CN1237652A - Laminated composite magnetic conductive polymer film and its preparation method - Google Patents
Laminated composite magnetic conductive polymer film and its preparation method Download PDFInfo
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- CN1237652A CN1237652A CN98111335.4A CN98111335A CN1237652A CN 1237652 A CN1237652 A CN 1237652A CN 98111335 A CN98111335 A CN 98111335A CN 1237652 A CN1237652 A CN 1237652A
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- polypyrrole
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- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 43
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000010935 stainless steel Substances 0.000 claims abstract description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 14
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 12
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 4
- 239000004332 silver Substances 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 3
- 239000012528 membrane Substances 0.000 claims description 43
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 12
- 230000001413 cellular effect Effects 0.000 claims description 8
- 150000003233 pyrroles Chemical class 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 230000005415 magnetization Effects 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000011358 absorbing material Substances 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
- 229960002089 ferrous chloride Drugs 0.000 abstract description 2
- DTLYQPFUPMDNNT-UHFFFAOYSA-N 4-methylbenzenesulfonic acid;1h-pyrrole Chemical compound C=1C=CNC=1.CC1=CC=C(S(O)(=O)=O)C=C1 DTLYQPFUPMDNNT-UHFFFAOYSA-N 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 9
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000012254 powdered material Substances 0.000 description 2
- 101100001675 Emericella variicolor andJ gene Proteins 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The preparation method of laminar composite magnetic conductive polymer film, belonging to the field of functional composite material, is characterized by that using three-electrode electrochemical electrolytic cell, respectively using stainless steel sheet and silver/silver chloride electrode as counter electrode and reference electrode, and using stainless steel sheet or aluminium alloy sheet as working electrode, and in the pyrrole-toluene-p-sulfonic acid electrolyte soluion and ferrous sulfate or ferrous nitrate or ferrous chloride electrolyte solution coating with polypyrrole and ferrite in turn to prepare polypyrrole/ferrite/polypyrrole laminar composite film or polypyrrole/ferrite/polypyrrole/ferrite/polypyrrole multi-layer laminar magnetic conductive composite film or honeycomb magnetic conductive composite film. Said film possesses good magnetic performance and conductivity, good flexibility, high strength and light weight, can be used as cryptomorphic wave-absorbing material and electromagnetic shielding material.
Description
The invention belongs to the functional composite material field
In recent years, not only had electroconductibility but also had the conducting polymer materials of macromolecular property to become a big focus in scientific research field.Because conductive polymers has that density is little, light weight, conductivity can series of advantages such as regulate according to the needs that use between conductor, semi-conductor and isolator, and has caused the concern of produce sectors such as microelectronics industry.Be applied at present in fields such as antistatic, high tension battery, microwave absorbing.Development along with many cross disciplines research fields such as light, electricity, magnetic develops existing conductive polymers, makes it to become the focus that the multi-functional conducting polymer materials with practical value becomes recent research.Wherein, develop the attention that the conducting polymer materials with magnetic enjoys people especially.Conductive polymers does not all have magnetic under the normal temperature, as gives conducting polymer materials with magnetic, and this type material then may produce new application in the electromagnetic field field.Only have electrically conductive polyaniline and multipolymer thereof under utmost point low temperature (being lower than-240 ℃) condition, to show the research report of certain magnetic at present, but such very low temperature conductive polymers magnet does not obviously have use value at normal temperatures.According to Electromagnetic theory, the material that has electroconductibility and magnetic concurrently has broadband, characteristics that the microwave absorbing rate is high, is the ideal material that satisfies electromagnetic shielding and microwave absorbing.Present employed absorbing material mostly is the magnetic inorganic Ferrite Material, and it is to exist with powder type, is difficult for forming process, and density is excessive, exists the problems such as easy-to-rust that are difficult to overcome in the use.It is little that conductive polymer membrane has density, advantage such as can directly be utilized, but exist the narrow shortcoming of microwave absorbing frequency band simultaneously.Utilize that the magnetic conductive polymkeric substance might prepare then that density is little, light weight, wide microwave absorbing and the electromagnetic shielding material of absorption band.Ordinary method is with conductive polymers powder and ferrite powder powder material simple blend, but the material of preparation exists mixing inequality, forming process difficulty, defectives such as ferrite easy-to-rust like this.Someone utilizes chemical process to make the ferritic powder of polyaniline parcel, and this powder has certain electric conductivity and has magnetic property simultaneously concurrently under the normal temperature, and on the low side (specific conductivity is less than 1Scm but this powdered material also exists specific conductivity
