CN114733098B - Nasal obstruction type respirator - Google Patents

Nasal obstruction type respirator Download PDF

Info

Publication number
CN114733098B
CN114733098B CN202210478024.2A CN202210478024A CN114733098B CN 114733098 B CN114733098 B CN 114733098B CN 202210478024 A CN202210478024 A CN 202210478024A CN 114733098 B CN114733098 B CN 114733098B
Authority
CN
China
Prior art keywords
fluid
substrate
filter chip
nasal
micro
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.)
Active
Application number
CN202210478024.2A
Other languages
Chinese (zh)
Other versions
CN114733098A (en
Inventor
杨国勇
史建伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou Suro Film Nano Tech Co ltd
Original Assignee
Suzhou Suro Film Nano Tech Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Suzhou Suro Film Nano Tech Co ltd filed Critical Suzhou Suro Film Nano Tech Co ltd
Priority to CN202210478024.2A priority Critical patent/CN114733098B/en
Publication of CN114733098A publication Critical patent/CN114733098A/en
Application granted granted Critical
Publication of CN114733098B publication Critical patent/CN114733098B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B23/00—Filters for breathing-protection purposes
    • A62B23/06—Nose filters
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B7/00—Respiratory apparatus
    • A62B7/10—Respiratory apparatus with filter elements
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B9/00—Component parts for respiratory or breathing apparatus
    • A62B9/06—Mouthpieces; Nose-clips
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y02A50/2351—Atmospheric particulate matter [PM], e.g. carbon smoke microparticles, smog, aerosol particles, dust

Landscapes

  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Pulmonology (AREA)
  • Otolaryngology (AREA)
  • Filtering Materials (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)

Abstract

The invention discloses a nasal obstruction type respirator, which comprises: the nose plug comprises a nose plug and a filter chip, wherein at least one end part of the nose plug can be inserted into a nasal cavity of a user, the nose plug comprises a gas channel communicated with the nasal cavity, the filter chip is used for filtering particles which are mixed in airflow to be treated and have a particle size larger than a set value, and the air to be treated flows through the filter chip and then enters the gas channel in the nose plug; and the filter chip protection structure is used for protecting the filter chip. The invention has the advantages of good filterability, convenient breathing, good comfort and the like, and has wide application.

