CN101691275B - Method for preparing nano mineral fiber - Google Patents
Method for preparing nano mineral fiber Download PDFInfo
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- CN101691275B CN101691275B CN2009100702978A CN200910070297A CN101691275B CN 101691275 B CN101691275 B CN 101691275B CN 2009100702978 A CN2009100702978 A CN 2009100702978A CN 200910070297 A CN200910070297 A CN 200910070297A CN 101691275 B CN101691275 B CN 101691275B
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Abstract
The invention discloses a method for preparing nano mineral fiber, relating to the preparation of mineral fiber. The steps of the method are as follows: (1) purifying by a purifying agent inorganic acid, (2) stirring at a high speed of 2500-3000r/min and adding a coupling agent for coupling modification, (3) drying at the temperature of 60-150 DEG C, and (4) carrying out supersonic speed airflow deep defasciculation treatment for 2min-3min by an airflow mill to obtain nano mineral fiber products with the average diameter of 60-90nm and the length of 2-8 mu m, wherein the airflow pressure is 0.6-1.0 MPa, and the stepped gear rotated speed is 2500-3000r/min. The method of the invention is simple and feasible, and has stable process, low equipment investment and small environmental load; the diameter of prepared nano mineral fiber has nano grade, and the length of fiber can be effectively maintained, thereby completely meeting the requirement of preparing organic and inorganic nano composite materials with high performance.
Description
Technical field
Technical scheme of the present invention relates to the preparation of mineral fibre, specifically a kind of method for preparing nano mineral fiber.
Background technology
Nano-fiber material has been widely used in fields such as building, aerospace, communications and transportation, petrochemical complex and the energy.The method for preparing nano-fiber material has the method for compound method and processing natural minerals.
Synthesis method prepares nanofiber and has following problem: 1. synthesize and at high temperature carry out, the surface tension that molten mass is huge makes to gather in the fibril becomes solid shape, and this series products specific surface area in theory is very little.2. with regard to the state of the art that present domestic synthesis method prepares nanofiber, general being difficult to obtains the nanofiber product in batches, can not satisfy the heavy demand that is used for nano composite material and support of the catalyst like it.3. along with the rising steadily of energy prices, the high energy consumption that synthesis method prepares nanofiber rises production cost, and since output constantly rising can cause energy input all to increase and increasing environmental pollution.
The method of utilizing the processing natural minerals to produce nano mineral fiber has the advantage that facility investment is little, technology is simple, cost is low and carrying capacity of environment is little.Yet, aspect processing natural minerals production nano mineral fiber, except that the minority mineral fibre of having been prohibited such as asbestos, utilize other kind natural minerals to produce nano mineral fiber and also do not form scale at present.China has abundant, the of a great variety and cheap mineral fibre resource of reserves, but is used on a large scale as yet at present.Like the sepiolite group mineral fibre is exactly a kind of aggregate of natural silicate mineral fibre, at the reserves of China above 2,000,000,000 tons.The utilization of China's sepiolite group mineral fibre at present mainly is cheap outlet, the domestic few field of consumption such as lagging material that only is used in.This added value that not only obtains is extremely low, and has wasted valuable mineral fibre resource.
The natural silicate mineral fibre is because big carbonate, quartz and the polynite that also contains association in a large number of size; Therefore only be used as sorbent material, typical catalyst carrier, drilling mud thickening material, sticker and fodder additives; Its using value is lower, can not satisfy the requirement of the high performance organic-inorganic nano matrix material of preparation.
Nano mineral fiber is because small-sized; Except having increased substantially the original application performance of natural silicate mineral fibre; Also can satisfy the requirement of the high performance organic-inorganic nano matrix material of preparation fully, thereby promote the using value and the range of application of mineral fibre significantly.
The preparation method of existing nano mineral fiber mainly contains two types.One type is the method for utilizing superfine grindings such as ball milling, promptly under the effect of impact of different crushing mediums, the natural silicate mineral fibre is carried out the superfine grinding processing and obtains the natural silicate nanometer powder.Yet,, seriously limited prepared nano mineral fiber and used because ball milling destroys staple length and pattern strongly.Also having class methods mainly is to adopt liquid phase dispersive method to carry out loosening of fibrous bundle, but existing document (mining industry research and development, 2004,24 (4): 25-30; China's papermaking, 2004,23 (7): 17-19; China's plastics; 2003; 17 (6): the liquid phase treatment process of being reported 48-51.) is not all at first carried out the purification processes of mineral fibre; And water disperses mineral coalescence again in the process of dehydrating, and be difficult to make natural silicate mineral fibre Shu Youxiao and dissociate completely, so can't batch preparations to go out diameter is nano level mineral fibre.
