CN116180451B - A continuous silicon carbide fiber sizing agent and its application - Google Patents
A continuous silicon carbide fiber sizing agent and its application Download PDFInfo
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- CN116180451B CN116180451B CN202310180165.0A CN202310180165A CN116180451B CN 116180451 B CN116180451 B CN 116180451B CN 202310180165 A CN202310180165 A CN 202310180165A CN 116180451 B CN116180451 B CN 116180451B
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- 238000004513 sizing Methods 0.000 title claims abstract description 152
- 239000000835 fiber Substances 0.000 title claims abstract description 145
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 92
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 68
- 229920002635 polyurethane Polymers 0.000 claims abstract description 89
- 239000004814 polyurethane Substances 0.000 claims abstract description 89
- 239000003822 epoxy resin Substances 0.000 claims abstract description 44
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 12
- 229920002545 silicone oil Polymers 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- GOCCREQJUBABAL-UHFFFAOYSA-N 2,2-dihydroxyacetic acid Chemical compound OC(O)C(O)=O GOCCREQJUBABAL-UHFFFAOYSA-N 0.000 claims description 7
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- -1 acrylic ester Chemical class 0.000 abstract description 18
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 15
- 239000004917 carbon fiber Substances 0.000 abstract description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 15
- 238000004132 cross linking Methods 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 206010004542 Bezoar Diseases 0.000 abstract 3
- 238000001816 cooling Methods 0.000 description 12
- 238000009941 weaving Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 2
- 238000009954 braiding Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000009730 filament winding Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- JYCQQPHGFMYQCF-UHFFFAOYSA-N 4-tert-Octylphenol monoethoxylate Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCO)C=C1 JYCQQPHGFMYQCF-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 206010020112 Hirsutism Diseases 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- 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, 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 an emulsifier and 0.2-2 parts of a 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
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 advantages that the sizing agent prepared by taking PVA (polyvinyl alcohol) as a main sizing agent has good film forming property and strong cohesiveness, fiber bundles can be well and tightly adhered together, the bundling property is very good, fiber filaments are greatly reduced, the wear resistance is increased, but the problems of improved fiber stiffness and poor flexibility exist. Zhang Xinyuan et al (CN 111704478B) propose a sizing method for high-strength high-modulus silicon carbide fibers, which prepares 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, avoid the situation that the fibers are too stiff to be brittle broken during weaving, but have poor bundling property, 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, which 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 fiber, but uses toxic organic matters such as ketone and amine as auxiliary agent, which 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 continuous carbonized fiber sizing agent comprises, 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 an emulsifier and 0.2-2 parts of a 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.
According to the preferable scheme, the continuous carbonized fiber sizing agent comprises, by mass, 80-100 parts of water, 5-15 parts of waterborne polyurethane modified epoxy resin, 0.7-1 part of acrylate modified polyurethane, 0.3-0.6 part of emulsifier and 0.6-1.2 parts of softener.
Further preferably, the continuous carbonized fiber sizing agent comprises, by mass, 80-90 parts of water, 10-15 parts of waterborne polyurethane modified epoxy resin, 0.7-0.8 part of acrylate modified polyurethane, 0.6 part of emulsifier and 0.8-1.2 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.
According to the preferred scheme, the preparation process of the waterborne polyurethane modified epoxy resin comprises the steps of uniformly stirring and mixing the waterborne polyurethane, the bisphenol A epoxy resin and the dibutyltin diacetate according to the mass ratio of 70-85:15-30:0.01-0.05, heating to 75-100 ℃, preserving heat for 2-5 hours, and cooling to obtain the waterborne polyurethane modified epoxy resin.
Further preferably, the preparation process of the waterborne polyurethane comprises the steps of uniformly stirring and mixing polyethylene glycol (PEG), diisocyanate and dihydroxyacetic acid according to a mass ratio of 50-70:30-40:5-10, heating to 60-80 ℃, preserving heat for 2-5 h, and cooling to obtain the waterborne 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.
The preparation process of the continuous carbon fiber sizing agent comprises the steps of preparing water, waterborne polyurethane modified epoxy resin, acrylic ester modified polyurethane, emulsifying agent and softener according to a designed proportion, and uniformly mixing and stirring.
The invention also provides application of the continuous carbon fiber sizing agent, the continuous carbon fiber sizing agent is used for sizing the carbon fiber, the sizing process is that the silicon carbide fiber is soaked in the continuous carbon fiber sizing agent to obtain silicon carbide fiber coated with the sizing agent, and then the silicon carbide fiber coated with the sizing agent is dried at 150-250 ℃ to obtain the sized silicon carbide fiber.
According to the application process, 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, 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, and at the specific temperature, the aqueous polyurethane modified epoxy resin and the acrylic ester modified polyurethane can undergo a crosslinking reaction, so that the molecular weight of the film is increased, loose fibers can be better bonded together, and the bundling property and the wear resistance of the fiber after sizing are improved.
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 and 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 filament winding at a speed of 1-3 m/min by a filament winding 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, smooth surfaces and no sundries are guaranteed, fiber damage is prevented, then the oven is started, and the temperature is raised to 150-250 ℃ and heat preservation is carried out.
Further preferably, the material is dried at 160-220 ℃.
Further preferably, the drying is carried out at 200-220 ℃.
