阅读说明：本技术 一种二硫化钼-钡铁氧体环氧树脂电磁屏蔽涂层及其制法 (Molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating and preparation method thereof ) 是由 杨勇华 于 2020-05-09 设计创作，主要内容包括：本发明涉及环氧树脂电磁屏蔽技术领域,且公开了一种二硫化钼-钡铁氧体环氧树脂电磁屏蔽涂层,包括以下配方原料及组分：改性MoS<Sub>2</Sub>纳米花负载Ni掺杂钡铁氧体、环氧树脂、酸酐固化剂、消泡剂。该一种二硫化钼-钡铁氧体环氧树脂电磁屏蔽涂层,软磁M型纳米Ni掺杂钡铁氧体BaNi<Sub>0.3-0.8</Sub>Fe<Sub>11.2-11.7</Sub>O<Sub>19</Sub>,具有更高的磁性能和磁损耗功能,环氧树脂固化过程中,酸酐固化剂同时与改性MoS<Sub>2</Sub>纳米花负载Ni掺杂钡铁氧体的环氧基团进行开环交联固化反应,改善了与环氧树脂的分散性,避免了团聚和沉降的现象,MoS<Sub>2</Sub>纳米花均匀生长在Ni掺杂钡铁氧体的表面,表现出优异的阻抗匹配,使环氧树脂涂层通过介电损耗和磁损耗,有效吸收和衰减电磁波。(The invention relates to the technical field of epoxy resin electromagnetic shielding, and discloses a molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating, which comprises the following formula raw materials and components: modified MoS 2 The nanoflower is loaded with Ni-doped barium ferrite, epoxy resin, an anhydride curing agent and a defoaming agent. The molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating is soft magnetic M-shaped nano Ni-doped barium ferrite BaNi 0.3‑0.8 Fe 11.2‑11.7 O 19 Has higher magnetic performance and magnetic loss function, and the anhydride curing agent and the modified MoS are simultaneously used in the epoxy resin curing process 2 The epoxide group of the nanoflower loaded Ni-doped barium ferrite is subjected to ring-opening crosslinking curing reaction, so that the dispersibility of the nanoflower loaded Ni-doped barium ferrite and the epoxy resin is improved, the phenomena of agglomeration and sedimentation are avoided, and MoS 2 The nanoflowers uniformly grow on the surface of the Ni-doped barium ferrite and show excellent impedance matching, so that the epoxy resin is preparedThe coating can effectively absorb and attenuate electromagnetic waves through dielectric loss and magnetic loss.)

1. The molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating comprises the following raw materials and components, and is characterized in that: modified MoS₂The nanoflower-loaded Ni-doped barium ferrite, epoxy resin, an anhydride curing agent and a defoaming agent are mixed according to a mass ratio of 20-60:100:50-80: 0.5-2.

2. The electromagnetic shielding coating of molybdenum disulfide-barium ferrite epoxy resin of claim 1, wherein: the preparation method of the molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating comprises the following steps:

(1) adding ferric chloride, barium chloride and nickel chloride into a distilled water solvent, uniformly stirring, adding sodium hydroxide, reacting for 4-6h at 30-50 ℃, filtering, washing and drying, placing in a tubular resistance furnace, heating to 900-1000 ℃ at the heating rate of 10-20 ℃/min, and carrying out heat preservation and calcination for 2-3h to prepare the nano Ni-doped barium ferrite;

(2) adding nano Ni-doped barium ferrite into distilled water solvent, adding surfactant sodium dodecyl sulfate, (NH) after ultrasonic dispersion is uniform₄)₆Mo₇O₂₄And thiourea, pouring the solution into a hydrothermal reaction kettle after uniformly stirring, placing the hydrothermal reaction kettle into a reaction kettle oven, heating to 190 ℃ for reaction for 20-30h, filtering, washing and drying to prepare the defective MoS₂The nanoflower is loaded with Ni-doped barium ferrite;

(3) defective MoS is added into mixed solvent of ethanol and distilled water₂The nanoflower is loaded with Ni-doped barium ferrite, the mixture is added with a silane coupling agent after being uniformly dispersed by ultrasonic, the mixture reacts for 5 to 10 hours at the temperature of between 60 and 80 ℃, a solvent is filtered, washed and dried, and the modified MoS modified by the epoxy group is prepared₂The nanoflower is loaded with Ni-doped barium ferrite;

(4) modified MoS modified by adding epoxy group into acetone solvent₂The nanometer flower is loaded with Ni-doped barium ferrite, epoxy resin, an anhydride curing agent and a defoaming agent are added after ultrasonic dispersion is uniform, the materials are placed in a mold after stirring is uniform to form a film by casting, and the molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating is prepared by drying, tabletting and thermosetting film forming processes.

