CN106563629B - Pre-treatment primer for thermoplastic pressing of polychlorotrifluoroethylene and metal substrate and preparation method thereof - Google Patents
Pre-treatment primer for thermoplastic pressing of polychlorotrifluoroethylene and metal substrate and preparation method thereof Download PDFInfo
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- CN106563629B CN106563629B CN201610997598.5A CN201610997598A CN106563629B CN 106563629 B CN106563629 B CN 106563629B CN 201610997598 A CN201610997598 A CN 201610997598A CN 106563629 B CN106563629 B CN 106563629B
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- polychlorotrifluoroethylene
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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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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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
- 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
- B05D3/02—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 baking
- B05D3/0254—After-treatment
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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
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/10—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an adhesive surface
-
- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/544—No clear coat specified the first layer is let to dry at least partially before applying the second layer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- 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
- B05D2451/00—Type of carrier, type of coating (Multilayers)
-
- 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
- B05D2506/00—Halogenated polymers
- B05D2506/10—Fluorinated polymers
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention provides a preparation method of a primer for thermoplastic pressing pretreatment of polychlorotrifluoroethylene and a metal substrate, which comprises the following steps: 2.6-7.5% of chromium trioxide by mass percent; 30-35% of distilled water by mass; 3.4-9.5% of phosphoric acid by mass percent; 45-59% of polychlorotrifluoroethylene dispersion liquid. The invention adopts a surface treatment method of coating the transition primer on the surface of the metal matrix adhered with the polychlorotrifluoroethylene, can effectively increase the bonding strength of the polychlorotrifluoroethylene and the metal, and simultaneously, the polychlorotrifluoroethylene has the functions of sealing performance and medium resistance.
Description
Technical Field
The invention relates to a primer formula for thermoplastic pressing pretreatment of polychlorotrifluoroethylene and metal for aerospace products, and also relates to a preparation method of the primer, belonging to the fields of polymer-metal matrix composite materials and new materials and being applied to aerospace valves and valve products.
Background
The valve rod type product material in the liquid hydrogen and liquid oxygen filling valve of the carrier rocket in China is metal, and when the filling valve moves, the metal is easy to wear, so that movement clamping stagnation is caused. In addition, debris and other redundant materials generated by metal abrasion enter the guide gap, and the movement of the filling valve is easy to be blocked.
The movement flexibility of the liquid hydrogen and liquid oxygen filling valve of a new generation carrier rocket is one of the keys of reliable work of the valve, therefore, a fluoroplastic lining is bonded on the valve rod, compared with a metal-metal matching pair without the lining, the lining can not only prevent intermetallic viscous abrasion, but also has resistance capacity to the excess, and even if the excess enters a gap of the valve rod, the influence of the excess on the movement of the guide rod can be reduced or eliminated, so that the movement flexibility of the filling valve is improved.
The valve rod product is a key part of the filling valve, and the valve rod is coated with polychlorotrifluoroethylene to protect the valve rod and improve the reliability of the valve. The traditional process is to coat a layer of polychlorotrifluoroethylene on the valve rod by a cold bonding method. The polychlorotrifluoroethylene fluoroplastic has chemically inert surface due to the characteristics of molecular composition, belongs to a typical material difficult to bond, and is difficult to bond by using a general adhesive without special surface treatment. Even if the adhesive is bonded, the reliability is not high, and the problem of debonding and the like is likely to occur in the later use.
Disclosure of Invention
The invention provides a preparation method of a primer for thermoplastic pressing pretreatment of polychlorotrifluoroethylene and a metal matrix, which adopts a transition primer to treat the surface of the metal matrix to obtain the polychlorotrifluoroethylene with the bonding strength of more than 14Mpa with the metal matrix.
The technical scheme for realizing the purpose of the invention is as follows: a primer for thermoplastic pressing pretreatment of polychlorotrifluoroethylene and a metal substrate, comprising: 2.6-7.5% of chromium trioxide by mass percent; 30-35% of distilled water by mass; 3.4-9.5% of phosphoric acid by mass percent; 45-59% of polychlorotrifluoroethylene dispersion liquid.
A primer for the pre-thermoplastic press treatment of polychlorotrifluoroethylene with a metal substrate as described above, which is suitable for use in a metal substrate comprising aluminum, steel, or GH4169 superalloy.
The invention relates to a preparation method of a primer for thermoplastic pressing pretreatment of polychlorotrifluoroethylene and a metal substrate, which comprises the following steps:
(1) weighing chromium trioxide, distilled water and phosphoric acid; dissolving chromic anhydride in distilled water, adding phosphoric acid, and stirring to obtain mixed acid solution; then weighing polychlorotrifluoroethylene dispersion liquid; wherein the mass percent of the chromium trioxide is 2.6-7.5%; 30-35% of distilled water by mass; 3.4-9.5% of phosphoric acid by mass percent; 45-59% of polychlorotrifluoroethylene dispersion liquid by mass;
(2) uniformly coating the mixed acid liquid obtained in the step (1) on the surface of a metal piece in a coating mode, and repeatedly coating the mixed acid liquid for 1-3 times after the mixed acid liquid is dried;
(3) after the mixed acid solution coated on the surface of the metal piece in the step (2) is dried, uniformly coating the polychlorotrifluoroethylene dispersion on the surface of the metal piece, and after the polychlorotrifluoroethylene dispersion is dried, repeatedly coating the polychlorotrifluoroethylene dispersion for 1-3 times;
(4) then, putting the dried metal piece into an oven at 50-60 ℃ to dry for 15-60 min; and storing the dried metal piece in a clean oven or a dryer for later use.
