CN113275217B - Preparation method of plasma graft copolymerization film layer - Google Patents
Preparation method of plasma graft copolymerization film layer Download PDFInfo
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- CN113275217B CN113275217B CN202110536961.4A CN202110536961A CN113275217B CN 113275217 B CN113275217 B CN 113275217B CN 202110536961 A CN202110536961 A CN 202110536961A CN 113275217 B CN113275217 B CN 113275217B
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/62—Plasma-deposition of organic layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0433—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a reactive gas
- B05D3/044—Pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a preparation method of a plasma graft copolymerization film layer, which comprises the following steps: placing a base material to be processed in a working chamber and enabling the working chamber to reach a vacuum state; introducing process gas into the working chamber reaching the vacuum state, wherein the process gas at least comprises nitrogen source gas, oxygen and fluorocarbon unsaturated hydrocarbon; starting a power supply, generating uniform plasma in a working chamber to excite free electrons from process gas, and promoting the nitrogen oxygen group introduced to the surface of the substrate to react with the fluorocarbon unsaturated hydrocarbon to generate a micro-etching and fluorocarbon cross-linking structure beneficial to the fixation of a subsequent graft copolymerization film layer; and stopping introducing the process gas, introducing monomer steam serving as a gas source of the graft copolymerization membrane layer into the working chamber, and depositing the monomer on the surface of the base material in the plasma atmosphere to perform graft copolymerization reaction to form the graft copolymerization hydrophobic membrane layer. The method realizes the deposition of the functional membrane layer with excellent adhesion performance and uniform appearance on the surface of the base material, particularly the surface of the heterogeneous piece with the complex structure.
Description
Technical Field
The invention belongs to the technical field of plasma chemical engineering, and particularly relates to a preparation method of a plasma graft copolymerization film layer.
Background
Currently, it is quite common to use various plasma sources to chemically vapor deposit functional films on the surface of a substrate for surface modification or protection. For example, chinese patent CN 105949836a discloses a method for forming a surface coating by gate-controlled plasma-initiated gas phase polymerization, which applies a positive pulse bias generated by a pulse bias power source to a metal grid, and the positive pulse bias applied to the metal grid controls and releases plasma into a processing chamber to initiate monomer vapor polymerization and deposition on the surface of a substrate to be processed to form a polymer coating. Chinese patent CN 102821873a discloses a method of applying conformal nanocoating by a low pressure plasma process. However, in the above method, due to the limitation of the distribution characteristics of the large-size space plasma, a large-area highly uniform plasma cannot be formed, so that the deposited film is discontinuous, and even the film thickness is not uniform, which results in a low yield (yield) of the product, and greatly limits the practical application of the plasma chemical vapor deposition polymer film. In addition, the existing plasma deposited film has poor adhesion and is easy to lose efficacy after multiple times of friction.
Disclosure of Invention
Aiming at the defects, the invention provides a preparation method of a plasma graft copolymerization hydrophobic membrane layer, which realizes the deposition of a functional membrane layer with excellent adhesion property and uniform appearance (thickness) on the surface of a base material, especially the surface of an heterogeneous piece with a complex structure.
In a first aspect, the invention provides a preparation method of a plasma graft copolymerization hydrophobic membrane layer, which comprises the following steps:
placing a base material to be processed in a working chamber and enabling the working chamber to reach a vacuum state;
introducing process gas into the working chamber reaching the vacuum state, wherein the process gas at least comprises nitrogen source gas, oxygen and fluorocarbon unsaturated hydrocarbon;
starting a power supply, generating uniform plasma in a working chamber to excite free electrons from process gas, and promoting the nitrogen oxygen group introduced to the surface of the substrate to react with the fluorocarbon unsaturated hydrocarbon to generate a micro-etching and fluorocarbon cross-linking structure beneficial to the fixation of a subsequent graft copolymerization film layer;
and stopping introducing the process gas, introducing monomer steam serving as a gas source of the graft copolymerization membrane layer into the working chamber, and depositing the monomer on the surface of the base material in the plasma atmosphere to perform graft copolymerization reaction to form the compact graft copolymerization hydrophobic membrane layer.
Before the monomer steam is used for forming the graft copolymerization film layer, the preparation method utilizes different gas combinations as process gas, and is beneficial to generating a fluorocarbon crosslinking structure after the subsequent monomer steam is introduced by virtue of the coordination of the oxynitride group and the fluorocarbon unsaturated hydrocarbon. The nitrogen-oxygen radical and the fluorine-carbon unsaturated hydrocarbon generate some structural units with reactivity, the structural units react with subsequent monomer steam to generate a fluorine-carbon cross-linking structure, and the nitrogen-oxygen radical mainly plays a role in capturing H atoms to form hydrophilic radicals such as-N-H-or-N-O-H-. Test results prove that the mixed gas containing nitrogen source gas, oxygen and fluorocarbon unsaturated hydrocarbon can play a role in hydrophilic treatment on the surface of the base material after being pretreated as process gas, however, hydrophobic monomer steam is used for coating in the subsequent process, and the final result still shows excellent hydrophobic characteristics, which means that after active groups such as-N-H-or-N-O-H-generated in the pretreatment are grafted and combined with the hydrophobic monomer steam, the final coating is dominated to show hydrophobicity due to the existence of fluorine element of the monomer steam, and meanwhile, the hydrophilic active groups are beneficial to the subsequent graft polymerization reaction and the fixation of a graft copolymerization film layer.
