CN101070250A - Integrated nano carbon-fiber composite porous materila and preparing method - Google Patents
Integrated nano carbon-fiber composite porous materila and preparing method Download PDFInfo
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Abstract
This invention relates to a whole type, nanometer carbon fibre, and compound porosint material and preparation method. The materials includes carbon fibre felt basal body, carbon coating that coat on carbon fibre felt, as well as nanometer carbon fibre grow from carbon coating. The process: soak carbon fibre felt in phenolic resin - ethanol solution with metal salt, take out, removed superfluous solution, heat in the air under 50 to 200deg, then carry out carbonization of phenolic resin under H2 atmosphere, subsequently switch carbonaceous gas, proceed catalysis growth reaction of nanometer carbon fibre in phenolic resin carbide, gain whole type nanometer carbon fibre compound porosint material. This material has high mechanical strength, plenty ventage, large specific surface area, and three kinds carbon stuff binding firmly, nanometer carbon fibre not easy shed from compound material, can used as sorbing material, filter material, catalysis material, electrode material and so on, is a newfashioned whole type carbon quality porosint material.
Description
Technical field
The present invention relates to a kind of Integrated nano carbon-fiber composite porous materila and preparation method.
Background technology
Since the nineties in last century, carbon nano fiber has caused people's extensive concern as a kind of novel carbonaceous material.Carbon nano fiber be a class diameter between 3～200nm, length is that 0.1～1000 μ m does not wait, and has the class graphite material than the quasi-one dimension fibre shape of big L/D ratio, has unique microtexture.
Because the diameter of carbon nano fiber is between CNT (carbon nano-tube) and gas-phase growth of carbon fibre, carbon nano fiber removes has the characteristic such as the low density of gas-phase growth of carbon fibre, high ratio modulus, high specific strength, outside the high conductivity etc., and in structure, performance is also similar to CNT (carbon nano-tube) with aspects such as application, it is few to have defective, compact structure, advantages such as specific surface area is big, so, can be used as catalytic material, sorbing material, electrode materials, electromagnetic shielding material, structural reinforcement material, high efficiency separation materials etc. are at present in aviation, electronics, the energy, catalysis etc. present wide prospect in industrial application in the increasing material field.
Meanwhile, flourish along with nanotechnology, the exploitation of nano composite material and preparation have become the hot issue in material field.No matter nano composite material is character or function, all has incomparable advantage than single-material, thereby becomes a quantum jump in material field.The carbon nano fiber matrix material is carried out design and development, can expand the application approach of carbon nano fiber on the one hand; On the other hand, in some engineering field, as in the Industrial Catalysis process, carbon nano fiber could satisfy filling and the service requirements of Industrial Catalysis reaction unit to catalytic material as necessary self-containedization (moulding of catalysis term meaning) of catalytic material.Carbon nano fiber and the matrix with macrostructure are carried out compound, can make primary pulverous carbon nano fiber possess macroscopical global shape, thereby meet the moulding requirement of carbon nano fiber.So how designing with preparing the carbon nano fiber matrix material is to carry out the problem that must solve in the carbon nano fiber application development process.
To this, document 1 (Zhu Dongbo etc., novel charcoal material, 2002, the 17th the 3rd phase of volume, the 66th～69 page) utilize PAN charcoal fiber acupuncture mat as matrix, method by catalytic chemical gaseous phase deposition, with the ferrocene is catalyzer, grows secondary charcoal fiber on matrix, forms carbon fiber composite.Document 2 (Leon Lefferts, et al, Journal of Materials Chemistry, 2004, the 14th volume, the 1590th～1597 page) be matrix with the trichroite single-column, with nickel is catalyzer, also, on matrix, grow carbon nano fiber, make carbon nano fiber/ceramic composite by the method for catalytic chemical gaseous phase deposition.Document 3 (Chinese patent publication number CN1736585A) then discloses a kind of nano carbon fiber/graphite felt compound catalytic material and preparation method thereof, has obtained the carbon nano fiber matrix material of large specific surface.
But, the above-mentioned document and the technology of patent disclosure, an one significant defective is, the connection of the carbon fiber in carbon nano fiber and the matrix is insecure, and carbon nano fiber comes off from described matrix material easily, and the carbon nano fiber diameter is inhomogeneous, the material property instability that is obtained, or be not suitable for the corrosive atmosphere of acid or alkali, therefore, be unfavorable in large-scale device, using.