Description

Nasal obstruction type respirator
The invention relates to a divisional application with the application number of 201610399521.8, the application date of 2016, 06 and 07, and the name of nasal obstruction type respirator.
Technical Field
The invention relates to a respirator, in particular to an improved nasal obstruction type respirator.
Background
In general, particulate contaminants such as dust are usually present in the air, and if such air is inhaled by a human body for a long period of time, the respiratory system of the human body and the like are often damaged. Particularly, for some special people, such as people allergic to pollen, inhalation of air containing these allergens will cause these people to develop symptoms such as asthma and dyspnea. In order to ensure the health and safety of human bodies, people have learned to filter out particulate pollutants in the air by using masks made of cotton cloth, gauze and other materials. However, such conventional masks are only effective for large sized particulate contaminants and can be contaminated after a short period of use.
Furthermore, the common mask has no problem of filtering effect on PM 2.5. There have also been proposed masks and respirators (e.g., N95 masks) comprising special filters such as electrostatic filters, which have good filterability for common contaminant particles in the air, but are also large in air resistance and difficult to breathe, and are also not basically effective for protection in haze weather.
Disclosure of Invention
The invention mainly aims to provide a nasal obstruction type respirator which is used for overcoming the defects in the prior art.
In order to achieve the above object, the technical scheme of the present invention is as follows:
embodiments of the present invention provide a nasal obstruction type respirator, comprising:
the nose plug comprises a nose plug and a filter chip, wherein at least one end part of the nose plug can be inserted into a nasal cavity of a user, the nose plug comprises a gas channel communicated with the nasal cavity, the filter chip is used for filtering particles which are mixed in airflow to be treated and have a particle size larger than a set value, and the air to be treated flows through the filter chip and then enters the gas channel in the nose plug; the method comprises the steps of,
and the filter chip protection structure is used for protecting the filter chip.
In some embodiments, the filter chip guard structure includes a first stationary rigid screen and a second stationary rigid screen, the filter chip being disposed between the first stationary rigid screen and the second stationary rigid screen.
In some embodiments, the nasal plug respirator further comprises a first filter fabric and/or a second filter fabric, the first filter fabric being disposed between the nasal plug and the filter chip, the filter chip being disposed between the second filter fabric and the nasal plug.
In some embodiments, the nasal plug respirator further comprises a first removable hard screen fixedly connected to the first filter fabric and/or a second removable hard screen fixedly connected to the second filter fabric.
In some embodiments, the nasal obstruction is a waist drum type nasal obstruction; and/or the nose plug type respirator further comprises a shell with two open ends, the nose plug is detachably arranged at one end of the shell, and the filter chip is accommodated in the shell.
In a more specific first embodiment of the present invention, the filter chip comprises:
a substrate having a first fluid channel, the first fluid channel having an air inlet and an air outlet, the air inlet of the first fluid channel being distributed over a first surface of the substrate;
the air conditioner comprises a plurality of convex parts which are arranged at intervals, wherein the convex parts continuously extend on the first surface of a base body along the transverse direction, the lower parts are fixedly arranged on the first surface of the base body, the upper parts are provided with cap-shaped structures which continuously extend along the transverse direction, two opposite side parts of the cap-shaped structures extend outwards along the lateral direction, an opening part which can be used for allowing air to pass through is formed between the adjacent cap-shaped structures, the caliber of the opening part is larger than 0 and smaller than the particle size of selected particles mixed in air to be treated, at least two convex parts are respectively arranged adjacent to two opposite sides of the air inlet of the first fluid channel, and at least one convex part directly passes through the air inlet of the first fluid channel, so that a plurality of cap-shaped structures, a plurality of convex parts and the base body are matched to form a second fluid channel which is communicated with the first fluid channel, and the air to be treated can only enter the first fluid channel through the second fluid channel.
In this first embodiment, at least two of said bosses pass directly over the air inlet of said first fluid passageway; and/or the plurality of protruding parts are distributed on the first surface of the matrix in parallel.
Preferably, the cap-shaped structure is integrally provided with the boss.
In this first embodiment, the cap-shaped structure may have an inverted trapezoidal cross-sectional structure.
Preferably, the aperture of the opening formed between the adjacent cap structures is 1nm to 50 [ mu ] m.
More preferably, the height of the cap-shaped structure is 50 nm-200 mu m.
More preferably, the distance between adjacent protruding portions is 0.1 [ mu ] m-100 [ mu ] m.
More preferably, the height of the protruding portion is 0.1 mu m-400 mu m, and the width is 0.1 mu m-100 mu m.
More preferably, the aperture of the first fluid channel is 1 mu m-1 mm.
More preferably, the thickness of the substrate is more than 1 mu m.
Preferably, at least the surface of any one of the convex portion, the cap structure and the base is further provided with a photocatalytic functional material layer and/or an antibacterial functional material layer.
Preferably, at least part of at least one of the convex portion, the cap-shaped structure and the base is a transparent structure.
In a more specific second embodiment of the present invention, the filter chip comprises:
a substrate having a first fluid channel, the first fluid channel having an air inlet and an air outlet, the air inlet of the first fluid channel being distributed over a first surface of the substrate;
the porous structure is formed by mutually crossing a plurality of linear bodies and is used for being matched with the first surface of the matrix to form a second fluid channel, one ends of the plurality of linear bodies are fixedly connected with the matrix, the diameters of holes in the porous structure are larger than 0 but smaller than the particle diameter of selected particles mixed in air to be treated, and the air to be treated can only enter the first fluid channel through the second fluid channel.
Further, one end of each of the plurality of linear bodies is fixedly connected with the first surface of the substrate and circumferentially distributed around the air inlet of the first fluid channel.
More preferably, the filter chip further includes a plurality of protruding portions disposed at intervals, the protruding portions are fixedly disposed on the first surface of the base body and extend continuously along a transverse direction on the first surface of the base body, at least two protruding portions are disposed adjacent to two opposite sides of the air inlet of the first fluid channel, at least one protruding portion directly passes through the air inlet of the first fluid channel, and at least two linear bodies are fixedly connected to the protruding portions.
Preferably, the plurality of linear bodies connected to one boss and the plurality of linear bodies connected to another boss adjacent to the boss intersect each other.
Preferably, the plurality of protruding portions are distributed in parallel on the first surface of the substrate.
Further, the shape of the protruding portion includes an elongated shape or a sheet shape, and is not limited thereto.
Further, the plurality of protruding portions are uniformly distributed or non-uniformly distributed on the first surface of the substrate.
More preferably, the width of the protruding portion is 0.1 mu m-100 mu m, and the height is 0.1 mu m-400 mu m.
More preferably, the distance between adjacent protruding portions is 0.1 [ mu ] m-100 [ mu ] m.
Preferably, the surface of the protruding part is further provided with a photocatalytic functional material layer and/or an antibacterial functional material layer.
Preferably, at least part of at least one of the base body, the plurality of thread-shaped bodies and the plurality of protruding parts is transparent.
More preferably, the diameter of the line-shaped body is 1 nm-50 mu m.
Preferably, the distance between one end of any one of the linear bodies and one end of the other linear body adjacent to the linear body is 1 nm-50 mu m.
More preferably, the length of the line-shaped body is 50 nm-200 mu m.
Preferably, at least the surface of the linear body is further distributed with a photocatalytic material or an antibacterial material.
Preferably, at least part of at least one of the matrix and the plurality of thread-like bodies is a transparent structure.
Preferably, the linear body is linear.
Further, the air inlet of the first fluid passage has a regular or irregular shape, the regular shape including polygonal, circular or elliptical.
More preferably, the aperture of the first fluid channel is 1 mu m-1 mm.
More preferably, the thickness of the substrate is more than 1 mu m.
Preferably, the filter chip further comprises a plurality of cross beams which are distributed on the first surface of the base body in parallel, the cross beams extend continuously on the first surface of the base body along the transverse direction, at least two cross beams are respectively arranged adjacent to two opposite sides of the air inlet of the first fluid channel, and at least one cross beam directly passes through the air inlet of the first fluid channel; and a plurality of thread-shaped bodies are distributed on any one of the cross beams, one end of at least part of the thread-shaped bodies is fixed on the surface of the cross beam, and the other end of the thread-shaped bodies extends obliquely along the direction gradually far away from any one of the cross beams and/or continuously extends on a plane parallel to the first surface of the matrix and is mutually intersected with a plurality of thread-shaped bodies distributed on the other cross beam adjacent to any one of the cross beams, so that the porous structure is formed.
Preferably, at least two cross beams pass directly over the air inlet of the first fluid passage.
Preferably, the linear body comprises a carbon nanowire, a carbon nanotube, a ZnO nanowire, a GaN nanowire, and TiO 2 Any one or a combination of two or more of nanowires, ag nanowires, au nanowires, but not limited thereto.
In a more specific third embodiment of the present invention, the filter chip comprises:
a substrate having a first fluid channel with an air inlet and an air outlet, the air inlet of the first fluid channel being distributed within a first region of a first surface of the substrate;
an air blocking portion having a second surface disposed opposite the first surface of the base for blocking air to be treated from directly entering an air inlet of the first fluid passage;
the air barrier comprises a plurality of convex parts which are arranged at intervals, one ends of the convex parts are fixedly arranged in a second area of the first surface of the matrix, the other ends of the convex parts are fixedly connected with the second surface of the air barrier, the distance between the adjacent convex parts is larger than 0 but smaller than the particle size of selected particles mixed in air to be treated, the second area of the first surface of the matrix is adjacent to the first area, so that a second fluid channel is formed by matching among the convex parts, the air barrier and the matrix, and the air to be treated can only enter the first fluid channel through the second fluid channel.
Further, the plurality of bosses are disposed around the air inlet of the first fluid passageway.
Further, a plurality of protruding portions are also arranged in a third area of the first surface of the substrate at intervals, and the second area is arranged between the third area and the first area.
More preferably, the aperture of the first fluid channel is 1 mu m-1 mm.
More preferably, the thickness of the substrate is more than 1 mu m.
More preferably, the thickness of the air blocking portion is 0.5-200 mu m.
Preferably, the surface of the protruding portion is further provided with a functional material layer, and the material of the functional material layer comprises a photocatalytic material or an antibacterial material.
Preferably, at least part of the components in the filter chip is transparent.
Further, a third region of the first surface of the substrate is disposed around the second region.
Further, the first area and the second area of the first surface of the substrate are distributed in the orthographic projection of the air blocking portion on the first surface of the substrate.
Preferably, the filter chip further comprises at least one support body, one end of the support body is fixedly connected with the base body, and the other end of the support body is fixedly connected with the air blocking portion.
Preferably, the plurality of protruding portions distributed in the third area of the first surface of the substrate are arranged to form a micro-scale or nano-scale array structure with super-hydrophobic or super-oleophobic performance.
Preferably, the filter chip includes more than two supporting bodies, and the more than two supporting bodies are symmetrically distributed around the air inlet of the first fluid channel.
More preferably, the air inlet of the first fluid channel is provided with more than one supporting beam, and the supporting beam is fixedly connected with the air blocking part.
Further, the protruding portion is any one of a linear, columnar, sheet-like, tubular, conical, and frustum-shaped structure provided standing, and is not limited thereto.
Further, the lateral cross section of the boss has a regular or irregular shape, and the regular shape includes, but is not limited to, a polygonal shape, a circular shape, or an elliptical shape.
Further, the plurality of protruding portions are uniformly distributed or non-uniformly distributed on the first surface of the substrate.
Further, the air inlet of the first fluid passage has a regular or irregular shape, including but not limited to polygonal, circular or elliptical shape.
More preferably, the protruding portion is a linear protrusion, and the aspect ratio of the protruding portion is 4: 1-200000: 1.
preferably, the ratio of the distance between adjacent protruding portions to the length of the protruding portion is 1: 4-1: 200000.
more preferably, the protruding portion is a vertically arranged micro wire or nano wire, the diameter of the protruding portion is 1 nm-50 mu m, the length of the protruding portion is 50 nm-200 mu m, and the distance between adjacent protruding portions is 1 nm-50 mu m.
In a more specific fourth embodiment of the present invention, the filter chip comprises:
a substrate having a first fluid channel with an air inlet and an air outlet, the air inlet of the first fluid channel being distributed within a first region of a first surface of the substrate;
an air blocking portion having a second surface disposed opposite the first surface of the base for blocking air to be treated from directly entering an air inlet of the first fluid passage;
the air treatment device comprises a plurality of convex parts, wherein the convex parts continuously extend along the transverse direction in a second area of the first surface of the substrate, grooves for air to pass through are formed between the adjacent convex parts, the aperture of the opening part of each groove is larger than 0 but smaller than the particle size of selected particles mixed in air to be treated, the upper ends of the convex parts are in sealing connection with the first surface of the substrate, the local areas of the lower ends of the convex parts are in sealing connection with the second surface of the air blocking part, so that more than one groove between the convex parts, the air blocking part and the substrate are matched to form a second fluid channel, and the air to be treated can only enter the first fluid channel through the second fluid channel.
Further, the second region of the first surface of the substrate is disposed around the first region.
Further, the local area of the second end of the protruding portion and the air inlet of the first fluid channel are distributed in an orthographic projection formed on the first surface of the substrate by the air blocking portion.
Further, the shape of the protrusion includes an elongated shape or a sheet shape, but is not limited thereto.
Further, the plurality of protruding portions are uniformly distributed or non-uniformly distributed on the first surface of the substrate.
Further, the air inlet of the first fluid passage has a regular or irregular shape, including but not limited to polygonal, circular or elliptical shape.
More preferably, the width of the protruding portion is 1 nm-50 mu m, and the height is 50 nm-200 mu m.
More preferably, the size of the groove opening formed between adjacent protruding portions is 1nm to 50 μm.
More preferably, the aperture of the first fluid channel is 1 mu m-1 mm.
More preferably, the thickness of the substrate is more than 1 mu m.
More preferably, the thickness of the air blocking portion is 0.5-200 mu m.
Preferably, the surface of the protruding portion is further provided with a functional material layer, and the material of the functional material layer comprises a photocatalytic material or an antibacterial material.
Preferably, at least part of at least one of the base body, the air blocking portion and the protruding portion is a transparent structure.
In a more specific fifth embodiment of the present invention, the filter chip comprises:
a substrate having a first fluid channel, the first fluid channel having an air inlet and an air outlet, the air inlet of the first fluid channel being distributed over a first surface of the substrate;
a plurality of protruding parts which are arranged at intervals, wherein the protruding parts are fixedly arranged on the first surface of the base body and continuously extend on the first surface of the base body along the transverse direction, grooves through which air can pass are formed between the adjacent protruding parts, the aperture of the opening parts of the grooves is larger than 0 and smaller than the particle diameter of selected particles mixed in air to be treated, and at least two protruding parts are respectively arranged adjacent to two opposite sides of the air inlet of the first fluid channel, at least one protruding part directly passes through the air inlet of the first fluid channel, so that a second fluid channel communicated with the first fluid channel is formed between the plurality of protruding parts and the base body in a matched mode, and the air to be treated can enter the first fluid channel only through the second fluid channel.
Preferably, the filter chip further comprises: the air blocking part is provided with a second surface which is opposite to the first surface of the base body, the air inlets of the first fluid channels are distributed in orthographic projection formed on the first surface of the base body by the air blocking part, the plurality of protruding parts are provided with first ends and second ends which are opposite to each other, the first ends are in sealing connection with the first surface of the base body, and local areas of the second ends are in sealing connection with the second surface of the shielding part.
Preferably, the plurality of protruding portions are distributed in parallel on the first surface of the substrate.
Preferably, the size of the opening of the groove formed between the adjacent protruding portions is 1nm to 50 μm.
More preferably, the aperture of the first fluid channel is 1 mu m-1 mm.
More preferably, the thickness of the substrate is more than 1 mu m.
Preferably, the surface of the protruding portion is further provided with a functional material layer, and the material of the functional material layer comprises a photocatalytic material or an antibacterial material.
More preferably, the thickness of the air blocking portion is 0.5-200 mu m.
Preferably, at least part of at least one of the base body, the air blocking portion and the protruding portion is a transparent structure.
In a more specific sixth embodiment of the present invention, the filter chip comprises:
matrix with fluid channels