Preferably, the volume percentage of the nitrogen source gas in the process gas is 55-80%, the volume percentage of the oxygen is 15-40%, and the balance is the fluorocarbon unsaturated hydrocarbon.
Preferably, the fluorocarbon unsaturated hydrocarbon is fluorine substituted straight chain alkane olefin gas and/or fluorine substituted straight chain alkane alkyne gas selected from C2H2F2、C2F4、C3F6、C4F8And C4F6A mixture of one or more of them.
Preferably, the flow rate of the process gas is 20-200 sccm.
Preferably, the monomer is one or more of fluorine substituted linear alkyl olefin unsaturated ester, fluorine substituted linear alkyl silicon oxygen compound, linear alkyl olefin unsaturated ester and fluorine substituted alkyl unsaturated cyclic compound.
Preferably, the flow rate of the monomer vapor is 20 to 100 sccm.
Preferably, the flow ratio of the process gas to the monomer vapour is 10-1: 5-0.5. By limiting the flow ratio of the process gas to the monomer vapor within the above range, the process gas and the monomer vapor molecules can effectively collide with each other and generate active radicals to promote ionization of the monomer vapor molecules.
Preferably, a carrier gas is also introduced while the monomer vapor is introduced, wherein the carrier gas is one or a mixture of several of helium, nitrogen, argon and hydrogen.
Preferably, the flow rate of the carrier gas is 50-300 sccm.
Preferably, the flow ratio of the monomer vapour to the carrier gas is from 0.5 to 5: 1-10. The flow ratio of the monomer vapor to the carrier gas is controlled within the range, the carrier gas molecules and the monomer vapor molecules are fully collided, the generation of beneficial active free radicals is facilitated, and meanwhile, the construction of the micro-nano structure on the surface of the base material and the formation of the graft copolymerization film layer are not influenced.
Preferably, the thickness of the graft copolymerization hydrophobic membrane layer is 50-1000 nm.
Preferably, the substrate is a complex special-shaped structure workpiece with curved surfaces and/or pores.
The invention has the following beneficial effects:
the yield of batch processed products and the thickness uniformity of the product film can be greatly improved;
the friction resistance is good;
the proportion of the materials can be changed as required to generate the nano-film layers with different functions, so that the method has great applicability;
especially has good film forming property for workpieces with complex curved surfaces.
Drawings
FIG. 1 is a graph showing the film thickness of a graft copolymerization film layer of example 1;
FIG. 2 is a film thickness profile of a graft copolymerization film layer of comparative example 1;
FIG. 3 is a schematic static contact angle for example 1 and comparative example 1;
FIG. 4 is a graph showing the film thickness of the graft copolymerization film layer of example 4;
FIG. 5 is a film thickness profile of a graft copolymerization film layer of comparative example 2;
FIG. 6 is a schematic illustration of the static contact angles of examples 3-4 and comparative example 2;
figure 7 is a comparison of the static contact angle change for the films of example 4 and comparative example 2 over 12 consecutive days.
Detailed Description
The present invention will be further described with reference to the following examples, which are intended to be illustrative of the invention only and are not intended to be limiting.
The following is an exemplary description of the preparation method of the plasma graft copolymerization hydrophobic membrane layer.
And placing the substrate to be processed in a working chamber of the vacuum cavity. The material of the substrate to be treated is not limited, and includes, but is not limited to, one or more of metal, glass, ceramic, plastic, rubber, paper, wood, and fabric.
The working chamber is evacuated to achieve a vacuum state. The vacuum state of the working chamber can be achieved by means of a vacuum pump. In some embodiments, the vacuum pump is pumped into the chamber to a predetermined operating pressure of 0.01 to 0.1 mbar.
And introducing process gas into the working chamber reaching the vacuum state. The process gas is a mixed gas of nitrogen source gas, oxygen and fluorocarbon unsaturated hydrocarbon. The process gas is introduced not only for cleaning or etching, but also for the purpose of specifically introducing a nitrogen-oxygen group and a fluorocarbon unsaturated hydrocarbon to form a cross-linked structure on the surface of the substrate.
Preferably, the sum of the volume percentages of the nitrogen source gas, the oxygen gas and the fluorocarbon unsaturated hydrocarbon is 100%. In the experiment, only C is introduced3F6Or C4F8When the fluorocarbon unsaturated olefin is pretreated, the grafting probability of a-C-F-group or-F-element on the surface of a base material in the vacuum coating process can be improved, but the hydrophobic function is mainly caused by the F element with low surface energy, so the-C-F-group or-F-element only enhances the surface hydrophobicity of the base material, and the positive effect on the hydrophilization of the base material cannot be achieved, but the hydrophilization is prevented(ii) a Secondly, the adhesion degree of the obtained coating on the surface of the base material is limited, so that the adhesion performance, the wear resistance and the compactness of the coating are limited. The invention introduces the mixed gas of nitrogen source gas, oxygen and fluorocarbon unsaturated hydrocarbon as the process gas, can obviously increase the types of free radicals, such as-NO-, -CF-, -F-, -CO-, -NH2Many active radicals-OH, -NCO-and-CN-positively promote the hydrophilization of the substrate surface. In addition, because the surface energy of different base materials is different, various active free radicals can be specifically activated and modified aiming at the base material surfaces of different materials, so that firm chemical bonds are formed with the base material surfaces, bridging is further formed with coating monomer vapor gas molecules, the firm degree of the surface chemical bonds of the base materials is increased, and the adhesive force, the wear resistance, the crosslinking degree and the film compactness of the film are favorably improved. The mixed gas can also make full use of the difference of atomic radii among different gas molecules, so as to achieve the effect of pertinently controlling the collision of each gas molecule and atom in the plasma atmosphere, and further controllably adjust the surface activation degree and the microstructure structure degree of the substrate.
