CN106835680A - A kind of calcium carbonate enhancing silk fabric and preparation method thereof - Google Patents
A kind of calcium carbonate enhancing silk fabric and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of calcium carbonate enhancing silk fabric and preparation method thereof, macromolecular material is dissolved into macromolecular material formic acid solution is obtained in formic acid；Boiled silk is dissolved in calcium chloride/formic acid mixed liquor and obtains silk fibroin solution；Silk fibroin solution is added dropwise in carbonate solution, reaction solution is obtained；Then filtering reacting liquid, filter cake by washing, dry after obtain calcium carbonate nano wire；Mixed liquor is obtained during calcium carbonate nano wire is added into macromolecular material formic acid solution；The silk fabric of degumming process is placed in mould, mixed liquor is then injected into, silk weave composite is obtained after dried process；Then silk weave composite is placed in water and is post-processed, obtain calcium carbonate enhancing silk fabric.The advantage of the invention is that preparation method is simple, easily controllable；Calcium carbonate is completely in nanometer level, there is draw ratio higher, can improve composite materials property.
Description
Technical field
The invention belongs to silk fabric technical field, and in particular to a kind of calcium carbonate strengthens silk fabric and its preparation side
Method.
Background technology
Calcium carbonate is a kind of abundant inorganic mineral resources, can natural degradation circulation, be widely used in building materials, rubber, modeling
Material, papermaking, coating, ink, food, medicine and other fields.Calcium carbonate mainly has three kinds of crystalline textures, calcite（Rhombohedron
Type）, vaterite (spherical), aragonite（Needle-like）.The formation of calcium carbonate, system can be controlled by various technological means both at home and abroad at present
For the calcium carbonate for going out various trait structure, such as, with fibroin albumen microballoon as template, prepare calcium carbonate tiny balloon；By two
The carbonation reaction of carbonoxide has prepared the calcium carbonate crystal whisker of morphology controllable.China is Calcium Carbonate resource big country, while also disappearing
Take a large amount of calcium carbonate products, but China still suffered from terms of the research and development and product development of calcium carbonate single varieties, it is of low quality,
The problems such as product deep processing is inadequate, high-grade calcium carbonate product dependence on import is relatively backward in world's calcium carbonate industry
Status.
The content of the invention
It is an object of the invention to provide a kind of calcium carbonate enhancing silk fabric and preparation method thereof, using preparing nanometer
Size, morphology controllable, the calcium carbonate wire material combination polymer modification silk fabric of quality better, with good mechanical property
Energy, fire resistance and biocompatibility.
It is including following the invention discloses the preparation method that a kind of calcium carbonate strengthens silk fabric to reach above-mentioned purpose
Step：
（1）Macromolecular material is dissolved into macromolecular material formic acid solution is obtained in formic acid；
（2）Boiled silk is dissolved in calcium chloride/formic acid mixed liquor and obtains silk fibroin solution；
（3）By step（2）Silk fibroin solution be added dropwise in carbonate solution, obtain reaction solution；Then filtering reacting liquid, filter cake warp
Calcium carbonate nano wire is obtained after crossing washing, drying；
（4）By step（3）Calcium carbonate nano wire add step（1）Macromolecular material formic acid solution in obtain mixed liquor；
（5）The silk fabric of degumming process is placed in mould, mixed liquor is then injected into, silk fabric is obtained after dried process and is answered
Condensation material；Then silk weave composite is placed in water and is post-processed, obtain calcium carbonate enhancing silk fabric.
In the present invention, in the calcium chloride/formic acid mixed liquor, calcium chloride concentration is 0.5~1.5wt%；The silk fibroin solution
In, fibroin concentration is 1~10wt%.
