CN115678196A - Polymer composite material toughened based on liquid metal and preparation method thereof - Google Patents
Polymer composite material toughened based on liquid metal and preparation method thereof Download PDFInfo
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- CN115678196A CN115678196A CN202211480436.6A CN202211480436A CN115678196A CN 115678196 A CN115678196 A CN 115678196A CN 202211480436 A CN202211480436 A CN 202211480436A CN 115678196 A CN115678196 A CN 115678196A
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Abstract
The invention discloses a liquid metal toughening-based polymer composite material and a preparation method thereof, wherein the production raw materials comprise a polymer material, a lubricating dispersant, an antioxidant and liquid metal; the liquid metal is simple substance gallium or gallium-based alloy particles, the melting point of the liquid metal is lower than 100 ℃, the particle size of the liquid metal is 10 nm-20 mu m, and the weight content of the liquid metal in production raw materials is 5% -30%. The preparation method comprises the steps of respectively drying the high polymer material and the liquid metal, uniformly mixing the dried high polymer material with the lubricating dispersant and the antioxidant, and adding the mixture into a double-screw extruder, an injection molding machine or a molding press for processing and forming to obtain the liquid metal toughening modified high polymer composite material. The invention adds liquid metal into various polymer matrixes, and has obvious toughening effect and good universality.
Description
Technical Field
The invention relates to a liquid metal toughening-based polymer composite material and a preparation method thereof, belonging to the field of polymer materials.
Background
Macromolecular compounds, also called high molecular polymers, are commonly found in nature and our daily lives. According to the property classification, the high polymer can be divided into plastics, rubber and fiber, and the application range of the products and the derivatives thereof prepared by the high polymer is very wide, and the products and the derivatives thereof can reach the advanced technical fields of military, aerospace, electronics and the like and can also reach the national economy fields of agriculture, industry, building, automobile traffic and the like. Polymers are commonly used as structural materials in these fields, and the strength and toughness as mechanical performance indexes of polymers are very strict requirements, so the toughening of plastics and rubbers is always an important research topic in the field of polymer material science. At present, a common toughening method is to introduce second-phase particles to toughen and modify macromolecules, wherein the second-phase particles are usually rubber elastomers, rigid nanoparticles, thermoplastic resins, core-shell structure polymers and the like, and all have a certain toughening effect, but some problems still exist. Such as rubber elastomers, inevitably reduce the heat resistance and modulus of the matrix while improving the toughness of the matrix; the rigid nano particle toughened polymer improves the toughness and the heat resistance modulus, but the nano particles are easy to agglomerate, and no method for uniformly dispersing the nano particles has been found in the industry.
Liquid Metals (LMs) are metal alloys having an amorphous atomic structure, are liquid at or near room temperature, and combine the excellent electrical conductivity, thermal conductivity, and fluid fluidity of metals. However, the report of using liquid metal to toughen the polymer material is not seen at home and abroad.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method and an application of a liquid metal-based polymer toughening agent, wherein the liquid metal has good fluidity, can be changed correspondingly along with the deformation of a polymer matrix, is repositioned, reduces the sensitivity of the polymer matrix to notches, and reduces the damage of stress concentration, so that the liquid metal can be added into various polymer matrices as a toughening agent, can effectively improve the mechanical properties of polymer materials, and has good universality.
In order to achieve the purpose, the invention is realized by the following technical scheme: a liquid metal toughening-based polymer composite material is prepared from production raw materials including a polymer material, a lubricating dispersant, an antioxidant and liquid metal; the high-molecular material is one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, ABS, polyamide, polyester, polycarbonate and polyformaldehyde; the lubricating dispersant is one of stearic acid soap, ethylene bis-oleamide (EBO) and pentaerythritol stearate (PETS); the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant DLTP, and antioxidant 168; the liquid metal is simple substance gallium or gallium-based alloy particles containing one or more elements of indium, tin, zinc, aluminum, magnesium, copper, cadmium and germanium, the melting point of the liquid metal is lower than 100 ℃, the particle size of the liquid metal is 10 nm-20 mu m, and the weight content of the liquid metal in production raw materials is 5% -30%.
Furthermore, in the production raw materials, the weight content of the lubricating dispersant is 0.5-1%, and the weight content of the antioxidant is 0.1-1.5%.
Further, the surface of the particles is covered with an oxide film with a thickness of 1-3 nm.
The invention also discloses a preparation method of the liquid metal toughening-based polymer composite material, which comprises the following steps:
(1) Drying the high molecular material at 80-180 deg.c for 1-8 hr and liquid metal particle at 30-60 deg.c for 1-2 hr;
(2) Adding the dried high polymer material and the liquid metal particles into a high-speed mixer according to the proportion, adding the lubricating dispersant and the antioxidant according to the weight proportion, stirring the materials together for 5 to 20 minutes, and discharging the materials after the materials are fully and uniformly mixed;
(3) And (3) adding the mixture obtained in the step (2) into a double-screw extruder, an injection molding machine or a molding press for processing and forming to obtain the liquid metal toughened polymer composite material.
Compared with the prior art, the invention has the following beneficial effects:
1. the liquid metal with the melting point below 100 ℃ is the prior art, different metals are mixed and ground to obtain liquid metal particles, the liquid metal particles have the advantages of excellent electrical conductivity, thermal conductivity and fluid fluidity of the metal, when the liquid metal toughens and modifies the polymer matrix, the liquid metal is correspondingly changed along with the deformation of the polymer matrix and is repositioned along with the deformation direction, and compared with a solid toughening agent, the liquid metal has better plasticity. In addition, the liquid metal can also increase the insensitivity of the polymer matrix to the notch, reduce the damage of stress concentration and achieve the aim of toughening.
2. When the liquid metal contacts with oxygen, a 1-3nm oxidation film shell layer is rapidly generated on the surface of the liquid metal, and the oxidation film layer not only prevents the further oxidation of the liquid metal, improves the stability of the liquid metal, but also prevents the fusion and agglomeration of liquid metal droplets, and is beneficial to the liquid metal to be changed into microdroplets which are uniformly dispersed in a polymer matrix.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below, but the contents of the present invention are not limited only to the following examples.
The material usage percentages in the examples of the invention and the comparative examples are weight percentages.
Example 1:
the liquid metal toughened polypropylene (PP) comprises the following components in percentage by weight: the lubricating dispersant adopts calcium stearate, and the using amount is 0.5 percent; 0.2 percent of antioxidant 1010 and 0.2 percent of antioxidant 168; the liquid metal consumption is 5 percent, and the rest is PP.
The liquid metal is gallium-based alloy particles containing indium, tin, zinc, aluminum, magnesium and cadmium, the melting point of the liquid metal is lower than 100 ℃, the particle size of the liquid metal is 10 nm-20 mu m, and the surface of the liquid metal is provided with an oxide film of 2 nm.
The preparation method comprises the following steps:
(1) Drying PP for 2 hours at the temperature of 80 ℃, and drying liquid metal for 1 to 2 hours at the temperature of 30 to 60 ℃ for later use;
(2) Weighing dry PP and liquid metal according to the weight ratio, adding the PP and the liquid metal into a high-speed mixer, adding a lubricating dispersant and an antioxidant according to the weight ratio, stirring for 5-20 minutes, and discharging after the PP and the liquid metal are fully and uniformly mixed;
(3) And (3) adding the mixture obtained in the step (2) into a double-screw extruder for processing and forming to obtain the PP/liquid metal polymer composite material.
Examples 2 to 4:
examples 2-4 were the same procedure as in example 1, with liquid metals used at 20%, 30%, 35%, respectively.
The properties of the composite material obtained from the above experiment are shown in table 1: it is understood that the tensile strengths of examples 1-3 are kept small compared to comparative example 1, and the impact strength of example 1 is improved by 108%, the impact strength of example 2 is improved by 138%, and the impact strength of example 3 is improved by 128%. The impact strength is improved in that the liquid metal can be elongated along with the stretching of the composite material, so that the composite material has higher deformation capacity under stress, the energy applied to the composite material is more effectively absorbed and released under the action of external force, and the toughness of the composite material is enhanced. The tensile strength and impact strength of example 4 were reduced because when the volume percentage of the liquid metal was too high, the dispersibility in the polymer material was deteriorated. Therefore, the liquid metal is used in an amount of 5 to 30% by weight.
TABLE 1 mechanical Properties of composites obtained with different liquid metal ratios
Example 5:
the liquid metal toughened polyamide 6 (PA 6) comprises the following components in percentage by weight: 0.6 percent of lubricating dispersant EBO, 0.3 percent of antioxidant 1076 and 0.3 percent of antioxidant DLTP; 10% of liquid metal; the rest is PA6.
The liquid metal is gallium-based alloy particles containing one or more elements of indium, tin, zinc, aluminum, magnesium, copper, cadmium and germanium, the melting point of the gallium-based alloy particles is lower than 100 ℃, the particle size of the gallium-based alloy particles is 10 nm-20 mu m, and the surfaces of the gallium-based alloy particles are covered with oxide films with the thickness of 1-3 nm.
The preparation method comprises the following steps: (1) Drying PA6 at 80-180 ℃ for 1-8 hours, and drying liquid metal at 30-60 ℃ for 1-2 hours for later use; (2) Weighing dry PA6 and liquid metal according to the weight ratio, adding the materials into a high-speed mixer, adding a lubricating dispersant and an antioxidant according to the weight ratio, stirring for 5-20 minutes, and discharging after the materials are fully and uniformly mixed; (3) And (3) adding the mixture obtained in the step (2) into an injection molding machine for processing and molding to obtain the PA 6/liquid metal polymer composite material.
Example 6:
the liquid metal toughened Polystyrene (PS) comprises the following components in percentage by weight: 0.4 percent of lubricating dispersant PETS, 0.2 percent of antioxidant 1010 and 0.4 percent of antioxidant 168; 15% of liquid metal; the remainder is PS.