Summary of the invention
Technical problem to be solved by this invention provides a kind of novel Integrated nano carbon-fiber composite porous materila and preparation method, to overcome the above-mentioned defective that prior art exists, to adapt to multipath application demand.
Integrated nano carbon-fiber composite porous materila of the present invention is made up of carbon coating that applies on carbon fiber felt matrix, the carbon fiber felt matrix and the carbon nano fiber in the carbon coating;
With carbon fiber felt matrix weight is benchmark, and the weight of carbon coating is 0.05～5 times of matrix weight, more preferably 0.1～3 times, is preferably 0.15～1.5 times;
The weight of carbon nano fiber is 0.1～10 times of matrix weight, more preferably 0.2～8 times, is preferably 0.5～5 times;
Term " coating " refers to " with physics, chemistry or other method, the layer of metal or the nonmetallic tectum that form at substrate material surface ", and (see document 4: Hu passes Xin etc. and writes coating technology principle and application, Chemical Industry Press, 2000, page 1), carbon coating just is meant that coated material is a carbon, as document 5 (Th.Vergunst, et al, Carbon, 2002, the 40th the volume, the 1891-1902 page or leaf) in carbon coating is had more detailed description.
The preparation method of integrated nano carbon-fiber composite porous materila of the present invention comprises the steps:
(1) with soak carbon fibre felt 0.5～5h in containing the resol-ethanolic soln of metal-salt, take out, the centrifugal redundant solution of removing is again under 50 ℃～200 ℃ temperature, in air, heat 0.5～20h, obtain to be coated with the carbon fiber felt of metal-salt and resol;
In the said resol-ethanolic soln that contains metal-salt, the weight concentration of metal-salt is 0.02%～10%, and resol and alcoholic acid weight proportion are 1: 0.2～1: 10;
Carbon fiber felt with the part by weight that contains the resol-ethanolic soln of metal-salt is: 1: 5～1: 500;
Metal-salt comprises solubility nitrate, haloid, carbonate or the vitriol of transition metal, the preferably nitrate of iron, cobalt, nickel or copper, haloid, carbonate or vitriol;
Described resol solid can adopt business-like product, as the SP11 type resol that Shuangshu Plastic Plant, Shanghai produces, is by formaldehyde and phenol reactant synthetic.
Described carbon fiber felt can adopt business-like product, and as the PAN-based carbon fiber felt that the emerging carbon element in Shanghai company limited produces, this is a kind of felt shape material that is formed by the PAN-based carbon fiber braiding.Other carbon fiber commodity also have viscose-based carbon fiber felt and asphalt base carbon fiber felt.The macroshape of carbon fiber felt and size can be carried out cutting as required, as the employing rectangle, and circle etc., thickness is generally 5～10mm.
(2) carbon fiber felt that is coated with metal-salt and resol that step (1) is obtained is placed on and contains 5～95% (volume) H
2Ar gas or N
2In the gas, be warming up to 500 ℃～900 ℃ and keep 1～6h, carry out the carbonization of resol, switch subsequently and feed carbonaceous gas, under 500 ℃～900 ℃ temperature, carry out the catalytic growth reaction of carbon nano fiber in the resol carbide, growth time is 0.5～20h, obtains integrated nano carbon-fiber composite porous materila at last;
Carbonaceous gas is selected from H
2With more than one the mixture in carbon monoxide, methane, ethane, propane, ethene or the propylene gas etc., wherein, H
2Volumetric concentration be 10～90%;
By above-mentioned disclosed technical scheme as seen, the integrated nano carbon-fiber composite porous materila that the inventive method obtained is by three kinds of carbon materials, that is: the carbon fiber felt matrix of macroshape and size, the carbon coating that applies on the carbon fiber felt matrix, and the carbon nano fiber that grows in the carbon coating is formed.Carbon coating among the present invention is to be formed by the resol carbonization, and itself has cohesiveness phenol resin solution, and is tight with the carbon fiber felt bond matrix.And carbon nano fiber is to grow out on the catalyzer in carbon coating, and the root of carbon nano fiber gos deep into carbon coating inside, and both are in conjunction with firmly.So the existence of carbon coating has strengthened the connection of carbon fiber in carbon nano fiber and the matrix, carbon nano fiber is difficult for coming off from described matrix material.
