CN111733589B - Carbon fiber monofilament micro-plasma surface micro-area processing device and using method - Google Patents

Abstract

The invention discloses a carbon fiber monofilament micro-plasma surface micro-area processing device and a using method thereof, and the device comprises a first micro-plasma generating assembly, a second micro-plasma generating assembly and a fixing assembly, wherein the first micro-plasma generating assembly generates a first micro-plasma jet and emits the first micro-plasma jet to the surface of a carbon fiber monofilament fixed on the fixing assembly, and the second micro-plasma generating assembly generates a second micro-plasma jet and emits the second micro-plasma jet to the surface of the carbon fiber monofilament fixed on the fixing assembly; the method can utilize the generated microplasma jet to carry out accurate and controllable micro-area processing on the surface of the carbon fiber monofilament under the atmospheric environment and the maskless condition, and has the advantages of simple process, convenient operation and low cost; meanwhile, multiple processing processes can be synchronously carried out, and nano particles are deposited on the surface of the carbon fiber monofilament while being etched, so that the processing means of the surface of the carbon fiber monofilament is enriched, and the processing efficiency is greatly improved.

Description

A kind of carbon fiber monofilament micro-plasma surface micro-region processing device and using method

technical field

The invention relates to the technical field of carbon fiber surface processing, in particular to a carbon fiber monofilament micro-plasma surface micro-region processing device and a use method.

Background technique

Carbon fiber refers to a microcrystalline graphite material with a carbon content of more than 95%. It has a series of excellent properties such as high modulus, high strength, low density, and corrosion resistance. It is widely used in aerospace, electronic products, medical equipment and other fields. . Carbon fiber monofilament is a carbon fiber bundle with a diameter of 5-7 microns. Because of its small cross-sectional size, good biocompatibility, and good electrochemical properties, it is often used to make microelectrodes. At present, carbon fiber microelectrodes have a wide range of applications in electrochemical analysis, cell biology, immunology, and in vivo detection.

However, due to the small specific surface area of the original carbon fiber monofilament, when it is used as a microelectrode, some treatments on the surface of the carbon fiber monofilament are required to improve its electrochemical properties, such as surface roughening, or surface modification such as carbon nanotubes. , conductive polymers or metal nanoparticles to improve the sensitivity and selectivity of microelectrodes. In addition, in order to improve the spatial detection resolution of carbon fiber microelectrodes, the carbon fiber monofilament needs to be refined and processed to further reduce the diameter of the carbon fiber monofilament to 1-2 micrometers or even nanometers. At present, flame etching and electrochemical machining methods are mainly used for the processing of carbon fiber monofilaments used as microelectrodes. The flame etching method is to place the carbon fiber monofilament on a butane flame, and realize the etching of the carbon fiber monofilament through the flame. The diameter of the etched carbon fiber filament can be reduced from about 7 microns to about 1 micron or less. The method is simple and efficient, and can reduce the diameter of carbon fiber monofilaments to the nanometer scale within seconds. However, this method is difficult to precisely control the etching rate and etching position of the carbon fiber monofilament, and the surface morphology of the carbon fiber monofilament after etching is not uniform. Another commonly used surface treatment method of carbon fiber monofilament is the surface processing method based on electrochemical treatment, that is, the carbon fiber monofilament is directly placed in a pre-prepared solution, and the surface etching of carbon fiber and the deposition of functional coating are realized by electrochemical method. . Compared with the flame etching method, this method can control the surface processing rate of carbon fiber monofilament, but this method is mainly wet processing, so some chemical reagents that are harmful to the environment are used, and it is difficult to realize the selection of carbon fiber monofilament surface. Sexual microprocessing.

In view of the above-mentioned defects, the creator of the present invention finally obtained the present invention after a long period of research and practice.

SUMMARY OF THE INVENTION

In order to solve the above-mentioned technical defects, the technical solution adopted in the present invention is to provide a carbon fiber monofilament micro-plasma surface micro-region processing device, which includes a first micro-plasma generating component, a second micro-plasma generating component and a fixing component, so The first micro-plasma generating component generates a first micro-plasma jet and shoots towards the surface of the carbon fiber monofilament fixed on the fixing component, and the second micro-plasma generating component generates a second micro-plasma jet and shoots towards the surface of the carbon fiber monofilament fixed on the fixing component the surface of the carbon fiber monofilament fixed on the fixing component.

