CN112375246A - Method for modifying polymer surface by carbon dioxide plasma discharge under atmospheric pressure - Google Patents

Method for modifying polymer surface by carbon dioxide plasma discharge under atmospheric pressure Download PDF

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Publication number
CN112375246A
CN112375246A CN202011364088.7A CN202011364088A CN112375246A CN 112375246 A CN112375246 A CN 112375246A CN 202011364088 A CN202011364088 A CN 202011364088A CN 112375246 A CN112375246 A CN 112375246A
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China
Prior art keywords
polymer
plasma
atmospheric pressure
carbon dioxide
discharge
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CN202011364088.7A
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CN112375246B (en
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张俊彦
贾倩
张斌
高凯雄
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Abstract

The invention discloses CO2The method for modifying the surface of the polymer by the discharge of the plasma under the atmospheric pressure adopts a plasma generator based on the atmospheric pressure discharge to carry out CO2Plasma is generated in the airflow, and the surface of the polymer (fluorosilicone rubber or silicon rubber) is modified to obtain the polymer with the surface with the low friction coefficient. The friction coefficient of the polymer surface is reduced to about 0.35. The invention is based on the CO produced2The high-energy particles bombard the surface of the polymer, the breaking of surface bonds and the synthesis reaction are completed by only a few atomic layers, so that the polymer has good cohesiveness while the performance of the polymer is maintained. CO 22The friction coefficient of the polymer can be reduced by the reaction between the plasma generated by the discharge of the gas in the atmospheric pressure and the polymer, and the polymer has good performanceThe surface modified polymer with tribological properties makes a contribution to a sustainable development path which is developed by meeting the needs of the contemporary people and not damaging the capability of the latter to meet the needs.

