CN106422522A - Silk nano-fiber-based air filtering device - Google Patents
Silk nano-fiber-based air filtering device Download PDFInfo
- Publication number
- CN106422522A CN106422522A CN201610539592.3A CN201610539592A CN106422522A CN 106422522 A CN106422522 A CN 106422522A CN 201610539592 A CN201610539592 A CN 201610539592A CN 106422522 A CN106422522 A CN 106422522A
- Authority
- CN
- China
- Prior art keywords
- air filter
- filter unit
- layer
- silkworm silk
- self
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
- A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/10—Particle separators, e.g. dust precipitators, using filter plates, sheets or pads having plane surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/047—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of fibres or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2275/00—Filter media structures for filters specially adapted for separating dispersed particles from gases or vapours
- B01D2275/10—Multiple layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/08—Animal fibres, e.g. hair, wool, silk
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physical Education & Sports Medicine (AREA)
- Textile Engineering (AREA)
- Filtering Materials (AREA)
Abstract
The invention provides an air filtering device. The air filtering device comprises an optional base layer, a self-supporting silk nano-fiber layer and an optional cover layer. In the especially preferable embodiment of the invention, the air filtering device is a mouth mask, and has the advantages of lightness and thinness, comfortableness and high filtering efficiency.
Description
Technical field
The present invention relates to the utilization of Bombyx bombycis silk and silk waste material, in particular to the air based on silkworm silk nanofiber
Filter plant.
Background technology
In recent years, air pollution especially particulate air pollution (haze) has become as a major issue.Haze sky
In gas, scattered particulate matter size is typically at several nanometers to tens microns.The particulate matter PM that wherein diameter is less than 2.5 microns2.5By
In can not directly be intercepted and can enter human respiratory by human body, and compare PM2.5More tiny particulate matter, can enter alveolar, very
Extremely enter other organs through cell membrane.It is chronically exposed to high concentration PM2.5Or respiratory tract will be caused under more fine particle substance environment
The even disease incidence such as heart increases.According to Chinese environmental air quality standard GB 3095-2012,24 hourly averages
PM2.5Particulate matter two-stage concentration limit value is 75 micrograms/cubic meter.As PM in environment2.5When concentration exceedes this limit value, people should wear
Wear masks and other air filter units are to avoid the harm of particulate matter.The more extensive air filting material is applied to be on market
Fiber filter material, the diameter of fiber is in micro-scaled range, and fiber mostly is synthetic polymer fiber and cotton fiber.But
Due to its micron order fibre diameter, there are some defects in existing air filting material, and such as (i) is efficient often to be had simultaneously
There are very big air drag and thick and heavy structure；(ii) contrast PM2.5The filter efficiency of more tiny particulate matter is relatively low；(iii) lack
Weary multifunctionality (as antibiotic property etc.) etc..Therefore, development has that the mankind are friendly, frivolous, ventilative, efficient, multi-functional air mistake
Filter material material is the trend of air filter unit of new generation.
Compared to traditional micrometer fibers, it is big that nanofiber has a specific surface area, the features such as high adsorption capacity；In addition, receiving
Due to its nanoscale, there is " longitudinal slip effect " in rice fiber, less to the resistance of air-flow.Now under study for action for air filtration
The synthetic polymer nanometer that the nanofiber of material mainly includes CNT and some are prepared using electrostatic spinning technique
Fiber, but these nanofibers have that toxicity does not know, preparation process is to environment or harmful
Problem.
And silkworm silk is a kind of native protein with good characteristic, it is made up of sericin and fibroin, wherein fibroin is main
Composition, accounts for the 70-80% of silk protein weight.In recent years, fibroin albumen was also gradually increased in the research in film field.As
Disclosed in prior art, a kind of fibroin nano fibrous membrane, with silkworm silk as primary raw material, is configured to spinning through series of processes
Liquid, is prepared into fibroin albumen based nano-fiber film through electrostatic spinning, eventually passes alcoholic solution and soaks acquisition finished product, membrane structure is stable
Controlled, good biocompatibility, can be used as biomaterial for medical purpose, but the film-strength being obtained is low, and support performance difference is it is impossible to directly
For air filtration.As prior art discloses a kind of fibroin nanofiber air protection product, with silkworm silk as raw material, pass through
Electrostatic spinning technique, deposits wire protein fiber film on weaving face fabric, has safeguard function to the air of pollution, but fibroin
Nanofiber layer is unable to self-supporting in addition it is also necessary to be compounded on other weaving face fabrics so that filtering material becomes weight, that wears is comfortable
Property reduce.And for example prior art discloses a kind of nano-filtration membrane, by adding Nano carbon balls or carbon in silk protein liquid
Nanotube, increases film strength.But CNT toxicity does not know, and life-time service can lead to health problem.And generally recognize
For, the intensity of silkworm silk nanofiber relatively low it is difficult to use separately as filtering material, and if single nano-fiber material is thick
Degree is too big, and as air filting material, breathability is not good enough.
Accordingly, it would be desirable to invent a kind of air filter unit based on fibroin albumen, its can self-supporting, lightweight, breathe freely
Property good, comfortable wearing, provide efficient protection to the air of pollution.
Content of the invention
An object of the present invention is to provide a kind of air filter unit,
The second object of the present invention is to provide a kind of preparation method of air filter unit.