The volume percentage of oxygen in the process gas is 5-80%, preferably 10-40%, more preferably 15-40%. The oxygen mainly plays a role in oxidizing and activating the surface of the substrate, which provides a basis for the subsequent chemical activity improvement of the surface of the substrate. In this case, the oxidation and etching are carried out simultaneously.
The volume percentage of the nitrogen source gas in the process gas is 10-90%, preferably 55-80%. The nitrogen source gas may be ammonia and/or nitrogen.
According to the invention, nitrogen source gas, oxygen and fluorocarbon unsaturated hydrocarbon are simultaneously used as the components of the process gas to be introduced, and the volume percentage of the nitrogen source gas is controlled to be higher than that of the oxygen, so that the method not only plays a role in activating and oxidizing the surface of the substrate, but also is beneficial to hydrophilic modification of the substrate and bridging of subsequent coating materials. In the experiment, if the base material is pretreated without introducing nitrogen source gas (only introducing oxygen), oxygen forms-OH groups (mostly belonging to hydrogen bond type, belonging to covalent bond, and the bond energy of the hydrogen bond is weaker than that of chemical bond type) with the surface of the base material under the plasma atmosphere, so that although the base material can be subjected to transient hydrophilization, the hydrophilic groups on the surface of the base material are easy to invert and lose the hydrophilic property due to the reason of time extension, air contact and the like, and the hydrophilic property of the surface of the base material is maintained for a short time. According to the invention, the process gas with a specific composition is used for treatment and then film coating is carried out, so that the number of introduced active groups is large, and the surface of the base material is combined with the free radical group in a chemical bond form, so that the surface of the base material is activated and modified sufficiently, the time for keeping the activity of the group on the surface of the base material is long, and the hydrophilization is sufficient, so that the surface of the base material after hydrophilic treatment still has a hydrophilic effect even if the base material is placed for a long time.
In some embodiments, the fluorocarbon unsaturated hydrocarbon is a fluorine-substituted linear alkane olefin gas and/or a fluorine-substituted linear alkane alkyne gas selected from C2H2F2、C2F4、C3F6、C4F8And C4F6A mixture of one or more of them. C4F6The coating material is alkyne gas, compared with alkene, the coating material contains more unsaturated bonds, has higher ionization degree, can form more bonding, correspondingly has higher micro-etching generated by the reaction of the alkyne gas with nitrogen oxygen groups and carbon oxygen groups and has higher crosslinking degree and firmness degree of a fluorocarbon crosslinking structure and a base material, and can be combined with more coating material molecules to improve the hydrophobicity.
The flow rate of the process gas is 10-300 sccm. Preferably 20-200 sccm.
During the process of introducing the process gas, the pressure in the working chamber is kept at 0.01 to 1.0 mbar. The time for introducing the process gas for pretreatment can be 1-10 min. Preferably 3-5 min.
And (3) starting a power supply, discharging the electromagnetic waves to the inner wall of the working chamber, and generating uniformly distributed plasmas. The power supply is not limited in kind, and can be a radio frequency power supply or a microwave power supply. The frequency of the radio frequency power supply is 20KHz to 13.56MHz, and the power is 50W to 5 KW. The frequency of the microwave power supply is 915MHz-2.45GHz, and the power is 50W-50 KW.
Preferably, by utilizing the principle that external high-frequency electromagnetic waves can induce plasmon polaritons generated at the interface of a medium and plasma, the high-frequency electromagnetic waves are attenuated exponentially in the normal direction to form electromagnetic surface waves propagating in the tangential direction, the physical process of the high-frequency electromagnetic waves is that the electromagnetic waves are coupled into a vacuum reaction chamber through a slit antenna between the reaction chamber (working chamber) and a power supply, gas discharge is firstly broken down right below the slit antenna to form high-density plasma, and then the high-density plasma is similar to a metal thin film, and the relative dielectric constant is negative. The high-frequency electromagnetic wave is reflected back to the critical density layer and propagates around the interface of the medium and the plasma, and the energy of the high-frequency electromagnetic wave is confined in the area near the interface, so that the surface wave is reflected back and forth in the reaction chamber, electrons are accelerated under the left and right electric fields of the surface wave to continuously provide energy for the plasma, and then large-area uniform high-density plasma can be generated, and the uniformity of the coating film is further improved. Multiple rounds of film thickness tests show that the difference of the film thickness at each position does not exceed +/-1nm, and better uniformity is shown.
At the moment, the coating device of the plasma graft copolymerization film layer is provided with a radio frequency power supply, a reaction unit, an air exhaust unit and an air distribution unit; wherein, the reaction unit is internally formed into a chamber for reaction; the radio frequency power supply is arranged outside the reaction unit and communicated with the cavity of the reaction unit to generate plasma; the air extraction unit is arranged outside the reaction unit, is communicated with the cavity of the reaction unit and is used for extracting gas in the reaction unit; the gas distribution unit is arranged outside the reaction unit, is communicated with the cavity of the reaction unit through a supply pipeline and is used for adding monomer steam serving as a gas source of the graft copolymerization film layer; and arranging a slit antenna at a position close to the radio frequency power supply in the chamber of the reaction unit. Preferably, the reaction unit includes: the radio frequency power supply comprises a reaction unit, an electrode plate, a planar quartz plate, a slit antenna and a reaction chamber, wherein the electrode plate is arranged in the reaction unit and connected with the radio frequency power supply, the planar quartz plate is arranged in the reaction unit in a mode of being close to the electrode plate, the slit antenna is arranged on the surface, facing the radio frequency power supply, of the quartz plate, and the reaction chamber is surrounded by the quartz plate and the inner wall of the reaction unit. More preferably, the slot antennas are arranged in parallel in a plurality on the quartz plate, and the excitation intensity is changed by changing the size and the array distribution of the slot antennas.