The preparation method of the primer before thermoplastic pressing of the polychlorotrifluoroethylene and the metal substrate is described, wherein the primer is suitable for the metal substrate comprising aluminum, steel or GH4169 high-temperature alloy.
The invention has the following effects:
the invention realizes the reliable bonding of the polychlorotrifluoroethylene and the metal matrix by a thermoplastic molding method aiming at the structural characteristics of products such as a valve rod, a composite ejector rod, a valve clack and the like in the filling valve and the physical and chemical properties of the polychlorotrifluoroethylene. The surface treatment method of coating the transition primer on the metal substrate with the polychlorotrifluoroethylene can effectively increase the bonding strength of the polychlorotrifluoroethylene and the metal. The primer has the functions of improving the adhesive force of the surface of the metal matrix, sealing micropores on the surface of the metal matrix, and enabling the polytrifluorochloroethylene to fully permeate into the special geometric structure of the surface of the matrix in a molten state by utilizing the mechanisms of mechanical interlocking and physical adsorption so as to attach to the highly expanded surface area and form the effect equivalent to anchoring.
Compared with the primer which is not adopted, the acidic transition primer which takes the polychlorotrifluoroethylene as the main component is adopted, the average tearing strength of the polychlorotrifluoroethylene and the metal matrix is higher than 20MPa, which shows that the tearing strength of the polychlorotrifluoroethylene and the metal matrix is greatly improved by the transition primer. When the transition primer is applied to products such as a valve rod, a composite ejector rod and a valve clack in a filling valve, under the liquid nitrogen environment, the polytrifluorochloroethylene bushing does not have the phenomena of debonding, cracking and the like, the bonding reliability of polytrifluorochloroethylene on the products such as the valve rod, the composite ejector rod and the valve clack in the filling valve is verified, the motion guide effect of the filling valve under special working conditions can be met, and the motion clamping stagnation problem possibly occurring in the filling valve is solved. After the rubber sealing ring is used in a rocket mechanism, the metal matrix is well protected by utilizing the wear resistance of the polychlorotrifluoroethylene in the motion process of a filling valve, and meanwhile, the polychlorotrifluoroethylene plays roles in sealing performance and medium resistance.
Detailed Description
The preparation method of the primer before thermoplastic pressing of polychlorotrifluoroethylene and a metal substrate according to the present invention is further described with reference to the following specific examples.
Example 1:
(1) 1g of chromium trioxide (chromic anhydride), 5g of distilled water and 1.3g of phosphoric acid were weighed.
(2) Dissolving chromic anhydride in distilled water, adding phosphoric acid, and stirring to obtain mixed acid solution.
(3) 7.3g of the polychlorotrifluoroethylene dispersion were weighed into another beaker.
(4) Dipping a small amount of mixed acid liquor by using a clean brush pen, coating the mixed acid liquor on the sand blowing surface of the metal piece in a thin and uniform manner, and carrying out coating for the 2 nd time after the metal piece coated with the acid liquor for the 1 st time is dried.
(5) After the metal piece coated with the mixed acid solution for 2 times is dried in the air, the polychlorotrifluoroethylene dispersion is thinly and uniformly coated on the sand-blown surface of the metal piece, and the coating times are 2 times.
(6) And (3) drying the metal piece coated with the polychlorotrifluoroethylene primer in an oven at 50-60 ℃ for half an hour.
The primer obtained by this method has a final hot-pressed polychlorotrifluoroethylene-metal average tear strength of 28.6 MPa.
Example 2:
(1) 1g of chromium trioxide (chromic anhydride), 5.5g of distilled water and 1.3g of phosphoric acid were weighed.
(2) Dissolving chromic anhydride in distilled water, adding phosphoric acid, and stirring to obtain mixed acid solution.
(3) 7.8g of the polychlorotrifluoroethylene dispersion were weighed into another beaker.
(4) Dipping a small amount of mixed acid liquor by using a clean brush pen, coating the mixed acid liquor on the sand blowing surface of the metal piece in a thin and uniform manner, and carrying out coating for the 2 nd time after the metal piece coated with the acid liquor for the 1 st time is dried.
(5) After the metal piece coated with the mixed acid solution for 2 times is dried in the air, the polychlorotrifluoroethylene dispersion is thinly and uniformly coated on the sand-blown surface of the metal piece, and the coating times are 2 times.
(6) And (3) drying the metal piece coated with the polychlorotrifluoroethylene primer in an oven at 55 ℃ for half an hour.
The primer obtained by this method has a final thermoplastically pressed polychlorotrifluoroethylene-metal average tear strength of 23 MPa.
