CN118254432A - Five-layer composite structure macromolecule-based PTC composite material and preparation method and application thereof - Google Patents
Five-layer composite structure macromolecule-based PTC composite material and preparation method and application thereof Download PDFInfo
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- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
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- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention discloses a high molecular Positive Temperature Coefficient (PTC) composite material with a five-layer structure, a preparation method and application thereof. The polymer-based PTC composite material with the five-layer structure comprises a conductive metal layer, a polymer PTC material layer 1 and a polymer PTC material layer 2. Wherein the conductive metal layer is used as an outermost layer; the macromolecule PTC material 2 is used as a secondary outer layer and has lower room temperature resistivity; the high-molecular PTC material 1 is positioned in the middle layer and has higher voltage resistance. The high-molecular PTC composite material combines the advantages of low room temperature resistivity and high voltage resistance through five-layer structural design, so that the high-molecular PTC composite material has great application potential in different thermistor devices.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and relates to a preparation method and application of a polymer-based PTC composite material with a five-layer composite structure.
Background
The high molecular positive temperature coefficient (Positive Temperature Coefficient, PTC) material is a composite material prepared by mixing a high molecular matrix and conductive filler. The characteristic of this material is that its resistivity shows a non-linear increasing trend with increasing temperature, i.e. it remains low at normal temperature and it rises sharply by several orders of magnitude in a very small temperature zone when a specific turning temperature is reached. Therefore, the high polymer PTC material is widely applied to overcurrent protection components, and can quickly raise temperature resistance when the circuit current is overloaded, so as to achieve the effect of overcurrent protection.
For high molecular PTC composites, the main problem is the high room temperature resistivity and poor voltage resistance, which limits their application in high power devices. For example, scientific report (SCIENTIFIC REPORTS,2014, volume 4, page 6684) reports a polymer PTC material using carbon nanotubes as conductive filler, which successfully reduces the room temperature resistivity of the material, but its voltage resistance is not yet improved. Therefore, the current technical challenge is to balance the room temperature resistivity and the voltage resistance of the polymer PTC composite material, which is significant for widening the application range of the polymer PTC material in the electronic and electric fields.
Disclosure of Invention
The invention aims to solve the technical problems that the room temperature resistivity of the high polymer PTC composite material is reduced, and the voltage resistance of the high polymer PTC composite material is improved, so that the high polymer PTC composite material has both low room temperature resistivity and high voltage resistance.
In order to solve the problems, the invention provides a five-layer composite structure polymer-based PTC composite material.
The invention is realized by the following technical scheme:
The polymer-based PTC composite material with the five-layer composite structure is characterized in that the top layer and the bottom layer of the PTC composite material are the outermost layers made of conductive metal, the polymer PTC material 2 is used as the secondary outer layer, and the polymer PTC material 1 is used as the middle layer;
the conductive metal is one selected from copper foil, silver foil, aluminum foil, nickel-plated copper foil and tin-plated copper foil;
The high-molecular PTC material 1 and the high-molecular PTC material 2 are composed of a high-molecular matrix and conductive filler, and the mass ratio of the high-molecular matrix to the conductive filler is (5-40%): (60-95%);
The high polymer PTC material 1 and the high polymer PTC material 2 are selected from the same high polymer matrix, and the high polymer matrix is one or a mixture of more than one selected from polyethylene, polyvinylidene chloride, polypropylene, polyvinylidene fluoride, polycarbonate, perfluoroethylene propylene copolymer, polyamide and fluorinated polypropylene;
The high polymer PTC material 1 and the high polymer PTC material 2 are selected from the same or different conductive fillers, wherein the conductive fillers are one or a mixture of more selected from carbon black, acetylene black, short carbon fiber, long carbon fiber, single-wall carbon nano tube, multi-wall carbon nano tube, graphite, titanium carbide, tungsten carbide, tantalum carbide, titanium nitride, titanium diboride, aluminum nitride, magnesium nitride and boron nitride.