Still not a kind of binding agent of phenol resin solution, or a kind of macromolecular tensio-active agent, have the dispersed catalyst particle and make the effect of its nanometer, thereby guaranteed that the carbon nano fiber that grows is can diameter even on catalyst particle, and high dispersing is on carbon fiber surface, thereby can obtain preparation good reproducibility, stable performance, high-quality integrated nano carbon-fiber composite porous materila.
It all is carbon material that three parts of integrated nano carbon-fiber composite porous materila of the present invention are formed, and three's physics intermiscibility is good, and chemical properties similar is particularly suitable for the corrosive atmosphere of acid or alkali, and high temperature resistant, anti-oxidant.
Carbon nano fiber matrix material of the present invention not only has one-piece construction, can in large-scale device, use, and quality is hard, and the porosity height, specific surface area is big.Because the carbon nano fiber in the matrix material exists with ecosystem, thereby the microtexture and the physicochemical characteristic of carbon nano fiber have been kept fully, so, carbon nano fiber matrix material of the present invention can be used as sorbing material, filtering material, catalytic material and electrode materials etc., is a kind of novel monolithic devices carbonaceous porous material.
Description of drawings
Fig. 1 is the stereoscan photograph of the microscopic appearance of carbon nano fiber composite porous material.
Embodiment is as follows:
Embodiment 1
(SP11 type, Shuangshu Plastic Plant, Shanghai) grinds in mortar with the resol solid, takes by weighing resol powder 15g, adds dehydrated alcohol 15g, mixes into solution; Add nickelous nitrate solid 1.5g again, continue to be stirred to whole dissolvings.The nickel weight content is 1% in the formed solution.
Get 5 the heavy altogether 0.25g of PAN-based carbon fiber felt (the emerging carbon element in Shanghai company limited) matrix that are of a size of φ 7*10 (mm), put into above-mentioned solution and soak 4h.
Take out the back centrifuge dripping, put into stink cupboard and dry naturally, put into 120 ℃ of dry 10h of baking oven then.Above-mentioned 5 carbon fiber felts that are coated with metal-salt and resol are put into quartz tube furnace, and feeding contains 25% (volume) H
2Ar gas, mixed gas flow is 160ml/min, is warming up to 600 ℃, the insulation 6h carry out the carbonization of resol; Switch to H subsequently
2/ C
2H
4(volume ratio is 1: 2) gas mixture, flow is 60ml/min, carries out the catalytic growth of carbon nano fiber, growth time is 9h.Promptly get 5 cylindric carbon nano fiber composite porous materials that are of a size of φ 7*10 (mm) after the cooling.
The weight that records carbon coating in the composite porous material is 0.33 times of matrix weight, and the weight of carbon nano fiber is 1.21 times of matrix weight, and the density of composite porous material is 0.34g/cm
3(density of original carbon fiber felt matrix is 0.13g/cm
3).The side pressure strength of cylindric composite porous material is 58N/cm; Wastage rate are 0.6%.The porosity that mercury penetration method records is 65%, and testing tool is the Autopore IV 9500 type mercury injection apparatuses of U.S. Merck ﹠ Co., Inc; The specific surface area that nitrogen low-temperature physics absorption method records is 40m
2/ g, testing tool are the ASAP 2010 type physical adsorption appearances of U.S. Merck ﹠ Co., Inc.
The stereoscan photograph of the microscopic appearance of carbon nano fiber composite porous material is seen Fig. 1.
The density of integrated nano carbon-fiber composite porous materila can be by calculating behind the weight and volume of measuring the gained material; Side pressure strength adopts HG/T2782-1966 (mensuration of chemical fertilizer catalyst particle anti-crushing power) standard testing.Wastage rate are represented carbon nano fiber composite porous material weight loss in use, and wastage rate are little, then show the matrix material each several part in conjunction with firm, the carbon nano fiber difficult drop-off.Testing method is as follows: it is in 25% the ethanolic soln that 0.5g exsiccant carbon nano fiber composite porous material is immersed in the 50ml volume content, in sonic oscillation instrument (U.S. Branson company, model is B3200S), carry out sonic oscillation, keep 1h, carry out drying after the taking-up, weigh at last.With the material initial weight is benchmark, calculates the changes in weight of material before and after test, obtains the wastage rate result.
