CN116043548B - Flexible fabric/gel composite material and preparation method and application thereof - Google Patents
Flexible fabric/gel composite material and preparation method and application thereof Download PDFInfo
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- CN116043548B CN116043548B CN202310090436.3A CN202310090436A CN116043548B CN 116043548 B CN116043548 B CN 116043548B CN 202310090436 A CN202310090436 A CN 202310090436A CN 116043548 B CN116043548 B CN 116043548B
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- polyvinyl alcohol
- fabric
- inorganic salt
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- salt water
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- 239000004744 fabric Substances 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000499 gel Substances 0.000 claims abstract description 50
- 239000002243 precursor Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 239000000017 hydrogel Substances 0.000 claims abstract description 31
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 30
- 239000000835 fiber Substances 0.000 claims abstract description 23
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 23
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 32
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 31
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 13
- 230000008014 freezing Effects 0.000 claims description 11
- 238000007710 freezing Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 239000012267 brine Substances 0.000 claims description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 9
- 238000010257 thawing Methods 0.000 claims description 9
- 210000004177 elastic tissue Anatomy 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 5
- 238000010345 tape casting Methods 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 230000008961 swelling Effects 0.000 claims description 3
- 229920002614 Polyether block amide Polymers 0.000 claims description 2
- 238000006136 alcoholysis reaction Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims description 2
- 238000010952 in-situ formation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920006306 polyurethane fiber Polymers 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000012424 Freeze-thaw process Methods 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 33
- 229920002334 Spandex Polymers 0.000 description 14
- 239000004759 spandex Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 230000033001 locomotion Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 210000001519 tissue Anatomy 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920006052 Chinlon® Polymers 0.000 description 1
- 229920004934 Dacron® Polymers 0.000 description 1
- 238000012425 Freezing-thawing process Methods 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/38—Polyurethanes
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Medical Uses (AREA)
Abstract
The application provides a flexible fabric/gel composite material, a preparation method and application thereof, wherein the composite material has skin-like characteristics, and consists of fabrics and hydrogel, the fabrics are made of fibers, the hydrogel is polyvinyl alcohol-inorganic salt water gel, and the hydrogel is formed in situ between the fabrics by a polyvinyl alcohol-inorganic salt water gel precursor liquid. The tensile curve of the flexible composite material is J-shaped, has sensitive strain sensitivity, has adhesion performance and long-term use stability, and can be applied to the fields of electronic skin, wearable devices, flexible touch screens and the like.
Description
Technical Field
The application relates to the field of composite material preparation, in particular to a flexible fabric/gel composite material and a preparation method and application thereof.
Background
Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field.
With the advent of advanced application fields, such as fields of electronic skin, flexible sensors, flexible touch screens and the like, flexible materials with ductility, high flexibility, high elasticity and conductivity are urgently required to be developed, and the wide attention of researchers at home and abroad is brought.
The fabric is used as a material with high flexibility, high elasticity and high strength, can be made into different shape types according to different requirements, and is an excellent substrate for materials such as electronic skin and the like. Currently, conductive yarns are integrated into fabrics by coating the fibers, yarns or fabrics with conductive materials, spinning composite fibers or in a woven manner. The composite conductive material on the fiber, yarn or fabric material is a simple method for manufacturing flexible intelligent materials.
However, the existing electronic skin material has a large difference from the characteristics and functions of the real biological skin. The main reasons are as follows: 1) Most of the imitation electronic skin materials are difficult to combine high flexibility and high elasticity; 2) On the premise of considering various characteristics, the sensing performance is fused, so that the portability or the wearable requirement of the material is often influenced; 3) Some dielectrics and matrix materials have low interfacial bond strength, limiting the ductility of the material and adversely deteriorating the properties after compounding. Common electronic devices such as free metal films prepared by Pashley that break (Pashley D W.A study of the deformation and fracture of single-crystal gold films of high strength inside an electron microscope[J].Proceedings of the Royal Society of London.Series A.Mathematical and Physical Sciences,1960,255(1281):218-231.). copper-aluminum alloys when stretched to 1% strain cannot be directly compounded on elastic substrates to prepare skin-like flexible elastic materials. It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative. Throughout the specification and claims, the words "comprise," "include," and the like are to be construed in an inclusive sense, rather than an exclusive or exhaustive sense, unless the context clearly requires otherwise; that is, it is interpreted in the light of "including, but not limited to".
