CN113736218B - Prepreg resin for reinforcing ship body and preparation method and application thereof - Google Patents
Prepreg resin for reinforcing ship body and preparation method and application thereof Download PDFInfo
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- CN113736218B CN113736218B CN202111310941.1A CN202111310941A CN113736218B CN 113736218 B CN113736218 B CN 113736218B CN 202111310941 A CN202111310941 A CN 202111310941A CN 113736218 B CN113736218 B CN 113736218B
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Abstract
The application discloses a prepreg resin for reinforcing a ship body and a preparation method and application thereof, and belongs to the technical field of marine ship reinforcement. The prepreg resin for reinforcing the ship body comprises, by weight, 60-110 parts of epoxy resin, 3-30 parts of a toughening agent, 5-25 parts of a filler and 7-15 parts of a curing agent; wherein the curing agent is at least one selected from isocyanates. The prepreg resin has high viscosity and strong bonding capacity with epoxy resin, is used in the field of hull reinforcement, can be tightly bonded with an epoxy resin coating on the surface of a hull, and realizes the reinforcement of the hull.
Description
Technical Field
The application relates to a prepreg resin for reinforcing a ship body and a preparation method and application thereof, and belongs to the technical field of marine ship reinforcement.
Background
The carbon fiber composite material has excellent performances of high specific strength, specific modulus, high temperature resistance, fatigue resistance, conductivity, light weight, easy processing and the like, and is widely applied to the fields of aerospace, rail transit, mechano-electronics, medical appliances, building reinforcement and the like. The load carrying capacity of a ship, which is the most important vehicle in a marine environment, is of paramount importance. Therefore, strengthening and reinforcing ships is a very hot topic. Compared with the traditional hull reinforcing material, the carbon fiber composite material has natural advantages. Firstly, the carbon fiber composite material is adopted to reinforce and reinforce the ship body, the construction process is relatively simple, the period is short, the forming is convenient, and in addition, the reinforced ship body has good mechanical performance. Meanwhile, the carbon fiber and the resin matrix material have good fatigue resistance and corrosion resistance after being combined, so that the service life of the ship body can be prolonged; in addition, due to the chemical inertness of the carbon fiber surface, aquatic organisms are difficult to grow on the surface of the ship body.
However, in the field of structure (hull structure, building structure, etc.) reinforcement, a traditional hand lay-up process is adopted, that is, carbon fiber cloth (unidirectional cloth or bidirectional cloth woven at 0/90 degrees) is wound on a base material, low-viscosity resin impregnating glue is coated on the carbon fiber cloth, and the structure can be reinforced after the resin is cured. However, the traditional hand pasting process is inconvenient to operate, the resin content is not uniformly controlled, the requirement on the viscosity of the resin is high, and meanwhile, the construction environment is not good, which all affect the reinforcing effect.
In addition, since the ship hull of the ship is basically of a metal structure, the matrix of the composite material is generally epoxy resin, and the two structures are different in nature, the bonding strength of the two is also low, so that the application of the resin-based composite material in the field of ship hull reinforcement is limited. The problem of the bonding strength of the composite material/metal interface is receiving increasing attention, and the problem becomes the key point of the research on the reinforcing technology of the composite material. The surface pretreatment of the metal substrate is an important factor influencing the bonding strength of the composite material/metal interface. Before the composite material is used for reinforcement, the metal surface is treated properly to remove loose surface oxide film (rust), water, dust, oil stain and other impurities to form new surface film and increase the bonding strength. Methods for treating metal surfaces can be roughly classified into mechanical methods and chemical methods. Mechanical methods are most commonly grinding and sand blasting; the chemical method includes acid washing, phosphating and the like. The mechanical polishing method has low polishing precision, unclean operating environment and strong dependence on workers; chemical methods are not environmentally friendly and are prone to excessive handling resulting in impaired bulk properties of the metal substrate. Plasma is a common method for modifying the surface of materials. However, the plasma process is often required to process metal materials in a vacuum environment, which is difficult to realize for large structures such as ships.
Disclosure of Invention
In order to solve the problems, the prepreg resin for reinforcing the ship body and the preparation method and application thereof are provided, the prepreg resin for impregnating the carbon fibers has high viscosity and strong bonding capability with epoxy resin, is used in the field of ship body reinforcement, can be tightly bonded with an epoxy resin coating on the surface of the ship body, and realizes the reinforcement of the ship body.
According to one aspect of the application, the prepreg resin for reinforcing the ship body comprises, by weight, 60-110 parts of epoxy resin, 3-30 parts of a toughening agent, 5-25 parts of a filler and 7-15 parts of a curing agent;
wherein the curing agent comprises at least one of isocyanates.
Optionally, the prepreg resin comprises 90 parts by weight of epoxy resin, 9 parts by weight of toughening agent, 15 parts by weight of filler and 10 parts by weight of curing agent.
Optionally, the isocyanate is selected from at least one of diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, toluene diisocyanate, 1, 5-naphthalene diisocyanate, and 3, 3-dimethyl-4, 4-biphenyl diisocyanate.
Optionally, the epoxy resin includes a first epoxy resin which is a liquid bisphenol a type epoxy resin and a second epoxy resin selected from at least one of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol type epoxy resin, and a urethane-modified epoxy resin. The bisphenol a epoxy resin in the second epoxy resin may be a liquid bisphenol a epoxy resin, a solid bisphenol a epoxy resin, or a combination thereof.
Optionally, the toughening agent is selected from at least one of thermoplastic resin, synthetic rubber, core shell rubber, polyurethane prepolymer and phthalate.
Optionally, the filler is selected from at least one of calcium carbonate, magnesium carbonate, silica, alumina, quartz powder, silica micropowder, and bentonite.
