CN116332541B - Thermal shrinkage induced anti-cracking fiber and preparation method thereof - Google Patents
Thermal shrinkage induced anti-cracking fiber and preparation method thereof Download PDFInfo
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- CN116332541B CN116332541B CN202310345788.9A CN202310345788A CN116332541B CN 116332541 B CN116332541 B CN 116332541B CN 202310345788 A CN202310345788 A CN 202310345788A CN 116332541 B CN116332541 B CN 116332541B
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- 238000005336 cracking Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000011162 core material Substances 0.000 claims abstract description 45
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 33
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 230000006698 induction Effects 0.000 claims abstract description 16
- 229920000728 polyester Polymers 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
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- 238000001035 drying Methods 0.000 claims description 8
- 239000010985 leather Substances 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 239000002667 nucleating agent Substances 0.000 claims description 5
- 239000004677 Nylon Substances 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000010440 gypsum Substances 0.000 claims description 4
- 229910052602 gypsum Inorganic materials 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 3
- 238000007373 indentation Methods 0.000 claims description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 230000008961 swelling Effects 0.000 claims 1
- 239000004567 concrete Substances 0.000 abstract description 69
- 230000005284 excitation Effects 0.000 abstract description 8
- 238000010276 construction Methods 0.000 abstract description 7
- 230000006835 compression Effects 0.000 abstract description 6
- 238000007906 compression Methods 0.000 abstract description 6
- 239000002002 slurry Substances 0.000 abstract description 6
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- 238000013461 design Methods 0.000 abstract description 3
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- 238000001125 extrusion Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004568 cement Substances 0.000 description 7
- 239000011372 high-strength concrete Substances 0.000 description 6
- 239000004575 stone Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
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- 230000008018 melting Effects 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 229920003023 plastic Polymers 0.000 description 3
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- 229910001285 shape-memory alloy Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/04—Macromolecular compounds
- C04B16/06—Macromolecular compounds fibrous
- C04B16/0675—Macromolecular compounds fibrous from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B16/0683—Polyesters, e.g. polylactides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/04—Macromolecular compounds
- C04B16/06—Macromolecular compounds fibrous
- C04B16/0616—Macromolecular compounds fibrous from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B16/0625—Polyalkenes, e.g. polyethylene
- C04B16/0633—Polypropylene
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/04—Macromolecular compounds
- C04B16/06—Macromolecular compounds fibrous
- C04B16/0675—Macromolecular compounds fibrous from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B16/0691—Polyamides; Polyaramides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/12—Multiple coating or impregnating
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/34—Non-shrinking or non-cracking materials
- C04B2111/343—Crack resistant materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a thermal shrinkage induction type anti-cracking fiber, which comprises a composite fiber composed of a thermal shrinkage core material and an outer thermal shrinkage skin material, and a water-soluble modified polyvinyl alcohol layer coated on the surface of the composite fiber; wherein the water-soluble modified polyvinyl alcohol layer contains polyvinyl alcohol and an expansion component. The invention adopts a multilayer skin-core structural design thought, fully utilizes the thermal excitation shrinkage of the high-modulus thermal shrinkage induced anti-crack fiber and the bonding coupling effect between the thermal excitation shrinkage and a cementing slurry interface, effectively counteracts the temperature difference and shrinkage stress generated by mass concrete, and improves the tensile strength and toughness of the concrete; meanwhile, the introduced expanding agent is used for compensating the shrinkage creep of the concrete, so that the loss of micro-pre-compression stress applied to the fiber caused by the shrinkage creep of the concrete is reduced, and the cracking resistance of the concrete is further ensured and improved. The thermal shrinkage induction type anti-cracking fiber has the advantages of low thermal shrinkage excitation temperature, high shrinkage rate and low cost, and the related preparation method and construction method are simpler and suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a thermal shrinkage induction type anti-cracking fiber with a shrinkage compensation function and a preparation method thereof.
