阅读说明：本技术 一种还原氧化石墨烯高灵敏传感电路与胶乳复合集成的方法 (Method for compositely integrating reduced graphene oxide high-sensitivity sensing circuit and latex ) 是由 张柏华 于 2020-06-19 设计创作，主要内容包括：本发明涉及材料集成及传感器领域,具体为一种还原氧化石墨烯高灵敏传感电路与胶乳复合集成的方法。首先,将纯铜箔在氧化石墨烯水溶液中,反复进行蘸提、干燥、还原。把贴附还原氧化石墨烯膜的铜箔一同进行激光刻蚀成需要的电路。然后,将铜箔投入天然胶乳中,反复进行蘸提干燥。将载有还原氧化石墨烯的铜箔电路放到刻蚀液中,静态溶解掉铜箔后,刻蚀液底部通入不溶于水的有机溶剂,形成有机相层托举起透明的还原氧化石墨烯电路膜。将刻蚀液从底部放掉,反复从底部充放置换清洗液进行置换清洗。最后,通入天然胶乳,反复进行蘸提、干燥,形成石墨烯电路与胶乳的复合集成,实现石墨烯高灵敏传感电路无损的集成在乳胶高分子膜内。(The invention relates to the field of material integration and sensors, in particular to a method for compositely integrating a reduced graphene oxide high-sensitivity sensing circuit and latex. First, a pure copper foil is repeatedly dipped in an aqueous graphene oxide solution, dried, and reduced. And carrying out laser etching on the copper foil attached with the reduced graphene oxide film to form a required circuit. Then, the copper foil was put into the natural latex, and dipping and drying were repeatedly performed. And (3) placing the copper foil circuit loaded with the reduced graphene oxide into an etching solution, statically dissolving the copper foil, and introducing a water-insoluble organic solvent into the bottom of the etching solution to form an organic phase layer to lift the transparent reduced graphene oxide circuit film. And (4) discharging the etching liquid from the bottom, and repeatedly discharging and replacing the cleaning liquid from the bottom for replacement and cleaning. And finally, introducing natural latex, repeatedly dipping and drying to form composite integration of the graphene circuit and the latex, and realizing lossless integration of the graphene high-sensitivity sensing circuit in a latex polymer film.)

1. A method for compositely integrating a reduced graphene oxide high-sensitivity sensing circuit and latex is characterized by comprising the following steps:

(1) dipping pure copper foil in a graphene oxide aqueous solution, lifting, drying, reducing, forming a reduced graphene oxide film on the surface of the copper foil, and carrying out laser etching on the copper foil attached with the reduced graphene oxide film to form a required circuit;

(2) putting the copper foil attached with the reduced graphene oxide film after laser etching into natural latex, dipping, lifting and drying;

(3) placing the copper foil circuit loaded with the reduced graphene oxide into an etching solution, statically dissolving the copper foil, and introducing a water-insoluble organic solvent from the bottom of a container containing the etching solution to form an organic phase layer with the thickness of 0.5-30 mm to lift up a transparent reduced graphene oxide circuit film;

(4) discharging the etching solution from the bottom of the container, charging and discharging the cleaning solution from the bottom of the container, and repeatedly performing replacement cleaning to form a membrane material;

(5) and introducing natural latex into the container, lifting the membrane material and drying to form the composite integration of the graphene circuit and the latex.

2. The method for compositely integrating the reduced graphene oxide high-sensitivity sensing circuit with the latex according to claim 1, wherein in the step (1), dipping, lifting → drying → reduction process is repeated for 2-30 times, and the thickness of the reduced graphene oxide film is 0.5-20 μm.

3. The method for compositely integrating the reduced graphene oxide high-sensitivity sensing circuit with the latex according to claim 1, wherein in the step (1), the mass concentration of the graphene oxide aqueous solution is 0.0001-0.001%.

4. The method for compositely integrating the reduced graphene oxide high-sensitivity sensing circuit and the latex according to claim 1, wherein in the step (1), a chemical reducing agent is used for reducing the graphene oxide, the chemical reducing agent is an aqueous solution of one or more than two of formaldehyde, hydroiodic acid and zinc acetate, and the mass concentration of the chemical reducing agent is 20-80%.

5. The method for compounding and integrating the reduced graphene oxide high-sensitivity sensing circuit and the latex according to claim 1 or 4, wherein in the step (1), the reduction temperature is 50-120 ℃, and the reduction time is 5-120 minutes.

6. The method for compositely integrating the reduced graphene oxide high-sensitivity sensing circuit with the latex according to claim 1, wherein in the step (2), dipping and lifting → drying processes are repeated for 2-10 times, and the thickness of the natural latex layer is 5-50 μm.