The macromolecule PTC material (1) of the middle layer has higher voltage resistance than the secondary outer layer; the polymer PTC material (2) of the secondary outer layer has lower room temperature resistivity than the middle layer.
The thickness of the middle layer high polymer PTC material 1 accounts for 15-60% of the total thickness of the composite material, the thickness of the secondary outer layer high polymer PTC material 2 accounts for 10-60% of the total thickness of the composite material, and the thickness of the conductive metal layer accounts for 10-60% of the total thickness of the composite material.
The invention also provides a preparation method of the polymer PTC composite material with the five-layer composite structure, which comprises the following preparation steps:
(1) The conductive filler is dispersed in the polymer matrix by adopting melt mixing or solution mixing;
(2) Manufacturing a PTC film;
(3) Hot pressing and compounding;
In the step (1), the solution mixing mode is to prepare macromolecule PTC slurry, and the solvent used for preparing the slurry is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, diphenylamine, toluene, xylene, diethylene glycol diethyl ether, m-cresol, phenol and the like; preferably, it is N, N-dimethylformamide; the mass ratio of the polymer resin matrix to the solvent is 1 (4-9); preferably 1:6;
in the step (1), the melt mixing mode is open mill hot-milling hot-press molding or single screw extruder extrusion molding. The molding temperature in the melting and mixing process is 200-230 ℃ and the rotating speed is 40-50 r/min;
In the step (2), the PTC film can be prepared by adopting the modes of coating, calendaring and the like; if the coating technology is utilized, the mixed solution is uniformly coated on the substrate, and the thickness of the coating film is controlled to meet the design requirement. If a calendaring method is adopted, the temperature, pressure and rolling speed of a roller of a calendaring machine are adjusted to ensure that the film has required uniform thickness and surface finish;
In step (3), the conductive metal layer (outermost layer), the polymer PTC material 2 (sub-outer layer) and the polymer PTC material 1 (intermediate layer) are sequentially stacked using a hot press and thermally press-compounded. Ensuring that each layer of material achieves good bonding effect in the hot pressing process. Wherein the temperature of the hot pressing is 200-230 ℃, the pressure intensity of the hot pressing is 10-20 MPa, and the time of the hot pressing is 15-30 min; preferably, the hot pressing temperature is 200 ℃, the hot pressing pressure is 15MPa, and the hot pressing time is 20min.
The invention also provides application of the five-layer composite structure polymer-based PTC composite material, which is characterized in that the PTC composite material is applied to a thermistor: and welding metal electrodes on the upper and lower layers, namely the outermost layers, of the PTC composite material to prepare the thermistor.
The conductive filler selection principle of the invention is as follows: the macromolecule PTC material 1 used as the middle layer has higher voltage resistance than the outer layer; the polymer PTC material 2 as the secondary outer layer has lower room temperature resistivity than the intermediate layer. The PTC composite material with the five-layer composite structure can integrate lower room temperature resistivity and higher voltage resistance of the two PTC composite materials, and can provide voltage resistance similar to that of the middle layer while reducing the room temperature resistivity of the PTC composite material.
For simplicity of expression, in the present disclosure, "a/B" is used to denote a polymeric PTC composite material composed of a polymeric matrix a and a conductive filler powder B, for example, HDPE/Ni refers to a polymeric PTC composite material composed of HDPE as the polymeric matrix and Ni as the conductive filler.
Drawings
FIG. 1 shows a schematic diagram of a five-layer composite structure of a polymer PTC composite material prepared by the invention;
Wherein, 1: intermediate layer, 2: secondary outer layer, 3: an outermost layer.
FIG. 2 is a cross-sectional SEM photograph of a five-layer structure polymer PTC composite material prepared in example 1 of the present invention;
FIG. 3 is a cross-sectional SEM photograph of a single-layer structure polymer PTC material prepared in comparative example 1 of the present invention;
fig. 4 is a schematic view of a PTC thermistor device made of the PTC composite materials of the present invention in a multi-layered structure.