-1), powdered material is difficult for being made it be subjected to certain restriction in actual applications by shortcomings such as forming process.The eighties mid-term, in the aqueous solution, electroplate ferrite membrane and obtained success, under not too high temperature, utilize this method can on some conductive bases, plate the ferrite membrane of uniform thickness.But electrochemical plating gained ferrite membrane does not possess the self-supporting ability, in case it is separated from electrode, just can only exist with powder type, and the corrosion problem of ferrite membrane is not resolved yet, thereby makes its application be subjected to certain restriction.[reference: (1) K.Yoshizawa, K.Tanaka, T.Yamabe, andJ.Yamauchi, J.Chem.Phys., 96,5516, (1992); (2) P.Yam, ScientificAmerican, 7,75, (1995); (3) Abe.M, Tamaura.Y, J.Appl.Phys.55,2614, (1984); (4) Wan Meixiang, Zhou Weixia, Li Jun is towards Chinese patent No.95124933.9]
The purpose of present technique invention
For solving current material and technical defective, in the present invention, be base material with the conductive polymer membrane, the conductive composite film that has magnetic concurrently that adopts the electrochemical plating preparation to have the self-supporting ability, can directly be used.This film adopts layered composite structure, and inorganic ferrite particle is wrapped in the middle of the two layers of polymers film tightly, makes ferrite and air isolated, thereby has good anti-corrosion.This composite membrane conductivity can be regulated between conductor, semi-conductor and isolator according to the needs that use, this film has also possessed high saturation and magnetic intensity and low-down coercive force (Hc=0) simultaneously, using under alternating magnetic field and will can not produce magnetic loss, is a kind of rare soft magnetic materials.This composite membrane snappiness is good, intensity is high, light weight, compares to existing admixture of powder type matrix material, and this film has more practical value.This magnetic conductive film all has satisfactory stability (heated 8 hours continuously down at 120 ℃, specific conductivity and magnetic all remain unchanged) in-150 ℃ to 120 ℃ temperature ranges.In addition, utilize method of the present invention can also prepare complex-shaped magnetic conductive composite membrane, the present invention has very wide application prospect.Preparation method of the present invention
Electrochemical cell is connected in PARC M273 type electrochemical analyser by three electrodes and forms, and stainless steel substrates and silver/silver chloride electrode are respectively counter electrode and reference electrode, and working electrode can be selected stainless steel substrates or aluminum alloy sheet as required for use.Polymerization single polymerization monomer is the pyrroles, and the divalence ferrous salt is ferrous sulfate, Iron nitrate, iron protochloride etc.The pyrroles is dissolved in the tosic acid electrolyte solution, obtains polypyrrole film after ten minutes, again to be wrapped in the working electrode of polypyrrole film with 0.5~8 milliampere/square centimeter current density continuous current aggregate number.In 60~120 ℃ divalence ferrous salt electrolyte solution, (regulate its pH value between 6.5~9) with sodium hydroxide, with 0.1~1 milliampere of/square centimeter current density constant-current electrolysis tens of minutes, powering at polypyrrole film plates ferrite membrane, will be wrapped in working electrode continuous current pyrrole polymerization in pyrroles's one tosic acid electrolyte solution of polypyrrole/composite hexaferrite film again.Then can make polypyrrole/ferrite/polypyrrole stratiform composite membrane, composite membrane is behind stripping electrode, and vacuum-drying is 24 hours under the room temperature, with the four-electrode method testing conductivity.Magnetic property is tested on superconduction magnetic parameter tester.In present method implementation process, can change the thickness of polymeric film and ferrite membrane by the electric weight that consumes in the controlled polymerization process according to the needs of application target; Controlled polymerization current density or polymerization potential can change the specific conductivity of polymeric membrane.The advantage that the present invention possessed
Among the present invention, be that base material is electroplated ferrite membrane with the conductive polymer membrane, the magnetic conductive composite membrane is with after working electrode separates, and ferrite layer is still keeping the film forming form of homogeneous.Because this film has layered composite structure, the inorganic iron ferrite is made ferrite and air completely cut off, thereby has possessed good anti-corrosion by tightly in the middle of parcel two layers of polymers film.
