Supporting composite material for low-temperature storage tank and forming method of supporting composite material

Abstract

The invention relates to a supporting composite material for a low-temperature storage tank and a forming method thereof, the supporting composite material comprises a composite material laminated wood body and a flame-retardant fireproof layer arranged on the surface of the composite material laminated wood body, and the composite material laminated wood body is composed of the following components in parts by weight: 100 parts of epoxy resin, 30-60 parts of a curing agent and 100-200 parts of glass fiber; the flame-retardant fireproof layer is prepared from the following components in parts by weight: 100 parts of epoxy resin, 30 to 60 parts of curing agent, 80 to 150 parts of glass fiber, 10 to 50 parts of inorganic filler and 5 to 10 parts of thermal insulation material. During use, the flame-retardant fireproof layers are manually coated on the two sides of the composite material laminated wood body, so that the surface flame spreading rate of a supporting composite material reaches 6, flame spreading is effectively prevented, the fire resistance is improved, and the composite material laminated wood body can keep mechanical strength and does not deform in structure for a long time under the conditions of high temperature and flame; and longer rescue and fire prevention time is won for the low-temperature storage tank, and the safety is improved.

Description

Technical Field

[0001] This invention relates to the technical field of composite materials, specifically to a supporting composite material for cryogenic storage tanks and its molding method, and more particularly to a low surface flame spread rate supporting composite laminate wood for liquefied gas cryogenic storage tanks and its molding method. Background Technology

[0002] In existing technologies, laminated wood is an important component of cryogenic liquefied gas ships and facilities, mainly located between the liquefied gas storage tank and the steel base, playing a vital role in load-bearing and heat insulation. In recent years, glass fiber reinforced resin matrix composite products have been gradually applied in this field, replacing traditional wood materials. Compared with wood, composite materials have better mechanical properties, corrosion and weather resistance, and cost advantages.

[0003] Ship fire safety has always been a major global concern, and in recent years, both domestic and international requirements for the fire safety performance of marine materials have been continuously improved. The GB / T 20368 standard requires a flame spread index of no more than 25 for insulation materials used in liquefied natural gas (LNG) ships, and the NFPA 59A code issued by the National Fire Protection Association (NFPA) in the United States also sets forth similar requirements. Neither traditional wood fiber reinforced laminated wood nor resin-based tank support composite laminated wood possesses fire-resistant properties.

[0004] A patent (CN 117430850 A) describes a molding preparation method for composite laminated wood and the laminated wood itself. It involves adding 5-25 parts of flame retardant to epoxy resin to improve the flame retardant properties of the composite laminated wood. The laminated wood is typically large (thickness usually over 300mm). This traditional flame retardant modification method requires a large amount of flame retardant, which severely affects the overall mechanical properties and water resistance of the composite material, posing a greater safety risk when used in liquefied gas facilities. Using fire-retardant coatings can reduce the flame spread rate on the surface of the composite material without affecting the structural mechanical properties. However, fire-retardant coatings are prone to peeling in complex marine environments with high temperature, high humidity, and thermal shock, resulting in high maintenance costs.

[0005] Therefore, in accordance with relevant domestic and international standards and specifications, there is an urgent need for a low surface flame spread rate, excellent mechanical properties, and weather resistance composite laminate wood for supporting cryogenic liquefied gas storage tanks. Summary of the Invention

[0006] The purpose of this invention is to provide an improved composite material for supporting cryogenic storage tanks and its molding method. Through improvements in structure and method, the laminated wood composite material for supporting cryogenic storage tanks has a low surface flame spread rate, while also possessing high mechanical strength and water resistance.

[0007] To achieve the above objectives, the technical solution of the present invention is: a supporting composite material for cryogenic storage tanks, characterized in that: the supporting composite material comprises a composite laminated wood body and a flame-retardant and fire-resistant layer disposed on the surface of the composite laminated wood body, the composite laminated wood body being composed of the following parts by weight: 100 parts epoxy resin, 30-60 parts curing agent and 100-200 parts glass fiber; the flame-retardant and fire-resistant layer being composed of the following parts by weight: 100 parts epoxy resin, 30-60 parts curing agent, 80-150 parts glass fiber, 10-50 parts inorganic filler and 5-10 parts heat insulation material.

