CN101402791A - Low-density high-strength nano-polyurethane wind wheel leaf blade composite material - Google Patents
Low-density high-strength nano-polyurethane wind wheel leaf blade composite material Download PDFInfo
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- CN101402791A CN101402791A CNA2008102027855A CN200810202785A CN101402791A CN 101402791 A CN101402791 A CN 101402791A CN A2008102027855 A CNA2008102027855 A CN A2008102027855A CN 200810202785 A CN200810202785 A CN 200810202785A CN 101402791 A CN101402791 A CN 101402791A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/70—Wind energy
- Y02E10/72—Wind turbines with rotation axis in wind direction
Abstract
The invention relates to a low-density high-strength nanometer polyurethane wind wheel blade composite material which comprises an A component and a B component. Calculated in accordance with the parts by weight, the A component includes: 20 portions to 50 portions of polyester polyol; 10 portions to 60 portions of polyether glycol; 10 portions to 25 portions of vegetable oil; 10 portions to 20 portions of inorganic nanometer material; 0.01 portion to 1 portion of catalyzer; 0.01 portion to 1 portion of antioxidant; and 10 portions to 30 portions of fiber reinforced material; the B component includes: polydiphenyl diisocyanate, toluol diisocyanate or isocyanate prepolymer; and the weight ratio of the fiber-reinforced-material-removed A component and the B component is that A : B equals to 1:1 to 1.5. The composite material overcomes the problems of high density, low temperature resistance, easy aging and the like of the current unsaturated resin and epoxy resin materials, is made by taking the nanometer material, fiberglass and volcanic rock fiber as reinforced materials and compounding with polyurethane; the composite material has special properties such as low density, stretching, shearing, high strength, low temperature resistance, corrosion resistance and the like, and is applicable to application of the wind wheel blade and the engineering structural material in wind power generation.
Description
Technical field
The present invention relates to a kind of low-density high-strength nano-polyurethane wind wheel leaf blade composite material, with unsaturated polyester, epoxide resin material contrast, have that density is low, tensile shear strength is high, heatproof is low, corrosion-resistant, be applicable to the making of wind wheel blade and structural timber in the wind-power electricity generation.
Background technology
At present, the wind wheel blade that wind-power electricity generation adopted is that material is made with unsaturated polyester, Resins, epoxy basically, exists that blade density is big, efficient is low, and particularly physical strength obviously reduces under low temperature environment.In order to improve the efficient of wind-power electricity generation, a kind of low density, novel material low temperature resistant, that intensity is high are badly in need of producing.
Summary of the invention
In order to solve the problem that prior art exists, the invention provides the nano-polyurethane wind-force impeller sheet matrix material that the low density of moulding, high strength, good weatherability are reacted in a kind of two-pack cast.
Another technical problem to be solved by this invention is to provide the preparation method of above-mentioned low-density high-strength nano-polyurethane wind-force impeller sheet matrix material.
A technical problem more to be solved by this invention is to provide the purposes of above-mentioned low-density high-strength nano-polyurethane wind-force impeller sheet matrix material.
The present invention addresses the above problem the technical scheme of being taked: the geometry feature of utilizing inorganic nano material, the stratiform micropore permeation, adsorptivity to organic molecule, superficiality and volumetric, combine with the continuous enhancing of glass fibre or volcanics fiber, as strongthener, constitute high strength, low density, structured material that heatproof is low with urethane.
A kind of low-density high-strength nano-polyurethane wind wheel leaf blade composite material is the two-pack matrix material, comprises A component and B component, comprise by weight,
The A component:
Polyester polyol 20～50
Polyether glycol 10～60
Vegetables oil 10～25
Inorganic nano material 10～20
Catalyzer 0.01～1
Antioxidant 0.01～1
Fiber reinforced material 10～30;
The B component:
Poly-diphenylmethanediisocyanate (poly-MDI), tolylene diisocyanate (TDI), many methylenebis phenyl isocyanates, adjacent ditolyl vulcabond, polymethylene multi-phenenyl isocyanate or isocyanic ester performed polymer;
Removing the A component of fiber reinforced material and the weight ratio of B component is A: B=1: 0.5～1.5.