Compare with the powder magnetic conductive matrix material of ordinary method preparation, the material that the present invention is prepared is the composite membrane that a snappiness is good, intensity is high, and this magnetic conductive film can be cut into arbitrary shape, satisfies the needs of different use occasions.This film all has extraordinary stability (heated 8 hours continuously down at 120 ℃, specific conductivity and magnetic property all remain unchanged) in-150 ℃ to 120 ℃ temperature ranges simultaneously, can use in-150 ℃ to 100 ℃ temperature ranges.
In present method implementation process, can change the thickness of polymeric film and ferrite membrane by the electric weight that consumes in the controlled polymerization process according to the needs of application target; Current density or polymerization potential can change the specific conductivity of polymeric membrane in the controlled polymerization process.In addition, can also prepare magnetic conductive composite membrane with multilayer ferrite membrane.
In present method implementation process, can also make the work electrode with material in irregular shape, prepare the composite membrane of respective shapes, promptly can prepare complex-shaped magnetic conductive composite membrane.
Because this magnetic conductive film is a kind of rare soft magnetic materials, can not produce magnetic loss when under alternating magnetic field, using, it can be used in the alternating electromagnetic field as good magneticsubstance.
Most preferred embodiment of the present invention
The preparation of example 1. magnetic conductive composite membranes
200 μ l pyrroles are dissolved in the 30ml0.1 mol tosic acid electrolyte solution, with 0.5~2 milliampere of/square centimeter current density, obtain polypyrrole film at continuous current polyase 13 on the stainless steel substrates after 0 minute, again to be wrapped in the working electrode of polypyrrole film, (pH value 6.5~9) was with 0.1~1 milliampere of/square centimeter current density constant-current electrolysis 10 minutes in the copperas solution of 65 ℃ of 100ml (0.01~0.03) mol, power at polypyrrole film and to plate ferrite membrane, be working electrode with the stainless steel substrates that is wrapped in polypyrrole/composite hexaferrite film once more, the continuous current polyase 13 is 0 minute in pyrroles-tosic acid electrolyte solution, make polypyrrole/ferrite/polypyrrole stratiform composite membrane, composite membrane is behind stripping electrode, room temperature vacuum-drying 24 hours, recording specific conductivity is 110Scm
-1, tensile strength is 51.7Mpa. saturation magnetization Ms=10.7emu/g, the prepared magnetic conductive film of Hc=0. can be cut into arbitrary shape with scissors.
Example 2. contains the preparation of the magnetic conductive composite membrane of two-layer ferrite membrane
Continuation is made the work electrode with the stainless steel substrates of the magnetic conductive film that is wrapped in the example 1, acierage oxysome and polypyrrole film in turn, make polypyrrole/ferrite/polypyrrole/ferrite/polypyrrole multilayer layered composite film, composite membrane is behind stripping electrode, room temperature vacuum-drying 24 hours, recording specific conductivity is 103Scm
-1, tensile strength is 46.7Mpa., saturation magnetization Ms=11.3emu/g, Hc=0.
The preparation of example 3. magnetic semiconductor composite membranes
200 μ l pyrroles are dissolved in the 30ml0.1 mol tosic acid electrolyte solution, with the stainless steel substrates is working electrode and counter electrode, with 6~8 milliamperes/square centimeter current density continuous current polymerizations 5 minutes, be working electrode with the stainless steel substrates that is wrapped in polypyrrole film again.(pH value 6.5~9) was with 0.1~1 milliampere of/square centimeter current density constant-current electrolysis 10 minutes in the ferrous nitrate solution of 100 ℃ of 100ml0.01~0.03 mol, power at polypyrrole film and to plate ferrite membrane, last is working electrode with the stainless steel substrates that is wrapped in polypyrrole/composite hexaferrite film again, the continuous current polymerization is 5 minutes in pyrroles's one tosic acid electrolyte solution, makes polypyrrole/ferrite/polypyrrole stratiform composite membrane.Composite membrane is behind stripping electrode, and vacuum-drying is 24 hours under the room temperature, and recording this composite membrane specific conductivity is 7.6Scm
-1, tensile strength is 46.7Mpa, saturation magnetization is Ms=10.4emu/g, Hc=0.
