CN116180451A - Continuous silicon carbide fiber sizing agent and application thereof - Google Patents

Continuous silicon carbide fiber sizing agent and application thereof Download PDF

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Publication number
CN116180451A
CN116180451A CN202310180165.0A CN202310180165A CN116180451A CN 116180451 A CN116180451 A CN 116180451A CN 202310180165 A CN202310180165 A CN 202310180165A CN 116180451 A CN116180451 A CN 116180451A
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sizing agent
parts
silicon carbide
epoxy resin
carbon fiber
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黄小忠
易君
刘鹏
吴李聪
肖义凡
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Hunan Zerui New Material Co ltd
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Hunan Zerui New Material Co ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/568—Reaction products of isocyanates with polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35—Abrasion, pilling or fibrillation resistance
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a continuous silicon carbide fiber sizing agent and application thereof, wherein the continuous silicon carbide fiber sizing agent comprises the following components in parts by mass: 80-100 parts of water, 5-20 parts of waterborne polyurethane modified epoxy resin, 0.3-3 parts of acrylate modified polyurethane, 0.2-2 parts of emulsifier and 0.2-2 parts of softener. According to the continuous carbon fiber sizing agent provided by the invention, the waterborne polyurethane modified epoxy resin and the acrylic ester modified polyurethane are combined, and in the process of sizing the continuous carbon fiber, the waterborne polyurethane modified epoxy resin and the acrylic ester modified polyurethane undergo a crosslinking reaction during drying, and due to the existence of crosslinking points among fibers, fiber filaments and hairballs can be attached, so that the bonding force among the fibers is improved, and monofilament fibers are prevented from being separated from fiber bundles, so that the hairballs and the hairballs are reduced, and the bundling property and the wear resistance are improved.

Description

Continuous silicon carbide fiber sizing agent and application thereof
Technical Field
The invention relates to a silicon carbide fiber sizing agent, in particular to a continuous silicon carbide fiber sizing agent and application thereof.
Background
The silicon carbide fiber prepared by the precursor method has the characteristics of high strength, high modulus, high temperature resistance, oxidation resistance and low density, has great application potential in the field of aerospace, and is a key material for improving the working temperature and thrust-weight ratio of an aeroengine. But the fibers need to be woven during processing of one-dimensional silicon carbide fibers into two-or multi-dimensional silicon carbide fiber reinforced composites. Because the silicon carbide fiber belongs to brittle materials, has low elongation at break and small elasticity, and the strength of fiber bundles can be reduced along with the increase of the length of the fiber, in the weaving process, when the fiber, the fiber and the creel are rubbed with each other, the situation of monofilament fracture easily occurs, so that the phenomena of a large number of broken filaments, even fracture and the like of the fiber bundles are caused, the performance of the silicon carbide fiber weaving body is reduced, the weaving efficiency of the silicon carbide fiber is influenced, and the product quality of the silicon carbide fabric is seriously reduced.
In order to improve the braiding of silicon carbide fibers, the fibers must be sized. Huang Xiangxian et al (CN 109853268A) have the problems of good film forming property, strong cohesiveness, very good bundling property, greatly reduced fiber filigree and increased wear resistance, but improved fiber stiffness and poor flexibility of sizing agents prepared by taking PVA (polyvinyl alcohol) as a main sizing agent. Zhang Xinyuan et al (CN 111704478B) propose a sizing method for high-strength high-modulus silicon carbide fibers, which comprises the steps of preparing deionized water, epoxy resin sizing agent and hydrophilic softening agent into sizing agent according to a certain proportion, wherein the epoxy resin and the hydrophilic softening agent ensure the flexibility of the fibers after sizing, and avoid the situation that the fibers are too stiff to be brittle broken during weaving, but the bundling property is deficient, and no emulsifying agent is added into the system, so that the stability of the sizing agent for long-term storage and use is problematic. Zong et al (CN 110172829A) prepared sizing agent by taking aqueous polyurethane as main sizing agent, effectively improves the softness of sizing film on the surface of silicon carbide fiber bundle, improves the bundling property, wear resistance and stretching property of the fiber, but uses toxic organic matters such as ketone and amine as auxiliary agents, and causes a certain threat to personal safety.