One of in order to achieve the above object, the technical solution used in the present invention is as follows, a kind of air filter unit, including：
Optional basal layer, self-supporting silkworm silk nanofiber layer, and optional cover layer.
Cover layer described herein refers to cover the structure on self-supporting silkworm silk nanofiber layer, can be by this area
Known various material is made, such as cotton, gauze, various synthetic fibers cloth, Inorganic Non-metallic Materials or metal grill,
Non-woven fabrics or plastics, can also be silk product.
The nanometer nano level diameter of silk fiber makes it have larger specific surface area, and more efficient catches to particulate matter
Obtain so that in the state of it independently supports, or the material ventilative with other, such as weaving face fabric, screen window or other filtering materials
In conjunction with when, can obtain to PM2.5Or more tiny particles content, such as PM0.3, very high mistake efficiency, there is very low air simultaneously
Resistance, in addition it increases with the increase of envionmental humidity to the filter efficiency of particulate matter, and under high humidity environment
It is capable of the integrity of holding structure so that it has the advantage of application under higher levels of humidity environment.And functional nano material
Being introduced into of material can introduce multifunctionality in silkworm silk nano-fiber air filter equipment.
Preferably, the basic weight 50g/m of described self-supporting silkworm silk nanofiber layer2Below so that silkworm silk nanofiber layer
Relatively frivolous, comfortable wearing.
Preferably, the basic weight 10g/m of described self-supporting silkworm silk nanofiber layer2Below.
Preferably, the basic weight 2g/m of described self-supporting silkworm silk nanofiber layer2Below.
Preferably, the basic weight of described self-supporting silkworm silk nanofiber layer is 0.1 1.5g/m2.
Preferably, the basic weight of described self-supporting silkworm silk nanofiber layer is 1.7g/m2More than.
Preferably, the basic weight of described self-supporting silkworm silk nanofiber layer is 3.4g/m2More than.
Preferably, the basic weight of described self-supporting silkworm silk nanofiber layer is 5.4g/m2More than.
Preferably, described self-supporting silkworm silk nanofiber layer is combined gained, the fibre of wherein every Rotating fields for multiple structure
Tie up diameter or vary in weight, multiple structure is gradient-structure, the fibre diameter of layer structure is bigger than the fibre diameter of endothecium structure,
Described multiple structure is at least two-layer, and every layer of basic weight is 0.1 20g/m2.Classification setting in self-supporting silkworm silk nanofiber layer,
Make self-supporting silkworm silk nanofiber layer more preferable to the filter effect of air.
Preferably, also including a bag like construction, bag like construction accommodates described air filter unit, air filter unit
Can replace.
Preferably, the basic weight of described basal layer and/or cover layer is 20 60g/m2, fibre diameter is micron order.
Preferably, the pressure drop of described air filter unit is less than 120Pa.
Preferably, the pressure drop of described air filter unit is less than 100Pa.
Preferably, quality factor QF of described air filter unit is more than 0.024, wherein QF=-ln (1-E)/Δ p
(E is filter efficiency, and Δ p is filtration resistance).
Preferably, quality factor QF of described air filter unit is more than 0.03.
Preferably, quality factor QF of described air filter unit is more than 0.039.
Preferably, the fibre diameter of described self-supporting silkworm silk nanofiber layer is in the range of 100-800nm.
Preferably, the fibre diameter of described self-supporting silkworm silk nanofiber layer is in the range of 120 780nm.
Preferably, described basal layer and cover layer be integrated bag-shaped, self-supporting silkworm silk nanofiber layer can be replaced
Change.
Preferably, the form that self-supporting silkworm silk nanofiber layer is passed through to be combined online combines on described basal layer.
Preferably, the filter efficiency of described air filter unit is more than 78.5%, more preferably more than 98.8%.
Preferably, described self-supporting silkworm silk nanofiber layer or basal layer or cover layer comprise functional materials,
Such as antibacterial, remove formaldehyde materials, radiation proof material, ultraviolet ray-resistant material, skincare material, off-color material, beauty treatment material.
Preferably, described air filter unit is through Electrostatic Treatment.
Preferably, described air filter unit is mask, air-conditioning, civilian air purifier or industrial air filtration
Device, described basal layer or cover layer are silk product.
By implementing technique scheme, the invention provides a kind of frivolous, ventilative, high based on silkworm silk nanofiber
Effect, multi-functional air filter unit.
In order to reach another purpose, the technical solution used in the present invention is as follows, a kind of preparation side of air filter unit
Method, comprises the steps,
(1) utilize Bombyx bombycis silk or silk waste material to obtain fibroin albumen spinning liquid, can be aqueous solution or organic solution；
(2) add functional materials in spinning liquid, introduce multi-functional；
(3) pass through electrostatic spinning technique silkworm silk nanofiber and conventional textile or nonwoven fabric are combined prepare micro-nano many
Level fibrous membrane or self-supporting silkworm silk nano fibrous membrane；
(4) can introduce multi-functional as needed to loading functional material on obtained silkworm silk nanofiber.