After excited by plasma, the process gas molecules and atoms impact the surface of the base material and heat the base material, and the surface of the base material is activated and cleaned to form micro-etching and at least partial cross-linking structure. By using the process gas with special composition, the fluorocarbon unsaturated hydrocarbon (especially fluorocarbon alkyne gas) has the characteristics of easy pi bond opening and high reaction activity, and the nitrogen oxygen group generated by the nitrogen source gas and the oxygen is favorable for reacting with the fluorocarbon unsaturated hydrocarbon to generate a micro-etching and fluorocarbon cross-linking structure for promoting the subsequent graft copolymerization film layer to be fixed. The method is favorable for generating the functional graft copolymerization hydrophobic film layer with compact film layer, excellent friction resistance and corrosion resistance.
The process gas feed is stopped and monomer vapor (also referred to as "chemical monomer vapor") is fed into the chamber. The composition of the monomer species is not limited. The monomer can be at least one of fluorine substituted linear alkyl olefin unsaturated ester, fluorine substituted linear alkyl silicon oxygen compound, linear alkyl olefin unsaturated ester and fluorine substituted alkyl unsaturated cyclic compound. For example, a perfluoro acrylate monomer. Of course, the monomer includes, but is not limited to, at least one of hexamethyldisiloxane, carbon tetrafluoride, triethoxysilane, and unsaturated organics of the acrylic type.
The flow rate of the monomer vapor is 10 to 300sccm, preferably 20 to 100 sccm.
The carrier gas is also introduced simultaneously with the monomer vapor. The carrier gas is one or a mixture of several of helium, argon, oxygen and hydrogen. The corresponding carrier gas species can be selected according to modification requirements. Helium and/or argon are preferred as process gases. The flow rate of the carrier gas is 50-300 sccm. During this process, the working chamber is maintained at a pressure of 0.01 to 1.0 mbar.
In the process of continuously introducing carrier gas and monomer steam, the monomer is deposited on the surface of the base material in the plasma atmosphere and undergoes graft copolymerization reaction, so that a continuous polymerization film layer is formed on the surface of the base material. The deposition time may be 5-60 min.
In some preferred embodiments, the process gas may further include a helium-argon mixture gas. Namely, the process gas consists of nitrogen source gas, oxygen, fluorocarbon unsaturated hydrocarbon and helium argon mixed gas. The helium-argon mixed gas can improve the ionization degree of the gas, and further promote the formation of micro-etching and fluorocarbon cross-linked structures. This is advantageous for the preparation of hydrophobic coatings. At this time, the composition of the process gas includes: 55-80% of nitrogen source gas, 15-40% of oxygen, 1-10% of fluorocarbon unsaturated hydrocarbon and the balance of helium-argon mixed gas in percentage by volume. The volume percentage of the helium-argon mixed gas is preferably 5 to 30%. The helium-argon mixed gas can be helium and argon in a volume ratio of 1: 10-1: 1, and a mixed gas.
The invention also provides a preparation method of the plasma graft copolymerization hydrophilic film layer. The preparation method comprises the following steps: placing a base material to be processed in a working chamber and enabling the working chamber to reach a vacuum state; introducing process gas into the working chamber reaching the vacuum state, wherein the process gas at least comprises nitrogen source gas, oxygen and helium-argon mixed gas; starting a power supply, generating uniform plasma in a working chamber to excite free electrons from the process gas, and promoting interaction of a nitrogen-oxygen group, a hydroxyl group, an ether group and an amino group introduced to the surface of the base material so as to avoid inversion of a hydrophilic group on the surface of the base material; and stopping introducing the process gas, introducing monomer steam serving as a gas source of the graft copolymerization film layer into the working chamber, and depositing the monomer on the surface of the base material in the plasma atmosphere to perform graft copolymerization reaction to form the graft copolymerization hydrophilic film layer.
When the graft copolymerization hydrophilic film is prepared, the oxygen introduction amount is not suitable to be excessive, because the excessive oxygen introduction can convert the oxidation into the etching, the surface energy of the base material is lower, the chemical inertness is presented, and the surface of the base material becomes hydrophobic, which is not beneficial to the construction of the subsequent hydrophilic film.
Preferably, the composition of the process gas comprises: 10-30% of oxygen, 40-60% of helium-argon mixed gas and the balance of nitrogen source gas in percentage by volume. The helium-argon mixed gas can be helium and argon in a volume ratio of 1: 10-1: 1, and a mixed gas.
The monomer comprises a monomer containing-OH/-COO-/-COOH-/-NO-/-NH2-/-SH-/-CO-group linear alkane compounds or linear alkylenic unsaturated esters or mixtures of one or more of alkyl unsaturated cyclic compounds.