Disclosure of Invention
In view of the above, a first object of the present invention is to provide a continuous carbon fiber sizing agent. The sizing agent disclosed by the invention is prepared from environment-friendly materials, has no toxicity, and is convenient for industrial mass production and use.
A second object of the present invention is to provide the use of a continuous carbon fiber sizing agent. After the continuous carbonized fiber sizing agent is used for sizing the continuous carbonized fiber, the sized fiber has good bundling property and wear resistance, has very good flexibility, and can effectively solve the problem that filaments and cracks are easy to generate in the weaving process.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention relates to a continuous carbonized fiber sizing agent which comprises the following components in parts by weight: 80-100 parts of water, 5-20 parts of waterborne polyurethane modified epoxy resin, 0.3-3 parts of acrylate modified polyurethane, 0.2-2 parts of emulsifier and 0.2-2 parts of softener.
The continuous carbonized fiber sizing agent provided by the invention adopts the combination of the waterborne polyurethane modified epoxy resin and the acrylic ester modified polyurethane, and the inventor discovers that if the waterborne polyurethane modified epoxy resin is singly used, the sized fiber is very flexible, but has poor bundling property, and more fiber fuzziness is obtained, and when the acrylic ester modified polyurethane is introduced, the obtained continuous carbonized fiber sizing agent has crosslinking reaction with the acrylic ester modified polyurethane in the continuous carbonized fiber sizing process, and the waterborne polyurethane modified epoxy resin and the acrylic ester modified polyurethane are subjected to crosslinking reaction, so that the fiber fuzziness and fuzziness are attached due to the existence of crosslinking points among fibers, the cohesive force among fibers is improved, and the monofilament fibers are restrained from being separated from fiber tows, so that the fuzziness and fuzziness are reduced, and the bundling property and the wear resistance are improved.
In the experimental exploration process, the inventor tries a large number of formulas, even though the polyurethane is modified, besides the acrylic ester modified polyurethane, the inventor also tries organosilicon modified polyurethane, organic fluorine modified polyurethane and the like, and as a result, when only the acrylic ester modified polyurethane is interacted with the aqueous polyurethane modified epoxy resin, the bundling property and the wear resistance are optimal, and the acrylic ester modified polyurethane also has the characteristics of strong hydrophilicity and good stability, so that the continuous carbonized fiber sizing agent is more uniform and stable.
Of course, the addition amount of the acrylic ester modified polyurethane needs to be effectively controlled, if the addition amount of the acrylic ester modified polyurethane is too much, the fiber after sizing is too stiff, the flexibility is poor, the weaving is not facilitated, if the addition amount is too little, the bundling property of the fiber after sizing is poor, and the yarn is easy to generate during the weaving.
In a preferred scheme, the continuous carbonized fiber sizing agent comprises the following components in parts by weight: 80 to 100 parts of water, 5 to 15 parts of waterborne polyurethane modified epoxy resin, 0.7 to 1 part of acrylic ester modified polyurethane, 0.3 to 0.6 part of emulsifier and 0.6 to 1.2 parts of softener.
Further preferably, the continuous carbonized fiber sizing agent comprises the following components in parts by weight: 80 to 90 parts of water, 10 to 15 parts of waterborne polyurethane modified epoxy resin, 0.7 to 0.8 part of acrylic ester modified polyurethane, 0.6 part of emulsifier and 0.8 to 1.2 parts of softener.
Preferably, the water is deionized water.
In a preferred scheme, the aqueous polyurethane modified epoxy resin is aqueous polyurethane modified bisphenol A type epoxy resin.
In a preferred scheme, the preparation process of the aqueous polyurethane modified epoxy resin comprises the following steps: the preparation method comprises the following steps of (by mass ratio) mixing aqueous polyurethane, bisphenol A epoxy resin and dibutyltin diacetate: 15-30: and (3) stirring and mixing uniformly 0.01-0.05, heating to 75-100 ℃, preserving heat for 2-5 h, and cooling to obtain the waterborne polyurethane modified epoxy resin.
Further preferably, the preparation process of the aqueous polyurethane comprises the following steps: polyethylene glycol (PEG), diisocyanate and dihydroxyacetic acid are mixed according to the mass ratio of 50-70: 30-40: and 5-10, stirring and mixing uniformly, heating to 60-80 ℃, preserving heat for 2-5 h, and cooling to obtain the aqueous polyurethane.