Preferably, the first micro-plasma generating assembly includes a first working gas source, a first plasma generating source, a first glass microneedle, a first protective gas source, and a first gas flow protective cover. The two ends of the plasma generating source are respectively connected to the first working gas source and the first glass microneedle, and the side of the first glass microneedle away from the first plasma generating source is arranged on the first gas flow protection Inside the hood, the first protective gas source is communicated with the first airflow protective hood, and protective gas is introduced into the first protective gas source.

Preferably, the second micro-plasma generating assembly includes a second airflow protection cover, a second shielding gas source, a second glass microneedle, a second plasma generating source, a second working gas source, an auxiliary gas source, and a precursor. The two ends of the second plasma generation source are respectively connected to the second glass microneedle and the second working gas source, and the auxiliary gas source passes through the precursor atomizer and the first gas atomizer. The two plasma generating sources are connected, and the precursor mist is passed into the second plasma generating source; the side of the second glass microneedles away from the second plasma generating source is arranged on the second gas flow protection Inside the hood, the second protective gas source is communicated with the second airflow protective hood, and the protective gas is introduced into the second airflow protective hood.

Preferably, the fixing component includes a carbon fiber monofilament holder and a bracket, the carbon fiber monofilament holder is fixed by the bracket, the carbon fiber monofilament holder clamps the carbon fiber monofilament, and the The carbon fiber monofilament holder drives the carbon fiber monofilament to rotate along its own axis, and the bracket drives the carbon fiber monofilament to move axially.

Preferably, a sealing plate and an equalizing plate composed of a plurality of circular holes are arranged in the first air flow protection cover and the second air flow protection cover, and the sealing plate and the corresponding first glass microneedle Or the second glass micro-needle is sealed and connected, the inlet of the first protective gas source or the second protective gas source is correspondingly arranged between the equalizing plate and the sealing plate, and the inlet is connected by The protective gas provided by the first protective gas source or the second protective gas source.

Preferably, the first working gas source provides helium/oxygen mixed gas, the second working gas source provides pure helium, and the auxiliary gas source provides pure helium.

Preferably, the protective gas provided by the first protective gas source and the second protective gas source is pure nitrogen.

Preferably, the precursor atomizer is filled with chloroauric acid solution with a concentration of 1.0 mol/L.

Preferably, the inner diameter of the tip exit of the first glass microneedle and the second glass microneedle is 1 micron, the first airflow protection cover and the axis of the first glass microneedle are in a straight line, and the The outlet of the first glass microneedle tip is 5 mm beyond the outlet of the first airflow protection cover; the second airflow protection cover and the axis of the second glass microneedle are in a straight line, and the tip of the second glass microneedle exits 5 mm beyond the outlet of the second airflow shield.

Preferably, a method of using the carbon fiber monofilament micro-plasma surface micro-region processing device, comprising the steps of:

S1, configure chloroauric acid solution to be placed in the precursor atomizer;

S2, turn on the first working gas source, the second working gas source, the auxiliary gas source, the first shielding gas source and the second shielding gas source, and control the corresponding flow;

S3, in the atmospheric environment obtained in the step S2, turn on the high-voltage power supply in the first plasma generation source or/and the second plasma generation source, generate atmospheric pressure plasma, and pass through the second plasma generation source respectively. A glass microneedle generates the first microplasma jet of helium/oxygen; the second microplasma jet of helium/auric acid is generated through the second glass microneedle;

S4, the carbon fiber monofilament and the carbon fiber monofilament holder are continuously rotated, and at the same time, the carbon fiber monofilament and the carbon fiber monofilament holder are made to follow the support along the axis direction of the carbon fiber monofilament Through the micro-plasma jet region obtained in the step S3, the micro-region processing on the surface of the carbon fiber monofilament is completed.

Compared with the prior art, the beneficial effects of the present invention are: the present invention can perform precise and controllable micro-region processing on the surface of carbon fiber monofilament by using the generated micro-plasma jet under the condition of atmospheric environment and no mask, and the process Simple, easy to operate, low cost; at the same time, it can realize multiple processing processes simultaneously, such as simultaneously etching the surface of carbon fiber monofilament and depositing nanoparticles, thus enriching the processing methods on the surface of carbon fiber monofilament, and also greatly improving the processing. efficiency.