Preferably, the filler comprises (6-10) by weight: (4-6): (1-3) calcium carbonate, quartz powder and bentonite;
more preferably, the filler comprises a weight ratio of 8: 5: 2 calcium carbonate, quartz powder and bentonite. The addition of the filler can increase the rigidity and hardness of the carbon fiber prepreg obtained by production, and increase the bonding property and mechanical strength of the carbon fiber prepreg.
Optionally, the weight ratio of the first epoxy resin to the second epoxy resin is (8-12): (10-90). Preferably 1: 8.
Optionally, the second epoxy resin comprises (30-50) by weight: (20-40) bisphenol A type epoxy resin, bisphenol F type epoxy resin and novolac type epoxy resin of (8-12).
Preferably, the second epoxy resin comprises a weight ratio of 20: 20: 30: 10 of liquid bisphenol A epoxy resin, solid bisphenol A epoxy resin, bisphenol F epoxy resin and o-cresol formaldehyde epoxy resin.
Optionally, the carbon fiber prepreg comprises, by weight, 20 parts of solid bisphenol a epoxy resin, 30 parts of bisphenol F epoxy resin, 10 parts of o-cresol novolac epoxy resin, 9 parts of polybutadiene rubber toughening agent, 30 parts of liquid bisphenol a epoxy resin, 8 parts of calcium carbonate, 5 parts of quartz powder, 2 parts of bentonite and 10 parts of toluene diisocyanate.
According to another aspect of the present application, there is provided a method for preparing a prepreg resin as defined in any one of the above, the method comprising the steps of:
mixing part of the epoxy resin and the curing agent at 10-30 ℃ to obtain a mixture A, mixing the rest of the epoxy resin, the toughening agent and the filler to obtain a mixture B, and mixing the mixture A and the mixture B to obtain the prepreg resin.
Optionally, the method comprises the steps of: mixing a first epoxy resin and a curing agent at 10-30 ℃ to obtain a mixture A, mixing a second epoxy resin, a toughening agent and a filler at 80-150 ℃ to obtain a mixture B, cooling the temperature of the mixture B to 50-60 ℃, and mixing the mixture B with the mixture A to obtain the prepreg resin;
wherein the first epoxy resin is liquid bisphenol A epoxy resin, and the second epoxy resin is at least one selected from bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenolic epoxy resin and polyurethane modified epoxy resin. The bisphenol a epoxy resin in the second epoxy resin may be a liquid bisphenol a epoxy resin, a solid bisphenol a epoxy resin, or a combination thereof.
By controlling the mixing temperature of the first epoxy resin and the curing agent, the first epoxy resin and the curing agent are prevented from reacting, so that the finally produced carbon fiber prepreg has high viscosity; the mixing temperature of the second epoxy resin and the toughening agent is controlled to ensure that the second epoxy resin and the toughening agent are mixed more uniformly, so that the epoxy resin in the finally produced carbon fiber prepreg is uniformly distributed; by controlling the mixing temperature of the mixture A and the mixture B, the viscosity of the prepreg resin is ensured to be moderate, and the reaction between the curing agent and the epoxy resin is avoided.
Optionally, the method comprises the following steps: stirring the first epoxy resin and the curing agent at 10-30 ℃ for 3-25 min in a vacuum environment, and then grinding by a three-roll grinder to obtain a mixture A; stirring the second epoxy resin, the toughening agent and the filler at 80-150 ℃ for 10-40 min under a vacuum environment to obtain a mixture B; and reducing the temperature of the mixture B to 50-60 ℃, and stirring the mixture A and the mixture B for 10-40 min in a vacuum environment to obtain the prepreg resin.
Preferably, the method comprises the steps of: stirring the first epoxy resin and the curing agent at 25 ℃ for 15min under a vacuum environment, and then grinding the mixture by a three-roll grinder to obtain a mixture A; stirring the second epoxy resin, the toughening agent and the filler at 95 ℃ for 25min under a vacuum environment to obtain a mixture B; and reducing the temperature of the mixture B to 55 ℃, and stirring the mixture A and the mixture B for 15min in a vacuum environment to obtain the prepreg resin.
According to yet another aspect of the present application, there is provided a method of reinforcing a hull, the method comprising the steps of:
after plasma treatment is carried out on a region to be reinforced of the ship body, continuously coating third epoxy resin on the region to be reinforced, then laying carbon fiber prepreg on the region to be reinforced, and curing in water, thereby reinforcing the region to be reinforced;
the carbon fiber prepreg is obtained by impregnating carbon fibers in a prepreg resin at the temperature of 60-80 ℃ and the relative humidity of not more than 30%, wherein the prepreg resin is selected from the prepreg resin or the prepreg resin prepared by the preparation method. Because the viscosity of the prepreg resin is high, in order to ensure the manufacturability in the production process of the carbon fiber prepreg and prevent the reaction between the epoxy resin and the curing agent, the temperature in the production process of the carbon fiber prepreg should be strictly controlled.
Optionally, the preparation process of the carbon fiber prepreg is as follows: coating the prepreg resin on a glue spreader to form glue films, adhering the glue films to two opposite surfaces of the carbon fiber respectively, and heating and softening the glue film resin at 60-80 ℃ to impregnate the carbon fiber with the glue films, thereby obtaining the carbon fiber prepreg.
Optionally, the plasma treated gas is air;
the pressure of the plasma treatment is 0.08 MPa-0.12 MPa, and preferably 0.1 MPa;
the power of the plasma treatment is 50W-1000W, preferably 100W-800W, preferably 200W, 300W, 400W, 500W, 600W and 700W, more preferably 500W;
the plasma treatment time is 0.5 min-60 min, preferably 25 min.