The aqueous polyurethane modified epoxy resin provided by the invention has good water solubility, does not need to use an organic solvent, can be well and stably present as a main component of a sizing agent, and does not have layering, mainly because hydrophilic groups are added in the process of preparing the aqueous polyurethane, the aqueous polyurethane modified epoxy resin can be better dissolved in water and is stable, and the problem that the non-modified polyurethane is difficult to dissolve when being added into the sizing agent, so that the sizing agent is uneven is avoided.
In a preferred embodiment, the emulsifier is alkylphenol ethoxylate (TX-10) or octylphenol ethoxylate (OP-10). The emulsifier adopted by the invention has high chemical stability, is easy to dissolve in water, has excellent emulsifying capacity and has an antistatic effect.
In a preferred scheme, the softener is polyether amino block modified silicone oil.
In the actual operation process, the type of the polyether amino block modified silicone oil which can be selected is NE 810 or NE820, and the inventor discovers that the polyether amino block modified silicone oil is taken as a fourth-generation softener, has the very excellent softening effect of the amino modified silicone oil, and the introduced polyether chain segment greatly improves the hydrophilicity of the amino modified silicone oil, plays a self-emulsifying effect and does not break emulsion.
In a preferred scheme, the preparation process of the continuous carbon fiber sizing agent comprises the following steps: and (3) preparing water, waterborne polyurethane modified epoxy resin, acrylic ester modified polyurethane, an emulsifier and a softener according to a designed proportion, and uniformly mixing and stirring to obtain the polyurethane.
The invention also provides an application of the continuous carbon fiber sizing agent, wherein the continuous carbon fiber sizing agent is used for sizing the carbon fiber, and the sizing process comprises the following steps: and soaking the silicon carbide fiber in a continuous carbon fiber sizing agent to obtain the silicon carbide fiber coated with the sizing agent, and drying the silicon carbide fiber coated with the sizing agent at 150-250 ℃ to obtain the sized silicon carbide fiber.
In the application process of the invention, after the silicon carbide fiber coated with the sizing agent is obtained, the silicon carbide fiber coated with the sizing agent is dried at 150-250 ℃, in the process, water is evaporated, and the rest of the aqueous polyurethane modified epoxy resin and the acrylic ester modified polyurethane naturally become a layer of film which is attached to the fiber.
In the invention, the drying temperature needs to be effectively controlled, the sizing agent can be excessively volatilized even in case of too high drying temperature, and even cracking reaction can occur, and the drying temperature is too low, so that the drying at the normal sizing speed cannot be ensured, and the rolled fibers are finally stuck together.
Further preferably, the sizing process is that the silicon carbide fiber bypasses a guide roller, then passes through a sizing tank containing a continuous carbon fiber sizing agent, so that the silicon carbide fiber is soaked in the continuous carbon fiber sizing agent to obtain the silicon carbide fiber coated with the sizing agent, the silicon carbide fiber coated with the sizing agent continuously passes through a sizing roller, then passes through an oven to be dried at 150-250 ℃, and then is subjected to wire collection at a speed of 1-3 m/min by a wire collecting machine, thus obtaining the sized silicon carbide fiber.
In the actual operation process, the guide roller, the sizing tank and the grouting rod are cleaned, the smooth surface is ensured to be free from sundries, the fiber is prevented from being damaged, then the oven is started, and the temperature is raised to 150-250 ℃ and the heat is preserved.
Further preferably, the mixture is dried at 160-220 ℃.
Further preferably, the mixture is dried at 200 to 220 ℃.
Principle and advantages
1. The continuous silicon carbide fiber sizing agent provided by the invention can effectively solve the problem that high-strength high-modulus silicon carbide fibers are difficult to weave, and the sizing agent is used to coat a layer of adhesive film on the surface of the silicon carbide fibers, so that cracks and defects on the silicon carbide fibers are overcome, loose silicon carbide fiber bundles are bonded together, the broken filaments are greatly reduced, and the bundle filament strength and wear resistance of the continuous silicon carbide fiber sizing agent are improved.
2. According to the continuous silicon carbide fiber sizing agent provided by the invention, the sizing agent compounded by adopting the waterborne polyurethane modified epoxy resin and the modified polyurethane can give consideration to both flexibility and bundling property, so that the silicon carbide fiber with excellent weaving performance is obtained.
