CN112961412A - Method and device for preparing ultrahigh-sensitivity natural rubber nano composite sensing material - Google Patents
Method and device for preparing ultrahigh-sensitivity natural rubber nano composite sensing material Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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Abstract
The invention discloses a method and a device for preparing a natural rubber nano composite sensing material with ultrahigh sensitivity, wherein CTAB with the mass of 0.5-2 wt% of the solid content of natural latex is stirred and mixed with the natural latex to form a sticky substance, then the sticky substance is milled and mixed with multi-walled carbon nanotubes on an open mill, then the thick substance is thinned for 5 minutes and is taken out, the thick substance is vulcanized for 10 minutes at the temperature of 155 +/-5 ℃ and under the pressure of 10MPa, finally the ultra-high sensitivity natural rubber nano composite sensing material is obtained by demoulding, the peeling and dispersion mixing effect of the multi-walled carbon nanotubes in a natural rubber matrix is improved by adding the CTAB, the force-electric response sensitivity and stability of the composite material are ensured, the shoulder phenomenon is avoided, the open mill effect of the natural rubber is improved, an organic solvent is not needed in the preparation process, and the method is non-toxic and harmless, and the invention is beneficial to the formation of a network of the multi-walled, the comprehensive performance of the natural rubber nano composite sensing material is improved.
Description
Technical Field
The invention relates to the technical field of preparation of high-molecular sensing materials, in particular to a method and a device for preparing a natural rubber nano composite sensing material with ultrahigh sensitivity.
Background
The natural rubber has the advantages of high elasticity, large deformation, damage resistance, high damping and the like, and is widely applied to the field of structural seismic isolation and reduction. In order to expand the performance of the seismic isolation and reduction material and enable the seismic isolation and reduction material to have the functions of force-electricity sensing and structural deformation monitoring, a modifier is added to modify the seismic isolation and reduction material. The carbon nano tube has excellent mechanical and electrical properties, and is the first choice of the natural rubber modifier. However, the strong intermolecular force of the carbon nanotube affects the dispersion of the carbon nanotube in the rubber matrix, and the modification effect of the carbon nanotube is limited. In order to obtain the natural rubber nano composite sensing material with excellent performance, the preparation process of the natural rubber nano composite sensing material is very important.
The natural rubber nano composite sensing material is used as a functional material, and the industrialization of the preparation process needs to be considered while the good performance is ensured. In the common preparation methods of a solution method, an aqueous emulsion method and an open mill method, the solution method can better disperse the carbon nanotubes, but consumes a large amount of organic solvent, pollutes the environment and harms the health of operators; the water emulsion method is beneficial to the dispersion of the carbon nano tubes, but neglects that when the carbon nano tube solution is mixed with the latex, particle agglomeration is generated, and the phenomenon of uneven dispersion occurs during emulsion breaking, which has great influence on the performance of the composite material; although the open mill method can realize the industrial production of the natural rubber nano composite sensing material, the carbon nano tube has light weight and strong intermolecular action, so that the filler flies and is agglomerated in the mixing process. The realization of the formation of a good conductive network of the carbon nano tube in the matrix and the industrial production of the natural rubber nano composite sensing material are important and research targets in the field.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method and an apparatus for preparing a natural rubber nanocomposite sensing material with ultra-high sensitivity, which can realize the functionality of the natural rubber nanocomposite sensing material and improve the comprehensive performance of the natural rubber nanocomposite sensing material.
In order to realize the aim, the invention provides a preparation method of an ultrahigh-sensitivity natural rubber nano composite sensing material, which comprises the following steps:
step 1: CTAB with the mass of 0.5-2 wt% of the solid content of the natural latex is stirred and mixed with the natural latex to form a viscous substance;
step 2: mixing the sticky substance obtained in the step 1 and the multi-walled carbon nano tube in an open mill;
and step 3: step 2, adding a vulcanizing agent after the mixing is finished, and keeping the temperature at 35 +/-5 ℃ for continuous open milling until all the contained liquid is volatilized;
and 4, step 4: thinly passing the mixture obtained in the step 3 for 5 minutes and then taking out the slices;
and 5: vulcanizing the unvulcanized mixture obtained in the step 4 at 155 +/-5 ℃ and 10MPa for 10 minutes;
step 6: and demolding to obtain the ultrahigh-sensitivity natural rubber nano composite sensing material.
