CN102277657B - Nanopore silicon fiber and preparation process thereof - Google Patents

Nanopore silicon fiber and preparation process thereof Download PDF

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CN102277657B
CN102277657B CN 201110173996 CN201110173996A CN102277657B CN 102277657 B CN102277657 B CN 102277657B CN 201110173996 CN201110173996 CN 201110173996 CN 201110173996 A CN201110173996 A CN 201110173996A CN 102277657 B CN102277657 B CN 102277657B
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fiber
nanopore
nanopore silicon
silicon fiber
acid
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CN102277657A (en
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金学范
朴成国
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Ningxia Ming Cheng New Material Co. Ltd.
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DALIAN HONGYU TECHNOLOGY CO LTD
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/66—Chemical treatment, e.g. leaching, acid or alkali treatment

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Abstract

The invention provides nanopore silicon fibers prepared from glass fibers and a preparation process thereof. The preparation process uses glass fibers the silica content of which is 45%-85% as raw materials and mainly comprises a salt decomposing step and an acid soaking step, thus preparing the nanopore silicon fibers of which the silica (SiO2) content is as high as 92%-99%, wherein the nanopore silicon fibers have excellent heat resistance, furthermore, due to irregular nanopore structures, the nanopore silicon fibers have excellent heat insulation and sound insulation and absorption effects. The nanopore silicon fibers are widely applied to fireproof heat preserving materials, heat insulating materials and fireproof heat isolating materials for buildings.

