4/MWCNTs paraffin composites |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018157400A1 (en) * | 2017-03-03 | 2018-09-07 | 深圳市佩成科技有限责任公司 | Preparation method for pani/fe3o4/mwcnts-paraffin composite material |
| CN114129724A (en) * | 2020-09-03 | 2022-03-04 | 天津大学 | Microwave-excited targeted sterilization nano particle, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161725A (en) * | 2007-09-29 | 2008-04-16 | 复旦大学 | Polyaniline coated magnetic carbon-nano tube composite material and preparation method thereof |
| CN103342980A (en) * | 2013-06-26 | 2013-10-09 | 哈尔滨工业大学 | Preparation method for MWCNT/Fe3O4/PANI/Au multilayer wrapped nanotube |
| CN104163919A (en) * | 2014-07-25 | 2014-11-26 | 北京科技大学 | Polyaniline/oxidized graphene/ferriferrous oxide absorbing material and preparation method |
-
2017
- 2017-03-03 CN CN201710124954.7A patent/CN106832272A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161725A (en) * | 2007-09-29 | 2008-04-16 | 复旦大学 | Polyaniline coated magnetic carbon-nano tube composite material and preparation method thereof |
| CN103342980A (en) * | 2013-06-26 | 2013-10-09 | 哈尔滨工业大学 | Preparation method for MWCNT/Fe3O4/PANI/Au multilayer wrapped nanotube |
| CN104163919A (en) * | 2014-07-25 | 2014-11-26 | 北京科技大学 | Polyaniline/oxidized graphene/ferriferrous oxide absorbing material and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| DEQING ZHANG ET AL.: ""Facile Preparation, Characterization, and Highly Effective Microwave Absorption Performance of CNTs/Fe3O4/PANI Nanocomposites"", 《JOURNAL OF NANOMATERIALS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018157400A1 (en) * | 2017-03-03 | 2018-09-07 | 深圳市佩成科技有限责任公司 | Preparation method for pani/fe3o4/mwcnts-paraffin composite material |
| CN114129724A (en) * | 2020-09-03 | 2022-03-04 | 天津大学 | Microwave-excited targeted sterilization nano particle, preparation method and application thereof |
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