Before step 2, the preparation method of the ultra-high sensitivity natural rubber nanocomposite sensing material further comprises the following steps: the desired multi-walled carbon nanotubes were ultrasonically wetted in an appropriate amount of deionized water for 10 minutes.
Wherein the vulcanizing agent is one or more of a sulfur vulcanizing agent and a peroxide vulcanizing agent.
Wherein, in the step 2, the open mixing time is 3-5 minutes.
Before step 6, the preparation method of the ultra-high sensitivity natural rubber nanocomposite sensing material further comprises the following steps: and (3) pressurizing and cooling the mixture obtained in the step (5).
Wherein the time of the pressurized cooling is 2 minutes.
The invention also provides a device for preparing the ultrahigh-sensitivity natural rubber nano composite sensing material, which comprises a box body and the open mill, wherein the box body is provided with the ionic water tank, and the open mill is fixedly arranged on the box body.
The invention has the beneficial effects that: in the process of blending the multi-walled carbon nanotube and natural latex, the peeling and dispersive mixing effect of the multi-walled carbon nanotube in a natural rubber matrix is improved by adding CTAB (cetyl trimethyl ammonium bromide), the force-electric response sensitivity and stability of the composite material are ensured, the occurrence of a shoulder phenomenon is avoided, the open milling effect of natural rubber is improved, the ultrahigh-sensitivity natural rubber nano composite sensing material prepared by the embodiment of the invention has a low percolation threshold (about 1 wt%), an organic solvent is not needed in the preparation process, and the preparation method is non-toxic and harmless, so that the preparation method is beneficial to the formation of a conductive network of the multi-walled carbon nanotube in the natural rubber matrix, and the comprehensive performance of the natural rubber nano composite sensing material is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of the preparation method of the ultra-high sensitivity natural rubber nanocomposite sensing material of the invention.
FIG. 2 is a graph comparing sensitivity factors in examples and comparative examples in the method for preparing the ultra-high sensitivity natural rubber nanocomposite sensing material of the present invention.
FIG. 3 is a graph comparing the results of elongation at break (%) experiments in examples and comparative examples at different multi-walled carbon nanotube contents of the present invention.
FIG. 4 is a graph of tensile-release cycling resistance change (R/R0)/loading time for examples of the present invention and comparative examples.
FIG. 5 is a structural sectional view of an apparatus for preparing an ultra-high sensitivity natural rubber nanocomposite sensing material according to the present invention.
1-box body, 11-ion water tank, 12-mixing cavity, 2-open mill, 3-stirring structure, 31-motor, 32-stirring rod and 33-stirring blade.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "length", "width", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships illustrated in the drawings, and are used merely for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, are not to be construed as limiting the present invention. Further, in the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
Referring to fig. 1 to 4, the present invention provides a technical solution: a preparation method of an ultrahigh-sensitivity natural rubber nano composite sensing material comprises the following steps:
s1: CTAB with the mass of 0.5-2 wt% of the solid content of the natural latex is stirred and mixed with the natural latex to form a viscous substance;
s2: mixing the sticky substance obtained in the step S1 with the multi-walled carbon nano-tube in an open mill;
s3: s2 adding a vulcanizing agent after mixing is finished, and keeping the temperature at 35 +/-5 ℃ for continuous open milling until all the contained liquid is volatilized;
s4: thinly passing the mixture obtained in the step S3 for 5 minutes, and then taking out a sheet;
s5: vulcanizing the unvulcanized mixture obtained in S4 at 155 ℃ + -5 ℃ and 10MPa for 10 minutes;
s6: and demolding to obtain the ultrahigh-sensitivity natural rubber nano composite sensing material.
Further, before S2, the method for preparing the ultra-high sensitivity natural rubber nanocomposite sensing material further includes: the desired multi-walled carbon nanotubes were ultrasonically wetted in an appropriate amount of deionized water for 10 minutes.
Further, the vulcanizing agent is one or more of a sulfur vulcanizing agent and a peroxide vulcanizing agent.
Further, in S2, the mixing time is 3-5 minutes.