3. The continuous carbonized fiber sizing agent provided by the invention avoids the problem that the fiber is stiff after sizing by PVA (polyvinyl alcohol) sizing agent, so that the fiber cannot be brittle broken due to bending; meanwhile, the problem of poor bundling property of fiber bundles after sizing by a simple epoxy resin sizing agent is solved, and the broken filaments in the weaving process are reduced, so that the weaving quality is greatly improved.
4. The continuous carbon fiber sizing agent provided by the invention does not use an organic reagent as a solvent, is environment-friendly and environment-friendly, is uniform and stable, can be stored for a long time without deterioration and layering, does not contain elements corroding fibers, can well protect the fibers, has cheap, simple and easily obtained raw materials, simple process equipment and can be applied to large-scale industry.
Drawings
FIG. 1 is a flow chart of the present invention for a silicon carbide fiber sizing process.
In the figure, 1, silicon carbide fiber, 2, a guide roller, 3, a sizing groove, 4, a sizing roller, 5, an oven, 6, sized silicon carbide fiber and 7, a wire collecting machine.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to better demonstrate the objects, technical solutions and advantages of the present invention. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
(1) Preparation of sizing agent
Firstly, polyethylene glycol (PEG), diisocyanate and dihydroxyacetic acid are mixed according to a mass ratio of 50:40:6, then heating to 70 ℃ and preserving heat for 3 hours, cooling to obtain aqueous polyurethane, and then mixing the aqueous polyurethane, bisphenol A epoxy resin and dibutyltin diacetate (catalyst) according to the mass ratio of 70:30: and (3) uniformly stirring and mixing the materials according to the proportion of 0.02, heating to 80 ℃, preserving heat for 5 hours, and cooling to obtain the waterborne polyurethane modified epoxy resin.
Deionized water, waterborne polyurethane modified epoxy resin, acrylic ester modified polyurethane, octyl phenol polyoxyethylene ether (OP-10) and polyether amino block modified silicone oil (NE 810) are mixed according to the mass ratio of 100:5:1:0.3:0.6, mixing and stirring uniformly to prepare the continuous carbon fiber sizing agent for standby.
(2) Preparation before sizing
The guide roller 2, the sizing tank 3 and the grouting rod 4 are cleaned, the smooth surface is ensured to be free from sundries, the fiber is prevented from being damaged, then the oven 5 is started, the temperature is raised to 160 ℃, and the heat is preserved.
(3) Sizing
The silicon carbide fiber 1 bypasses the guide roller 2, sequentially passes through the sizing tank 3, the grouting roller 4 and the oven 5, finally reaches the wire collecting machine 7, then the sizing agent is poured into the sizing tank 3, the silicon carbide fiber 1 is fully infiltrated, and finally the wire collecting is carried out at the speed of 3m/min, so that the sized silicon carbide fiber 6 is obtained.
Example 2
(1) Preparation of sizing agent
Polyethylene glycol (PEG), diisocyanate and dihydroxyacetic acid are mixed according to the mass ratio of 60:30:10, then heating to 80 ℃ and preserving heat for 2 hours, cooling to obtain aqueous polyurethane, and then mixing bisphenol aqueous polyurethane, A-type epoxy resin and dibutyltin diacetate (catalyst) according to the mass ratio of 75:25: and (3) uniformly stirring and mixing the components according to the proportion of 0.03, heating to 100 ℃, preserving heat for 2 hours, and cooling to obtain the waterborne polyurethane modified epoxy resin.
Deionized water, waterborne polyurethane modified epoxy resin, acrylic ester modified polyurethane, alkylphenol ethoxylate (TX-10) and polyether amino block modified silicone oil (NE 810) are mixed according to the mass ratio of 90:10:0.8:0.6:0.8, mixing and stirring uniformly to prepare sizing agent for standby.
(2) Preparation before sizing
The guide roller 2, the sizing tank 3 and the grouting rod 4 are cleaned, the smooth surface is ensured to be free from sundries, the fiber is prevented from being damaged, then the oven 5 is started, the temperature is raised to 200 ℃, and the heat is preserved.
