CN112480787B - Polymer mineral gap filler for engine containment ring and preparation method thereof - Google Patents

Polymer mineral gap filler for engine containment ring and preparation method thereof Download PDF

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Publication number
CN112480787B
CN112480787B CN202011487580.3A CN202011487580A CN112480787B CN 112480787 B CN112480787 B CN 112480787B CN 202011487580 A CN202011487580 A CN 202011487580A CN 112480787 B CN112480787 B CN 112480787B
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primer
coupling agent
silane coupling
bisphenol
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CN112480787A (en
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崔海霞
陈磊
周惠娣
陈建敏
李红轩
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Lanzhou Institute of Chemical Physics LICP of CAS
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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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • 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
    • B05D7/542—No clear coat specified the two layers being cured or baked together
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention discloses a polymerized mineral gap filler for a room-temperature curing type engine containment ring, which comprises surface glue and bottom glue, wherein the surface glue is a putty-like material formed by two-component materials, and the component A consists of bisphenol A epoxy resin, butadiene-acrylonitrile rubber and aluminum oxide; the component B consists of polyamide resin, aliphatic amine, a silane coupling agent and glass fiber powder; the component A and the component B are mixed according to the mass ratio of 2: 1-2.5: 1; the primer is an C, D bi-component material, and the component C consists of bisphenol A epoxy resin and butyl cyanide rubber; the component D consists of polyamide resin, aliphatic amine and a silane coupling agent; the C component and the D component of the primer are mixed according to the mass ratio of 1.5: 1-2: 1. The protective material has proper bonding strength, can be used for the inner surface of a containing ring of a fan casing of an engine, and has the applicable working temperature of-60-120 ℃.