Further, before S6, the method for preparing the ultra-high sensitivity natural rubber nanocomposite sensing material further includes: the mixture obtained in S5 was pressure-cooled.
Further, the time for the pressurized cooling is 2 minutes.
Referring to fig. 5, the invention further provides a device for preparing the ultra-high sensitivity natural rubber nanocomposite sensing material, which comprises a box body 1 and an open mill 2, wherein the box body 1 is provided with an ion water tank 11, the open mill 2 is fixedly installed on the box body 1, the ion water tank 11 is used for wetting the multi-walled carbon nanotubes, and the open mill 2 is used for milling and discharging sheets from the viscous substance and the multi-walled carbon nanotubes.
Further, the device for preparing the ultra-high sensitivity natural rubber nanocomposite sensing material further comprises a stirring structure 3, the box body 1 is provided with a mixing cavity 12, the mixing cavity 12 and the ion water tank 11 are arranged at intervals, the stirring structure 3 comprises a motor 31, a stirring rod 32 and a plurality of stirring blades 33, the motor 31 is fixedly arranged at the top of the mixing cavity 12, the stirring rod 32 is fixedly connected with the output end of the motor 31, the stirring rod 32 is positioned in the mixing cavity 12, the stirring blades 33 are respectively fixedly connected with the stirring rod 32, the stirring blades 33 are arranged on the stirring rod 32 at intervals, the mixing cavity 12 is used for mixing the CTAB and the natural latex, the stirring structure 3 is used for stirring when the CTAB and the natural latex are mixed so as to improve the mixing rate, the output end of the motor 31 is fixedly connected with the stirring rod 32, the motor 31 drives the stirring rod 32 to rotate, and the stirring blades 33 are arranged on the stirring rod 32 at intervals to improve the stirring effect.
Example 1:
stirring and mixing CTAB (cetyl trimethyl ammonium bromide) with the mass being 0.5 wt% of the solid content of natural latex and the natural latex to form a viscous substance, adding a dispersing emulsifier into the natural latex to promote the dispersion of multi-walled carbon nanotubes in a natural rubber matrix and the masticability of the natural rubber, ultrasonically wetting the required multi-walled carbon nanotubes in a proper amount of deionized water for 10 minutes to achieve the effect of wetting the multi-walled carbon nanotubes, mixing the wetted multi-walled carbon nanotubes and the viscous substance in an open mill for 3-5 minutes, adding a diiso-styrene peroxide vulcanizing agent into the open mill for mixing, controlling the temperature at 35 +/-5 ℃, continuing the open mill until all the contained liquid volatilizes, then continuously thinly passing the obtained mixture for 5 minutes, then taking out a sheet, vulcanizing the obtained unvulcanized mixture for 10 minutes at 155 +/-5 ℃ under 10MPa, then pressurizing and cooling at room temperature for 2 minutes, and taking out and demoulding to obtain the natural rubber nano composite sensing material with ultrahigh sensitivity.
Example 2:
stirring and mixing CTAB (cetyl trimethyl ammonium bromide) with the mass being 1 wt% of the solid content of natural latex and the natural latex to form a viscous substance, adding a dispersing emulsifier into the natural latex to promote the dispersion of multi-walled carbon nanotubes in a natural rubber matrix and the mastication of the natural rubber, ultrasonically wetting the required multi-walled carbon nanotubes in a proper amount of deionized water for 10 minutes to achieve the effect of wetting the multi-walled carbon nanotubes, mixing the wetted multi-walled carbon nanotubes and the viscous substance on an open mill for 3-5 minutes, adding a diisophenylpropyl peroxide vulcanizing agent into the open mill for mixing, controlling the temperature to be 35 +/-5 ℃, continuing the open mill until all the contained liquid is volatilized, then continuously passing the obtained mixture for 5 minutes, then discharging sheets, vulcanizing the obtained unvulcanized mixture for 10 minutes at 155 +/-5 ℃ under 10MPa, then pressurizing and cooling for 2 minutes at room temperature, and taking out and demoulding to obtain the natural rubber nano composite sensing material with ultrahigh sensitivity.