Optionally, after the area to be reinforced of the ship body is subjected to plasma treatment, the area to be reinforced is coated with a third epoxy resin within no more than 30 min.
Optionally, the painting thickness of the third epoxy resin is 1 mm to 10mm, preferably 3 mm.
Optionally, the third epoxy resin is selected from at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, and glycidylamine type epoxy resin, preferably bisphenol F type epoxy resin. The bisphenol F epoxy resin has lower viscosity, and can be coated on the surface of the area to be reinforced as the third epoxy resin, so that the epoxy resin is more uniform.
The carbon fiber is at least one selected from carbon fiber unidirectional cloth and carbon fiber bidirectional cloth with tensile strength not lower than T300 grade, and carbon fiber bidirectional plain woven cloth with tensile strength of T300 grade is preferred.
Benefits of the present application include, but are not limited to:
1. the prepreg resin has high viscosity which can reach 10000 cPs-80000 cPs generally, can be used as the prepreg resin of carbon fibers, can control the content of the resin more accurately, ensures the uniformity of the resin in different areas of the carbon fiber prepreg produced by the prepreg resin, and has wide material selection range due to wide viscosity range; the prepreg resin has strong bonding capacity with epoxy resin, is used in the field of hull reinforcement, can be tightly bonded with an epoxy resin coating on the surface of a hull, and realizes the reinforcement of the hull.
2. According to the prepreg resin, when carbon fibers are impregnated in the prepreg resin to produce the carbon fiber prepreg, the carbon fiber prepreg is required to be produced in a dry air environment (the relative humidity is less than or equal to 30%) at 60-80 ℃, so that the prepreg resin takes isocyanate compounds as a curing agent to ensure that the curing agent and epoxy resin can coexist in a process environment for producing the carbon fiber prepreg, and the epoxy resin is prevented from being cured in the process environment and cannot be applied to hull reinforcement; meanwhile, the isocyanate can be hydrolyzed in water to form amine substances, and the amine substances can be used as curing agents of the epoxy resin to perform a crosslinking reaction with the epoxy resin at normal temperature, so that the underwater curing reinforcement of the ship structure is realized.
3. The preparation method of the prepreg resin is simple in steps, and the prepreg resin is uniformly mixed, moderate in viscosity and long in storage period by controlling the charging sequence and the mixing temperature.
4. According to the method for reinforcing the ship body, the epoxy resin coating can be tightly combined with the ship body, so that the corrosion resistance of the ship body is improved, the carbon fiber prepreg is paved on the surface of the epoxy resin coating, and aquatic organisms can be prevented from attaching to the surface of the ship body due to the chemical inertia of the surface of the carbon fiber, so that the service life of the ship body is prolonged.
5. According to the method for reinforcing the ship body, air is used as plasma gas to treat the surface of the ship body, inert gas such as nitrogen in the air is used for physically sputtering the surface of the ship body, active plasma gas such as oxygen is used for chemically modifying the surface of the ship body, and the radiated metal material of the ship body can generate active substances in unstable states such as metal oxides and carbonates, so that the roughness of the surface of the ship body can be increased by the active substances, the bonding strength of the surface of the ship body and an epoxy resin coating is further improved, and the corrosion resistance of the surface of the ship body is improved; after the hull is subjected to plasma irradiation, the epoxy resin coating is quickly coated to prevent the stabilization of active substances on the surface of the hull and ensure the binding capacity of the epoxy resin coating and the surface of the hull; in addition, the carbon fibers are well impregnated in the prepreg resin in advance, so that the prepreg resin on the carbon fibers is uniformly impregnated, and the reinforcing effect on the ship body is ensured.
6. According to the method for reinforcing the ship body, air is used as plasma gas to carry out plasma irradiation on the ship body under normal pressure, the operation is convenient, the production cost is low, and the method is favorable for popularization in the field of ship body reinforcement.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
Example 1 carbon fiber prepreg No. 1#
The preparation steps of the carbon fiber prepreg No. 1 are as follows:
(1) stirring 10.0 parts of toluene diisocyanate and 10.0 parts of liquid bisphenol A epoxy resin for 15min at 25 ℃ in a vacuum environment, and then grinding for 3 times by a three-roll grinder to obtain a mixture A;
(2) stirring 20.0 parts of solid bisphenol A epoxy resin, 20.0 parts of liquid bisphenol A epoxy resin, 30.0 parts of bisphenol F epoxy resin, 10.0 parts of o-cresol formaldehyde epoxy resin, 8.0 parts of calcium carbonate, 5.0 parts of quartz powder, 2.0 parts of bentonite and 9.0 parts of polybutadiene rubber toughening agent (Japanese Brillouin chemical toughening agent MX-154) at 95 ℃ for 25min in a vacuum environment to obtain a mixture B;
(3) reducing the temperature of the mixture B to 55 ℃, mixing the mixture B with the mixture A, and stirring the mixture A for 15min in a vacuum environment to obtain prepreg resin # 1;
(4) uniformly coating the prepreg resin No. 1 on release paper at 60 ℃ by using a glue spreader to obtain a resin glue film No. 1;
(5) taking T300-grade carbon fiber bidirectional plain woven cloth, respectively combining the two sides of the woven cloth with the glue film No. 1 in step (4), and soaking for 2min at 70 ℃ and under the relative humidity of not more than 30% to obtain carbon fiber prepreg No. 1.
Example 2 carbon fiber prepreg No. 2#
Example 2 differs from example 1 in that: in the step (1), 10.0 parts of 1, 5-naphthalene diisocyanate and 10.0 parts of liquid bisphenol A epoxy resin are stirred for 15min at 25 ℃ in a vacuum environment, and then ground for 3 times by a three-roll grinder to obtain a mixture A; the remaining conditions were the same as in example 1, to obtain prepreg resin # 2;
uniformly coating the prepreg resin 2# on release paper at 60 ℃ by using a glue spreader to obtain a resin adhesive film 2 #;
taking T300-grade carbon fiber bidirectional plain woven cloth, respectively combining the two sides of the woven cloth with an adhesive film No. 2, and soaking for 2min at 70 ℃ under the condition that the relative humidity does not exceed 30% to obtain carbon fiber prepreg No. 2.