Wherein, 4: PTC composite core, 5: nickel electrode, 6: and (3) plating a nickel-plated copper foil layer.
Detailed Description
The invention provides a five-layer composite structure macromolecule based PTC composite material, a preparation method and application thereof. In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
(1) And (3) dissolving fluorinated polypropylene (PP), adding Carbon Black (CB) powder according to the mass ratio of 1:0.5, and carrying out dispersion treatment to obtain PP/CB high-molecular PTC material 1 slurry (slurry 1 for short).
(2) And (3) dissolving fluorinated polypropylene, adding titanium carbide (TiC) powder according to the mass ratio of 1:10, and carrying out dispersion treatment to obtain PP/TiC high-molecular PTC material 2 slurry (short for slurry 2).
(3) The copper foil is coated with the slurry 2 and then dried, the thickness of each layer of the polymer PTC material 2 is controlled to be 0.1mm, and the polymer PTC material is cut into two identical parts.
(4) The upper half of the copper foil which has been dried and coated with the paste 2 was coated with the paste 1 and then dried, and the thickness of the layer of PTC material 1 was controlled to 0.1mm.
(5) The PTC material layer in the two-part dried copper foil was hot pressed face to face, setting the temperature to 200 ℃.
(6) After hot pressing, a multi-layer PTC composite material with the total thickness of 0.3mm is formed, and the structure is as follows: copper foil/PTC material layer 2/PTC material layer 1/PTC material layer 2/copper foil.
Comparative example 1
(1) And (3) dissolving fluorinated polypropylene, adding carbon black powder according to the mass ratio of 1:0.5, and carrying out dispersion treatment to obtain the PP/CB polymer PTC material 1 slurry (short for slurry 1).
(2) The copper foil is coated with the slurry 1 and then dried, the thickness of the polymer PTC material 1 is controlled to be 0.15mm, and the polymer PTC material 1 is cut into two identical parts.
(3) The PTC material layer in the two-part dried copper foil was hot pressed face to face, setting the temperature to 200 ℃.
(4) And hot-pressing to obtain the single-layer high-polymer PTC material with the total thickness of the PTC layer of 0.3 mm.
Example 2
(1) Plasticating high-density polyethylene (HDPE), and adding carbon black powder for mixing (mass ratio of 1:0.2); and (3) uniformly mixing, discharging the sheet, and calendaring to a thickness of 0.1mm to obtain the HDPE/CB polymer PTC material layer 1.
(2) Plasticating the high-density polyethylene, adding carbon black powder, and mixing (mass ratio of 1:0.7); and (3) uniformly mixing, discharging the sheet, and calendaring to a thickness of 0.1mm to obtain the HDPE/CB polymer PTC material layer 2.
(3) Mixing sheets prepared by a two-roll mill were stacked in the following order: copper foil/PTC material layer 2/PTC material layer 1/PTC material layer 2/copper foil.
(4) And hot-pressing at 200 ℃ to obtain the multi-layer high-polymer PTC composite material with the total thickness of the PTC layer of 0.3 mm.
Comparative example 2
(1) Plasticating the high-density polyethylene, adding carbon black powder, and mixing (mass ratio of 1:0.2); and (3) uniformly mixing, discharging the sheet, and calendaring to a thickness of 0.3mm to obtain the HDPE/CB high-molecular PTC material layer.
(2) Copper foil is attached to two sides of the prepared mixing sheet, and the single-layer high-polymer PTC material with the total thickness of 0.3mm is prepared after hot press molding at 200 ℃.
Example 3
(1) Polyvinylidene fluoride (PVDF) is dissolved, titanium carbide powder is added according to the mass ratio of 1:6, and PVDF/TiC macromolecule PTC material 1 sizing agent (short for sizing agent 1) is prepared through dispersion treatment.
