CN116555942A - Preparation method and application of sheath-core structure hydraulic organic-inorganic composite material - Google Patents
Preparation method and application of sheath-core structure hydraulic organic-inorganic composite material Download PDFInfo
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- CN116555942A CN116555942A CN202310314209.4A CN202310314209A CN116555942A CN 116555942 A CN116555942 A CN 116555942A CN 202310314209 A CN202310314209 A CN 202310314209A CN 116555942 A CN116555942 A CN 116555942A
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- 229910003471 inorganic composite material Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010410 layer Substances 0.000 claims abstract description 72
- 239000002131 composite material Substances 0.000 claims abstract description 60
- 229920000620 organic polymer Polymers 0.000 claims abstract description 59
- 239000010954 inorganic particle Substances 0.000 claims abstract description 28
- 238000009987 spinning Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000012792 core layer Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 230000015271 coagulation Effects 0.000 claims abstract description 11
- 238000005345 coagulation Methods 0.000 claims abstract description 11
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 10
- 230000005514 two-phase flow Effects 0.000 claims abstract description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
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- 239000004568 cement Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 27
- 239000000499 gel Substances 0.000 claims description 26
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 25
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
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- 238000004519 manufacturing process Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 230000001172 regenerating effect Effects 0.000 claims description 5
- 238000005452 bending Methods 0.000 claims description 4
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims description 3
- 229920001817 Agar Polymers 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 229920002907 Guar gum Polymers 0.000 claims description 3
- 239000008272 agar Substances 0.000 claims description 3
- 229940023476 agar Drugs 0.000 claims description 3
- 239000000783 alginic acid Substances 0.000 claims description 3
- 235000010443 alginic acid Nutrition 0.000 claims description 3
- 229920000615 alginic acid Polymers 0.000 claims description 3
- 229960001126 alginic acid Drugs 0.000 claims description 3
- 150000004781 alginic acids Chemical class 0.000 claims description 3
- 238000009954 braiding Methods 0.000 claims description 3
- 239000000679 carrageenan Substances 0.000 claims description 3
- 235000010418 carrageenan Nutrition 0.000 claims description 3
- 229920001525 carrageenan Polymers 0.000 claims description 3
- 229940113118 carrageenan Drugs 0.000 claims description 3
- 229940045110 chitosan Drugs 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229940014259 gelatin Drugs 0.000 claims description 3
- 239000000665 guar gum Substances 0.000 claims description 3
- 235000010417 guar gum Nutrition 0.000 claims description 3
- 229960002154 guar gum Drugs 0.000 claims description 3
- 239000010440 gypsum Substances 0.000 claims description 3
- 229910052602 gypsum Inorganic materials 0.000 claims description 3
- 229920002674 hyaluronan Polymers 0.000 claims description 3
- 229960003160 hyaluronic acid Drugs 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 claims description 3
- 229920001184 polypeptide Polymers 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 150000004804 polysaccharides Chemical class 0.000 claims description 2
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 2
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 136
- 238000003756 stirring Methods 0.000 description 35
- 239000003469 silicate cement Substances 0.000 description 30
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- 238000010438 heat treatment Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 10
- 239000001110 calcium chloride Substances 0.000 description 10
- 229910001628 calcium chloride Inorganic materials 0.000 description 10
- 230000006872 improvement Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000012634 fragment Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000011398 Portland cement Substances 0.000 description 5
- 150000004645 aluminates Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
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- 230000008859 change Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron aluminate Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- 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
- D01D5/06—Wet spinning methods
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Multicomponent Fibers (AREA)
Abstract
The invention discloses a preparation method and application of a hydraulic organic-inorganic composite material with a sheath-core structure. The composite material is prepared by dissolving an organic polymer material in a non-aqueous solvent to obtain an organic polymer solution, dispersing inorganic particles into part of the organic polymer solution to obtain a blending solution, taking part of the organic polymer solution as a sheath solution or a core layer solution, taking the blending solution as a corresponding core layer solution or a sheath solution, obtaining a two-phase flow with a sheath layer and a core layer through a coaxial spinning technology, placing the two-phase flow into a non-aqueous coagulation bath for simultaneous regeneration to obtain gel with a sheath-core structure, and finally drying the gel to obtain the hydraulic organic-inorganic composite material with the sheath-core structure. The whole reaction is carried out in a non-aqueous system, and the prepared sheath-core structure hydraulic organic-inorganic composite material has the characteristics of strong short-time water-contacting plasticity and stable long-time hydraulic performance.
Description
Technical Field
The invention belongs to the technical field of functional composite material preparation, and particularly relates to a preparation method and application of an organic-inorganic composite material with a sheath-core structure and hydraulic property.
Background
Portland cement is a basic raw material for many products such as buildings and structures, initial concrete, reinforced concrete, and the like, and is a typical high-strength inorganic material. At present, cement subjected to multiple improvements is widely applied to the construction and related fields. However, it is notable that in the course of the development of cement-based materials, the formability of the materials is neglected during the hardening thereof, and that the ultra-high-strength cement materials are inferior in elongation, toughness (pseudo toughness), fracture resistance and tensile strength, which also limits the application of cement in the fields of construction, artwork and the like requiring local details.
Currently, researchers have progressively replaced some of the reinforcing asbestos fibers with cellulosic fibers. However, cellulose-reinforced cement products are more susceptible to damage from water than asbestos cement products. Moreover, the preparation method of the cellulose and cement composite material adopted in the prior art is mostly a conventional water blend curing method, and has low toughness and plasticity and large application limitation.