Disclosure of Invention
Conductive hydrogels are considered useful for the preparation of flexible electronic skin materials because of their high water content and similar structure and excellent conductive properties to human soft tissues. However, hydrogels sometimes cannot withstand deformation actions such as bending, stretching, twisting, etc., and have low strength. Therefore, in order to improve the defects of the prior art, the invention provides a flexible fabric/gel composite material, which consists of fabric and hydrogel, wherein the hydrogel is formed in situ between fabric fibers after being frozen and thawed, the hydrogel is polyvinyl alcohol-inorganic salt hydrogel, more free polar groups are endowed to the hydrogel by introducing specific inorganic salt, a firm interface is formed between the hydrogel and the polar fabric, and the obtained composite material has excellent comprehensive performance, not only has good mechanical performance, but also has multifunction such as sensibility, adhesiveness, moisture retention, high elasticity, ductility and flexibility, especially shows skin-like characteristics, and a stress-strain curve shows J shape and accords with the mechanical performance of biological tissues such as human skin and the like.
Specifically, the technical scheme of the invention is as follows:
In a first aspect of the invention, the invention provides a flexible composite material having skin-like properties including stress-strain curves exhibiting a "J" shape; the flexible composite material comprises fabric and hydrogel, or the flexible composite material consists of fabric and hydrogel, and the hydrogel is formed in situ between the fabric to realize the combination of the fabric and the hydrogel; the fabric is made of fibers, and the hydrogel is a polyvinyl alcohol-inorganic brine gel, which is formed in situ between the fabrics from a polyvinyl alcohol-inorganic brine gel precursor solution.
In embodiments of the invention, the means of in situ formation include stirring, soaking and knife coating.
In an embodiment of the invention, the fibers are selected from the group consisting of composite fibers of one or more of polyurethane fibers (spandex), polyester fibers (polyester), polyetherester elastic fibers, polyetheramide elastic fibers, polyamide fibers (nylon), polyolefin elastic fibers (such as DOW-XLA fibers) and composite elastic fibers (such as T400 composite fibers), preferably elastic fibers rich in polar functional groups. In some embodiments of the invention, the fibers are predominantly one or a combination of at least two of spandex, dacron, and chinlon. In embodiments of the present invention, the preferred spandex fiber is a high elastic spandex (elastic elongation of 30% to 50%) or a medium elastic spandex (elastic elongation of 20% to 30%), and in embodiments of the present invention, the composite fiber is in the form of a composite fiber such as spandex and polyester, for example, a milk silk fabric.
In the embodiment of the invention, the polyvinyl alcohol-inorganic salt water gel precursor liquid takes polyvinyl alcohol (PVA) and inorganic salt water solution as raw materials, wherein the concentration of the inorganic salt water solution is 1-7 mol/L, and the concentration of the polyvinyl alcohol solution is 10-30wt%; in particular, in some embodiments of the present invention, the concentration of the inorganic salt aqueous solution is 2 to 6mol/L, may be further 3 to-6 mol/L, 3 to 5mol/L, etc.; in some embodiments of the present invention, the concentration of the polyvinyl alcohol solution is 10-20wt%, and may further be 10-15 wt%, 13-20 wt%, 15-20 wt%, etc.
The concentration of the polyvinyl alcohol or the polyvinyl alcohol solution refers to the concentration of the polyvinyl alcohol in the solvent after the polyvinyl alcohol is dissolved in the solvent, the polyvinyl alcohol-inorganic brine gel precursor liquid is a ternary system, and the concentration of the polyvinyl alcohol solution is [ b/(b+c) ] by 100% assuming that the mass of inorganic salt, the mass of the polyvinyl alcohol and the mass of water (solvent) are a, b and c respectively.