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 solves the problem that fibers are stiff after sizing by using PVA (polyvinyl alcohol) sizing agent, so that the fibers cannot be brittle broken due to bending, and simultaneously solves the problem that the bundling property of fiber bundles is poor after sizing by using pure epoxy resin sizing agent, thereby reducing broken filaments in the weaving process and greatly improving the weaving quality.
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, uniformly stirring and mixing polyethylene glycol (PEG), diisocyanate and dihydroxyacetic acid according to the mass ratio of 50:40:6, then heating to 70 ℃, preserving heat for 3 hours, cooling to obtain aqueous polyurethane, uniformly stirring and mixing the aqueous polyurethane, bisphenol A epoxy resin and dibutyltin diacetate (catalyst) according to the mass ratio of 70:30:0.02, then heating to 80 ℃, preserving heat for 5 hours, and cooling to obtain the aqueous 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 and stirred uniformly according to the mass ratio of 100:5:1:0.3:0.6, and the continuous carbon fiber sizing agent is prepared 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 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
Uniformly stirring and mixing polyethylene glycol (PEG), diisocyanate and dihydroxyacetic acid according to the mass ratio of 60:30:10, heating to 80 ℃, preserving heat for 2 hours, cooling to obtain aqueous polyurethane, uniformly stirring and mixing bisphenol aqueous polyurethane, A-type epoxy resin and dibutyltin diacetate (catalyst) according to the mass ratio of 75:25:0.03, heating to 100 ℃, preserving heat for 2 hours, and cooling to obtain the aqueous 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 and stirred uniformly according to the mass ratio of 90:10:0.8:0.6:0.8, and the sizing agent is prepared 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 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 stirred and mixed uniformly according to the mass ratio of 65:36:7, then the temperature is raised to 75 ℃, the temperature is kept for 5 hours, the aqueous polyurethane is obtained after cooling, the aqueous polyurethane, bisphenol A epoxy resin and dibutyltin diacetate (catalyst) are stirred and mixed uniformly according to the mass ratio of 80:15:0.05, then the temperature is raised to 90 ℃, the temperature is kept for 4 hours, and the aqueous polyurethane modified epoxy resin is obtained after cooling.
Deionized water, aqueous epoxy resin, acrylic ester modified polyurethane, alkylphenol ethoxylate (TX-10) and polyether amino block modified silicone oil (NE 820) are mixed and stirred uniformly according to the mass ratio of 80:15:0.7:0.6:1.2, and the sizing agent is prepared 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 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 and stirred uniformly according to the mass ratio of 80:2:0.6:1.2, and the sizing agent is prepared 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, uniformly stirring and mixing polyethylene glycol (PEG), diisocyanate and dihydroxyacetic acid according to the mass ratio of 65:36:7, then heating to 75 ℃, preserving heat for 5 hours, cooling to obtain aqueous polyurethane, uniformly stirring and mixing bisphenol A epoxy resin, aqueous polyurethane and dibutyltin diacetate (catalyst) according to the mass ratio of 80:15:0.05, then heating to 90 ℃, preserving heat for 4 hours, and cooling to obtain the aqueous 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 and stirred uniformly according to the mass ratio of 80:15:0.6:1.2, and the sizing agent is prepared 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 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 stirred and mixed uniformly according to the mass ratio of 65:36:7, then the temperature is raised to 75 ℃, the temperature is kept for 5 hours, the aqueous polyurethane is obtained after cooling, the aqueous polyurethane, bisphenol A epoxy resin and dibutyltin diacetate (catalyst) are stirred and mixed uniformly according to the mass ratio of 80:15:0.05, then the temperature is raised to 90 ℃, the temperature is kept for 4 hours, and the aqueous polyurethane modified epoxy resin is obtained after cooling.
Deionized water, aqueous epoxy resin, acrylic ester modified polyurethane, alkylphenol ethoxylate (TX-10) and polyether amino block modified silicone oil (NE 820) are mixed and stirred uniformly according to the mass ratio of 80:15:5:0.6:1.2, and the sizing agent is prepared 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 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 fuzz amount index of the silicon carbide fibers of examples 1-3 and comparative examples 1-2 were tested according to the method of the literature (novel carbon materials, 2006,21 (4): 337-341; title: temperature resistant carbon fiber emulsion sizing agent). The specific testing method is that the sizing silicon carbide fiber bundling performance is compared by adopting a hand feeling visual inspection method, the flexibility of the fiber is represented by adopting a flexibility angle, the smaller the angle is, the better the fiber flexibility is, the flexibility angle testing method is that a fiber bundle with the length of 30cm is taken and placed on a rod-shaped object to enable the fiber bundle to naturally sag, at the moment, the angles formed by the fiber bundles at two sides of the rod-shaped object are the flexibility angles, and the performance evaluation results of the sizing carbon fiber 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, the comparative example 2 only adopts aqueous polyurethane modified epoxy resin as the sizing agent of the main sizing agent, the bundling property of the fiber bundles after sizing is poor, and hairiness is easy to generate, and the sizing agent compounded by adopting the aqueous polyurethane modified epoxy resin and modified polyurethane can achieve both the flexibility and the bundling property, so that the silicon carbide fiber with excellent weaving property 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.
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| CN109957969A (en) * | 2017-12-25 | 2019-07-02 | 比亚迪股份有限公司 | A carbon fiber sizing agent, its preparation method, reinforced carbon fiber and carbon fiber composite material |
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