(3) Sizing
The silicon carbide fiber 1 bypasses the guide roller 2, sequentially passes through the sizing tank 3, the grouting roller 4 and the oven 5, finally reaches the wire collecting machine 7, then the sizing agent is poured into the sizing tank 3, the silicon carbide fiber 1 is fully infiltrated, and finally the wire collecting is carried out at the speed of 2m/min, so that the sized silicon carbide fiber 6 is obtained.
Example 3
(1) Preparation of sizing agent
Polyethylene glycol (PEG), diisocyanate and dihydroxyacetic acid are mixed according to the mass ratio of 65:36:7, uniformly stirring and mixing, heating to 75 ℃, preserving heat for 5 hours, cooling to obtain waterborne polyurethane, and then mixing the waterborne polyurethane, bisphenol A epoxy resin and dibutyltin diacetate (catalyst) according to the mass ratio of 80:15: and (3) uniformly stirring and mixing the materials according to the proportion of 0.05, heating to 90 ℃, preserving heat for 4 hours, and cooling to obtain the waterborne polyurethane modified epoxy resin.
Deionized water, aqueous epoxy resin, acrylic ester modified polyurethane, alkylphenol ethoxylate (TX-10) and polyether amino block modified silicone oil (NE 820) are mixed according to the mass ratio of 80:15:0.7:0.6:1.2, mixing and stirring uniformly to prepare sizing agent for standby.
(2) Preparation before sizing
The guide roller 2, the sizing tank 3 and the grouting rod 4 are cleaned, the smooth surface is ensured to be free from sundries, the fiber is prevented from being damaged, then the oven 5 is started, the temperature is raised to 220 ℃, and the heat is preserved.
(3) Sizing
The silicon carbide fiber 1 bypasses the guide roller 2, sequentially passes through the sizing tank 3, the grouting roller 4 and the oven 5, finally reaches the wire collecting machine 7, then the sizing agent is poured into the sizing tank 3, the silicon carbide fiber 1 is fully infiltrated, and finally the wire collecting is carried out at the speed of 1m/min, so that the sized silicon carbide fiber 6 is obtained.
Comparative example 1
(1) Preparation of sizing agent
Deionized water, polyvinyl alcohol (PVA), alkylphenol ethoxylates (TX-10) and polyether amino block modified silicone oil (NE 820) are mixed according to the mass ratio of 80:2:0.6:1.2, mixing and stirring uniformly to prepare sizing agent for standby.
(2) Preparation before sizing
The guide roller 2, the sizing tank 3 and the grouting rod 4 are cleaned, the smooth surface is ensured to be free from sundries, the fiber is prevented from being damaged, then the oven 5 is started, and the temperature is raised to 250 ℃ and the heat is preserved.
(3) Sizing
The silicon carbide fiber 1 bypasses the guide roller 2, sequentially passes through the sizing tank 3, the grouting roller 4 and the oven 5, finally reaches the wire collecting machine 7, then the sizing agent is poured into the sizing tank 3, the silicon carbide fiber 1 is fully infiltrated, and finally the wire collecting is carried out at the speed of 1m/min, so that the sized silicon carbide fiber 6 is obtained.
The sized fiber bundles were found to be very stiff, but have poor abrasion resistance, and broken during weaving, although the bundling properties were very good.
Comparative example 2
(1) Preparation of sizing agent
Firstly, polyethylene glycol (PEG), diisocyanate and dihydroxyacetic acid are mixed according to the mass ratio of 65:36:7, uniformly stirring and mixing, heating to 75 ℃, preserving heat for 5 hours, cooling to obtain aqueous polyurethane, and then mixing bisphenol A epoxy resin, aqueous polyurethane and dibutyltin diacetate (catalyst) according to the mass ratio of 80:15: and (3) uniformly stirring and mixing the materials according to the proportion of 0.05, heating to 90 ℃, preserving heat for 4 hours, and cooling to obtain the waterborne polyurethane modified epoxy resin.
Deionized water, waterborne polyurethane modified epoxy resin, alkylphenol ethoxylate (TX-10) and polyether amino block modified silicone oil (NE 820) are mixed according to the mass ratio of 80:15:0.6:1.2, mixing and stirring uniformly to prepare sizing agent for standby.