Example 3:
stirring and mixing CTAB (cetyl trimethyl ammonium bromide) with the mass being 2 wt% of the solid content of natural latex and the natural latex to form a viscous substance, adding a dispersing emulsifier into the natural latex to promote the dispersion of multi-walled carbon nanotubes in a natural rubber matrix and the mastication of the natural rubber, ultrasonically wetting the required multi-walled carbon nanotubes in a proper amount of deionized water for 10 minutes to achieve the effect of wetting the multi-walled carbon nanotubes, mixing the wetted multi-walled carbon nanotubes and the viscous substance on an open mill for 3-5 minutes, adding a diisophenylpropyl peroxide vulcanizing agent into the open mill for mixing, controlling the temperature to be 35 +/-5 ℃, continuing the open mill until all liquid contained in the mixture is volatilized, then continuously passing the obtained mixture for 5 minutes, discharging sheets, vulcanizing the obtained unvulcanized mixture for 10 minutes at 155 +/-5 ℃ under 10MPa, then pressurizing and cooling for 2 minutes at room temperature, and taking out and demoulding to obtain the natural rubber nano composite sensing material with ultrahigh sensitivity.
Example 4:
mixing CTAB (cetyl trimethyl ammonium bromide) with the mass being 2 wt% of the solid content of natural latex and the natural latex by stirring to form a viscous substance, adding a dispersing emulsifier into the natural latex to promote the dispersion of multi-walled carbon nanotubes in a natural rubber matrix and the mastication of natural rubber, ultrasonically wetting the required multi-walled carbon nanotubes in a proper amount of deionized water for 10 minutes to achieve the effect of wetting the multi-walled carbon nanotubes, mixing the wetted multi-walled carbon nanotubes and the viscous substance by an open mill for 3-5 minutes, simultaneously adding 3 parts of sulfur, 2 parts of stearic acid, 5 parts of zinc oxide, 4010NA 2 parts of anti-aging agent and 3 parts of accelerating agent NS into the open mill for mixing, controlling the temperature at 35 +/-5 ℃, continuing the open milling until all the contained liquid is volatilized, then continuing to thin the obtained mixture for 5 minutes and then taking out a sheet, then enabling the obtained unvulcanized mixture to be subjected to the temperature of 155 +/-5 ℃, and vulcanizing at 10MPa for 10 minutes, then pressurizing and cooling at room temperature for 2 minutes, taking out and demolding to obtain the ultrahigh-sensitivity natural rubber nano composite sensing material.
Comparative example 1:
the water emulsion method is adopted to prepare the natural rubber nano composite sensing material, and the preparation process comprises the following steps:
s201, using deionized water as a solvent, and ultrasonically dispersing the multi-walled carbon nano-tube for 30 minutes, wherein the water temperature is controlled at 25 ℃;
s202, adding natural latex into the mixture obtained in the step S201, and continuing performing ultrasonic treatment for 60 minutes at the water temperature of 25 ℃ to obtain a multi-walled carbon nanotube/natural latex mixture which is uniformly mixed;
s203, dripping 2-3 drops of hydrochloric acid into the mixture obtained in the S202, and flocculating to obtain a flocculated mixture;
s204, taking out the mixture obtained in the step S203, washing the mixture for 3 to 5 times by using deionized water, and soaking the mixture for 12 hours to remove redundant hydrochloric acid;
s205, placing the mixture obtained in the step S204 in a forced air drying oven to remove contained moisture and other liquid, and adding a diisophenylpropyl peroxide vulcanizing agent by adopting an open mill process;
and S206, vulcanizing at the temperature of 155 +/-5 ℃ and under the pressure of 10MPa for 10 minutes, and pressurizing and cooling at room temperature to obtain the natural rubber nano composite sensing material.
Comparative example 2:
the preparation process of the multiwalled carbon nanotube/natural rubber composite sensing material by adopting a solution method comprises the following steps:
s301, tetrahydrofuran is used as a solvent, and the multi-walled carbon nano-tube is dispersed for 30 minutes in an ultrasonic mode, wherein the ultrasonic condition is the same as that of the comparative example 1.
And S302, dispersing the natural latex by adopting tetrahydrofuran for 30 minutes under the conditions of ultrasound and stirring to obtain uniform natural latex dispersion liquid.