When preparing fibroin albumen spinning liquid, Bombyx bombycis silk or silk waste material can be removed silk by aqueous slkali high-temperature boiling
Glue obtains fibroin fiber, then passes through the unitary saline solution system such as LiBr aqueous solution, NaSCN aqueous solution or CaCl2/
C2H5OH/H2O、CaCl2/CH3OH/H2O、Ca(NO3)2/CH3OH/H2O、LiBr/C2H5OH/H2The ternary saline solution system such as O is suitable
When under high temperature (60～80 DEG C), dissolving, desalination obtain fibroin albumen hydrotropic solution spinning liquid, or by desalination, be dried after obtain
Fibroin albumen is dissolved in formic acid, prepared fibroin albumen formic acid spinning liquid (such as concentration can be 9wt%～40wt%).
When carrying out electrospinning, spinning liquid can be loaded electrostatic spinning generating apparatus (as the spinning of many shower nozzles, no shower nozzle spinning
Silk etc.), when applying high voltage (10 50kV), spinning liquid jet is stretched under electric field force effect, and solvent volatilizees, and forms silkworm
Silk nanofiber, this silkworm silk nanofiber can form self-supported membrane or deposit and stick to conventional textile, nonwoven fabric, screen window
Or nano-micrometre multistage composite structure is formed on other filtering materials (by controlling the electrostatic spinning time can control silkworm silk nanometer
The thickness of fibrous membrane).
Preferably, can introduce to spinning liquid situ method and there is antibacterial, remove the functional nano such as formaldehyde, uvioresistant
Material, or to dispersing functionality nano material in spinning liquid, obtain feature spinning liquid, then utilize electrostatic spinning technique system
Standby self-supporting silkworm silk nano fibrous membrane or deposited and stick to that to form nano-micrometre on conventional textile or nonwoven fabric many
Level sandwich.Additionally, subsequently as desired by dipping or the form such as function round dot can also be added to obtained
Loading functional material on silkworm silk nano fibrous membrane.
In the preferred embodiment of the present invention, described air filter unit can have advantages below：
(1) biocompatibility is high, and the mankind are friendly, have fine breathability, humidity regulation, heat stability and very strong power
Learn the advantage of intensity and compliance；
(2) the silkworm silk nanofiber layer obtaining can self-supporting, weight is little, although and its fibre diameter is little, its
Breathability is very good, and overall filter quality is also very good.
(3) silkworm silk nanofiber has very big specific surface area, and the filtering material that it prepares has very high
Filter efficiency；
(4) by the parameters such as the running voltage during regulation electrostatic spinning, operating distance, concentration of dope, Ke Yishi
Now to silkworm silk nanofiber filtration material diameter Distribution, thickness, the isoparametric regulation and control of porosity, thus realizing silkworm silk nanofiber
Material macro property, such as filter efficiency, pressure drop, the isoparametric controlled modulation of dust containing capacity.
Term " silkworm silk nanofiber " used herein refers to the regenerated silk fibroin fiber in nanometer (nm) yardstick for the diameter,
For example diameter can be in the range of 10-1500nm, in the range of particularly 50-1000nm.In some embodiments of the present invention,
The diameter of described silkworm silk nanofiber is in the range of 100-800nm." the silkworm silk nanofiber " of the present invention can adopt natural silkworm
Silk or silk offcut are obtained as parent material it is also possible to be obtained by other modes known in the art, its former material
Material is not limited to natural silk.
Other compositions, such as antibacterial or stain can also be comprised in " the silkworm silk nanofiber " of the present invention.
Term " silkworm silk nanofiber layer " used herein and " silkworm silk nano fibrous membrane " can be referred to used interchangeably again
Fibroin protein nano fibroplastic non-woven constructions fibrous layer.
Term " self-supporting nanofiber layer " used herein refers to support can be with self-existent silkworm silk Nanowire
Dimension film.Compared with needing deposition nanofiber/basal layer complex on the base layer, self-supporting nanofiber layer can be realized
Independent support, mechanical property and machinability are more preferable.
Term " basic weight " used herein refers to the quality of the material of unit area size.Basic weight can be used for describing silkworm silk
The thickness of nano fibrous membrane.For example, the basic weight of silkworm silk nano fibrous membrane of the present invention can be less than 10g/m2.
Term " air filter unit " used herein should do the understanding of broad sense, net including mask, air-conditioning, civilian air
Change device, industrial air filter etc..
Term " mask " used herein should do the understanding of broad sense, refers to the air filter unit worn for people.Allusion quotation
The mask of type such as cotton yarn mask, KN90 mask etc..
Term " functional materials " used herein refers to the material with specific function, for example, have the Yin Na of antibiotic property
Rice grain.In a preferred embodiment of the invention, described functional materials can be added to the silkworm silk Nanowire of the present invention
In dimension, to produce extra function.
Term " quality factor " (Qualification Factor, QF) used herein can be used to the different mistake of comparison
The strainability of filter material material, it considers the filter efficiency of filtering material and filtration resistance, and expression is QF=-ln
(1-E)/Δ p (QF is quality factor, and E is filter efficiency, and Δ p is filtration resistance).Quality factor its mistake of higher filtering material
Filter performance is better.
Term " optional " (optional) used herein represents the implication of " not essential " or " nonessential ".For example, " appoint
The basal layer of choosing " refers to have this basal layer it is also possible to not have this basal layer, and this can be by those skilled in the art's root
Selected according to practical situation.
Brief description
Fig. 1 shows the schematic diagram of one specific embodiment of the present invention.Including cover layer, self-supporting nanofiber
Layer and basal layer.