Concrete, in the A component, the consumption of polyester polyol can be 20,25,30,35,40,45 or 50 weight parts; The consumption of polyether glycol can be 10,20,30,40,50 or 60 weight parts; The consumption of vegetables oil can be 10,12,15,18,20,22 or 25 weight parts; The consumption of inorganic nano material can be 10,12,14,16,18 or 20 weight parts; Catalyst consumption can be 0.01,0.05,0.1,0.2,0.3,0.5,0.8 or 1 weight part; Antioxidant can be 0.01,0.05,0.1,0.2,0.3,0.5,0.8 or 1 weight part; Fiber reinforced material can be 10,15,20,25 or 30 weight parts;
In the B component, the consumption of poly-diphenylmethanediisocyanate, tolylene diisocyanate, many methylenebis phenyl isocyanates, adjacent ditolyl vulcabond, polymethylene multi-phenenyl isocyanate or isocyanic ester performed polymer can be specifically as follows 50,60 for 50～150 weight parts, 70,80,90,100,110,120,130,140 or 150 weight parts;
Remove the A component of fiber reinforced material and the weight ratio of B component and be specifically as follows 0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4 or 1.5: 1.
On the basis of such scheme, in the A component, described polyester polyol or polyether glycol are the terminal hydroxy group polyvalent alcohol, are polyfunctionality.The hydroxyl value of described polyester polyol is 50～500, and functionality is 2～3; The hydroxyl value of described polyether glycol is 100～900, and functionality is 2～5.
Described vegetables oil is a kind of in natural Viscotrol C, the modified castor oil.
Described inorganic nano material is a montmorillonite-based nano level super-fine material, and its particle diameter is 30～100nm.
Described catalyzer is that amines catalyst comprises triethylenediamine, tetramethyl-Alkylenediamine, dimethylcyclohexylamine, and the metal species catalyzer comprises a kind of or its combination in dibutyl tin laurate, stannous octoate, mercaptan two fourth tin, the dibutyltin diacetate.
Described antioxidant is a tetramethylene (3,5-di-t-butyl-4-hydroxy phenylpropionic acid) methyl esters, triglycol two-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], 2, a kind of or its combination in 6-di-tert-butyl-4-methy phenol, the 2,6 ditertiary butyl p cresol.
Described fiber reinforced material is glass fibre and/or volcanics fiber.
In the B component, described isocyanic ester performed polymer comprises by weight,
Terminal hydroxy group polyvalent alcohol 20～70
Vegetables oil 5～20
Diphenylmethanediisocyanate 20～80,
The terminal hydroxy group polyvalent alcohol is polyester polyol or polyether glycol, and functionality is 2～3; Vegetables oil is a kind of in natural Viscotrol C, the modified castor oil; Described diphenylmethanediisocyanate is 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 2, a kind of or its combination in 2 '-diphenylmethanediisocyanate, the adjacent tolylene diisocyanate, functionality is 2～2.1.
Concrete, the consumption of terminal hydroxy group polyvalent alcohol can be 20,25,30,35,40,45,50,55,60,65 or 70 weight parts; The consumption of vegetables oil can be 5,8,10,12,15 or 20 weight parts; The consumption of vulcabond can be 20,30,40,50,60,70 or 80 weight parts.
Described B component isocyanic ester performed polymer is by the terminal hydroxy group polyvalent alcohol, and vegetables oil is made with the diphenylmethanediisocyanate reaction.The preparation method is: with the terminal hydroxy group polyvalent alcohol, vegetables oil places reactor, adds diphenylmethanediisocyanate, stirs and heats to 70～120 ℃, and insulated and stirred 0.5～2 hour is to reacting completely.
The preparation method of low-density high-strength nano-polyurethane wind wheel leaf blade composite material of the present invention is:
1, remove the preparation of the A component of fiber reinforced material:
Take by weighing each component by above-mentioned prescription, put into agitator, add polyester polyol, polyether glycol, vegetables oil, inorganic nano material, catalyzer, antioxidant then, mixed 1～2 hour, make the A component;
2, the preparation of B component isocyanic ester performed polymer:
With the terminal hydroxy group polyvalent alcohol, vegetables oil places reactor, stirs and heats to 70～120 ℃, adds the diphenylmethanediisocyanate insulated and stirred 0.5～2 hour, to reacting completely, is cooled to normal temperature, makes the B component;
Select poly-diphenylmethanediisocyanate, tolylene diisocyanate, many methylenebis phenyl isocyanates, adjacent ditolyl vulcabond or polymethylene multi-phenenyl isocyanate for use as the B component, then need not special preparation, purchase gets final product;
3, casting
With fiber reinforced material, glass fibre and/or volcanics fiber are positioned in the mould, after with the A component of above-mentioned preparation and B component isocyanic ester performed polymer by weight A: B=1: 0.5～1.5 cast, crosslinking reaction obtains high-strength nano-polyurethane wind-force impeller sheet matrix material of the present invention.