And S303, pouring the natural latex dispersion liquid obtained in the step S302 into the multi-walled carbon nanotube dispersion liquid obtained in the step S301, stirring and ultrasonically treating for 60 minutes, then adding a vulcanizing agent, and continuously stirring and ultrasonically treating for 10 minutes.
And S304, putting the mixture obtained in the S303 into a forced air drying oven to remove tetrahydrofuran and other liquid, drying, and vulcanizing under the same vulcanizing condition as the comparative example 1.
Comparison of the sensitivity of the invention and the sensitivity of the reference:
references corresponding to the reference:
compared with the flocculation method and the solution method which are commonly used in the technical field, the preparation method and the device of the ultrahigh-sensitivity natural rubber nano composite sensing material have the advantages that through the comparison of the examples 1, 2, 3 and 4 with the comparative examples 1 and 2, the examples have ultrahigh sensitivity, excellent stable elongation at break, excellent force-electric response and good monotonicity (no shoulder phenomenon) of resistance change, the sensitivity of the comparative examples is far lower than that of the examples, the elongation at break is obviously reduced along with the increase of the content of the multi-wall carbon nano tube, the shoulder phenomenon is obvious in the attached figure 4, the monotonicity is poor, particularly the comparative example 2, chemical solvents are used in the comparative examples, and the use of the solvents can seriously affect the environmental problems and the body health of operators in industrial production, therefore, the embodiment of the invention not only shows the potential of being used as a large-deformation high-sensitivity sensor, but also accords with the sustainable green development concept, and accords with the application of the sensor in various fields of structural health monitoring, human motion monitoring, aerospace and the like, and the ultrahigh-sensitivity natural rubber nano composite sensing material prepared by the embodiment of the invention has a low percolation threshold (about 1 wt%), does not need an organic solvent in the preparation process, is non-toxic and harmless, and is beneficial to the formation of a conductive network of a multi-walled carbon nanotube in a natural rubber matrix, and the comprehensive performance of the natural rubber nano composite sensing material is improved.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A preparation method of an ultrahigh-sensitivity natural rubber nano composite sensing material is characterized by comprising the following steps:
step 1: CTAB with the mass of 0.5-2 wt% of the solid content of the natural latex is stirred and mixed with the natural latex to form a viscous substance;
step 2: mixing the sticky substance obtained in the step 1 and the multi-walled carbon nano tube in an open mill;
and step 3: step 2, adding a vulcanizing agent after the mixing is finished, and keeping the temperature at 35 +/-5 ℃ for continuous open milling until all the contained liquid is volatilized;
and 4, step 4: thinly passing the mixture obtained in the step 3 for 5 minutes and then taking out the slices;
and 5: vulcanizing the unvulcanized mixture obtained in the step 4 at 155 +/-5 ℃ and 10MPa for 10 minutes;
step 6: and demolding to obtain the ultrahigh-sensitivity natural rubber nano composite sensing material.
2. The method for preparing the ultra-high sensitivity natural rubber nanocomposite sensing material of claim 1,
before step 2, the preparation method of the ultra-high sensitivity natural rubber nanocomposite sensing material further comprises the following steps: the desired multi-walled carbon nanotubes were ultrasonically wetted in an appropriate amount of deionized water for 10 minutes.
3. The method for preparing the ultra-high sensitivity natural rubber nanocomposite sensing material of claim 2,
the vulcanizing agent is one or more of a sulfur vulcanizing agent and a peroxide vulcanizing agent.
4. The method for preparing the ultra-high sensitivity natural rubber nanocomposite sensing material of claim 3,
in step 2, the mixing time of the open mill is 3-5 minutes.
5. The method for preparing the ultra-high sensitivity natural rubber nanocomposite sensing material of claim 4,
before step 6, the preparation method of the ultra-high sensitivity natural rubber nanocomposite sensing material further comprises the following steps: and (3) pressurizing and cooling the mixture obtained in the step (5).
6. The method for preparing the ultra-high sensitivity natural rubber nanocomposite sensing material of claim 5,
the pressure cooling time was 2 minutes.
7. An apparatus for preparing the ultra-high sensitivity natural rubber nanocomposite sensing material according to claim 6,
the device comprises a box body and an open mill, wherein the box body is provided with an ionic water tank, and the open mill is fixedly arranged on the box body.
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