Example 3 carbon fiber prepreg 3#
Example 3 differs from example 1 in that: in the step (1), in a vacuum environment, 10.0 parts of toluene diisocyanate and 10.0 parts of liquid bisphenol F type epoxy resin are stirred for 15min at 25 ℃, and then ground for 3 times by a three-roll grinder to obtain a mixture A; the remaining conditions were the same as in example 1, to obtain prepreg resin # 3;
uniformly coating the prepreg resin No. 3 on release paper at 60 ℃ by using a glue spreader to obtain a resin glue film No. 3;
taking T300-grade carbon fiber bidirectional plain woven cloth, respectively combining the two sides of the woven cloth with a glue film No. 3, and soaking for 2min at 70 ℃ under the condition that the relative humidity does not exceed 30% to obtain carbon fiber prepreg No. 3.
Example 4 carbon fiber prepreg 4#
Example 4 differs from example 1 in that: in the step (1), in a vacuum environment, 15.0 parts of toluene diisocyanate and 10.0 parts of liquid bisphenol A epoxy resin are stirred for 15min at 25 ℃, and then ground for 3 times by a three-roll grinder to obtain a mixture A; the remaining conditions were the same as in example 1, to obtain prepreg resin # 4;
uniformly coating prepreg resin No. 4 on release paper at 60 ℃ by using a glue spreader to obtain a resin glue film No. 4;
taking T300-grade carbon fiber bidirectional plain woven cloth, respectively combining the two sides of the woven cloth with a glue film No. 4, and soaking for 2min at 70 ℃ under the condition that the relative humidity does not exceed 30% to obtain carbon fiber prepreg No. 4.
Example 5 carbon fiber prepreg 5#
Example 5 differs from example 1 in that: in the step (2), in a vacuum environment, 50.0 parts of bisphenol F type epoxy resin, 30.0 parts of o-cresol formaldehyde type epoxy resin, 8.0 parts of calcium carbonate, 5.0 parts of quartz powder, 2.0 parts of bentonite and 9.0 parts of polybutadiene rubber toughening agent (Japanese Brillouin chemical toughening agent MX-154) are stirred for 25min at 95 ℃ to obtain a mixture B; the remaining conditions were the same as in example 1, to obtain prepreg resin # 5;
uniformly coating the prepreg resin No. 5 on release paper at 60 ℃ by using a glue spreader to obtain a resin glue film No. 5;
taking T300-grade carbon fiber bidirectional plain woven cloth, respectively combining the two sides of the woven cloth with a glue film No. 5, and soaking for 2min at 70 ℃ under the condition that the relative humidity does not exceed 30% to obtain carbon fiber prepreg No. 5.
Example 6 carbon fiber prepreg 6#
Example 6 differs from example 1 in that: in the step (2), in a vacuum environment, stirring 20.0 parts of solid bisphenol A type epoxy resin, 20.0 parts of liquid bisphenol A type epoxy resin, 30.0 parts of bisphenol S type epoxy resin, 10.0 parts of o-cresol formaldehyde type epoxy resin, 8.0 parts of calcium carbonate, 5.0 parts of quartz powder, 2.0 parts of bentonite and 9.0 parts of polybutadiene rubber toughening agent (Japanese Brillouin chemical toughening agent MX-154) at 95 ℃ for 25min to obtain a mixture B; the remaining conditions were the same as in example 1, to obtain prepreg resin # 6;
uniformly coating the prepreg resin No. 6 on release paper at 60 ℃ by using a glue spreader to obtain a resin glue film No. 6;
taking T300-grade carbon fiber bidirectional plain woven cloth, respectively combining the two sides of the woven cloth with an adhesive film 6#, and soaking for 2min at 70 ℃ and at a relative humidity of no more than 30% to obtain carbon fiber prepreg 6 #.
Example 7 carbon fiber prepreg 7#
Example 7 differs from example 1 in that: in the step (2), in a vacuum environment, stirring 20.0 parts of solid bisphenol A type epoxy resin, 20.0 parts of liquid bisphenol A type epoxy resin, 30.0 parts of bisphenol F type epoxy resin, 10.0 parts of o-cresol formaldehyde type epoxy resin, 8.0 parts of calcium carbonate, 5.0 parts of quartz powder, 2.0 parts of bentonite and 9.0 parts of polybutadiene rubber toughening agent (Japanese Brillouin chemical toughening agent MX-154) at 150 ℃ for 25min to obtain a mixture B; the remaining conditions were the same as in example 1, to obtain prepreg resin # 7;
uniformly coating the prepreg resin 7# on release paper at 60 ℃ by using a glue spreader to obtain a resin glue film 7 #;
taking T300-grade carbon fiber bidirectional plain woven cloth, respectively combining the two sides of the woven cloth with an adhesive film No. 7, and soaking for 2min at 70 ℃ under the condition that the relative humidity does not exceed 30% to obtain carbon fiber prepreg No. 7.