Description of drawings

1 is a structural view of the carbon fiber monofilament micro-plasma surface micro-region processing device;

2 is a view of the connection structure of the first glass microneedle and the first airflow protection cover;

3 is a structural view of the first glass microneedle;

4 is a structural cross-sectional view of the first airflow protection cover;

5 is an exploded view of the structure of the carbon fiber monofilament holder;

6 is a structural view of the support;

7 is a schematic diagram of the first processing effect of the carbon fiber monofilament micro-plasma surface micro-region processing device;

8 is a schematic diagram of the second processing effect of the carbon fiber monofilament micro-plasma surface micro-region processing device;

9 is a schematic diagram of the third processing effect of the carbon fiber monofilament micro-plasma surface micro-region processing device;

FIG. 10 is a schematic diagram of the fourth processing effect of the carbon fiber monofilament micro-plasma surface micro-region processing device.

The numbers in the figure represent:

1- the first working gas source; 2- the first plasma generation source; 3- the first glass micro-needle; 4- the first protective gas source; 5- the first airflow protection cover; 6- the first micro-plasma jet; 7-Second micro-plasma jet; 8-Second airflow protection cover; 9-Second shielding gas source; 10-Second glass microneedle; 11-Second plasma generating source; 12-Second working gas source; 13-Auxiliary air source; 14-Precursor atomizer; 15-Carbon fiber monofilament holder; 16-Carbon fiber monofilament; 17-Support.

Detailed ways

The above and other technical features and advantages of the present invention will be described in more detail below with reference to the accompanying drawings.

Example 1

As shown in FIG. 1, FIG. 1 is a structural view of the carbon fiber monofilament micro-plasma surface micro-region processing device; the carbon fiber mono-filament micro-plasma surface micro-region processing device according to the present invention includes a first micro-plasma generating component, The second micro-plasma generating component and the fixing component, the first micro-plasma generating component generates the first micro-plasma jet 6 and shoots the surface of the carbon fiber monofilament 16 fixed on the fixing component, the second micro-plasma jet 6 is The plasma generating component generates a second micro-plasma jet 7 and shoots towards the surface of the carbon fiber monofilament 16 fixed on the fixing component.

The first micro-plasma generating assembly includes a first working gas source 1, a first plasma generating source 2, a first glass microneedle 3, a first protective gas source 4, and a first airflow protective cover 5. The first The two ends of the plasma generation source 2 are respectively connected to the first working gas source 1 and the first glass microneedle 3 , and the side of the first glass microneedle 3 away from the first plasma generation source 2 is arranged on the side of the first working gas source 1 and the first glass microneedle 3 . Inside the first airflow protection cover 5 , the first protection gas source 4 communicates with the first airflow protection cover 5 , and a protection gas is introduced into the first protection gas source 4 .

The second micro-plasma generating assembly includes a second airflow protective cover 8 , a second protective gas source 9 , a second glass microneedle 10 , a second plasma generating source 11 , a second working gas source 12 , and an auxiliary gas source 13 , a precursor atomizer 14, the two ends of the second plasma generation source 11 are respectively connected to the second glass microneedle 10 and the second working gas source 12, and the auxiliary gas source 13 passes through the precursor The atomizer 14 is in communication with the second plasma generation source 11, and the precursor mist is introduced into the second plasma generation source 11; the second glass microneedles 10 are generated away from the second plasma One side of the source 11 is arranged in the second airflow protection cover 8 , and the second protection gas source 9 communicates with the second airflow protection cover 8 and passes into the second airflow protection cover 8 for protection gas.

The fixing assembly includes a carbon fiber monofilament holder 15 and a bracket 17, the carbon fiber monofilament holder 15 is fixed by the bracket 17, and the carbon fiber monofilament holder 15 clamps the carbon fiber monofilament 16, The carbon fiber monofilament holder 15 can drive the carbon fiber monofilament 16 to rotate along its own axis, and the bracket 17 can drive the carbon fiber monofilament 16 to move axially.

Specifically, the first plasma generating source 2 provides working gas from the first working gas source 1 and generates atmospheric pressure plasma, and the generated plasma generates the first micro-needle 3 through the first glass micro-needle 3 The plasma jet 6 is directed to the surface of the carbon fiber monofilament 16 .