Description

Nanopore silicon fiber and preparation technology thereof
Technical field
The present invention relates to construction material, relating in particular to a kind of is nanopore silicon fiber and the preparation technology thereof who utilizes glass fibre to be processed into.
Technical background
Along with the fast development of industry facility and dwelling construction, just very high to the demand of insulation material in building trade, especially along with each department of society emphasizes under the overall situation of energy-saving and environmental protection, stricter to the requirement of insulation, thermal insulation and acoustic material at present.
The insulation material of current extensive employing has organic polymer Foamex (as the foaming of ps, pu) and inorfil (as glass fibre, ore rock fiber etc.).
Although the organic polymer Foamex is lightweight, high insulating effect, easy construction, poor heat resistance, toxic gas occurs and occurs in inflammable and when burning, and therefore fatal shortcoming is arranged.
The developed countries such as the U.S. have used the inorganic heat insulating fiber material in a large number.Glass fibre and ore rock fiber etc. are arranged in inorfil.Wherein the heat resisting temperature of glass fibre is 350 ℃ of left and right, and the heat resisting temperature of ore rock fiber is 850 ℃ of left and right, and the heat insulating ability of these fibers and noninflammability are all fine.In addition, inorfil also comprises silica fibre, ceramic fibre etc., and the heat resisting temperature of these fibers can reach 1000 ℃, so is widely adopted in high-temperature work environment.But the shortcoming of this inorganic heat insulating fiber material is heat-insulating property or the heat insulating ability that is not so good as organic polymer type Foamex.
Summary of the invention
Based on the existing technical problem of prior art and deficiency, the present invention is intended to disclose a kind of new technology that is processed into nanopore silicon fiber with glass fibre, namely glass fibre is as raw material, the material of other composition except silica (SiO2) in glass fibre is separated out, form nanopore silicon fiber.
Technical solution of the present invention is achieved in that
The glass fibre of the present invention take dioxide-containing silica as 45～85% prepares the technique of nanopore silicon fiber as raw material, mainly comprise step that salt decomposes and the step of acid soak.
Described glass fibre is the strong following metal oxide Na2O-RO of relative activity that distributing in silica (SiO2) skeleton, as Na2O-CaO, Na2O-B2O3, and Na2O-Al2O3, Na2O-MgO etc., wherein R is the element of IIA family or IIIA family;
The step that described salt decomposes is to utilize the reaction of the active strong metal oxide of ammonium salt and fiberglass surfacing that the latter is become soluble-salt to make described fiber surface form the stage of fine nano-pore;
Its chemical equation is as follows:
Na2O-RO+4NH4NO3＝2NaNO3+R(NO3)2+4NH3+2H2O
Na2O-RO+4NH4Cl＝2NaCl+RCl2+4NH3+2H2O
Described salt decomposes that in step, salt used is the mixture of ammonium nitrate and ammonium chlorate, and ammonium nitrate and ammonium chlorate mixing ratio are 1: 0.1～0.6 more suitable.The formation of nano-pore is relevant with concentration and the decomposition temperature of salt distintegrant, difference along with distintegrant concentration and decomposition temperature, the nano-pore that forms on glass fibre is also different, and this moment, the suitable concentration with the salt distintegrant was 0.8～12.5%, and suitable decomposition temperature is 100～500 ℃.
The step of described acid soak is the stage that the satisfactory nano-pore fiber of hole depth and aperture was separated out and obtained to the soluble-salt that makes salt decompose the fine nano-pore that produces in step fully.
Making by acid soak the process that forms nano-pore on fiber surface is that the fiber of salt decomposition Surface During formation nanometer minute aperture is immersed in the micropore of expansion fiber surface in nitric acid or hydrochloric acid or sulfuric acid, thereby obtains the nano-pore fiber in required hole depth and aperture.When utilizing nitric acid, its concentration is 7～20%, and when utilizing hydrochloric acid, its concentration is 15～30%, and when utilizing sulfuric acid, its concentration is 25～45%.
The acid soak process is solable matter diffusion process in solution, therefore, will obtain even and effective nano-pore on fiber surface, must stir equably, carries out 1～5 hour in 50～100 ℃ of temperature.
Fiber after above-mentioned acid soak is cleaned in 50～100 ℃ of clear water, wash time 0.5～2 hour, then resulting nanopore silicon fiber is carried out drying at 100～150 ℃ of temperature, then heat-treat the formation in stabilized nanoscale hole and increase the intensity of fiber at 550～650 ℃ of temperature.Be noted that when heat treatment temperature is too high this moment, although can improve the intensity of fiber, formed nano-pore shrinks in large quantities; Otherwise, when heat treatment temperature is too low, forming minute aperture quantity too much, low-fiber mechanical strength is fallen on the contrary.