The flow rate of the process gas, the flow rate of the monomer steam, the flow rate of the carrier gas, the thickness of the membrane layer and the deposition time are the same as those of the preparation method of the hydrophobic membrane layer. The flow rate of the monomer vapor is 10 to 300sccm, preferably 20 to 100 sccm. The flow ratio of the process gas to the monomer steam is 10-1: 5-0.5. The flow rate of the carrier gas is 50-300 sccm. The flow ratio of the monomer vapor to the carrier gas is 0.5-5: 1-10. The thickness of the graft copolymerization hydrophilic film layer is 50-1000 nm. The deposition time may be 5-60 min.
The carrier gas is preferably a mixture of one or more of argon, helium, oxygen, nitrogen. Wherein, the time for the pretreatment of the process gas is preferably 1-5 min.
The preparation method adopts low-temperature plasma chemical vapor deposition to uniformly deposit the heterogeneous member with the complex structure to generate the functional graft copolymerization membrane layer.
And (3) testing the adhesive force: adopting a check method. In the case of dry film, ten connected 'well-shaped' marks are marked on the surface of the film layer by an art designer knife, and then the positions of the marks are torn by using a 3M P600 adhesive tape for three times. The film layer is OK when not dropped and NG when dropped.
And (3) testing the waterproof performance: static contact angle test method is adopted. And (3) dripping water drops on the surface of the coated substrate by using a dropper, and measuring an included angle between a boundary line between air and the water drops and a boundary line between the water drops and the substrate by using a contact angle measuring instrument when the water drops reach balance on the surface of the substrate, namely a static contact angle. When the angle of the static contact angle is more than 150 degrees, the super-hydrophobic performance of the coated substrate reaches the standard.
And (3) wear resistance test: reciprocating motion abrasion test method. A500 g load was applied to a special sand test eraser (Heibojia, Germany, having a length of 3.8cm, a width of 1.3cm and a thickness of 0.8 cm), a stroke of about 20cm was made on the surface of the film layer at a speed of 40 to 60 times/min, and the surface of the sample was rubbed back and forth for 300 cycles. And (4) finishing the test, wherein the surface of the sample coating is not scratched or does not penetrate through the bottom, and the test is qualified, otherwise, the test is unqualified.
And (4) carrying out corrosion resistance test through neutral salt spray test and acid and alkali resistance test.
The salt spray test refers to the GB T2423.17-2008 salt spray test method. Placing the sample in a neutral salt spray testing machine, carrying out automatic continuous spray testing, and defining a test period: 16h, 24h, 48h, 72h and 96h, after the test period is finished, taking out the sample, washing the sample for 5min by using tap water, then washing the sample by using distilled water or deionized water, and then shaking or drying the sample by using air flow to remove water drops. And observing the appearance change condition of the sample, and evaluating the test result. The analysis method comprises the following steps: the temperature is 35 plus or minus 2 ℃, the humidity is more than 85 percent, and the pH value of the solution is 6.5 to 7.2. Solution preparation: the mass concentration of the salt solution is (5 +/-1)%. The solution should be prepared by the following method: dissolving (5 +/-1) parts by mass of salt in 95 parts by mass of distilled water or deionized water, and uniformly stirring. And (4) evaluating the result: and (5) completing the test, wherein the sample meets the requirements of universal description on appearance, function and performance. The appearance of the sample has no obvious change, such as corrosion, discoloration, plating layer peeling and the like, and the sample is qualified.
After a specified recovery period of hours, this check and comparison is repeated. And (5) after the test is finished, observing whether the surface of the sample film layer has phenomena of light loss, color change, bubbling, spots, falling off and the like. The adopted reagent is as follows: dilute sulfuric acid solution (5% by mass) and sodium hydroxide solution (5% by mass). 24 or 16 30 mm. To reduce the loss of the test solution due to evaporation or splashing, the container is capped. After the standard soaking time is reached, the samples are thoroughly washed with water and wiped with suitable absorbent paper or cloth to remove the residual liquid, and the samples are immediately examined for film layer changes, comparable to the un-soaked samples, at 30mm, if several samples are immersed in the same bath, with portions at least apart, immersed in a defined acid or base solution, and the samples can be immersed in a nearly vertical position with a suitable holder. The immersed sample is at least separated from the inner wall 2/3 of the groove to be tested for acid and alkali resistance: under the test conditions of 23 +/-2 ℃ and 50 +/-5% relative humidity, the whole sample or
The oscillogram and film thickness comparison were observed by a film thickness meter. And water dripping test or corrosion resistance test can be carried out on different parts, and whether the film is uniform or not can be obtained through comparison.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing description are intended to be included within the scope of the invention. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. The substrate in the following examples is a PC substrate.
Example 1
The preparation method of the plasma graft copolymerization hydrophobic membrane layer comprises the following steps:
1) placing a substrate to be processed in a working chamber of a vacuum cavity;
2) pumping a vacuum pump until the vacuum in the working chamber reaches a preset working pressure of 0.01 mbar;
3) after the vacuum pumping is finished, introducing process gases into the working chamber reaching the vacuum state, wherein the process gases comprise nitrogen, oxygen and C4F6The pressure in the working chamber is kept at 0.25 mbar; in the process, the flow rate of the process gas is 150 sccm;
4) turning on a radio frequency power supply to generate plasma in the working chamber;
5) after being excited by the surface wave plasma, the process gas molecules and atoms impact the surface of the base material and heat the base material, and the surface of the base material is activated and cleaned to form a micro-etching and fluorocarbon cross-linking structure;
6) stopping introducing the process gas, and introducing hydrophilic monomer steam into the working chamber, wherein the monomer is perfluorinated acrylate, and the flow of the monomer steam is 50 sccm; introducing carrier gas while introducing monomer steam, wherein the carrier gas is argon, and the flow of the argon is 100 sccm; during this process, the pressure of the working chamber was maintained at 0.15 mbar;
7) in the process of continuously introducing carrier gas and monomer steam, the monomer is deposited and subjected to graft copolymerization on the surface of the substrate in the surface wave plasma atmosphere for 30min, so that a continuous graft copolymerization hydrophobic film layer is formed on the surface of the substrate.