Fig. 2 utilizes the scanning electron microscope diagram of silkworm silk nano fibrous membrane and the light of electrostatic spinning technique preparation for the present invention
Learn microscope figure.
Fig. 3 shows that the present invention utilizes the capture energy to particulate matter for the silkworm silk nano fibrous membrane of electrostatic spinning technique preparation
Power.
Fig. 4 utilizes the self-supporting silkworm silk nano fibrous membrane of electrostatic spinning technique preparation to PM for the present invention2.5(a) and sub-micro
Scale particles thing (100-400nm) (b, filter efficiency；C, quality factor) strainability test result.
Fig. 5 for the present invention utilize electrostatic spinning technique preparation silkworm silk nanofiber/business micrometer fibers filter membrane (a-b,
PP filter cloth；C-d, glass fibre；E-d, quartz fibre) composite construction to submicron particles thing (100-400nm) filterability
Can result.
Fig. 6 shows that the present invention utilizes the ultralight characteristic of the self-supporting silkworm silk nano fibrous membrane of electrostatic spinning technique preparation.
Fig. 7 utilizes the self-supporting silkworm silk nano fibrous membrane of electrostatic spinning technique preparation to PM for the present invention2.5Strainability
(a, filter efficiency；B, filtration resistance and quality factor) with ambient humidity change result.
Fig. 8 utilizes the silkworm silk nano fibrous membrane of electrostatic spinning technique preparation in the environment of relative humidity 95% for the present invention
Locate the scanning electron microscope diagram after placing 9 hours.
Fig. 9 is that the present invention utilizes electrostatic spinning technique to prepare silver nanoparticle with the spinning liquid of the silver nano-grain containing antibiotic property
The transmission electron microscope figure of silkworm silk nanofiber of granule doping and electron spectrum scanning figure.
Figure 10 prepares silver with the spinning liquid of the silver nano-grain containing antibiotic property using electrostatic spinning technique for the present invention and receives
The anti-microbial property of the silkworm silk nanofiber of rice grain doping.
Specific embodiment
With reference to specific embodiment, the present invention is explained further.
Embodiment 1：Silkworm silk nano fibrous membrane is prepared for raw material using single needle electrostatic spinning technique with Bombyx bombycis silk
First Bombyx bombycis are boiled in 0.5wt% sodium bicarbonate aqueous solution 30min removing sericin, then that fibroin albumen is fine
Dimension is in CaCl2/C2H5OH/H2O (mol ratio 1:2:8) 70 DEG C of dissolving 4h in ternary saline solution system, then by it in deionized water
Middle dialysis obtains silk fibroin water solution in three days, then its lyophilization is obtained fibroin albumen sponge.By the fibroin albumen obtaining sea
Silk floss is dissolved in 98 100% anhydrous formic acids and obtains 10wt% fibroin albumen formic acid solution.Then electrostatic spinning technique, work electricity are utilized
Pressure 20kV, operating distance 20cm, fibroin albumen formic acid solution injection speed 1ml/h, carry out electrostatic spinning, by silkworm silk nanofiber
It is deposited on conventional textile/nonwoven fabric (such as silk scarf, cotton yarn, polypropylene PP filter cloth, glass fibre membrane, quartz fibre film, screen window
Deng) upper Nano/micron composite filter material or be available from support silkworm silk nano fibrous membrane by controlling the time of electrostatic spinning.
The shape appearance figure of Static Spinning silk fibroin nano-fiber is shown in accompanying drawing 2, the silkworm silk nanofiber diameter scope obtaining under the conditions of this electrospinning
0.12-0.78 μm, about 0.48 μm of average diameter.By controlling electrostatic spinning sedimentation time, the silkworm silk nanometer obtaining can be controlled
The thickness of fibrous membrane, basic weight and transparency.As when using transparent conventional screen window screen cloth (glass fibre) as silkworm silk nanofiber
When accepting substrate, under the conditions of above-mentioned electrospinning, during electrospinning 5min, silkworm silk nano fibrous membrane assumes translucence, and electrospinning
The basic weight of the silkworm silk nano fibrous membrane that 5min, 10min, 20min obtain is respectively 1.7g/m2、3.4g/m2、5.4g/m2, respectively less than
10g/m2(see accompanying drawing 6), and can self-supporting, and the basic weight about 200g/m of typical KN90 mask2.
The basic weight of the silkworm silk nano fibrous membrane that wherein electrospinning 20min obtains is 5.4g/m2, its can self-supporting, and right
PM2.5Filter efficiency reach 98.8%, and pressure drop is only 100pa.PM2.5In protective mask standard, filter efficiency more than 95%
Mask, inspiratory resistance should be less than 150Pa, and expiratory resistance should be less than 120Pa it is seen then that the self-supporting silkworm silk nanometer of the present invention
Air filter unit obtained by fibrous membrane complies fully with standard, and its basic weight other filtration far smaller than on the market is made
Product.
