CN107434857B - Graphene-loaded cerium oxide and rubber composite material and preparation method thereof - Google Patents

Abstract

The invention relates to a graphene-supported cerium oxide and rubber composite material and a preparation method thereof. The preparation method comprises: dropping a cerium nitrate solution into a graphene oxide solution while stirring; adding it to a hydrothermal synthesis reactor for calcination, and cooling to room temperature; washing with ethanol, drying to obtain graphene-loaded cerium oxide; filling graphene-loaded cerium oxide into natural rubber-styrene-butadiene rubber, adding a vulcanization system and kneading to obtain a mixed rubber, vulcanized on a flat vulcanizer to obtain graphite The olefin-supported cerium oxide and rubber composites can be used to prepare radiation-resistant windshields of various shapes. The invention combines graphene and cerium oxide, uses graphene as a carrier to improve the speed of electron transfer, and fills it into natural rubber and styrene-butadiene rubber, which not only plays the role of electromagnetic shielding, but also plays the role of preventing natural rubber and styrene-butadiene rubber. It also has excellent mechanical properties, antioxidant properties and flexibility properties, and can be used to prepare anti-radiation windshields to protect human health.

Description

Graphene-supported cerium oxide and rubber composite material and preparation method thereof

technical field

The invention relates to the field of anti-radiation materials, in particular to an anti-radiation windshield and a preparation method thereof. The anti-radiation windshield is prepared by adding graphene-loaded cerium oxide to a polymer elastic material, so as to have good electromagnetic shielding effect and With the mechanical properties of elastomers, it can be used to prepare various protective covers to protect human health, such as baby stroller protective covers.

Background technique

With the development of modern science and technology, various electronic and electrical equipment have provided high efficiency for social production and brought great convenience to people's daily life. At the same time, the electromagnetic radiation and interference generated in the working process of electronic and electrical equipment will affect people's production and life, resulting in the deterioration of the electromagnetic environment in the human living space. The wide application of electromagnetic waves in science and technology has also brought new social problems, becoming a new source of pollution that is more dangerous, difficult to protect, and easily ignored by people after water sources, atmosphere and noise. Normal communication even directly threatens the health of human beings, especially infants and young children due to their weak physical resistance, their brains and bodies have not yet developed, and they are more seriously harmed by electromagnetic radiation. Therefore, it is necessary to design a device that can effectively protect human bodies from Products that emit electromagnetic waves.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a graphene-loaded cerium oxide and rubber composite material and a preparation method thereof, and the present invention also relates to the graphene-loaded cerium oxide and rubber composite material in the preparation of radiation-resistant windshields of various shapes applications in .

The preparation method of the graphene-loaded cerium oxide and rubber composite material of the present invention is as follows:

(1) Graphene oxide is dissolved in water to prepare a 0.1mg/ml--2mg/ml solution; cerium nitrate is completely dissolved in water; the mass ratio of cerium nitrate and graphene oxide is 40--60:1;

(2) The cerium nitrate solution is added dropwise to the graphene oxide solution and stirred at the same time for 60-210 minutes, left standing at room temperature for 10-15 hours, and the pH is adjusted to 8-14 with ammonia water;

(3) add it into the hydrothermal synthesis reactor, calcinate at 80℃-220℃ for 8-48 hours, and cool to room temperature;

(4) Washing with water and ethanol, drying at 60°C-100°C for 20-30 hours to obtain graphene-supported cerium oxide;

(5) Fill the graphene-supported cerium oxide into natural rubber-styrene-butadiene rubber by mechanical blending, add a vulcanization system and knead to obtain a mixed rubber, and vulcanize it on a flat vulcanizer to obtain graphene-supported cerium oxide and rubber. A composite material that can be used to prepare radiation-resistant windshields of various shapes.

In step (1), in order to fully dissolve and disperse the graphene oxide, the graphene oxide is first treated with ultrasonic waves for 3-10 minutes before being dissolved in water.