The researchers in the present case have proposed a technology to solve the above-mentioned problems, for example, patent document 1, which is capable of preparing an organic-inorganic composite material having hydraulic properties based on organic polymer and inorganic particles, wherein the organic and inorganic materials are network structures which are mutually communicated, and have the characteristics of softening in a short time and hardening in a long time when meeting water. However, the technology still has certain defects, such as poor mechanical properties and poor extensibility of the obtained dry fiber, and the composite material is extremely easy to damage in the application process and cannot support the specific application of the composite material.
Patent document 1: publication number CN113831067a.
In order to solve the problem, researchers in the scheme propose a further improvement scheme.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method and application of a hydraulic organic-inorganic composite material with a sheath-core structure. The material skin layer is a hydrophilic organic matter, and the core layer is a blend of the hydrophilic organic matter and an inorganic matter hardening when meeting water; or the skin layer is a blend of hydrophilic organic matters and inorganic matters hardened by water, and the core layer is hydrophilic organic matters.
Compared with the prior art, the hydraulic organic-inorganic composite material with the sheath-core structure can enhance the mechanical property (breaking strength) and extensibility (elongation at break) of the original composite material.
The material has obvious performance super-superposition effect, fully plays the reinforcing effect of hydrophilic organic matters, improves the extensibility and toughness (pseudo-toughness), improves the performances of folding resistance, tensile resistance and the like, has strong short-time water-meeting plasticity, can be used for knotting, bending, folding and other operations, has stable long-time hydrodynamic performance, is not easy to change the shape of the material when external force is applied, and has high plasticity, thus being widely applied to building materials.
In order to achieve the above object, the present invention provides a method for preparing a hydraulic organic-inorganic composite material having a sheath-core structure, comprising at least the steps of:
1) Dissolving an organic polymer material in a non-aqueous solvent to obtain an organic polymer solution, wherein the content of the organic polymer in the organic polymer solution is 0.5-2wt%;
2) Dispersing inorganic particles into part of the organic polymer solution obtained in the step 1) to obtain a blending solution, wherein the mass ratio of the organic polymer to the inorganic particles in the blending solution is 1:1-100;
3) Taking part of the organic polymer solution obtained in the step 1) as a skin layer solution or a core layer solution, taking the blending solution obtained in the step 2) as a corresponding core layer solution or a skin layer solution, and obtaining a two-phase flow with a skin layer and a core layer through a coaxial spinning technology by the skin layer solution and the core layer solution;
4) Regenerating the two-phase flow obtained in the step 3) in a non-aqueous coagulating bath simultaneously to obtain gel with a skin-core structure;
5) And (3) drying the gel obtained in the step (4) to obtain the hydraulic organic-inorganic composite material with the skin-core structure.
As a further improvement of the present invention, in step 1), the organic polymer is an organic polymer containing a hydrophilic group.
As a further improvement of the present invention, the organic polymer containing a hydrophilic group is a polysaccharide organic polymer or a polypeptide organic polymer.
As a further improvement of the invention, the organic polymer containing hydrophilic groups is one or more of cellulose, chitin, chitosan, agar, alginic acid, hyaluronic acid, gelatin, carrageenan and guar gum.
As a further improvement of the invention, the non-aqueous solvent of the cellulose is LiCl/DMAc; the non-aqueous solvent of chitin or silk is CaCl 2/methanol, caCl 2/ethanol, or CaCl 2/formic acid.
As a further development of the invention, in step 2), the mineral particles are water-hardened mineral particles or powders.
As a further improvement of the present invention, the water-hardenable inorganic particles or powder are one or more of cement, cement clinker, clay or gypsum.
As a further improvement of the invention, the non-aqueous coagulation bath is one or more of methanol, ethanol, propanol, DMAc, DMF, acetone, dichloromethane.
As a further development of the invention, in step 5), the morphology of the sheath-core structured hydraulic organic-inorganic composite material includes, but is not limited to, filiform, membranous, blocky, annular or tubular.
Meanwhile, the invention also relates to application of the sheath-core structure hydraulic organic-inorganic composite material prepared by the preparation method, the sheath-core structure hydraulic organic-inorganic composite material is soaked in water for 0.1-30 min to be softened, then the softened composite material is knotted, bent, folded or woven, and finally the composite material is soaked in water for 1-30h to be solidified and shaped, so that the high-strength material with the preset shape and tissue structure is obtained.
The beneficial effects of the invention are as follows:
1. in the preparation method, in the coagulating bath, the solvent for dissolving the organic polymer in the inner layer solution and the outer layer solution gradually diffuses into the coagulating bath, and the material gradually forms gel-like substances from the surface to the inside through acting forces such as intermolecular hydrogen bonds and the like. In the organic polymer solution, an organic polymer network is formed; in the blending solution, the hydraulic inorganic particles are encapsulated in an organic polymer network. In the drying process, the volatile coagulating bath organic matters are gradually volatilized, the interface between the polymer layer and the blending layer is vivid, and the hydraulic composite material is formed by further combining organic polymer chains and organic polymer and inorganic particles through hydrogen bonds.