In the present invention, the preparation method of the macromolecular material is, by trimethylene carbonate, acrylate trihydroxy methyl
Ethane cyclic carbonate ester is dissolved in dichloromethane, is stirred 8~15 minutes；It is subsequently adding trimethyl phosphite and double（Double trimethyls
Silicon substrate）The dichloromethane solution of amine zinc, stirs 20~35 minutes；Propilolic alcohol is subsequently adding, is stirred 30~45 minutes；Then in 40
DEG C sealing reaction 40~55 hours, then use glacial acetic acid terminating reaction, reaction solution precipitates in ice ether, sediment vacuum is done
It is dry to obtain macromolecular material；Trimethylene carbonate, acrylate trimethylolethane cyclic carbonate ester, trimethyl phosphite,
It is double（Double trimethyl silicon substrates）Amine zinc, the mass ratio of propilolic alcohol are 100: 80: 20: 0.1:（5~8）；The macromolecular material formic acid
The concentration of solution is 5~8wt%.
In the present invention, the carbonate is in sodium carbonate, sodium acid carbonate, ammonium carbonate, ammonium hydrogen carbonate, potassium carbonate, ferric carbonate
One or several；In the carbonate solution, the concentration of carbonate is 2~5wt%；The time that the silk fibroin solution is added dropwise
It is 0.5~5h；The silk fibroin solution is 1 with the mass ratio of carbonate solution:（30~50）.Carbon prepared according to the methods of the invention
Sour calcium enhancing silk fabric has unexpected architectural feature, and particularly, a diameter of 10-100nm, length is 5-50 μm, tool
There is excellent high length-diameter ratio.
In the present invention, the dried process is that room temperature is placed 0.5 hour, and then 60 DEG C are heated 2 hours, last 90 DEG C of heating
30~50 seconds；The time that silk weave composite is post-processed in water is 30~45 minutes；Then infra-red drying is obtained
Calcium carbonate strengthens silk fabric.Dried process process is also the mistake that macromolecular material and silk fabric form good interface performance
Journey, room temperature is placed contributes to dispersion and infiltration of the macromolecular material combination calcium carbonate nano wire in silk fabric, then carries out
Progressively heat, the treatment of final high temperature short time, on the one hand avoid local excessive polymerization caused by macromolecular material quick response
Problem, two aspects avoid silk fabric heat damage, and three aspects can obtain the good inorganic-macromolecule-silk of interfacial effect
Interface.
In the present invention, calcium carbonate nano wire, macromolecular material formic acid solution, the mass ratio of the silk fabric of degumming process are
（5~8）∶80∶100.
The draw ratio of calcium carbonate nano wire of the invention is big, is conducive to improving the mechanical property of composite, and in height
Under the synergy of molecular material, silk fabric has excellent mechanical property.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
（1）The present invention obtains natural fibroin albumen fibril with calcium salt/formic acid dissolving silk first, and then with fibril as template-mediated
Calcium ion mineralising generates calcium carbonate nano wire, in nano-scale, diameter most I to 10nm, and with excellent high length-diameter ratio,
For strengthening silk fabric, its performance is remarkably improved.
（2）The present invention, by adding rational modifying agent and limiting propilolic alcohol, is tied on the basis of carbonate monomer
The consumption of each component is closed, modified carbonate polymer is prepared as macromolecular material, not only with good biological nature, and
And for silk fabric, moreover it is possible to fire-retardant, toughness reinforcing effect is provided, is particularly held with inorganic carbonate calcium phase.
（3）Process is simple disclosed by the invention, easily controllable, short preparation period, low production cost, energy consumption are small, it is easy to work
Industry metaplasia is produced.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of calcium carbonate nano wire obtained in the embodiment of the present invention one.