(2) Preparation before sizing
The guide roller 2, the sizing tank 3 and the grouting rod 4 are cleaned, the smooth surface is ensured to be free from sundries, the fiber is prevented from being damaged, then the oven 5 is started, the temperature is raised to 220 ℃, and the heat is preserved.
(3) Sizing
The silicon carbide fiber 1 bypasses the guide roller 2, sequentially passes through the sizing tank 3, the grouting roller 4 and the oven 5, finally reaches the wire collecting machine 7, then the sizing agent is poured into the sizing tank 3, the silicon carbide fiber 1 is fully infiltrated, and finally the wire collecting is carried out at the speed of 1m/min, so that the sized silicon carbide fiber 6 is obtained.
Comparative example 3
(1) Preparation of sizing agent
Polyethylene glycol (PEG), diisocyanate and dihydroxyacetic acid are mixed according to the mass ratio of 65:36:7, uniformly stirring and mixing, heating to 75 ℃, preserving heat for 5 hours, cooling to obtain waterborne polyurethane, and then mixing the waterborne polyurethane, bisphenol A epoxy resin and dibutyltin diacetate (catalyst) according to the mass ratio of 80:15: and (3) uniformly stirring and mixing the materials according to the proportion of 0.05, heating to 90 ℃, preserving heat for 4 hours, and cooling to obtain the waterborne polyurethane modified epoxy resin.
Deionized water, aqueous epoxy resin, acrylic ester modified polyurethane, alkylphenol ethoxylate (TX-10) and polyether amino block modified silicone oil (NE 820) are mixed according to the mass ratio of 80:15:5:0.6:1.2, mixing and stirring uniformly to prepare sizing agent for standby.
(2) Preparation before sizing
The guide roller 2, the sizing tank 3 and the grouting rod 4 are cleaned, the smooth surface is ensured to be free from sundries, the fiber is prevented from being damaged, then the oven 5 is started, the temperature is raised to 220 ℃, and the heat is preserved.
(3) Sizing
The silicon carbide fiber 1 bypasses the guide roller 2, sequentially passes through the sizing tank 3, the grouting roller 4 and the oven 5, finally reaches the wire collecting machine 7, then the sizing agent is poured into the sizing tank 3, the silicon carbide fiber 1 is fully infiltrated, and finally the wire collecting is carried out at the speed of 1m/min, so that the sized silicon carbide fiber 6 is obtained.
Performance comparison: the abrasion resistance and the fuzziness index of the silicon carbide fibers of examples 1 to 3 and comparative examples 1 to 2 were measured according to the method of the literature (novel carbon materials, 2006,21 (4): 337 to 341; title: temperature-resistant carbon fiber emulsion sizing agent). The specific testing method is to compare the bundling performance of the sized silicon carbide fiber by adopting a hand feeling visual inspection method, and the flexibility of the fiber is represented by adopting a flexibility angle, wherein the smaller the angle is, the better the flexibility of the fiber is, and the flexibility angle testing method comprises the following steps: the fiber bundles with the length of 30cm are taken and placed on a rod-shaped object to enable the fiber bundles to naturally sag, at the moment, the angles formed by the fiber bundles at the two sides of the rod-shaped object are the flexibility angles, and the performance evaluation results of the obtained sizing carbon fibers are shown in the following table 1.
TABLE 1
Abrasion resistance/secondary Quantity of filigree/mg Bundling property Compliant angle/°
Example 1 145 3.6 Excellent and excellent properties 35
Example 2 163 2.8 Excellent and excellent properties 40
Example 3 187 1.9 Excellent and excellent properties 50
Comparative example 1 109 1.5 Excellent and excellent properties 120
Comparative example 2 97 7.3 In general 30
Comparative example 3 113 1.1 Excellent and excellent properties 110
In the comparative example 1, polyvinyl alcohol (PVA) is adopted as a sizing agent of main sizing agent, fiber bundles after sizing are too stiff, the wear resistance is weak, the flexibility angle requirement is wide, and in the comparative example 2, only aqueous polyurethane modified epoxy resin is adopted as the sizing agent of the main sizing agent, the bundling property of the fiber bundles after sizing is poor, and fuzzing is easy to generate; the sizing agent compounded by adopting the waterborne polyurethane modified epoxy resin and the modified polyurethane can take both the flexibility and the bundling property into account, so that the silicon carbide fiber with excellent weaving performance is obtained. Comparative example 3 used too much acrylate modified polyurethane, which resulted in too stiff and very poor flexibility of the sized fibers, which was detrimental to improved braiding performance.