Description

Method for modifying polymer surface by carbon dioxide plasma discharge under atmospheric pressure
Technical Field
The invention relates to a method for modifying a polymer surface, in particular to a method for modifying a polymer surface by discharging carbon dioxide plasma under atmospheric pressure.
Background
As early as in the original social period, people have perceived CO in life practice2Until 1840, the presence of (c) was confirmed to be named "carbon dioxide". CO 22Has many applications, and can be used as gas fertilizer, fire extinguisher filling material, industrial raw material, and solid CO2(Dry Ice) can be used for producing stage effect, refrigeration, etc. But CO2The greenhouse gas is a greenhouse gas, brings great harm to the environment, and the continuous intensification of the atmospheric greenhouse effect can cause global warming, so that some global climate problems which cannot be predicted by current science are generated. But inevitably produces CO in our daily life2Such as: organic substances (including animals and plants) can release CO in the processes of decomposition, fermentation, decay and deterioration2(ii) a CO is also released in the combustion process of petroleum, paraffin, coal and natural gas2(ii) a CO is also released in the process of producing chemical products by petroleum and coal2(ii) a CO can be released during fermentation and curing of all excrement and humic acid2(ii) a Even all animals exhaled CO during their breath2. Therefore, CO is minimized2At the same time of emission, the aim should be to deal with CO2The development of more utilization modes is necessary.
Disclosure of Invention
The invention aims to provide a method for modifying a polymer surface by carbon dioxide plasma discharge under atmospheric pressure so as to improve the friction performance of the polymer surface.
Based on atmospheric pressure in CO2Discharge plasma modification of polymer surfaces in gas streams
The invention is based on the atmospheric presence of CO2The method for modifying the surface of the polymer by plasma discharge adopts a plasma generator based on atmospheric pressure discharge and uses CO2Generating plasma in the gas flow, and modifying the surface of the polymer to obtain the surface modified polymer. The specific surface modification method is as follows:
(1) and (3) respectively washing the polymers in deionized water for 5-10 min, and repeating for 3-5 times to remove pollutants on the surfaces of the polymers. The polymer is fluorine silicon rubber or silicon rubber;
(2) putting the cleaned polymer into a plasma generator based on atmospheric pressure discharge, turning on a direct current power supply, and adjusting the current to be 60-100 mA, the working voltage to be 2500V and the average power to be 100W;
(3) working gas CO is introduced2Controlling the air flow to be 1-5L/min, and generating plasma with the density of about 1011/cm-3(ii) a Carrying out plasma treatment on the surface of the polymer for 20-40 min; and taking out the plasma generator after the cavity of the plasma generator is cooled to obtain the plasma modified polymer.
Tribological properties of plasma-modified polymers
The test method comprises the following steps: atmospheric CO detection on friction tester2The GCr15 steel ball with the diameter of 5 mm is selected as a dual ball on the surface of the polymer modified by plasma discharge. The specific parameters are as follows: the friction load was 3N, the linear velocity was 68 mm/s, the radius of rotation was 4mm, the humidity was 27%, and the test time was 30 min.
And (3) testing results: the plasma modified polymer has low friction performance, and the friction coefficient is reduced to about 0.35.
The invention is based on the CO produced2The high-energy particles bombard the surface of the polymer, the breaking of surface bonds and the synthesis reaction are completed by only a few atomic layers, so that the polymer has good cohesiveness while the performance of the polymer is maintained. CO 22The plasma generated by the gas discharge in the atmospheric pressure can react with the polymer to reduce the friction coefficient of the polymer, and the surface modified polymer with good tribological performance can be obtained.
In summary, the invention utilizes the greenhouse gas CO2Under the action of atmospheric pressure, in CO2The plasma is generated by discharging in the airflow, and the surface of the polymer is modified to obtain the polymer with low friction coefficient, so that a new method is provided for obtaining high-performance polymer, and the method contributes to a sustainable development road which needs to meet the requirements of the current generation and does not damage the capability development of the later generation meeting the requirements.
Detailed Description
The process of the present invention for modifying the surface of the polymer by the carbon dioxide plasma discharge under atmospheric pressure and the properties of the polymer are further illustrated by the following specific examples.
Example 1
(1) Putting the fluorosilicone rubber into deionized water to be washed for 6min, repeating for 5 times, and removing surface pollutants;
(2) putting the cleaned fluorosilicone rubber into a plasma generator based on atmospheric pressure discharge; turning on a direct-current power supply, adjusting the current to be 100 mA, the working voltage to be 2500V and the average power to be 100W;
(3) working gas CO is introduced2Controlling the gas flow to be 3L/min, and generating plasma with the density of 1011/cm-3Treating the surface of the fluorosilicone rubber for 30min, and taking out the fluorosilicone rubber after the cavity is cooled to obtain the plasma modified fluorosilicone rubber;
(4) the friction performance of the plasma modified fluorosilicone rubber is detected on a friction tester: GCr15 steel balls with a diameter of 5 mm were selected as the couple balls. The specific parameters are as follows: the friction load is 3N, the linear velocity is 68 mm/s, the rotation radius is 4mm, the humidity is 27%, the test time is 30min, and the friction coefficient is 0.31.
Example 2
(1) Respectively cleaning fluorosilicone rubber in deionized water for 6min, repeating for 5 times, and removing surface pollutants;
(2) putting the cleaned fluorosilicone rubber into a plasma generator based on atmospheric pressure discharge; turning on a direct-current power supply, adjusting the current to be 80 mA, the working voltage to be 2500V and the average power to be 100W;
(3) working gas CO is introduced2Controlling the gas flow to be 5L/min, and generating plasma with the density of 1011/cm-3(ii) a Treating the surface of the fluorosilicone rubber for 20 min, and taking out the fluorosilicone rubber after the cavity is cooled to obtain the plasma modified fluorosilicone rubber;
(4) the friction performance of the plasma modified fluorosilicone rubber is detected on a friction tester: GCr15 steel balls with a diameter of 5 mm were selected as the couple balls. The specific parameters are as follows: the friction load is 3N, the linear velocity is 68 mm/s, the rotation radius is 4mm, the humidity is 27 percent, and the test time is 30 min; the coefficient of friction was 0.34.
Example 3
(1) Respectively cleaning the silicon rubber in deionized water for 6min, repeating for 5 times, and removing surface pollutants;
(2) putting the cleaned silicon rubber into a plasma generator based on atmospheric pressure discharge; turning on a direct-current power supply, adjusting the current to be 60 mA, the working voltage to be 2500V and the average power to be 100W;
(3) working gas CO is introduced2Controlling the gas flow to be 1L/min, and generating plasma with the density of 1011/cm-3(ii) a Treating the surface of the silicon rubber for 40 min; taking out the silicon rubber after the cavity is cooled to obtain the plasma modified silicon rubber;
(4) friction properties of plasma-modified silicone rubber on a friction tester: GCr15 steel balls with a diameter of 5 mm were selected as the couple balls. The specific parameters are as follows: the friction load is 3N, the linear velocity is 68 mm/s, the rotation radius is 4mm, the humidity is 27 percent, and the test time is 30 min; the coefficient of friction was 0.36.