As shown in Fig. 2, Fig. 3, Fig. 4, Fig. 2 is a view of the connection structure of the first glass microneedle and the first airflow protection cover; Fig. 3 is a view of the structure of the first glass microneedle; Fig. 4 is a structural cross-sectional view of the first airflow protection cover; the first airflow protection cover 5 is provided with a flow equalizing plate composed of a plurality of circular holes, and is arranged on the side close to the first plasma generating source 2 A sealing plate, the sealing plate and the first glass micro-needles 3 are hermetically connected, the inlet of the first protective gas source 4 is arranged between the equalizing plate and the sealing plate, and the inlet is connected by The protective gas provided by the first protective gas source 4 realizes the uniform flow of the protective gas to the outlet of the first airflow protective cover 5 through the circular holes on the equalizing plate, thereby protecting the first micro-plasma The volume jet 6 is protected from air and the beam spot diameter of the first microplasma jet 6 is controlled within a certain range.

The precursor atomizer 14 is fed with the auxiliary gas provided by the auxiliary gas source 13 , and the atomized precursor is brought into the second plasma generating source 11 by the auxiliary gas.

The second plasma generating source 11 provides working gas from the second working gas source 12 and generates atmospheric pressure plasma, and the generated plasma generates the second microplasma jet through the second glass microneedle 10 7, and shoot to the surface of the carbon fiber monofilament 16.

The structure of the second airflow protection cover 8 is similar to that of the first airflow protection cover 5 , and a flow equalizing plate composed of a plurality of circular holes is also arranged inside, and is located at a side close to the second plasma generating source 11 . A sealing plate is arranged on the side, and the sealing plate is sealed with the second glass microneedle 10. The inlet of the second protective gas source 9 is arranged between the equalizing plate and the sealing plate, and the inlet is open to the Enter the protective gas provided by the second protective gas source 9, and realize the uniform flow of the protective gas to the outlet of the second airflow protective cover 8 through the circular holes on the equalizing plate, thereby protecting the second protective gas. The micro-plasma jet 7 is protected from air and the beam spot diameter of the second micro-plasma jet 7 is controlled within a certain range.

As shown in FIGS. 5 and 6 , FIG. 5 is an exploded view of the structure of the carbon fiber monofilament holder; FIG. 6 is a structural view of the bracket; the carbon fiber monofilament 16 is inserted into the carbon fiber monofilament holder 15, and rotates around the axis with the carbon fiber monofilament holder 15; the carbon fiber monofilament holder 15 is inserted into the bracket 17, and can move along the X-axis and the Y-axis direction with the bracket 17.

Generally, the first working gas source 1 provides helium/oxygen mixed gas, the second working gas source 12 provides pure helium gas, and the auxiliary gas source 13 provides pure helium gas. The protective gas provided by the first protective gas source 4 and the second protective gas source 9 is pure nitrogen. The precursor atomizer 14 is filled with chloroauric acid solution with a concentration of 1.0 mol/L.

Preferably, the inner diameter of the tip exits of the first glass microneedle 3 and the second glass microneedle 10 is 1 micron.

The axis of the first airflow protection cover 5 and the first glass microneedle 3 is in a straight line, and the tip outlet of the first glass microneedle 3 exceeds the outlet of the first airflow protection cover 5 by 5 mm; The axis of the second airflow protection cover 8 and the second glass microneedle 10 is in a straight line, and the tip exit of the second glass microneedle 10 is 5 mm beyond the exit of the second airflow protection cover 8 .

Preferably, the axes of the first micro-plasma jet 6 and the second micro-plasma jet 7 are on a straight line, and are perpendicular to the axis of the carbon fiber monofilament 16 .

The invention can perform precise and controllable micro-region processing on the surface of carbon fiber monofilament by using the generated micro-plasma jet under atmospheric environment and mask-free conditions, and has the advantages of simple process, convenient operation and low cost; The processing process is carried out synchronously, for example, the surface of the carbon fiber monofilament is etched and deposited at the same time, thus enriching the processing methods for the surface of the carbon fiber monofilament, and also greatly improving the processing efficiency.

