CN105714432A - Fiber division method of silk fibroin fibers - Google Patents
Fiber division method of silk fibroin fibers Download PDFInfo
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- CN105714432A CN105714432A CN201610301914.0A CN201610301914A CN105714432A CN 105714432 A CN105714432 A CN 105714432A CN 201610301914 A CN201610301914 A CN 201610301914A CN 105714432 A CN105714432 A CN 105714432A
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- fiber
- fibroin
- alkali metal
- soak
- silk fibroin
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/18—Separating or spreading
Abstract
The invention belongs to the technical field of preparation of nano materials and relates to a fiber division method of silk fibroin fibers, aiming at solving the problems that a fiber division effect on the silk fibroin fibers is not good when only ultrasonic waves are used so that the yield of the silk fibroin nano fibers keeps a relatively low level all the time. The fiber division method of the silk fibroin fibers comprises the following steps: adding the silk fibroin fibers into a soaking solution and soaking to obtain soaked fibers; carrying out fiber division on the soaked fibers in a treatment solution by using the ultrasonic waves to obtain a rough product; and finally, removing the treatment solution in the rough product to obtain the silk fibroin nano fibers, wherein the soaking solution is a water solution of sodium carbonate and alkali metal phosphate, the treatment solution is the soaking solution or water, the alkali metal phosphate is trisodium phosphate or tripotassium phosphate, and the concentration of the sodium carbonate and the alkali metal phosphate is 0.05%-5%. With the adoption of the technical scheme, the technical problems above can be effectively solved.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, relate to point method for fiber of a kind of fibroin fiber, fibroin fiber of the present invention, if do not done special declaration, refer generally to the fibroin fiber prepared by silkworm silk by degumming, certainly, for other fibroin fibers, those skilled in the art still can carry out a point fibre according to the present invention, and obtains fibroin nanofiber.
Background technology
Silkworm silk quilt is called the second skin of human body, is the textile raw material of high-quality, and recently as the exploitation to the further investigation of silkworm silk structural behaviour and Novel Materials of Silk, silkworm silk has been widely used in the fields such as food, cosmetics, health product and medical science.The fibroin fiber that natural silk degumming prepares has plurality of advantages as a kind of natural polymer protein material via natural selection and biological evolution, has very long history as operation suture thread in the application of surgical field.Along with the development of modern medicine, fibroin fiber the fibroin nanofiber prepared becomes the important natural material in artificial organ material with its good biocompatibility and biodegradability, has important Research Significance and application prospect in technical field of biological material.
The diameter of natural silk cellulose fiber is between 10～30 microns, and individual thread cellulose fiber is made up of thousands of nanofibers.In order to obtain nano wire cellulose fiber, process commonly used in industry is method of electrostatic spinning, the method needs with regenerated silk fibroin solution for raw material, and obtain the relatively costly of regenerated silk fibroin, because preparing the step generally including dialysis in 72 hours in the technique of regenerated silk fibroin in order to remove inorganic salt, adding the complexity of technique, reduce production efficiency, causing cannot scale of mass production.
In recent years, people prepare nanofiber by ultrasound wave, but ultrasound wave scope of about 1 micron within the zone of action of fibroin fiber is generally stayed in fiber surface, a point fine actual efficiency is greatly reduced.
Summary of the invention
Through substantial amounts of production practices, divide fine action effect not good fibroin fiber with ultrasound wave merely so that the productivity of fibroin nanofiber remains at relatively low level.A kind of adoptable scheme is that fibroin fiber repeatedly divides fibre, specifically, it is exactly be placed in fibroin fiber to have in hyperacoustic environment, through after a period of time, extract fibroin nanofiber, and the fibroin fiber not forming fibroin nanofiber is still placed in hyperacoustic environment, so repeatedly, to improve the overall production rate of fibroin nanofiber.But, the productivity of fibroin nanofiber does not obtain significant raising.
Present invention employs diverse technical measures, these technical measures are point method for fiber of a kind of fibroin fiber, including:
A, fibroin fiber is added in soak soak, obtain soak fiber；
B, the immersion fiber being opposite in treatment fluid with ultrasound wave carry out point fine, obtain crude product；
C, the treatment fluid removed in crude product, obtain fibroin nanofiber；
Described soak is the aqueous solution of sodium carbonate and alkali metal phosphate, and described treatment fluid is soak or water,
Described alkali metal phosphate is tertiary sodium phosphate or tripotassium phosphate, and the concentration of described sodium carbonate and alkali metal phosphate is 0.05%-5%.
According to technology well-known to those skilled in the art, after implementing b step, will containing fibroin nanofiber in treatment fluid, treatment fluid is poured out, just can obtain fibroin nanofiber through filtering, and present invention discover that, after implementing b step, it is fibroin nanofiber that fibroin fiber is divided fine by entirety substantially, and wherein only a small amount of fibroin nanofiber departs from fibroin fiber and dissociates in treatment fluid, extracts fibroin nanofiber thereby through filtration treatment liquid nonsensical.It is fibroin nanofiber that so most fibroin fiber can divide fine, and the conversion ratio of described fibroin nanofiber at least can reach 70%, and the yardstick of the fibroin nanofiber obtained is 50nm-300nm.
Before making the present invention, there is some technological requirements that fibroin fiber is simply processed, such as University Of Suzhou's thesis for the doctorate " micropore of silk fiber generates and landfill characteristics research " is before carrying out ultrasonic wavelength-division fibre to fibroin fiber, first process fibroin fiber with calcium chloride solution, see Fig. 1, calcium chloride solution processes fibroin fiber initial stage fibroin fiber can produce Swelling, fiber surface produces longitudinal erosion striped, after process, there are micropore cave and fibrillation feature in fibroin fiber back, the method mentioned in this article is used to process fibroin fiber, and do supersound process (A and B), as can be seen from Figure 2, in calcium chloride solution, fibroin albumen comes off from fiber surface with graininess, after process, sample does not significantly separate the phenomenon appearance of nanofiber, but these technology can not expand the ultrasound wave zone of action to fibroin fiber substantially, thus the productivity of fibroin nanofiber cannot be improved significantly.
Treatment fluid of the present invention is the aqueous solution of sodium carbonate and alkali metal phosphate, and described treatment fluid is soak or water, and described alkali metal phosphate is tertiary sodium phosphate or tripotassium phosphate, and the concentration of described sodium carbonate and alkali metal phosphate is 0.05%-5%.After the treated liquid of fibroin fiber processes, hydroxy radical content within fibroin fiber is significantly increased, fibroin fiber internal structure is loosened, active force between the fibroin nanofiber of composition fibroin fiber dies down, thus dividing fibre to obtain fibroin nanofiber fibroin fiber easily via hyperacoustic mode so that fibroin fiber is by fully point fibre.
In order to improve the sedimentation of fibroin fiber internal structure, the mol ratio of described sodium carbonate and alkali metal phosphate is preferably 1:0.2-5, and optimum scheme is that the mol ratio of sodium carbonate Yu alkali metal phosphate is adjusted to 1:1.
For sodium carbonate and alkali metal sodium phosphate, the present invention generally tends to select higher concentration, for instance 0.5%-5%, and the temperature of soak is generally 20 DEG C-80 DEG C, and more excellent scheme is that the temperature of soak is arranged on 40 DEG C-50 DEG C.
Accompanying drawing explanation
Fig. 1 is in Summary, and calcium chloride solution processes the scanning electron microscope (SEM) photograph after fibroin fiber；
Fig. 2 is in Summary, and the fibroin fiber after calcium chloride solution is processed carries out the scanning electron microscope (SEM) photograph after ultrasonic wavelength-division fibre；
Fig. 3 is the scanning electron microscope (SEM) photograph without ultrasonic wavelength-division fibre of the raw material thread cellulose fiber in comparative example；
Fig. 4 is the scanning electron microscope (SEM) photograph after the ultrasonic wavelength-division fibre of the fibroin fiber in comparative example；
Fig. 5 is the scanning electron microscope (SEM) photograph after the ultrasonic wavelength-division fibre of the fibroin fiber in embodiment 1；
Fig. 6 is the raw material thread cellulose fiber in comparative example and the infrared spectrum comparison diagram soaking fiber in embodiment 1；
Fig. 7 is the X-ray diffractogram of the raw material thread cellulose fiber in comparative example；
Fig. 8 is the X-ray diffractogram soaking fiber in embodiment 1.
Fig. 9 is the scanning electron microscope (SEM) photograph after the ultrasonic wavelength-division fibre of the fibroin fiber in embodiment 2；
Figure 10 is the scanning electron microscope (SEM) photograph after the ultrasonic wavelength-division fibre of the fibroin fiber in embodiment 3；
Detailed description of the invention
Point method for fiber of fibroin fiber of the present invention is after processing fibroin fiber with soak, carry out ultrasonic wavelength-division more fine, in the frequency range that ultrasound wave is conventional (such as 10KHz-30KHz), the fibroin fiber after soaking immersion bubble all can be made to produce good point fine effect, and ultrasonic power at least can be adjusted according to the fibroin fiber required point fine quantity in unit space, improve a point fine speed.
Comparative example:
For showing the technique effect of the present invention more intuitively, the present invention is scheduled that following comparative example, and fibroin fiber is directly carried out a point fibre by ultrasound wave by this comparative example, concretely comprises the following steps:
Being put into by fibroin fiber in aqueous solution and directly use ultrasonic Treatment 15min, described hyperacoustic power is 800 watts, and frequency is 20KHz, electron-microscope scanning comparison diagram respectively Fig. 3 and Fig. 4 before and after processing.
Embodiment 1:
Configuration soak, the mixed aqueous solution that described soak is the sodium carbonate by 0.05% and 0.05% tertiary sodium phosphate forms, it is subsequently heated soak, the temperature making soak maintains 40 DEG C, raw material thread cellulose fiber in comparative example is put into after soak soaks 1 hour, take out, dry, obtain treating the immersion fiber that ultrasonic wavelength-division fibre processes.It is placed in aqueous solution adopts the condition identical with comparative example to carry out ultrasonic wavelength-division fibre processes soaking fiber, Fig. 5 is obtained after fibroin fiber being carried out electron-microscope scanning after process, as can be seen from Figure 5 fibroin fiber has been converted into nano wire cellulose fiber substantially, its conversion ratio is 70%, and the yardstick of the fibroin nanofiber of formation is 50nm-300nm.
Additionally, the immersion fiber of the raw material thread cellulose fiber in comparative example and the present embodiment is done X-ray diffraction test by the present embodiment respectively, its result is shown in Fig. 6, as seen from Figure 6, the characteristic absorption peak amide I, amide II of fibroin fiber, amide III, amide IV there is no significant change before treatment afterwards.But pretreatment makes N-H key stretching vibration effect in molecule strengthen, and intermolecular N-H key stretching vibration declines.All C-H stretching vibration absworption peaks move 5cm to long wave direction-1, it was shown that after process, fibroin fiber internal structure becomes loose.
Simultaneously, raw material thread cellulose fiber in comparative example and the immersion fiber in the present embodiment are also done X-ray diffraction analysis by the present embodiment, its result is shown in and can be seen that in Fig. 7 and Fig. 8, figure that the crystalline phase of fibroin fiber is had no significant effect by soak, but significantly reduces the degree of crystallinity of fibroin fiber.By the analysis of Fig. 7 and 8 it can be seen that fibroin fiber is soaked by the present embodiment so that the active force between the nanofiber of composition fibroin fiber dies down, and nanofiber internal structure stability is not had appreciable impact.
Embodiment 2:
Basically identical with embodiment 1, difference is in that the concentration of sodium carbonate and tertiary sodium phosphate is 0.1%, the temperature of soak is 35 DEG C, soak time is 3 hours, Fig. 9 is obtained after fibroin fiber being carried out electron-microscope scanning after process, as can be seen from Figure 9 fibroin fiber has been converted into nano wire cellulose fiber substantially, and its conversion ratio is 75%, and the yardstick of the fibroin nanofiber of formation is 50nm-300nm.
Embodiment 3:
Basically identical with embodiment 1, difference is in that the concentration of sodium carbonate and tertiary sodium phosphate is 0.4%, the temperature of soak is 50 DEG C, soak time is 5 hours, Figure 10 is obtained after fibroin fiber being carried out electron-microscope scanning after process, as can be seen from Figure 10 fibroin fiber has been converted into nano wire cellulose fiber substantially, and its conversion ratio is 80%, and the yardstick of the fibroin nanofiber of formation is 50nm-300nm.
Claims (7)
1. a point method for fiber for fibroin fiber, including:
A, fibroin fiber is added in soak soak, obtain soak fiber；
B, the immersion fiber being opposite in treatment fluid with ultrasound wave carry out point fine, obtain crude product；
C, the treatment fluid removed in crude product, obtain fibroin nanofiber；
Described soak is the aqueous solution of sodium carbonate and alkali metal phosphate, and described treatment fluid is soak or water, and described alkali metal phosphate is tertiary sodium phosphate or tripotassium phosphate, and the concentration of described sodium carbonate and alkali metal phosphate is 0.05%-5%.
2. point method for fiber of a kind of fibroin fiber according to claim 1, it is characterised in that the mol ratio of described sodium carbonate and alkali metal phosphate is 1:0.2-5.
3. point method for fiber of a kind of fibroin fiber according to claim 1, it is characterised in that the temperature of described soak controls at 20 DEG C-80 DEG C.
4. point method for fiber of a kind of fibroin fiber according to claim 1, it is characterised in that described hyperacoustic frequency is 10khz-30khz.
5. point method for fiber of a kind of fibroin fiber according to claim 2, it is characterised in that the mol ratio of described sodium carbonate and alkali metal phosphate is 1:1.
6. point method for fiber of a kind of fibroin fiber according to claim 3, it is characterised in that the temperature of soak controls at 40 DEG C-50 DEG C.
7. point method for fiber of a kind of fibroin fiber according to claim 1, it is characterised in that the concentration of described sodium carbonate and alkali metal phosphate is 0.5%-5%.
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| CN201610301914.0A CN105714432A (en) | 2016-05-09 | 2016-05-09 | Fiber division method of silk fibroin fibers |
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| CN201610301914.0A CN105714432A (en) | 2016-05-09 | 2016-05-09 | Fiber division method of silk fibroin fibers |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106521643A (en) * | 2016-12-07 | 2017-03-22 | 广西凯喜雅丝绸有限公司 | Technique for splitting silk |
| CN114908433A (en) * | 2021-02-07 | 2022-08-16 | 浙江大学 | Method for preparing fibroin nano-fiber by physical method and product |
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| CN1730734A (en) * | 2005-08-19 | 2006-02-08 | 清华大学 | Natural nanometer fiber preparation method |
| KR101187493B1 (en) * | 2011-04-26 | 2012-10-02 | 경북대학교 산학협력단 | The wool fiber with fine denier feeling by splitting cortex part and its preparation method |
| CN103060930A (en) * | 2012-12-24 | 2013-04-24 | 东北林业大学 | Device for preparing natural nanometer fibers through continuous ultrasonic method and continuous ultrasonic method |
| CN103451746A (en) * | 2013-08-06 | 2013-12-18 | 苏州三和开泰花线织造有限公司 | Degumming method of silk |
| CN104532365A (en) * | 2015-01-15 | 2015-04-22 | 武汉纺织大学 | Silk nanofiber manufacturing method |
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2016
- 2016-05-09 CN CN201610301914.0A patent/CN105714432A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730734A (en) * | 2005-08-19 | 2006-02-08 | 清华大学 | Natural nanometer fiber preparation method |
| KR101187493B1 (en) * | 2011-04-26 | 2012-10-02 | 경북대학교 산학협력단 | The wool fiber with fine denier feeling by splitting cortex part and its preparation method |
| CN103060930A (en) * | 2012-12-24 | 2013-04-24 | 东北林业大学 | Device for preparing natural nanometer fibers through continuous ultrasonic method and continuous ultrasonic method |
| CN103451746A (en) * | 2013-08-06 | 2013-12-18 | 苏州三和开泰花线织造有限公司 | Degumming method of silk |
| CN104532365A (en) * | 2015-01-15 | 2015-04-22 | 武汉纺织大学 | Silk nanofiber manufacturing method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106521643A (en) * | 2016-12-07 | 2017-03-22 | 广西凯喜雅丝绸有限公司 | Technique for splitting silk |
| CN114908433A (en) * | 2021-02-07 | 2022-08-16 | 浙江大学 | Method for preparing fibroin nano-fiber by physical method and product |
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