Embodiment 2：The self-supporting silkworm silk nano fibrous membrane preparing or silkworm silk nanofiber/conventional textile or nonwoven face
Material composite is to PM2.5Strainability with submicron particles thing
Under the conditions of above-mentioned electrospinning, transparent conventional screen window screen cloth (glass fibre) is as undertaking substrate, Static Spinning silkworm silk
Nanofibres deposit 5min, 10min, 20min can obtain the self-supporting nano fibrous membrane of different basic weights, are respectively designated as silkworm silk and receive
Rice fibrous membrane -1#, silkworm silk nano fibrous membrane -2#, silkworm silk nano fibrous membrane -3#.Silkworm silk nano fibrous membrane is to PM2.5Filterability
Accompanying drawing 4a can be seen, silkworm silk nano fibrous membrane -3# is to PM2.5Filter efficiency reach 98.8%, but its filtration resistance relatively has phase with it
When the glass fibre membrane of filter efficiency is much smaller.Compare with polypropylene PP filter cloth, silkworm silk nano fibrous membrane -1# has similar mistake
Filtration resistance power, but it is to PM2.5Filter efficiency is much higher, and (efficiency of PP filter cloth is 14.2%, and silkworm silk nano fibrous membrane -1# mistake
Filter efficiency is 78.5%).Quality factor, it considers the filter efficiency of filtering material and filtration resistance, and expression is
QF=-ln (1-E)/Δ p (QF is quality factor, and E is filter efficiency, and Δ p is filtration resistance), is often used to the different filtration of comparison
The strainability quality of material, quality factor its strainability of higher filtering material is better.As can be seen that silkworm silk nanofiber
Film more commercial micrometer fibers film has the higher quality factor.And the submicron particles for 100-400nm, silkworm silk Nanowire
Dimension film -3# filter efficiency be above 90%, compare with the glass fibre membrane with suitable filter efficiency, due to its have less
Filtration resistance so having the higher quality factor.(see accompanying drawing 4b and 4c) and the mistake to particulate matter for the silkworm silk nano fibrous membrane
Filter efficiency increases with the increase of envionmental humidity.
When silkworm silk nano fibrous membrane is deposited on polypropylene PP filter cloth, glass fibre membrane, forms nanometer/micro- on quartz fibre film
During rice composite filter material, composite construction increases with the increase of silkworm silk nano fibrous membrane deposition to the filter efficiency of particulate matter
Greatly.Such as accompanying drawing 5 illustrates silkworm silk nanofiber/conventional textile or nonwoven fabric composite filter material to 100-400nm sub-micro
The strainability result of scale particles, when depositing minimal amount of silkworm silk nanofiber, filter efficiency can have higher increase,
But resistance increase is less, therefore quality factor increases.
Embodiment 3：The self-supporting silkworm silk nano fibrous membrane preparing is to PM2.5Strainability and fiber morphology are with environment
The change of humidity
Under the conditions of above-mentioned electrospinning, obtain self-supporting silkworm silk nano fibrous membrane, it is to the filter efficiency of PM2.5 with environment
The increase of relative humidity and significantly increase (see accompanying drawing 7a), corresponding filtration resistance with relative humidity increase and appropriateness increase,
Therefore its quality factor shows slight reduction (see accompanying drawing 7b).For example when relative humidity is when 10% increases to 50%, silkworm
Silk nano fibrous membrane is to PM2.5Filter efficiency increase to 90.2% from 72.1%, and quality factor reduced by only 2%.Additionally,
Silkworm silk nano fibrous membrane remains to keep the integrity of its structure under high humidity environment, and such as silkworm silk nano fibrous membrane is 95%
Place after 9 hours under relative humidity, its overall structure remains in that, simply fiber appearance is slightly swelling.(see accompanying drawing 8)
Embodiment 4：The preparation of silkworm silk nano fibrous membrane of silver nano-grain doping and its anti-microbial property
To in the fibroin albumen formic acid spinning liquid of 10wt%, a certain amount of silver nitrate is added (to make silver with respect to fibroin albumen
Mass concentration be 10wt%), be stirred continuously, using formic acid, silver nano-grain acted on obtaining to the in-situ reducing of silver nitrate, and
Fibroin albumen plays stable dispersion effect to the silver nano-grain generating, and finally obtains the fibroin albumen formic acid of silver nano-grain doping
Spinning liquid.Adjustment electrostatic spinning running voltage is 15kV, operating distance 15cm, spinning liquid injection speed 0.6ml/h, and electrospinning obtains silver-colored
The silkworm silk nanofiber of nano-particle doping, its transmission electron microscope figure and electron spectrum scanning figure are shown in accompanying drawing 9, silver nanoparticle
About several nanometers of the diameter of grain, and be evenly distributed in silkworm silk nanofiber.The silkworm silk nano fibrous membrane table of silver nano-grain doping
Reveal good anti-microbial property.As with escherichia coli and staphylococcus aureuses for antibacterial experiment bacterium, silver nano-grain adulterates
Significantly antibacterial area occurs around silkworm silk nano fibrous membrane, sees accompanying drawing 10.
Claims (21)
1. a kind of air filter unit is it is characterised in that include：
Optional basal layer,
Self-supporting silkworm silk nanofiber layer, and
Optional cover layer.
2. the air filter unit described in claim 1 is it is characterised in that described air filter unit includes self-supporting silkworm silk receives
Rice fibrous layer, does not include basal layer and/or cover layer.
3. the air filter unit described in claim 1, it is characterised in that described air filter unit includes basal layer, props up certainly
Support silkworm silk nanofiber layer, and cover layer.