The liquid metal is gallium-based alloy particles containing indium, tin and magnesium, the melting point of the liquid metal is lower than 100 ℃, the particle size of the liquid metal is 10 nm-20 mu m, and the surface of the liquid metal is covered with an oxide film with the thickness of 1-3 nm.
The preparation method comprises the following steps: (1) Drying PS at 80-180 deg.c for 1-8 hr, and drying liquid metal at 30-60 deg.c for 1-2 hr; (2) Weighing dry PS and liquid metal according to the weight ratio, adding the PS and the liquid metal into a high-speed mixer, adding a lubricating dispersant and an antioxidant according to the weight ratio, stirring for 5-20 minutes, and discharging after the PS and the liquid metal are fully and uniformly mixed; (3) And (3) adding the mixture obtained in the step (2) into a molding press for processing and molding to obtain the PS/liquid metal polymer composite material.
Example 7:
the liquid metal toughened PBT/PC composite material comprises the following components in percentage by weight: 0.4 percent of lubricating dispersant PETS, 0.2 percent of antioxidant 1010 and 0.2 percent of antioxidant 168; 18% of liquid metal; the balance of PBT and PC, wherein the composition ratio of PBT/PC is 3:7.
The experimental procedure was as in example 1.
Example 8:
the liquid metal toughened PVC/ABS/PE composite material comprises the following components in percentage by weight: 0.5 percent of lubricating dispersant PETS, 0.4 percent of antioxidant 1010 and 0.4 percent of antioxidant 168; 22% of liquid metal; the balance of PVC, ABS and PE, wherein the composition ratio of PVC/ABS/PE is 2.
The experimental procedure was as in example 1.
The properties of the composites obtained from the above experiments are shown in table 2: therefore, the liquid metal has obvious toughening and reinforcing effects on different types of polymer materials, the strength of the composite material is not reduced while toughening, and the polymer composite material with excellent performance is obtained.
TABLE 2 mechanical properties of different liquid metal toughened polymeric materials
Through further tests, when the high-molecular material is one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, ABS, polyamide, polyester, polycarbonate and polyformaldehyde; the lubricating dispersant is one of stearic acid soaps, ethylene bis-oleamide and pentaerythritol stearate; when the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant DLTP and antioxidant 168; liquid metal particles with the weight content of 5-30 percent are added, and the toughening effect is achieved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (4)
1. A liquid metal toughening-based polymer composite material is characterized in that production raw materials comprise a polymer material, a lubricating dispersant, an antioxidant and liquid metal; the high-molecular material is one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, ABS, polyamide, polyester, polycarbonate and polyformaldehyde; the lubricating dispersant is one of stearic acid soaps, ethylene bis-oleamide and pentaerythritol stearate; the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant DLTP, and antioxidant 168; the liquid metal is simple substance gallium or gallium-based alloy particles containing one or more elements of indium, tin, zinc, aluminum, magnesium, copper, cadmium and germanium, the melting point of the liquid metal is lower than 100 ℃, the particle size of the liquid metal is 10 nm-20 mu m, and the weight content of the liquid metal in production raw materials is 5-30%.
2. The liquid metal toughening-based polymer composite of claim 1, wherein: in the production raw materials, the weight content of the lubricating dispersant is 0.5-1%, and the weight content of the antioxidant is 0.1-1.5%.
3. The liquid metal toughening-based polymer composite of claim 1, wherein: the surface of the particles is covered with an oxide film with the thickness of 1-3 nm.
4. The preparation method of the liquid metal toughening-based polymer composite material according to claim 1, comprising the following steps:
(1) Drying the high molecular material at 80-180 deg.c for 1-8 hr, and drying the liquid metal particle at 30-60 deg.c for 1-2 hr;
(2) Adding the dried high polymer material and the liquid metal particles into a high-speed mixer according to the proportion, adding the lubricating dispersant and the antioxidant according to the weight proportion, stirring the materials together for 5 to 20 minutes, and discharging the materials after the materials are fully and uniformly mixed;
(3) And (3) adding the mixture obtained in the step (2) into a double-screw extruder, an injection molding machine or a molding press for processing and forming to obtain the liquid metal toughened polymer composite material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117153453A (en) * | 2023-08-30 | 2023-12-01 | 广东和通科技有限公司 | Conductive polymer composite material, preparation method thereof and grounding electrode comprising conductive polymer composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110105758A (en) * | 2019-05-15 | 2019-08-09 | 东南大学 | A kind of preparation of the electronic package material based on liquid metal and its application method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110105758A (en) * | 2019-05-15 | 2019-08-09 | 东南大学 | A kind of preparation of the electronic package material based on liquid metal and its application method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117153453A (en) * | 2023-08-30 | 2023-12-01 | 广东和通科技有限公司 | Conductive polymer composite material, preparation method thereof and grounding electrode comprising conductive polymer composite material |
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