7. The method for compositely integrating the reduced graphene oxide high-sensitivity sensing circuit with the latex according to claim 1, wherein in the step (3), the copper foil etching solution comprises the following components in percentage by mass: 25-35% of ferric chloride, 0.5-2% of disodium bicarbonate, 1-2% of ammonium persulfate, 15-25% of ethanol and the balance of water.

8. The method for compositely integrating the reduced graphene oxide high-sensitivity sensing circuit with the latex according to claim 1, wherein in the step (3), the organic solvent is one or a mixture of more than two of n-C16-21 alkanes.

9. The method for compositely integrating the reduced graphene oxide high-sensitivity sensing circuit with the latex according to claim 1, wherein in the step (4), the components of the displacement cleaning solution are as follows by mass percent: ethanol 20-40%, ether 5-20%, acetone 15-40%, and water in balance, and the replacement and cleaning are repeated for 2-10 times.

10. The method for compositely integrating the reduced graphene oxide high-sensitivity sensing circuit with the latex according to claim 1, wherein in the step (5), dipping and lifting → drying process of the membrane material is repeated for 2-10 times, and the thickness of the natural latex layer is 5-50 μm.

Technical Field

The invention relates to the field of material integration and sensors, in particular to a method for compositely integrating a reduced graphene oxide high-sensitivity sensing circuit and latex.

Background

The products such as gloves, condoms, medical rubber tubes and the like in the latex products have the advantages of softness, skin affinity, biological safety and the like. The products are easy to contact with bacteria and viruses, and how to realize intelligent detection of the viruses or the bacteria on the products and realize biosensing self-checking functions of the products is a significant development direction.

Graphene oxide can be easily attached to a metal surface due to the abundant functional groups on the surface. After the graphene oxide is reduced, the graphene oxide has good conductivity. As a two-dimensional material, the reduced graphene oxide can realize high-sensitivity integration when being compounded with latex to manufacture a biosensor. However, how to completely transfer the reduced graphene oxide nano film to the latex film and package the reduced graphene oxide nano film by the latex film is an unexplored process, and the invention is an important breakthrough to the process.

Disclosure of Invention

The invention aims to provide a method for compounding and integrating a reduced graphene oxide high-sensitivity sensing circuit and latex, wherein the obtained compound latex does not contain metal components, is only the circuit integration of high-molecular polymer latex and pure carbon, and the reduced graphene oxide high-sensitivity sensing circuit and latex compound product has the characteristics of ultrathin thickness, high sensitivity, high biological safety and the like.

In order to achieve the purpose, the invention adopts the following technical scheme:

a method for compositely integrating a reduced graphene oxide high-sensitivity sensing circuit and latex comprises the following steps:

(1) dipping pure copper foil in a graphene oxide aqueous solution, lifting, drying, reducing, forming a reduced graphene oxide film on the surface of the copper foil, and carrying out laser etching on the copper foil attached with the reduced graphene oxide film to form a required circuit;

(2) putting the copper foil attached with the reduced graphene oxide film after laser etching into natural latex, dipping, lifting and drying;

(3) placing the copper foil circuit loaded with the reduced graphene oxide into an etching solution, statically dissolving the copper foil, and introducing a water-insoluble organic solvent from the bottom of a container containing the etching solution to form an organic phase layer with the thickness of 0.5-30 mm to lift up a transparent reduced graphene oxide circuit film;

(4) discharging the etching solution from the bottom of the container, charging and discharging the cleaning solution from the bottom of the container, and repeatedly performing replacement cleaning to form a membrane material;

(5) and introducing natural latex into the container, lifting the membrane material and drying to form the composite integration of the graphene circuit and the latex.

The method for compounding and integrating the reduced graphene oxide high-sensitivity sensing circuit and the latex comprises the step (1), dipping and lifting → drying → repeating the reduction process for 2-30 times, wherein the thickness of the reduced graphene oxide film is 0.5-20 mu m.

According to the method for compositely integrating the reduced graphene oxide high-sensitivity sensing circuit and the latex, in the step (1), the mass concentration of the used graphene oxide aqueous solution is 0.0001-0.001%.

In the method for compositely integrating the reduced graphene oxide high-sensitivity sensing circuit and the latex, in the step (1), a chemical reducing agent is used for reducing the graphene oxide, the chemical reducing agent is an aqueous solution of one or more than two of formaldehyde, hydroiodic acid and zinc acetate, and the mass concentration of the chemical reducing agent is 20-80%.

The method for compounding and integrating the reduced graphene oxide high-sensitivity sensing circuit and the latex comprises the step (1) that the reduction temperature is 50-120 ℃ and the reduction time is 5-120 minutes.