4. the air filter unit described in any one of claim 13 is it is characterised in that described self-supporting silkworm silk nanofiber
The basic weight 50g/m of layer2Hereinafter, preferably 10g/m2Hereinafter, further preferably 2g/m2Hereinafter, more preferably 0.1 1.5g/m2.
5. the air filter unit described in any one of claim 13 is it is characterised in that described self-supporting silkworm silk nanofiber
The basic weight of layer is 1.7g/m2More than, preferably 3.4g/m2More than, more preferably 5.4g/m2More than.
6. the air filter unit described in claim 1 is it is characterised in that described self-supporting silkworm silk nanofiber layer is tied for multilamellar
Structure is combined gained, the fibre diameter of wherein every Rotating fields or vary in weight.
7. the air filter unit described in claim 6 it is characterised in that multiple structure be gradient-structure, the fibre of layer structure
Dimension diameter is bigger than the fibre diameter of endothecium structure.
8. the air filter unit described in claim 6 is it is characterised in that multiple structure is at least two-layer, each layer of basic weight
For 0.1 20g/m2.
9. it is characterised in that also including a bag like construction, bag like construction accommodates the air filter unit described in claim 1
Described air filter unit, air filter unit can be replaced.
10. the air filter unit described in claim 1 is it is characterised in that the basic weight of described basal layer and/or cover layer is
20‐60g/m2, preferably fibre diameter is micron order.
Air filter unit described in 11. claim 1 is it is characterised in that the pressure drop of described air filter unit is less than
120Pa, preferably smaller than 100Pa.
Air filter unit described in 12. claim 1 is it is characterised in that quality factor QF of described air filter unit is
More than 0.024, wherein QF=-ln (1-E)/Δ p (E is filter efficiency, and Δ p is filtration resistance), preferably more than 0.03, more excellent
Select more than 0.039.
Air filter unit described in 13. claim 1 is it is characterised in that the fiber of described self-supporting silkworm silk nanofiber layer
Diameter in the range of 100-800nm, in the range of preferably 120 780nm.
Air filter unit described in 14. claim 1 is it is characterised in that the filter efficiency of described air filter unit is
More than 78.5%, preferably more than 98.8%.
Air filter unit described in 15. claim 1 is it is characterised in that described self-supporting silkworm silk nanofiber layer or base
Bottom or cover layer comprise functional materials, such as antibacterial, remove formaldehyde materials, radiation proof material, ultraviolet ray-resistant material, shield
Skin material, off-color material, beauty treatment material, stain, preferably pass through dipping or the form of microcapsule or function round dot is added, more
Preferably described air filter unit is through Electrostatic Treatment.
Air filter unit described in 16. claim 1 is it is characterised in that described air filter unit is mask, air-conditioning, the people
With air purifier or industrial air filter, preferably described basal layer or cover layer are silk product.
A kind of 17. preparation methoies preparing air filter unit as claimed in claim 1, comprise the steps,
(1), silkworm silk is removed sericin by aqueous slkali high-temperature boiling and obtain fibroin fiber；
(2), pass through to dissolve under suitable high temperature in solution system, desalination obtains spinning liquid；
(3), the spinning liquid obtaining is carried out electrostatic spinning, obtain self-supporting silkworm silk nanofiber layer；
(4), air filter unit is obtained.
Preparation method described in 18. claim 17, described aqueous slkali is calcium bicarbonate, the preferably calcium bicarbonate of 0.5wt%.
Preparation method described in 19. claim 17, described solution system is unitary saline solution or ternary saline solution, described one
First saline solution is preferably LiBr aqueous solution or NaSCN aqueous solution, and described ternary saline solution is preferably CaCl2/C2H5OH/H2O、
CaCl2/CH3OH/H2O、Ca(NO3)2/CH3OH/H2O or LiBr/C2H5OH/H2O, preferably in described CaCl2/CH3OH/H2O
In, each component molar is than for 1：2：8.
Preparation method described in 20. claim 17, after step (2), in-situ method introduces functional materials, or to spinning
Dispersing functionality material in liquid, obtains feature spinning liquid.
Preparation method described in 21. claim 17, in step (3), the voltage of electrostatic spinning is 10 50KV, operating distance
For 5 20CM, injection speed is 0.5 1ml/h, and the time is 5 20min.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2015104910960 | 2015-08-11 | ||
| CN201510491096 | 2015-08-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106422522A true CN106422522A (en) | 2017-02-22 |
Family
ID=58183993
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201620722627.2U Active CN206597379U (en) | 2015-08-11 | 2016-07-08 | Air filter unit based on silk nanofiber |
| CN201610539592.3A Pending CN106422522A (en) | 2015-08-11 | 2016-07-08 | Silk nano-fiber-based air filtering device |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201620722627.2U Active CN206597379U (en) | 2015-08-11 | 2016-07-08 | Air filter unit based on silk nanofiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN206597379U (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107373822A (en) * | 2017-09-08 | 2017-11-24 | 梅玉杰 | A kind of protective mask |
| CN107441848A (en) * | 2017-08-08 | 2017-12-08 | 华东理工大学 | A kind of surface has fibroin albumen nano-filtration membrane, the preparation method and applications of micro nano structure |
| CN108159779A (en) * | 2018-02-10 | 2018-06-15 | 北京清正泰科技术有限公司 | A kind of filtering material and the air filter unit based on the filtering material |
| CN108379932A (en) * | 2018-02-10 | 2018-08-10 | 北京清正泰科技术有限公司 | A kind of nanofiber filtration material and the air filter unit based on the filtering material |
| CN108379933A (en) * | 2018-02-10 | 2018-08-10 | 北京清正泰科技术有限公司 | A kind of silk fibroin nano-fiber filtering material and the air filter unit based on the filtering material |
| CN109847594A (en) * | 2018-12-13 | 2019-06-07 | 中国科学院理化技术研究所 | A kind of asymmetric nano pore composite membrane and its preparation method and application |
| CN111329151A (en) * | 2020-03-26 | 2020-06-26 | 温州医科大学附属第一医院 | Multifunctional mask |
| CN113426202A (en) * | 2021-06-30 | 2021-09-24 | 美埃(南京)纳米材料有限公司 | Multi-stage fiber multifunctional gradient filter material and preparation method thereof |
| WO2021243776A1 (en) * | 2020-06-02 | 2021-12-09 | 张逸晖 | Filter fabric, mask, and production method for filter fabric |
| CN114232344A (en) * | 2022-01-24 | 2022-03-25 | 苏州大学 | PM2.5 filtering SPAP membrane with antibacterial and antifouling functions and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111938230B (en) * | 2020-06-16 | 2022-10-14 | 中国科学院苏州生物医学工程技术研究所 | Respiratory tract transmitted pathogen enrichment spinning membrane, sampling mask paster and sampling mask |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709618A (en) * | 2005-07-08 | 2005-12-21 | 昆明理工大学 | Method for preparing nano or submicron silver powder |
| CN101623763A (en) * | 2009-08-03 | 2010-01-13 | 北京印刷学院 | Method for synthesizing nano silver by taking macromolecules as template on surface of film |
| CN102036773A (en) * | 2008-03-19 | 2011-04-27 | 巴斯夫欧洲公司 | Metallic nanoparticles stabilised with derivatisied polyethylenimines or polyvinylamines |
| CN103319731A (en) * | 2013-07-08 | 2013-09-25 | 苏州大学 | Regenerated silk fibroin solution and preparation method thereof |
| CN103341209A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin nanofiber membrane and preparation method thereof |
| CN103628314A (en) * | 2013-10-21 | 2014-03-12 | 广西科技大学 | Preparation method of nano silver-protein composite aqueous solution and protein-modified nano silver antibacterial textiles |
| CN103879120A (en) * | 2014-02-28 | 2014-06-25 | 鑫缘茧丝绸集团股份有限公司 | Fibroin nanofiber haze protection product based on waste cocoon silk raw materials |
| CN104114265A (en) * | 2012-01-27 | 2014-10-22 | 宙斯工业产品股份有限公司 | Electrospun Porous Media |
-
2016
- 2016-07-08 CN CN201620722627.2U patent/CN206597379U/en active Active
- 2016-07-08 CN CN201610539592.3A patent/CN106422522A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709618A (en) * | 2005-07-08 | 2005-12-21 | 昆明理工大学 | Method for preparing nano or submicron silver powder |
| CN102036773A (en) * | 2008-03-19 | 2011-04-27 | 巴斯夫欧洲公司 | Metallic nanoparticles stabilised with derivatisied polyethylenimines or polyvinylamines |
| CN101623763A (en) * | 2009-08-03 | 2010-01-13 | 北京印刷学院 | Method for synthesizing nano silver by taking macromolecules as template on surface of film |
| CN104114265A (en) * | 2012-01-27 | 2014-10-22 | 宙斯工业产品股份有限公司 | Electrospun Porous Media |
| CN103319731A (en) * | 2013-07-08 | 2013-09-25 | 苏州大学 | Regenerated silk fibroin solution and preparation method thereof |
| CN103341209A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin nanofiber membrane and preparation method thereof |
| CN103628314A (en) * | 2013-10-21 | 2014-03-12 | 广西科技大学 | Preparation method of nano silver-protein composite aqueous solution and protein-modified nano silver antibacterial textiles |
| CN103879120A (en) * | 2014-02-28 | 2014-06-25 | 鑫缘茧丝绸集团股份有限公司 | Fibroin nanofiber haze protection product based on waste cocoon silk raw materials |
Non-Patent Citations (4)
| Title |
|---|
| 吴章伟;冯新星;朱海霖;刘娜;孙斌;吴斌伟;陈建勇;: "不同溶解体系的丝素蛋白分子质量及对再生丝素膜性能的影响", 蚕业科学, no. 04 * |
| 张锋;: "溶剂对静电纺丝素纳米纤维结构特征的影响", 国外丝绸, no. 04, pages 6 - 8 * |
| 罗军;: "三种不同溶剂静电纺丝素纳米纤维的研究进展", 化纤与纺织技术, no. 03 * |