The complex-shaped magnetic conductive composite membrane of example 4. preparations
200 μ l pyrroles are dissolved in the 30ml0.1 mol tosic acid electrolyte solution, make work electrode and counter electrode with cellular Al alloy block and stainless steel substrates respectively, silver/silver chloride electrode is made reference electrode, 0.8~1.0 volt of constant potential polyase 13 0 minute, and then make the work electrode in the solution of ferrous chloride of 120 ℃ of 100ml0.01~0.03 mol (pH value 6.5~9) with the cellular Al alloy block that is wrapped in polypyrrole film, with 1.5 volts of potentiostatic depositions 10 minutes, power at polypyrrole film and to plate ferrite membrane, and be working electrode with the cellular Al alloy block that is wrapped in polypyrrole/composite hexaferrite film once more, repeat the constant potential pyrrole polymerization.Cellular Al alloy block then is wrapped in tightly by polypyrrole/ferrite/polypyrrole stratiform composite magnetic conductive film.With 1 mol HCl solution dissolved aluminum alloy block, then can obtain a cellular hollow magnetic conductive film.
Purposes of the present invention
According to EM theory, the material with magnetic and electric conductivity is to satisfy electricity simultaneously The ideal material of magnetic screen and microwave absorption. The prepared magnetic conductive film of the present invention is pliable and tough Property is good, intensity is high, quality is light, and the ambient stable performance is good, can be used as hidden The shape absorbing material has broad application prospects at aerospace field, and this film also simultaneously Can be used on mobile phone, micro-wave oven etc. and easily produce electromagnetic radiation, human body is damaged Electromagnetic shielding material is made in the place.
Because this magnetic film is a kind of rare soft magnetic materials, when under alternating magnetic field, using not Can produce magnetic loss, so it can be used in alternating electromagnetism as good magnetic material In.
Claims (3)
1. laminated composite magnetic conductive polymer film and preparation method thereof belongs to field of compound material.In the electrochemical cell, counter electrode and reference electrode are respectively stainless steel substrates and silver/silver chloride electrode, and working electrode is stainless steel substrates or aluminum alloy sheet.The pyrroles is dissolved in the tosic acid electrolyte solution, current density continuous current polymerization with 0.5~8 milliampere/square centimeter obtained polypyrrole film after 5~30 minutes, the stainless steel substrates or the aluminum alloy sheet that will be wrapped in polypyrrole film again place the ferrous sulfate of 60~120 ℃ of pH values between 6.5~9, in Iron nitrate or the iron protochloride electrolyte solution, with 0.1~1 milliampere of/square centimeter current density, constant-current electrolysis 10 minutes, power at polypyrrole film and to plate uniform ferrite membrane, the working electrode that will be wrapped in polypyrrole/composite hexaferrite film again places pyrroles-tosic acid electrolyte solution, continuous current polymerization 5~30 minutes, make polypyrrole/ferrite/polypyrrole stratiform composite membrane, this composite membrane is behind stripping electrode, vacuum-drying is 24 hours under the room temperature, and recording specific conductivity is 7.6~110Scm
-1, tensile strength is 46.1~51.7Mpa, saturation magnetization is Ms=10.4~11.3emu/g.Hc=0.
2. according to the described invention of claim 1, when its feature also is to make the work electrode with cellular Al alloy block, behind polypyrrole/ferrite in the polymerization/polypyrrole stratiform composite membrane, cellular Al alloy block is dissolved with 1 mol HCl solution, then can prepare a cellular hollow magnetic conductive film.
3. according to the described invention of claim 1, its feature also is the repetition plating step, can prepare polypyrrole/ferrite/polypyrrole/ferrite/polypyrrole multilayer stratiform magnetic conductive composite membrane.
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US11942716B2 (en) | 2020-09-22 | 2024-03-26 | Amphenol Commercial Products (Chengdu) Co., Ltd. | High speed electrical connector |
US11817655B2 (en) | 2020-09-25 | 2023-11-14 | Amphenol Commercial Products (Chengdu) Co., Ltd. | Compact, high speed electrical connector |
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