Embodiment 2

A method for using the carbon fiber monofilament micro-plasma surface micro-region processing device, comprising the following steps:

S1, the chloroauric acid solution with a configuration concentration of 1.0 mol/L is placed in the precursor atomizer 14;

S2, open the corresponding air source valve, and control the flow of each air source as follows:

The first working gas source 1: 95sccm helium and 5sccm oxygen; the second working gas source 12: 60sccm pure helium; the auxiliary gas source 13: 40sccm pure helium; the first protective gas source 4 : 200sccm nitrogen; the second protective gas source 9: 200sccm nitrogen;

S3, in the atmospheric environment obtained in the step S2, turn on the high-voltage power supply in the first plasma generation source 2 and the second plasma generation source 11 to generate uniform and stable atmospheric pressure plasma, and respectively via The first glass microneedle 3 and the second glass microneedle 10 generate the first microplasma jet 6 of helium/oxygen and the second microplasma jet 7 of helium/auric acid;

S4, the carbon fiber monofilament 16 and the carbon fiber monofilament holder 15 are continuously rotated at an angular speed of 0.1 rad/s, and at the same time, the carbon fiber monofilament 16 and the carbon fiber monofilament holder 15 are made to follow each other. The support 17 passes through the micro-plasma jet region obtained by S3 along the Y direction at a speed of 1 μm/s, that is, the micro-region processing on the surface of the carbon fiber monofilament 16 is completed. The end region of the processed carbon fiber monofilament 16 is uniformly etched to a predetermined diameter, and a layer of oxygen-containing active groups (such as carboxyl groups) is formed on the processed surface, and a layer of gold nanoparticles is uniformly deposited. The Y direction is the axial direction of the carbon fiber monofilament 16 .

In other embodiments, glass microneedles with different shapes, sizes and surface properties can be prepared by selecting different precursor solutions, different gas source types and flow rates, glass microneedles with different tip exit diameters, and different carbon fiber monofilament rotation and moving speeds. Carbon fiber monofilaments, allowing specific carbon fiber microelectrodes to be customized for different applications.

Specifically, the present invention can achieve four different processing effects through different working states, mainly by adjusting whether the moving speed of the support is a constant speed or a variable speed, and the first micro-plasma generating component and the second micro-plasma generating component are only opened separately. Group or both groups are open, four different processing effects can be achieved.

The four different processing effects are as follows:

As shown in FIG. 7 , when only the first plasma generating source 2 is working, there is only etching without nanoparticle deposition, and the support 17 moves at a uniform speed, so that only cylindrical micro-domains are generated for the carbon fiber monofilament 16 etching effect.

As shown in FIG. 8 , when only the first plasma generating source 2 is working, there is only etching without nanoparticle deposition, and the support 17 moves at a variable speed, so that a tapered micro-domain can be generated on the carbon fiber monofilament 16 etching effect.

As shown in FIG. 9 , when both the first plasma generating source 2 and the second plasma generating source 11 are operating, the carbon fiber monofilament 16 is simultaneously etched and nanoparticle deposited, and the The support 17 moves at a uniform speed, so that the carbon fiber monofilament 16 can be etched with cylindrical micro-domains and deposited with nanoparticles.

As shown in FIG. 10 , when both the first plasma generating source 2 and the second plasma generating source 11 are working, the carbon fiber monofilament 16 is simultaneously etched and nanoparticle deposited, and the The support 17 moves at a variable speed, so that the etching effect of tapered micro-domains and the deposition effect of nanoparticles can be produced on the carbon fiber monofilament 16 .

The above descriptions are only preferred embodiments of the present invention, which are merely illustrative rather than limiting for the present invention. Those skilled in the art understand that many changes, modifications and even equivalents can be made within the spirit and scope defined by the claims of the present invention, but all fall within the protection scope of the present invention.