(2) And dissolving polyvinylidene fluoride, adding titanium carbide powder according to the mass ratio of 1:12, and carrying out dispersion treatment to obtain PVDF/TiC polymer PTC material 2 slurry (short for slurry 2).
(3) The copper foil is coated with the slurry 2 and then dried, the thickness of each layer of the polymer PTC material 2 is controlled to be 0.1mm, and the polymer PTC material is cut into two identical parts.
(4) The upper half copper foil which has been dried and coated with the paste 2 is coated with the paste 1 and then dried, and the thickness of the layer of PTC material 1 is controlled to be 0.1mm.
(5) The PTC material layer in the two-part dried copper foil was hot pressed face to face, setting the temperature to 200 ℃.
(6) After hot pressing, a multi-layer PTC composite material with the total thickness of 0.3mm is formed, and the structure is as follows: copper foil/PTC material layer 2/PTC material layer 1/PTC material layer 2/copper foil.
Comparative example 3
(1) And dissolving polyvinylidene fluoride, adding titanium carbide powder according to the mass ratio of 1:6, and carrying out dispersion treatment to obtain PVDF/TiC high-molecular PTC material 1 slurry (short for slurry 1).
(2) The copper foil is coated with the slurry 1 and then dried, the thickness of the polymer PTC material 1 is controlled to be 0.15mm, and the polymer PTC material 1 is cut into two identical parts.
(3) The PTC material layer in the two-part dried copper foil was hot pressed face to face, setting the temperature to 200 ℃.
(4) And hot-pressing to obtain the single-layer high-polymer PTC material with the total thickness of the PTC layer of 0.3 mm.
Table 1 comparison of the Performance of the single layer structured PTC composite material and the multilayer structured PTC composite material prepared by the present invention
From the experimental results, the multi-layer PTC composite material can combine the advantages of the single-layer PTC composite material, effectively improves the room temperature conductivity on the basis of the intermediate layer composite material, and still has higher voltage resistance. The structural design realizes the cooperative enhancement of the performance by optimizing the interlayer material, and provides a new direction for the further development of the PTC material in high-voltage application.
Example 4
(1) And (3) dissolving fluorinated polypropylene, adding carbon black powder according to the mass ratio of 1:0.5, and carrying out dispersion treatment to obtain the PP/CB polymer PTC material 1 slurry (short for slurry 1).
(2) And (3) dissolving fluorinated polypropylene, adding titanium carbide powder according to the mass ratio of 1:10, and carrying out dispersion treatment to obtain the PP/TiC polymer PTC material 2 slurry (short for slurry 2).
(3) The copper foil was coated with the paste 2 and then dried, and the thickness of each layer of the polymer PTC material 2 was controlled to 0.125mm, and cut into two identical parts.
(4) The upper half of the copper foil which has been dried and coated with the paste 2 was coated with the paste 1 and then dried, and the thickness of the layer of PTC material 1 was controlled to 0.05mm.
(5) The PTC material layer in the two-part dried copper foil was hot pressed face to face, setting the temperature to 200 ℃.
(6) After hot pressing, a multi-layer PTC composite material with the total thickness of 0.3mm is formed, and the structure is as follows: copper foil/PTC material layer 2/PTC material layer 1/PTC material layer 2/copper foil.
Example 5
(1) And (3) dissolving fluorinated polypropylene, adding carbon black powder according to the mass ratio of 1:0.5, and carrying out dispersion treatment to obtain the PP/CB polymer PTC material 1 slurry (short for slurry 1).
(2) And (3) dissolving fluorinated polypropylene, adding titanium carbide powder according to the mass ratio of 1:10, and carrying out dispersion treatment to obtain the PP/TiC polymer PTC material 2 slurry (short for slurry 2).
(3) The copper foil was coated with the paste 2 and then dried, and the thickness of each layer of the polymer PTC material 2 was controlled to 0.075mm, and cut into two identical parts.
(4) The upper half of the copper foil which has been dried and coated with the paste 2 was coated with the paste 1 and then dried, and the thickness of the layer of PTC material 1 was controlled to 0.15mm.