Example 3:
(1) 0.8g of chromium trioxide (chromic anhydride), 4.5g of distilled water and 1.0g of phosphoric acid were weighed out.
(2) Dissolving chromic anhydride in distilled water, adding phosphoric acid, and stirring to obtain mixed acid solution.
(3) 6.9g of the polychlorotrifluoroethylene dispersion were weighed into another beaker.
(4) Dipping a small amount of mixed acid liquor by using a clean brush pen, coating the mixed acid liquor on the sand blowing surface of the metal piece in a thin and uniform manner, and carrying out coating for the 2 nd time after the metal piece coated with the acid liquor for the 1 st time is dried.
(5) After the metal piece coated with the mixed acid solution for 2 times is dried in the air, the polychlorotrifluoroethylene dispersion is thinly and uniformly coated on the sand-blown surface of the metal piece, and the coating times are 2 times.
(6) And (3) drying the metal piece coated with the polychlorotrifluoroethylene primer in an air drying oven at 60 ℃ for 15 min.
The primer is obtained by the method, and the final hot-pressed polychlorotrifluoroethylene-metal average tear strength is 22 MPa.
Example 4:
(1) 1g of chromium trioxide (chromic anhydride), 13.5g of distilled water and 1.3g of phosphoric acid were weighed.
(2) Dissolving chromic anhydride in distilled water, adding phosphoric acid, and stirring to obtain mixed acid solution.
(3) 22.8g of the polychlorotrifluoroethylene dispersion were weighed into another beaker.
(4) Dipping a small amount of mixed acid liquor by using a clean brush pen, coating the mixed acid liquor on the sand blowing surface of the metal piece in a thin and uniform manner, and carrying out coating for the 3 rd time after the metal piece coated with the acid liquor for the 1 st time is dried.
(5) After the metal piece coated with the mixed acid solution for 3 times is dried in the air, the polychlorotrifluoroethylene dispersion is thinly and uniformly coated on the sand-blown surface of the metal piece, and the coating times are 3 times.
(6) And (3) drying the metal piece coated with the polychlorotrifluoroethylene primer in an air drying oven at 50 ℃ for 1 hour.
By this method a primer is obtained, and the final thermoplastically pressed polychlorotrifluoroethylene-metal product has an average tear strength of 26.9 MPa.
The metal member in the above examples 1 to 4 may be aluminum, steel, or GH4169 high temperature alloy.
Claims (2)
1. A preparation method of a primer before thermoplastic pressing of polychlorotrifluoroethylene and a metal substrate is characterized in that: the method comprises the following steps:
(1) weighing chromium trioxide, distilled water and phosphoric acid; dissolving chromic anhydride in distilled water, adding phosphoric acid, and stirring to obtain mixed acid solution;
then weighing polychlorotrifluoroethylene dispersion liquid;
wherein the mass percent of the chromium trioxide is 2.6-7.5%; 30-35% of distilled water by mass; 3.4-9.5% of phosphoric acid by mass percent; 45-59% of polychlorotrifluoroethylene dispersion liquid by mass; the total mass percent of the above substances is 100%;
(2) uniformly coating the mixed acid liquid obtained in the step (1) on the surface of a metal piece in a coating mode, and repeatedly coating the mixed acid liquid for 1-3 times after the mixed acid liquid is dried;
(3) after the mixed acid solution coated on the surface of the metal piece in the step (2) is dried, uniformly coating the polychlorotrifluoroethylene dispersion on the surface of the metal piece, and after the polychlorotrifluoroethylene dispersion is dried, repeatedly coating the polychlorotrifluoroethylene dispersion for 1-3 times;
(4) then, putting the dried metal piece into an oven at 50-60 ℃ to dry for 15-60 min; and storing the dried metal piece in a clean oven or a dryer for later use.
2. The method for preparing the primer used before the thermoplastic pressing of the polychlorotrifluoroethylene and the metal substrate according to claim 1, wherein: the primer is suitable for metal substrates comprising aluminum, steel, or GH4169 superalloy.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610997598.5A CN106563629B (en) | 2016-11-14 | 2016-11-14 | Pre-treatment primer for thermoplastic pressing of polychlorotrifluoroethylene and metal substrate and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610997598.5A CN106563629B (en) | 2016-11-14 | 2016-11-14 | Pre-treatment primer for thermoplastic pressing of polychlorotrifluoroethylene and metal substrate and preparation method thereof |
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| CN106563629A CN106563629A (en) | 2017-04-19 |
| CN106563629B true CN106563629B (en) | 2020-11-20 |
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| CN109206990B (en) * | 2018-10-30 | 2021-04-13 | 首都航天机械有限公司 | Primer as well as preparation method and application thereof |
| CN111570229A (en) * | 2020-05-26 | 2020-08-25 | 梦天家居集团股份有限公司 | Roller coating process for UV roller color primer and water-based white finish |
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Non-Patent Citations (1)
| Title |
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| 氟树脂的乳液喷涂;顾元栋;《工程塑料应用》;19890228(第2期);第24-29页 * |
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