An aggregate of a plurality of wire-shaped bodies for treating air flowing through the fluid passage mixed with selected particles;
the aggregates are distributed within the fluid channel and have a porous structure with pores having diameters greater than 0 but less than the particle size of the selected particles.
Further, one end of the linear body is fixedly connected with the inner wall of the fluid channel, and the other end of the linear body extends along the radial direction of the fluid channel.
Further, the plurality of linear bodies are mutually intersected or interweaved with each other to form the porous structure.
Further, the plurality of linear bodies are arranged at intervals and are arranged in parallel to form the porous structure.
Further, the substrate is provided with a first surface and a second surface which are opposite to each other, and the air inlets of the fluid channels are distributed on the first surface of the substrate.
Further, the first surface of the base body is further provided with a plurality of upright line-shaped bodies which are arranged at intervals, and the plurality of upright line-shaped bodies are arranged around the fluid channel.
Further, the filter chip further comprises an air blocking portion, the air blocking portion is provided with a third surface which is opposite to the first surface of the base body, one end of each of the plurality of upright linear bodies is fixedly arranged on the first surface of the base body, the other end of each of the plurality of upright linear bodies is fixedly connected with the third surface of the air blocking portion, and the distance between the adjacent upright linear bodies is larger than 0 but smaller than the particle size of the selected particles.
Preferably, the first surface of the substrate is further provided with a functional material layer, and the material of the functional material layer includes a photocatalytic material or an antibacterial material.
Preferably, at least part of the components in the filter chip have a transparent structure.
Further, the air inlet of the fluid passage has a regular or irregular shape including, but not limited to, a polygonal shape, a circular shape, or an elliptical shape.
More preferably, the aperture of the fluid channel is 1 mu m-1 mm.
More preferably, the thickness of the substrate is more than 1 mu m.
Further, the air inlet of the fluid channel and the plurality of upright linear bodies are distributed in the orthographic projection of the air barrier part on the first surface of the base body.
More preferably, the length-diameter ratio of the upright linear body is 4: 1-200000: 1.
preferably, the ratio of the distance between adjacent upright wire-shaped bodies to the length of the upright wire-shaped bodies is 1: 4-1: 200000.
more preferably, the diameter of the line-shaped body is 1 nm-500 mu m.
More preferably, the linear body is selected from nanowires or nanotubes.
Preferably, at least the surface of the linear body is further distributed with a photocatalytic material or an antibacterial material.
Preferably, the linear body comprises a carbon nanowire, a carbon nanotube, a ZnO nanowire, a GaN nanowire, and TiO 2 Any one or a combination of two or more of nanowires, ag nanowires, au nanowires, but not limited thereto.
Compared with the prior art, the invention has at least the following advantages:
1) The nasal obstruction type respirator provided by the invention has the advantages of good filterability, convenience in breathing, good comfort, reusability and long service life;
2) The filter chip has the characteristics of large flux, small flow resistance, capability of efficiently removing micro/nano particles in air, thicker matrix, high mechanical strength, capability of (ultrasonic) cleaning and repeated use, long service life, preferably self-cleaning function, simple and controllable preparation process and suitability for large-scale mass preparation.
Drawings
In order to more clearly illustrate the structural features and technical gist of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and detailed description.
FIG. 1 is a schematic illustration of a nasal obstruction type respirator according to an exemplary embodiment of the present invention;
FIG. 2 is a top view of a filter chip according to a first embodiment of the present disclosure;
FIG. 3 is a partial cross-sectional view (A-A) of a filter chip according to a first embodiment of the present application;
FIG. 4 is a flowchart of a process for manufacturing a filter chip according to a first embodiment of the present disclosure;
FIG. 5 is a top view of a filter chip according to a second embodiment of the present disclosure;
FIG. 6 is a partial cross-sectional view of a filter chip according to a second embodiment of the present application;
FIG. 7 is a flowchart of a process for manufacturing a filter chip according to a second embodiment of the present disclosure;
FIG. 8 is a cross-sectional view of a filter chip according to a third embodiment of the present application;
9 a-9 e are transverse cross-sectional views of some of the bosses in a third embodiment of the present application;
FIGS. 10 a-10 c are schematic illustrations of arrangements of a number of protrusions according to a third embodiment of the present application;
FIGS. 11 a-11 c are top views of various filter chips according to a third embodiment of the present application;
FIG. 12 is a cross-sectional view of a filter chip according to a fourth embodiment of the present application;
FIG. 13 is a cross-sectional view of a filter chip according to a fifth embodiment of the present application;
FIG. 14 is a cross-sectional view of a filter chip according to a sixth embodiment of the present application;
FIG. 15 is a cross-sectional view of a filter chip according to a seventh embodiment of the present application;
FIG. 16 is a flowchart of a process for manufacturing a filter chip according to an eighth embodiment of the present disclosure;
FIG. 17 is a flowchart of a process for manufacturing a filter chip according to a ninth embodiment of the present disclosure;
FIG. 18 is a top view of a filter chip according to a tenth embodiment of the present disclosure;
FIG. 19 is a partial cross-sectional view of a filter chip according to a tenth embodiment of the present application;
FIG. 20 is a top view of a filter chip according to an eleventh embodiment of the present disclosure;
FIG. 21 is a partial cross-sectional view of a filter chip according to a twelfth embodiment of the present application;
FIG. 22 is a partial cross-sectional view of a filter chip according to a thirteenth embodiment of the present application;
FIG. 23 is a top view of a filter chip according to a fourteen embodiment of the present application;
FIG. 24 is a partial cross-sectional view of a filter chip according to fifteen embodiments of the present application;
fig. 25 is a process flow diagram of a preparation process of a filter chip according to sixteen embodiments of the present application.
Detailed Description
The embodiment of the invention provides a nasal obstruction type respirator, which comprises the following components:
The nose plug comprises a nose plug and a filter chip, wherein at least one end part of the nose plug can be inserted into a nasal cavity of a user, the nose plug comprises a gas channel communicated with the nasal cavity, the filter chip is used for filtering particles which are mixed in airflow to be treated and have a particle size larger than a set value, and the air to be treated flows through the filter chip and then enters the gas channel in the nose plug; the method comprises the steps of,
and the filter chip protection structure is used for protecting the filter chip.
In some embodiments, the filter chip guard structure includes a first stationary rigid screen and a second stationary rigid screen, the filter chip being disposed between the first stationary rigid screen and the second stationary rigid screen.
In some embodiments, the nasal plug respirator further comprises a first filter fabric and/or a second filter fabric, the first filter fabric being disposed between the nasal plug and the filter chip, the filter chip being disposed between the second filter fabric and the nasal plug.
In some embodiments, the nasal plug respirator further comprises a first removable hard screen fixedly connected to the first filter fabric and/or a second removable hard screen fixedly connected to the second filter fabric.
Preferably, the nose plug adopts a waist drum type nose plug which can be partially or wholly inserted into the nasal cavity of a human body.
Preferably, the nose plug type respirator further comprises a shell with two open ends, the nose plug is detachably arranged at one end of the shell, and the filter chip is accommodated in the shell. The shell can realize further protection of the filter chip on one hand and can accommodate the various components, so that the respirator is compact and firm in structure. The housing is preferably a rigid housing.
Referring to FIG. 1, a nasal obstruction type respirator in accordance with an exemplary embodiment of the present invention may comprise:
the hard shell 11 is provided with a hard outer shell,
an embedded hard wire mesh assembly comprising two pieces of embedded hard wire mesh 12 transversely and at intervals arranged in a housing 11;
the filter silk fabric piece assembly comprises two filter silk fabric pieces 13 which are transversely and alternately arranged in the shell 11, wherein the two filter silk fabric pieces 13 are positioned between the two embedded hard silk screens 12 and are respectively and fixedly arranged on the embedded hard silk screens 12;
a fixed hard wire mesh assembly comprising two fixed hard wire meshes 14 transversely and at intervals arranged in the housing 11, the fixed hard wire meshes 14 being positioned between two pieces of filter wire fabric 13;
The filter chip 16 is transversely arranged in the shell 11 and is positioned between the two fixed hard silk screens 14;
the waist drum type nose plug 15 comprises a connecting sheet body 151 and two nose plug main bodies 152 protruding outwards from one surface of the connecting sheet body 151, wherein the waist drum type nose plug 15 is embedded at one end of the inner cavity of the shell 11 through the connecting sheet body 151, and the nose plug main bodies 152 are communicated with the inner cavity of the shell 11.
Preferably, both ends of the embedded hard wire mesh 12 are detachably connected with the inner cavity wall of the housing 11, respectively. Two ends of the filter silk fabric piece 13 are respectively connected with the inner cavity wall of the shell 11, one surface of the filter silk fabric piece is fixedly connected with the embedded hard silk screen 12, and the other surface of the filter silk fabric piece is arranged on a boss protruding out of the inner cavity wall of the shell 11. Both ends of the fixed hard wire mesh 14 are respectively fixed on the inner cavity wall of the shell 11. The two ends of the filter chip are respectively fixed on the inner cavity wall of the shell 11.
In the present invention, the aforementioned filter chip may be manufactured using MEMS (micro electro mechanical system process), and thus may also be named as MEMS filter chip.
Referring to fig. 2-3, in an embodiment of the present invention (named as a first embodiment), a filter chip includes a substrate 101, where the substrate 101 has a first surface 1011 and a second surface 1012 opposite to each other, and a plurality of through holes 102 serving as fluid channels are distributed in the substrate 101, the first surface is provided with an array formed by arranging a plurality of beams 103 (named as protrusions) in parallel, where the plurality of beams 103 directly span the through holes 102 and the plurality of beams 103 are distributed on two sides of the through holes 102, and a cap structure 104 (abbreviated as a cap layer) is further distributed on top of each beam 103, and each cap layer also extends continuously along with each beam in a transverse direction and forms an array of cap structures, and air to be treated cannot bypass the array of cap structures and directly enter the through holes 102.
By adjusting the pitch between the cap structures, an opening (which may be referred to as a micro flow channel) having a selected size can be formed, and particles having different particle size ranges in the air can be removed.
The aforementioned cross beams may be strip-shaped and have a greater width and thickness so that they may have a higher mechanical strength to provide better support for the cap layer, while the spacing of the cross beams may be greater to provide greater air flux.
The cap layer may also have a greater thickness and extend laterally on both sides so that the spacing between adjacent cap layers may be small, for example as low as 1nm, thereby trapping very small particles that may be mixed in the air to be treated.
The cap layer and the protruding portion may be integrally formed, for example, may be directly formed on the upper portion of the protruding portion by evaporation, deposition, growth, etc. (typically, such as metal sputtering, MOCVD, PECVD, electrochemical deposition, etc.), and the cap structure may also extend continuously along the lateral direction along with the protruding portion, so that an opening portion extending continuously along the lateral direction is formed between adjacent cap structures, which on the one hand may ensure the treatment of selected particles mixed in the air to be treated, and also maintain a high flux, and reduce the processing difficulty and save the cost.
The cap layer may be made of dielectric material such as silicon oxide, silicon nitride aluminum oxide, borophosphosilicate glass, etc., or semiconductor material such as Si, znO, gaN, tiO 2 InN, etc., or a metallic material such as Ag, au, al, ni, cr, ti, etc., but is not limited thereto.
The substrate 101 may have a larger thickness, so that the substrate may form a better support for the micro/nano sheet array, and may further enhance the mechanical strength of the filter chip, so that the filter chip may be pressure-resistant, bending-resistant, collision-resistant, and impact-resistant, and further may be applied in various environments without damage, for example, may be applied in treating high-pressure and high-speed air, which is not achieved by the existing porous membrane.
The material selection range of each part (101, 102, 103, 104) of the filter chip is various, and the filter chip can be made of inorganic materials or organic materials, such as metals, nonmetallic inorganic materials, plastics, ceramics, semiconductors, glass, polymers and the like. When inorganic materials are selected for these parts, the filter chip also has the characteristic of temperature variation resistance, and can process high-temperature and low-temperature air.
The filter chip adopting the design can be cleaned (ultrasonically) and used for multiple times, and still has good air treatment capability.
When air is treated by the filter chip, air containing impurity particles (the air flow direction is shown by an arrow with a broken line in fig. 3) enters the array of the hat-shaped structures, particles (or some droplets incompatible with air, such as water droplets in air or water droplets in oil) with particle sizes larger than a certain value are blocked outside the array of the hat-shaped structures, and then the air reaches the entrance of the through holes 102 through the opening part between the hat-shaped structures and then enters the through holes 102, so that air purification and/or enrichment recovery of the required particles (droplets) are realized.
In some specific application schemes of the embodiment, the gap between the cap layers can be 1 nm-50 mu m, and the height of the cap layers can be 50 nm-200 mu m.
In some specific application schemes of this embodiment, the aperture of the through hole may be 1 μm to 1mm, and the thickness of the substrate may be >1 μm.
In some specific application schemes of the embodiment, the height of the cross beam can be 0.1 mu m-400 mu m, the width can be 0.1 mu m-100 mu m, and the distance between the cross beams can be 0.1 mu m-100 mu m.
The longitudinal cross section of the opening formed in front of the adjacent cap layer and the adjacent cross beam may be regular or irregular in shape, for example, may be trapezoidal, polygonal (triangular, quadrangular or otherwise), circular, elliptical, star-shaped, or the like.
The beams and cap layer may be regularly or irregularly, uniformly or non-uniformly distributed on the first surface of the substrate.
In addition, in the first embodiment, the shape of the aforementioned through hole 102 may be various, for example, may be a circle, a square, a rectangle, or other shapes.
In other embodiments of the present application, a filter chip may have a similar structure to any of the previous embodiments, except that: the surface of the cross beam, the cap-shaped layer and the basal body can be also provided with a photocatalysis material layer. When the filter chip containing the photocatalytic material layer is used for treating the air, if ultraviolet irradiation and the like are used for assistance, photocatalytic degradation can be further carried out on some organic pollutants and the like in the air, so that multiple purification of the air is realized.
Wherein, in order to facilitate the penetration of light, part or all of the cap layer, the cross beam and the matrix can be made of transparent materials. In some embodiments of the present example, the cap layer and the beam may be integrally formed of a transparent material, such as light injection.
Among them, the photocatalytic material may be titanium dioxide or the like, but is not limited thereto.
Wherein, for forming the photocatalytic material layer, a person skilled in the art may use various ways known in the art, such as coating (spin coating, spray coating, printing, etc.), physical or chemical vapor deposition (such as MOCVD, PECVD, atomic layer deposition, etc.), sputtering, etc., and is not limited thereto.
Wherein the thickness of the photocatalytic material layer can be controlled at the nanometer level to minimize its effect on the air flux of the filter chip.
The structures, arrangement forms, materials, etc. of the substrate, cap layer, cross beam, through hole, etc. used in this embodiment may be the same as or similar to those described above, and thus will not be described here again.
In other embodiments of the present application, a filter chip may have a similar structure to any of the previous embodiments, except that: the surface of the cross beam, the cap-shaped layer and the basal body can be provided with an antibacterial material layer. When the filter chip containing the antibacterial material layer is used for treating the air, bacteria, viruses and the like in the air can be killed synchronously in the air treatment process, so that multiple purification of the air is realized.
Among them, a more typical antibacterial material may be a noble metal such as Au, ag, etc., but is not limited thereto.
Among them, for forming the antibacterial material layer, those skilled in the art may use various means known in the art, such as coating (spin coating, spray coating, printing, etc.), physical or chemical vapor deposition (such as MOCVD, PECVD, atomic layer deposition, etc.), sputtering, etc., and are not limited thereto.
Wherein the thickness of the antimicrobial material layer can be controlled at the nanometer level to minimize its effect on the air flux of the filter chip.
The structures, arrangement forms, materials, etc. of the substrate, cap layer, cross beam, through hole, etc. used in this embodiment may be the same as or similar to those described above, and thus will not be described here again.
The filter chip of the present application may be prepared by physical and chemical methods, for example, chemical growth methods, physical processing methods, and the like, and in particular, MEMS (micro electro mechanical system, microelectromechanical Systems) methods, and the like.
In other embodiments of the present application, a process for preparing a filter chip may include the steps of:
s1: providing a substrate (e.g., a silicon wafer);
s2: photoetching micro-nano scale lines on one side surface (named as a first surface) of a substrate, namely forming a patterned photoresist mask;
S3: etching (RIE, ICP, wet etching, electrochemical etching, etc.) a plurality of beams on the micro-nano scale on the first surface of the substrate, and then removing the photoresist mask;
s4: providing a photoresist etching mask on the other side surface (named second surface) of the substrate opposite to the first surface;
s5: etching the other side surface of the substrate until a through hole serving as a fluid channel is formed on the other side surface of the substrate;