Embodiment 2
The resol solid is ground in mortar, take by weighing resol powder 10g, add dehydrated alcohol 20g, mix into solution; Add nickelous nitrate solid 0.75g again, continue to be stirred to whole dissolvings.The nickel weight content is 0.5% in the formed solution.
Get 5 of PAN-based carbon fiber felt matrixes that are of a size of φ 7*10 (mm), heavy altogether 0.25g puts into above-mentioned solution and soaks 0.5h.
Take out the back centrifuge dripping, put into stink cupboard and dry naturally, put into 200 ℃ of dry 0.5h of baking oven then.Above-mentioned 5 carbon fiber felts that are coated with metal-salt and resol are put into quartz tube furnace, and feeding contains 10% (volume) H
2N
2Gas, mixed gas flow is 160ml/min, is warming up to 600 ℃, insulation 6h carries out the carbonization of resol; Switch to H subsequently
2/ C
2H
4(volume ratio is 1: 2) gas mixture, flow is 120ml/min, carries out the catalytic growth of carbon nano fiber, growth time is 6h.Promptly get 5 cylindric carbon nano fiber composite porous materials that are of a size of φ 7*10 (mm) after the cooling.
The weight that records carbon coating in the composite porous material is 0.17 times of matrix weight, and the weight of carbon nano fiber is 0.48 times of matrix weight, and the density of compound catalyze material is 0.22g/cm
3Side pressure strength is 31N/cm, and wastage rate are 0.3%.Porosity is 71%, and specific surface area is 18m
2/ g.
Embodiment 3
The resol solid is ground in mortar, take by weighing resol powder 30g, add dehydrated alcohol 30g, mix into solution; Add copper sulfate solid 4.7g again, continue to be stirred to whole dissolvings.Weight of copper content is 2% in the formed solution.
Get 10 of PAN-based carbon fiber felt matrixes that are of a size of φ 7*10 (mm), heavy altogether 0.5g puts into above-mentioned solution and soaks 5h.
Take out the back centrifuge dripping, put into stink cupboard and dry naturally, put into 120 ℃ of dry 8h of baking oven then.Above-mentioned 5 carbon fiber felts that are coated with metal-salt and resol are put into quartz tube furnace, and feeding contains 25% (volume) H
2N
2Gas, mixed gas flow is 160ml/min, is warming up to 600 ℃, insulation 3h carries out the carbonization of resol; Switch to H subsequently
2/ C
2H
6(volume ratio is 1: 3) gas mixture, flow is 80ml/min, carries out the catalytic growth of carbon nano fiber, growth time is 12h.Obtain the carbon nano fiber composite porous material after the cooling.
The weight that records carbon coating in the composite porous material is 0.57 times of matrix weight, and the weight of carbon nano fiber is 1.43 times of matrix weight, and the density of compound catalyze material is 0.40g/cm
3, side pressure strength is 98N/cm, wastage rate are 0.7%.Porosity is 63%, and specific surface area is 53m
2/ g.
Embodiment 4
The resol solid is ground in mortar, take by weighing resol powder 20g, add dehydrated alcohol 10g, mix into solution; Add nickelous nitrate solid 3g again, continue to be stirred to whole dissolvings.The nickel weight content is 2% in the formed solution.
Get 5 of PAN-based carbon fiber felt matrixes that are of a size of φ 14*10 (mm), heavy altogether 0.5g puts into above-mentioned solution and soaks 5h.
Take out the back centrifuge dripping, put into stink cupboard and dry naturally, put into 80 ℃ of dry 15h of baking oven then.Above-mentioned 5 carbon fiber felts that are coated with metal-salt and resol are put into quartz tube furnace, and feeding contains 40% (volume) H
2Ar gas, mixed gas flow is 160ml/min, is warming up to 600 ℃, the insulation 3h carry out the carbonization of resol; Switch to H subsequently
2/ CH
4(volume ratio is 1: 1) gas mixture, flow is 60ml/min, carries out the catalytic growth of carbon nano fiber, growth time is 6h.Promptly get 5 cylindric carbon nano fiber composite porous materials that are of a size of φ 14*10 (mm) after the cooling.
The weight that records carbon coating in the composite porous material is 3.02 times of matrix weight, and the weight of carbon nano fiber is 1.87 times of matrix weight, and the density of compound catalyze material is 0.65g/cm
3, side pressure strength is 114N/cm, wastage rate are 1.3%.Porosity is 56%, and specific surface area is 118m
2/ g.
Embodiment 5
The resol solid is ground in mortar, take by weighing resol powder 5g, add dehydrated alcohol 25g, mix into solution; Add 2 again and go into nickelous nitrate solid 7.5g, continue to be stirred to whole dissolvings.The nickel weight content is 5% in the formed solution.
Get 5 of PAN-based carbon fiber felt matrixes, heavy altogether 0.25g puts into above-mentioned solution and soaks 1h.
Take out the back centrifuge dripping, put into stink cupboard and dry naturally, put into 120 ℃ of dry 20h of baking oven then.Above-mentioned 5 carbon fiber felts that are coated with metal-salt and resol are put into quartz tube furnace, and feeding contains 90% (volume) H
2Ar gas, mixed gas flow is 160ml/min, is warming up to 800 ℃, the insulation 6h carry out the carbonization of resol; Be cooled to 550 ℃ subsequently, and switch to H
2/ C
2H
4(volume ratio is 1: 2) gas mixture, flow is 120ml/min, carries out the catalytic growth of carbon nano fiber, growth time is 1h.Promptly get the carbon nano fiber composite porous material after the cooling.
The weight that records carbon coating in the composite porous material is 0.12 times of matrix weight, and the weight of carbon nano fiber is 3.55 times of matrix weight, and side pressure strength is 86N/cm, and wastage rate are 1.7%.Porosity is 59%, and specific surface area is 135m
2/ g.
Embodiment 6
The resol solid is ground in mortar, take by weighing resol powder 20g, add dehydrated alcohol 20g, mix into solution; Add nickelous nitrate solid 0.1g again, continue to be stirred to whole dissolvings.The nickel weight content is 0.05% in the formed solution.
Get 8 of PAN-based carbon fiber felt matrixes, heavy altogether 0.8g puts into above-mentioned solution and soaks 0.5h.
Take out the back centrifuge dripping, put into stink cupboard and dry naturally, put into 100 ℃ of dry 7h of baking oven then.The above-mentioned carbon fiber felt that is coated with metal-salt and resol is put into quartz tube furnace, and feeding contains 5% (volume) H
2Ar gas, mixed gas flow is 80ml/min, is warming up to 500 ℃, the insulation 5h carry out the carbonization of resol; Switch to H subsequently
2/ C
2H
4(volume ratio is 1: 2) gas mixture, flow is 60ml/min, and is warming up to 700 ℃, carries out the catalytic growth of carbon nano fiber, growth time is 20h.Promptly get the carbon nano fiber composite porous material after the cooling.
The weight that records carbon coating in the composite porous material is 1.28 times of matrix weight, and the weight of carbon nano fiber is 0.06 times of matrix weight, and the density of compound catalyze material is 0.31g/cm
3, side pressure strength is 45N/cm.Porosity is 73%, and specific surface area is 6m
2/ g.
Embodiment 7
The resol solid is ground in mortar, take by weighing resol powder 3g, add dehydrated alcohol 27g, mix into solution; Add nickelous nitrate solid 20g again, continue to be stirred to whole dissolvings.The nickel weight content is 8% in the formed solution.
Get 3 of PAN-based carbon fiber felt matrixes that are of a size of φ 14*10 (mm), heavy altogether 0.3g puts into above-mentioned solution and soaks 7h.
Take out the back centrifuge dripping, put into stink cupboard and dry naturally, put into 110 ℃ of dry 18h of baking oven then.Above-mentioned 3 carbon fiber felts that are coated with metal-salt and resol are put into quartz tube furnace, and feeding contains 80% (volume) H
2Ar gas, mixed gas flow is 160ml/min, is warming up to 600 ℃, the insulation 1h carry out the carbonization of resol; Switch to H subsequently
2/ C
2H
4(volume ratio is 1: 4) gas mixture, flow is 100ml/min, carries out the catalytic growth of carbon nano fiber, growth time is 2h.Promptly get 3 cylindric carbon nano fiber composite porous materials that are of a size of φ 14*10 (mm) after the cooling.
The weight that records carbon coating in the composite porous material is 0.05 times of matrix weight, and the weight of carbon nano fiber is 4.94 times of matrix weight, and wastage rate are 2.1%, and specific surface area is 169m
2/ g.