3. The electromagnetic shielding coating of molybdenum disulfide-barium ferrite epoxy resin of claim 2, characterized in that: the mass ratio of the ferric chloride, the barium chloride, the nickel chloride and the sodium hydroxide in the step (1) is 11.2-11.7:1:0.3-0.8:13-20, and the chemical molecular formula of the Ni-doped barium ferrite is BaNi_0.3-0.8Fe_11.2-11.7O₁₉。

4. The electromagnetic shielding coating of molybdenum disulfide-barium ferrite epoxy resin of claim 2, characterized in that: the nano Ni-doped barium ferrite, a surfactant sodium dodecyl sulfate and (NH)₄)₆Mo₇O₂₄The mass ratio of the thiourea to the thiourea is 0.6-1.2:0.8-2:10:15-20。

5. The electromagnetic shielding coating of molybdenum disulfide-barium ferrite epoxy resin of claim 2, characterized in that: the reaction kettle oven in the step (2) comprises an internal fixedly connected rotating device, a rotating device movably connected with a rotating shaft, a rotating shaft fixedly connected with a base, and a reaction kettle, a base fixedly connected with a spring plate, a spring fixedly connected with a spring and a spring fixedly connected with a limiting clamping plate.

6. The electromagnetic shielding coating of molybdenum disulfide-barium ferrite epoxy resin of claim 2, characterized in that: the silane coupling agent in the step (3) is any one of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane or 3- (2, 3-epoxypropoxy) propyl triethoxy silane and defective MoS₂The mass ratio of the nanoflower-loaded Ni-doped barium ferrite is 6-10: 1.

Technical Field

The invention relates to the technical field of epoxy resin electromagnetic shielding, in particular to a molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating and a preparation method thereof.

Background

With the rapid development of broadcasting, microwave technology and electronic information technology, electromagnetic pollution has become an effective way for solving the problem of electromagnetic pollution, wherein the electromagnetic pollution exists widely in daily life of people, long-term contact with electromagnetic radiation and electromagnetic waves can cause disorders to immune systems, reproductive systems and the like of human bodies, induce diseases such as immune function reduction, memory impairment and the like, the electromagnetic radiation can interfere communication systems, cause explosive substances, control failure of electric explosive weapons and the like, and the development of electromagnetic shielding materials with large wave-absorbing loss, wide wave-absorbing frequency band and light weight is an effective way for solving the problem of electromagnetic pollution.

The existing electromagnetic shielding material mainly comprises a ceramic series wave absorbing material, an iron series wave absorbing material, a carbon series wave absorbing material and the like, wherein ferrites such as manganese zinc ferrite, barium ferrite and the like have excellent magnetic properties and are magnetic loss electromagnetic shielding materials with wide application prospects, the barium ferrite can be used as an inorganic filler to carry out filling modification on organic polymer materials such as acrylic resin, epoxy resin and the like, so that the materials have a certain electromagnetic shielding function, but the single barium ferrite has poor impedance matching performance, electromagnetic waves and electromagnetic radiation are difficult to completely shield through magnetic loss, and the nano barium ferrite has poor compatibility with the epoxy resin, so that solution in a base material is agglomerated and settled, and the mechanical properties of the epoxy resin can be influenced.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating and a preparation method thereof, which solve the problems of low impedance matching performance and electromagnetic shielding performance of barium ferrite and solve the problems of easy agglomeration and sedimentation of nano barium ferrite in epoxy resin.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: a molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating comprises the following raw materials and components: modified MoS₂The nanoflower-loaded Ni-doped barium ferrite, epoxy resin, an anhydride curing agent and a defoaming agent are mixed according to a mass ratio of 20-60:100:50-80: 0.5-2.

Preferably, the preparation method of the molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating comprises the following steps:

(1) adding distilled water solvent, ferric chloride, barium chloride and nickel chloride into a reaction bottle, uniformly stirring, adding sodium hydroxide, uniformly stirring at 30-50 ℃ for reaction for 4-6h, filtering the solution to remove the solvent, washing the precipitate with ethanol, drying, placing in a tubular resistance furnace, heating to 900-1000 ℃ at a speed of 10-20 ℃/min, and carrying out heat preservation and calcination for 2-3h to obtain the nano Ni-doped barium ferrite.