Background
High-strength and large-volume concrete is a key material required by engineering construction, and has the problems that the durability and bearing capacity of a concrete structure are affected due to common cracking; in particular, the cement ratio of the concrete with high volume and strong volume above C50 is lower, the consumption of cementing material is higher, and the hydration heat release amount and shrinkage are larger. Engineering practice shows that even if the measures of middle-low hot cement, large doping amount of mineral admixture, cooling water passing, mold entering temperature control and the like are adopted, the highest temperature in the interior of the mold still reaches 70-90 ℃, the temperature difference of the interior surface exceeds 25 ℃, and the tensile stress caused by shrinkage and temperature difference is large, so that the mold is generally cracked; in addition, some parts belong to variable cross sections, the steel bars are densely distributed, prestressing force is needed to be applied, cooling water pipes cannot be distributed, and the cracking of the parts is more serious.
In order to solve the cracking problem, means such as prestressing the concrete member and introducing anti-cracking fibers are further generally adopted. The prestress method mainly comprises the steps of tensioning the steel bars before concrete pouring, so that a tension zone of a concrete member is subjected to compressive stress in advance, and the tensile stress of external load on the member can be counteracted; however, the method is not easy to implement in mass concrete, and the cost is too high; and meanwhile, the cracking problem caused by early temperature rise of mass concrete cannot be improved. The toughness of the concrete can be effectively improved by adding the polypropylene fiber, and cracks caused by shrinkage of the concrete in a plastic stage are obviously reduced, but the modulus is lower, the dispersibility is poorer, and the pumping construction performance of the concrete is affected; the steel fiber elastic die and the tensile strength are higher, but the related engineering construction cost is higher. In addition, the conventional fiber and concrete are thermal expansion and cold shrinkage materials, taking steel fiber as an example, and have larger thermal expansion coefficient than concrete, and in the temperature rising stage of the mass concrete, the interface gel slurry is pulled, micro cracks are generated at the interface, and the shrinkage of the fiber in the temperature lowering stage further promotes the development of the cracks; the effect of controlling crack formation in the high-volume concrete temperature rise and fall stage is limited.
At present, researchers introduce shape memory alloy fibers into a concrete matrix, and apply compaction acting force to the concrete by using retraction force of the shape memory alloy fibers so as to close cracks in the concrete, thereby improving the cracking resistance of the concrete. However, shape memory alloy fibers have problems of high cost, high shrinkage temperature, low shrinkage, and the like, which limit their application in concrete structures. The high-shrinkage polyester is modified by the patent CN114477820A, and the thermal shrinkage fiber is obtained after extrusion and stretching; however, the polyester fiber is not alkali-resistant, and when the polyester fiber is applied to concrete (the pH value of a concrete pore solution is more than 12), the problems of alkali corrosion and the like exist, so that the use effect of the polyester fiber is affected. In addition, the concrete with high strength and volume has obvious temperature rising and reducing stages, and the concrete is heated and expanded in the temperature rising stage; the heat shrinkage type fiber is excited by heat to shrink, and micro pre-compression stress is applied to the concrete; in the cooling stage of high-strength concrete, the shrinkage of the heat-shrinkable fiber is completed, the concrete is subjected to temperature shrinkage, self-shrinkage, drying shrinkage and the like, and the shrinkage causes the loss of the micro-pre-compression stress action applied to the fiber, so that the crack resistance reinforcing effect is weakened, and the expected crack control effect is not realized.
Disclosure of Invention
Aiming at the problems and defects existing in the prior art, the invention provides a thermal shrinkage type induced anti-cracking fiber with a multilayer sheath-core structure and shrinkage compensation performance, which has higher tensile strength and elastic modulus, low shrinkage excitation temperature and high shrinkage rate; the dispersion in the concrete is good, and the high-strength concrete is applied to the preparation of large-volume high-strength concrete, so that the compressive strength and the splitting tensile strength of the concrete are improved, and the high-strength concrete can be effectively balanced with good volume stability and crack resistance; the preparation method and the operation method are simpler, and the method is suitable for popularization and application.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A thermal shrinkage induction type anti-cracking fiber comprises thermal shrinkage composite fiber with a sheath-core structure, which consists of a columnar thermal shrinkage core material and an outer thermal shrinkage sheath material, and a water-soluble modified polyvinyl alcohol layer coated on the surface of the thermal shrinkage composite fiber; wherein the water-soluble modified polyvinyl alcohol layer contains polyvinyl alcohol and an expansion component.