s6: the photoresist etch mask is removed and then a cap layer structure is evaporated or deposited or grown on the surface of the beam side of the substrate. The phenomenon of lateral extension exists in the vapor plating or deposition or growth process, so that the gap between the cap layers can be reduced along with the increase of the thickness, and the minimum can reach several nanometers.
S7: dicing, packaging, and making a filter chip (this step is not shown in the figures).
The etching method adopted in the foregoing steps may also be photolithography, mechanical etching, dry etching, wet etching, or the like.
For example, in the foregoing steps, a method of forming a patterned photoresist mask includes: photolithography, nanosphere masking, nano (metal) particle masking, and the like, and are not limited thereto.
Obviously, the preparation process of the filter chip in the first embodiment is simple and controllable, is suitable for mass production, and the obtained filter chip has at least the following advantages: (1) large flux and small flow resistance; (2) The particles larger than the nano gaps can be effectively removed by physical filtration; (3) The crossing type cross beam and the larger substrate thickness can ensure high mechanical strength; (5) can be cleaned by ultrasonic waves and used for multiple times.
Referring to fig. 5, in a second embodiment of the present application, a filter chip includes a substrate 201, where the substrate 201 has a first surface 2011 and a second surface 2012 opposite to each other, and a plurality of through holes 204 serving as fluid channels are distributed on the substrate 201. The first surface 2011 is provided with a plurality of cross beams 203 arranged in parallel, the cross beams 203 extend continuously in the transverse direction on the first surface, and a plurality of cross beams 203 continuously span the through holes 204, so that the cross beams 203 can also be regarded as a spanning type cross beam 203. Wherein, a plurality of nanowires 202 are distributed on any one of the cross beams 203, one ends of the plurality of nanowires 202 are fixed on the surface of the any one of the cross beams 203, and the other ends extend obliquely (can also be regarded as extending sideways) along a direction gradually away from the any one of the cross beams 203, and cross each other with the plurality of nanowires 202 distributed on another cross beam adjacent to the any one of the cross beams 203, thereby forming the porous structure 205. Referring again to fig. 5, the porous structure 205 is seen from a top view as a grid structure that masks the through holes 204. The pores in the porous structure 205 have a diameter greater than 0 a but less than the particle size of the selected particles intermixed within the fluid to be treated. Referring to fig. 5-6, it can be seen that the porous structure 205 formed by intersecting the nanowires 102 cooperates with the first surface 2011 of the substrate 201 to form another fluid channel, so that the fluid 206 to be treated can only enter the through hole 204 through the other fluid channel.
The nanowires can be densely arranged on the first surface of the substrate due to the fact that the nanowires have larger height-diameter ratio (or length-diameter ratio), particles with different particle size ranges in the fluid can be removed by adjusting the distance between the cross beams, the density, the length, the extending direction and the like of the nanowires, and particularly when the nanowires are adopted, extremely small particles in the fluid can be removed by controlling the pore diameters of holes formed by crossing the nanowires to be in a nanoscale, and the resistance of the nanowires to the fluid can be controlled to be at a very low level due to the extremely small diameter of the nanowires, so that a very large fluid flux is formed, and the method is far superior to the existing porous membrane, the filtration chip based on transverse flow channels and the like.
If the arrangement mode of the nanowires is designed to a certain degree according to the known scheme in the industry, the nanowires can also form a super-hydrophobic structure and a super-oleophobic structure, so that particles in fluid can be removed, and blocked particles can not be accumulated in a functional area (the surface of the nanowire array) of the filter chip through self-cleaning, and the filter chip is prevented from being invalid after long-term use.
Wherein the cross-beam 203 may be distributed at a suitable density on the first surface 2011 of the substrate 201 to provide the filter chip with as high a fluid handling throughput as possible. And, the cross-beam 203 may have a suitable width so that the cross-beam 203 may have sufficient mechanical strength while also avoiding excessive impact on the flux of the filter chip. For example, the height of the cross beams can be 0.1-100 [ mu ] m, the width of the cross beams can be 0.1-400 [ mu ] m, and the distance between the cross beams can be 0.1-100 [ mu ] m.
The substrate 201 may have a larger thickness and the cross beam 203 may have a larger height, so that the cross beam may form a better support for the nanowire array, and may further enhance the mechanical strength of the filter chip, so that the filter chip may be pressure-resistant, bending-resistant, collision-resistant, impact-resistant, and further may be applied in various environments without damage, for example, may be applied in treating high-pressure and high-speed fluids, which is not acceptable for the existing porous membrane.
The filter chip parts (201, 202, 203) can be made of various materials, such as inorganic materials or organic materials. When inorganic materials are selected for these parts, the filter chip also has the property of resisting temperature change, and can process high-temperature and low-temperature fluids.
The filter chip adopting the design can be cleaned (ultrasonically) and used for multiple times, and still has good fluid processing capability.
When the fluid is treated by the filter chip, the fluid containing impurity particles enters the porous structure 205, particles (or some droplets incompatible with the fluid, such as droplets in air or droplets in oil) with particle sizes larger than a certain value are blocked outside the porous structure 205, and then the fluid reaches the inlet of the through hole 204 through gaps among the nanowires and enters the through hole 204, so that the purification of the fluid and/or the enrichment and recovery of the required particles (droplets) are realized.
Referring to fig. 5 again, in some specific application schemes of this embodiment, the diameter and the pitch of the nanowires 202 may be 1nm to 50 μm, and the length 6 degrees (height) may be 50nm to 200 μm. The aperture of the through hole 104 may be 1 μm to 1mm. The thickness of the substrate may be above 1 μm.
The transverse cross-sectional structure of the aforementioned nanowires may be regular or irregular in shape, for example, polygonal (triangular, quadrangular or otherwise), circular, elliptical, star-shaped, etc.
The nanowires 202 may be regularly or irregularly, uniformly or non-uniformly distributed on the first surface of the substrate 201.
The array formed by these nanowires 202 may have a superhydrophobic structure, thereby enabling the filter chip to have a self-cleaning function.
The nanowire 202 may preferably be selected from a carbon nanowire, a carbon nanotube, a ZnO nanowire, a GaN nanowire, and TiO 2 Nanowires, ag nanowires, au nanowires, and the like, and are not limited thereto.
The nanowires 202 may be immobilized on or grown on the surface of the substrate by external transfer, in situ growth (e.g., chemical growth, electrochemical growth), or deposition (e.g., physical, chemical vapor deposition, electrodeposition), etc.
The shape of the through-holes 204 (particularly the shape of the transverse cross-section) may be varied, for example, circular, square, rectangular, diamond-shaped, polygonal, or other regular or irregular shapes.
In some specific applications of this embodiment, the nanowire 202 may be formed of a photocatalytic material or a material having an antibacterial and bactericidal function, or the nanowire 202 may be coated with a photocatalytic material or a material having an antibacterial and bactericidal function.
For example, the nanowire 202 may be a nanowire having photocatalytic properties, such as a ZnO nanowire, a GaN nanowire, or a TiO2 nanowire, and may be capable of degrading an organic substance in a fluid under light-assisted irradiation.
For example, the nanowires 202 may employ Ag nanowires, au nanowires, etc., to kill bacteria, viruses, microorganisms in the fluid.
In some specific applications of this embodiment, a layer of photocatalytic material or an antibacterial material is further disposed on the first surface 2011 of the substrate 201.
When the fluid is treated by the filter chip containing the photocatalytic material layer, if ultraviolet irradiation and the like are used, some organic pollutants and the like in the fluid can be subjected to photocatalytic degradation, so that multiple purification of the fluid is realized.
Wherein, in order to facilitate the penetration of light, part or all of the matrix, the convex part and the nanowire can be made of transparent materials.
Among them, the photocatalytic material may be titanium dioxide or the like, but is not limited thereto.
Wherein, for forming the photocatalytic material layer, a person skilled in the art may use various ways known in the art, such as coating (spin coating, spray coating, printing, etc.), physical or chemical vapor deposition (such as MOCVD, PECVD, atomic layer deposition, etc.), sputtering, etc., and is not limited thereto.
Wherein the thickness of the photocatalytic material layer can be controlled at the nanometer level to minimize its effect on the fluid flux of the filter chip.
When the fluid is treated by the filter chip containing the antibacterial material layer, bacteria, viruses and the like in the fluid can be killed synchronously in the treatment process of the fluid, so that multiple purification of the fluid is realized.
Among them, a more typical antibacterial material may be a noble metal such as Au, ag, etc., but is not limited thereto.
Among them, for forming the antibacterial material layer, those skilled in the art may use various means known in the art, such as coating (spin coating, spray coating, printing, etc.), physical or chemical vapor deposition (such as MOCVD, PECVD, atomic layer deposition, etc.), sputtering, etc., and are not limited thereto.
Wherein the thickness of the antimicrobial material layer can be controlled at the nanometer level to minimize its effect on the fluid flux of the filter chip.
The filter chip of the present application may be prepared by physical and chemical methods, for example, chemical growth methods, physical processing methods, and the like, and in particular, MEMS (micro electro mechanical system, microelectromechanical Systems) methods, and the like.
For example, referring to fig. 7, in this embodiment, a process for preparing a filter chip may include the steps of:
S1: a seed layer for nanowire growth is deposited on a first surface of a substrate, such as a silicon wafer.
S2: and a patterned photoresist mask is arranged on the seed layer and comprises micro-nano scale lines which are photoetched.
S3: and etching the first surface of the substrate by using the photoresist mask, so as to form a plurality of micro-nano scale beam structures which are arranged at intervals on the first surface of the substrate, and removing the photoresist mask.
S4: a patterned etch mask of photoresist is disposed on the second surface of the substrate.
S5: etching the second surface of the substrate to the bottom of the beam, thereby forming a slot hole serving as a fluid channel on the second surface of the substrate, and removing the photoresist.
S6: and growing the nanowire on the seed layer, controlling the growth condition of the nanowire, enabling the nanowire to have a certain lateral growth rate, and forming a micro-nano cross grid.
S7: scribing and packaging to obtain the filter chip.
The etching method adopted in the foregoing steps may be photolithography, mechanical etching, dry etching, wet etching, or the like.
For example, in the foregoing steps, a method of forming a patterned (nanopatterned) photoresist mask includes: photolithography, nanosphere masking, nano (metal) particle masking, and the like, and are not limited thereto.
For example, in the foregoing steps, the beam 203, the via 204, etc. may be etched by means known in the art, such as RIE, ICP, wet etching, electrochemical etching, etc.
Obviously, the preparation process of the filter chip is simple and controllable, and is suitable for mass production.
Referring to fig. 8 and 11 a-11 b, in a third embodiment of the present application, a filter chip includes a substrate 301, where the substrate 301 has a first surface 301a, and a plurality of through holes 304 serving as fluid channels are distributed in a first area 3011 (an area surrounded by a dashed line in the drawing) of the substrate 301, an array of a plurality of vertical micro/nano wires/tubes 303 (i.e., any one or more of a micron-sized wire, a micron-sized tube, a nano wire, and a nano tube) is disposed on the first surface, and a fluid blocking portion 302 is further connected to a top portion of the plurality of micro/nano wires/tubes 303 distributed in a second area 3012 surrounding the first area 3011, where the fluid blocking portion 302 is disposed above a fluid inlet of the through holes 304, so that a fluid to be treated cannot bypass the micro/nano wire/tube array and directly enter the through holes 304, and the fluid blocking portion 302 has a second surface 302b disposed opposite to the first surface 3011. While a plurality of vertical micro/nanowires/tubes 303 may also be densely distributed within the remaining region 3013 (which may be designated as a third region) of the first surface 3011. In fig. 8, arrows with broken lines show the direction of travel of the fluid.
The micro/nano wires/tubes can be densely arranged on the first surface of the matrix due to the fact that the micro/nano wires/tubes have larger height-diameter ratio (or length-diameter ratio), particles with different particle size ranges in the fluid can be removed through adjusting the distance between the micro/nano wires/tubes, and particularly when the nano wires/tubes are adopted, extremely small particles in the fluid can be removed through controlling the distance between the nano wires/tubes at the nano level, and the resistance of the nano wires/tubes to the fluid can be controlled at a very low level due to the extremely small diameter of the nano wires/tubes, so that very large fluid flux is formed, and the micro/nano wires/tubes are far superior to the existing porous membranes, filter chips based on transverse flow channels and the like.
If the above-mentioned micro/nano wire/tube array is designed to a certain extent by referring to the known scheme in the industry, the micro/nano wire/tube array can also be formed into a super-hydrophobic structure and a super-oleophobic structure, so that not only particles in fluid can be removed, but also blocked particles can not be accumulated in a functional area (the surface of the micro/nano wire/tube array) of the filter chip through self-cleaning action, thereby avoiding the filter chip from losing efficacy after long-term use.
The substrate 301 may have a larger thickness, so that it forms a better support for the micro/nano wire/tube array, and may further enhance the mechanical strength of the filter chip, so that the filter chip is pressure-resistant, bending-resistant, collision-resistant, impact-resistant, and further may be applied in various environments without damage, for example, may be applied in treating high-pressure and high-speed fluid, which is not achieved by the existing porous membrane.
The fluid blocking part can be sheet-shaped, and the thickness and the like of the fluid blocking part can be adjusted according to practical application requirements.
The material selection range of each part (301, 302, 303, 304) of the filter chip is various, and the filter chip can be inorganic materials or organic materials, such as metals, nonmetallic inorganic materials, plastics, ceramics, semiconductors, glass, polymers and the like. When inorganic materials are selected for these parts, the filter chip also has the property of resisting temperature change, and can process high-temperature and low-temperature fluids.
The filter chip adopting the design can be cleaned (ultrasonically) and used for multiple times, and still has good fluid processing capability.
When the fluid is treated by the filter chip, the fluid containing impurity particles enters the array of micro/nano wires 303, wherein particles (or some droplets incompatible with the fluid, such as droplets in air or droplets in oil) with particle diameters larger than a certain value are blocked outside the array of micro/nano wires/tubes, and then the fluid reaches the entrance of the through hole 304 through the gap between the micro/nano wires/tubes and then enters the through hole 304, thereby realizing the purification of the fluid and/or the enrichment recovery of the required particles (droplets).
Referring again to fig. 8, in some specific applications of the third embodiment, the diameter of the micro/nano wire may be 1nm to 50 μm, and the length (height) h 1 Can be 50 nm-200 mu m, and the distance between adjacent micro/nano wires can be 1 nm-50 mu m. The aperture w of the through hole 304 may be 1 μm to 1mm. Thickness h of the substrate 2 Can be inAnd more than 1 mu m. Thickness h of the fluid barrier 3 Can be 0.5 mu m-200 mu m.
Referring again to fig. 9 a-9 e, the cross-sectional structure of the micro/nanowires may be regular or irregular, such as polygonal (triangular, quadrilateral or otherwise), circular, elliptical, star-shaped, etc.
Referring again to fig. 10 a-10 c, the foregoing micro/nanowires may be regularly or irregularly, uniformly or non-uniformly distributed on the first surface of the substrate. In some more specific application schemes, the average spacing between adjacent micro/nanowires is 1nm to 50 μm.
In addition, referring to fig. 11 a-11 c, in the third embodiment, the shapes (particularly the shapes of the transverse cross-section) of the through hole 304 and the fluid barrier 302 may be various, such as circular, square, rectangular or other shapes.
Referring to fig. 12, in a fourth embodiment of the present application, preferably, a filter chip includes a substrate 401, where the substrate 401 has a first surface and opposite and third surfaces, and a plurality of through holes 404 serving as fluid channels are distributed on the substrate 401, an array formed by a plurality of vertical micro/nano wires/tubes 403 is disposed on the first surface, top portions of the plurality of micro/nano wires/tubes 403 distributed around the through holes 404 are further connected with a fluid blocking portion 402, and the fluid blocking portion 402 is disposed above a fluid inlet of the through holes 404, so that a fluid to be treated cannot bypass the aforementioned micro/nano wire/tube array and directly enter the through holes 404. And, more than one supporting body 405, for example, four supporting bodies 405, are symmetrically or asymmetrically distributed around the through hole 404, so that the supporting body 405 can also be used for supporting the fluid blocking portion 402, so that a more firm and stable fit between the fluid blocking portion and the matrix is realized, and the micro/nano wire/tube array distributed between the fluid blocking portion and the matrix can be effectively protected, so that the problems of collapse, damage and the like of the micro/nano wire/tube 403 caused by the extrusion of the micro/nano wire/tube array after the fluid blocking portion and/or the matrix are subjected to external force are avoided.
The support body may be in various forms, for example, may have a rectangular, trapezoidal, stepped longitudinal section (the longitudinal direction herein may be understood as a direction perpendicular to the first surface of the base body), etc., and is not limited thereto. In some embodiments of this second embodiment, the support may be a boss or the like protruding upward from an edge portion of the through hole 404, and an upper end thereof is connected to the fluid blocking portion 402.
The number, diameter, distribution density and the like of the supporting bodies can be adjusted according to actual needs, but the space occupying the first surface of the matrix is as small as possible, so that the large influence on the fluid flux of the micro/nano wires is avoided.
The structures, arrangement forms, materials, etc. of the substrate, the micro/nano wire/tube array, the fluid barrier, the through holes, etc. used in the second embodiment may be the same as or similar to those described above, and thus will not be repeated here.