Specific embodiment
With reference to embodiment, the invention will be further described：
Synthesis example
Trimethylene carbonate, acrylate trimethylolethane cyclic carbonate ester are dissolved in dichloromethane, are stirred 15 minutes；So
Trimethyl phosphite and double is added afterwards（Double trimethyl silicon substrates）The dichloromethane solution of amine zinc, stirs 35 minutes；It is subsequently adding
Propilolic alcohol, stirs 30 minutes；Then reacted 40 hours in 40 DEG C of sealings, then use glacial acetic acid terminating reaction, reaction solution is in ice second
Precipitated in ether, sediment vacuum drying is obtained into high-molecular material A；Trimethylene carbonate, acrylate trimethylolethane
It is cyclic carbonate ester, trimethyl phosphite, double（Double trimethyl silicon substrates）Amine zinc, the mass ratio of propilolic alcohol are 100: 80: 20: 0.1: 5；
High-molecular material A is dissolved in formic acid（It is pure）It is the macromolecular material formic acid solution A of 5wt% to prepare concentration；
Trimethylene carbonate, acrylate trimethylolethane cyclic carbonate ester are dissolved in dichloromethane, are stirred 8 minutes；So
Trimethyl phosphite and double is added afterwards（Double trimethyl silicon substrates）The dichloromethane solution of amine zinc, stirs 20 minutes；It is subsequently adding
Propilolic alcohol, stirs 30 minutes；Then reacted 40 hours in 40 DEG C of sealings, then use glacial acetic acid terminating reaction, reaction solution is in ice second
Precipitated in ether, sediment vacuum drying is obtained into macromolecular material B；Trimethylene carbonate, acrylate trimethylolethane
It is cyclic carbonate ester, trimethyl phosphite, double（Double trimethyl silicon substrates）Amine zinc, the mass ratio of propilolic alcohol are 100: 80: 20: 0.1: 8；
Macromolecular material B is dissolved in formic acid（It is pure）It is the macromolecular material formic acid solution B of 8wt% to prepare concentration；
Trimethylene carbonate, acrylate trimethylolethane cyclic carbonate ester are dissolved in dichloromethane, are stirred 15 minutes；So
Trimethyl phosphite and double is added afterwards（Double trimethyl silicon substrates）The dichloromethane solution of amine zinc, stirs 35 minutes；It is subsequently adding
Propilolic alcohol, stirs 45 minutes；Then reacted 50 hours in 40 DEG C of sealings, then use glacial acetic acid terminating reaction, reaction solution is in ice second
Precipitated in ether, sediment vacuum drying is obtained into macromolecular material C；Trimethylene carbonate, acrylate trimethylolethane
It is cyclic carbonate ester, trimethyl phosphite, double（Double trimethyl silicon substrates）Amine zinc, the mass ratio of propilolic alcohol are 100: 80: 20: 0.1: 6；
Macromolecular material C is dissolved in formic acid（It is pure）It is the macromolecular material formic acid solution C of 7wt% to prepare concentration.
Embodiment one
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；Fibroin
Azelon is dissolved in 1% calcium chloride-formic acid solution, silk fibroin solution concentration 2wt%；
（2）The sodium carbonate liquor that fibroin albumen fibril solution is slowly dropped into mass concentration 2% is carried out into mineralising reaction, time for adding
0.5h；Fibroin albumen fibril solution is 1: 30 with the mass ratio of carbonate solution；By the filtering of reacted solution, washing, dry
Obtain appearance white, powdered calcium carbonate nano wire；It is sweeping for calcium carbonate nano wire manufactured in the present embodiment referring to accompanying drawing 1
Retouch electron microscopic picture；Calcium carbonate linear diameter is in 50-100nm as seen from the figure, about 30-50 μm of length；
（3）Mixed liquor is obtained during calcium carbonate nano wire is added into macromolecular material formic acid solution A；
（4）The silk fabric of degumming process is placed in mould, mixed liquor is then injected into, silk fabric is obtained after dried process and is answered
Condensation material；Then silk weave composite is placed in water carries out post processing 45 minutes；Then infra-red drying, obtains calcium carbonate
Enhancing silk fabric；The dried process is that room temperature is placed 0.5 hour, and then 60 DEG C are heated 2 hours, last 90 DEG C of heating 30
Second；Calcium carbonate nano wire, macromolecular material formic acid solution, the mass ratio of the silk fabric of degumming process are 5: 80: 100.
The tensile strength of above-mentioned calcium carbonate enhancing silk fabric is 192.1MPa, elongation at break 38.9%, Young's modulus
4.1GPa, oxygen index (OI) 29；The tensile strength of pure silk fabric be 142MPa, elongation at break 29.5%, Young's modulus 2.7GPa,
Oxygen index (OI) 23.
Embodiment two
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；Fibroin
Azelon is dissolved in 1.5% calcium chloride-formic acid solution, silk fibroin solution concentration 1wt%；
（2）The sodium carbonate liquor that fibroin albumen fibril solution is slowly dropped into mass concentration 5% is carried out into mineralising reaction, time for adding
5h；Fibroin albumen fibril solution is 1: 50 with the mass ratio of carbonate solution；By reacted solution filtering, washing, dry
To appearance white, powdered calcium carbonate nano wire；Calcium carbonate linear diameter in 10-60nm, about 10-30 μm of length；
（3）Mixed liquor is obtained during calcium carbonate nano wire is added into macromolecular material formic acid solution B；
（4）The silk fabric of degumming process is placed in mould, mixed liquor is then injected into, silk fabric is obtained after dried process and is answered
Condensation material；Then silk weave composite is placed in water carries out post processing 45 minutes；Then infra-red drying, obtains calcium carbonate
Enhancing silk fabric；The dried process is that room temperature is placed 0.5 hour, and then 60 DEG C are heated 2 hours, last 90 DEG C of heating 50
Second；Calcium carbonate nano wire, macromolecular material formic acid solution, the mass ratio of the silk fabric of degumming process are 8: 80: 100.
The tensile strength of above-mentioned calcium carbonate enhancing silk fabric is 192.6MPa, elongation at break 38.6%, Young's modulus
3.8 GPa, oxygen index (OI) 29.
Embodiment three
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；Fibroin
Azelon is dissolved in 0.5% calcium chloride-formic acid solution, silk fibroin solution concentration 4wt%；
（2）The sodium carbonate liquor that fibroin albumen fibril solution is slowly dropped into mass concentration 3% is carried out into mineralising reaction, time for adding
3h；Fibroin albumen fibril solution is 1: 40 with the mass ratio of carbonate solution；By reacted solution filtering, washing, dry
To appearance white, powdered calcium carbonate nano wire；Calcium carbonate linear diameter in 20-90nm, about 20-40 μm of length；
（3）Mixed liquor is obtained during calcium carbonate nano wire is added into macromolecular material formic acid solution B；
（4）The silk fabric of degumming process is placed in mould, mixed liquor is then injected into, silk fabric is obtained after dried process and is answered
Condensation material；Then silk weave composite is placed in water carries out post processing 30 minutes；Then infra-red drying, obtains calcium carbonate
Enhancing silk fabric；The dried process is that room temperature is placed 0.5 hour, and then 60 DEG C are heated 2 hours, last 90 DEG C of heating 50
Second；Calcium carbonate nano wire, macromolecular material formic acid solution, the mass ratio of the silk fabric of degumming process are 6: 80: 100.
The tensile strength of above-mentioned calcium carbonate enhancing silk fabric is 191.2MPa, elongation at break 40.3%, Young's modulus
3.8GPa, oxygen index (OI) 29.
Example IV
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；Fibroin
Azelon is dissolved in 1% calcium chloride-formic acid solution, silk fibroin solution concentration 6wt%；
（2）The sodium carbonate liquor that fibroin albumen fibril solution is slowly dropped into mass concentration 3% is carried out into mineralising reaction, time for adding
3h；Fibroin albumen fibril solution is 1: 35 with the mass ratio of carbonate solution；By reacted solution filtering, washing, dry
To appearance white, powdered calcium carbonate nano wire；Calcium carbonate linear diameter in 60-100nm, about 40-50 μm of length；
（3）Mixed liquor is obtained during calcium carbonate nano wire is added into macromolecular material formic acid solution C；
（4）The silk fabric of degumming process is placed in mould, mixed liquor is then injected into, silk fabric is obtained after dried process and is answered
Condensation material；Then silk weave composite is placed in water carries out post processing 30 minutes；Then infra-red drying, obtains calcium carbonate
Enhancing silk fabric；The dried process is that room temperature is placed 0.5 hour, and then 60 DEG C are heated 2 hours, last 90 DEG C of heating 40
Second；Calcium carbonate nano wire, macromolecular material formic acid solution, the mass ratio of the silk fabric of degumming process are 7: 80: 100.
The tensile strength of above-mentioned calcium carbonate enhancing silk fabric is 189MPa, elongation at break 39.7%, Young's modulus
3.9GPa, oxygen index (OI) 29.
Embodiment five
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；Fibroin
Azelon is dissolved in 1% calcium chloride-formic acid solution, silk fibroin solution concentration 8wt%；
（2）The sodium carbonate liquor that fibroin albumen fibril solution is slowly dropped into mass concentration 4% is carried out into mineralising reaction, time for adding
4h；Fibroin albumen fibril solution is 1: 45 with the mass ratio of carbonate solution；By reacted solution filtering, washing, dry
To appearance white, powdered calcium carbonate nano wire；Calcium carbonate linear diameter in 20-60nm, about 20-30 μm of length；
（3）Mixed liquor is obtained during calcium carbonate nano wire is added into macromolecular material formic acid solution C；
（4）The silk fabric of degumming process is placed in mould, mixed liquor is then injected into, silk fabric is obtained after dried process and is answered
Condensation material；Then silk weave composite is placed in water carries out post processing 40 minutes；Then infra-red drying, obtains calcium carbonate
Enhancing silk fabric；The dried process is that room temperature is placed 0.5 hour, and then 60 DEG C are heated 2 hours, last 90 DEG C of heating 40
Second；Calcium carbonate nano wire, macromolecular material formic acid solution, the mass ratio of the silk fabric of degumming process are 6: 80: 100.
The tensile strength of above-mentioned calcium carbonate enhancing silk fabric is 189MPa, elongation at break 40.1%, Young's modulus
3.8GPa, oxygen index (OI) 29.
Embodiment six
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；Fibroin
Azelon is dissolved in 1% calcium chloride-formic acid solution, silk fibroin solution concentration 10wt%；
（2）The sodium carbonate liquor that fibroin albumen fibril solution is slowly dropped into mass concentration 3% is carried out into mineralising reaction, time for adding
2h；Fibroin albumen fibril solution is 1: 42 with the mass ratio of carbonate solution；By reacted solution filtering, washing, dry
To appearance white, powdered calcium carbonate nano wire；Calcium carbonate linear diameter in 20-70nm, about 20-50 μm of length；
（3）Mixed liquor is obtained during calcium carbonate nano wire is added into macromolecular material formic acid solution A；
（4）The silk fabric of degumming process is placed in mould, mixed liquor is then injected into, silk fabric is obtained after dried process and is answered
Condensation material；Then silk weave composite is placed in water carries out post processing 40 minutes；Then infra-red drying, obtains calcium carbonate
Enhancing silk fabric；The dried process is that room temperature is placed 0.5 hour, and then 60 DEG C are heated 2 hours, last 90 DEG C of heating 30
Second；Calcium carbonate nano wire, macromolecular material formic acid solution, the mass ratio of the silk fabric of degumming process are 7: 80: 100.
The tensile strength of above-mentioned calcium carbonate enhancing silk fabric is 191MPa, elongation at break 38.2%, Young's modulus
3.9GPa, oxygen index (OI) 29.
Claims (10)
1. a kind of calcium carbonate strengthens the preparation method of silk fabric, it is characterised in that comprise the following steps：
（1）Macromolecular material is dissolved into macromolecular material formic acid solution is obtained in formic acid；
（2）Boiled silk is dissolved in calcium chloride/formic acid mixed liquor and obtains silk fibroin solution；
（3）By step（2）Silk fibroin solution be added dropwise in carbonate solution, obtain reaction solution；Then filtering reacting liquid, filter cake warp
Calcium carbonate nano wire is obtained after crossing washing, drying；
（4）By step（3）Calcium carbonate nano wire add step（1）Macromolecular material formic acid solution in obtain mixed liquor；
（5）The silk fabric of degumming process is placed in mould, mixed liquor is then injected into, silk fabric is obtained after dried process and is answered
Condensation material；Then silk weave composite is placed in water and is post-processed, obtain calcium carbonate enhancing silk fabric.
2. preparation method according to claim 1, it is characterised in that in the calcium chloride/formic acid mixed liquor, calcium chloride is dense
It is 0.5~1.5wt% to spend；In the silk fibroin solution, fibroin concentration is 1~10wt%.
3. preparation method according to claim 1, it is characterised in that the preparation method of the macromolecular material is, by three
Carbonate, acrylate trimethylolethane cyclic carbonate ester are dissolved in dichloromethane, are stirred 8~15 minutes；Then plus
Enter trimethyl phosphite and double（Double trimethyl silicon substrates）The dichloromethane solution of amine zinc, stirs 20~35 minutes；It is subsequently adding
Propilolic alcohol, stirs 30~45 minutes；Then reacted 40~55 hours in 40 DEG C of sealings, then use glacial acetic acid terminating reaction, reacted
Liquid is precipitated in ice ether, and sediment vacuum drying is obtained into macromolecular material.
4. preparation method according to claim 3, it is characterised in that trimethylene carbonate, acrylate trihydroxy methyl
It is ethane cyclic carbonate ester, trimethyl phosphite, double（Double trimethyl silicon substrates）Amine zinc, the mass ratio of propilolic alcohol are 100: 80: 20:
0.1∶（5~8）；The concentration of the macromolecular material formic acid solution is 5~8wt%.
5. preparation method according to claim 1, it is characterised in that the carbonate is sodium carbonate, sodium acid carbonate, carbonic acid
One or several in ammonium, ammonium hydrogen carbonate, potassium carbonate, ferric carbonate；In the carbonate solution, the concentration of carbonate for 2~
5wt%。
6. preparation method according to claim 1, it is characterised in that the time that the silk fibroin solution is added dropwise is 0.5~5h；
The silk fibroin solution is 1 with the mass ratio of carbonate solution:（30~50）.
7. preparation method according to claim 1, it is characterised in that the dried process is that room temperature places 0.5 hour, so
60 DEG C are heated 2 hours afterwards, and last 90 DEG C are heated 30~50 seconds.
8. preparation method according to claim 1, it is characterised in that silk weave composite is post-processed in water
Time be 30~45 minutes；Then infra-red drying obtains calcium carbonate enhancing silk fabric.
9. preparation method according to claim 1, it is characterised in that calcium carbonate nano wire, macromolecular material formic acid solution,
The mass ratio of the silk fabric of degumming process is（5~8）∶80∶100.
10. the calcium carbonate enhancing silk fabric that prepared by any one preparation method according to claims 1 to 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108441977A (en) * | 2018-02-07 | 2018-08-24 | 广西大学 | Nano-meter CaCO33Strengthen the preparation method of silk fiber |
| TWI721357B (en) * | 2019-01-04 | 2021-03-11 | 鴻海精密工業股份有限公司 | Cloth using a heat sink, and clothes and mouth mask using the cloth |
| CN113279282A (en) * | 2021-06-25 | 2021-08-20 | 陕西科技大学 | Silk-reinforced aramid nanofiber film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081932A (en) * | 2007-06-06 | 2007-12-05 | 浙江理工大学 | Silk fibroin /calcium carbonate nano composite material and preparation method thereof |
| CN103341209A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin nanofiber membrane and preparation method thereof |
| CN105648652A (en) * | 2016-01-10 | 2016-06-08 | 福建省晋江市恒丰喷胶棉织造有限公司 | High-elasticity silk complex fiber thermal cotton |
-
2016
- 2016-12-13 CN CN201611146202.2A patent/CN106835680A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081932A (en) * | 2007-06-06 | 2007-12-05 | 浙江理工大学 | Silk fibroin /calcium carbonate nano composite material and preparation method thereof |
| CN103341209A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin nanofiber membrane and preparation method thereof |
| CN105648652A (en) * | 2016-01-10 | 2016-06-08 | 福建省晋江市恒丰喷胶棉织造有限公司 | High-elasticity silk complex fiber thermal cotton |
Non-Patent Citations (1)
| Title |
|---|
| 唐磊等: "《轻量化材料技术》", 31 January 2014, 国防工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108441977A (en) * | 2018-02-07 | 2018-08-24 | 广西大学 | Nano-meter CaCO33Strengthen the preparation method of silk fiber |
| TWI721357B (en) * | 2019-01-04 | 2021-03-11 | 鴻海精密工業股份有限公司 | Cloth using a heat sink, and clothes and mouth mask using the cloth |
| CN113279282A (en) * | 2021-06-25 | 2021-08-20 | 陕西科技大学 | Silk-reinforced aramid nanofiber film and preparation method thereof |
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