Claims (3)

1. A method for modifying polymer surface by carbon dioxide plasma discharge under atmospheric pressure adopts a plasma generator based on atmospheric pressure discharge and utilizes CO2Plasma is generated in the airflow, and the surface of the polymer is modified, so that the polymer with the surface with the low friction coefficient is obtained.
2. The method for atmospheric pressure discharge modification of a polymer surface by carbon dioxide plasma as claimed in claim 1, wherein: the method comprises the following steps:
(1) respectively cleaning the polymers in deionized water for 5-10 min, and repeating for 3-5 times to remove pollutants on the surfaces of the polymers;
(2) putting the cleaned polymer into a plasma generator based on atmospheric pressure discharge, turning on a direct current power supply, and adjusting the current to be 60-100 mA, the working voltage to be 2500V and the average power to be 100W;
(3) working gas CO is introduced2Controlling the air flow to be 1-5L/min, and generating plasma with the density of 1011/cm-3(ii) a Carrying out plasma treatment on the surface of the polymer for 20-40 min; thus obtaining the plasma modified polymer.
3. The method for atmospheric pressure discharge modification of a polymer surface by carbon dioxide plasma as claimed in claim 1 or 2, wherein: the polymer is fluorosilicone rubber or silicon rubber.
CN202011364088.7A 2020-11-27 2020-11-27 Method for modifying polymer surface by carbon dioxide plasma discharge under atmospheric pressure Active CN112375246B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120107525A1 (en) * 2009-07-08 2012-05-03 Nobuo Ohmae CO2 Recycling Method and CO2 Reduction Method and Device
CN108220908A (en) * 2017-12-18 2018-06-29 中国科学院兰州化学物理研究所 A kind of method that frictional interface is formed in situ graphene and onion realizes superslide
CN109503878A (en) * 2018-10-24 2019-03-22 中国科学院兰州化学物理研究所 A kind of preparation method of rubber seal surface antifriction and oil storage film layer
CN109750271A (en) * 2019-02-27 2019-05-14 中国科学院兰州化学物理研究所 A kind of heat resistant and wear resistant damage vibrating screen ball and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120107525A1 (en) * 2009-07-08 2012-05-03 Nobuo Ohmae CO2 Recycling Method and CO2 Reduction Method and Device
CN108220908A (en) * 2017-12-18 2018-06-29 中国科学院兰州化学物理研究所 A kind of method that frictional interface is formed in situ graphene and onion realizes superslide
CN109503878A (en) * 2018-10-24 2019-03-22 中国科学院兰州化学物理研究所 A kind of preparation method of rubber seal surface antifriction and oil storage film layer
CN109750271A (en) * 2019-02-27 2019-05-14 中国科学院兰州化学物理研究所 A kind of heat resistant and wear resistant damage vibrating screen ball and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LEI HUO等: "Exploring the low friction of diamond-like carbon films in carbon dioxide atmosphere by experiments and first-principles calculations", 《APPLIED SURFACE SCIENCE》 *
SEKHAR C.RAY等: "A facile method for the deposition of thermally stable diamond like carbon thin films via carbon dioxide precursor gas", 《DIAMOND & RELATED MATERIALS》 *
白常宁等: "空气等离子预处理改善橡胶表面碳膜结合强度和耐磨性研究", 《真空与低温》 *

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