Embodiment 8
The resol solid is ground in mortar, take by weighing resol powder 25g, add dehydrated alcohol 5g, mix into solution; Add iron(ic) chloride solid 2.2g again, continue to be stirred to whole dissolvings.The iron weight content is 1.5% in the formed solution.
Get 6 of PAN-based carbon fiber felt matrixes that are of a size of φ 14*10 (mm), heavy altogether 0.6g puts into above-mentioned solution and soaks 2h.
Take out the back centrifuge dripping, put into stink cupboard and dry naturally, put into 120 ℃ of dry 12h of baking oven then.Above-mentioned 5 carbon fiber felts that are coated with metal-salt and resol are put into quartz tube furnace, and feeding contains 20% (volume) H
2Ar gas, mixed gas flow is 160ml/min, is warming up to 600 ℃, the insulation 3h carry out the carbonization of resol; Switch to H subsequently
2/ C
3H
6(volume ratio is 1: 2) gas mixture, flow is 120ml/min, carries out the catalytic growth of carbon nano fiber, growth time is 9h.Promptly get 6 cylindric carbon nano fiber composite porous materials that are of a size of φ 14*10 (mm) after the cooling.
The weight that records carbon coating in the composite porous material is 3.68 times of matrix weight, and the weight of carbon nano fiber is 1.75 times of matrix weight, and the density of compound catalyze material is 0.82g/cm
3, side pressure strength is 132N/cm, and wastage rate are 2.3%, and specific surface area is 71m
2/ g.
Claims (7)
1. an integrated nano carbon-fiber composite porous materila is characterized in that, is made up of carbon coating that applies on carbon fiber felt matrix, the carbon fiber felt matrix and the carbon nano fiber in the carbon coating;
With carbon fiber felt matrix weight is benchmark, and the weight of carbon coating is 0.05～5 times of matrix weight;
The weight of carbon nano fiber is 0.1～10 times of matrix weight.
2. integrated nano carbon-fiber composite porous materila according to claim 1 is characterized in that, is benchmark with carbon fiber felt matrix weight, and the weight of carbon coating is 0.1～3 times of matrix weight, and the weight of carbon nano fiber is 0.2～8 times of matrix weight.
3. prepare the method for claim 1 or 2 described integrated nano carbon-fiber composite porous materilas, comprise the steps:
(1) with soak carbon fibre felt in containing the resol-ethanolic soln of metal-salt, take out, remove redundant solution, under 50 ℃～200 ℃ temperature, in air, heat 0.5～20h again, obtain to be coated with the carbon fiber felt of metal-salt and resol;
In the said resol-ethanolic soln that contains metal-salt, the weight concentration of metal-salt is 0.02%～10%, and resol and alcoholic acid weight proportion are 1: 0.2～1: 10;
Metal-salt comprises solubility nitrate, haloid, carbonate or the vitriol of transition metal;
(2) carbon fiber felt that is coated with metal-salt and resol that step (1) is obtained is placed on and contains 5～95% (volume) H
2In the gas, carrier gas is Ar gas or N
2Gas, be warming up to 500 ℃～900 ℃ and keep 1～6h, carry out the carbonization of resol, switch subsequently and feed carbonaceous gas, under 500 ℃～900 ℃ temperature, carry out the catalytic growth reaction of carbon nano fiber in the resol carbide, growth time is 0.5～20h, obtains integrated nano carbon-fiber composite porous materila at last;
Carbonaceous gas is selected from H
2With more than one the mixture in carbon monoxide, methane, ethane, propane, ethene or the propylene gas etc., wherein, H
2Volumetric concentration be 10～90%.
4. method according to claim 3 is characterized in that, with soak carbon fibre felt 0.5～5h in containing the resol-ethanolic soln of metal-salt.
5. method according to claim 3 is characterized in that, metal-salt is solubility nitrate, haloid, carbonate or the vitriol of iron, cobalt, nickel or copper.
6. method according to claim 3 is characterized in that, carbon fiber felt with the part by weight that contains the resol-ethanolic soln of metal-salt is: 1: 5～1: 500.
7. method according to claim 3 is characterized in that, the macroshape of carbon fiber felt and size adopt rectangle, circle etc., and thickness is 5～10mm.
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