In step (2), in order to fully mix cerium nitrate and graphene oxide, the cerium nitrate solution is added dropwise to the graphene oxide solution and stirred for 30 minutes, then ultrasonically treated for 3-10 minutes, and then stirred for 30-180 minutes, Magnetic stirring is preferred; the pH value of the mixed solution is adjusted with 25% concentrated ammonia water.

In step (4), it is better to wash with water and ethanol 3 times.

In step (5), the amount of cerium oxide supported by graphene accounts for 5--40% of the total mass; the mass ratio of natural rubber to styrene-butadiene rubber is 0--70:100-30; Vulcanize at 170°C for 20min on a flat vulcanizer.

Graphene oxide can be commercially available or prepared by Hummers method.

Graphene has a two-dimensional structure with only one atomic layer thickness, so it has the advantages of high specific surface area, high conductivity, high electron mobility, etc. In addition, the surface of graphene can evenly support metal oxides, which greatly improves its Due to the reversible redox between Ce ⁴⁺ -Ce ³⁺ , ceria is widely used in catalysis, solar cells, solid oxide fuel cells and other fields. Therefore, the combination of graphene and cerium oxide can promote the transfer of cerium oxide electrons on the surface of graphene, and the cerium oxide nanoparticles can realize multiple reflections of electromagnetic waves on the surface of graphene. By loading cerium oxide on graphene, graphene stacking can be prevented. and cerium oxide agglomeration. At the same time, the graphene-supported cerium oxide has the effect of anti-oxidative aging of rubber.

Compared with the prior art, the present invention has the following advantages:

1. Composite graphene and cerium oxide, take advantage of the electron transfer characteristics of Ce ⁴⁺ and Ce ³⁺ in cerium oxide, and use graphene as a carrier

The speed of electron transfer is improved, and this compound is filled into natural rubber and styrene-butadiene rubber, which not only plays the role of electromagnetic shielding, but also plays an anti-aging effect on natural rubber and styrene-butadiene rubber.

2. The graphene-loaded cerium oxide and rubber composite material prepared by the present invention has the characteristics of thin, light, wide and strong wave absorbing material, as well as excellent mechanical properties, oxidation resistance and flexibility, and can be used to prepare various The shape is used to protect human health, especially the anti-radiation windshield of the stroller.

Description of drawings

Fig. 1 is the scanning electron microscope picture of graphene;

Fig. 2 is the scanning electron microscope picture of cerium oxide;

Fig. 3 is the scanning electron microscope picture of the graphene-loaded cerium oxide prepared by embodiment 1;

Fig. 4 is the scanning electron microscope image of the graphene-loaded cerium oxide filled natural rubber prepared in Example 1;

Fig. 5 is the scanning electron microscope image of the graphene-loaded cerium oxide filled styrene-butadiene rubber prepared in Example 2;

Fig. 6 is the scanning electron microscope image of the graphene-loaded cerium oxide filled natural rubber and styrene-butadiene rubber prepared in Example 3;

Fig. 7 is the absorbing effect figure of the graphene-loaded cerium oxide filled natural rubber prepared in Example 1;

Fig. 8 is the absorbing effect diagram of the graphene-loaded cerium oxide filled styrene-butadiene rubber prepared in Example 2;

9 is a graph of the wave-absorbing effect of the graphene-supported cerium oxide-filled natural rubber and styrene-butadiene rubber mixed rubber prepared in Example 3.

Specific implementation method

Example 1

Graphene oxide was prepared by Hummers method.