In an embodiment of the present invention, the polyvinyl alcohol has a number average molecular weight of 40000 to 180000 and an alcoholysis degree of 80 to 99.9%; in some embodiments of the present invention, the polyvinyl alcohol has a number average molecular weight of 40000 to 100000, and may further be 50000 to 90000, 70000 to 90000, and the like.
In an embodiment of the present invention, the inorganic salt is selected from the group of inorganic salts capable of significantly lowering the freezing point of water, such as one or more selected from calcium chloride, zinc sulfate, lithium chloride, sodium phosphate, potassium acetate, preferably calcium chloride and/or lithium chloride.
In a second aspect of the present invention, there is provided a method of preparing a flexible composite as described in the first aspect above, comprising: and compounding the polyvinyl alcohol-inorganic salt water gel precursor liquid with the fabrics, and carrying out freezing-thawing treatment, wherein the polyvinyl alcohol-inorganic salt water gel is formed in situ between the fabrics to form the flexible composite material.
In an embodiment of the present invention, a method for preparing a polyvinyl alcohol-inorganic salt aqueous gel precursor solution includes: the polyvinyl alcohol is added into inorganic salt water solution to be swelled, and the mixture is stirred until no impurity exists after the swelling, and then ultrasonic defoaming is carried out. In some embodiments of the present invention, a polyvinyl alcohol-inorganic brine gel precursor is prepared, polyvinyl alcohol is added to the prepared inorganic brine solution to swell, and after swelling for 4-12 hours, stirring is performed at 95 ℃ until no impurity is present, followed by ultrasonic deaeration. The concentration of the aqueous inorganic salt solution and the polyvinyl alcohol is as described above.
In the embodiment of the invention, the polyvinyl alcohol-inorganic salt water gel precursor liquid and the fabric are fully surrounded around the fabric fibers (the surface of the fabric and the fibers thereof) by stirring, soaking or knife coating, so that the polyvinyl alcohol-inorganic salt water gel precursor liquid and the fabric are fully compounded, and the polyvinyl alcohol-inorganic salt water gel is formed in situ between the fabrics in the subsequent freezing-thawing process.
In the hydrogel formed in situ between fabrics, inorganic salt ions and water molecules form bound water, so that the freezing of water below zero in the freezing process is effectively prevented, the formation of hydrogen bonds of PVA chains in the freezing and thawing process is prevented, the crystallinity of a physical crosslinking network is reduced, more free hydroxyl groups are endowed to the hydrogel by the introduction of inorganic salt, and the strong interface bonding with polar fabrics is greatly promoted; meanwhile, in the thawing process, PVA chains crystallize to form a porous structure, which is favorable for ion transportation and ensures that the material has excellent conductivity; in addition, the polar groups in the fabric fibers and the polar groups in the hydrogel form hydrogen bonds, fixing the gel to the internal voids and surfaces of the fabric material. Therefore, the flexible composite material has excellent comprehensive performance, not only has good mechanical properties, but also has multifunction, such as sensibility, adhesiveness, moisture retention, high elasticity, ductility and flexibility, and especially shows skin-like characteristics, and the stress-strain curve of the flexible composite material is J-shaped and accords with the mechanical properties of biological tissues such as human skin and the like.
In an embodiment of the present invention, the stirring compounding means includes: placing the fabric in gel precursor liquid and stirring; preferably, the temperature during stirring is 5-90 ℃, and the stirring time is 0.5-12 h.
In an embodiment of the present invention, the composite mode of soaking includes: soaking the fabric in gel precursor liquid; preferably, the temperature during soaking is 5-90 ℃, and the stirring time is 0.5-12 h.
In an embodiment of the present invention, the doctor blade compounding method includes: the fabric was placed in a mold, the gel precursor was poured, and the fabric surface was then knife coated.