Description

Polymer mineral gap filler for engine containment ring and preparation method thereof
Technical Field
The invention relates to a polymeric mineral gap filler, in particular to a polymeric mineral gap filler for a room-temperature curing type engine containment ring, and belongs to the technical field of composite materials.
Background
The rapid development of the aeronautical industry places increasing demands on aircraft engines, and high thrust, high efficiency, low fuel consumption have become an overall goal of engine design and manufacture. In order to do this, the turbine inlet gas temperature should be increased as much as possible and the clearance between the rotor and stator components should be reduced. The gas path sealing technology for reducing the clearance between the compressor, the turbine blade tip and the casing becomes an important means for improving the performance of the engine. In order to improve engine efficiency and protect blades and casings from scratch damage, a caulking agent and an abradable seal coating are introduced in the design and development of the aeroengine gas path seal to maintain a minimum gas path gap to improve engine performance. In the early days, the fan casings of low bypass ratio turbofan engines were designed as normal casings, and no containment ring was considered. By the time high bypass ratio turbofan engines developed in the late 60 s of the 20 th century, fan cases began to be designed as containment rings. According to foreign data, the coating materials used for the casing (i.e., containment ring) surrounding the fan blades include: the three materials are all applied to the containing ring, have different specific use parts and different functions and cannot be replaced mutually. The existing domestic polymer gap filler cannot meet the process and use requirements of related parts, and in order to ensure the development and application of a novel engine with a large bypass ratio, domestic related models develop domestic development and performance optimization of the polymer gap filler for the containment ring by referring to the thinking of similar products abroad so as to meet the use requirements of the related parts of the engine.
Disclosure of Invention
The invention aims to provide a polymeric mineral gap filler for an engine containment ring.
The invention relates to a polymeric mineral gap filler, which comprises surface glue and bottom glue;
the surface glue is a putty-like material composed of A, B double components, wherein the component A is composed of 20-30 wt% of bisphenol A type epoxy resin, 1-10 wt% of cyanogen butadiene rubber and 60-70 wt% of aluminum oxide; the component B comprises 30-40 wt% of polyamide resin, 0.5-5 wt% of aliphatic amine, 0.5-5 wt% of silane coupling agent and 60-70 wt% of glass fiber powder.
The primer is a putty-like material consisting of C, D bi-components; the component C consists of 80-90 wt% of bisphenol A type epoxy resin and 10-20 wt% of butadiene cyanide rubber; the component D comprises 80-99 wt% of polyamide resin, 0.5-5 wt% of aliphatic amine and 0.5-5 wt% of silane coupling agent.
In the components, bisphenol A type epoxy resin is used as a binder, the epoxy value is 0.23-0.56, and the purity is more than or equal to 98%. The thermosetting resin is one of thermosetting resins which are most widely applied, and has the characteristics of large binding power, small shrinkage rate, good corrosion resistance, excellent electrical property, good durability, easy modification, easy obtainment of raw materials and the like; epoxy groups in epoxy resin molecules are very active and can generate cross-linking reaction with various curing agents to form a high-molecular polymer with a three-dimensional network structure, so that the mechanical strength, the solvent resistance and the heat resistance are improved.
Polyamide resin and aliphatic amine are taken as curing agents, wherein the amine value of the polyamide resin is 180-220 mgKOH/g; the aliphatic amine is one of diethylenetriamine, triethylene tetramine, polyethylene polyamine and tetramethyl ethylene diamine. The low molecular weight polyamide is an excellent curing agent and toughening agent of the epoxy resin, has wider proportion with the epoxy resin, is simple and convenient to operate, can be cured at normal temperature, has strong cohesive force and good toughness, and is obviously superior to the common monomer amine curing agent. The aliphatic amine is one of diethylenetriamine, triethylene tetramine, polyethylene polyamine and tetramethyl ethylene diamine. The aliphatic amine molecule contains longer unsaturated aliphatic hydrocarbon carbon chain and active groups such as amino, carboxyl, amido and the like, and can generate crosslinking and solidification with the epoxy resin molecule. The aliphatic hydrocarbon carbon chain can play an internal plasticizing role during crosslinking, so that the impact strength of a cured product is greatly improved, the shrinkage of the cured product is small, and the cured product has better bonding strength, flexibility, insulativity and chemical resistance.
The liquid nitrile butadiene rubber is taken as a toughening agent, and the acrylonitrile content of the liquid nitrile butadiene rubber is 40 percent.
The aluminum oxide and the glass fiber powder are used as fillers and are used as high-temperature-resistant and flame-retardant reinforcing fillers in the invention.
The silane coupling agent is gamma-glycidyl ether propyl trimethoxy silane, wherein the silane oxygen radical has reactivity to inorganic substances, and the organic functional group has reactivity or compatibility to organic substances. Therefore, when the silane coupling agent is between the inorganic and organic interfaces, a bonding layer of an organic matrix-the silane coupling agent-the inorganic matrix can be formed, and two materials with different properties are connected together, so that the performance of the composite material is improved, and the bonding strength is increased.
The preparation method of the polymeric mineral caulking agent comprises the following steps:
and (3) treatment of the filler: baking aluminum oxide and glass fiber powder at 280 +/-5 ℃ for 2h to remove moisture;
surface glue: weighing bisphenol A epoxy resin, butadiene-acrylonitrile rubber and aluminum oxide according to the proportion of the component A, and kneading the mixture in a kneading machine for 1-2 hours; and weighing the polyamide resin, the aliphatic amine, the silane coupling agent and the glass fiber powder according to the proportion of the component B, and uniformly stirring by using a stirrer.
Primer coating: weighing bisphenol A type epoxy resin and butadiene-acrylonitrile rubber according to the proportion of the component C, and stirring and mixing uniformly; and weighing the polyamide resin, the aliphatic amine and the silane coupling agent according to the proportion of the component D, and uniformly mixing.
When in use, the components A and B of the face glue are weighed and mixed uniformly according to the mass ratio of 2: 1-2.5: 1; the C component and the D component of the primer are weighed according to the mass ratio of 1.5: 1-2: 1) and are uniformly mixed.
During construction, a blade coating method is adopted, a layer of primer is coated on the surface of the part, and then a layer of face glue is coated on the primer to ensure that the whole primer layer is covered; and (5) fully curing.
Curing conditions are as follows: the environment temperature is 18-23 ℃, and the mixture is placed for at least 48 hours; the temperature of the environment is 23-35 ℃, and the product is required to be placed for at least 24 h. The properties are optimal after sufficient post-curing (typically 7 days).
The polymer mineral caulking agent prepared by the invention has the following product performance:
1. the appearance of the paint is as follows: the surface glue and the bottom glue have no foreign impurities.
2. Appearance of the coating: uniform and continuous, no obvious air bubble, no bulge and no peeling, and the block does not fall off when being mechanically added.
3. Coating tensile strength: not less than 5 MPa.
4. Storage life: the product is stored under sealed condition at room temperature, and the storage period is 12 months.
The polymeric mineral gap filler has proper bonding strength, uniform and continuous coating, does not fall off during machining, can be used for the inner surface of the containment ring of the fan casing of the engine, and has the applicable working temperature of-60-120 ℃. The product obtained by the invention has good effect when being applied to an aeroengine.
Detailed Description
The components, preparation process and properties of the polymeric mineral caulk of the present invention are further illustrated by the following specific examples.
Example 1
Surface glue: weighing 83g of bisphenol A epoxy resin with an epoxy value of 0.48-0.54, 32g of butadiene-acrylonitrile rubber and 242g of aluminum oxide, and kneading in a kneader for 2h to obtain a surface glue A component; weighing 90g of polyamide resin, 3g of diethylenetriamine, 4g of silane coupling agent and 183g of glass fiber powder, and uniformly stirring in a stirrer to obtain the component B of the surface adhesive. The mass ratio of the component A to the component B of the surface glue is 2: 1;
primer coating: weighing 84g of bisphenol A epoxy resin with the epoxy value of 0.48-0.54 and 16g of butadiene-acrylonitrile rubber, and uniformly stirring in a stirrer to obtain a primer C component; and weighing 95g of polyamide resin, 2g of diethylenetriamine and 3g of silane coupling agent, and uniformly stirring in a stirrer to obtain the component D of the primer. The mass ratio of the components C and D of the primer is 1.5: 1;
uniformly mixing the components A and B of the surface glue and the components C and D of the primer respectively in a mechanical or manual mode. A thin layer of primer is firstly coated on a test piece in a scraping way, and then a layer of face glue is coated on the primer. The tensile strength of the cured coating was: 9 MPa.
Example 2
Surface glue: weighing 91g of bisphenol A epoxy resin with an epoxy value of 0.55-0.56, 16g of butadiene-acrylonitrile rubber and 250g of aluminum oxide, and kneading in a kneader for 2h to obtain a surface glue A component; and weighing 95g of polyamide resin, 4g of diethylenetriamine, 6g of silane coupling agent and 175g of glass fiber powder, and uniformly stirring in a stirrer to obtain the surface adhesive B component. The mass ratio of the component A to the component B of the surface glue is 2.25: 1;
primer coating: weighing 90g of bisphenol A type epoxy resin with the epoxy value of 0.55-0.56 and 10g of butadiene-acrylonitrile rubber, and uniformly stirring in a stirrer to obtain a primer C component; 93g of polyamide resin, 3g of diethylenetriamine and 4g of silane coupling agent are weighed and put in a stirrer to be uniformly stirred, so as to obtain the primer component B. The mass ratio of the components C and D of the primer is 1.7: 1;
and respectively and mechanically or manually mixing the components A and B of the surface glue and the components C and D of the primer uniformly. A thin layer of primer is firstly coated by blade coating, and then a layer of face glue is coated on the primer. The tensile strength of the cured coating was: 11 MPa.
Example 3
Surface glue: weighing 108g of bisphenol A epoxy resin with an epoxy value of 0.41-0.47, 35g of butadiene-acrylonitrile rubber and 214g of aluminum oxide, and kneading in a kneader for 2h to obtain a surface glue A component; weighing 98g of polyamide resin, 5g of diethylenetriamine, 7g of silane coupling agent and 172g of glass fiber powder, and uniformly stirring in a stirrer to obtain the component B of the surface adhesive. The mass ratio of the component A to the component B of the surface glue is 2.5: 1;
primer coating: weighing 80g of bisphenol A type epoxy resin with the epoxy value of 0.41-0.47 and 20g of butadiene-acrylonitrile rubber, and uniformly stirring in a stirrer to obtain a primer A component; and weighing 90g of polyamide resin, 4g of diethylenetriamine and 6g of silane coupling agent, and uniformly stirring in a stirrer to obtain the primer component B. The mass ratio of the components C and D of the primer is 2: 1;
and respectively and mechanically or manually mixing the components A and B of the surface glue and the components C and D of the primer uniformly. A thin layer of primer is firstly coated by blade coating, and then a layer of face glue is coated on the primer. The tensile strength of the cured coating was: 12 MPa.
In each of the above examples, the silane coupling agent used was gamma-glycidoxypropyltrimethoxysilane.
The curing conditions were: the environment temperature is 18-23 ℃, and the mixture is required to be placed for at least 48 h; the environment temperature is 23-35 ℃, and the mixture is required to be placed for at least 24 hours. The properties are optimal after sufficient post-curing (typically 7 days).

