CN110911075B - Preparation method of high-molecular thermistor and high-molecular thermistor - Google Patents
Preparation method of high-molecular thermistor and high-molecular thermistor Download PDFInfo
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- CN110911075B CN110911075B CN201911299955.0A CN201911299955A CN110911075B CN 110911075 B CN110911075 B CN 110911075B CN 201911299955 A CN201911299955 A CN 201911299955A CN 110911075 B CN110911075 B CN 110911075B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/006—Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistor chips
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/02—Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistors with envelope or housing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/28—Apparatus or processes specially adapted for manufacturing resistors adapted for applying terminals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
- H01C7/027—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient consisting of conducting or semi-conducting material dispersed in a non-conductive organic material
Abstract
The invention provides a high-molecular thermistor and a preparation method thereof, wherein the preparation method comprises the following steps: heat-treating the high-molecular thermistor chip at 10-40 deg.C above the polymer melting point for 4-10 hr; wherein the polymer is a polymer contained in the high-molecular thermistor chip material; carrying out irradiation treatment with the dose of 0-3Mrad on the high-molecular thermistor chip; welding metal wires on the upper and lower surfaces of the high-molecular thermistor chip to obtain a semi-finished product; and (4) carrying out irradiation treatment on the semi-finished product, wherein the irradiation dose is 7-15 Mrad. The high-molecular thermistor obtained by adopting the technical scheme of the invention has higher PTC strength, higher voltage-resistant grade and better reliability and stability.
Description
Technical Field
The invention belongs to the technical field of thermistor manufacturing, relates to a preparation method of a high-molecular thermistor and the high-molecular thermistor, and particularly relates to a preparation method of a high-molecular thermistor with high PTC (positive temperature coefficient) strength and high voltage-resistant grade and the high-molecular thermistor.
Background
The polymer thermistor is made of a mixture of semi-crystalline polymer and conductive particles, has positive resistance temperature characteristics (i.e., PTC characteristics), and is therefore referred to as a PPTC device for short. At normal temperatures, the conductive particles form a low resistance conductive network in the polymer. However, when the temperature is raised above the operating temperature of the device, whether due to high current flow through the device or due to an increase in ambient temperature, the grains in the polymer melt and form an amorphous state. During the process of crystal phase melting, the increase in volume separates the conductive particles on the conductive chains, so that the resistance of the PPTC device is increased in a nonlinear way by three or more orders of magnitude, and the PPTC device plays a role in current limiting protection of a circuit. The logarithmic value of the non-linear increase in the resistance of the PPTC device during this process is referred to as the PTC strength. After the fault is eliminated, the temperature of the device is reduced, and the polymer is gradually recrystallized to recover the resistance of the PPTC to a low-resistance state again, so that the PPTC is an overcurrent protection device with recoverable resistance.
Safety and reliability are important technical indexes of the circuit protection element, but in practical use, the PPTC can be burnt due to long-term protection, namely a voltage-resistant state, and can be subjected to failure phenomena such as burning due to multiple protection, namely multiple current impact, caused by circuit faults. The failure of the PPTC brings potential safety hazards to a circuit, so that the improvement of the voltage resistance and current resistance of the PPTC is an important subject. An important index for measuring the voltage resistance and the current resistance of the PPTC is the PTC strength. Chinese patents CN1267939C and CN102543329A respectively disclose a method for performing high-temperature heat treatment for 4-6 hours at 40-80 ℃ and 10-30 ℃ above the melting point of a polymer substrate of a thermistor core material after the thermistor core material is subjected to irradiation treatment to improve the voltage-resistant grade of the thermistor, and the principle is that the long-time high-temperature heat treatment can improve the dispersion uniformity of carbon black in the polymer and improve the PTC strength, and patent CN102543329A discloses that the method has the beneficial effect that the PTC strength is improved by one order of magnitude. However, the above-mentioned patent does not disclose that the resistance of the PTC device is increased by more than one time by performing a long-time heat treatment above the melting point after the heat-sensitive core material is subjected to irradiation crosslinking, which is not favorable for manufacturing a PTC device with higher holding current by using the method, and the method only improves the PTC strength by one order of magnitude and is not sufficient for improving the PTC voltage-resistant grade.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a preparation method of a high-molecular thermistor and the high-molecular thermistor, and the obtained high-molecular thermistor has higher PTC (positive temperature coefficient) strength and higher voltage grade.
In contrast, the technical scheme adopted by the invention is as follows:
a preparation method of a high-molecular thermistor comprises the following steps:
step S1, heat-treating the high-molecular thermistor chip for 4-10 hours at 10-40 ℃ above the melting point of the polymer;
wherein the polymer is a polymer contained in the high-molecular thermistor chip material;
step S2, carrying out irradiation treatment with the dose of 0-3Mrad on the high polymer thermistor chip;
step S3, welding metal wires on the upper and lower surfaces of the polymer thermistor chip to obtain a semi-finished product;
and step S4, performing irradiation treatment on the semi-finished product, wherein the irradiation dose is 7-15 Mrad.
The working principle of the high-molecular thermistor is based on the volume thermal expansion effect, namely, the temperature of the device is gradually increased due to overcurrent or overheating of a circuit, so that a polymer crystal region is melted to generate volume expansion, and the volume expansion causes the conductive chains formed by conductive particles in a polymer to break, so that the resistance value of the PPTC device is subjected to nonlinear rapid increase. The value obtained by taking the logarithm of the nonlinear increase amplitude of the resistance of the PPTC device is called PTC intensity. To obtain higher PTC strength values, it is desirable that the PPTC core material have sufficient expansion space and that the conductive chains are susceptible to breakage during volume expansion. To make the conductive chain easily broken, it is required that the conductive carbon black be dispersed as uniformly as possible in the polymer.
The technical scheme of the invention adopts heat treatment for 4-10 hours at the temperature of 10-40 ℃ above the melting point of the polymer, on one hand, enough preset expandable space is created for the PPTC core material, and on the other hand, opportunities are created for migration and redistribution of carbon black particles after the carbon black particles are melted in a polymer crystal region. In the conventional manufacturing method of the PPTC, heat treatment is carried out on the chip above the melting point of the polymer, but in order to avoid aging, the time of the heat treatment is generally not more than 1 hour, and experimental researches show that the time of the heat treatment is not enough to create enough preset expandable space for the PPTC core material, and the heat treatment for 4 to 10 hours at the temperature of 10 to 40 ℃ above the melting point of the polymer can create enough preset expandable space for the PPTC core material without causing the influence of accelerated aging on the polymer.
The irradiation aims to enable the compound of the polymer, the conductive carbon black and the flame-retardant filler to form a cross-linked network structure, so that the stability of the PPTC device is improved, but on one hand, the irradiation process enables the volume of the PPTC core material to be shrunk and cross-linked into the network structure, so that the degree of volume increase during PTC action is reduced, the abnormal increase value of the resistance value is limited, and the PTC strength of the thermistor is reduced; on the other hand, the crystallization area of the polymer is reduced and the crystallization capability is reduced, so that the resistance of the PTC device cannot be recovered and is increased by adopting long-time heat treatment above the melting point temperature of the polymer on the chip after irradiation, and the larger the irradiation dose is, the more the resistance cannot be recovered and is increased.
The conventional manufacturing process of the polymer thermistor is to perform high-dose irradiation crosslinking (irradiation dose is generally 10-30 Mrad) on the PTC chip after short-time heat treatment. The technical scheme of the invention is that a lead is directly welded on the surface of the PTC chip after the chip is subjected to long-time high-temperature heat treatment, and the purpose is to utilize the short-time high temperature of the soldering tin at 260 ℃ during dip soldering to greatly expand the volume of the PPTC core material. With the continuous increase of the holding current of the PPTC device, the area of the chip of the PPTC device is continuously increased, in order to reduce the deformation of the chip caused by direct dip soldering after the heat treatment of the chip with larger area, preferably, the chip can be subjected to small dose irradiation of not more than 3Mrad and then subjected to dip soldering of a lead, and experiments show that the irradiation dose is too large, and if the irradiation dose exceeds 5Mrad, the PTC intensity of the thermistor can be adversely affected. The prior technical scheme includes that a chip is irradiated with conventional large dose (such as more than 5Mrad) firstly, and then is subjected to heat treatment for 4-6 hours at 10-30 ℃ above the melting point of a polymer, and the defect is that the irradiation process firstly solidifies the network structure of a composite system of the polymer and carbon black, and reduces the effect of subsequent high-temperature heat treatment for 4-6 hours on volume expansion of a PTC core material, so that the PTC strength is only improved by one order of magnitude, and meanwhile, the irradiation dose is higher firstly, so that the resistance value of a device after the subsequent heat treatment is inevitably increased to a greater extent compared with the resistance value of the device after the subsequent heat treatment.
As a further improvement of the present invention, in step S3, after the metal wires are soldered, the semi-finished product is obtained by encapsulating with epoxy resin. By adopting the technical scheme, the next step can be directly carried out after the metal wire is welded for the product which does not need to be encapsulated with the epoxy resin, and the next step is carried out after the epoxy resin is encapsulated for the product which needs to be encapsulated with the epoxy resin.
As a further improvement of the present invention, in step S3, a metal wire is soldered by a solder dip soldering process.
As a further improvement of the invention, the temperature of the soldering tin is not lower than 260 ℃ in the dip soldering process.
As a further improvement of the present invention, in steps S2 and S4, the irradiation is performed with an accelerator or a cobalt source (Co)60Gamma rays) are irradiated.
As a further improvement of the invention, the polymer thermistor chip comprises a polymer thermistor substrate and a metal foil attached to the surface of the polymer thermistor substrate; the high-molecular thermistor base material comprises, by mass, 25-35% of a polymer, 20-35% of conductive carbon black and 35-55% of a flame-retardant filler.
Furthermore, the polymer thermistor chip is prepared by melting and mixing a polymer base material, conductive carbon black and a flame-retardant filler to prepare a sheet, adhering nickel-plated copper foils to the upper surface and the lower surface of the sheet by hot pressing to form a thermistor core material, and punching the thermistor core material into a specific size to obtain the polymer thermistor chip.
Wherein the polymer is a polyolefin resin.
As a further improvement of the invention, the polymer comprises one or a mixture of at least two of high density polyethylene HDPE, low density polyethylene LDPE, linear low density polyethylene LLDPE. Further, the melt index of the polymer is less than 1.0g/10 min.
As a further improvement of the invention, the particle size of the conductive carbon black is 50 nm-120 nm, and the dibutyl phthalate absorption value (DBP value) of the conductive carbon black is 50-130 cm3/100g。
Further, the conductive carbon black is selected from Raven 410 (particle size 101nm, DBP value 65 cm)3100g, Columbian company), Raven 430 (particle size 82nm, DBP value 78cm3100g, Columbian company), Sterling N550 (particle size 55nm, DBP 120cm3100g, Cabot corporation), SP5000 (particle diameter 90nm, DBP value 120cm3100g, Cabot corporation).
As a further improvement of the present invention, the flame retardant filler includes at least one of magnesium hydroxide or aluminum hydroxide. The flame-retardant coating is used as a flame-retardant filler to improve the pressure resistance of a thermistor device and increase the hardness of a thermistor material.
The invention also discloses a polymer thermistor which is prepared by adopting the preparation method of the polymer thermistor, and the PTC strength of the polymer thermistor is not less than 6. Further, the PTC strength of the polymer thermistor is not less than 6.5.
Compared with the prior art, the invention has the beneficial effects that:
by adopting the technical scheme of the invention, the volume of the PPTC material is greatly expanded to be an action preset expandable space of the PPTC through the heat treatment of the high-molecular thermistor for 4-10 hours at a temperature of 10-40 ℃ above the polymer melting point of the chip and the subsequent soldering tin dip welding process, carbon black particles are migrated after being melted in a polymer crystal region in a long-term high-temperature process to obtain more uniform redistribution, and then irradiation is carried out, so that the PTC strength of the high-molecular thermistor is improved by at least 3 orders of magnitude, the voltage-resistant grade of the PPTC is greatly improved, the voltage-resistant grade of a high-voltage PPTC device is improved, the safety risk of combustion ignition of the PPTC to various circuit faults when in use is reduced, and the high-voltage PPTC has better reliability and stability.
Drawings
Figure 1 is a graph of the PTC strength of PPTC obtained in example 2 of the present invention.
Figure 2 is a graph comparing the PTC strength curves of PPTC obtained in example 3 of the present invention.
Figure 3 is a graph of the PTC strength of PPTC according to comparative example 5 of the present invention.
Figure 4 is a graph of PTC strength for PPTC according to comparative example 1 of the present invention.
Figure 5 is a schematic diagram of a PPTC device in accordance with the present invention.
The reference numbers in the figures are as follows:
1-a layer of PPTC conductive material; 2-a metal foil layer; 3-chip; 4-metal pins; 5-PPTC devices.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
The high-molecular thermistor material provided by the embodiment of the invention comprises the following components:
as shown in fig. 5, a polymer thermistor includes a polymer thermistor chip 3, and metal pins 4 are welded to two sides of the polymer thermistor chip 3. The polymer thermistor chip comprises a PPTC (polymeric positive temperature coefficient) conductive material layer 1 and metal foil layers 2 positioned on two sides of the PPTC conductive material layer.
The composition of the PPTC conductive material layer comprises, by mass percent, 29% of high density polyethylene (HDPE, LB832, melt index: 0.35g/10min, density 0.968g/cm3, melting point 135 ℃, Ewing chemical), 28% of carbon black (Raven 430, particle size 82nm, DBP value 78cm3/100g, Columbia chemical), and 43% of magnesium hydroxide (Aitemag10, Etex).
Melting and mixing high-density polyethylene, carbon black and flame-retardant filler, pressing into sheets, carrying out hot pressing on the upper and lower surfaces of the sheets to attach 35 mu m nickel-plated copper foils to prepare 1.4-1.6 mm thick thermistor core materials, and then punching into a specific size to obtain the high-molecular thermistor chip.
The preparation method of the polymer thermistor provided by the embodiment includes the following specific steps:
firstly, performing high-temperature heat treatment on a high-molecular thermistor chip at the temperature which is 10-40 ℃ higher than the melting point of a polymer base material (the melting point of HDPE is 135 ℃) for 4-10 hours, and then slowly cooling to room temperature;
second, the chip is subjected to electron beam gamma ray (Co)60) Performing irradiation with 0-3Mrad dose;
thirdly, welding a metal wire by adopting a dip soldering process, then coating epoxy resin powder on the surface of the chip and curing to obtain a semi-finished product of the PPTC device;
and fourthly, performing irradiation treatment on the semi-finished product by using electron beams or gamma rays (Co60) with the irradiation dose of 7-15Mrad to obtain the high polymer thermistor with higher PTC strength and voltage-resistant grade.
The selection and matching experiments are carried out according to different heat treatment temperatures, different heat treatment times and different chip irradiation intensities, meanwhile, two chip punching sizes are selected for carrying out the experiments, and the process conditions of the embodiments 1 to 3 are shown in the table 1.
The components of the polymeric thermistor materials of the comparative examples of the present invention are the same as those of the above examples, except that the processes are different, and the differences are different in the methods of heat treatment and irradiation, as detailed in table 1.
Data of the chip sizes, chip resistances, and measured finished product resistances and PTC strengths of examples 1 to 9 and comparative examples 1 to 8 are shown in table 1. The PTC strength curve of PPTC obtained in example 2 is shown in fig. 1, the PTC strength curve of example 3 is shown in fig. 2, the PTC strength curve of comparative example 5 is shown in fig. 3, and the PTC strength curve of comparative example 1 is shown in fig. 4.
As can be seen from table 1 and a comparison of fig. 1 to 4, the finished product of the polymer thermistor of this embodiment has higher PTC strength and higher voltage resistance than the comparative example at two different chip sizes. The PTC intensity of the polymer thermistor of the embodiment of the invention is not lower than 6.3, and basically is more than 6.5.
TABLE 1 comparison of Process parameters and Performance for examples 1-9 and comparative examples 1-8
In the table, the data of the chip resistance, the finished product resistance and the PTC strength are typical values.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (8)
1. A preparation method of a high-molecular thermistor is characterized by comprising the following steps: which comprises the following steps:
step S1, heat-treating the high-molecular thermistor chip for 4-10 hours at 10-40 ℃ above the melting point of the polymer;
wherein the polymer is a polymer contained in the high-molecular thermistor chip material;
step S2, carrying out irradiation treatment with the dose of 0-3Mrad on the high polymer thermistor chip;
step S3, welding metal wires on the upper and lower surfaces of the polymer thermistor chip to obtain a semi-finished product;
step S4, performing irradiation treatment on the semi-finished product, wherein the irradiation dose is 7-15 Mrad;
the high-molecular thermistor chip comprises a high-molecular thermistor base material and a metal foil attached to the surface of the high-molecular thermistor base material; the high-molecular thermistor base material comprises, by mass, 25-35% of a polymer, 20-35% of conductive carbon black and 35-55% of a flame-retardant filler;
the polymer comprises one or a mixture of at least two of high density polyethylene HDPE, low density polyethylene LDPE and linear low density polyethylene LLDPE, and the melt index of the polymer is lower than 1.0g/10 min.
2. The method for producing a polymer thermistor according to claim 1, characterized in that: and step S3, after the metal wire is welded, packaging by adopting epoxy resin to obtain a semi-finished product.
3. The method for producing a polymer thermistor according to claim 1, characterized in that: in step S3, a solder dip soldering process is used to solder the metal wire.
4. The method for producing a polymer thermistor according to claim 3, characterized in that: in the dip soldering process, the temperature of soldering tin is not lower than 260 ℃.
5. The method for producing a polymer thermistor according to claim 1, characterized in that: in steps S2 and S4, irradiation is performed using an accelerator or a cobalt source.
6. The method for producing a polymer thermistor according to claim 1, characterized in that: the particle size of the conductive carbon black is 50-120 nm, and the DBP value is 50-130 cm3/100g。
7. The method for producing a polymer thermistor according to claim 1, characterized in that: the flame retardant filler includes at least one of magnesium hydroxide or aluminum hydroxide.
8. A polymer thermistor is characterized in that: the polymer thermistor is prepared by the method for preparing the polymer thermistor according to any one of claims 1 to 7, and the PTC strength of the polymer thermistor is not less than 6.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE69634777T2 (en) * | 1995-03-22 | 2006-02-02 | Tyco Electronics Corp. | ELECTRICAL DEVICE |
| CN1050926C (en) * | 1998-04-17 | 2000-03-29 | 黄恒超 | High molecular heat sensitive component and mfg. method thereof |
| CN100426424C (en) * | 2004-12-21 | 2008-10-15 | 上海长园维安电子线路保护股份有限公司 | Method for manufacturing high-temp PTC thermosensitive resistor |
| CN100437840C (en) * | 2005-02-24 | 2008-11-26 | 深圳市固派电子有限公司 | Macromolecular thermosensitive resistor and method for making same |
| CN102543329A (en) * | 2011-12-31 | 2012-07-04 | 上海长园维安电子线路保护股份有限公司 | Heat treatment method for improving strength of PTC (Positive Temperature Coefficient) thermistor core materials |
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