In an embodiment of the present invention, the freeze-thaw treatment includes: freezing at-10 deg.c to-80 deg.c for 1-48 hr, thawing at-10 deg.c to-30 deg.c for 0-48 hr, and freeze-thawing for 1-10 times.
In a third aspect of the present invention there is provided the use of the flexible composite material described in the first aspect above in the fields of electronic skin, wearable devices and flexible touch screens.
Compared with the prior art, the invention has the advantages that:
The flexible composite material has excellent comprehensive performance, skin-like characteristics and mechanical properties, and the stress-strain curve of the flexible composite material presents J-shape and accords with the mechanical properties of biological tissues such as human skin, and the maximum breaking strength of the flexible composite material is 18-20 MPa and the maximum breaking elongation of the flexible composite material is 100-500%. The flexible composite material provided by the invention has good strain sensitivity, good sensing performance, and can accurately and sensitively detect joint motions of fingers, elbows and the like of a human body, meanwhile, the flexible composite material also has good adhesiveness, ductility and flexibility, and can be fully covered on the back of the hand of the human body, and the composite material can still be firmly attached to the skin surface when the back of the hand is turned down, and in addition, the composite material still has good ductility and flexibility after being frozen at ultralow temperature for 24 hours and then tested again.
In addition, the method is simple and easy to operate, does not involve any toxic materials in the preparation process, and is environment-friendly.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. Embodiments of the present application are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a stress-strain curve of the flexible fabric/gel composites prepared in examples 1-3; wherein examples 1,2,3 correspond to curves ①、②、③, respectively, curve ①、② has a lower strength at 0-200% strain, a sudden increase in strength at 200-500% strain, and curve ③ has a lower strength at 0-50% strain; at 50% -200% strain, the strength is suddenly increased; all three curves are J-shaped, and have good skin-like characteristics.
FIG. 2 shows the sensing properties of the flexible fabric/gel composite prepared in example 1 at small strain (a) and large strain (b).
Figure 3 shows the sensing stability of the flexible fabric/gel composite prepared in example 1 at a specific strain.
Fig. 4 shows the sensing properties of the flexible fabric/gel composite prepared in example 1 for use in the monitoring of human body joint movement of finger (a) and elbow (b).
Fig. 5 shows the adhesion properties of the flexible fabric/gel composite material prepared in example 1, which can firmly adhere to substrates of different materials.
Figure 6 shows the ductility (left) and flexibility (right) of the flexible fabric/gel composite prepared in example 1 after freezing for 24 hours at low temperature (-30 ℃).
Fig. 7 shows the tensile curve of the material obtained in comparative example 2, without presenting a skin-like J-shape.
Fig. 8 shows the results of the sensing test of the material obtained in comparative example 4, which is inferior in sensing performance stability compared to example 1 of fig. 3.
Detailed Description
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or materials used in the present application may be purchased in conventional manners, and unless otherwise indicated, they may be used in conventional manners in the art or according to the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present application. The preferred methods and materials described herein are presented for illustrative purposes only.
Example 1
Lithium chloride and deionized water were blended at a concentration of 4mol/L and magnetically stirred at 300rpm for 0.5h. 15wt% polyvinyl alcohol (m=70000) was weighed and added to the aqueous lithium chloride solution to swell for 12 hours. The swollen solution was stirred at 95 ℃ for 1h to be free of impurities to ensure uniform mixing. After ultrasonic defoaming, placing the high-elastic spandex fabric into gel precursor liquid, and uniformly stirring for 1h at a constant temperature of 40 ℃ to fully impregnate the hydrogel precursor liquid into the fabric material. The fabric was laid flat in a previously prepared mold, and then frozen in a refrigerator at-20 ℃ for 12 hours, thawed at 20 ℃ for 12 hours, and the number of freeze-thaw cycles was 3.