Example 8 carbon fiber prepreg 8#
Example 8 differs from example 1 in that: in the step (2), in a vacuum environment, stirring 20.0 parts of solid bisphenol A epoxy resin, 20.0 parts of liquid bisphenol A epoxy resin, 30.0 parts of bisphenol F epoxy resin, 10.0 parts of o-cresol formaldehyde epoxy resin, 8.0 parts of calcium carbonate, 5.0 parts of quartz powder, 2.0 parts of bentonite and 9.0 parts of dibutyl phthalate for 25min at 95 ℃ to obtain a mixture B; the remaining conditions were the same as in example 1, to obtain prepreg resin # 8;
uniformly coating the prepreg resin No. 8 on release paper at 60 ℃ by using a glue spreader to obtain a resin glue film No. 8;
taking T300-grade carbon fiber bidirectional plain woven cloth, respectively combining the two sides of the woven cloth with an adhesive film No. 8, and soaking for 2min at 70 ℃ under the condition that the relative humidity does not exceed 30% to obtain carbon fiber prepreg No. 8.
Example 9 carbon fiber prepreg 9#
Example 9 differs from example 1 in that: in the step (2), 16.0 parts of solid bisphenol A epoxy resin, 16.0 parts of liquid bisphenol A epoxy resin, 24.0 parts of bisphenol F epoxy resin, 8.0 parts of o-cresol formaldehyde epoxy resin, 8.0 parts of calcium carbonate, 5.0 parts of quartz powder, 2.0 parts of bentonite and 9.0 parts of polybutadiene rubber toughening agent (Japanese Brillouin chemical toughening agent MX-154) are stirred for 25min at 95 ℃ in a vacuum environment to obtain a mixture B; the remaining conditions were the same as in example 1, to obtain prepreg resin # 9;
uniformly coating prepreg resin No. 9 on release paper at 60 ℃ by using a glue spreader to obtain a resin glue film No. 9;
taking T300-grade carbon fiber bidirectional plain woven cloth, respectively combining the two sides of the woven cloth with a glue film 9#, and soaking for 2min at 70 ℃ and at a relative humidity of no more than 30% to obtain a carbon fiber prepreg 9 #.
Example 10 carbon fiber prepreg 10#
Example 10 differs from example 1 in that: in the step (3), the temperature of the mixture B is reduced to 30 ℃, and then the mixture B is mixed with the mixture A and stirred for 15min in a vacuum environment to obtain prepreg resin No. 10; the rest of the conditions were the same as in example 1;
uniformly coating the prepreg resin 10# on release paper at 60 ℃ by using a glue spreader to obtain a resin glue film 10 #;
taking T300-grade carbon fiber bidirectional plain woven cloth, respectively combining the two sides of the woven cloth with an adhesive film 10#, and soaking for 2min at 70 ℃ and at a relative humidity of no more than 30% to obtain a carbon fiber prepreg 10 #.
Comparative example 1 carbon fiber prepreg D1#
Comparative example 1 differs from example 1 in that: in the step (1), stirring 10.0 parts of ethylenediamine and 10.0 parts of liquid bisphenol A epoxy resin at 25 ℃ for 15min in a vacuum environment, and then grinding for 3 times by a three-roll grinder to obtain a mixture A; the remaining conditions were the same as in example 1, to obtain prepreg resin D1 #;
uniformly coating prepreg resin D1# on release paper at 60 ℃ by using a glue spreader to obtain a resin glue film D1 #;
taking T300-grade carbon fiber bidirectional plain woven cloth, respectively combining the two sides of the woven cloth with an adhesive film D1#, and soaking for 2min at 70 ℃ and with the relative humidity not more than 30% to obtain carbon fiber prepreg D1 #.
Comparative example 2 carbon fiber prepreg D2#
Comparative example 2 differs from example 1 in that: in the step (1), in a vacuum environment, 10.0 parts of toluene diisocyanate and 10.0 parts of liquid bisphenol A epoxy resin are stirred for 15min at 50 ℃, and then ground for 3 times by a three-roll grinder to obtain a mixture A; the remaining conditions were the same as in example 1, to obtain prepreg resin D2 #;
uniformly coating prepreg resin D2# on release paper at 60 ℃ by using a glue spreader to obtain a resin glue film D2 #;
taking T300-grade carbon fiber bidirectional plain woven cloth, respectively combining the two sides of the woven cloth with an adhesive film D2#, and soaking for 2min at 70 ℃ and with the relative humidity not more than 30% to obtain carbon fiber prepreg D2 #.
Comparative example 3 carbon fiber prepreg D3#
Comparative example 3 differs from example 1 in that: in the step (1), 5.0 parts of toluene diisocyanate and 10.0 parts of liquid bisphenol A epoxy resin are stirred for 15min at 25 ℃ in a vacuum environment, and then ground for 3 times by a three-roll grinder to obtain a mixture A; the remaining conditions were the same as in example 1, to obtain prepreg resin D3 #;
uniformly coating prepreg resin D3# on release paper at 60 ℃ by using a glue spreader to obtain a resin glue film D3 #;
taking T300-grade carbon fiber bidirectional plain woven cloth, respectively combining the two sides of the woven cloth with an adhesive film D3#, and soaking for 2min at 70 ℃ and with the relative humidity not more than 30% to obtain carbon fiber prepreg D3 #.
Comparative example 4 carbon fiber prepreg D4#
The preparation steps of the carbon fiber prepreg D4# are as follows:
(1) stirring 10.0 parts of toluene diisocyanate, 30.0 parts of liquid bisphenol A epoxy resin, 20.0 parts of solid bisphenol A epoxy resin, 30.0 parts of bisphenol F epoxy resin, 10.0 parts of o-cresol formaldehyde epoxy resin, 8.0 parts of calcium carbonate, 5.0 parts of quartz powder, 2.0 parts of bentonite and 9.0 parts of polybutadiene rubber toughening agent (Japanese Brillouin chemical toughening agent MX-154) at 95 ℃ for 15min in a vacuum environment, and then grinding for 3 times by using a three-roll grinder to obtain prepreg resin D4 #;
(2) uniformly coating prepreg resin D4# on release paper at 60 ℃ by using a glue spreader to obtain a resin glue film D4 #;
taking T300-grade carbon fiber bidirectional plain woven cloth, respectively combining the two sides of the woven cloth with an adhesive film D4#, and soaking for 2min at 70 ℃ and with the relative humidity not more than 30% to obtain carbon fiber prepreg D4 #.