As can be seen from fig. 1, the graft copolymer film obtained in this example has a smooth wave-shaped curve and more regular peak-to-valley cycles appear in a specific region, which means that the film layer is dense.
Comparative example 1
The preparation method of the plasma graft copolymerization hydrophobic membrane layer comprises the following steps:
1) placing a substrate to be processed in a working chamber of a vacuum cavity;
2) pumping a vacuum pump until the vacuum in the working chamber reaches a preset working pressure of 0.01 mbar;
3) after the vacuum pumping is finished, introducing a process gas C into the working chamber reaching the vacuum state4F6Keeping the pressure in the working chamber at 0.25 mbar; in the process, the flow rate of the process gas is 150 sccm;
4) turning on a radio frequency power supply to generate plasma in the working chamber;
5) after being excited by the surface wave plasma, the process gas molecules and atoms impact the surface of the base material and heat the base material;
6) stopping introducing the process gas, and introducing monomer steam into the working chamber, wherein the monomer is perfluorinated acrylate, and the flow of the monomer steam is 50 sccm; introducing carrier gas while introducing monomer steam, wherein the carrier gas is argon, and the flow of the argon is 100 sccm; during this process, the pressure of the working chamber was maintained at 0.15 mbar;
7) in the process of continuously introducing carrier gas and monomer steam, the monomer is deposited and subjected to graft copolymerization on the surface of the substrate in the surface wave plasma atmosphere for 30min, so that a continuous graft copolymerization hydrophobic film layer is formed on the surface of the substrate.
It can be observed by a film thickness meter that the structure of the film obtained in comparative example 1 is loose because plasma polymerization is absent between the monomer vapor molecules and the substrate and between the monomer vapor molecules, and the monomer vapor molecules are attached to the surface of the substrate in a physical form or in a unit structure with low degree of polymerization, and thus the film structure is loose because the attachment is not strong enough and the bonding tends to break.
Example 2
The preparation method of the plasma graft copolymerization hydrophobic membrane layer comprises the following steps:
1) placing a substrate to be processed in a working chamber of a vacuum cavity;
2) pumping a vacuum pump until the vacuum in the working chamber reaches a preset working pressure of 0.01 mbar;
3) after the vacuum pumping is finished, introducing process gases into the working chamber reaching the vacuum state, wherein the process gases comprise nitrogen, oxygen and C3F6Maintaining the pressure in the working chamber at 0.25 mbar; in the process, the flow rate of the process gas is 150 sccm;
4) turning on a radio frequency power supply to generate plasma in the working chamber;
5) after being excited by the surface wave plasma, the process gas molecules and atoms impact the surface of the base material and heat the base material;
6) stopping introducing the process gas, and introducing monomer steam into the working chamber, wherein the monomer is perfluorinated acrylate, and the flow of the monomer steam is 50 sccm; introducing carrier gas while introducing monomer steam, wherein the carrier gas is argon, and the flow of the argon is 100 sccm; during this process, the pressure of the working chamber was maintained at 0.15 mbar;
7) in the process of continuously introducing carrier gas and monomer steam, the monomer is deposited and subjected to graft copolymerization on the surface of the substrate in the surface wave plasma atmosphere for 30min, so that a continuous graft copolymerization hydrophobic film layer is formed on the surface of the substrate.
Example 3
The preparation method of the plasma graft copolymerization hydrophilic film layer comprises the following steps:
1) placing a substrate to be processed in a working chamber of a vacuum cavity;
2) pumping a vacuum pump until the vacuum in the working chamber reaches a preset working pressure of 0.02 mbar;
3) after the vacuum pumping is finished, introducing process gas into the working chamber reaching the vacuum state, wherein the process gas consists of nitrogen, helium-argon mixed gas and oxygen, and the pressure in the working chamber is kept at 0.20 mbar; in the process, the flow rate of the process gas is 100 sccm;
4) starting a radio frequency power supply to generate plasma in the working chamber;
5) after being excited by the surface wave plasma, the process gas molecules and atoms impact the surface of the base material and heat the base material, and the surface of the base material is activated and cleaned to form a micro-etching and partial cross-linking structure;
6) stopping introducing the process gas, and introducing monomer steam into the working chamber, wherein the monomer is a silicon oxide compound containing hydrophilic groups such as-OH/-COO-/-COOH-/-NO-/-NH 2-/-SH-/-CO-, and the flow rate of the monomer steam is 80 sccm; introducing carrier gas while introducing monomer steam, wherein the carrier gas is argon, and the flow of the argon is 80 sccm; during this process, the pressure of the working chamber was maintained at 0.12 mbar;
7) in the process of continuously introducing carrier gas and monomer steam, the monomer is deposited on the surface of the substrate in the surface wave plasma atmosphere and undergoes graft copolymerization reaction for 30min, so that a continuous graft copolymerization hydrophilic film layer is formed on the surface of the substrate.