Example 2
Calcium chloride and deionized water were blended at a concentration of 3.5mol/L and magnetically stirred at 300rpm for 0.5h. 13% by weight of polyvinyl alcohol (m=70000) was weighed and added to an aqueous solution of calcium chloride to swell for 12 hours. The swollen solution was stirred at 95 ℃ for 1h to be free of impurities to ensure uniform mixing. After ultrasonic defoaming, placing the high-elastic spandex fabric into gel precursor liquid, and uniformly stirring for 1h at a constant temperature of 40 ℃ to fully impregnate the hydrogel precursor liquid into the fabric material. The fabric was laid flat in a previously prepared mold, and then frozen in a refrigerator at-20 ℃ for 12 hours, thawed at 20 ℃ for 12 hours, and the number of freeze-thaw cycles was 3.
Example 3
Lithium chloride and deionized water were blended at a concentration of 6mol/L and magnetically stirred at 300rpm for 0.5h. 15wt% polyvinyl alcohol (m=90000) was weighed and added to an aqueous lithium chloride solution to swell for 12h. The swollen solution was stirred at 95 ℃ for 1h to be free of impurities to ensure uniform mixing. After ultrasonic defoaming, the high-elastic spandex fabric is placed into a die, gel precursor liquid is poured, and the gel precursor liquid is soaked for 2 hours under the constant temperature condition of 30 ℃ so that the hydrogel precursor liquid is fully soaked into the fabric material. The fabric is tiled in a pre-prepared mould, and then is put into a refrigerator for freezing, the freezing temperature is minus 20 ℃, the freezing time is 6 hours, the fabric is thawed for 12 hours at 20 ℃, and the number of times of freezing and thawing cycles is 3.
Example 4
Lithium chloride and calcium chloride were blended with deionized water at a concentration of 2mol/L and 2mol/L, respectively, and magnetically stirred at 300rpm for 0.5h. 15wt% polyvinyl alcohol (m=70000) was weighed and added to the formulated mixed inorganic salt aqueous solution to swell for 12 hours. The swollen solution was stirred at 95 ℃ for 1h to be free of impurities to ensure uniform mixing. After ultrasonic defoaming, placing the high-elastic spandex fabric into gel precursor liquid, and uniformly stirring for 1h at a constant temperature of 45 ℃ to fully impregnate the hydrogel precursor liquid into the fabric material. The fabric was laid flat in a previously prepared mold, and then frozen in a refrigerator at-20 ℃ for 24 hours, thawed at 20 ℃ for 6 hours, and the number of freeze-thaw cycles was 3.
Example 5
Lithium chloride and deionized water were blended at a concentration of 4mol/L and magnetically stirred at 300rpm for 0.5h. 15wt% polyvinyl alcohol (m=70000) was weighed and added to the aqueous lithium chloride solution to swell for 12 hours. The swollen solution was stirred at 95 ℃ for 1h to be free of impurities to ensure uniform mixing. After ultrasonic defoaming, putting the milk silk fabric (95% terylene and 5% spandex) into a die, pouring the prepared hydrogel precursor liquid, and then scraping the surface of the fabric to fully impregnate the hydrogel precursor liquid into the fabric. The fabric was laid flat in a previously prepared mold, and then frozen in a refrigerator at-30 ℃ for 12 hours, thawed at 15 ℃ for 12 hours, and the number of freeze-thaw cycles was 3.
Example 6
Lithium chloride and deionized water were blended at a concentration of 4mol/L and magnetically stirred at 300rpm for 0.5h. 15wt% polyvinyl alcohol (m=70000) was weighed and added to the aqueous lithium chloride solution to swell for 12 hours. The swollen solution was stirred at 95 ℃ for 1h to be free of impurities to ensure uniform mixing. After ultrasonic defoaming, a nylon fabric is put into gel precursor liquid, and the gel precursor liquid is stirred at a constant speed for 1h at a constant temperature of 40 ℃ so that the hydrogel precursor liquid is fully immersed into the fabric material. The fabric was laid flat in a previously prepared mold, and then frozen in a refrigerator at-20 ℃ for 24 hours, thawed at 20 ℃ for 6 hours, and the number of freeze-thaw cycles was 3.