[0008] Preferably, the supporting composite material includes at least two layers of composite laminated wood body, and each layer of composite laminated wood body has a flame-retardant and fire-resistant layer manually coated on both sides.

[0009] Furthermore, in the composite laminate wood matrix, the epoxy resin is bisphenol A type epoxy resin with a viscosity of 300-500 m·Pas, the curing agent is an amine curing agent with a curing temperature of 60-100℃, and the glass fiber is glass fiber cloth with an areal density of 200-1200 g / m³. 2 .

[0010] Furthermore, in the flame-retardant and fire-resistant layer composition, the epoxy resin is bisphenol A type epoxy resin with a viscosity of 300-500 m·Pas, the curing agent is an aliphatic amine epoxy resin curing agent with a curing temperature of 20-40℃, and the glass fiber is glass fiber cloth with an areal density of 200-1200 g / m². 2 The inorganic filler is any one of the following: kaolin, mica, low-melting-point glass powder, glass fiber powder, zinc borate, aluminum hydroxide, or expanded graphite. The thermal insulation material is hollow glass microspheres with a D50 particle size of 10-50 μm and a density of 0.3-0.6 g / cm³. 3 .

[0011] Furthermore, the epoxy resin and glass fiber used in the composite laminate wood body and its corresponding flame-retardant and fire-resistant layer must be the same.

[0012] A molding method for a supporting composite material for cryogenic storage tanks, characterized by the following steps: a) preparing the resin for the composite laminate wood body by mixing epoxy resin and curing agent and dispersing the mixture evenly using a disperser to form a composite wood body mixture; b) fiber impregnation by uniformly coating the composite wood body mixture prepared in step a onto a cut fiberglass cloth using a scraper; c) layering and curing by laying the impregnated fiberglass cloth into a mold, laying a specified number of layers (50-200), and then pressing the mold into a press for curing; d) demolding by demolding the cured composite structural layer and sanding both sides of the composite structural layer to form the composite wood body; e) preparing the resin for the flame-retardant and fire-resistant layer by mixing epoxy resin, curing agent, inorganic filler, and heat insulation material and dispersing the mixture evenly using a disperser to form a fire-resistant layer mixture; f) fireproofing layer application by laying the fiberglass cloth flat on a dry... On the clean surface, manually and evenly apply the prepared fire-resistant layer adhesive mixture to one side of the fiberglass cloth. Then, align and adhere the fiberglass cloth with the fire-resistant layer adhesive-coated side to the sanded surface of the composite laminate wood body. Next, evenly apply the fire-resistant layer adhesive mixture to the other side of the fiberglass cloth. Then, use another piece of composite laminate wood body to adhere it. Repeat the above steps, laying a total of 3-10 layers; g. Fireproof layer curing: Let the bonded composite laminate wood body and flame-retardant fire-resistant layer cure statically. After curing, the supporting composite material is obtained.

[0013] Furthermore, in step a, the epoxy resin is a bisphenol A type epoxy resin with a viscosity of 300-500 m·Pas, the curing agent is an amine curing agent, and the disperser speed is 2000 r / min.

[0014] In step c, the curing temperature is 60-100℃ and the curing time is 3-8 hours; in step d, an electric sander is used for sanding, and the sandpaper grit is 50-200.

[0015] Furthermore, in step e, the disperser speed is 2000 r / min; in step g, the curing temperature is 30-60℃, and the humidity is ≤70%. The curing time is 8-24h.

[0016] Compared with the prior art, the technical solution of the present invention not only improves the overall technical solution, but also includes many improvements in details. Specifically, it has the following beneficial effects: 1. The improved solution of the present invention includes a composite material laminated wood body and a flame-retardant and fire-resistant layer on the surface of the composite material laminated wood body. By setting a flame-retardant and fire-resistant layer on the surface of the composite material laminated wood body, the flame spread rate on the surface of the supporting composite material is significantly reduced. In the event of a fire, it can effectively prevent the spread of flames. The flame spread index (FSI) measured according to ASTM E84 can reach 10. 2. In the technical solution of the present invention, the flame-retardant and fire-resistant layer is composed of the following parts by weight: 100 parts of epoxy resin, 30-60 parts of curing agent, 80-150 parts of glass fiber, 10-50 parts of inorganic filler and 5-10 parts of heat insulation material. The setting of the flame-retardant and fire-resistant layer does not affect the overall mechanical strength of the supporting composite material, and at the same time avoids the problems of increased water absorption and decreased weather resistance caused by the direct addition of flame retardant. 3. In the preparation method of the present invention, when the fireproof layer is laid, the prepared fireproof layer mixed adhesive is manually and evenly coated on one side of the glass fiber cloth. Compared with the direct coating, this hand lay-up method has better integrity and compatibility. It is less prone to cracking and peeling in the complex marine environment of high temperature, high humidity, high salt and cold and heat cycle impact. 4. This invention has a simple structure, is easy to manufacture, has good fire-retardant properties, and is easy to promote and utilize. Detailed Implementation