In the scheme, the main raw materials of the heat-shrinkable core material can be one or more of high-shrinkage plastics such as polyester, polypropylene, nylon and the like, wherein the molecular weight of the polyester is 2 ten thousand to 3 ten thousand, the molecular weight of the polypropylene is 6000 to 8000, and the molecular weight of the nylon is 2 ten thousand to 3 ten thousand; the shrinkage rate is 5-15%, the response temperature is 40-100 ℃, the tensile strength is 300-500 MPa, and the elastic modulus is 3-12 GPa.
In the scheme, the raw materials of the heat-shrinkable core material also comprise stiffening nucleating agent, and the content (accounting for the total mass of the raw materials) of the stiffening nucleating agent is 1-5wt%; comprises more than one of dibenzylidene sorbitol, aluminum aromatic carboxylic acid aluminum, sodium benzoate and the like.
In the scheme, the main raw materials of the heat-shrinkable leather can be one or more of high-strength plastics such as polyvinyl alcohol, ultra-high modulus polyethylene, polyformaldehyde and the like, wherein the molecular weight of the polyvinyl alcohol is 17 ten thousand-22 ten thousand, the molecular weight of the polyethylene is 100 ten thousand-200 ten thousand, the molecular weight of the polyformaldehyde is 2 ten thousand-3 ten thousand, the tensile strength is 500-1200 MPa, and the elastic modulus is 7-35 GPa; the shrinkage rate is 0.5-2%, and the response temperature is 30-100 ℃.
In the above scheme, the raw materials of the heat-shrinkable leather further comprise a plasticizer and a compatilizer; wherein the content of the plasticizer (accounting for the total raw material mass, the same applies hereinafter) is 1-5wt% and the content of the compatilizer is 1-3wt%; the compatilizer comprises more than one of maleic anhydride grafted compatilizer, imide modified polypropylene resin and the like; the plasticizer comprises more than one of phthalate, aliphatic dibasic acid ester, fatty acid ester, benzene polyacid ester, polyol ester, epoxy hydrocarbon and alkyl sulfonate.
In the scheme, the ratio of the diameter of the core material to the thickness of the skin layer in the heat-shrinkable composite fiber is 1-3:1.
Further, the diameter of the core material in the heat-shrinkable composite fiber is 0.1-0.15 mm, and the thickness of the skin layer is 0.05-0.1 mm.
In the scheme, the water-soluble modified polyvinyl alcohol layer is obtained by coating the skin-core structure with a modified polyvinyl alcohol solution added with an expansion component and drying.
In the scheme, the thickness of the water-soluble modified polyvinyl alcohol layer is 0.01-0.02 mm.
Further, the modified polyvinyl alcohol solution consists of a polyvinyl alcohol solution and a liquid expanding agent; the liquid expanding agent mainly comprises an expanding component, a shrinkage reducing component, a stable dispersing component and water.
In the above embodiment, the concentration of the polyvinyl alcohol solution (aqueous solution) is 4 to 10wt% and the viscosity is 20.5 to 24.5 Pa.s.
In the above scheme, each component and the dosage thereof in the liquid expanding agent comprise: 60-150 parts of expansion component, 20-60 parts of shrinkage reducing component, 10-70 parts of stable dispersion component and 600-1000 parts of water.
In the scheme, the expansion component is formed by compounding anhydrous aluminum sulfate and gypsum, wherein the mass ratio of the anhydrous aluminum sulfate to the gypsum is 1 (0.66-1.5); the shrinkage reducing component is one or more of amphiphilic diethylene glycol monobutyl ether and dipropylene glycol; the stable dispersion component is cationic polyacrylamide.
In the scheme, the mass ratio of the polyvinyl alcohol solution to the liquid expanding agent is 1 (0.4-0.9).
The preparation method of the thermal shrinkage induction type anti-cracking fiber comprises the following steps:
1) Extruding a heat-shrinkable core material mixture and a heat-shrinkable sheath material mixture into a die head with two cavities respectively by adopting two extruders, wherein the heat-shrinkable sheath material enters the cavity corresponding to the sheath material, the heat-shrinkable core material enters the cavity corresponding to the core material, the materials in the two cavities are converged at the position of a spinneret plate of the extruder, wherein the spinneret plate is provided with an inner ring and an outer ring, the inner ring of the spinneret plate is connected with the cavity of the core material, the outer ring of the spinneret plate is connected with the cavity of the sheath material, the two materials in a molten state are extruded (melt extruded) through the spinneret plate and are adhered together in air, cooling is carried out through a cold water tank, and then drawing is carried out in hot water at 90-100 ℃ to form the composite fiber with the sheath-core structure;
2) Adding the composite fiber obtained in the step 1) into a silicon solution or a silane coupling agent solution for modification, and drying and then surface indentation to increase the bonding performance with concrete slurry;
3) And (3) adding the composite fiber obtained in the step (2) into a modified polyvinyl alcohol solution added with an expansion component for coating modification, taking out and drying to obtain the thermal shrinkage induction type anti-cracking fiber.
In the scheme, the melting temperature of the mixture of the heat-shrinkable core materials is 200-280 ℃; the extrusion pressure of the corresponding cavity is 7-10 MPa.
In the scheme, the melting temperature of the heat-shrinkable leather material mixture is 150-220 ℃, and the extrusion pressure of the corresponding cavity is 3-10 MP.
In the final extrusion section corresponding to the spinneret plate, the extrusion temperature of the two materials in a molten state is kept at a proper temperature of both materials, namely 200-220 ℃, and the extrusion pressure is 3-10 MPa.
In the scheme, the coating modification temperature is room temperature and the standing time is 10-24 hours.
The thermal shrinkage induction type anti-cracking fiber prepared according to the scheme has the shrinkage initial temperature of 30 ℃, the shrinkage rate of 0.5-15%, the shrinkage recovery stress of 1-30 MPa, the tensile strength of 500-1500 MPa and the elastic modulus of 7-30 GPa.
Compared with the prior art, the invention has the beneficial effects that:
1) The fiber adopts a multi-layer sheath-core structural design, and the efficient compounding of the core material and the sheath layer is realized by optimizing the material selection and the compounding process of the core material and the sheath layer; the introduced core layer fiber mainly plays the characteristic of large shrinkage rate, the introduced skin layer fiber mainly plays the roles of high strength, high elastic modulus, good dispersibility, strong interface bonding with cement paste and the like, and meanwhile, the protection of the core layer fiber is realized, the difficult problems of weak alkali corrosion resistance and the like existing in single resin-based heat-shrinkable fiber and the like can be solved, and the strength, elastic modulus and other mechanical properties of the obtained composite fiber can be improved; meanwhile, the method has the advantages of low heat shrinkage excitation temperature, high shrinkage rate, low cost and the like;
2) The invention applies three-dimensional micro-prestress to concrete by utilizing the thermal excitation shrinkage effect of high-modulus thermal shrinkage induced anti-crack fiber and the bonding coupling effect of the thermal excitation shrinkage induced anti-crack fiber and a cementing slurry interface to counteract the temperature and shrinkage stress generated by mass concrete; compared with the common polyester-based heat-shrinkable fiber, the sheath-core structural design of the invention can solve the difficult problem of alkali resistance; the multi-layer sheath-core structural fiber has good dispersibility, and is bonded with the cement paste at a strong interface, so that the tensile strength and toughness of the concrete are improved; meanwhile, the expanding agent wrapped in the water-soluble polyvinyl alcohol film can play a role in compensating shrinkage in the concrete, so that the cracking resistance of the concrete is further improved;
3) According to the invention, a composite expanding agent is further introduced into the surface modified polyvinyl alcohol according to the development rule of shrinkage creep of the mass concrete, so that the shrinkage creep of the concrete can be compensated in situ, on one hand, the loss of micro-pre-compression stress applied by fibers caused by shrinkage creep is solved, and the anti-cracking effect of the pre-compression stress applied by the heat-shrinkable fibers is enhanced; meanwhile, the shrinkage of the concrete is compensated, and the cracking resistance of the concrete is further improved; according to the invention, the thermal shrinkage fiber thermal excitation shrinkage and the cementing slurry interface bonding coupling effect are utilized to apply three-dimensional micro-pre-compression stress to the concrete, and meanwhile, the fiber reinforcement, toughening and crack resistance of the mass concrete can be effectively improved by combining the shrinkage compensation performance of the expanding agent; the environment-friendly problems that the expanding agent is not easy to add (the mixing amount is generally about 8.0 percent, manual metering and adding are often needed when the expanding agent is used), dust is generated and the like in construction can be effectively solved;
4) The anti-cracking fiber disclosed by the invention has the advantages that the construction is simple, the anti-cracking fiber and the expansion component can be added at one time, and the construction quality is convenient to control.
Drawings
FIG. 1 is a schematic structural view of a temperature-shrinkage-induced crack resistant fiber according to an embodiment of the present invention;
In the figure, 1 is a core layer fiber, 2 is a sheath layer fiber, and 3 is a water-soluble modified polyvinyl alcohol layer.
Detailed Description
The invention is not limited to the embodiments described above, but a number of modifications and adaptations can be made by a person skilled in the art without departing from the principle of the invention, which modifications and adaptations are also considered to be within the scope of the invention. What is not described in detail in this specification is prior art known to those skilled in the art.
In the following examples, the main core material used is polyester, which is provided by Shanghai Fengmei plasticizing Co Ltd, and has a molecular weight of 25000, a maximum shrinkage of 15%, a response temperature of designable (40-100 ℃), a tensile strength of 400MPa, and an elastic modulus of 12.0GPa;
The main raw material of the adopted skin material is polyformaldehyde, which is provided by a cloud and heaving group Limited liability company, the molecular weight of the skin material is 28000, the maximum shrinkage rate is 2%, the response temperature can be designed (40-100 ℃), the tensile strength is 800MPa, and the elastic modulus is 20.5GP.
The expansion component adopted in the liquid expansion agent is formed by mixing anhydrous aluminum sulfate and gypsum according to the mass ratio of 1:1; the shrinkage reducing component is amphiphilic diethylene glycol monobutyl ether provided by Jiangsu Bote New Material Co., ltd; the stable dispersion component is cationic polyacrylamide provided by Henan Hongkong chemical industry Co, and the molecular weight of the stable dispersion component is 980 ten thousand.
In the mass concrete, the adopted cement is P.O42.5 cement provided by Huaxin cement Co., ltd; the fly ash is provided by Wu Hanyang power plants, the water demand ratio is less than 100%, and the loss on ignition is less than 5%; the mineral powder adopts S95 grade mineral powder provided by Wuxin novel building materials, and the specific surface area of the S95 grade mineral powder is 420m 2/kg; the sand adopts machine-made sand provided by a certain stone crushing plant of Wuhan, the fineness modulus is 3.2, the MB value is 1.2, and the stone powder content is 7.0%; the broken stone adopts 5-20 mm continuous graded limestone broken stone provided by a certain broken stone factory of Wuhan; the adopted additive is a polycarboxylic acid high-performance water reducer provided by Wuhan Subo novel building material Co.Ltd, the water reducing rate is 28%, and the 28d shrinkage ratio is 105%.
Example 1
The temperature shrinkage induction type anti-cracking fiber has a structure schematically shown in figure 1, and the specific preparation method comprises the following steps:
1) Extruding a heat-shrinkable core material mixture and a heat-shrinkable sheath material mixture into a die head with two cavities respectively by adopting two extruders, wherein the heat-shrinkable sheath material enters the cavity corresponding to the sheath material, the heat-shrinkable core material enters the cavity corresponding to the core material, the materials in the two cavities are converged at the position of a spinneret plate of the extruder, wherein the spinneret plate is provided with an inner ring and an outer ring, the inner ring of the spinneret plate is connected with the cavity of the core material, the outer ring of the spinneret plate is connected with the cavity of the sheath material, the two materials in a molten state are extruded (melt extruded) through the spinneret plate and are adhered together in air, cooling is carried out through a cold water tank, and then drawing is carried out in hot water at 90-100 ℃ to form the composite fiber with the sheath-core structure;
Wherein, in the heat-shrinkable leather mixture, the raw materials and the mass percentages thereof are as follows: 1.5% of polyoxymethylene, 1.5% of maleic anhydride grafting compatilizer (model PP-G-MAH, supplied by Dongguan Corp., ltd.) and 1% of phthalate (plasticizer); the extrusion pressure of the skin cavity is 8MPa, and the melting temperature is kept at 250 ℃;
In the heat-shrinkable core material mixture, the raw materials and the mass percentages thereof are as follows: 98% of polyester and 2% of steel-increasing nucleating agent (comprising dibenzylidene sorbitol and sodium benzoate according to the mass ratio of 1:1); the extrusion pressure is 6MPa, and the melting temperature is kept at 210 ℃;
After the skin material and the core material are converged, extruding through a spinneret plate, wherein the extruding temperature of the two materials in a molten state is 220 ℃, and the extruding pressure is 7MPa;
The average diameter of the obtained core fiber 1 is 0.15mm, and the thickness of the sheath fiber 2 is 0.05-0.1 mm;
2) Adding the obtained composite fiber into octamethyl cyclotetrasiloxane organic silicon solution for modification (the time is 12 h), and drying and then surface indentation to increase the bonding performance with concrete slurry;
3) Adding the obtained composite fiber into a modified polyvinyl alcohol solution added with an expansion component for coating modification (the time is 24 hours), taking out and drying to obtain a thermal shrinkage induction type anti-cracking fiber (marked as thermal shrinkage induction type anti-cracking fiber A);
Wherein the modified polyvinyl alcohol solution is obtained by uniformly mixing polyvinyl alcohol solution (5 wt%) and liquid expanding agent according to the mass ratio of 7:3 (1:0.43).
The expansion components and the like on the surface of the thermal shrinkage induction type anti-cracking fiber A can be subjected to expansion reaction with concrete after being dissolved, and the free expansion rate of the expansion agent in a closed environment is 0.02%; the bonding strength of the sheath-core fiber and the concrete is more than 20MPa; the shrinkage rate of the obtained composite fiber is 0.5-12%, the response temperature is 30-100 ℃ (by adopting the formula and the preparation process provided by the invention, the initial response temperature can be further reduced), the tensile strength is 700MPa, and the elastic modulus is 15.0GPa.
Comparative example 1
A temperature shrinkage-induced type anti-crack fiber, the preparation method of which is approximately the same as that of example 1, except that no compatilizer and plasticizer are introduced into the heat shrinkage skin material, and no nucleating agent is introduced into the core material; the fiber is marked as a thermal shrinkage induction type anti-cracking fiber B.
The skin material has high modulus and high rigidity, and the deformation is small during melt extrusion; the core material has low modulus, high shrinkage, high flexibility and large deformation during melt extrusion; in the preparation process, when the skin layer and the core material are simultaneously melt extruded, the skin material and the core material in the obtained composite fiber are separated and unshelled due to large deformation difference of the two materials, so that the composite fiber is not beneficial to effective application in concrete.
Comparative example 2
A temperature shrinkage-induced crack resistant fiber, the preparation method of which is substantially the same as that of example 1, except that the coating modification step of step 3) is not performed; the fiber is marked as temperature shrinkage induction type anti-cracking fiber C.
Through testing, the bonding strength between the obtained thermal shrinkage induction type anti-cracking fiber C and concrete is more than 20MPa; the shrinkage rate of the obtained composite fiber is 0.5-12%, the response temperature is 30-100 ℃, the tensile strength is 700MPa, and the elastic modulus is 15.0GPa.
The anti-cracking fibers obtained in the example 1 and the comparative examples 1-2, the common non-heat shrinkage fibers and the common heat shrinkage functional fibers are respectively applied to preparing high-strength volume concrete, wherein the adopted reference mixing ratio is shown in the table 1, and the fiber mixing amount is 2kg/m 3; the types of the fibers and the curing modes are shown in Table 2.
TABLE 1C 50 high-strength concrete basic mix ratio (kg/m 3)
| Cement and its preparation method | Fly ash | Mineral powder | Sand and sand | Broken stone | Water and its preparation method | Additive agent |
| 310 | 90 | 80 | 712 | 1065 | 155 | 5.0 |
TABLE 2 fiber types and curing modes
Wherein, the specific curing steps of the standard curing and water bath curing (the introduced water bath curing conditions are mainly used for simulating exothermic heating conditions generated in the actual mass concrete preparation process) process comprise: after concrete is poured and formed, curing is carried out for 24 hours under a standard curing environment, then the concrete is placed in a water bath box, the temperature is raised to 90 ℃ at a speed of 10 ℃/h, the concrete is cured for 12 hours at a constant temperature, the temperature is lowered to 20 ℃ at a speed of 20 ℃/h, and finally the concrete is placed in the standard curing environment, and the concrete is continuously cured for 28 days.
The non-heat-shrinkable polypropylene fiber (molecular weight of polypropylene is 8800) used in comparative application example 3 was supplied by Shandong Xinfuman chemical technology Co., ltd, and had an equivalent diameter of 50 μm, a tensile strength of 400MPa, an elastic modulus of 3GPa and an average fiber length of 12mm; the non-thermal shrinkage polyester fiber (the molecular weight of the polyester is 35000) is provided by super engineering materials of Changzhou market, the equivalent diameter is 20 mu m, the tensile strength is 500MPa, the elastic modulus is 4GPa, and the average fiber length is 12mm; the non-thermal shrinkage polyformaldehyde fiber (the molecular weight of polyformaldehyde is 38000) is provided by Yuntian group Limited liability company, the equivalent diameter is 0.2mm, the average fiber length is 12mm, the tensile strength is 800MPa, and the elastic modulus is 20.0GP.
The common heat shrinkage functional fiber adopted in comparative application examples 4 and 5 is heat shrinkage polyester fiber (polyester molecular weight is 22000) provided by China petrochemical instrumentation chemical fiber Limited liability company, the density is 920kg/m 3, the tensile breaking strength is 80MPa, the elastic modulus is 3.5GPa, the initial shrinkage temperature is 80 ℃, the shrinkage rate at 80 ℃ is 1%, and the boiling water shrinkage rate is 8%; comparative application example 7A type II expander supplied by Wuhan three source specialty materials Co., ltd was further additionally incorporated at 35kg/m 3 relative to comparative application example 2.
The compressive strength, the split tensile strength shrinkage and the crack resistance of the concrete were tested according to the test method standard of the mechanical properties of ordinary concrete (GB/T50081-2019) and the test method standard of the long-term properties and the durability of ordinary concrete (GB/T50082-2009), and the dispersion and the corrosion condition of the fibers were observed at the sections, and the results are shown in Table 3.
TABLE 3 Performance test results of C50 high-strength concrete obtained under different fibers and curing conditions
The results show that: the thermal shrinkage induced anti-cracking fiber obtained by the invention can effectively improve the compressive strength and the tensile strength of the concrete, and the obtained concrete has micro-expansion characteristic and can obviously improve the anti-cracking performance of the concrete.
Compared with the common fiber (polyester fiber, polypropylene fiber or polyoxymethylene fiber) without heat shrinkage function, the temperature shrinkage induced anti-cracking fiber A obtained by the invention has higher tensile strength and elastic modulus; after being mixed into concrete, the concrete has better dispersibility, higher compressive strength and splitting tensile strength, better volume stability (having micro-expansion performance) and obviously improved cracking resistance.
Compared with the scheme of doping common polyester heat shrinkage functional fibers which are not subjected to expansion component coating modification and temperature shrinkage induced anti-cracking fibers C which are not coated with expansion components and doping commercially available expansion agents (comparative application examples 5 and 7), the fiber prepared by the invention has better dispersibility, higher compressive strength and splitting tensile strength after being doped into concrete, better volume stability (micro expansion performance) and obviously improved anti-cracking performance compared with polyester fibers without alkaline corrosion of the fibers.
Compared with concrete without the fiber, the temperature shrinkage induced anti-cracking fiber obtained by the method has better concrete dispersibility, higher compressive strength and splitting tensile strength, better volume stability (with micro-expansion performance) and obviously improved anti-cracking performance.
The invention is not limited to the embodiments described above, but a number of modifications and adaptations can be made by a person skilled in the art without departing from the principle of the invention, which modifications and adaptations are also considered to be within the scope of the invention. What is not described in detail in this specification is prior art known to those skilled in the art.
Claims (7)
1. The thermal shrinkage induction type anti-cracking fiber is characterized by comprising a thermal shrinkage composite fiber formed by a thermal shrinkage core material and an outer thermal shrinkage skin material, and a water-soluble modified polyvinyl alcohol layer further coated on the surface of the thermal shrinkage composite fiber; wherein the water-soluble modified polyvinyl alcohol layer comprises polyvinyl alcohol and an expansion component;
The main raw materials of the heat-shrinkable core material are one or more of polyester, polypropylene and nylon, wherein the molecular weight of the polyester is 2-3 ten thousand, the molecular weight of the polypropylene is 6000-8000, and the molecular weight of the nylon is 2-3 ten thousand; the shrinkage rate is 5-15%, the response temperature is 40-100 ℃, the tensile strength is 300-500 MPa, and the elastic modulus is 3-12 GPa;
the main raw materials of the heat-shrinkable leather are one or more of polyvinyl alcohol, polyethylene and polyformaldehyde, wherein the molecular weight of the polyvinyl alcohol is 17-22 ten thousand, the molecular weight of the polyethylene is 100-200 ten thousand, and the molecular weight of the polyformaldehyde is 2-3 ten thousand; the tensile strength is 500-1200 MPa, the elastic modulus is 7-35 GPa, the shrinkage rate is 0.5-2%, and the response temperature is 30-100 ℃;
The raw materials of the heat-shrinkable core material also comprise stiffening nucleating agents; the raw materials of the heat-shrinkable leather also comprise a plasticizer and a compatilizer.
2. The temperature-shrinkage-induced crack-resistant fiber of claim 1, wherein the ratio of core diameter to skin thickness in the heat-shrinkable composite fiber is 1-3:1.
3. The temperature shrinkage-induced anti-crack fiber according to claim 1, wherein the water-soluble modified polyvinyl alcohol layer is obtained by coating and modifying a skin-core structure by adopting a modified polyvinyl alcohol solution added with an expansion component.
4. The temperature-shrinkage-induced crack-resistant fiber of claim 3, wherein the modified polyvinyl alcohol solution consists of a polyvinyl alcohol solution and a liquid swelling agent; the liquid expanding agent mainly comprises an expanding component, a shrinkage reducing component, a stable dispersing component and water.
5. The temperature shrinkage-induced crack resistant fiber according to claim 4, wherein the concentration of the polyvinyl alcohol solution is 4-10wt% and the viscosity is 20.5-24.5pa.s; the liquid expanding agent comprises the following components in part by weight: 60-150 parts of expansion component, 20-60 parts of shrinkage reducing component, 10-70 parts of stable dispersion component and 600-1000 parts of water.
6. The temperature-shrinkage-induced crack-resistant fiber of claim 4, wherein the expansion component is compounded from anhydrous aluminum sulfate and gypsum; the shrinkage reducing component is one or a mixture of diethylene glycol monobutyl ether and dipropylene glycol; the stable dispersion component is cationic polyacrylamide.
7. The method for preparing the thermal shrinkage-induced anti-cracking fiber according to any one of claims 1 to 6, which is characterized by comprising the following steps:
1) Extruding the heat-shrinkable core material mixture and the heat-shrinkable sheath material mixture into a die head with two cavities respectively by adopting two extruders, wherein the heat-shrinkable sheath material mixture enters the cavity corresponding to the sheath material, the heat-shrinkable core material mixture enters the cavity corresponding to the core material, and the materials in the two cavities are converged at the position of a spinneret plate of the extruder; the spinneret plate is provided with an inner ring and an outer ring, the inner ring of the spinneret plate is connected with a cavity of the core material, the outer ring of the spinneret plate is connected with a cavity of the sheath material, two materials in a molten state are extruded through the spinneret plate and are adhered together in air, cooling is carried out, and then the fiber is drawn in hot water to form the composite fiber with the sheath-core structure;
2) Adding the composite fiber obtained in the step 1) into a silicon solution or a silane coupling agent solution for modification, and drying and then carrying out surface indentation;
3) And (3) adding the composite fiber obtained in the step (2) into a modified polyvinyl alcohol solution added with an expansion component for coating modification, taking out and drying to obtain the thermal shrinkage induction type anti-cracking fiber.
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