(2) Adding distilled water solvent and nano Ni-doped barium ferrite into a reaction bottle, ultrasonically dispersing uniformly, and adding surfactant sodium dodecyl sulfate, (NH)₄)₆Mo₇O₂₄And thiourea, pouring the solution into a hydrothermal reaction kettle after uniformly stirring, placing the hydrothermal reaction kettle into a reaction kettle oven, heating to 190 ℃ for reaction for 20-30h, filtering the solution, washing a solid precipitation product by using distilled water and ethanol, and drying to prepare the defective MoS₂The nanoflower is loaded with Ni-doped barium ferrite.

(3) Adding a mixed solvent of ethanol and distilled water into a reaction bottle, and adding defective MoS₂The nanoflower is loaded with Ni-doped barium ferrite, the mixture is uniformly dispersed by ultrasonic, then a silane coupling agent is added, the mixture is stirred at a constant speed for reaction for 5 to 10 hours at a temperature of between 60 and 80 ℃, the solvent is removed by filtration, the solid product is washed by ethanol and dried, and the epoxy group modified MoS is prepared₂The nanoflower is loaded with Ni-doped barium ferrite.

(4) Adding acetone solvent and epoxy group modified MoS into a reaction bottle₂The nanometer flower is loaded with Ni-doped barium ferrite, epoxy resin, an anhydride curing agent and a defoaming agent are added after ultrasonic dispersion is uniform, the materials are placed in a mold after stirring is uniform to form a film by casting, and the molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating is prepared by drying, tabletting and thermosetting film forming processes.

Preferably, the mass ratio of the ferric chloride, the barium chloride, the nickel chloride and the sodium hydroxide in the step (1) is 11.2-11.7:1:0.3-0.8:13-20, and the chemical formula of the Ni-doped barium ferrite is BaNi_0.3-0.8Fe_11.2-11.7O₁₉。

Preferably, the nano Ni-doped barium ferrite, surfactant sodium dodecyl sulfate and (NH)₄)₆Mo₇O₂₄The mass ratio of the thiourea to the thiourea is 0.6-1.2:0.8-2:10: 15-20.

Preferably, the reaction kettle oven in the step (2) comprises an internal fixedly connected rotating device, a rotating device movably connected with a rotating shaft, a rotating shaft fixedly connected with a base, and a reaction kettle, a base fixedly connected with a spring plate, a spring fixedly connected with a spring, and a spring fixedly connected with a limiting clamping plate.

Preferably, the silane coupling agent in the step (3) is any one of 3- (2, 3-glycidoxy) propyltrimethoxysilane and 3- (2, 3-glycidoxy) propyltriethoxysilane, and the defective MoS₂The mass ratio of the nanoflower-loaded Ni-doped barium ferrite is 6-10: 1.

(III) advantageous technical effects

Compared with the prior art, the invention has the following beneficial technical effects:

the molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating is prepared into the nano-morphology Ni-doped barium ferrite BaNi through a coprecipitation method and high-temperature calcination_0.3-0.8Fe_11.2-11.7O₁₉，Ni²⁺Occupying part of Fe³⁺The crystal lattice increases the dielectric real part and the dielectric imaginary part of the barium ferrite, reduces the coercive force, promotes the conversion from the hard magnetic barium ferrite to the soft magnetic M type barium ferrite, and integrally improves the magnetic performance and the magnetic loss function of the Ni-doped barium ferrite.

The molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating takes nano Ni-doped barium ferrite as a carrier and is coated with (NH)₄)₆Mo₇O₂₄Preparing defective MoS by material ratio of thiourea₂Nanoflower loaded Ni-doped barium ferrite, defective MoS₂The nanoflower has an ultra-high specific surface area, a large number of hydroxyl active reaction sites are introduced into the defect structure at the edge in the growth process of a hot solvent, and the nanoflower can easily react with an epoxy silane coupling agent to obtain the epoxy group modified MoS₂Nano flower loaded Ni-doped barium ferrite, anhydride curing agent and modified MoS simultaneously₂The epoxide group of the nanoflower loaded Ni-doped barium ferrite and the epoxide group of the epoxy resin are subjected to ring-opening cross-linking curing reaction, and the MoS is improved through the covalent grafting effect of chemical bonds₂The nanometer flower loads the dispersivity of the Ni-doped barium ferrite and the epoxy resin, thereby avoiding MoS₂The nanoflower-loaded Ni-doped barium ferrite is agglomerated and precipitated in an epoxy resin matrixA drop phenomenon.

The molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating, MoS₂The nanometer flower grows on the surface of the Ni-doped barium ferrite uniformly, and MoS₂Has excellent dielectric property and dielectric loss property, MoS₂Interfacial polarization and dielectric relaxation can be formed between the nanoflower and the Ni-doped barium ferrite, and meanwhile, incident electromagnetic waves can be in MoS with a two-dimensional structure₂The petal-shaped lamella of the nanoflower continuously reflects and attenuates, and MoS is enabled under the synergistic effect₂The nanoflower-loaded Ni-doped barium ferrite shows excellent impedance matching, so that the epoxy resin coating can effectively absorb and attenuate electromagnetic waves through dielectric loss and magnetic loss.

Drawings

FIG. 1 is a schematic front view of a gas reactor oven;

FIG. 2 is an enlarged schematic view of the base;

figure 3 is a schematic diagram of the adjustment of the limiting clamp plate.

1-a reaction kettle oven; 2-a rotating device; 3-a rotating shaft; 4-a base; 5-a reaction kettle; 6-a spring plate; 7-a spring; 8-limiting clamping plate.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: a molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating comprises the following raw materials and components: modified MoS₂The nanoflower-loaded Ni-doped barium ferrite, epoxy resin, an anhydride curing agent and a defoaming agent are mixed according to a mass ratio of 20-60:100:50-80: 0.5-2.

Preferably, the preparation method of the molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating comprises the following steps:

(1) adding distilled water solvent, ferric chloride, barium chloride and nickel chloride into a reaction bottle, uniformly stirring, adding sodium hydroxide, wherein the mass ratio of the four substances is 11.2-11.7:1:0.3-0.8:13-20, uniformly stirring and reacting for 4-6h at 30-50 ℃, filtering the solution to remove the solvent, washing and drying the precipitated product by using ethanol, placing the product in a tubular resistance furnace, raising the temperature to 1000 ℃ at the rate of 10-20 ℃/min, and carrying out heat preservation and calcination for 2-3h to obtain the nano-silver catalystThe chemical formula of the Ni-doped barium ferrite is BaNi_0.3-0.8Fe_11.2-11.7O₁₉。

(2) Adding distilled water solvent and nano Ni-doped barium ferrite into a reaction bottle, ultrasonically dispersing uniformly, and adding surfactant sodium dodecyl sulfate, (NH)₄)₆Mo₇O₂₄And thiourea, the mass ratio of the four is 0.6-1.2:0.8-2:10:15-20, the solution is poured into a hydrothermal reaction kettle after being uniformly stirred and is placed in a reaction kettle oven, the reaction kettle oven comprises a rotating device fixedly connected inside, a rotating shaft is movably connected with the rotating device, a base is fixedly connected with the rotating shaft, a reaction kettle is arranged above the base, a spring plate is fixedly connected with the base, a spring is fixedly connected with the spring plate, a limiting clamping plate is fixedly connected with the spring, the reaction is carried out for 20-30 hours after the temperature is increased to 190 ℃, the solution is filtered, the solid precipitate is washed by using distilled water and ethanol and dried, and the defect MoS is prepared₂The nanoflower is loaded with Ni-doped barium ferrite.

(3) Adding a mixed solvent of ethanol and distilled water into a reaction bottle, and adding defective MoS₂The nanoflower is loaded with Ni-doped barium ferrite, after uniform ultrasonic dispersion, silane coupling agent 3- (2, 3-epoxypropoxy) propyl trimethoxy silane or 3- (2, 3-epoxypropoxy) propyl triethoxy silane is added, the mass ratio of the two is 1:6-10, the mixture is stirred and reacted at a constant speed for 5-10 hours at the temperature of 60-80 ℃, the solvent is removed by filtration, the solid product is washed by ethanol and dried, and the epoxy group modified MoS is prepared₂The nanoflower is loaded with Ni-doped barium ferrite.

(4) Adding acetone solvent and epoxy group modified MoS into a reaction bottle₂The nanometer flower is loaded with Ni-doped barium ferrite, epoxy resin, an anhydride curing agent and a defoaming agent are added after ultrasonic dispersion is uniform, the materials are placed in a mold after stirring is uniform to form a film by casting, and the molybdenum disulfide-barium ferrite epoxy resin electromagnetic shielding coating is prepared by drying, tabletting and thermosetting film forming processes.