[0017] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0018] This invention provides a supporting composite material for cryogenic storage tanks, which differs from existing technologies in that: the supporting composite material includes a composite laminate wood body and a flame-retardant and fire-resistant layer disposed on the surface of the composite laminate wood body. The composite laminate wood body is composed of the following parts by weight: 100 parts epoxy resin, 30-60 parts curing agent, and 100-200 parts glass fiber; the flame-retardant and fire-resistant layer is composed of the following parts by weight: 100 parts epoxy resin, 30-60 parts curing agent, 80-150 parts glass fiber, 10-50 parts inorganic filler, and 5-10 parts thermal insulation material.

[0019] Specifically, the flame-retardant and fire-resistant layer is manually coated on both sides of the composite laminate wood body, which makes the flame spread rate of the supporting composite surface reach 6, effectively preventing flame propagation, improving fire resistance, and enabling the composite laminate wood body to maintain mechanical strength and structural non-deformation for a long time under high temperature and flame conditions, thus providing a longer rescue and fire prevention time for cryogenic storage tanks and improving safety.

[0020] Example 1 This embodiment describes a supporting composite material for cryogenic storage tanks. The supporting composite material comprises two layers of composite laminated wood body, with a flame-retardant and fire-resistant layer manually coated on both sides of each composite laminated wood body. The composite laminated wood body consists of the following parts by weight: 100 parts epoxy resin, 40 parts curing agent, and 150 parts glass fiber; the flame-retardant and fire-resistant layer consists of the following parts by weight: 100 parts epoxy resin, 35 parts curing agent, 120 parts glass fiber, 30 parts inorganic filler, and 8 parts thermal insulation material. The epoxy resin and glass fiber used in both the composite laminated wood body and its corresponding flame-retardant and fire-resistant layer must be the same.

[0021] Specifically, in the composite laminate wood matrix, the epoxy resin is bisphenol A type epoxy resin with a viscosity of 300-500 m·Pas, the curing agent is an amine curing agent, such as polyetheramine or 1,3-bis(aminomethyl)cyclohexane, and the curing temperature is 60-100℃. The glass fiber is glass fiber cloth, which can be E-BX800 biaxial cloth produced by Taishan Fiberglass or E-DB-800 biaxial cloth produced by Changzhou Hongfa. In this embodiment, polyetheramine and E-BX800 biaxial cloth produced by Taishan Fiberglass are used, with an areal density of 200-1200 g / m2.

[0022] Furthermore, in the flame-retardant and fire-resistant layer composition, the epoxy resin is bisphenol A type epoxy resin with a viscosity of 300-500 m·Pas; the curing agent is an aliphatic amine epoxy resin curing agent, such as diethylenetriamine or triethylenetetramine, with a curing temperature of 20-40℃; the glass fiber is glass fiber cloth, such as E-BX800 biaxial cloth produced by Taishan Fiberglass or E-DB-800 biaxial cloth produced by Changzhou Hongfa, with a surface density of 200-1200 g / m2; the thermal insulation material is hollow glass microspheres, such as N32 from Zhongke Huaxing, S15 from 3M (USA), or HN50 from Shanxi Hainuo. In this embodiment, the curing agent is diethylenetriamine, the glass fiber is E-BX800 biaxial cloth from Taishan Fiberglass, and the inorganic filler is aluminum hydroxide. The inorganic filler provides flame-retardant properties and, through decomposition, melting, and expansion at high temperatures, prevents flame propagation. The thermal insulation material is hollow glass microspheres from Zhongke Huaxing N32, with a D50 particle size of 10-50μm and a density of 0.3-0.6g / cm3. The hollow glass microspheres have a low thermal conductivity and are used to block the transfer of flame heat to the structural layer.

[0023] The supporting composite material in this embodiment has a low surface flame spread rate, as well as high mechanical strength and water resistance. Furthermore, the addition of a flame-retardant and fire-resistant layer does not affect the overall mechanical strength of the supporting composite material, and avoids the problems of increased water absorption and decreased weather resistance caused by directly adding flame retardants.

[0024] Example 2 This embodiment describes a molding method for a supporting composite material for cryogenic storage tanks, comprising the following steps: a) preparing the resin for the composite laminate wood body by mixing epoxy resin and curing agent and dispersing the mixture evenly using a disperser to form a composite wood body mixed adhesive; b) fiber impregnation by uniformly coating the composite wood body mixed adhesive prepared in step a onto a cut fiberglass cloth using a scraper; c) layering and curing by laying the adhesive-impregnated fiberglass cloth into a mold, laying a specified number of layers (200 layers), and then placing the mold into a press for pressure curing; d) demolding by demolding the cured composite structural layer and sanding both sides of the composite structural layer to form the composite wood body; e) preparing the resin for the flame-retardant and fire-resistant layer by mixing epoxy resin, curing agent, inorganic filler, and heat insulation material and dispersing the mixture evenly using a disperser to form a fire-resistant layer mixed adhesive; f) fireproofing layer application by laying the fiberglass cloth flat on a clean surface. On the work surface, the prepared refractory layer mixture is manually and evenly applied to one side of the fiberglass cloth. Then, the fiberglass cloth coated with the refractory layer mixture is aligned with the sanded surface of the composite laminate wood body and bonded together. The refractory layer mixture is then evenly applied to the other side of the fiberglass cloth, and another piece of composite laminate wood body is used for bonding. The above steps are repeated, with a total of 3-10 layers laid. g. Fireproof layer curing: The bonded composite laminate wood body and flame-retardant refractory layer are left to cure statically. After curing, the supporting composite material is obtained.

[0025] Further, in step a, the resin for the composite structural layer is prepared by mixing 100 parts (by weight, the same below) of bisphenol A type epoxy resin and 30 parts of amine curing agent, and then dispersing them evenly using a disperser at a speed of 2000 r / min. In step b, the fibers are impregnated by uniformly coating the prepared adhesive onto 120 parts of cut glass fiber cloth using a scraper.

[0026] In step c, the curing temperature is 80℃ and the curing time is 6 hours; in step d, an electric sander is used for sanding, and the sandpaper grit is 50-200.

[0027] In step e, the fireproof layer resin is prepared by mixing 100 parts of bisphenol A type epoxy resin, 25 parts of polyethylene polyamine curing agent, 25 parts of kaolin, 15 parts of low melting point glass powder, 15 parts of aluminum hydroxide, 1 part of expanded graphite and 5 parts of hollow glass microspheres, and then dispersing them evenly with a disperser at a speed of 2000 r / min.

[0028] In step f, the fireproof layer is laid out by laying the fiberglass cloth flat on a clean surface. The prepared fireproof resin is evenly applied to one side of the fiberglass cloth. Then, the resin-coated side of the fiberglass cloth is aligned and bonded to the polished side of the composite material structural layer. The resin is then evenly applied to the other side of the fiberglass. This process is repeated twice.

[0029] In step g, the curing temperature is 30℃ and the humidity is ≤70%. The curing time is 8 hours. After curing, composite laminated wood is obtained.

[0030] The low surface flame spread rate composite laminate wood prepared in this embodiment, through the addition of structural and fire-resistant layers, exhibits excellent surface fire-retardant properties while ensuring the mechanical strength and water resistance of the laminate wood. The flame spread index (FSI) measured according to ASTM E84 reaches 10, and it maintains good bonding under high and low temperature shocks. Specific performance details are shown in Table 1 below. Table 1 Test results of Example 1 The above description, in conjunction with specific preferred embodiments, provides a further detailed explanation of the present invention. It should not be construed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, various simple deductions or substitutions can be made without departing from the concept of the present invention, and all such modifications and substitutions should be considered within the scope of protection of the present invention.

Claims

1. A supporting composite material for cryogenic storage tanks, characterized in that: The supporting composite material includes a composite laminated wood body and a flame-retardant and fire-resistant layer disposed on the surface of the composite laminated wood body. The composite laminated wood body consists of the following parts by weight. Composition: 100 parts epoxy resin, 30-60 parts curing agent, and 100-200 parts glass fiber; the flame-retardant and fire-resistant layer consists of the following parts by weight. Composition: 100 parts epoxy resin, 30-60 parts curing agent, 80-150 parts glass fiber, 10-50 parts inorganic filler, and 5-10 parts thermal insulation material.

2. The supporting composite material for cryogenic storage tanks according to claim 1, characterized in that: The supporting composite material comprises at least two layers of composite laminated wood body, with each layer of composite laminated wood body having a flame-retardant and fire-resistant layer manually coated on both sides.

3. The supporting composite material for cryogenic storage tanks according to claim 1, characterized in that: In the composite laminate wood matrix, the epoxy resin is bisphenol A type epoxy resin with a viscosity of 300-500 m·Pas, the curing agent is an amine curing agent with a curing temperature of 60-100℃, and the glass fiber is glass fiber cloth with an areal density of 200-1200 g / m³. 2 .

4. The supporting composite material for cryogenic storage tanks according to claim 1, characterized in that: In the flame-retardant and fire-resistant layer composition, the epoxy resin is bisphenol A type epoxy resin with a viscosity of 300-500 m·Pas, the curing agent is an aliphatic amine epoxy resin curing agent with a curing temperature of 20-40℃, and the glass fiber is glass fiber cloth with an areal density of 200-1200 g / m². 2 The inorganic filler is any one of the following: kaolin, mica, low-melting-point glass powder, glass fiber powder, zinc borate, aluminum hydroxide, or expanded graphite. The thermal insulation material is hollow glass microspheres with a D50 particle size of 10-50 μm and a density of 0.3-0.6 g / cm³. 3 .

5. The supporting composite material for cryogenic storage tanks according to claim 1, characterized in that: The epoxy resin and glass fiber used in the composite laminate wood body and its corresponding flame-retardant and fire-resistant layer must be the same.

6. A molding method for a supporting composite material for cryogenic storage tanks according to claim 1, characterized in that: The molding method includes the following steps: a) preparing the resin for the composite laminate wood body, mixing epoxy resin and curing agent, and then dispersing evenly using a disperser to form a laminate wood body mixed adhesive; b) fiber impregnation, uniformly coating the laminate wood body mixed adhesive prepared in step a onto the cut glass fiber cloth using a scraper; c) lay-up and curing, laying the adhesive-impregnated fiber cloth in the mold, laying a specified number of layers, 50-200 layers, and after laying, placing the mold into a press for pressure curing; d. Demolding: Demold the cured composite material structural layer and sand both sides of the composite material structural layer to form the composite material laminate wood body; e. Preparing the flame-retardant and fire-resistant layer resin: Mix epoxy resin, curing agent, inorganic filler, and heat insulation material, and disperse evenly using a disperser to form a fire-resistant layer mixture; f. Fireproof layer application: Lay fiberglass cloth flat on a clean surface, manually and evenly apply the prepared fire-resistant layer mixture to one side of the fiberglass cloth, then align and adhere the fiberglass cloth with the sanded side of the composite material laminate wood body, then evenly apply the fire-resistant layer mixture to the other side of the fiberglass cloth, and re-attach it with another piece of composite material laminate wood body. Repeat the above steps, applying a total of 3-10 layers; g. Fireproof layer curing: Allow the bonded composite material laminate wood body and flame-retardant and fire-resistant layer to cure statically. After curing, the supporting composite material is obtained.

7. A molding method for a supporting composite material for cryogenic storage tanks according to claim 6, characterized in that: In step a, the epoxy resin is bisphenol A type epoxy resin with a viscosity of 300-500 m·Pas, the curing agent is an amine curing agent, and the disperser speed is 2000 r / min.

8. A molding method for a supporting composite material for cryogenic storage tanks according to claim 6, characterized in that: In step c, the curing temperature is 60-100℃ and the curing time is 3-8 hours; in step d, an electric sander is used for sanding, and the sandpaper grit is 50-200.

9. A molding method for a supporting composite material for cryogenic storage tanks according to claim 6, characterized in that: In step e, the disperser speed is 2000 r / min; in step g, the curing temperature is 30-60℃, and the humidity is ≤70%. The curing time is 8-24 h.

Images