Claims (7)

1. A carbon fiber monofilament micro-plasma surface micro-area processing device is characterized by comprising a first micro-plasma generating assembly, a second micro-plasma generating assembly and a fixing assembly, wherein the first micro-plasma generating assembly generates a first micro-plasma jet and emits the first micro-plasma jet to the surface of a carbon fiber monofilament fixed on the fixing assembly, and the second micro-plasma generating assembly generates a second micro-plasma jet and emits the second micro-plasma jet to the surface of the carbon fiber monofilament fixed on the fixing assembly;

the first micro-plasma generation assembly comprises a first working gas source, a first plasma generation source, a first glass micro-needle, a first protection gas source and a first airflow protection cover, wherein two ends of the first plasma generation source are respectively connected with the first working gas source and the first glass micro-needle, one side, far away from the first plasma generation source, of the first glass micro-needle is arranged in the first airflow protection cover, the first protection gas source is communicated with the first airflow protection cover, and protection gas is introduced into the first airflow protection cover;

the second micro-plasma generating assembly comprises a second airflow protective cover, a second protective gas source, a second glass micro-needle, a second plasma generating source, a second working gas source, an auxiliary gas source and a precursor atomizer, wherein two ends of the second plasma generating source are respectively connected with the second glass micro-needle and the second working gas source, the auxiliary gas source is communicated with the second plasma generating source through the precursor atomizer, and precursor mist is introduced into the second plasma generating source; one side, far away from the second plasma generating source, of the second glass micro-needle is arranged in the second airflow protection cover, and the second protection gas source is communicated with the second airflow protection cover and is used for introducing protection gas into the second airflow protection cover;

the fixing component comprises a carbon fiber monofilament holder and a support, the carbon fiber monofilament holder is fixed through the support, the carbon fiber monofilament holder holds the carbon fiber monofilament, the carbon fiber monofilament holder drives the carbon fiber monofilament to rotate along the axis of the carbon fiber monofilament, and the support drives the carbon fiber monofilament to axially move.

2. The carbon fiber monofilament microplasma surface micro-area processing device according to claim 1, wherein a sealing plate and a flow equalizing plate consisting of a plurality of circular holes are respectively disposed in the first air flow protection cover and the second air flow protection cover, the sealing plate is hermetically connected with the corresponding first glass microneedle or the second glass microneedle, an inlet of the first protective gas source or the second protective gas source is correspondingly disposed between the flow equalizing plate and the sealing plate, and the inlet is fed with protective gas provided by the first protective gas source or the second protective gas source.

3. The carbon fiber monofilament microplasma surface micro-zone processing apparatus of claim 1 wherein said first working gas source provides a helium/oxygen mixture gas, said second working gas source provides pure helium gas, and said auxiliary gas source provides pure helium gas.

4. The carbon fiber monofilament microplasma surface micro-zone processing device according to claim 1, wherein the shielding gas provided by said first shielding gas source and said second shielding gas source is pure nitrogen.

5. The carbon fiber monofilament microplasma surface micro-zone processing device according to claim 1, wherein the precursor atomizer contains chloroauric acid solution with a concentration of 1.0 mol/L.

6. The carbon fiber monofilament microplasma surface micro-area processing device according to claim 1, wherein the inside diameter of the outlet at the tip of the first glass microneedle and the inside diameter of the outlet at the tip of the second glass microneedle are 1 μm, the axis of the first airflow protection cover and the axis of the first glass microneedle are in a straight line, and the outlet at the tip end of the first glass microneedle exceeds the outlet of the first airflow protection cover by 5 mm; the second airflow protection cover and the second glass micro-needle are arranged on the same straight line, and the outlet of the tip end of the second glass micro-needle exceeds the outlet of the second airflow protection cover by 5 mm.

7. Use of a carbon fiber monofilament microplasma surface micro-area processing device according to any of claims 1-6, characterized in that it comprises the steps of:

s1, preparing a chloroauric acid solution and placing the chloroauric acid solution in the precursor atomizer;

s2, opening the first working air source, the second working air source, the auxiliary air source, the first protection air source and the second protection air source, and controlling the corresponding flow;

s3, turning on the high voltage power source in the first plasma generating source or/and the second plasma generating source under the atmosphere environment obtained in the step S2, generating atmospheric pressure plasma, and generating the first microplasma jet of helium/oxygen via the first glass microneedle, respectively; generating the second microplasma jet of helium/chloroauric acid via the second glass microneedle;

s4, continuously rotating the carbon fiber monofilaments and the carbon fiber monofilament holders, and simultaneously enabling the carbon fiber monofilaments and the carbon fiber monofilament holders to pass through the micro plasma jet zone obtained in the step S3 along the axis direction of the carbon fiber monofilaments along the support, so that micro-zone processing on the surfaces of the carbon fiber monofilaments is completed.

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