Comparative example 5 carbon fiber prepreg D5#
Comparative example 3 differs from example 1 in that: in the step (2), in a vacuum environment, stirring 20.0 parts of solid bisphenol A type epoxy resin, 20.0 parts of liquid bisphenol A type epoxy resin, 30.0 parts of bisphenol F type epoxy resin, 10.0 parts of o-cresol formaldehyde type epoxy resin and 9.0 parts of polybutadiene rubber toughening agent (Japanese Brillouin chemical toughening agent MX-154) at 95 ℃ for 25min to obtain a mixture B; the remaining conditions were the same as in example 1, to obtain prepreg resin D5 #;
uniformly coating prepreg resin D5# on release paper at 60 ℃ by using a glue spreader to obtain a resin glue film D5 #;
taking T300-grade carbon fiber bidirectional plain woven cloth, respectively combining the two sides of the woven cloth with an adhesive film D5#, and soaking for 2min at 70 ℃ and with the relative humidity not more than 30% to obtain carbon fiber prepreg D5 #.
Experimental example 1
The prepreg resins 1# -10# and D1# -D5# obtained in examples 1-10 and comparative examples 1-4 were subjected to viscosity tests, and after curing the prepreg resins in water, tensile strength, tensile modulus, elongation, flexural strength and flexural modulus were measured, respectively, as follows, and the test results are shown in table 1.
Viscosity: the viscosity of the prepreg resins was measured using a Brookfield CAP2000+ cone and plate viscometer according to ASTM D4287-1994.
Tensile property: testing the tensile strength, the tensile elastic modulus and the elongation of the cured prepreg resin by using a universal tensile testing machine according to ASTM D638-2014;
bending property: the cured prepreg resin was tested for flexural strength and flexural modulus of elasticity using an all-purpose tensile tester according to ASTM D638-2014.
TABLE 1
| Numbering | Viscosity (cPs) | Tensile Strength (MPa) | Tensile modulus of elasticity (GPa) | Elongation (%) | Flexural Strength (MPa) | Flexural modulus of elasticity (GPa) |
| Prepreg resin 1# | 28150 | 91.9 | 3.63 | 4.21 | 158.8 | 3.61 |
| Prepreg resin 2# | 28353 | 75.6 | 3.44 | 2.15 | 135.3 | 3.41 |
| Prepreg resin 3# | 27985 | 74.5 | 3.46 | 2.16 | 130.2 | 3.42 |
| Prepreg resin 4# | 28355 | 75.6 | 3.51 | 2.18 | 134.1 | 3.45 |
| Prepreg resin 5# | 26350 | 76.2 | 3.50 | 2.17 | 133.2 | 3.48 |
| Prepreg resin 6# | 31250 | 77.1 | 3.59 | 1.99 | 135.4 | 3.53 |
| Prepreg resin 7# | 21145 | 72.5 | 3.43 | 2.15 | 128.4 | 3.41 |
| Prepreg resin 8# | 21420 | 76.5 | 3.58 | 1.98 | 129.4 | 3.55 |
| Prepreg resin 9# | 22565 | 71.5 | 3.47 | 2.19 | 130.2 | 3.42 |
| Prepreg resin 10# | 28250 | 77.6 | 3.44 | 2.14 | 133.2 | 3.41 |
| Prepreg resin D1# | 27560 | 63.4 | 2.28 | 1.08 | 135.4 | 2.25 |
| Prepreg resin D2# | 27951 | 54.2 | 3.07 | 1.39 | 114.2 | 2.43 |
| Prepreg resin D3# | 25652 | 55.1 | 3.11 | 1.11 | 103.2 | 2.07 |
| Prepreg resin D4# | 26482 | 62.3 | 2.27 | 1.15 | 111.5 | 2.25 |
| Prepreg resin D5# | 25845 | 50.8 | 2.26 | 1.13 | 102.9 | 2.23 |
| Traditional hand lay-up process resin | 385 | 51.3 | 2.15 | 1.17 | 107.4 | 2.07 |
As can be seen from Table 1, the prepreg resin has high viscosity, has higher freedom of selection of raw materials compared with the traditional hand lay-up process resin, can produce better performance, has good mechanical performance after being cured, is used for reinforcing a ship body, and has good effect.
Application example 1
The carbon fiber prepregs 1# -10# and the carbon fiber prepregs D1# -D5# obtained in the examples 1-10 and the comparative examples 1-5 are respectively used for reinforcing the ship hull metal to obtain metal substrates 1# -10# and metal substrates D1# -D5#, and the specific steps are as follows:
(1) irradiating the steel substrate with the metal structure of the ship body for 25min under the discharge power of 500W by using air as plasma gas under the atmospheric pressure;
(2) coating bisphenol F type epoxy resin on the steel substrate of the hull metal structure obtained in the step (1) within 10min after the step (1) is finished, wherein the coating thickness is 3 mm;
(3) laying carbon fiber prepreg on the steel substrate of the hull metal structure obtained in the step (2);
(4) and (4) placing the steel substrate with the hull metal structure obtained in the step (3) in water for curing.
Application example 2
Application example 2 the carbon fiber prepreg 1# obtained in example 1 was used for reinforcing a ship metal, and the difference from application example 1 is that in step (1), a ship metal structure steel substrate was irradiated with argon gas as a plasma gas at a discharge power of 500W for 25min under atmospheric pressure; the rest conditions are the same as in application example 1; the metal substrate E1# was obtained.