According to the method for compounding and integrating the reduced graphene oxide high-sensitivity sensing circuit and the latex, in the step (2), dipping and lifting → drying processes are repeated for 2-10 times, and the thickness of a natural latex layer is 5-50 microns.

In the method for compositely integrating the reduced graphene oxide high-sensitivity sensing circuit and the latex, in the step (3), the copper foil etching solution comprises the following components in percentage by mass: 25-35% of ferric chloride, 0.5-2% of disodium bicarbonate, 1-2% of ammonium persulfate, 15-25% of ethanol and the balance of water.

According to the method for compounding and integrating the reduced graphene oxide high-sensitivity sensing circuit and the latex, in the step (3), an organic solvent is one or a mixture of more than two of alkane with normal C16-21.

In the method for compositely integrating the reduced graphene oxide high-sensitivity sensing circuit and the latex, in the step (4), the replaced cleaning solution comprises the following components in percentage by mass: ethanol 20-40%, ether 5-20%, acetone 15-40%, and water in balance, and the replacement and cleaning are repeated for 2-10 times.

According to the method for compounding and integrating the reduced graphene oxide high-sensitivity sensing circuit and the latex, in the step (5), a membrane material is dipped and lifted → the drying process is repeated for 2-10 times, and the thickness of a natural latex layer is 5-50 microns.

The design idea of the invention is as follows:

the rich functional groups on the surface of the graphene oxide can be tightly attached to the copper foil. After reduction, the conductive and flexible alloy has good conductivity and flexibility. The reduced graphene oxide film can be well attached to the flexible latex film, and the reduced graphene oxide film is suitable for being processed into a circuit by laser etching. Meanwhile, the reduced graphene oxide has biological safety, and biochemical substances are stable on the surface of the membrane. The stable biological flexible sensing film device with high conductivity and high sensitivity can be prepared by compounding the reduced graphene oxide circuit and latex.

Compared with the prior art, the invention has the advantages and beneficial effects that:

1. the film material compositely integrated by the reduced graphene oxide high-sensitivity sensing circuit and the latex has small resistance and high sensitivity, and the overall resistance is 1-8 omega.

2. The thickness of the film compositely integrated by the reduced graphene oxide high-sensitivity sensing circuit and the latex can be very thin, the thinnest overall thickness can reach 10.5 mu m, and the film can be repeatedly folded without foreign body sensation.

3. The film compositely integrated by the reduced graphene oxide high-sensitivity sensing circuit and the latex can be repeatedly rolled and folded for at least more than 200 times without damage, the resistance value basically keeps stable, and the change is +/-3 omega.

Drawings

FIG. 1 is a schematic diagram of the overall appearance and partial longitudinal section of a latex condom with a reduced graphene oxide circuit integrated therein.

In the figure, 1, a condom; 2. a reduced graphene oxide circuit integrated in the interlayer; 3. inner and outer emulsion layers.

FIG. 2 is a schematic diagram of the overall appearance and partial longitudinal section of a latex glove with a reduced graphene oxide circuit integrated therein.

In the figure, 2. reduced graphene oxide circuits integrated in the interlayer; 3. an inner and outer latex layer; 4. latex gloves.

Detailed Description

In the specific implementation process, firstly, pure copper foil is dipped and extracted once in the graphene oxide aqueous solution and dried, then reduction is carried out, and the dipping and reduction operations are repeated for several times. And carrying out laser etching on the copper foil attached with the reduced graphene oxide film to form a required circuit. Then, the copper foil is put into the natural latex to dip and extract for one time, and the drying is repeated for several times, and the effects are as follows: and compounding latex on one surface of the graphene membrane to form a membrane surface supporting substrate. The copper foil circuit carrying the reduced graphene oxide is placed in an etching solution, after the copper foil is statically dissolved, a water-insoluble organic solvent is slowly introduced from the bottom of a container containing the etching solution, an organic phase layer with a certain thickness is formed to lift a transparent reduced graphene oxide circuit film, and the organic phase layer plays a role of: the liquid phase lifts the fragile graphene composite membrane surface, so that no folds or damages are generated. Slowly release the etching solution from the container bottom, organic phase layer remains, fills the displacement washing liquid from the container bottom again and fills and to replace and wash, and its effect is: the water-insoluble organic phase is effectively diluted and cleaned by successively using an organic mixed solvent which can be dissolved in the characteristics of the organic phase and the water phase, and the subsequent addition of the water-based latex is facilitated to form the compounding and lifting of the membrane material. Finally, the natural latex is filled into the container, and then the membrane material is lifted and dried. And repeating the steps for several times to form the composite integration of the graphene circuit and the latex. The method can realize the lossless integration of the graphene high-sensitivity sensing circuit in the latex polymer film.

The present invention will be described in further detail with reference to examples and test results.