Claims (10)

1. A continuous carbon fiber sizing agent, characterized in that: the components in parts by weight are as follows: 80-100 parts of water, 5-20 parts of waterborne polyurethane modified epoxy resin, 0.3-3 parts of acrylate modified polyurethane, 0.2-2 parts of emulsifier and 0.2-2 parts of softener.
2. A continuous carbon fiber sizing agent according to claim 1, wherein: the continuous carbonized fiber sizing agent comprises the following components in parts by mass: 80 to 100 parts of water, 5 to 15 parts of waterborne polyurethane modified epoxy resin, 0.7 to 1 part of acrylic ester modified polyurethane, 0.3 to 0.6 part of emulsifier and 0.6 to 1.2 parts of softener.
3. A continuous carbon fiber sizing agent according to claim 1, wherein: the continuous carbonized fiber sizing agent comprises the following components in parts by mass: 80 to 90 parts of water, 10 to 15 parts of waterborne polyurethane modified epoxy resin, 0.7 to 0.8 part of acrylic ester modified polyurethane, 0.6 part of emulsifier and 0.8 to 1.2 parts of softener.
4. A continuous carbon fiber sizing agent according to any one of claims 1 to 3, wherein: the aqueous polyurethane modified epoxy resin is aqueous polyurethane modified bisphenol A type epoxy resin;
the preparation process of the aqueous polyurethane modified epoxy resin comprises the following steps: the preparation method comprises the following steps of (by mass ratio) mixing aqueous polyurethane, bisphenol A epoxy resin and dibutyltin diacetate: 15-30: and (3) stirring and mixing uniformly 0.01-0.05, heating to 75-100 ℃, preserving heat for 2-5 h, and cooling to obtain the waterborne polyurethane modified epoxy resin.
5. A continuous carbon fiber sizing agent according to claim 4, wherein: the preparation process of the aqueous polyurethane comprises the following steps: polyethylene glycol, diisocyanate and dihydroxyacetic acid are mixed according to the mass ratio of 50-70: 30-40: and 5-10, stirring and mixing uniformly, heating to 60-80 ℃, preserving heat for 2-5 h, and cooling to obtain the aqueous polyurethane.
6. A continuous carbon fiber sizing agent according to claim 1, wherein: the emulsifier is alkylphenol ethoxylate or octylphenol ethoxylate.
7. A continuous carbon fiber sizing agent according to claim 1, wherein: the softener is polyether amino block modified silicone oil.
8. A continuous carbon fiber sizing agent according to claim 1, wherein: the preparation process of the continuous carbonized fiber sizing agent comprises the following steps: and (3) preparing water, waterborne polyurethane modified epoxy resin, acrylic ester modified polyurethane, an emulsifier and a softener according to a designed proportion, and uniformly mixing and stirring to obtain the polyurethane.
9. Use of a continuous carbon fiber sizing agent according to any of claims 1-8, characterized in that: the continuous carbon fiber sizing agent is used for sizing the carbon fiber, and the sizing process comprises the following steps: and soaking the silicon carbide fiber in a continuous carbon fiber sizing agent to obtain the silicon carbide fiber coated with the sizing agent, and drying the silicon carbide fiber coated with the sizing agent at 150-250 ℃ to obtain the sized silicon carbide fiber.
10. The use of a continuous carbon fiber sizing agent according to claim 9, wherein: the sizing process is that the silicon carbide fiber bypasses a guide roller and then passes through a sizing tank containing a continuous carbon fiber sizing agent to enable the silicon carbide fiber to be soaked in the continuous carbon fiber sizing agent to obtain the silicon carbide fiber coated with the sizing agent, the silicon carbide fiber coated with the sizing agent continuously passes through a sizing roller, then passes through an oven to be dried at 150-250 ℃, and then is subjected to filament winding at a speed of 1-3 m/min by a filament winding machine, thus obtaining the sized silicon carbide fiber.
CN202310180165.0A 2023-03-01 2023-03-01 Continuous silicon carbide fiber sizing agent and application thereof Pending CN116180451A (en)

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