Referring to fig. 13, preferably, in a fifth embodiment of the present application, a filter chip includes a substrate 501, where the substrate 501 has a first surface and opposite and third surfaces, a plurality of through holes 504 serving as fluid channels are distributed on the substrate 501, an array of a plurality of vertical micro/nano wires/tubes 503 is disposed on the first surface, a fluid blocking portion 502 is further connected to the top of the plurality of micro/nano wires/tubes 503 distributed around the through holes 504, and the fluid blocking portion 502 is disposed above a fluid inlet of the through holes 504, so that a fluid to be treated cannot bypass the micro/nano wires/tubes array and directly enter the through holes 504. And, more than one supporting beam 505, for example, symmetrically or asymmetrically arranged, is further erected on the through hole 504, and the supporting beam 505 can further increase the support to the fluid blocking portion 502, so as to realize a more firm and stable fit between the fluid blocking portion and the substrate, and can effectively form protection for the micro/nano wire/tube array distributed between the fluid blocking portion and the substrate, so as to avoid the problems of collapse, damage and the like of the micro/nano wire/tube 503 caused by extrusion of the micro/nano wire/tube array after the fluid blocking portion and/or the substrate are subjected to external force.
The support beam may be in various forms, for example, may be in an arch shape, etc., and is not limited thereto. And further the support beam may also be fitted with other supports, such as the ones described in the fifth embodiment.
The number, the size, the distribution density and the like of the supporting beams can be adjusted according to actual needs, but the fluid inlets of the through holes are shielded as little as possible, so that the large influence on the fluid flux of the filter chip is avoided.
The structures, arrangement forms, materials, etc. of the substrate, the micro/nano wire/tube array, the fluid barrier, the through holes, etc. used in the fifth embodiment may be the same as or similar to those described above, and thus will not be repeated here.
Referring to fig. 14, in a sixth embodiment of the present application, a filter chip preferably includes a substrate 601, where the substrate 601 has a first surface 6011 and a third surface 6012 opposite to the first surface, a plurality of through holes 604 serving as fluid channels are distributed on the substrate 601, an array of a plurality of vertical nano-pillars 603 is disposed on the first surface, a fluid blocking portion 602 is further connected to the top of the plurality of nano-pillars 603 distributed around the through holes 604, and the fluid blocking portion 602 is disposed above a fluid inlet of the through holes 604, so that a fluid to be treated cannot bypass the aforementioned nano-pillar array and directly enter the through holes 604. A photocatalytic material layer 605 is further provided on the surface of the nanopillar 603 and the first surface of the substrate 601. When the fluid is treated by the filter chip comprising the photocatalytic material layer 605, if ultraviolet irradiation and the like are used, some organic pollutants and the like in the fluid can be subjected to photocatalytic degradation, so that multiple purification of the fluid is realized.
Wherein, in order to facilitate the penetration of light, part or all of the fluid barrier, the matrix and the bulge can be made of transparent materials. In some embodiments of the present example, the fluid barrier may be integrally formed of a transparent material, such as light injection.
Among them, the photocatalytic material may be titanium dioxide or the like, but is not limited thereto.
Wherein, to form the photocatalytic material layer 605, those skilled in the art can use various ways known in the art, such as coating (spin coating, spray coating, printing, etc.), physical or chemical vapor deposition (such as MOCVD, PECVD, atomic layer deposition, etc.), sputtering, etc., and are not limited thereto.
Wherein the thickness of the photocatalytic material layer 605 may be controlled to be on the order of nanometers to minimize its effect on the fluid flux of the filter chip.
The structures, arrangement forms, materials, etc. of the substrate, the micro/nano wire/tube array, the fluid barrier, the through holes, etc. used in the sixth embodiment may be the same as or similar to those described above, and thus will not be repeated here.
Referring to fig. 15, in a seventh embodiment of the present application, a filter chip preferably includes a substrate 701, where the substrate 701 has a first surface 7011 and a third surface 7012 opposite to the first surface, a plurality of through holes 704 serving as fluid channels are distributed on the substrate 701, an array of a plurality of vertical nano columns 703 is disposed on the first surface, top portions of the plurality of nano columns 703 distributed around the through holes 704 are further connected with a fluid blocking portion 702, and the fluid blocking portion 702 is disposed above a fluid inlet of the through holes 704, so that a fluid to be treated cannot bypass the aforementioned nano column array and directly enter the through holes 704. An antibacterial material layer 705 is also provided on the surface of the nano-pillar 703 and the first surface of the substrate 701. When the fluid is treated by the filter chip comprising the antibacterial material layer 705, bacteria, viruses and the like in the fluid can be killed synchronously in the treatment process of the fluid, so that multiple purification of the fluid can be realized.
Among them, a more typical antibacterial material may be a noble metal such as Au, ag, etc., but is not limited thereto.
Wherein, to form the antibacterial material layer 705, those skilled in the art can use various methods known in the art, such as coating (spin coating, spray coating, printing, etc.), physical or chemical vapor deposition (such as MOCVD, PECVD, atomic layer deposition, etc.), sputtering, etc., and are not limited thereto.
Wherein the thickness of the antimicrobial material layer 705 may be controlled to be on the order of nanometers to minimize its effect on the fluid flux of the filter chip.
The structures, arrangement forms, materials, etc. of the substrate, the micro/nano wire/tube array, the fluid barrier, the through holes, etc. used in the seventh embodiment may be the same as or similar to those described above, and thus will not be repeated here.
The filter chip of the present application may be prepared by physical and chemical methods, for example, chemical growth methods, physical processing methods, and the like, and in particular, MEMS (micro electro mechanical system, microelectromechanical Systems) methods, and the like.
For example, referring to fig. 16, in an eighth embodiment of the present application, a process for preparing a filter chip may include the following steps:
S1: providing a patterned photoresist mask on one side surface (defined as a first surface a) of a substrate (e.g., a silicon wafer);
s2: etching the first surface of the substrate to form a plurality of vertical nanowires disposed at intervals from each other on the first surface of the substrate, and then removing the first photoresist mask;
s3: coating soluble or corrodible organic matters and/or inorganic matters on the first surface of the substrate, and filling gaps among the vertical nanowires with the organic matters and/or inorganic matters to form a sacrificial layer;
s4: setting photoresist on the sacrificial layer and performing photoetching;
s5: etching the sacrificial layer to expose the tops of the plurality of vertical nanowires distributed in the second area of the first surface of the substrate, and then removing the photoresist;
s6: providing a photoresist mask on a first surface of the substrate, and exposing a region on the first surface of the substrate corresponding to the fluid barrier;
s7: depositing a fluid barrier in the exposed region corresponding to the fluid barrier;
s8: stripping to remove the photoresist;
s9: providing a patterned etch mask on a second surface of the substrate;
S10: etching the other side surface (defined as a third surface b) of the substrate opposite to the first surface until the sacrificial material filled between the adjacent vertical nanowires is exposed, so as to form a slot on the third surface of the substrate, wherein the position of the slot corresponds to a first area of the first surface of the substrate, and a second area of the first surface of the substrate is arranged around the first area;
s11: and removing the etching mask and the sacrificial material filled between the vertical nanowires to obtain the filter chip.
The etching method adopted in the foregoing steps may be photolithography, mechanical etching, dry etching, wet etching, or the like.
For example, in the aforementioned step S1, the method of forming a patterned (nanopatterned) photoresist mask includes: photolithography, nanosphere masking, nano (metal) particle masking, and the like, and are not limited thereto.
For example, in the foregoing step S2, the vertical nanowire array may be etched by means known in the art, such as RIE, ICP, wet etching, electrochemical etching, etc.
For example, in the aforementioned step S3, the filled soluble organic matter may be a photoresist or the like or a corrodible inorganic matter such as metal, siO 2 Silicon nitride, and the like.
For example, in the foregoing step S10, the slots may be etched by means known in the art, such as RIE, ICP, wet etching, electrochemical etching, and the like.
Obviously, the preparation process of the filter chip is simple and controllable, and is suitable for mass production.
Referring to fig. 17, in a ninth embodiment of the present application, a process for manufacturing a filter chip may include the following steps:
s1: growing a plurality of vertical nanowires/tubes disposed in spaced relation to each other on a first surface of a substrate (e.g., a silicon wafer);
s2: coating a soluble or corrodible organic matter and/or inorganic matter on the first surface of the substrate, and filling gaps among the vertical nanowires/tubes with the organic matter and/or inorganic matter to form a sacrificial layer;
s3: setting photoresist on the sacrificial layer and performing photoetching;
s4: etching the sacrificial layer to expose the tops of the plurality of vertical nanowires distributed in the second area of the first surface of the substrate, and then removing the photoresist;
s5: providing a photoresist mask on a first surface of the substrate, and exposing a region on the first surface of the substrate corresponding to the fluid barrier;
S6: depositing a fluid barrier in the exposed region corresponding to the fluid barrier;
s7: stripping to remove the photoresist;
s8: providing a patterned etching mask on a third surface of the substrate opposite the first surface;
s9: etching the third surface of the substrate until the sacrificial material filled between the adjacent vertical nanowires is exposed, so that a slot is formed on the third surface of the substrate, the position of the slot corresponds to a first area of the first surface of the substrate, and a second area of the first surface of the substrate is arranged around the first area;
s10: and removing the etching mask and the sacrificial material filled between the vertical nanowires to obtain the filter chip.
The manner in which the vertical nanowires/tubes are grown in the foregoing steps may be selected from a variety of manners known in the art, such as MOCVD, PECVD, electrochemical deposition, and the like.
The etching method adopted in the foregoing steps may be photolithography, mechanical etching, dry etching, wet etching, or the like.
For example, the method of forming a patterned (nanopatterned) photoresist mask in the foregoing steps includes: photolithography, nanosphere masking, nano (metal) particle masking, and the like, and are not limited thereto.
For example, the substrate may be etched in the foregoing steps by means known in the art, such as RIE, ICP, wet etching, electrochemical etching, and the like.
For example, in the foregoing step, the filled soluble organic matter may be a photoresist or the like or a corrodible inorganic matter such as metal, siO 2 SiN, etc.
Referring to fig. 18, in a tenth embodiment of the present application, a filter chip includes a substrate 801, the substrate 801 has a first surface 8011 and a second surface 8012 opposite to each other, a plurality of through holes 804 serving as fluid channels are distributed in a first area 8013 on the substrate 801, an array formed by arranging a plurality of micro/nano sheets 803 (micro sheets and/or nano sheets) in parallel is disposed in a second area 8014 on the first surface, a local area on top of the plurality of micro/nano sheets 803 distributed around the through holes 804 is connected to a fluid blocking portion 802, and the fluid blocking portion 802 is disposed above a fluid inlet of the through holes 804, so that a fluid to be processed cannot bypass the micro/nano sheet array and directly enter the through holes 804.
The micro/nano sheets have a thinner thickness, so that the micro/nano sheets can be densely arranged on the first surface of the substrate, and grooves (which can be called micro channels) with opening parts with selected sizes can be formed by adjusting the spacing between the micro/nano sheets, so that particles with different particle size ranges in fluid can be removed.
The substrate 801 may have a larger thickness, so that the substrate may form a better support for the micro/nano sheet array, and may further enhance the mechanical strength of the filter chip, so that the filter chip may be pressure-resistant, bending-resistant, collision-resistant, impact-resistant, and further may be applied in various environments without damage, for example, may be applied in treating high-pressure and high-speed fluid, which is not achieved by the existing porous membrane.
The material selection range of each part (801, 802, 803, 804) of the filter chip is various, and the filter chip can be inorganic materials or organic materials, such as metals, nonmetallic inorganic materials, plastics, ceramics, semiconductors, glass, polymers and the like. When inorganic materials are selected for these parts, the filter chip also has the property of resisting temperature change, and can process high-temperature and low-temperature fluids.
The fluid blocking part can be sheet-shaped, and the thickness and the like of the fluid blocking part can be adjusted according to practical application requirements.
Further, in this embodiment, more than one supporting body may be symmetrically or asymmetrically disposed around the through hole, and by using the supporting body, the supporting of the fluid blocking portion may be further increased, so as to achieve a more firm and stable fit between the fluid blocking portion and the substrate, and may effectively protect the micro/nano sheet array distributed between the fluid blocking portion and the substrate, so as to avoid the problems of collapse and damage of the micro/nano sheet caused by extrusion of the micro/nano sheet array after the fluid blocking portion and/or the substrate are subjected to an external force.
The support body may be in various forms, for example, may have a rectangular, trapezoidal, stepped cross section, etc., and is not limited thereto. In some specific embodiments of this tenth embodiment, the support body may be a boss or the like formed to protrude upward from the edge portion of the through hole, and an upper end thereof is supported to be connected to the fluid blocking portion.
The number, diameter, distribution density and the like of the supporting bodies can be adjusted according to actual needs, but the space occupying the first surface of the matrix is as small as possible, so that the large influence on the fluid flux of the micro/nano sheet array is avoided.
The filter chip with the design can be cleaned (ultrasonically) and used for multiple times, and still has good fluid processing capability.
When the filter chip is used for treating the fluid, the fluid containing impurity particles enters the micro/nano sheet array, particles (or some droplets incompatible with the fluid, such as water droplets in air or water droplets in oil) with the particle size larger than a certain value are blocked outside the micro/nano sheet array, and then the fluid reaches the entrance of the through hole 104 through the groove between each micro/nano sheet and then enters the through hole 104, so that the purification of the fluid and/or the enrichment recovery of the required particles (droplets) are realized.
Referring to fig. 18 to fig. 19 again, in some specific application schemes of the tenth embodiment, the thickness of the foregoing micro/nano sheets may be 1nm to 50 μm, the height may be 50nm to 200 μm, and the width of the groove between adjacent micro/nano sheets may be 1nm to 50 μm. The aperture of the through hole 804 may be 1 μm to 1mm. The thickness of the substrate may be above 1 μm. The thickness of the fluid barrier may be 0.5 [ mu ] m to 200 [ mu ] m.
The cross-section of the trench formed before the adjacent micro/nano-sheets may be regular or irregular in shape, and may be polygonal (triangular, quadrangular or otherwise), circular, elliptical, star-shaped, or the like, for example.
The aforementioned micro/nanoplatelets may be regularly or irregularly, homogeneously or non-homogeneously distributed on the first surface of the substrate.
In addition, in this tenth embodiment, the shape (particularly, the shape of the longitudinal or transverse cross section) of the aforementioned through hole 804 and the fluid barrier 802 may be various, and may be, for example, circular, square, rectangular, or other shapes.
Referring to fig. 20, preferably, in an eleventh embodiment of the present application, a filter chip includes a substrate 901, where the substrate 901 has a first surface and a second surface opposite to each other, and a plurality of through holes 904 serving as fluid channels are distributed on the substrate 901, and an array of micro/nano sheets 903 extending continuously in a lateral direction is disposed on the first surface, where grooves for allowing a fluid to pass through are formed between the micro/nano sheets, and an opening of the grooves is larger than 0 but smaller than a particle size of a selected particle mixed in the fluid to be treated, and a plurality of micro/nano sheets directly pass through the through holes 904, so that the micro/nano sheets and the substrate cooperate to form a fluid channel communicating with the through holes 904, and the fluid to be treated can only enter the through holes 904 through the fluid channel.
Further, in this embodiment, a fluid blocking portion 902 may be further connected to the micro/nano sheet array, and the fluid blocking portion 902 is disposed above the fluid inlet of the through hole 904, so that the fluid to be treated cannot bypass the micro/nano sheet array and directly enter the through hole 904.
Further, one or several supports may also be provided around the through hole 904.
The structures, arrangement forms, materials, etc. of the substrate, micro/nano-sheet array, fluid barrier, through hole, support, etc. used in the eleventh embodiment may be the same as or similar to those described above, and thus will not be repeated here.
In an eleventh embodiment of the present application, the filter chip may have a similar structure to the first and second embodiments, and is different in that one or more support beams, for example, a plurality of support beams arranged symmetrically or asymmetrically, may be further erected on the through hole, and the support beams may further increase the support for the fluid blocking portion, so as to achieve a more firm and stable fit between the fluid blocking portion and the substrate, and may effectively form a protection for the micro/nano sheet array distributed between the fluid blocking portion and the substrate, so as to avoid the problems of collapse, damage, etc. of the micro/nano sheet caused by the extrusion of the fluid blocking portion and/or the substrate to the micro/nano sheet array after the fluid blocking portion and/or the substrate are subjected to an external force.
The support beam may be in various forms, for example, may be in an arch shape, etc., and is not limited thereto. And further the support beam may also be fitted with other supports, such as those described in the second embodiment.
The number, the size, the distribution density and the like of the supporting beams can be adjusted according to actual needs, but the fluid inlets of the through holes are shielded as little as possible, so that the large influence on the fluid flux of the filter chip is avoided.
The structures, arrangement forms, materials, etc. of the substrate, the micro/nanowire array, the fluid barrier, the through holes, etc. used in the eleventh embodiment may be the same as or similar to those described above, and thus will not be repeated here.