Example 7
Lithium chloride and deionized water were blended at a concentration of 3mol/L and magnetically stirred at 300rpm for 0.5h. 30wt% polyvinyl alcohol (m=70000) was weighed and added to the aqueous lithium chloride solution to swell for 12 hours. The swollen solution was stirred at 95 ℃ for 1h to be free of impurities to ensure uniform mixing. After ultrasonic defoaming, placing the high-elastic spandex fabric into gel precursor liquid, and soaking for 2 hours at the constant temperature of 40 ℃ to fully impregnate the hydrogel precursor liquid into the fabric material. The fabric was laid flat in a previously prepared mold, and then frozen in a refrigerator at-30 ℃ for 24 hours, thawed at 20 ℃ for 24 hours, and the number of freeze-thaw cycles was 5.
The test results of the flexible fabric/gel composite materials prepared in the above examples 1-7 show that the composite materials have good skin-like characteristics, the stress-strain curve of the composite materials is J-shaped, the composite materials accord with the mechanical properties of biological tissues such as human skin, the maximum breaking strength of the composite materials is 18-20 MPa, and the maximum breaking elongation of the composite materials is 100-500%. The composite materials prepared in examples 1 to 7 show good strain sensitivity under both small strain (40% strain) and large strain (150% strain), have good sensing performance, can accurately and sensitively detect joint movements of fingers, elbows and the like of a human body, are respectively attached to the bent positions of the fingers or the elbows according to measurement results, respectively perform rapid bending and keeping actions and then rapid straightening actions for multiple times, monitor, increase resistance when the fingers or the elbows are bent, and rapidly show resistance changes corresponding to the movement conditions of the fingers or the elbows by a graph curve, and respond sensitively; meanwhile, the composite materials show good adhesiveness, extensibility and flexibility, and can be fully covered on the back of a human body, and the composite materials can still be firmly attached to the skin surface when the back of the human body is turned over to move downwards and can be firmly attached to substrates made of different materials; in addition, these composites were tested again after being frozen at low temperature (-30 ℃) for 24 hours, and still had good ductility and flexibility.
Comparative example 1
Lithium chloride and deionized water were blended at a concentration of 4mol/L and magnetically stirred at 300rpm for 0.5h. 15wt% polyvinyl alcohol (m=70000) was weighed and added to the aqueous lithium chloride solution to swell for 12 hours. The swollen solution was stirred at 95℃for 1 hour until no impurities were present to ensure uniform mixing, and after ultrasonic defoaming, it was injected into a mold, and then frozen in a refrigerator at-20℃for 12 hours, thawed at 20℃for 12 hours, and the number of freeze-thaw cycles was 3.
The prepared material is tested, has certain adhesiveness, has sensing capability under small strain (40% strain) stretching and poor sensing capability under large strain (150% strain) stretching, but has a stress-strain curve which presents conventional near linearity and does not have skin-like characteristics.
Comparative example 2
15Wt% polyvinyl alcohol (m=70000) was weighed and added to deionized water to swell for 12h. The swollen solution was stirred at 95 ℃ for 1h to be free of impurities to ensure uniform mixing. After ultrasonic defoaming, putting a middle elastic spandex fabric into gel precursor liquid, and uniformly stirring for 1h at a constant temperature of 40 ℃ to fully impregnate the gel precursor liquid into the fabric material. The fabric was laid flat in a previously prepared mold, and then frozen in a refrigerator at-20 ℃ for 12 hours, thawed at 20 ℃ for 12 hours, and the number of freeze-thaw cycles was 3.
The prepared material is tested, and has no adhesiveness and sensing capability, and the stress-strain curve does not show J shape and does not have skin-like characteristics.
Comparative example 3
Lithium chloride and deionized water were blended at a concentration of 3mol/L and magnetically stirred at 300rpm for 0.5h. After ultrasonic defoaming, putting the terylene elastic fabric into a lithium chloride solution for soaking for 2 hours to obtain the composite material.
The prepared material is detected, the material has no adhesiveness, is easy to lose water under the room temperature condition, and has unstable sensing performance.
Comparative example 4
Lithium chloride and deionized water were blended at a concentration of 4mol/L and magnetically stirred at 300rpm for 0.5h. 15wt% polyvinyl alcohol (m=70000) was weighed and added to the aqueous lithium chloride solution to swell for 12 hours. The swollen solution was stirred at 95 ℃ for 1h to be free of impurities to ensure uniform mixing. After ultrasonic defoaming, placing a high-elastic spandex fabric into a mold, pouring the prepared hydrogel precursor liquid, and then carrying out knife coating on the surface of the fabric to fully impregnate the hydrogel precursor liquid into the fabric.
The prepared material is detected, the material has no adhesiveness, is easy to lose water under the room temperature condition, and has unstable sensing performance.
The foregoing description is only a preferred embodiment of the present application, and the present application is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present application has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (9)
1. A flexible composite material characterized in that the flexible composite material has skin-like properties, consisting of a fabric and a hydrogel; the fabric is made of fibers; the hydrogel is polyvinyl alcohol-inorganic salt water gel, and is formed by polyvinyl alcohol-inorganic salt water gel precursor liquid in situ among fabric fibers;
The skin-like characteristic includes a stress-strain curve exhibiting a "J" shape;
the fiber is selected from one or more of polyurethane fiber, polyester fiber, polyether ester elastic fiber or polyether amide elastic fiber;
The polyvinyl alcohol-inorganic brine gel precursor liquid takes polyvinyl alcohol and inorganic brine solution as raw materials, wherein the concentration of the inorganic brine solution is 1-7 mol/L, and the concentration of the polyvinyl alcohol is 10-30wt%;
the inorganic salt is one or more selected from calcium chloride, zinc sulfate, lithium chloride, sodium phosphate and potassium acetate;
the method for the flexible composite material is to compound the precursor liquid of the polyvinyl alcohol-inorganic salt water gel with the fabric, freeze-defrost the fabric, and form the polyvinyl alcohol-inorganic salt water gel in situ between the fabrics to form the flexible composite material.
2. The flexible composite of claim 1, wherein the in situ formation is by stirring, dipping or knife coating.
3. The flexible composite of claim 1, wherein the polyvinyl alcohol has a number average molecular weight of 40000 to 180000 and an alcoholysis degree of 80 to 99.9%.
4. A method of making the flexible composite of any of claims 1-3, comprising: and compounding the polyvinyl alcohol-inorganic salt water gel precursor liquid with the fabrics, and carrying out freezing-thawing treatment, wherein the polyvinyl alcohol-inorganic salt water gel is formed in situ between the fabrics to form the flexible composite material.
5. The method according to claim 4, wherein the method for preparing the polyvinyl alcohol-inorganic brine gel precursor solution comprises: the polyvinyl alcohol particles are added into inorganic salt water solution to be swelled, and the mixture is stirred until no impurity exists after the swelling, and then ultrasonic defoaming is carried out.
6. The method of claim 4, wherein the polyvinyl alcohol-inorganic salt water gel precursor is combined with the fabric by stirring, soaking or knife coating;
wherein the stirring comprises: placing the fabric in gel precursor liquid and stirring; the soaking comprises the following steps: soaking the fabric in gel precursor liquid; the blade coating comprises: the fabric was placed in a mold, the gel precursor was poured, and the fabric surface was then knife coated.
7. The method according to claim 6, wherein the temperature during stirring is 5-90 ℃ and the stirring time is 0.5-12 h;
the temperature during soaking is 5-90 ℃, and the stirring time is 0.5-12 h.
8. The method of claim 4, wherein the freeze-thaw process comprises: freezing at-10deg.C to-80deg.C for 1-48 h times, thawing at-10deg.C to 30deg.C for 6-48 h times, and performing freeze-thawing cycle for 1-10 times.
9. Use of the flexible composite material of any of claims 1 to 3 in the fields of electronic skin, wearable devices and flexible touch screens.
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