Application example 3
Application example 3 the carbon fiber prepreg 1# obtained in example 1 was used for reinforcing a ship metal, and the difference from application example 1 is that in step (1), air was used as a plasma gas to irradiate a ship metal structure steel substrate for 25min under a discharge power of 1000W under atmospheric pressure; the rest conditions are the same as in application example 1; the metal substrate E2# was obtained.
Application example 4
Application example 4 the carbon fiber prepreg 1# obtained in example 1 was used for reinforcing a ship metal, and the difference from application example 1 is that in step (2), 30min after completion of step (1), the ship metal structure steel substrate obtained in step (1) was coated with bisphenol F type epoxy resin to a coating thickness of 3 mm; the rest conditions are the same as in application example 1; the metal substrate E3# was obtained.
Application example 5
Application example 5 the carbon fiber prepreg 1# obtained in example 1 is used for reinforcing ship metal, and the difference from application example 1 is that in step (2), within 10min after step (1) is completed, the ship metal structure steel substrate obtained in step (1) is coated with liquid bisphenol a epoxy resin, and the coating thickness is 3 mm; the rest conditions are the same as in application example 1; the metal substrate E4# was obtained.
Application example 6
Application example 6 the carbon fiber prepreg 1# obtained in example 1 was used for reinforcing a ship metal, and the difference from application example 1 is that in step (2), within 10min after completion of step (1), the ship metal structure steel substrate obtained in step (1) was coated with bisphenol F type epoxy resin to a coating thickness of 12 mm; the rest conditions are the same as in application example 1; the metal substrate E5# was obtained.
Experimental example 2
The carbon fiber prepregs 1# -10# and the carbon fiber prepregs D1# -D5# obtained in examples 1-10 and comparative examples 1-5 were cured in water and then subjected to tensile strength, bending strength and interlaminar shear strength tests, and the metal substrates 1# -10#, D1# -D5# and E1# -E5# obtained in application examples 1-6 were subjected to positive tensile bond strength tests, respectively, and the carbon fibers and the metal substrates obtained from the conventional hand lay-up process resin were subjected to the tests, respectively, according to the following methods, and the test results are shown in table 2:
tensile strength: the tensile strength of the carbon fiber prepreg was tested with reference to ASTM D3039-2017.
Bending strength: the carbon fiber prepreg was tested for flexural strength with reference to ASTM D7264-2015.
Interlaminar shear strength: the carbon fiber prepreg was tested for interlaminar shear strength with reference to ASTM D2344-2016.
Positive tensile bond strength: the metal substrate was tested for positive pull bond strength with reference to GB 50728-.
TABLE 2
| Numbering | Tensile Strength (MPa) | Flexural Strength (MPa) | Interlaminar shear strength (MPa) | Numbering | Positive tensile bond strength (MPa)） |
| Carbon fiber prepreg 1# | 945 | 945 | 80.3 | Metal substrate 1# | 6.5 |
| Carbon fiber prepreg 2# | 789 | 721 | 53.6 | Metal substrate 2# | 4.1 |
| Carbon fiber prepreg 3# | 792 | 716 | 52.1 | Metal substrate 3# | 3.9 |
| Carbon fiber prepreg 4# | 801 | 722 | 55.2 | Metal substrate 4# | 3.8 |
| Carbon fiber prepreg 5# | 811 | 718 | 56.3 | Metal substrate 5# | 3.9 |
| Carbon fiber prepreg 6# | 802 | 716 | 55.1 | Metal substrate 6# | 3.8 |
| Carbon fiber prepreg 7# | 799 | 721 | 49.9 | Metal substrate 7# | 4.0 |
| Carbon fiber prepreg 8# | 806 | 736 | 51.3 | Metal substrate No. 8 | 3.8 |
| Carbon fiber prepreg 9# | 811 | 731 | 52.6 | Metal substrate 9# | 3.9 |
| Carbon fiber prepreg 10# | 819 | 722 | 54.2 | Metal substrate 10# | 3.8 |
| Carbon fiber prepreg D1# | - | - | - | Metal substrate D1# | - |
| Carbon fiber prepreg D2# | 706 | 430 | 41.2 | Metal substrate D2# | 3.1 |
| Carbon fiber prepreg D3# | 607 | 419 | 42.6 | Metal substrate D3# | 2.9 |
| Carbon fiber prepreg D4# | 611 | 422 | 43.6 | Metal substrate D4# | 3.0 |
| Carbon fiber prepreg D5# | 613 | 426 | 44.2 | Metal substrate D5# | 2.8 |
| Carbon fiber prepared by traditional hand pasting process | 328 | 217 | 47.6 | Metal base material | 2.3 |
| Carbon fiber prepreg 1# | 945 | 945 | 80.3 | Metal substrate E1# | 4.0 |
| Carbon fiber prepreg 1# | 945 | 945 | 80.3 | Metal substrate E2# | 4.2 |
| Carbon fiber prepreg 1# | 945 | 945 | 80.3 | Metal substrate E3# | 4.0 |
| Carbon fiber prepreg 1# | 945 | 945 | 80.3 | Metal substrate E4# | 2.9 |
| Carbon fiber prepreg 1# | 945 | 945 | 80.3 | Metal substrate E5# | 4.2 |
As can be seen from the table 2, when the carbon fiber prepreg is used for reinforcing a ship body, the carbon fiber prepreg can be tightly combined with an epoxy resin layer and can be cured in water, and the underwater curing and reinforcing of a ship body structure can be realized. Because the ethylene diamine is used as the curing agent in the prepreg D1#, the amine substance can generate a crosslinking reaction with the epoxy resin at room temperature to cure the epoxy resin, so that when the carbon fiber prepreg D1# is used for hull reinforcement, the carbon fiber prepreg D1# is already cured before being laid on the metal structure steel base material, and cannot be continuously combined with the epoxy resin coating on the metal structure steel base material, and the reinforcement for a hull structure cannot be realized; in addition, the prepreg resin D4# directly mixes the curing agent, the toughening agent, the filler and the epoxy resin at high temperature, and partial functional groups in the curing agent toluene diisocyanate can react with the epoxy resin at high temperature, so that the amine curing agent obtained by the reaction with water is greatly reduced when the prepreg resin is cured underwater, and the curing performance is poor; in addition, the carbon fiber produced by the traditional hand pasting process cannot control the resin content, so the mechanical property is poor, and when the carbon fiber is used for reinforcing a ship body, the bonding strength between the carbon fiber and a metal base material is small, and the reinforcing effect is poor.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The prepreg resin for reinforcing the ship body is characterized by comprising 60-110 parts of epoxy resin, 3-30 parts of a toughening agent, 5-25 parts of a filler and 7-15 parts of a curing agent in parts by weight;