2. When the hydraulic organic-inorganic composite material prepared by the method is soaked in water, the hydraulic inorganic particles react to harden to generate strength after meeting water, brittleness is improved, and an internal polymer network and an external polymer network layer effectively provide toughness to prevent network fracture formed by the hydraulic inorganic particles in the editing process of the material or promote the re-networking of broken networks. The hydraulic inorganic particles harden to form a network with the time being prolonged, and the organic matters and the inorganic matters are respectively communicated network structures in the composite material. Therefore, the plastic has the characteristics of strong plasticity when meeting water for a short time and stable hydraulic property when meeting water for a long time. The high plasticity in short time is mainly the characteristic of organic polymer materials in the composite material, and the stable long-time hydraulics performance is mainly the characteristic of inorganic particles in the composite material.
3. Because the hydraulic organic-inorganic composite material prepared by the method has the characteristics of softening in short time and hardening in long time, after softening in short time, the hydraulic organic-inorganic composite material can be subjected to various forming processes such as bending, knotting, braiding and the like, and finally is solidified and formed, so that the plasticity of the composite material is obviously improved, and the application range of the composite material is widened.
4. The prepared sheath-core structure hydraulic organic-inorganic composite material has a double-layer structure of a sheath layer and a core layer, and when hydraulic inorganic particles start to form a network when meeting water, the high polymer layer can macroscopically provide mechanical support or protection for the formation of an integral network, and can effectively prolong the editable time when meeting water for a short time. After the hydraulic inorganic particle network is formed, besides the double-network structure inside the material, the macroscopic polymer layer also provides mechanical property enhancement for the material.
5. When the sheath-core structure hydraulic organic-inorganic composite material prepared by the invention is practically applied, compared with the prior art, the sheath-core structure hydraulic organic-inorganic composite material can enhance the mechanical property (breaking strength) and extensibility (elongation at break) on the basis of the original composite material, namely, the sheath-core structure hydraulic organic-inorganic composite material can obtain better mechanical property, the breaking stress can reach 90.65MPa, and the breaking strain can reach 45.08%.
Drawings
FIG. 1 is a flow chart of a preparation method of the present invention;
FIG. 2 is a characteristic illustration of the hydraulic organic-inorganic composite material with a sheath-core structure prepared by the preparation method of the present invention;
FIG. 3 is an SEM image of a hydraulic organic-inorganic composite material having a sheath-core structure obtained by the production method of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to specific embodiments.
It should be further noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the specific embodiments, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of a hydraulic organic-inorganic composite material with a sheath-core structure, which at least comprises the following steps:
1) Dissolving an organic polymer material in a non-aqueous solvent to obtain an organic polymer solution, wherein the content of the organic polymer in the organic polymer solution is 0.5-2wt%;
2) Dispersing inorganic particles into part of the organic polymer solution obtained in the step 1) to obtain a blending solution, wherein the mass ratio of the organic polymer to the inorganic particles in the blending solution is 1:1-100;
3) Taking the rest organic polymer solution obtained in the step 1) as a skin layer solution or a core layer solution, taking the blending solution obtained in the step 2) as a corresponding core layer solution or a skin layer solution, and obtaining a two-phase flow with a skin layer and a core layer through a coaxial spinning technology by the skin layer solution and the core layer solution;
4) Regenerating the two-phase flow obtained in the step 3) in a non-aqueous coagulating bath simultaneously to obtain gel with a skin-core structure;
5) And (3) drying the gel obtained in the step (4) to obtain the hydraulic organic-inorganic composite material with the skin-core structure.
By adopting the technical scheme, the whole preparation method is carried out in a non-aqueous system, hydrophilic organic polymers and hydraulic inorganic particles are in a non-aqueous coagulation bath, according to similar compatibility, non-Shui Liang solvents of the organic polymers are gradually diffused into the non-aqueous coagulation bath, and the hydrophilic organic polymers gradually form gel substances from the surface to the inside through acting forces such as intermolecular hydrogen bonds.
In the organic polymer solution, an organic polymer network is formed; in the blending solution, the hydraulic inorganic particles are encapsulated in an organic polymer network.
In the drying process, the volatile coagulation bath organic matters are gradually volatilized, and a clear interface between the polymer layer and the blending layer is formed; and, the organic polymer chains and the organic polymer and the inorganic particles are further bonded by hydrogen bonds to form a hydraulic composite material.
When the composite material is soaked in water, hydraulic inorganic particles react to harden to generate strength after meeting water, brittleness is improved, and an internal polymer network and an external polymer network layer effectively provide toughness to prevent network fracture formed by the hydraulic inorganic particles in the editing process of the material or promote the re-networking of broken networks. The hydraulic inorganic particles harden to form a network with the time being prolonged, and the organic matters and the inorganic matters are respectively communicated network structures in the composite material.
Therefore, the prepared sheath-core structure hydraulic organic-inorganic composite material has the characteristics of strong short-time water-meeting plasticity and stable long-time water-meeting mechanical property; the high plasticity in short time is mainly the characteristic of organic polymer materials in the composite material, and the stable long-time hydraulics performance is mainly the characteristic of inorganic particles in the composite material.
The organic polymer containing hydrophilic group is one or more of cellulose, chitin, chitosan, agar, alginic acid, hyaluronic acid, gelatin, carrageenan and guar gum. Natural hydrophilic organic polymers are selected, so that on one hand, the sources of raw materials are wide, and the sustainable development concept is met; on the other hand, the material can form good colloid with inorganic minerals such as cement, and the composite material with the characteristics of softening in short time and hardening in long time can be obtained through the process.
In some embodiments, the organic polymer containing hydrophilic groups is cellulose, and the nonaqueous solvent is LiCl/DMAc (lithium chloride/N, N-dimethylacetamide).
In other embodiments, when chitin is used as the organic polymer containing hydrophilic groups, caCl is selected as the non-aqueous solvent 2 Methanol and CaCl 2 Ethanol and CaCl 2 Formic acid.
When the inorganic particles are water-hardened inorganic powder or particles, one or more of cement, cement clinker, clay or gypsum may be selected.
In some specific embodiments, when the inorganic powder or the particle hardened by water is selected from cement, silicate cement, aluminate water, sulphoaluminate cement, iron aluminate cement, fluoroaluminate cement, phosphate cement, etc. may be selected; meanwhile, inorganic fillers such as calcium oxide, calcium carbonate, silicon dioxide, fly ash, aluminum oxide, iron oxide and the like can be considered to be added.
The non-aqueous coagulation bath employs a volatile coagulation bath other than water, such as one or more of methanol, ethanol, propanol, DMAc, DMF, acetone, dichloromethane.
It will be appreciated that in order to facilitate the subsequent regeneration of the gel, a non-aqueous coagulation bath having a certain compatibility with the non-aqueous solvent in step 1) may be considered for the non-aqueous coagulation bath herein.
The two-phase flow with the skin layer and the core layer is obtained by the coaxial spinning technology of the skin layer solution and the core layer solution, wherein the coaxial spinning technology can be wet spinning technology and electrostatic spinning technology.
The form of the sheath-core structure hydraulic organic-inorganic composite material obtained in the step 5) includes, but is not limited to, filament, film, block, ring or tube, etc. The filaments can be realized by extrusion or injection, the films can be realized by casting film, and the blocks, rings or tubes can be obtained by curing and regenerating in corresponding dies.
Meanwhile, the invention also provides application of the sheath-core structure hydraulic organic-inorganic composite material prepared based on the preparation method. Specifically, the sheath-core structure hydraulic organic-inorganic composite material prepared based on the preparation method is soaked in water for 0.1-30 min to soften the composite material, then the softened composite material is knotted, bent, folded or woven, and finally the composite material is soaked in water for 1-30h to be solidified and shaped, so that the high-strength material with the preset shape and tissue structure is obtained.
The hydraulic organic-inorganic composite material with the skin-core structure has the characteristics of softening in short time and hardening in long time, so that the composite material can be molded after being softened in short time and finally cured and molded, the plasticity of the composite material is obviously improved, and the application range of the composite material is widened.
The invention is further illustrated by the following examples:
the invention is obtained by adopting an INSTRON Instron 5943 universal material tester in the United states, before testing, the material is balanced for 12 hours at the temperature of 25 ℃ and the humidity of 65 percent, during testing, the tensile speed of a sample is 10mm/min, and the testing length is 20mm, namely, the length of a fiber sample is 20mm under the condition of pretension.
In the drawing, fig. 2 is a flow chart of preparing fibers by the method, connecting an inner layer solution prepared in advance with an outer layer solution by using a coaxial spinning needle, simultaneously regenerating the inner layer and the outer layer in a coagulating bath of ethanol, collecting the inner layer and the outer layer by a collecting device, and airing the inner layer and the outer layer to obtain one of products prepared by the method.
Fig. 2 is a demonstration of the properties of the finished product prepared by the process of fig. 1, with shape stability in the dry state, increased flexibility and toughness after short exposure to water, editable material, increased shape stability after prolonged exposure to water, stable mechanical properties, and shaped material.
Fig. 3 is an SEM image of the finished product prepared by the process of fig. 1, and the whole and part of the skin-core structure of the product are clearly shown.
Example 1
1) Crushing cellulose wood pulp with polymerization degree of 400-800 into fragments with length of 0.1-0.5mm, and drying in a 60 ℃ oven for 12 hours;
2) 18g of lithium chloride (LiCl) and 192g of N, N-dimethylacetamide (DMAc) are weighed and mixed in a 250ml sample bottle and dissolved by ultrasonic;
3) Adding 3g of cellulose wood pulp obtained in the step 1) and 297g of DMAc/LiCl solution into a three-neck flask, heating and stirring for 2.5h to obtain a transparent cellulose solution with the mass fraction of 1wt%, wherein the heating temperature is 112 ℃, and the stirring speed is 550rpm;
4) Adding 0.5g of silicate cement powder into the cellulose solution in the step 3), stirring at the speed of 250rpm, and continuously stirring for 1min to obtain silicate cement/cellulose spinning solution, wherein the mass of the silicate cement powder is 0.5 times that of cellulose;
5) Taking two needle tubes, one extracting the transparent cellulose solution obtained in the step 3) as an outer layer solution, and the other extracting the silicate cement/cellulose spinning solution obtained in the step 4) as an inner layer solution;
6) Placing the two needle tubes obtained in the step 5) on different push pumps, and simultaneously connecting the two needle points with the same coaxial needle head.
7) Immersing the coaxial needle in the step 6) into the coagulating bath of ethanol, and starting two pushing pumps simultaneously, wherein the injection speed of the inner layer solution pushing pump and the injection speed of the outer layer solution pushing pump are both 0.4mL/min, so as to obtain gel with a skin-core structure;
8) And drying the obtained gel to obtain the hydraulic organic-inorganic composite material with the sheath-core structure.
Examples 2 to 11
Examples 2-11 differ from example 1 in that the quality of the portland cement powder in step 4 was changed, and the operations were the same except for the above differences, and detailed description thereof was omitted, and specific experimental condition parameters and measurement results are shown in table 1; the change in mechanical properties of the composite material in the dry and wet state is shown in Table 2 (dry state: as-prepared state; wet state: after being put into water).
TABLE 1
TABLE 2
As can be seen from table 1, as the silicate cement content in the inner layer solution increases, the fracture stress of the composite material gradually decreases, and the fracture strain also substantially shows a tendency to gradually decrease, and only the fracture strain of example 5 increases.
In Table 2, a negative value of the change in fracture stress indicates that the mechanical properties of the composite material are reduced, and the composite material is easy to fracture when stress and stretching are applied; the larger the fracture strain change value is, the flexibility and toughness of the material are increased after the material is exposed to water, and the material has better editability.
As can be seen from table 2, as the Portland cement content in the inner layer solution increases, the strength of the composite material gradually increases when it is stretched under stress, but the flexibility and toughness decrease after it encounters water, and the material editability also decreases.
Therefore, the flexibility and toughness, the convenience and the mechanical property of the composite material under the final form after meeting water are comprehensively considered, and the mass ratio of silicate cement to cellulose in the inner layer solution is between 1 and 10, so that a better effect can be obtained.
Example 12
1) Crushing cellulose wood pulp with polymerization degree of 400-800 into fragments with length of 0.1-0.5mm, and drying in a 60 ℃ oven for 12 hours;
2) 18g of lithium chloride (LiCl) and 192g of N, N-dimethylacetamide (DMAc) are weighed and mixed in a 250ml sample bottle and dissolved by ultrasonic;
3) Into a three-necked flask, 4.5g of the cellulose wood pulp obtained in step 1) and 295.5g of DMAc/LiCl solution were charged, and the mixture was stirred with heating at 112℃for 2.5 hours to obtain a transparent cellulose solution having a mass fraction of 1.5% by weight, with a stirring rate of 550rpm. And obtaining transparent cellulose solution with the mass fraction of 1 wt%;
4) Adding 10g of silicate cement powder into the cellulose solution with the mass fraction of 1wt% in the step 3), stirring at the stirring speed of 250rpm, and continuously stirring for 1min to obtain silicate cement/cellulose spinning solution, wherein the mass of the silicate cement powder is 10 times that of cellulose;
5) Taking two needle tubes, one extracting transparent cellulose solution with the mass fraction of 1.5wt% obtained in the step 3) as an outer layer solution, and the other extracting silicate cement/cellulose spinning solution obtained in the step 4) as an inner layer solution;
6) Placing the two needle tubes obtained in the step 5) on different push pumps, wherein the two needle points are simultaneously connected with the same coaxial needle head;
7) Immersing the coaxial needle in the step 6) into the coagulating bath of ethanol, and simultaneously starting two pushing pumps, wherein the injection speed is 0.4mL/min, so as to obtain gel with a skin-core structure;
8) And drying the obtained gel to obtain the hydraulic organic-inorganic composite material with the sheath-core structure.
Example 13
Example 13 differs from example 12 in that the quality of the cellulose wood pulp in step 3 was changed, and the operations were the same except for the above differences, and detailed description thereof was omitted, and specific experimental condition parameters and measurement results are shown in table 3.
TABLE 3 Table 3
From the results of examples 7 and 12 and 13, it is understood that the concentration of the outer organic solution is positively correlated with the fracture stress and fracture strain of the composite material.
With the increase of the concentration of the outer layer organic matter solution, more organic macromolecules participate in the construction of an organic matter macromolecular network, the interaction force between molecules is stronger, and the integral strength and strain of the composite material are improved.
However, when the concentration of the cellulose solution reaches 2%, the problem of needle blockage can occur in the process of preparing the skin-core structural material by adopting coaxial spinning. Since the technical purpose of the present invention is to obtain a composite material with a sheath-core structure, the concentration of the cellulose solution should not be too high.
Example 14
1) Crushing cellulose wood pulp with polymerization degree of 400-800 into fragments with length of 0.1-0.5mm, and drying in a 60 ℃ oven for 12 hours;
2) 18g of lithium chloride (LiCl) and 192g of N, N-dimethylacetamide (DMAc) are weighed and mixed in a 250ml sample bottle and dissolved by ultrasonic;
3) Adding 3g of cellulose wood pulp obtained in the step 1) and 297g of DMAc/LiCl solution into a three-neck flask, heating and stirring for 2.5h to obtain a transparent cellulose solution with the mass fraction of 1wt%, wherein the heating temperature is 112 ℃, and the stirring speed is 550rpm;
4) Adding 0.5g of silicate cement powder into the cellulose solution in the step 3), stirring at the speed of 250rpm, and continuously stirring for 1min to obtain silicate cement/cellulose spinning solution, wherein the mass of the silicate cement powder is 10 times that of cellulose;
5) Taking two needle tubes, one extracting the transparent cellulose solution obtained in the step 3) as an outer layer solution, and the other extracting the silicate cement/cellulose spinning solution obtained in the step 4) as an inner layer solution;
6) Placing the two needle tubes obtained in the step 5) on different push pumps, wherein the two needle points are simultaneously connected with the same coaxial needle head;
7) Immersing the coaxial needle in the step 6) into the coagulating bath of ethanol, and starting two pushing pumps simultaneously, wherein the injection speed of the outer layer solution pushing pump is 0.2mL/min, and the injection speed of the inner layer solution pushing pump is 0.4mL/min, so as to obtain gel with a skin-core structure;
8) And drying the obtained gel to obtain the hydraulic organic-inorganic composite material with the sheath-core structure.
Examples 15 to 23
Examples 15-21 differ from example 15 in that the injection rate of the push pump in step 7 was changed, and the operations were the same except for the above differences, and detailed experimental condition parameters and measurement results are shown in table 4.
TABLE 4 Table 4
As can be seen from the results of comparative examples 7 and examples 14-17, increasing the outer layer solution push pump speed resulted in a decrease in the strain at break of the composite material, which was due to the increase in the amount of needle-extruded organic solution over time, the slow down of the regeneration rate of the organic network in the coagulation bath, and the failure of the network to regenerate completely.
The composite material obtained in example 14 has improved mechanical properties and extensibility, and has hydraulic characteristics, as compared with the other examples.
As can be seen from the results of comparative examples 7 and examples 18-21, decreasing the internal solution push pump speed increases the strain at break of the composite. Over time, the amount of inorganic material extruded by the needle is reduced, and the composite material as a whole is closer to an organic network, and the fracture stress and fracture strain performance are improved.
As can be seen from the results of comparative examples 7 and examples 22 to 23, the composite material prepared by the inner layer solution containing only Portland cement/cellulose spinning solution in example 22 has mechanical properties and extensibility which cannot achieve the effects of the other examples; whereas example 23, which was prepared by the outer layer solution containing only cellulose solution, had higher mechanical strength and extensibility, but did not possess hydraulic properties, did not meet the technical use scenario expected in the present invention, and failed to achieve the performance of example 2.
Meanwhile, as can be seen from the comparison of example 22 with other examples, the performance of the composite material at various injection flow rates was improved after the skin-free composite material was introduced with the skin material having excellent performance.
Example 24
1) Drying the chitin powder in a 60 ℃ oven for 12 hours;
2) Weighing 5g of calcium chloride (CaCl) 2 ) And 95g Formic Acid (FA) in a 250ml sample bottle, and then stirring and dissolving;
3) 1g of the chitin powder obtained in step 1) and FA/CaCl were put into a three-necked flask 2 99g of solution, stirring at room temperature for 1h, and then preserving at low temperature for 1h to obtain transparent chitin solution with mass fraction of 1wt%, wherein the preserving temperature is 8 ℃, and the stirring speed is 550rpm;
4) Adding 0.5g of silicate cement powder into the chitin solution in the step 3), stirring at the speed of 250rpm, and continuously stirring for 1min to obtain silicate cement/chitin spinning solution, wherein the mass of the silicate cement powder is 0.5 times that of the chitin;
5) Taking two needle tubes, one extracting the transparent chitin solution obtained in the step 3) as an outer layer solution, and the other extracting the silicate cement/chitin spinning solution obtained in the step 4) as an inner layer solution;
6) Placing the two needle tubes obtained in the step 5) on different push pumps, wherein the two needle points are simultaneously connected with the same coaxial needle head;
7) Immersing the coaxial needle in the step 6) into the coagulating bath of ethanol, and starting two pushing pumps simultaneously, wherein the injection speed of the outer layer solution pushing pump and the inner layer solution pushing pump is 0.4mL/min, so as to obtain gel with a skin-core structure;
8) And drying the obtained gel to obtain the hydraulic organic-inorganic composite material with the sheath-core structure.
Example 25
1) With 0.5wt% NaCO 3 Degumming silk by using the solution at the temperature of 100 ℃ for 1.5 hours, filtering and drying the degummed silk, and drying the dried silk in an oven at 80 ℃ for 12 hours;
2) Weighing 5g of calcium chloride (CaCl) 2 ) And 95g Formic Acid (FA) in a 250ml sample bottle, and then stirring and dissolving;
3) Adding 1g of silk obtained in the step 1) and FA/CaCl into a three-neck flask 2 99g of solution, stirring for 30min at room temperature to obtain transparent silk solution with mass fraction of 1wt%, wherein the stirring speed is 550rpm;
4) Adding 0.5g of silicate cement powder into the chitin solution in the step 3), stirring at the speed of 250rpm, and continuously stirring for 1min to obtain silicate cement/silk spinning solution, wherein the mass of the silicate cement powder is 0.5 times that of silk;
5) Taking two needle tubes, one extracting the transparent silk solution obtained in the step 3) as an outer layer solution, and the other extracting the silicate cement/silk spinning solution obtained in the step 4) as an inner layer solution;
6) Placing the two needle tubes obtained in the step 5) on different push pumps, wherein the two needle points are simultaneously connected with the same coaxial needle head;
7) Immersing the coaxial needle in the step 6) into the coagulating bath of ethanol, and starting two pushing pumps simultaneously, wherein the injection speed of the outer layer solution pushing pump and the inner layer solution pushing pump is 0.4mL/min, so as to obtain gel with a skin-core structure;
8) And drying the obtained gel to obtain the hydraulic organic-inorganic composite material with the sheath-core structure.
Example 26
1) Adding 1g of gelatin into 99g of deionized water to obtain transparent gelatin solution, wherein the temperature is 65 ℃ and the time is 10min;
2) Adding the gelatin solution with the mass fraction of 1wt% obtained in the step 1) and 0.5g of silicate cement powder into a three-neck flask, wherein the stirring speed is 550rpm, so as to obtain silicate cement/gelatin spinning solution, and the mass of the silicate cement powder is 0.5 times that of gelatin;
3) Taking two needle tubes, wherein one needle tube is used for extracting the transparent gelatin solution obtained in the step 1) to serve as an outer layer solution, and the other needle tube is used for extracting the Portland cement/gelatin spinning solution obtained in the step 2) to serve as an inner layer solution;
4) Placing the two needle tubes obtained in the step 3) on different push pumps, wherein the two needle points are simultaneously connected with the same coaxial needle head;
5) Immersing the coaxial needle in the step 4) into a coagulating bath of cold water at the temperature of 10 ℃, and simultaneously starting two pushing pumps, wherein the injection speed of the outer layer solution pushing pump and the inner layer solution pushing pump is 0.4mL/min, so as to obtain gel with a skin-core structure;
6) And drying the obtained gel to obtain the hydraulic organic-inorganic composite material with the sheath-core structure.
Example 27
1) Crushing cellulose wood pulp with polymerization degree of 400-800 into fragments with length of 0.1-0.5mm, and drying in a 60 ℃ oven for 12 hours;
2) 18g of lithium chloride (LiCl) and 192g of N, N-dimethylacetamide (DMAc) are weighed and mixed in a 250ml sample bottle and dissolved by ultrasonic;
3) Adding 3g of cellulose wood pulp obtained in the step 1) and 297g of DMAc/LiCl solution into a three-neck flask, heating and stirring for 2.5h to obtain a transparent cellulose solution with the mass fraction of 1wt%, wherein the heating temperature is 112 ℃, and the stirring speed is 550rpm;
4) Adding 0.5g of silicate cement powder into the cellulose solution in the step 3), stirring at the speed of 250rpm, and continuously stirring for 1min to obtain silicate cement/cellulose spinning solution, wherein the mass of the silicate cement powder is 0.5 times that of cellulose;
5) Taking two needle tubes, one extracting the transparent cellulose solution obtained in the step 3) as an outer layer solution, and the other extracting the silicate cement/cellulose spinning solution obtained in the step 4) as an inner layer solution;
6) Placing the two needle tubes obtained in the step 5) on different push pumps, wherein the two needle points are simultaneously connected with the same coaxial needle head;
7) Immersing the coaxial needle in the step 6) into a coagulating bath of water, and simultaneously starting two pushing pumps, wherein the injection speed is 0.4mL/min, so as to obtain gel with a skin-core structure;
8) And drying the obtained gel to obtain the hydraulic organic-inorganic composite material with the sheath-core structure.
Example 28
1) Crushing cellulose wood pulp with polymerization degree of 400-800 into fragments with length of 0.1-0.5mm, and drying in a 60 ℃ oven for 12 hours;
2) 18g of lithium chloride (LiCl) and 192g of N, N-dimethylacetamide (DMAc) are weighed and mixed in a 250ml sample bottle and dissolved by ultrasonic;
3) Adding 3g of cellulose wood pulp obtained in the step 1) and 297g of DMAc/LiCl solution into a three-neck flask, heating and stirring for 2.5h to obtain a transparent cellulose solution with the mass fraction of 1wt%, wherein the heating temperature is 112 ℃, and the stirring speed is 550rpm;
4) Adding 0.5g of aluminate cement powder into the cellulose solution in the step 3), stirring at the speed of 250rpm, and continuously stirring for 1min to obtain aluminate cement/cellulose spinning solution, wherein the mass of the aluminate cement powder is 0.5 times that of cellulose;
5) Taking two needle tubes, one extracting the transparent cellulose solution obtained in the step 3) as an outer layer solution, and the other extracting the aluminate cement/cellulose spinning solution obtained in the step 4) as an inner layer solution;
6) Placing the two needle tubes obtained in the step 5) on different push pumps, wherein the two needle points are simultaneously connected with the same coaxial needle head;
7) Immersing the coaxial needle in the step 6) into the coagulating bath of ethanol, and simultaneously starting two pushing pumps, wherein the injection speed is 0.4mL/min, so as to obtain gel with a skin-core structure;
8) And drying the obtained gel to obtain the hydraulic organic-inorganic composite material with the sheath-core structure.
Example 29
1) Crushing cellulose wood pulp with polymerization degree of 400-800 into fragments with length of 0.1-0.5mm, and drying in a 60 ℃ oven for 12 hours;
2) 18g of lithium chloride (LiCl) and 192g of N, N-dimethylacetamide (DMAc) are weighed and mixed in a 250ml sample bottle and dissolved by ultrasonic;
3) Adding 3g of cellulose wood pulp obtained in the step 1) and 297g of DMAc/LiCl solution into a three-neck flask, heating and stirring for 2.5h to obtain a transparent cellulose solution with the mass fraction of 1wt%, wherein the heating temperature is 112 ℃, and the stirring speed is 550rpm;
4) Adding 0.5g of sulfoaluminate cement powder into the cellulose solution in the step 3), stirring at the speed of 250rpm, and continuously stirring for 1min to obtain a sulfoaluminate cement/cellulose spinning solution, wherein the mass of the sulfoaluminate cement powder is 0.5 times that of cellulose;
5) Taking two needle tubes, one extracting transparent cellulose solution obtained in the step 3) as an outer layer solution, and the other extracting sulfoaluminate cement/cellulose spinning solution obtained in the step 4) as an inner layer solution;
6) Placing the two needle tubes obtained in the step 5) on different push pumps, wherein the two needle points are simultaneously connected with the same coaxial needle head;
7) Immersing the coaxial needle in the step 6) into the coagulating bath of ethanol, and simultaneously starting two pushing pumps, wherein the injection speed is 0.4mL/min, so as to obtain gel with a skin-core structure;
8) And drying the obtained gel to obtain the hydraulic organic-inorganic composite material with the sheath-core structure.
The specific experimental condition parameters and measurement results are shown in table 5.
TABLE 5
The results of comparative example 1 and examples 24-25 show that changing the organic species in the composite does not have a significant effect on the functionality of the composite.
As can be seen from the results of comparative examples 1 and examples 26-27, changing the inorganic species in the composite material does not affect the functionality of the composite material either.
The sheath-core structure hydraulic organic-inorganic composite materials prepared by the method in the comprehensive examples 1-27 have the characteristics of strong short-time water-meeting plasticity and stable long-time water-meeting mechanical property.
In summary, according to the preparation method of the sheath-core structure hydraulic organic-inorganic composite material, provided by the invention, the organic polymer and the inorganic substance are compounded in a non-water system, so that the hydraulic organic-inorganic composite material with the characteristics of softening in short time and hardening in long time can be obtained. By utilizing the characteristics, after the composite material is softened by short-time soaking, various forming processes (such as knotting, bending, folding or braiding) can be carried out on the composite material, and finally, the composite material is solidified and formed, so that the plasticity of the composite material can be improved, the application range of the composite material is widened, and better mechanical properties can be obtained.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A method for preparing a hydraulic organic-inorganic composite material with a sheath-core structure, which is characterized by at least comprising the following steps:
1) Dissolving an organic polymer material in a non-aqueous solvent to obtain an organic polymer solution, wherein the content of the organic polymer in the organic polymer solution is 0.5-2wt%;
2) Dispersing inorganic particles into part of the organic polymer solution obtained in the step 1) to obtain a blending solution, wherein the mass ratio of the organic polymer to the inorganic particles in the blending solution is 1:1-100;
3) Taking part of the organic polymer solution obtained in the step 1) as a skin layer solution or a core layer solution, taking the blending solution obtained in the step 2) as a corresponding core layer solution or a skin layer solution, and obtaining a two-phase flow with a skin layer and a core layer through a coaxial spinning technology by the skin layer solution and the core layer solution;
4) Regenerating the two-phase flow obtained in the step 3) in a non-aqueous coagulating bath simultaneously to obtain gel with a skin-core structure;
5) And (3) drying the gel obtained in the step (4) to obtain the hydraulic organic-inorganic composite material with the skin-core structure.
2. The method for producing a sheath-core structured hydraulic organic-inorganic composite according to claim 1, wherein in step 1), the organic polymer is an organic polymer having a hydrophilic group.
3. The method for producing a sheath-core structured hydraulic organic-inorganic composite material according to claim 2, wherein the organic polymer containing a hydrophilic group is a polysaccharide organic polymer or a polypeptide organic polymer.
4. The method for producing a sheath-core structured hydraulic organic-inorganic composite material according to claim 3, wherein the organic polymer containing a hydrophilic group is one or more of cellulose, chitin, chitosan, agar, alginic acid, hyaluronic acid, gelatin, carrageenan, and guar gum.
5. The method for producing a sheath-core structured hydraulic organic-inorganic composite according to claim 4, wherein the non-aqueous solvent of cellulose is LiCl/DMAc; the non-aqueous solvent of chitin or silk is CaCl 2 Methanol and CaCl 2 Ethanol and CaCl 2 Formic acid.
6. The method for producing a sheath-core structured hydraulic organic-inorganic composite according to claim 1, wherein in step 2), the inorganic particles are water-hardened inorganic particles or powder.
7. The method for producing a sheath-core structured hydraulic organic-inorganic composite material according to claim 6, wherein the water-hardenable inorganic particles or powder are one or more of cement, cement clinker, clay or gypsum.
8. The method for producing a sheath-core structured hydraulic organic-inorganic composite according to claim 7, wherein the non-aqueous coagulation bath is one or more of methanol, ethanol, propanol, DMAc, DMF, acetone, and dichloromethane.
9. The method of preparing a sheath-core hydraulic organic-inorganic composite according to claim 1, wherein in step 5), the morphology of the sheath-core hydraulic organic-inorganic composite includes, but is not limited to, a thread, a film, a block, a ring or a tube.
10. Use of the sheath-core structure hydraulic organic-inorganic composite material prepared by the preparation method according to any one of claims 1 to 9, characterized in that the sheath-core structure hydraulic organic-inorganic composite material is softened by soaking in water for 0.1 to 30min, then knotting, bending, folding or braiding is performed on the softened composite material, and finally the composite material is soaked in water for 1 to 30h for solidification and shaping, thus obtaining the high-strength material with preset shape and tissue structure.
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