Referring to fig. 21, in a twelfth embodiment of the present application, a filter chip may have a similar structure to any of the tenth and eleventh embodiments, except that: a layer 1105 of photocatalytic material is also disposed on the surface of the nanoplatelets 1103 and the first surface of the substrate 1101. When the fluid is treated by the filter chip comprising the photocatalytic material layer 1105, if ultraviolet irradiation and the like are used, some organic pollutants and the like in the fluid can be subjected to photocatalytic degradation, so that multiple purification of the fluid is realized.
Wherein, in order to facilitate light penetration, some or all of the fluid barrier 1102, the substrate, and the protrusions may be made of transparent materials. In some embodiments of the present example, the fluid barrier may be integrally formed of a transparent material, such as light injection.
Among them, the photocatalytic material may be titanium dioxide or the like, but is not limited thereto.
Wherein, to form the photocatalytic material layer 1105, those skilled in the art can use various ways known in the art, such as coating (spin coating, spray coating, printing, etc.), physical or chemical vapor deposition (such as MOCVD, PECVD, atomic layer deposition, etc.), sputtering, etc., and are not limited thereto.
Wherein the thickness of the photocatalytic material layer 1105 may be controlled to be on the order of nanometers to minimize its effect on the fluid flux of the filter chip.
The structures, arrangement forms, materials, etc. of the substrate, the micro/nanowire array, the fluid barrier, the through holes, etc. used in the twelfth embodiment may be the same as or similar to those described above, and thus will not be repeated here.
Referring to fig. 22, in a thirteenth embodiment of the present application, a filter chip may have a similar structure to any of the tenth, eleventh and twelfth embodiments, except that: an antimicrobial material layer 1205 is also disposed on the surface of the nanoplatelets 1203 and on the first surface of the substrate 1201. When the fluid is treated by the filter chip including the antibacterial material layer 1205, bacteria, viruses and the like in the fluid can be killed simultaneously during the treatment of the fluid, thereby realizing multiple purification of the fluid.
Among them, a more typical antibacterial material may be a noble metal such as Au, ag, etc., but is not limited thereto.
Wherein, to form the antibacterial material layer 1205, those skilled in the art can use various ways known in the art, such as coating (spin coating, spray coating, printing, etc.), physical or chemical vapor deposition (such as MOCVD, PECVD, atomic layer deposition, etc.), sputtering, etc., and are not limited thereto.
Wherein the thickness of the antimicrobial material layer 1205 can be controlled at the nanometer level to minimize its effect on the fluid flux of the filter chip.
The structures, arrangement forms, materials, etc. of the substrate, the micro/nanowire array, the fluid barrier, the through holes, etc. used in the thirteenth embodiment may be the same as or similar to those described above, and thus will not be repeated here.
The filter chip of the present application may be prepared by physical and chemical methods, for example, chemical growth methods, physical processing methods, and the like, and in particular, MEMS (micro electro mechanical system, microelectromechanical Systems) methods, and the like.
In a fourteenth embodiment of the present application, a process for preparing a filter chip may include the steps of:
s1: providing a patterned photoresist mask on one side surface (designated as a first surface) of a substrate (e.g., a silicon wafer);
S2: etching the first surface of the substrate to form a plurality of vertical nano-sheets extending in a lateral direction at intervals from each other on the first surface of the substrate, and then removing the first photoresist mask;
s3: coating soluble or corrodible organic matters and/or inorganic matters on the first surface of the substrate, and filling the grooves among the vertical nano sheets with the organic matters and/or inorganic matters to form a sacrificial layer;
s4: setting photoresist on the sacrificial layer and performing photoetching;
s5: etching the sacrificial layer to expose the tops of the plurality of vertical nano-sheets distributed in the second area of the first surface of the substrate, and then removing the photoresist;
s6: providing a photoresist mask on a first surface of the substrate, and exposing a region on the first surface of the substrate corresponding to the fluid barrier;
s7: depositing a fluid barrier part in the exposed area corresponding to the fluid barrier part, and stripping to remove the photoresist;
s8: a patterned etching mask is arranged on the other side surface (named as a third surface) of the substrate, which is opposite to the first surface, and then the other side surface of the substrate is etched until the sacrificial material filled between the adjacent vertical nano sheets is exposed, so that a slot hole is formed on the other side surface of the substrate, the position of the slot hole corresponds to a first area of the first surface of the substrate, and a second area of the first surface of the substrate is arranged around the first area;
S9: and removing the etching mask and the sacrificial material filled between the vertical nano-sheets to obtain the filter chip.
The etching method adopted in the foregoing steps may be photolithography, mechanical etching, dry etching, wet etching, or the like.
For example, in the aforementioned step S1, the method of forming a patterned (nanopatterned) photoresist mask includes: photolithography, nanosphere masking, nano (metal) particle masking, and the like, and are not limited thereto.
For example, in the foregoing step S2, the vertical nanoplatelet array may be etched by means known in the art, such as RIE, ICP, wet etching, electrochemical etching, etc.
For example, in the aforementioned step S3, the filled soluble organic matter may be a photoresist or the like or a corrodible inorganic matter such as metal, siO 2 SiN, etc.
For example, in the foregoing step S8, the slots may be etched by means known in the art, such as RIE, ICP, wet etching, electrochemical etching, etc.
Referring to fig. 23, in a fifteenth embodiment of the present application, a filter chip is mainly used for treating a fluid mixed with selected particles, and includes a substrate 1300, the substrate 1300 has a first surface 1301 and a second surface 1302 opposite to each other, and a plurality of through holes 1303 serving as fluid channels are distributed on the substrate 1300. Within any one of the through holes 1303 are distributed a number of micro/nanowires/tubes 1400 (i.e. any one or more of micro-wires, micro-tubes, nanowires, nanotubes), in particular nanowires/tubes (nanowires and/or nanotubes). One end of the micro/nano wire/tube 1400 is fixed on the wall of the through hole 1303, and the other end extends along the radial direction of the through hole. These micro/nanowires/tubes 2 are aggregated into a porous structure in the form of interdigitation. The pores within the porous structure have a diameter greater than 0 a but less than the particle size of the selected particles.
Referring to fig. 24, the porous structure is a grid structure distributed in the through holes 1303 from a top view.
The micro/nano wires/tubes 1400 have a larger height-diameter ratio (or length-diameter ratio), so that the micro/nano wires/tubes 1400 can be densely arranged in the through holes, particles with different particle size ranges in the fluid 1500 can be removed by adjusting the distribution density, the length and the like of the micro/nano wires/tubes 1400, and particularly, when the nano wires/tubes are adopted, the pore diameters of holes formed by the crossing of the nano wires/tubes are controlled to be in the nano level, so that not only very small particles in the fluid can be removed, but also the resistance to the fluid can be controlled to be at a very low level due to the extremely small diameter of the nano wires/tubes, and a very large fluid flux can be formed, which is far superior to the existing porous membrane, the filter chip based on the transverse flow channel and the like.
The substrate 1300 may have a larger thickness, so as to further enhance the mechanical strength of the filter chip, so that the filter chip is pressure-resistant, bending-resistant, collision-resistant, impact-resistant, and further may be applied in various environments without damage, for example, may be applied to treatment of high-pressure and high-speed fluid, which is not achieved by the existing porous membrane.
In particular, since the micro/nano wires/tubes 1400 are all distributed in the through holes 1303, the micro/nano wires/tubes 1400 are actually protected by the substrate 1300, and even if the filter chip is subjected to pressure, the micro/nano wires/tubes 1400 are not damaged.
The material selection ranges of the parts (1301, 1302, 1303) of the filter chip are various, and the filter chip can be made of inorganic materials or organic materials, such as metals, ceramics, polymers, and the like. When inorganic materials are selected for these parts, the filter chip also has the property of resisting temperature change, and can process high-temperature and low-temperature fluids.
The filter chip with the design can be cleaned (ultrasonically) and used for multiple times, and still has good fluid processing capability.
When the fluid is treated by the filter chip, the fluid containing impurity particles enters the porous structure, particles (or some droplets incompatible with the fluid, such as droplets in air or droplets in oil) with particle sizes larger than a certain value are blocked outside the porous structure, and then the fluid flows out of the through holes 1303, so that the fluid is purified and/or the needed particles (droplets) are enriched and recovered.
In some specific applications of this embodiment, the diameter of the foregoing micro/nanowire/tube 1400 may be 1nm to 500 μm.
In some specific application schemes of this embodiment, the hole diameter of the through hole 1303 may be 1 μm to 1mm.
In some specific applications of this embodiment, the thickness of the aforementioned substrate may be above 1 μm.
The transverse cross-sectional structure of the aforementioned nanowires may be regular or irregular in shape, for example, polygonal (triangular, quadrangular or otherwise), circular, elliptical, star-shaped, etc.
The micro/nano wires/tubes 1400 may be regularly or irregularly, uniformly or non-uniformly distributed within the through holes 1303.
The micro/nanowire/tube 1400 may preferably be selected from the group consisting of carbon nanowires, carbon nanotubes, znO nanowires, gaN nanowires, and TiO 2 Nanowires, ag nanowires, au nanowires, and the like, and are not limited thereto.
The micro/nano wires/tubes 1400 may be formed by external transfer, in situ growth (e.g. chemical growth, electrochemical growth) or deposition (e.g. physical, chemical vapor deposition, electrodeposition), etc. on the inner wall of the through holes 1303.
The shape of the aforementioned through holes 1303 (in particular, the shape of the transverse cross section) may be various, and may be, for example, circular, square, rectangular, diamond-shaped, polygonal, or other regular or irregular shapes.
In some specific applications of this embodiment, the micro/nano wire/tube 1400 may be formed of a photocatalytic material or a material having an antibacterial and bactericidal function, or the micro/nano wire/tube 1400 may be coated with a photocatalytic material or a material having an antibacterial and bactericidal function.
For example, the micro/nanowire/tube 1400 may be a nanowire having photocatalytic properties such as ZnO nanowire, gaN nanowire, or TiO2 nanowire, and may be capable of degrading organic substances in a fluid under light-assisted irradiation.
For example, the foregoing micro/nanowires/tubes 1400 may employ Ag nanowires, au nanowires, etc. to kill bacteria, viruses, microorganisms in the fluid.
In some specific applications of this embodiment, the surface of the substrate 1300, particularly the first surface 1301 thereof, may further be provided with a layer of photocatalytic material or an antibacterial material, etc.
When the fluid is treated by the filter chip containing the photocatalytic material layer, if ultraviolet irradiation and the like are used, some organic pollutants and the like in the fluid can be subjected to photocatalytic degradation, so that multiple purification of the fluid is realized.
Wherein, in order to facilitate light penetration, part or all of the components in the filter chip can be made of transparent materials.
Among them, the photocatalytic material may be titanium dioxide or the like, but is not limited thereto.
Wherein, for forming the photocatalytic material layer, a person skilled in the art may use various ways known in the art, such as coating (spin coating, spray coating, printing, etc.), physical or chemical vapor deposition (such as MOCVD, PECVD, atomic layer deposition, etc.), sputtering, etc., and is not limited thereto.
Wherein the thickness of the photocatalytic material layer can be controlled at the nanometer level to minimize its effect on the fluid flux of the filter chip.
When the fluid is treated by the filter chip containing the antibacterial material layer, bacteria, viruses and the like in the fluid can be killed synchronously in the treatment process of the fluid, so that multiple purification of the fluid is realized.
Among them, a more typical antibacterial material may be a noble metal such as Au, ag, etc., but is not limited thereto.
Among them, for forming the antibacterial material layer, those skilled in the art may use various means known in the art, such as coating (spin coating, spray coating, printing, etc.), physical or chemical vapor deposition (such as MOCVD, PECVD, atomic layer deposition, etc.), sputtering, etc., and are not limited thereto.
Wherein the thickness of the antimicrobial material layer can be controlled at the nanometer level to minimize its effect on the fluid flux of the filter chip.
As one of the preferred embodiments of this example, a plurality of standing nanowires spaced apart from each other may also be provided on the first surface of the substrate, and the nanowires may be provided around the aforementioned through-holes as fluid passages.
More preferably, the aspect ratio of these upstanding nanowires is 4: 1-200000: 1, the ratio of the distance between adjacent vertical nanowires to the length of the vertical nanowires is 1: 4-1: 200000.
by adopting the vertical nanowire with the structure and the distribution form, a plurality of vertical nanowires can be densely arranged (the proportion of the raised part per se in the unit area is small), so that the treatment of tiny particles in fluid is facilitated, and meanwhile, the filtration chip is endowed with larger fluid flux (the pores among the vertical nanowires are larger than the volume of the vertical nanowire per se).
Preferably, the upstanding nanowire may have the same material, size, structure, etc. as the micro/nanowire/tube 1400 described above.
Particularly, if the technical scheme known in the industry is referred to, the arrangement density of the upright nanowires and the like are properly designed to form a nanowire array, and the nanowire array can also form a super-hydrophobic structure and a super-oleophobic structure, so that particles in fluid can be removed, and blocked particles can not be accumulated on the surface of the filter chip through self-cleaning.
Wherein, the substrate can have a larger thickness, so that the upright nanowire can be well supported.
As one of the preferred embodiments of this example, a fluid barrier may be further provided on the aforementioned upright nanowires, which may have a surface (which may be named a third surface) disposed opposite to the first surface of the substrate, and the plurality of upright wires are fixedly provided at one end to the first surface of the substrate and at the other end fixedly connected to the third surface of the fluid barrier, wherein a distance between adjacent upright wires is greater than 0 but less than a particle size of the selected particles.
The fluid blocking portion may have various forms, for example, a sheet shape, a thin shell shape, a rectangular body shape, a polyhedral shape, or the like.
Preferably, the vertical nanowires, the fluid blocking portion and the substrate cooperate to form a fluid channel, and the fluid to be treated can only enter the fluid inlet of the fluid channel (through hole 1303) distributed on the first surface of the substrate through the fluid channel, so as to implement the first treatment of the fluid, and then enter the fluid channel distributed on the substrate, and the aggregate of the micro/nano wires/tubes 1400 is used for the second treatment, so that multiple treatments of the fluid can be implemented.
The step treatment of particles of different sizes in the fluid can be realized by designing the pitch of the vertical nanowires to be different from the pore diameter of the pores formed by crossing the micro/nanowires/tubes 1400, in particular, by making the pitch between the vertical nanowires larger than the pore diameter of the pores formed by crossing the micro/nanowires/tubes 1400.
The fluid blocking portion may be disposed in various manners, for example, may be disposed entirely at a distance from the base body, may be partially connected to the base body, or may be integrally formed with the base body in some cases.
Wherein the fluid inlet of the fluid channel (through hole 1303) and the plurality of upright nanowires may be distributed in an orthographic projection of the fluid barrier on the first surface of the substrate.
The shape of the aforementioned fluid barrier may be varied, for example, circular, square, rectangular or other shapes.
The material of the fluid barrier may be selected from metal, nonmetal, organic material, inorganic material, etc., such as silicon wafer, polymer, ceramic, etc., but is not limited thereto.
Preferably, the photocatalytic material, the sterilizing material, and the like may be distributed on the surface of the fluid blocking portion, or the surface of the fluid blocking portion may be entirely composed of the photocatalytic material, the sterilizing material, and the like.
Preferably, the fluid blocking portion may have a partially transparent structure or be entirely transparent, for example, for light injection.
The filter chip of the present application may be prepared by physical and chemical methods, for example, chemical growth methods, physical processing methods, and the like, and in particular, MEMS (micro electro mechanical system, microelectromechanical Systems) methods, and the like.
For example, referring to fig. 25, in a sixteenth embodiment of the present invention, a process for manufacturing a filter chip may include the steps of:
s1: providing a patterned photoresist mask on a first surface of a substrate (e.g., a silicon wafer) comprising lithographically patterning micro-nano scale lines;
s2: etching the first surface of the substrate by using the photoresist mask, so as to form a plurality of through holes penetrating through the first surface of the substrate and a second surface opposite to the first surface, wherein the through holes are used as fluid channels;
s3: depositing a seed layer for micro/nanowire/tube growth on an inner wall of a fluid channel and a first surface of the substrate;
s4: forming a plurality of micro/nano wires/tubes on the seed layer, controlling the growth conditions of the micro/nano wires/tubes, thereby forming a plurality of vertical micro/nano wires/tubes which are spaced from each other on the first surface of the substrate, and forming a plurality of micro/nano wires/tubes which extend along the radial direction in the fluid channel, wherein the plurality of micro/nano wires/tubes in the fluid channel are intersected with each other to form a micro/nano-scale crossed grid;
S5: removing micro/nanowires/tubes (which may also remain) distributed on the first surface of the substrate;
s6: scribing and packaging to obtain the filter chip.
The etching method adopted in the foregoing steps may be photolithography, mechanical etching, dry etching, wet etching, or the like.
For example, in the foregoing steps, a method of forming a patterned (nanopatterned) photoresist mask includes: photolithography, nanosphere masking, nano (metal) particle masking, and the like, and are not limited thereto.
For example, in the foregoing steps, the fluid channels may be etched by means known in the art, such as RIE, ICP, wet etching, electrochemical etching, and the like.
The foregoing detailed description will set forth only for the purposes of illustrating the general principles and features of the invention, and is not meant to limit the scope of the invention in any way, but rather should be construed in view of the appended claims.