Adopt said method to process and can obtain nanopore silicon fiber, its glass fibre take dioxide-containing silica as 45～85% is prepared silica (SiO2) content up to the porous silicon fiber of 92-99% as raw material, has good heat resistance; Simultaneously, nano-pore structure makes it have good insulation thermal insulation and sound insulating and absorbing effect.
The diameter of described nanopore silicon fiber: 0.5～20.0 μ m, length: more than 1.0mm, its surface apertures: 3～200nm, more than hole depth 10nm, porosity (the nanoaperture volume of unit mass fiber): 0.1～0.2ml/g, porosity (volume ratio of nanoaperture and fiber): 20～50%, thermal conductivity coefficient: in the time of 20 ℃, 0.021～0.033w/mmk, sound-absorption coefficient: 0.65～1.00.
Compared with prior art, the present invention has following significant advantage: its cost of material is low, technique is simple, and especially prepared nanopore silicon fiber superior performance can be widely used in the optimal high-tech tip materials in fire-type building thermal insulation material, heat-insulating material, acoustic material field.
Description of drawings
Fig. 1 is nanopore silicon fiber preparation technology's of the present invention flow chart.
The specific embodiment
Embodiment 1
A kind of technique for preparing nanopore silicon fiber take glass fibre as raw material mainly comprises the step of salt decomposition and the step of acid soak, specifically,
Glass fibre: composition: 7Na 2O-23B 2O 3-70SiO 2
Diameter: Φ 7 μ m
It is in 7.9% ammonium salt mixed solution that above-mentioned pyrex fiber 100g is put into concentration, NH 4NO 3: NH 4Cl=10: 2, be heated to 250 ℃, after having soaked 10min, take out dry; Be 11.7% nitric acid (HNO 70 ℃ of concentration 3) soak 2h in solution; And then after having washed 30min in boiling water at 120 ℃ of temperature dry 15min.
The last nanopore silicon fiber that obtains after cooling lentamente after 590 ℃ of heat treatment of carrying out 5min:
Composition: SiO 2-96%
B 2O 3-3.5％
Na 2O-0.5％
Diameter: Φ 49nm
Softening temperature: 1470 ℃
Embodiment 2
Glass fibre: composition: 8Na 2O-16CaO-76SiO 2
Diameter: Φ 5 μ m
Above-mentioned soda lime glass fibre 100g is carried out salt by the duplicate processing step of embodiment 1 to be decomposed and acid soak, again resulting fiber in the hot water of 70 ℃ the washing 1.5h after, dry 20min at 120 ℃ of temperature, then having got back after cooling lentamente after the heat treatment of having carried out 1min at the temperature of 550 ℃ has the silica fibre of following parameters.
Composition: SiO 2-94%
CaO-5.6％
Na 2O-0.4％
Bore dia: Φ 64nm
Softening temperature: 1350 ℃
Embodiment 3:
Glass fibre: composition: 6MgO-13B 2O 3-12Al 2O 3-69SiO 2
Diameter: Φ 9 μ m
It is that 5% the salting liquid of 300 ℃ (is NH that above-mentioned E glass fibre 100g is put into concentration 4NO 3: NH 4Cl=10: soak 3) take out drying after 10min after, then at 15% nitric acid (HNO 3) soak 3h in solution after, wash 30min in Buddhist water; Then cooling lentamente after the heat treatment of carrying out 5min at the temperature of 600 ℃ after dry 15min at 120 ℃ of temperature, can draw following silica fibre:
Composition: SiO 2-98.5%
Al 2O 3-0.9％
B 2O 3-0.4％
MgO-0.2％
Bore dia: Φ 59nm
Softening temperature: 1560 ℃
As seen, the carrying out of decomposing reaction along with salt constantly dissolves soluble component from fiberglass surfacing, thereby improves the SiO of fiber 2Content, heat resisting temperature and the heat-insulating property of the fiber that raise simultaneously.
The described nanopore silicon fiber of table 1 and the coefficient of heat conduction of current material under different temperatures
Figure BDA0000070911760000041
Figure BDA0000070911760000051
Wherein, fiber proportion 60～180kg/m 3
As can be seen from Table 2, the prepared nanopore silicon fiber of the present invention is more much lower than the coefficient of heat conduction of the insulation materials such as ore deposit rock wool, and described nano-pore fiber heat resisting temperature can reach 1000 ℃.Its reason is: form the space except intersecting between described nanopore silicon fiber, also have nanopore silicon fiber self just to have a lot of fine nano-pores that its thermal-insulation heat-resistant performance is improved greatly.
Table 2 has represented the formation condition of nanopore silicon fiber and the relation between the fiber properties relation
Figure BDA0000070911760000052
Figure BDA0000070911760000061
Wherein, A:Na 2O-CaO-SiO 2B:Na 2O-B 2O 3-SiO 2
Table 3 has represented the sound-absorption coefficient of nanopore silicon fiber
Figure BDA0000070911760000062
Wherein, nanopore silicon fiber proportion is 130kg/m 3
The acoustic absorptivity of the nanopore silicon fiber of making by technical matters of the present invention as can be seen from Table 3 is very high, is desirable sound-absorbing material.
The present invention can use SiO 2Content at all glass fibres of 45-85% all as raw material, preferably silicate glass fiber and borosilicate glass fiber, prepared nanopore silicon fiber can be widely used as fire-type building thermal insulation material, heat-insulating material, acoustic material.
The above; only be the better specific embodiment of the present invention; but protection scope of the present invention is not limited to this; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to replacement or changed according to technical scheme and the inventive concept thereof of invention, within all should being encompassed in protection scope of the present invention.

Claims (3)

1. the preparation technology of a nanopore silicon fiber, comprise the steps:
(1) salt decomposes: glass fibre is placed in ammonium salt solution and heating, makes the strong metal oxide Na of relative activity that distributes in the skeleton of silica of glass fibre 2O-RO and ammonium salt reaction form soluble-salt and separate out, and form the nanoscale minute aperture at fiberglass surfacing;
The dioxide-containing silica of described glass fibre is 45～85%;
Heating-up temperature is: 100～500 ℃;
Wherein, R is the element of IIA family or IIIA family;
(2) acid soak: and then described fiber is immersed in acid solution, and ceaselessly stir, to expand the nanoscale minute aperture on described fiber surface, obtain suitable hole depth and aperture;
Described acid solution is nitric acid, hydrochloric acid or sulfuric acid;
The temperature of acid solution: 50～100 ℃;
The concentration of acid solution (mass ratio): concentration of nitric acid, 7～20%; Concentration of hydrochloric acid, 15～30%; Sulfuric acid concentration: 25～45%;
Soak time: 1～5 hour;
(3) washing, drying and heat treatment: carry out drying after described fiber is cleaned with clear water, then at high temperature heat-treat with the formation in stabilized nanoscale hole and increase the intensity of fiber, and finally obtaining described nanopore silicon fiber; Wherein,
Slurry temperature: 50～100 ℃;
Wash time: 0.5～2 hour;
Baking temperature: 100～150 ℃;
Heat treatment temperature: 550～650 ℃;
Heat treatment time: 0.5～5 minute.
2. the preparation technology of nanopore silicon fiber according to claim 1 is characterized in that:
In step (1), described ammonium salt solution is the mixed solution of ammonium nitrate and ammonium chloride, and its chemical equation is as follows:
Na 2O-RO+4NH 4NO 3=2NaNO 3+R(NO 3) 2+4NH 3+2H 2O
Na 2O-RO+4NH 4Cl=2NaCl+RCl 2+4NH 3+2H 2O
Wherein, the mixed proportion of ammonium nitrate and ammonium chloride (mass ratio): 1:0.1～0.6;
The concentration of the mixed solution of ammonium nitrate and ammonium chloride (mass ratio): 0.8～12.5%.
3. nanopore silicon fiber of preparation technology preparation as claimed in claim 1 is characterized in that:
To be the dioxide-containing silica that is prepared from as raw material of the glass fibre take dioxide-containing silica as 45～85% be 92～99% silica fibre to described nanopore silicon fiber;
The diameter of nanopore silicon fiber: 0.5～20.0 μ m
The length of nanopore silicon fiber: more than 1.0mm
Nanopore silicon fiber surface apertures: 3～200nm
Hole depth: more than 10nm
Porosity: 0.1～0.2ml/g
Porosity: 20～50%
Thermal conductivity coefficient: in the time of 20 ℃, 0.021～0.033w/mmk
Sound-absorption coefficient: 0.65～1.00.
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CN102277657B (en) * 2011-06-24 2013-05-08 大连宏燠科技有限公司 Nanopore silicon fiber and preparation process thereof
CN105541129B (en) * 2015-12-29 2018-09-07 四川航天拓鑫玄武岩实业有限公司 Sound-absorbing material and preparation method thereof with tail gas purifying function
CN105862157A (en) * 2016-06-12 2016-08-17 李光武 Thermal insulation and heat preservation fiber material and preparation method and application thereof
CN106941023B (en) * 2017-04-20 2019-12-13 温州网牌电线电缆有限公司 Polyvinyl chloride sheath cable
CN114481443B (en) * 2022-02-15 2024-02-27 广州市樱杰汽车零部件有限公司 Soundproof cotton for automobile air duct

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Address after: 750001 Yinchuan Yongning Industrial Park, the Ningxia Hui Autonomous Region Industrial Park

Patentee after: Ningxia Ming Cheng New Material Co. Ltd.

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Patentee before: Dalian Hongyu Technology Co.,Ltd.