(1) Graphene oxide was ultrasonically treated for 10 minutes, dissolved in water to prepare a 0.1 mg/ml solution; cerium nitrate was completely dissolved in water; the mass ratio of cerium nitrate to graphene oxide was 60:1;

(2) After the cerium nitrate solution was added dropwise to the graphene oxide solution and stirred for 30 minutes, ultrasonically treated for 10 minutes, stirred for 30 minutes, left at room temperature for 15 hours, and adjusted to pH 8 with ammonia water;

(3) add it into the hydrothermal synthesis reactor, calcinate at 220°C for 8 hours, and cool to room temperature;

(4) washing with water and ethanol three times, and drying at 100 °C for 20 hours to obtain graphene-supported cerium oxide;

(5) Fill the graphene-supported cerium oxide into natural rubber-styrene-butadiene rubber by mechanical blending, add a vulcanization system and knead to obtain a mixed rubber, and vulcanize it on a flat vulcanizer to obtain graphene-supported cerium oxide and rubber. The composite material is used for preparing radiation-resistant windshields of various shapes; the consumption of cerium oxide supported by graphene accounts for 5% of the total mass; the mass ratio of natural rubber and styrene-butadiene rubber is 100: 0; the mixing The rubber was vulcanized on a flat vulcanizer at 170°C for 20 minutes.

As shown in Figure 1, a large number of graphenes are stacked together, and it is difficult to see the existence of a single layer of graphene.

As shown in Figure 2, the particle size of cerium oxide is about 20 nm. Since the particle size of cerium oxide is in the nanometer scale, the surface energy of cerium oxide is high, and most of the cerium oxide agglomerates together to form large agglomerates.

As shown in Figure 3, cerium oxide is evenly supported on the graphene sheet, and the particle size of cerium oxide on the graphene sheet is about 20 nm, which is not much different from pure cerium oxide. The stacking of graphene sheets can be prevented, and the agglomeration between cerium oxide nanoparticles can also be prevented.

As shown in Figure 4, the cerium oxide nanoparticles are distributed in the styrene-butadiene rubber, and the dispersion is relatively uniform, and the contact surface between the cerium oxide nanoparticles and the graphene and the styrene-butadiene rubber can lose part of the electromagnetic wave through the interface polarization.

As shown in Figure 7, the lowest reflection loss of the graphene-loaded ceria-filled natural rubber composite is -10.70 dB, and the absorption bandwidth of less than -10 dB (90% loss to electromagnetic waves) is 1.04 GHz.

Example 2

Graphene oxide was prepared by Hummers method.

(1) Graphene oxide was treated with ultrasonic waves 3, dissolved in water to prepare a 2mg/ml solution; cerium nitrate was completely dissolved in water; the mass ratio of cerium nitrate to graphene oxide was 40:1;

(2) After the cerium nitrate solution was added dropwise to the graphene oxide solution and stirred for 30 minutes at the same time, ultrasonically treated for 3 minutes, then magnetically stirred for 180 minutes, allowed to stand at room temperature for 10 hours, and the pH of the mixed solution was adjusted with 25% concentrated ammonia water value to 14;

(3) add it to the hydrothermal synthesis reactor, calcinate at 80°C for 48 hours, and cool to room temperature;

(4) washing 4 times with water and ethanol, and drying at 60°C for 30 hours to obtain graphene-supported cerium oxide;

(5) Fill the graphene-supported cerium oxide into natural rubber-styrene-butadiene rubber by mechanical blending, add a vulcanization system and knead to obtain a mixed rubber, and vulcanize it on a flat vulcanizer to obtain graphene-supported cerium oxide and rubber. The composite material is used to prepare radiation-resistant windshields of various shapes; the amount of cerium oxide supported by graphene accounts for 40% of the total mass; the mass ratio of natural rubber and styrene-butadiene rubber is 0:100; the mixing The rubber was vulcanized on a flat vulcanizer at 170°C for 20 minutes.

As shown in Figure 5, graphene forms interconnected conductive paths in the styrene-butadiene rubber matrix, which is conducive to the conversion of electromagnetic waves into heat energy through a point-to-point approach, thereby improving its wave-absorbing effect.

As shown in Figure 8, the lowest reflection loss of the graphene-loaded ceria-filled styrene-butadiene rubber composite is -17.90 dB, and the absorption bandwidth of less than -10 dB (90% loss to electromagnetic waves) is 2.16 GHz.

Example 3

Commercially available graphene oxide was used.

(1) Graphene oxide is ultrasonically treated for 5 minutes, dissolved in water to make a 1mg/ml solution; cerium nitrate is completely dissolved in water; the mass ratio of cerium nitrate to graphene oxide is 40--60:1;

(2) After the cerium nitrate solution was added dropwise to the graphene oxide solution and stirred for 30 minutes at the same time, ultrasonically treated for 5 minutes, then magnetically stirred for 100 minutes, and the pH value of the mixed solution was adjusted to 10 with 25% concentrated ammonia;

(3) add it to the hydrothermal synthesis reactor, calcinate at 150°C for 30 hours, and cool to room temperature;

(4) washing with water and ethanol, and drying at 80°C for 25 hours to obtain cerium oxide supported by graphene;

(5) Fill the graphene-supported cerium oxide into natural rubber-styrene-butadiene rubber by mechanical blending, add a vulcanization system and knead to obtain a mixed rubber, and vulcanize it on a flat vulcanizer to obtain graphene-supported cerium oxide and rubber. The composite material is used to prepare radiation-resistant windshields of various shapes; the amount of cerium oxide supported by graphene accounts for 30% of the total mass; the mass ratio of natural rubber and styrene-butadiene rubber is 50:50; the mixing The rubber was vulcanized on a flat vulcanizer at 170°C for 20 minutes.

As shown in Figure 6, the graphene-supported cerium oxide formed a double-percolating conductive network in the natural rubber and styrene-butadiene rubber mixed rubber system, that is, the conductive path of the graphene-supported cerium oxide in the natural rubber and the graphene-loaded conductive network. The conductive path between cerium oxide and natural rubber in styrene-butadiene rubber, this double percolation conductive path can effectively improve the wave-absorbing performance of the composite material.

As shown in Figure 9, the lowest reflection loss of the graphene-loaded ceria-filled natural rubber and styrene-butadiene rubber composite is -48.76 dB, and the absorption bandwidth of less than -10 dB (90% loss to electromagnetic waves) is 4.24 GHz.

Claims (6)

1. the preparation method of the cerium oxide of a graphene load and rubber composite material, it is characterized in that comprising the steps: (1) Graphene oxide is dissolved in water and configured into 0.1mg/ml--2mg/ml solution; cerium nitrate is completely soluble in water; the mass ratio of cerium nitrate and graphene oxide is 40--60:1; (2) The cerium nitrate solution was added dropwise to the graphene oxide solution and stirred for 60-210 minutes at the same time, and allowed to stand at room temperature for 10-15 hours, and the pH was adjusted to 8-14 with ammonia water; (3) add 80 ℃-220 ℃ of reactions in the hydrothermal synthesis reactor for 8-48 hours, and cool to room temperature; (4) washing with water and ethanol, and drying at 60°C-100°C for 20-30 hours to obtain graphene-supported cerium oxide; (5) filling the graphene-loaded cerium oxide into natural rubber-styrene-butadiene rubber by mechanical blending method, adding a vulcanization system and kneading to obtain a mixed rubber, and vulcanizing at 170° C. for 20min on a flat vulcanizer to obtain graphene-loaded oxidation In the cerium rubber composite material, the amount of cerium oxide supported by graphene accounts for 5-40% of the total mass; the mass ratio of natural rubber to styrene-butadiene rubber is 0--70:100-30. 2. method according to claim 1, is characterized in that in step (1), before graphene oxide is dissolved in water, first use ultrasonic treatment 3-10 minutes. 3. method according to claim 1 and 2, is characterized in that in step (2), cerium nitrate solution is added dropwise in graphene oxide solution and stirred simultaneously after 30 minutes, with ultrasonic treatment 3-10 minutes, magnetic force again Stir for 30-180 minutes, and adjust the pH of the mixture with 25% concentrated ammonia water. 4. The method according to claim 3, wherein in step (4), washing with water and ethanol 3 times. 5. The graphene-supported cerium oxide and rubber composite material prepared by the method described in one of claims 1-4. 6. the application of the graphene-loaded cerium oxide and rubber composite material in the preparation of radiation-resistant windshield of claim 5.

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