Purposes at above-mentioned low-density high-strength nano-polyurethane wind-force impeller sheet matrix material is used for wind-power electricity generation wind wheel blade and railway, bridge construction structured material.
The present invention is a response type bicomponent high-strength degree nano-polyurethane wind-force impeller sheet matrix material, and the reaction shaping speed is fast, utilizes reaction injection molding machine tool equipment to pour into a mould during application; With existing unsaturated polyester, properties such as Resins, epoxy wind-force impeller sheet matrix material contrast has that density is low, a stretching, shearing, intensity height, and is low temperature resistant, corrosion-resistant, be applicable to wind wheel blade and railway in the wind-power electricity generation, the application of structural timbers such as bridge.
The invention has the beneficial effects as follows:
1, the present invention utilizes inorganic nano material, glass fibre and so on to combine as strongthener, and the blade mechanical strength of moulding is significantly improved;
2, the density of blade reduces, and the utilising efficiency of wind-force is improved;
3, the consumption of organic resin reduces, and cost reduces;
4, utilize the low characteristic of polyurethane material heatproof, use temperature reduces, and is useful in-50～120 ℃ the environment to use;
5, resin does not contain any organic solvent, and objectionable impuritiess such as phenol are harmless nontoxic, environmentally safe;
6, curing speed is fast, and the production efficiency height need not to be heating and curing, and is energy-conservation.
Embodiment
A kind of low-density high-strength nano-polyurethane wind wheel leaf blade composite material is the two-pack matrix material, comprises A component and B component, comprise by weight,
The A component:
Polyester polyol 20～50
Polyether glycol 10～60
Vegetables oil 10～25
Inorganic nano material 10～20
Catalyzer 0.01～1
Antioxidant 0.01～1
Fiber reinforced material 10～30;
The B component:
Poly-diphenylmethanediisocyanate, tolylene diisocyanate, many methylenebis phenyl isocyanates, adjacent ditolyl vulcabond, polymethylene multi-phenenyl isocyanate or isocyanic ester performed polymer
Remove the A component and the weight ratio A of B component: the B=1: 0.5～1.5 of fiber reinforced material.
Select the isocyanic ester performed polymer in the B component for use, comprise by weight,
Terminal hydroxy group polyvalent alcohol 20～70
Vegetables oil 5～20
Diphenylmethanediisocyanate 20～80,
The terminal hydroxy group polyvalent alcohol is polyester polyol or polyether glycol, and functionality is 2～3; Vegetables oil is a kind of in natural Viscotrol C, the modified castor oil; Diphenylmethanediisocyanate is 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 2,2 '-diphenylmethanediisocyanate, adjacent tolylene diisocyanate.
Embodiment 1
1, removes the preparation of the A component of fiber reinforced material
Get polyester polyol 20 weight parts, polyether glycol 40 weight parts, Viscotrol C 10 weight parts, inorganic nano material 10 weight parts, catalyzer 0.04 weight part, antioxidant 0.02 weight part is put into agitator, mixes 1～2 hour;
2, the preparation of B component isocyanic ester performed polymer
With terminal hydroxy group polyvalent alcohol 35 weight parts, Viscotrol C 15 weight parts add in the reactor, add diphenylmethanediisocyanate 70 weight parts (functionality 2～2.1) stirring and heat to 70～120 ℃, insulated and stirred reaction 1～2 hour, to reacting completely, be cooled to normal temperature;
3, casting
Glass fibre 20 weight parts are positioned in the mould, after with the A component of above-mentioned preparation and B component isocyanic ester performed polymer by weight A: B=1: 1～1.3 cast, crosslinking reaction obtains low-density high-strength nano-polyurethane wind-force impeller sheet matrix material of the present invention.
Embodiment 2
1, removes the preparation of the A component of fiber reinforced material
Get polyester polyol 25 weight parts, polyether glycol 35 weight parts, Viscotrol C 25 weight parts, inorganic nano material 10 weight parts, catalyzer 0.04 weight part, antioxidant 0.02 weight part is put into agitator, mixes 1～2 hour.