(5) The PTC material layer in the two-part dried copper foil was hot pressed face to face, setting the temperature to 200 ℃.
(6) After hot pressing, a multi-layer PTC composite material with the total thickness of 0.3mm is formed, and the structure is as follows: copper foil/PTC material layer 2/PTC material layer 1/PTC material layer 2/copper foil.
Example 6
(1) And (3) dissolving fluorinated polypropylene, adding carbon black powder according to the mass ratio of 1:0.5, and carrying out dispersion treatment to obtain the PP/CB polymer PTC material 1 slurry (short for slurry 1).
(2) And (3) dissolving fluorinated polypropylene, adding titanium carbide powder according to the mass ratio of 1:10, and carrying out dispersion treatment to obtain the PP/TiC polymer PTC material 2 slurry (short for slurry 2).
(3) The copper foil was coated with the paste 2 and then dried, and the thickness of each layer of the polymer PTC material 2 was controlled to 0.05mm, and cut into two identical parts.
(4) The upper half of the copper foil which has been dried and coated with the paste 2 was coated with the paste 1 and then dried, and the thickness of the layer of PTC material 1 was controlled to 0.2mm.
(5) The PTC material layer in the two-part dried copper foil was hot pressed face to face, setting the temperature to 200 ℃.
(6) After hot pressing, a multi-layer PTC composite material with the total thickness of 0.3mm is formed, and the structure is as follows: copper foil/PTC material layer 2/PTC material layer 1/PTC material layer 2/copper foil.
Example 7
(1) And (3) dissolving fluorinated polypropylene, adding carbon black powder according to the mass ratio of 1:0.5, and carrying out dispersion treatment to obtain the PP/CB polymer PTC material 1 slurry (short for slurry 1).
(2) And (3) dissolving fluorinated polypropylene, adding titanium carbide powder according to the mass ratio of 1:10, and carrying out dispersion treatment to obtain the PP/TiC polymer PTC material 2 slurry (short for slurry 2).
(3) The copper foil is coated with the slurry 2 and then dried, the thickness of each layer of the polymer PTC material 2 is controlled to be 0.025mm, and the polymer PTC material is cut into two identical parts.
(4) The upper half of the copper foil which has been dried and coated with the paste 2 was coated with the paste 1 and then dried, and the thickness of the PTC material 1 layer was controlled to 0.25mm.
(5) The PTC material layer in the two-part dried copper foil was hot pressed face to face, setting the temperature to 200 ℃.
(6) After hot pressing, a multi-layer PTC composite material with the total thickness of 0.3mm is formed, and the structure is as follows: copper foil/PTC material layer 2/PTC material layer 1/PTC material layer 2/copper foil.
TABLE 2 comparison of the performance of Multi-layer structured PTC composites with different minor outer and intermediate layer thicknesses
From the experimental results, the conductivity and the voltage resistance of the PTC composite material with the multilayer structure can be effectively adjusted by precisely adjusting the thickness of each layer in the PTC composite material with the multilayer structure. This regulation provides a viable strategy for designing PTC composites with specific electrical performance requirements. By varying the thickness ratio of the secondary outer layer and the intermediate layer, the room temperature conductivity and the voltage resistance of the material can be balanced to some extent.
Example 8
The PTC composite material of the multilayer structure described in example 1 was die cut into round chips with a radius of 2 mm. And then welding nickel electrodes on the two smooth surfaces of the chip by a soldering tin dip soldering method, wherein the welding process is temperature programming, the highest temperature is 260 ℃, and the welding time is 30min. After the welding is completed, the prepared thermistor device is shown in fig. 4, and has the structure as follows: nickel electrode 5, nickel-plated copper foil layer 6 and PTC composite material core layer 4. Which is used for analog testing in circuits. The experimental results showed that the resistivity of the device smoothly increased from 0.4 Ω·cm to 20.8 Ω·cm in the temperature range of 25 ℃ to 140 ℃. When the temperature is further increased to 140-180 ℃, the resistivity of the thermistor is sharply increased to about 700000 ohm cm, the typical characteristics of the PTC material are reflected by the abrupt change, and the test result of the thermistor shows that the thermistor can effectively perform overcurrent response in a circuit, limit the current by remarkably increasing the resistivity, and prevent the circuit from being damaged due to overcurrent.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that would occur to one skilled in the art are included within the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is defined by the appended claims.
Claims (6)
1. The polymer-based PTC composite material with the five-layer composite structure is characterized in that the top layer and the bottom layer of the PTC composite material are the outermost layer (3) prepared from conductive metal, the polymer PTC material 2 is used as the secondary outer layer (2), and the polymer PTC material 1 is used as the middle layer (1);
the conductive metal is one selected from copper foil, silver foil, aluminum foil, nickel-plated copper foil and tin-plated copper foil;
The high-molecular PTC material 1 and the high-molecular PTC material 2 are composed of a high-molecular matrix and conductive filler, wherein the mass ratio of the high-molecular matrix to the conductive filler is (5-40%): (60-95%);
The high polymer PTC material 1 and the high polymer PTC material 2 are selected from the same high polymer matrix, and the high polymer matrix is one or a mixture of more than one selected from polyethylene, polyvinylidene chloride, polypropylene, polyvinylidene fluoride, polycarbonate, perfluoroethylene propylene copolymer, polyamide and fluorinated polypropylene;
The high polymer PTC material 1 and the high polymer PTC material 2 are selected from the same or different conductive fillers, wherein the conductive fillers are one or a mixture of more selected from carbon black, acetylene black, short carbon fiber, long carbon fiber, single-wall carbon nano tube, multi-wall carbon nano tube, graphite, titanium carbide, tungsten carbide, tantalum carbide, titanium nitride, titanium diboride, aluminum nitride, magnesium nitride and boron nitride.
2. A polymer-based PTC composite material according to claim 1, wherein the polymer PTC material (1) of the intermediate layer has a higher voltage resistance than the lower outer layer; the polymer PTC material (2) of the secondary outer layer has lower room temperature resistivity than the middle layer.
3. A polymer based PTC composite material according to claim 1 wherein the thickness of the intermediate layer of the polymer PTC material 1 is 15 to 60% of the total thickness of the composite material, the thickness of the sub-outer layer of the polymer PTC material 2 is 10 to 60% of the total thickness of the composite material, and the thickness of the conductive metal layer is 10 to 60% of the total thickness of the composite material.
4. A method of preparing a PTC composite material according to claim 1, comprising the steps of
1) Dispersing conductive filler in a polymer matrix according to the proportion by adopting melt mixing or solution mixing;
Wherein, when the solution is mixed, the solvent is used for preparing polymer matrix slurry, and the mass ratio of the polymer matrix to the solvent is 1 (4-9); the melt mixing is hot-milling hot-press molding by an open mill or extrusion molding by a single screw extruder, the molding temperature is 200-230 ℃, and the rotating speed is 40-50 r/min;
2) Preparing a PTC film by adopting a coating or calendaring mode;
3) And sequentially stacking the conductive metal layer of the outermost layer, the polymer PTC material 2 of the secondary outer layer and the polymer PTC material 1 of the middle layer by using a hot press, and carrying out hot press compounding to obtain the polymer-based PTC composite material with the five-layer composite structure.
5. The process according to claim 4, wherein the solvent in step 1) is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, diphenylamine, toluene, xylene, diethylene glycol diethyl ether, m-cresol, phenol and the like.
6. Use of a five-layer composite structure polymer-based PTC composite material according to claim 1, in a thermistor: and welding metal electrodes on the upper and lower layers, namely the outermost layers, of the PTC composite material to prepare the thermistor.
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| Publication Number | Publication Date |
|---|---|
| CN118254432A true CN118254432A (en) | 2024-06-28 |
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