Claims (1)

1. A polymeric mineral caulking agent for an engine containment ring is prepared by the following raw material components and processes:
the raw material components are as follows: comprises surface glue and bottom glue; the surface glue is a putty-like material composed of A, B double components, and the component A is composed of 20-30 wt% of bisphenol A epoxy resin, 1-10 wt% of liquid nitrile rubber and 60-70 wt% of aluminum oxide; the component B consists of 30-40 wt% of polyamide resin, 0.5-5 wt% of aliphatic amine, 0.5-5 wt% of silane coupling agent and 60-70 wt% of glass fiber powder, and the sum of the raw materials in the component B is 100 wt%; the component A and the component B of the surface glue are mixed according to the mass ratio of 2: 1-2.5: 1; the primer consists of C, D bi-components, and the component C consists of 80-90 wt% of bisphenol A epoxy resin and 10-20 wt% of liquid nitrile rubber; the component D consists of 80-99 wt% of polyamide resin, 0.5-5 wt% of aliphatic amine and 0.5-5 wt% of silane coupling agent, and the sum of the raw materials in the component D is 100 wt%; the C and D components of the primer are mixed according to the mass ratio of 1.5: 1-2: 1;
the preparation method comprises the following steps:
and (3) treatment of the filler: baking and dehumidifying the aluminum oxide and the glass fiber powder at 275-285 ℃;
preparing the surface glue: weighing bisphenol A epoxy resin, liquid nitrile rubber and aluminum oxide according to the proportion of the component A, and kneading the components in a kneader for 1-2 h; weighing the polyamide resin, the aliphatic amine, the silane coupling agent and the glass fiber powder according to the proportion of the component B, and uniformly stirring by using a stirrer;
preparing a primer: weighing bisphenol A type epoxy resin and liquid nitrile rubber according to the proportion of the component C, and stirring and mixing uniformly; weighing polyamide resin, aliphatic amine and a silane coupling agent according to the proportion of the component D, and uniformly mixing;
during construction, a blade coating method is adopted, a layer of primer is coated on the surface of the part, and then a layer of face glue is coated on the primer to ensure that the whole primer layer is covered; fully curing to obtain the product;
the epoxy value of the bisphenol A type epoxy resin is 0.23-0.56, and the purity is more than or equal to 98%; the acrylonitrile content of the liquid nitrile rubber is 40 percent; the amine value of the polyamide resin is 180-220 mgKOH/g; the aliphatic amine is one of diethylenetriamine, triethylene tetramine, polyethylene polyamine and tetramethyl ethylene diamine; the silane coupling agent is gamma-glycidyl ether propyl trimethoxy silane.
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CN105567145A (en) * 2016-03-15 2016-05-11 南京诺邦新材料有限公司 Double-component structural adhesive and preparation method thereof
CN109837032A (en) * 2017-11-27 2019-06-04 中国科学院大连化学物理研究所 A kind of structure and application of metal surface high tensile rapid curing adhesive
CN109439245A (en) * 2018-09-11 2019-03-08 法施达(大连)工程材料有限公司 A kind of two-component epoxy interface adhesive and preparation method thereof
CN109679444A (en) * 2018-11-16 2019-04-26 中国航发西安动力控制科技有限公司 The wear-resistant coating of mechanical surface and preparation method in high molecular weight gas atmosphere

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