Claims (12)

1. A nasal plug respirator, comprising:
the nose plug comprises a nose plug and a filter chip, wherein at least one end part of the nose plug can be inserted into a nasal cavity of a user, the nose plug comprises a gas channel communicated with the nasal cavity, the filter chip is used for filtering particles which are mixed in airflow to be treated and have a particle size larger than a set value, and the air to be treated flows through the filter chip and then enters the gas channel in the nose plug;
The filter chip protection structure is used for protecting the filter chip and comprises a first fixed hard filter screen and a second fixed hard filter screen, and the filter chip is arranged between the first fixed hard filter screen and the second fixed hard filter screen;
wherein, filter the chip and include:
a substrate having a fluid passageway therein and a plurality of fluid channels,
the air treatment device comprises a fluid channel, a plurality of linear bodies, a plurality of vertical linear bodies and a substrate, wherein the fluid channel is provided with a plurality of holes, the holes are used for treating air mixed with selected particles, one end of each linear body is fixedly connected with the inner wall of the fluid channel, the other end of each linear body extends along the radial direction of the fluid channel, the plurality of linear bodies are gathered into a porous structure in a mutually crossed mode, the porous structure is a grid structure distributed in the fluid channel in a top view, the diameters of holes in the porous structure are larger than 0 and smaller than the particle diameter of the selected particles, the first surface of the substrate is also provided with a plurality of vertical linear bodies which are arranged at intervals, and the plurality of vertical linear bodies are arranged around the fluid channel;
the wire-shaped body is a nanowire, and the pore diameter of a hole formed by the crossing of the nanowire is controlled at the nanometer level.
2. A nasal plug respirator according to claim 1, wherein: the nasal obstruction type respirator further comprises a first filtering fabric and/or a second filtering fabric, wherein the first filtering fabric is distributed between the nasal obstruction and the filtering chip, and the filtering chip is distributed between the second filtering fabric and the nasal obstruction.
3. A nasal plug respirator according to claim 1, wherein: the nasal plug type respirator further comprises a first detachable hard filter screen and/or a second detachable hard filter screen, wherein the first detachable hard filter screen is fixedly connected with the first filter fabric, and the second detachable hard filter screen is fixedly connected with the second filter fabric.
4. A nasal plug respirator according to claim 1, wherein: the nose plug adopts a waist drum type nose plug.
5. A nasal plug respirator according to claim 1, wherein: the nasal obstruction type respirator also comprises a shell with two open ends, the nasal obstruction is detachably arranged at one end of the shell, and the filter chip is accommodated in the shell.
6. A nasal plug respirator according to claim 1, wherein: the substrate is provided with a first surface and a second surface which are opposite to each other, and the air inlets of the fluid channels are distributed on the first surface of the substrate.
7. A nasal plug type respirator according to claim 6, wherein: the first surface of the matrix is also provided with a functional material layer, and the material of the functional material layer comprises a photocatalytic material or an antibacterial material.
8. A nasal plug respirator according to claim 1, wherein: at least part of the components in the filter chip have a transparent structure.
9. A nasal plug respirator according to claim 1, wherein: the aperture of the fluid channel is 1 mu m-1 mm.
10. A nasal plug respirator according to claim 1, wherein: the thickness of the matrix is more than 1 mu m.
11. A nasal plug respirator according to claim 1, wherein: the linear body comprises a carbon nanowire, a ZnO nanowire, a GaN nanowire and TiO 2 Any one or a combination of two or more of nanowires, ag nanowires and Au nanowires.
12. A nasal plug respirator according to claim 1, wherein: at least the surface of the linear body is also distributed with photocatalysis material or antibacterial material.
CN202210478024.2A 2016-06-07 2016-06-07 Nasal obstruction type respirator Active CN114733098B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210478024.2A CN114733098B (en) 2016-06-07 2016-06-07 Nasal obstruction type respirator