wherein the epoxy resin comprises a first epoxy resin and a second epoxy resin, and the curing agent comprises at least one of isocyanate; the isocyanate is selected from at least one of polyphenyl methane polyisocyanate, toluene diisocyanate, 1, 5-naphthalene diisocyanate and 3, 3-dimethyl-4, 4-biphenyl diisocyanate;
the prepreg resin comprises the following steps when used for reinforcing a ship body:
after plasma treatment is carried out on a region to be reinforced of the ship body, continuously coating third epoxy resin on the region to be reinforced, then laying carbon fiber prepreg on the region to be reinforced, and curing in water, thereby reinforcing the region to be reinforced;
wherein the carbon fiber prepreg is obtained by impregnating carbon fibers in prepreg resin at the temperature of 60-80 ℃ and the relative humidity of not more than 30%.
2. The prepreg resin of claim 1, wherein the first epoxy resin is a liquid bisphenol a type epoxy resin, and the second epoxy resin is at least one selected from the group consisting of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol type epoxy resin, and a urethane-modified epoxy resin;
the toughening agent is at least one selected from thermoplastic resin, synthetic rubber, core-shell rubber, polyurethane prepolymer and phthalate;
the filler is at least one selected from calcium carbonate, magnesium carbonate, silicon dioxide, alumina, quartz powder, silicon micropowder and bentonite.
3. The prepreg resin according to claim 1 or 2, which comprises 20 parts by weight of a solid bisphenol a-type epoxy resin, 30 parts by weight of a bisphenol F-type epoxy resin, 10 parts by weight of an o-cresol formaldehyde type epoxy resin, 9 parts by weight of a polybutadiene rubber toughening agent, 30 parts by weight of a liquid bisphenol a-type epoxy resin, 8 parts by weight of calcium carbonate, 5 parts by weight of quartz powder, 2 parts by weight of bentonite and 10 parts by weight of toluene diisocyanate.
4. A process for preparing the prepreg resin of claim 1 or 2, characterized in that the process comprises the steps of:
mixing the curing agent and part of the epoxy resin at 10-30 ℃ to obtain a mixture A, mixing the rest of the epoxy resin, the toughening agent and the filler to obtain a mixture B, and mixing the mixture A and the mixture B to obtain the prepreg resin.
5. Method according to claim 4, characterized in that it comprises the following steps: mixing a first epoxy resin and a curing agent at 10-30 ℃ to obtain a mixture A, mixing a second epoxy resin, a toughening agent and a filler at 80-150 ℃ to obtain a mixture B, cooling the temperature of the mixture B to 50-60 ℃, and mixing the mixture B with the mixture A to obtain the prepreg resin;
wherein the first epoxy resin is liquid bisphenol A epoxy resin, and the second epoxy resin is at least one selected from bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenolic epoxy resin and polyurethane modified epoxy resin.
6. A method of reinforcing a hull, the method comprising the steps of:
after plasma treatment is carried out on a region to be reinforced of the ship body, continuously coating third epoxy resin on the region to be reinforced, then laying carbon fiber prepreg on the region to be reinforced, and curing in water, thereby reinforcing the region to be reinforced;
wherein the carbon fiber prepreg is obtained by impregnating carbon fibers in a prepreg resin selected from the prepreg resins described in any one of claims 1 to 3 or prepared by the method described in claim 4 or 5 at a temperature of 60 ℃ to 80 ℃ and a relative humidity of not more than 30%.
7. A method of reinforcing a ship hull according to claim 6, wherein said plasma treated gas is air;
the pressure of the plasma treatment is 0.08 MPa-0.12 MPa;
the power of the plasma treatment is 50W-1000W;
the plasma treatment time is 0.5 min-60 min.
8. The method of claim 6, wherein the area to be reinforced is painted with the third epoxy resin within no more than 30 minutes after the plasma treatment of the area to be reinforced of the hull.
9. The method of reinforcing a hull according to claim 6, wherein said third epoxy is applied at a thickness of 1 mm to 10 mm.
10. The method of reinforcing a ship hull according to any one of claims 6 to 9, wherein said third epoxy resin is selected from at least one of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin and a glycidylamine type epoxy resin;
the carbon fiber is at least one selected from carbon fiber unidirectional cloth and carbon fiber bidirectional cloth with the tensile strength of not less than 300.
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Denomination of invention: A kind of prepreg resin for reinforcing ship hull and its preparation method and application Effective date of registration: 20220831 Granted publication date: 20220218 Pledgee: Pingyuan County sub branch of Postal Savings Bank of China Ltd. Pledgor: Shandong Jiangshan Fiber Technology Co.,Ltd. Registration number: Y2022980014105 |