Example 4
The preparation method of the plasma graft copolymerization hydrophilic film layer comprises the following steps:
1) placing a substrate to be processed in a working chamber of a vacuum cavity;
2) pumping a vacuum pump until the vacuum in the working chamber reaches a preset working pressure of 0.08 mbar;
3) after the vacuum pumping is finished, introducing process gas into the working chamber reaching the vacuum state, wherein the process gas consists of nitrogen, helium-argon mixed gas and oxygen, and the pressure in the working chamber is kept at 0.10 mbar; in the process, the flow rate of the process gas is 100 sccm;
4) turning on a radio frequency power supply to generate plasma in the working chamber;
5) after being excited by the surface wave plasma, the process gas molecules and atoms impact the surface of the base material and heat the base material, and the surface of the base material is activated and cleaned to form a micro-etching and partial cross-linking structure;
6) stopping introducing the process gas, and introducing monomer steam into the working chamber, wherein the monomer is a linear alkane compound or a linear olefin unsaturated ester or an alkyl unsaturated cyclic compound containing-OH/-COO-/-COOH-/-NO-/-NH 2-/-SH-/-CO-groups, and the flow rate of the monomer steam is 80 sccm; introducing carrier gas while introducing monomer steam, wherein the carrier gas is argon, and the flow of the argon is 80 sccm; during this process, the pressure of the working chamber was maintained at 0.12 mbar;
7) in the process of continuously introducing carrier gas and monomer steam, the monomer is deposited and subjected to graft copolymerization on the surface of the substrate in the surface wave plasma atmosphere for 20min, so that a continuous graft copolymerization hydrophilic film layer is formed on the surface of the substrate.
Comparative example 2
The preparation method of the plasma graft copolymerization hydrophilic film layer comprises the following steps:
1) placing a base material to be processed in a working chamber of a vacuum cavity;
2) pumping a vacuum pump until the vacuum in the working chamber reaches a preset working pressure of 0.08 mbar;
3) after the vacuum pumping is finished, introducing process gas into the working chamber reaching the vacuum state, wherein the process gas is oxygen, and the pressure in the working chamber is kept at 0.10 mbar; in the process, the flow rate of the process gas is 100 sccm;
4) starting a radio frequency power supply to generate plasma in the working chamber;
5) after being excited by the surface wave plasma, the process gas molecules and atoms impact the surface of the base material and heat the base material, and the surface of the base material is activated and cleaned to form a micro-etching and partial cross-linking structure;
6) stopping introducing the process gas, and introducing monomer steam into the working chamber, wherein the monomer is a linear alkane compound or linear olefin unsaturated ester or alkyl unsaturated cyclic compound containing-OH/-COO-/-COOH-/-NO-/-NH 2-/-SH-/-CO-groups, and the flow rate of the monomer steam is 80 sccm; introducing carrier gas while introducing monomer steam, wherein the carrier gas is oxygen, and the flow of argon is 80 sccm; during this process, the pressure of the working chamber was maintained at 0.12 mbar;
7) in the process of continuously introducing carrier gas and monomer steam, the monomer is deposited on the surface of the substrate in the surface wave plasma atmosphere and undergoes graft copolymerization reaction for 20min, so that a continuous graft copolymerization hydrophilic film layer is formed on the surface of the substrate.
TABLE 1 Performance test Table for graft copolymer film
After the hydrophilic film layer obtained in the comparative example 3 is placed for 24 hours, the hydrophilic attenuation of the surface of the base material is obvious, and the timeliness is short. This means that only oxygen is introduced as a process gas for preparing the hydrophilic film layer, and oxidation and plasma polymerization are mainly used for the purpose, and the hydrophilic groups on the surface of the substrate are easy to invert due to time extension, air contact and the like, so that the hydrophilic property of the surface of the substrate is maintained for a short time.
TABLE 2 comparison of static contact angle of hydrophilic film layer for 12 consecutive days
The above embodiments are intended to illustrate and not to limit the scope of the invention, which is defined by the claims, but rather by the claims, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a plasma graft copolymerization hydrophobic membrane layer is characterized by comprising the following steps:
placing a base material to be processed in a working chamber and enabling the working chamber to reach a vacuum state;
introducing process gas into the working chamber reaching the vacuum state, wherein the process gas at least comprises nitrogen source gas, oxygen and fluorocarbon unsaturated hydrocarbon;
starting a power supply, generating uniform plasma in a working chamber to excite free electrons from process gas, and promoting the nitrogen oxygen group introduced to the surface of the substrate to react with the fluorocarbon unsaturated hydrocarbon to generate a micro-etching and fluorocarbon cross-linking structure beneficial to the fixation of a subsequent graft copolymerization film layer;
and stopping introducing the process gas, introducing monomer steam serving as a gas source of the graft copolymerization membrane layer into the working chamber, and depositing the monomer on the surface of the base material in the plasma atmosphere to perform graft copolymerization reaction to form the graft copolymerization hydrophobic membrane layer.
2. The method according to claim 1, wherein the process gas contains 55-80% by volume of the nitrogen source gas, 15-40% by volume of the oxygen gas, and the balance of the fluorocarbon unsaturated hydrocarbon.
3. The method according to claim 1, wherein the fluorocarbon-based unsaturated hydrocarbon is selected from C2H2F2、C2F4、C3F6、C4F8And C4F6A mixture of one or more of them.
4. The method according to claim 1, wherein the flow rate of the process gas is 20 to 200 sccm.
5. The preparation method of claim 1, wherein the monomer is one or more of fluorine substituted linear alkyl olefin unsaturated ester, fluorine substituted linear alkyl silica compound, linear alkyl olefin unsaturated ester, fluorine substituted alkyl unsaturated cyclic compound.