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210478024.2A CN114733098B (en) 2016-06-07 2016-06-07 Nasal obstruction type respirator
CN201610399521.8A CN107469246B (en) 2016-06-07 2016-06-07 Nose plug type respirator

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201610399521.8A Division CN107469246B (en) 2016-06-07 2016-06-07 Nose plug type respirator

Publications (2)

Publication Number Publication Date
CN114733098A CN114733098A (en) 2022-07-12
CN114733098B true CN114733098B (en) 2023-06-27

Family

ID=60593417

Family Applications (6)

Application Number Title Priority Date Filing Date
CN202210477956.5A Active CN114796918B (en) 2016-06-07 2016-06-07 Nasal obstruction type respirator
CN202210478024.2A Active CN114733098B (en) 2016-06-07 2016-06-07 Nasal obstruction type respirator
CN201610399521.8A Active CN107469246B (en) 2016-06-07 2016-06-07 Nose plug type respirator
CN202210477854.3A Active CN114733097B (en) 2016-06-07 2016-06-07 Nasal obstruction type respirator
CN202210478272.7A Active CN114796919B (en) 2016-06-07 2016-06-07 Nose plug type respirator
CN202210478025.7A Active CN114733099B (en) 2016-06-07 2016-06-07 Nasal obstruction type respirator

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN202210477956.5A Active CN114796918B (en) 2016-06-07 2016-06-07 Nasal obstruction type respirator

Family Applications After (4)

Application Number Title Priority Date Filing Date
CN201610399521.8A Active CN107469246B (en) 2016-06-07 2016-06-07 Nose plug type respirator
CN202210477854.3A Active CN114733097B (en) 2016-06-07 2016-06-07 Nasal obstruction type respirator
CN202210478272.7A Active CN114796919B (en) 2016-06-07 2016-06-07 Nose plug type respirator
CN202210478025.7A Active CN114733099B (en) 2016-06-07 2016-06-07 Nasal obstruction type respirator

Country Status (1)

Country Link
CN (6) CN114796918B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111054185B (en) * 2020-01-17 2024-01-23 广东工业大学 Toxic gas adsorption device and preparation method thereof
CN111202865A (en) * 2020-03-12 2020-05-29 优仕康生（天津）科技发展有限公司 Rhinobyon type Pi-shaped four-way ultraviolet breathing sterilizer
CN111729402B (en) * 2020-05-06 2022-07-12 青岛大学 Electroactive air filtering material and preparation method thereof

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997031703A1 (en) * 1996-02-28 1997-09-04 Hoya Corporation Glass material for carrying a photocatalyst, filter device using the same and light irradiating method
US6524488B1 (en) * 1998-06-18 2003-02-25 3M Innovative Properties Company Method of filtering certain particles from a fluid using a depth loading filtration media
US6267251B1 (en) * 1997-12-18 2001-07-31 Lexmark International, Inc. Filter assembly for a print cartridge container for removing contaminants from a fluid
CN2331379Y (en) * 1998-06-08 1999-08-04 马丹 Nasal filter
CN2610958Y (en) * 2003-03-28 2004-04-14 陈君武 Inserting into noose type anti poison gas filtering device
US8025960B2 (en) * 2004-02-02 2011-09-27 Nanosys, Inc. Porous substrates, articles, systems and compositions comprising nanofibers and methods of their use and production
DE102006041038A1 (en) * 2006-03-31 2007-10-04 Weinmann Geräte für Medizin GmbH + Co. KG Mask e.g. nasal mask, for e.g. respiration, has structural parts such as mask base body, connecting piece and securing ring, formed in modular system and developed such that structural parts are used for different types of masks
CN2925521Y (en) * 2006-06-17 2007-07-25 赵大文 Nasal-cavity filtering protector
AU2010212282A1 (en) * 2009-08-13 2011-03-03 Crowe, Julie Improved Respirator
CN201664477U (en) * 2010-03-23 2010-12-08 田振杰 Dust-free plug for noses
US20120255375A1 (en) * 2011-04-11 2012-10-11 LMS Technologies, Inc. Apparatuses and methods for capturing and retaining particles
CN202569235U (en) * 2012-06-12 2012-12-05 姜杨 Novel nose plug
CN103111127B (en) * 2013-03-01 2014-09-03 江苏物联网研究发展中心 PM 2.5 filtration structure and preparation method thereof
CN103657276B (en) * 2013-12-23 2016-02-10 北京大学 A kind of Fine particulate matter filter structure and preparation method thereof
JP6229515B2 (en) * 2014-01-28 2017-11-15 大日本印刷株式会社 Filter and manufacturing method thereof
CN105013102A (en) * 2014-04-28 2015-11-04 吴凤松 Hidden healthy breathing machine
CN206880966U (en) * 2016-06-07 2018-01-16 杨国勇 Nasal obstruction type respirator

Also Published As

Publication number Publication date
CN107469246A (en) 2017-12-15
CN114733099B (en) 2023-06-23
CN114796919B (en) 2023-04-18
CN114733097B (en) 2023-06-27
CN114733099A (en) 2022-07-12
CN114733097A (en) 2022-07-12
CN114796919A (en) 2022-07-29
CN107469246B (en) 2022-05-27
CN114733098A (en) 2022-07-12
CN114796918A (en) 2022-07-29
CN114796918B (en) 2023-06-27

Similar Documents

Publication Publication Date Title
CN114733098B (en) Nasal obstruction type respirator
JP2017070949A (en) Electronic air purifier, its associated system, and method therefor
JP2009514667A (en) Filter for removal of physical and / or biological impurities
US20240024809A1 (en) Porous Materials For Treating Contaminants
WO2017211215A1 (en) Fluid processing device and preparation method therefor
CN210407181U (en) Nano zinc oxide mask combined with graphene
CN206880966U (en) Nasal obstruction type respirator
CN107807001B (en) Filtering performance testing system and method
CN206881319U (en) Fluid treating device
CN107469478B (en) Fluid treatment device and preparation method thereof
CN207153289U (en) Fluid treating device
CN116747614B (en) Fluid treatment device based on porous film
CN116747613A (en) Porous membrane-based fluid treatment device and preparation method thereof
CN206881318U (en) Fluid treating device
CN107473434B (en) Fluid treatment device and preparation method thereof
CN206881305U (en) Fluid treating device
CN107469479B (en) Fluid treatment device
CN116747615A (en) Fluid treatment device based on porous film and preparation process thereof
US20230330578A1 (en) Filtration Apparatus and Method
CN116747614A (en) Fluid treatment device based on porous film
KR200338240Y1 (en) Anit infection mask by permanent electrostatic nanofilter
JP4824809B2 (en) Respiratory nano-level filter structure and manufacturing method thereof
CN206950822U (en) Fluid treating device
JP4846245B2 (en) Air purifier and air conditioner
US20230311039A1 (en) Advanced filtration structures for mask and other filter uses

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant