CN113174133A - High-frequency dielectric composite material used in communication technology and preparation method thereof - Google Patents
High-frequency dielectric composite material used in communication technology and preparation method thereof Download PDFInfo
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- CN113174133A CN113174133A CN202110568357.XA CN202110568357A CN113174133A CN 113174133 A CN113174133 A CN 113174133A CN 202110568357 A CN202110568357 A CN 202110568357A CN 113174133 A CN113174133 A CN 113174133A
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Abstract
The invention discloses a high-frequency dielectric composite material used in communication technology and a preparation method thereof, wherein the high-frequency dielectric composite material comprises, by weight, 30-45 parts of cyanate ester, 18-25 parts of epoxy resin, 22-30 parts of dielectric filler and 6-10 parts of curing agent. The preparation method comprises the steps of uniformly mixing calcium carbonate, lanthanum sesquioxide and nano titanium dioxide, adding the mixture into a ball mill, adding deionized water, carrying out ball milling for 15-20 hours, drying at 120-130 ℃, further placing the mixture into a tube furnace, introducing nitrogen, calcining for 3-4 hours at 1100-1200 ℃, and cooling to obtain Ca0.75La0.15TiO3Mixing Ca0.75La0.15TiO3Mixing with barium titanate uniformly, adding into a ball mill, adding deionized water, ball milling for 1.5-3 h, and sprayingAnd (3) performing spray granulation, calcining at 1300-1400 ℃ for 2.5-5 h, cooling, and performing ball milling again to ensure that the particle size is 12-14 mu m, thereby obtaining the dielectric filler. And adding the dielectric filler, the cyanate ester, the epoxy resin and the curing agent into a double-screw extruder according to the specific weight, injecting into a die, and curing to obtain the high-frequency dielectric composite material.
Description
Technical Field
The invention belongs to the technical field of high-frequency dielectric composite materials, and particularly relates to a high-frequency dielectric composite material used in a communication technology and a preparation method thereof.
Background
The rapid development of communication technology has put higher demands on the miniaturization of equipment, and it is known from microwave theory that since the size of a dielectric device is inversely proportional to the square root of the dielectric constant (epsilon), a material having a high dielectric constant and a low dielectric loss (tan delta) is required to reduce the size of the dielectric device. The high-dielectric ceramic material has excellent dielectric property, but has large brittleness and high sintering temperature; the polymer material has good mechanical property and processability, but the dielectric constant is generally low (epsilon < 10), and the use of the polymer material as a dielectric material is influenced. The composite material taking the polymer material as the matrix and the high-dielectric ceramic as the filler well integrates the advantages of the polymer material and the high-dielectric ceramic, not only retains the excellent dielectric property of the ceramic material, but also gives consideration to the good processability and mechanical property of the polymer material, and has good application prospect in the fields of high-frequency communication, integrated circuits and the like.
Although some ceramic/thermoplastic resin-based composites also have good dielectric properties, they have poor heat resistance, while ceramic/thermosetting resin-based composites have good heat resistance, such as polyimide, epoxy resin, cyanate ester, etc. But the PI resin has higher melting point and poorer processing performance. The epoxy resin has large dielectric loss, such as BaTiO prepared by researchers3an/EP composite having a filler volume fraction of 40 vol% and a tan δ of 0.0400(100 MHz); sr prepared by Subodh et al9Ce2Ti12O36The filler volume fraction of 40 vol% of the/EP composite material is tan delta 0.0220(8GHz), which limits the application of the epoxy resin in the high-frequency field. The cyanate ester resin has appropriate dielectric properties (epsilon is 2.9, tan delta is 0.0070, 10GHz), and a cured product network structure contains rigid benzene rings and triazine rings, so that the mechanical strength is high, and meanwhile, the cyanate ester resin has strong caking property and can show excellent caking force in a more severe environment. These advantages make cyanate ester resins an ideal matrix for ceramic/resin-based composites.
Disclosure of Invention
The invention aims to provide a high-frequency dielectric composite material used in communication technology, which comprises, by weight, 30-45 parts of cyanate ester, 18-25 parts of epoxy resin, 22-30 parts of dielectric filler and 6-10 parts of curing agent.
Further, the epoxy resin is any one of hydrogenated bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, bisphenol 5 diglycidyl ether, or bisphenol AD diglycidyl ether.
Further, the curing agent is any one of diethylenetriamine, triethylene tetramine or diethylaminopropylamine.
The invention aims to provide a preparation method of a high-frequency dielectric composite material used in communication technology, which comprises the following steps:
s1: uniformly mixing calcium carbonate, lanthanum oxide and nano titanium dioxide, adding the mixture into a ball mill, adding deionized water, ball-milling for 15-20 h, drying at 120-130 ℃, further placing the mixture into a tube furnace, introducing nitrogen, calcining for 3-4 h at 1100-1200 ℃, and cooling to obtain Ca0.75La0.15TiO3And then standby.
S2: ca obtained in step S10.75La0.15TiO3And uniformly mixing with barium titanate, adding into a ball mill, adding deionized water, performing ball milling for 1.5-3 h, performing spray granulation, calcining at 1300-1400 ℃ for 2.5-5 h, cooling, performing ball milling again, and ensuring the particle size to be 12-14 mu m to obtain the dielectric filler.
S3: and (4) adding the dielectric filler, cyanate ester, epoxy resin and curing agent obtained in the step (S2) into a double-screw extruder according to the specific weight, wherein the first zone is 120-140 ℃, the second zone is 160-170 ℃, the third zone is 175-180 ℃, the head is 185-188 ℃, extruding and injecting into a mold, curing at 210-220 ℃ for 3-6 h, and cooling to obtain the high-frequency dielectric composite material.
Preferably, the mass ratio of the calcium carbonate, the lanthanum oxide and the nano titanium dioxide is (0.7-0.8): (0.12-0.17): 0.95-1.24).
Preferably, the dielectric filler is Ca with a mass ratio of (0.6-0.7) to (0.25-0.36)0.75La0.15TiO3And BaTiO3A mixture of (a).
Compared with the prior art, the invention has the following beneficial effects:
in the present invention, the coal mining methodThe cyanate ester and the epoxy resin are compounded, so that the defect of high dielectric loss of the epoxy resin can be effectively overcome, the mechanical property and the bonding property of the composite material are ensured, and Ca is adopted as a dielectric filler0.75La0.15TiO3And BaTiO3The addition of La ions effectively reduces the dielectric loss of the composite material, and the mechanical property of the composite material can be improved by the mixed dielectric filler.
Drawings
FIG. 1 is an SEM photograph of a high-frequency dielectric composite prepared in example 1 of the present invention;
FIG. 2 is a bar graph showing the bending strength of the high frequency dielectric composite materials prepared in examples 1 to 4 of the present invention.
Detailed Description
The following embodiments of the present invention are described in detail, and the embodiments are implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Example 1
A preparation method of a high-frequency dielectric composite material used in communication technology specifically comprises the following steps:
s1: uniformly mixing calcium carbonate, lanthanum oxide and nano titanium dioxide, adding the mixture into a ball mill, adding deionized water, ball-milling for 15 hours, drying at 120 ℃, further placing the mixture into a tube furnace, introducing nitrogen, calcining for 3 hours at 1100 ℃, and cooling to obtain Ca0.75La0.15TiO3And is ready for use; wherein the mass ratio of the calcium carbonate to the lanthanum oxide to the nano titanium dioxide is 0.7:0.12: 0.95.
S2: ca obtained in step S10.75La0.15TiO3Mixing with barium titanate, adding into ball mill, adding deionized water, ball milling for 1.5 hr, spray granulating, calcining at 1300 deg.C for 2.5 hr, cooling, ball milling again to ensure particle diameter of 12 μm to obtain dielectric filler(ii) a Wherein the dielectric filler is Ca with a mass ratio of 0.6:0.250.75La0.15TiO3And BaTiO3A mixture of (a).
S3: adding 30 parts of cyanate ester, 18 parts of hydrogenated bisphenol A diglycidyl ether, 22 parts of dielectric filler and 6 parts of diethylenetriamine into a double-screw extruder, wherein the first zone is 120 ℃, the second zone is 160 ℃, the third zone is 175 ℃, the head is 185 ℃, extruding and injecting into a die, curing for 3 hours at 210 ℃, and cooling to obtain the high-frequency dielectric composite material.
Example 2
A preparation method of a high-frequency dielectric composite material used in communication technology specifically comprises the following steps:
s1: uniformly mixing calcium carbonate, lanthanum oxide and nano titanium dioxide, adding the mixture into a ball mill, adding deionized water, performing ball milling for 20 hours, drying at 130 ℃, further placing the mixture into a tube furnace, introducing nitrogen, calcining for 4 hours at 1200 ℃, and cooling to obtain Ca0.75La0.15TiO3And is ready for use; wherein the mass ratio of the calcium carbonate to the lanthanum oxide to the nano titanium dioxide is 0.8:0.17: 1.24.
S2: ca obtained in step S10.75La0.15TiO3Mixing the dielectric filler with barium titanate uniformly, adding the mixture into a ball mill, adding deionized water, performing ball milling for 3 hours, performing spray granulation, calcining at 1400 ℃ for 5 hours, cooling, performing ball milling again, and ensuring that the particle size is 14 mu m to obtain the dielectric filler; wherein the dielectric filler is Ca with a mass ratio of 0.7:0.360.75La0.15TiO3And BaTiO3A mixture of (a).
S3: adding 45 parts of cyanate ester, 25 parts of bisphenol F-glycidyl ether, 30 parts of dielectric filler and 10 parts of triethylene tetramine into a double-screw extruder, wherein the first zone is 140 ℃, the second zone is 170 ℃, the third zone is 180 ℃, the head is 188 ℃, extruding and injecting into a die, curing at 220 ℃ for 6 hours, and cooling to obtain the high-frequency dielectric composite material.
Example 3
A preparation method of a high-frequency dielectric composite material used in communication technology specifically comprises the following steps:
s1: uniformly mixing calcium carbonate, lanthanum oxide and nano titanium dioxide, adding the mixture into a ball mill, adding deionized water, carrying out ball milling for 17 hours, then drying the mixture at 125 ℃, further placing the dried mixture into a tube furnace, introducing nitrogen, calcining the mixture for 3.5 hours at 1150 ℃, and cooling the calcined mixture to obtain Ca0.75La0.15TiO3And is ready for use; wherein the mass ratio of the calcium carbonate to the lanthanum oxide to the nano titanium dioxide is 0.74:0.14: 1.03.
S2: ca obtained in step S10.75La0.15TiO3Mixing with barium titanate, adding into a ball mill, adding deionized water, ball milling for 2h, spray granulating, calcining at 1350 deg.C for 3h, cooling, and ball milling again to obtain dielectric filler with particle size of 13 μm; wherein the dielectric filler is Ca with a mass ratio of 0.64:0.290.75La0.15TiO3And BaTiO3A mixture of (a).
S3: adding 35 parts of cyanate ester, 20 parts of bisphenol 5 diglycidyl ether, 25 parts of dielectric filler and 8 parts of diethylaminopropylamine into a double-screw extruder, wherein the first zone is 125 ℃, the second zone is 165 ℃, the third zone is 177 ℃, the head is 186 ℃, extruding and injecting into a die, curing for 4 hours at 215 ℃, and cooling to obtain the high-frequency dielectric composite material.
Example 4
A preparation method of a high-frequency dielectric composite material used in communication technology specifically comprises the following steps:
s1: uniformly mixing calcium carbonate, lanthanum oxide and nano titanium dioxide, adding the mixture into a ball mill, adding deionized water, performing ball milling for 18 hours, drying at 126 ℃, further placing the mixture into a tube furnace, introducing nitrogen, calcining for 4 hours at 1200 ℃, and cooling to obtain Ca0.75La0.15TiO3And is ready for use; wherein the mass ratio of the calcium carbonate to the lanthanum oxide to the nano titanium dioxide is 0.78:0.16: 1.18.
S2: ca obtained in step S10.75La0.15TiO3Mixing with barium titanate, adding into ball mill, adding deionized water, ball milling for 2.5 hr, spray granulating, calcining at 1400 deg.C for 4 hr, cooling, ball milling again to obtain medium with particle diameter of 12 μmAn electrically-charged agent; wherein the dielectric filler is Ca with a mass ratio of 0.68:0.340.75La0.15TiO3And BaTiO3A mixture of (a).
S3: adding 40 parts of cyanate ester, 23 parts of bisphenol AD diglycidyl ether, 28 parts of dielectric filler and 9 parts of diethylenetriamine into a double-screw extruder, wherein the first zone is 128 ℃, the second zone is 168 ℃, the third zone is 178 ℃, the head is 187 ℃, extruding and injecting into a die, curing for 5 hours at 217 ℃, and cooling to obtain the high-frequency dielectric composite material.
Performance testing: the dielectric properties (10GHz) at normal temperature of the high-frequency dielectric composite materials prepared in examples 1 to 4 were measured by using a NOVO-CONTROL network analyzer E83683A; the bending strength of the samples of the high frequency dielectric composite materials prepared in examples 1 to 4 was measured by using an INSTRON-5566 model universal tester manufactured by INSTRON, USA, and the results are shown in Table 1,
table 1. test results:
as can be seen from Table 1, the dielectric constant of the high-frequency dielectric composite material prepared in the embodiments 1-4 of the invention can reach as high as 30.2, and the dielectric loss is only about 0.0050, which shows that the composite material of the invention has excellent dielectric properties; meanwhile, the composite material has good mechanical property, and the bending strength is more than 134.8 MPa.
Claims (6)
1. The high-frequency dielectric composite material for the communication technology is characterized by comprising, by weight, 30-45 parts of cyanate ester, 18-25 parts of epoxy resin, 22-30 parts of dielectric filler and 6-10 parts of curing agent.
2. A high frequency dielectric composite material for use in communication technology according to claim 1, wherein the epoxy resin is any one of hydrogenated bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, bisphenol 5 diglycidyl ether, or bisphenol AD diglycidyl ether.
3. A high frequency dielectric composite material for use in communication technology as claimed in claim 1, wherein the curing agent is any one of diethylenetriamine, triethylenetetramine or diethylaminopropylamine.
4. A method for preparing a high frequency dielectric composite for use in communication technology as claimed in claim 1, wherein the method comprises the steps of:
s1: uniformly mixing calcium carbonate, lanthanum oxide and nano titanium dioxide, adding the mixture into a ball mill, adding deionized water, ball-milling for 15-20 h, drying at 120-130 ℃, further placing the mixture into a tube furnace, introducing nitrogen, calcining for 3-4 h at 1100-1200 ℃, and cooling to obtain Ca0.75La0.15TiO3And is ready for use;
s2: ca obtained in step S10.75La0.15TiO3Uniformly mixing the dielectric filler with barium titanate, adding the mixture into a ball mill, adding deionized water, performing ball milling for 1.5-3 h, performing spray granulation, calcining at 1300-1400 ℃ for 2.5-5 h, cooling, performing ball milling again, and ensuring the particle size to be 12-14 mu m to obtain the dielectric filler;
s3: and (4) adding the dielectric filler, cyanate ester, epoxy resin and curing agent obtained in the step (S2) into a double-screw extruder according to the specific weight, wherein the first zone is 120-140 ℃, the second zone is 160-170 ℃, the third zone is 175-180 ℃, the head is 185-188 ℃, extruding and injecting into a mold, curing at 210-220 ℃ for 3-6 h, and cooling to obtain the high-frequency dielectric composite material.
5. The method as claimed in claim 4, wherein the mass ratio of calcium carbonate, lanthanum oxide and nano titanium dioxide is (0.7-0.8): (0.12-0.17): (0.95-1.24).
6. The method as claimed in claim 4, wherein the dielectric filler is Ca in a mass ratio of (0.6-0.7): (0.25-0.36)0.75La0.15TiO3And BaTiO3A mixture of (a).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659408A (en) * | 2012-05-23 | 2012-09-12 | 南京工业大学 | La2O3-TiO2Microwave dielectric ceramic and preparation method thereof |
| JP2016128574A (en) * | 2016-01-19 | 2016-07-14 | Dic株式会社 | Curable resin composition, cured article thereof, semiconductor encapsulation material, prepreg, circuit board and build-up film |
| CN106046691A (en) * | 2016-08-22 | 2016-10-26 | 威海光威复合材料股份有限公司 | Nanometer ceramic modified cyanate resin/epoxy resin composite material preparation method |
| CN106084667A (en) * | 2016-07-12 | 2016-11-09 | 刘世超 | A kind of high-k composition epoxy resin and application thereof |
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- 2021-05-25 CN CN202110568357.XA patent/CN113174133A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659408A (en) * | 2012-05-23 | 2012-09-12 | 南京工业大学 | La2O3-TiO2Microwave dielectric ceramic and preparation method thereof |
| JP2016128574A (en) * | 2016-01-19 | 2016-07-14 | Dic株式会社 | Curable resin composition, cured article thereof, semiconductor encapsulation material, prepreg, circuit board and build-up film |
| CN106084667A (en) * | 2016-07-12 | 2016-11-09 | 刘世超 | A kind of high-k composition epoxy resin and application thereof |
| CN106046691A (en) * | 2016-08-22 | 2016-10-26 | 威海光威复合材料股份有限公司 | Nanometer ceramic modified cyanate resin/epoxy resin composite material preparation method |
Non-Patent Citations (1)
| Title |
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| 戴金辉等: "《无机非金属材料概论》", 31 July 2018, 哈尔滨工业大学出版社 * |
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