6. The production method according to claim 1, wherein the flow rate of the monomer vapor is 20 to 100 sccm.
7. The method according to claim 1, wherein the flow ratio of the process gas to the monomer vapor is 10-1: 5-0.5.
8. The preparation method of claim 1, wherein a carrier gas is introduced while introducing the monomer vapor, wherein the carrier gas is one or a mixture of several of helium, nitrogen, argon and hydrogen; the flow rate of the carrier gas is 50-300 sccm.
9. The production method according to claim 8, wherein the flow ratio of the monomer vapor to the carrier gas is 0.5 to 5: 1-10.
10. The production method according to claim 1, wherein the thickness of the graft copolymerization hydrophobic membrane layer is 50 to 1000 nm.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5468560A (en) * | 1994-04-19 | 1995-11-21 | The Boc Group, Inc. | Product and process for polymeric article with improved surface |
| US6342275B1 (en) * | 1993-12-24 | 2002-01-29 | Seiko Epson Corporation | Method and apparatus for atmospheric pressure plasma surface treatment, method of manufacturing semiconductor device, and method of manufacturing ink jet printing head |
| CN1467798A (en) * | 2002-06-24 | 2004-01-14 | �����ɷ� | Method for forming a polymer layer on a patterned material |
| CN101682998A (en) * | 2007-02-19 | 2010-03-24 | 克龙比123有限公司 | Printed circuit boards |
| CN102803552A (en) * | 2009-06-26 | 2012-11-28 | 东京毅力科创株式会社 | Plasma treatment method |
| CN102821873A (en) * | 2010-01-22 | 2012-12-12 | 欧洲等离子公司 | Method for the application of a conformal nanocoating by means of a low pressure plasma process |
| CN105949836A (en) * | 2016-05-13 | 2016-09-21 | 无锡荣坚五金工具有限公司 | Device and method for forming surface coating with adoption of grid control and plasma-initiated gas-phase polymerization |
| CN109622344A (en) * | 2018-12-28 | 2019-04-16 | 东南大学苏州医疗器械研究院 | The coating process of medical function coating and application |
| CN110042649A (en) * | 2019-05-20 | 2019-07-23 | 江南大学 | A kind of atmospheric pressure plasma equipment and its application arranged for fabric functional |
| CN110438475A (en) * | 2019-08-15 | 2019-11-12 | 佛山市思博睿科技有限公司 | A kind of preparation method of plasma chemical vapor deposition fabric yarn nano-sized hydrophobic film |
| CN110665768A (en) * | 2019-07-26 | 2020-01-10 | 江苏菲沃泰纳米科技有限公司 | Waterproof nano film and preparation method, application and product thereof |
| CN111519171A (en) * | 2020-02-17 | 2020-08-11 | 佛山市思博睿科技有限公司 | Hydrophobic film plating method by plasma chemical vapor deposition method with compact film layer |
-
2021
- 2021-05-18 CN CN202110536961.4A patent/CN113275217B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6342275B1 (en) * | 1993-12-24 | 2002-01-29 | Seiko Epson Corporation | Method and apparatus for atmospheric pressure plasma surface treatment, method of manufacturing semiconductor device, and method of manufacturing ink jet printing head |
| US5468560A (en) * | 1994-04-19 | 1995-11-21 | The Boc Group, Inc. | Product and process for polymeric article with improved surface |
| CN1467798A (en) * | 2002-06-24 | 2004-01-14 | �����ɷ� | Method for forming a polymer layer on a patterned material |
| CN101682998A (en) * | 2007-02-19 | 2010-03-24 | 克龙比123有限公司 | Printed circuit boards |
| CN102803552A (en) * | 2009-06-26 | 2012-11-28 | 东京毅力科创株式会社 | Plasma treatment method |
| CN102821873A (en) * | 2010-01-22 | 2012-12-12 | 欧洲等离子公司 | Method for the application of a conformal nanocoating by means of a low pressure plasma process |
| CN105949836A (en) * | 2016-05-13 | 2016-09-21 | 无锡荣坚五金工具有限公司 | Device and method for forming surface coating with adoption of grid control and plasma-initiated gas-phase polymerization |
| CN109622344A (en) * | 2018-12-28 | 2019-04-16 | 东南大学苏州医疗器械研究院 | The coating process of medical function coating and application |
| CN110042649A (en) * | 2019-05-20 | 2019-07-23 | 江南大学 | A kind of atmospheric pressure plasma equipment and its application arranged for fabric functional |
| CN110665768A (en) * | 2019-07-26 | 2020-01-10 | 江苏菲沃泰纳米科技有限公司 | Waterproof nano film and preparation method, application and product thereof |
| CN110438475A (en) * | 2019-08-15 | 2019-11-12 | 佛山市思博睿科技有限公司 | A kind of preparation method of plasma chemical vapor deposition fabric yarn nano-sized hydrophobic film |
| CN111519171A (en) * | 2020-02-17 | 2020-08-11 | 佛山市思博睿科技有限公司 | Hydrophobic film plating method by plasma chemical vapor deposition method with compact film layer |
Non-Patent Citations (1)
| Title |
|---|
| 解鹏等.等离子体引发丙烯酸在LDPE薄膜表面接枝共聚的研究（І）.《化学工业与工程技术》.2009,第30卷(第1期),第6-9页. * |
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