| 钱小刚;吴中元;张恒;: "双组份纺粘非织造过滤材料的结构设计", 天津纺织科技, no. 01 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107441848A (en) * | 2017-08-08 | 2017-12-08 | 华东理工大学 | A kind of surface has fibroin albumen nano-filtration membrane, the preparation method and applications of micro nano structure |
| CN107441848B (en) * | 2017-08-08 | 2020-04-03 | 华东理工大学 | Silk fibroin nanofiltration membrane with micro-nano structure on surface, preparation method and application thereof |
| CN107373822A (en) * | 2017-09-08 | 2017-11-24 | 梅玉杰 | A kind of protective mask |
| CN108379932A (en) * | 2018-02-10 | 2018-08-10 | 北京清正泰科技术有限公司 | A kind of nanofiber filtration material and the air filter unit based on the filtering material |
| CN108379933A (en) * | 2018-02-10 | 2018-08-10 | 北京清正泰科技术有限公司 | A kind of silk fibroin nano-fiber filtering material and the air filter unit based on the filtering material |
| CN108159779A (en) * | 2018-02-10 | 2018-06-15 | 北京清正泰科技术有限公司 | A kind of filtering material and the air filter unit based on the filtering material |
| CN108379932B (en) * | 2018-02-10 | 2020-09-01 | 北京清科丝宇技术有限公司 | Nanofiber filtering material and air filtering equipment based on same |
| CN108379933B (en) * | 2018-02-10 | 2021-01-15 | 北京清科丝宇技术有限公司 | Silk fibroin nanofiber filtering material and air filtering equipment based on filtering material |
| CN109847594A (en) * | 2018-12-13 | 2019-06-07 | 中国科学院理化技术研究所 | A kind of asymmetric nano pore composite membrane and its preparation method and application |
| CN111329151A (en) * | 2020-03-26 | 2020-06-26 | 温州医科大学附属第一医院 | Multifunctional mask |
| CN111329151B (en) * | 2020-03-26 | 2022-03-22 | 温州医科大学附属第一医院 | Multifunctional mask |
| WO2021243776A1 (en) * | 2020-06-02 | 2021-12-09 | 张逸晖 | Filter fabric, mask, and production method for filter fabric |
| CN113426202A (en) * | 2021-06-30 | 2021-09-24 | 美埃(南京)纳米材料有限公司 | Multi-stage fiber multifunctional gradient filter material and preparation method thereof |
| CN114232344A (en) * | 2022-01-24 | 2022-03-25 | 苏州大学 | PM2.5 filtering SPAP membrane with antibacterial and antifouling functions and preparation method thereof |
| CN114232344B (en) * | 2022-01-24 | 2024-01-09 | 苏州大学 | PM2.5 filtering SPAP film with antibacterial and antifouling functions and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN206597379U (en) | 2017-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106422522A (en) | Silk nano-fiber-based air filtering device | |
| CN105642018B (en) | A kind of haze acetate fiber filtering material and preparation method thereof | |
| CN102872654B (en) | Filtering material for mask and method for manufacturing filtering material | |
| CN103520999A (en) | Antibacterial composite nanometer fiber high-efficiency air filtering material and preparation method thereof | |
| CN111962211A (en) | Method for preparing nanofiber medical protective clothing fabric based on electrostatic spinning technology | |
| CN109730378B (en) | PM2.5 protective mask with electrostatic spinning film and preparation method thereof | |
| CN109589688A (en) | A kind of Static Spinning haze composite fibre filter disc and preparation method thereof | |
| CN104740934A (en) | Three-dimensional type electrostatic spinning filter material for mask and preparation method of filter material | |
| CN105624927B (en) | The industrialized preparing process of sack cleaner base material nanofiber composite filtering material | |
| CN109339681A (en) | A kind of PVDF/GO composite nano fiber haze window screening and preparation method thereof | |
| CN1837435B (en) | Composite nano-grade silk fiber product and method for preparing the same | |
| CN103879120A (en) | Fibroin nanofiber haze protection product based on waste cocoon silk raw materials | |
| CN115302866A (en) | Antibacterial ultraviolet-proof high-efficiency low-resistance micro-nanofiber mask fabric and preparation method thereof | |
| Babar et al. | Introduction and historical overview | |
| CN108786492A (en) | A kind of regulatable air-filtering membrane of quality factor and preparation method thereof | |
| CN106626588B (en) | A kind of preparation method of the micro/nano level regenerated fiber non-woven fabrics of wet-guide quick-drying | |
| CN107177934A (en) | A kind of preparation method of high printing opacity dustproof screen window material and screen window | |
| CN107754493B (en) | Photocatalytic transparent PM2.5 filtering membrane and preparation method thereof | |
| CN211311787U (en) | High waterproof high ventilative nanofiber membrane | |
| CN108379932B (en) | Nanofiber filtering material and air filtering equipment based on same | |
| CN112663330B (en) | Fiber, non-woven fabric, mask cloth and mask containing nano graphene and preparation method | |
| CN104368245A (en) | Air filtration membrane preparation method | |
| CN109594325B (en) | Zinc oxide nanorod array modified moisture-conductive cotton fiber or fabric thereof and preparation method thereof | |
| CN108379933B (en) | Silk fibroin nanofiber filtering material and air filtering equipment based on filtering material | |
| RYU et al. | Effects of Electrospinning Parameters on the Fiber Formation and Application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200415 Address after: Room A104, 1st floor, No. 79, Shuangqing Road, Haidian District, Beijing Applicant after: BEIJING QINGKE SIYU TECHNOLOGY Co.,Ltd. Address before: 100084 Haidian District Tsinghua Yuan Beijing No. 1 Applicant before: TSINGHUA University |