2, the preparation of B component isocyanic ester performed polymer
With terminal hydroxy group polyvalent alcohol 45 weight parts, Viscotrol C 20 weight parts add in the reactor, add diphenylmethanediisocyanate 75 weight parts (functionality 2～2.1) stirring and heat to 70～120 ℃, insulated and stirred reaction 1～2 hour, to reacting completely, be cooled to normal temperature.
3, casting
Glass fibre 10 weight parts are positioned in the mould, after with the A component of above-mentioned preparation and B component isocyanic ester performed polymer by weight A: B=1: 1.2 cast, crosslinking reaction obtains low-density high-strength nano-polyurethane wind-force impeller sheet matrix material of the present invention.
Embodiment 3
1, removes the preparation of the A component of fiber reinforced material
Get polyester polyol 22 weight parts, polyether glycol 38 weight parts, Viscotrol C 19 weight parts, inorganic nano material 9 weight parts, catalyzer 0.03 weight part, antioxidant 0.02 weight part is put into agitator, mixes 1～2 hour.
2, the poly-diphenylmethanediisocyanate of B component
3, casting
Volcanics fiber 15 weight parts are positioned in the mould, after with the A component of above-mentioned preparation and the poly-MDI of B component by weight A: B=1: 0.8 cast, crosslinking reaction obtains low-density high-strength nano-polyurethane wind-force impeller sheet matrix material of the present invention
Embodiment 4
1, removes the preparation of the A component of fiber reinforced material
Get polyester polyol 25 weight parts, polyether glycol 35 weight parts, Viscotrol C 25 weight parts, inorganic nano material 10 weight parts, catalyzer 0.04 weight part, antioxidant 0.02 weight part is put into agitator, mixes 1～2 hour.
2, B component tolylene diisocyanate
3, casting
Glass fibre 18 weight parts are positioned in the mould, after with the A component of above-mentioned preparation and B component TDI by weight A: B=1: 0.65 cast, crosslinking reaction obtains low-density high-strength nano-polyurethane wind-force impeller sheet matrix material of the present invention.
Claims (10)
1, a kind of low-density high-strength nano-polyurethane wind wheel leaf blade composite material is characterized in that: is the two-pack matrix material, comprises A component and B component, comprise by weight,
The A component:
Polyester polyol 20～50
Polyether glycol 10～60
Vegetables oil 10～25
Inorganic nano material 10～20
Catalyzer 0.01～1
Antioxidant 0.01～1
Fiber reinforced material 10～30;
The B component:
Poly-diphenylmethanediisocyanate, tolylene diisocyanate, many methylenebis phenyl isocyanates, adjacent ditolyl vulcabond, polymethylene multi-phenenyl isocyanate or isocyanic ester performed polymer;
Removing the A component of fiber reinforced material and the weight ratio of B component is A: B=1: 0.5～1.5.
2, low-density high-strength nano-polyurethane wind wheel leaf blade composite material according to claim 1 is characterized in that: the hydroxyl value of described polyester polyol is 50～500, and functionality is 2～3.
3, low-density high-strength nano-polyurethane wind wheel leaf blade composite material according to claim 1 is characterized in that: the hydroxyl value of described polyether glycol is 100～900, and functionality is 2～5.
4, low-density high-strength nano-polyurethane wind wheel leaf blade composite material according to claim 1 is characterized in that: described vegetables oil is a kind of in natural Viscotrol C, the modified castor oil.
5, low-density high-strength nano-polyurethane wind wheel leaf blade composite material according to claim 1 is characterized in that: described inorganic nano material is a nano imvite, and its granularity is at 30～100nm.
6, low-density high-strength nano-polyurethane wind wheel leaf blade composite material according to claim 1, described catalyzer is triethylenediamine, tetramethyl-Alkylenediamine, dimethylcyclohexylamine, a kind of or its combination in dibutyl tin laurate, stannous octoate, mercaptan two fourth tin, the dibutyltin diacetate.
7, low-density high-strength nano-polyurethane wind wheel leaf blade composite material according to claim 1, it is characterized in that: described antioxidant is a tetramethylene (3,5-di-t-butyl-4-hydroxy phenylpropionic acid) methyl esters, triglycol two-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], 2, a kind of or its combination in 6-di-tert-butyl-4-methy phenol, the 2,6 ditertiary butyl p cresol.
8, low-density high-strength nano-polyurethane wind wheel leaf blade composite material according to claim 1 is characterized in that: described isocyanic ester performed polymer, comprise by weight,
Terminal hydroxy group polyvalent alcohol 20～70
Vegetables oil 5～20
Diphenylmethanediisocyanate 20～80,
The terminal hydroxy group polyvalent alcohol is polyester polyol or polyether glycol, and functionality is 2～3; Vegetables oil is a kind of in natural Viscotrol C, the modified castor oil; Diphenylmethanediisocyanate is 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 2,2 '-diphenylmethanediisocyanate, adjacent tolylene diisocyanate.
9, at the preparation method of the described low-density high-strength nano-polyurethane wind wheel leaf blade composite material of one of claim 1 to 8, it is characterized in that: prepare A component and the B component of removing fiber reinforced material earlier respectively, then fiber reinforced material is put in the mould, with A component and the B component of preparation A: B=1 by weight: 0.5～1.5 pours into a mould, and crosslinking reaction obtains low-density high-strength nano-polyurethane wind-force impeller sheet matrix material.
10,, be used for wind-power electricity generation wind wheel blade and railway, bridge construction structured material at the purposes of the described low-density high-strength nano-polyurethane wind wheel leaf blade composite material of one of claim 1 to 8.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008102027855A CN101402791A (en) | 2008-11-14 | 2008-11-14 | Low-density high-strength nano-polyurethane wind wheel leaf blade composite material |
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| CNA2008102027855A CN101402791A (en) | 2008-11-14 | 2008-11-14 | Low-density high-strength nano-polyurethane wind wheel leaf blade composite material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985542A (en) * | 2010-10-25 | 2011-03-16 | 北京首创纳米科技有限公司 | Wind blade coating and preparation method thereof |
| CN102753345A (en) * | 2009-12-12 | 2012-10-24 | 拜尔知识产权有限责任公司 | Use of layer superstructures in wind power plants |
| CN102753333A (en) * | 2009-09-04 | 2012-10-24 | 拜尔材料科学有限公司 | Automated processes for the production of polyurethane wind turbine blades |
| CN110564222A (en) * | 2019-09-01 | 2019-12-13 | 合众（佛山）化工有限公司 | Rare earth hybrid luminescent radiation-proof water-based paint and preparation method thereof |
| CN114316201A (en) * | 2022-01-27 | 2022-04-12 | 浙江天和树脂有限公司 | Double-component polyurethane resin system |
| CN114478998A (en) * | 2022-02-28 | 2022-05-13 | 山东交通学院 | Composite material for plate spring and preparation method thereof |
-
2008
- 2008-11-14 CN CNA2008102027855A patent/CN101402791A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102753333A (en) * | 2009-09-04 | 2012-10-24 | 拜尔材料科学有限公司 | Automated processes for the production of polyurethane wind turbine blades |
| CN102753345A (en) * | 2009-12-12 | 2012-10-24 | 拜尔知识产权有限责任公司 | Use of layer superstructures in wind power plants |
| CN102753345B (en) * | 2009-12-12 | 2015-08-12 | 拜尔知识产权有限责任公司 | The application of sandwich construction in wind power station |
| US10293586B2 (en) | 2009-12-12 | 2019-05-21 | Covestro Deutschland Ag | Use of layer structures in wind power plants |
| US11904582B2 (en) | 2009-12-12 | 2024-02-20 | Covestro Deutschland Ag | Use of layer structures in wind power plants |
| CN101985542A (en) * | 2010-10-25 | 2011-03-16 | 北京首创纳米科技有限公司 | Wind blade coating and preparation method thereof |
| CN101985542B (en) * | 2010-10-25 | 2013-06-05 | 北京首创纳米科技有限公司 | Wind blade coating and preparation method thereof |
| CN110564222A (en) * | 2019-09-01 | 2019-12-13 | 合众（佛山）化工有限公司 | Rare earth hybrid luminescent radiation-proof water-based paint and preparation method thereof |
| CN114316201A (en) * | 2022-01-27 | 2022-04-12 | 浙江天和树脂有限公司 | Double-component polyurethane resin system |
| CN114316201B (en) * | 2022-01-27 | 2023-12-22 | 浙江天和树脂有限公司 | Two-component polyurethane resin system |
| CN114478998A (en) * | 2022-02-28 | 2022-05-13 | 山东交通学院 | Composite material for plate spring and preparation method thereof |
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Open date: 20090408 |