Summary of the invention
Technical problem to be solved by this invention is: a kind of method for preparing nano mineral fiber is provided; Separate the bundle step through purification, high-speed stirring and coupling modification, drying and the supersonic airstream degree of depth and make nano mineral fiber; The preparation method who has overcome existing nano mineral fiber so can't batch preparations go out the shortcoming that diameter is nano level mineral fibre because ball milling destroys and adopts liquid phase dispersive method to be difficult to make natural silicate mineral fibre Shu Youxiao and dissociate completely staple length and pattern are strong.
The present invention solves this technical problem the technical scheme that is adopted: a kind of method for preparing nano mineral fiber the steps include:
The first step is purified
Natural fiber pencil silicate is immersed in the water; Add purificant, through stirring 1.5～2.5 hours, washing, sedimentation and drying, natural fiber pencil silicate obtains purifying; Said purificant is a mineral acid, and its consumption is counted 0.5%～20% of natural fiber pencil silicate weight by pure acid;
Second step, high-speed stirring and coupling modification
The purification natural fiber pencil silicate that the first step is made places polarizable medium; The amount of this fiber bundle-like silicate shared weight percent in this overall mixture is 5%～35%; With the speed dispersed with stirring of 2500～3000r/min 1.5～2.5 hours, stir in this mix slurry and to heat to 50～90 ℃ and keep constant temperature simultaneously, add coupling agent then; Reacted 0.5～8 hour; Stop to stir, make the purification natural fiber pencil silicate slurry of coupling modification, the coupling agent consumption is 3%～60% of a purification fiber bundle-like silicate weight;
The 3rd step, drying
The purification natural fiber pencil silicate slurry that second step was made the coupling modification carries out vacuum-drying, fluidized drying or spraying drying under 60～150 ℃, all remove to the polarity medium, makes the dry thing of the purification natural fiber pencil silicate of coupling modification;
In the 4th step, the supersonic airstream degree of depth is separated bundle
Dry thing with the purification natural fiber pencil silicate of the 3rd coupling modification that make of step; After 20 mesh sieves sieve, carry out the supersonic airstream degree of depth and separate bundle with airflow milling; Stream pressure is 0.6～1.0MPa, and the grading wheel rotating speed is 2500～3000r/min, under the effect of supersonic airstream, carries out the degree of depth and separates bundle processing 2min-30min; Making mean diameter is 60～90nm, and length is the nano mineral fiber product of 2～8 μ m.
Above-mentioned a kind of method for preparing nano mineral fiber, the natural fiber pencil silicate described in the first step are any one in sepiolite, attapulgite or the polygorskite.
Above-mentioned a kind of method for preparing nano mineral fiber, the mineral acid described in the first step is the commercially available chemical reagent mineral acid after diluting with 1～20 times of water.
Above-mentioned a kind of method for preparing nano mineral fiber, the mineral acid described in the first step is hydrochloric acid, sulfuric acid or nitric acid.
Above-mentioned a kind of method for preparing nano mineral fiber, the polarizable medium described in second step is water, ethanol or Virahol.
Above-mentioned a kind of method for preparing nano mineral fiber, the coupling agent described in second step is vinyltriethoxysilane, three Triple Pressed Stearic Acid iso-butyl titanates or distearyl acyl-oxygen aluminum isopropoxide acid esters.
Above-mentioned a kind of method for preparing nano mineral fiber, the airflow milling described in the 4th step are flat airflow milling, fluidized bed jet mill or cyclonic air flow mill.
Above-mentioned a kind of method for preparing nano mineral fiber, the stirring described in the first step, washing, sedimentation and drying process method and apparatus all are chemical technique method and apparatus of conventional, well-known; Vacuum-drying, fluidized drying or spraying drying described in the 3rd step are known chemical technique methods, do not have the certain conditions restriction; Above-mentioned airflow milling comprises flat airflow milling, fluidized bed jet mill or cyclonic air flow mill, is the chemical plant of conventional, well-known.
The invention has the beneficial effects as follows: use a kind of method for preparing nano mineral fiber of the present invention why can overcome existing nano mineral fiber the preparation method since ball milling to staple length and pattern strong destroy and adopt liquid phase dispersive method to be difficult to make natural silicate mineral fibre Shu Youxiao therefore can't batch preparations go out the shortcoming that diameter is nano level mineral fibre with dissociating completely, its reason of giving prominence to is:
1. the inventive method is purified to natural fiber pencil silicate with mineral acid; React through the carbonate impurity in mineral acid and the natural fiber pencil silicate; Further through stirring, washing and sedimentation, just removed the most of impurity that is contained in the primary natural fiber pencil silicate mine effectively again.
2. why the inventive method adopts high-speed stirring, and promptly the speed with 2500～3000r/min stirs the natural fiber pencil silicate of purifying, and it is disperseed in polarizable medium, and the fiber bundle-like silicate that causes being scattered in the polarizable medium is loosened.
Preferably water of the present invention or ethanol are polarizable medium (being dispersion medium), not only economy but also nontoxic.For the further effect of loosening of reinforcing fibre pencil silicate, stablize its dispersion state in polarizable medium, unlikely generation sedimentation, key be control purification fiber bundle-like silicate with the overall mixture of polarizable medium in shared weight percent.Purification fiber bundle-like silicate shared weight percent in overall mixture is too low, and mechanical agitation power is difficult for passing to fiber bundle-like silicate, is unfavorable for loosening of fiber bundle-like silicate, and influences the coupling modified effect of fiber.Purification fiber bundle-like silicate shared weight percent in overall mixture is too high; Fiber bundle-like silicate is not easy to be dispersed in the polarizable medium; Slurry viscosity is high; Stir difficulty, just drawing purification fiber bundle-like silicate shared weight percent in this overall mixture through experiment repeatedly is 5%～35% the best.
The coupling modification is in order to reduce the surface tension of nano crystal mineral fibre, increase its hydrophobicity and with the affinity of organic polymer, strengthen the interface interaction between organic and the inorganics.The inventive method selects to have titanate coupling agent, aluminate coupling agent or the silane coupling agent of carboxyl, ester group or epoxy base class reactive functional groups; Can with silicon hydroxyl generation intensive physics or the chemical action in the mineral; But chemical reaction can not take place rapidly with dispersion medium in it; The coupling agent of being selected for use simultaneously contains long organic chain, preferably contains the carbon atom more than 12, to form certain thickness modified layer.Through the key that experiment showed, the coupling modification repeatedly is control reaction temperature, reaction times and coupling agent consumption, and through experiment repeatedly, these all are able to embody in the methods of the invention.
3. because the power that acts on the mineral fibre material is main with shearing force and frictional force; Adopting the supersonic airstream degree of depth to separate bundle handles; Especially under the effect of supersonic airstream, carry out the degree of depth with fluidized bed counter jet mill and separate the bundle processing, can obtain the complete 1-dimention nano mineral fibre of crystalline structure.Its principle is: because the interaction between sepiolite, attapulgite or the polygorskite fibrid pencil silicate monocrystalline is mainly Van der Waals force and hydrogen bond force; Although the shared cationic situation of a spot of monocrystalline is arranged; But plane of action is very little; Therefore the reactive force between nano crystal is little far beyond the reactive force between the phyllosilicate nano crystal layer, has formed a large amount of spaces because the geometry of nanometer is piled up simultaneously, thereby in theory; Dispersion can loosened or peeled off to natural fiber pencil silicate under intense shear power, frictional force and impact force effect, realize that the diameter of fiber reaches nano level.Along with the degree of depth is separated the carrying out that bundle is handled; Mineral fibre attenuates; The new ionic activity point in mineral fibre surface constantly produces; Because mineral fibre is handled through the coupling modification, these new ionic activity points are separated in the bundle treating processes effective group with coupling agent in the degree of depth and are carried out moment and combine, at the further coupling modified effect of reinforcement mineral fibre of dissociated while of mineral fibre bundle.
The method that the present invention is a kind of to prepare nano mineral fiber compared with prior art, its obvious improvement is:
1. the inventive method process simple possible, process stabilizing; Facility investment is little little with carrying capacity of environment; Wherein used purificant, polarizable medium and coupling agent are inexpensive commercial chemicals; Cost is low, and is safe in utilization, therefore overcome high this significant disadvantage of traditional synthetic legal system nanofiber cost.
2. the inventive method is separated the bundle processing owing to adopted supersonic airstream that fibrous bundle is carried out the degree of depth, not only makes the diameter of mineral fibre have Nano grade, and mineral fibre length is effectively kept, and has widened the Application Areas of product.
3. the method for preparing nano mineral fiber of the present invention has improved China's sepiolite group mineral Mineral resources process and utilization technology level, has realized the industry restructuring and the updating and upgrading of a product, has widened the Application Areas of product.
4. the nano mineral fiber of the inventive method preparation is dissociated into the nano crystal fiber easily in polymkeric substance; In polymeric matrix, realize the dispersion of nanoscale; The requirement of the high performance organic-inorganic nano matrix material of preparation can be satisfied fully, a series of high-performance and polymer nanocomposites cheaply can be applied to prepare.
The nano mineral fiber one dimension size that can observe the inventive method preparation through sem is less than 100nm, and length reaches micron order; Can observe the deployment conditions of nano mineral fiber in polymeric matrix of the inventive method preparation through sem; The nano mineral fiber of observing the inventive method preparation one dimension size in polymeric matrix and has good dispersiveness less than 100nm.(seeing accompanying drawing and embodiment for details)
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Fig. 1 is a kind of process flow sheet for preparing the method for nano mineral fiber of the present invention.
Fig. 2 is that the dry thing to the purification natural fiber pencil silicate of coupling modification carries out the synoptic diagram that the supersonic airstream degree of depth is separated the bundle treating processes in the inventive method.
Fig. 3 is the scanning electron microscope diagram sheet of the nano mineral fiber product that makes of the embodiment of the invention 1.
Fig. 4 is the scanning electron microscope diagram sheet of the purification sepiolite fibre of Comparative Examples 1 preparation.
Fig. 5 is that the nano mineral fiber product that the embodiment of the invention 2 makes is dispersed in the scanning electron microscope diagram sheet in the epoxy resin.
Fig. 6 is that the purification sepiolite fibre of Comparative Examples 2 preparations is dispersed in the scanning electron microscope diagram sheet in the epoxy resin.
Embodiment
Fig. 1 shows that a kind of technical process for preparing the method for nano mineral fiber of the present invention is: with mineral fibre is natural fiber pencil silicate and water and mineral acid; Through stirring, washing and depositing is ore dressing purification and exsiccant solid-liquid separation process; The breeze that obtains purifying is a natural fiber pencil silicate; Add polarizable medium again and carry out high-speed stirring and make purification natural fiber pencil silicate ore pulp; Add coupling agent again and stir and make liquid phase to handle the back mineral fibre be the purification natural fiber pencil silicate slurry of coupling modification, separate the bundle processing through the super-dry and the high velocity air degree of depth again, finally make nano mineral fiber.
Fig. 2 shows; In the inventive method the dry thing of the purification natural fiber pencil silicate of coupling modification being carried out the supersonic airstream degree of depth separates the bundle treating processes and be: supersonic airstream utilizes the compressed-air actuated pressure can; Form the supersonic airstream track in crushiing chamber; Supersonic airstream is given by pulverized fiber pencil material with high speed, makes the fiber bundle-like material in crushing chamber, produce fierce collision, friction and shearing.This wherein; With impact (seeing (e) among the figure) between the mutual impact of fiber bundle-like material (seeing (a)～(d) among the figure) or fiber bundle-like material and wall is main grinding mode; With shearing action is main; Particularly in the air-flow corner, make the fiber bundle-like material self receive the effect of shearing force, fiber bundle-like material itself produces friction mutually with the line contact each other in crushing process; When external stress during greater than the internal stress of fiber bundle-like material itself, the fiber bundle-like material prolongs direction of principal axis and rives and pulverize.
The first step is purified
It is in the 3L water of being adorned in the beaker of 5L that the 500g scpiolitc is immersed in volume; The purificant hydrochloric acid of scpiolitc weight 3% is counted in adding by pure acid; Through stirring 2 hours, washing, sedimentation and drying; The sepiolite 365g that obtains purifying, the yield of purification is 73%, used hydrochloric acid is the commercially available chemical reagent hydrochloric acid after diluting with 1 times of water;
Second step, high-speed stirring and coupling modification
Getting purification sepiolite that the first step makes, to place volume be the 3L polarizable medium deionized water of being adorned in the beaker of 5L; Be made into weight percent and be 6% slurries,, stir at slurries and to heat to 50 ℃ and keep constant temperature simultaneously with the speed dispersed with stirring of 3000r/min 2 hours; Be incorporated as the vinyltriethoxysilane of purification sepiolite weight 3% then; Reacted 0.83 hour, and stopped to stir, make the purification sepiolite slurry of coupling modification;
The 3rd step, drying
Placing temperature to be 60 ℃ in the purification sepiolite slurry of the second coupling modification that make of step is in the vacuum drying oven of 130Pa with vacuum tightness, all removes to moisture, makes the dry thing of the purification sepiolite of coupling modification;
In the 4th step, the supersonic airstream degree of depth is separated bundle
Dry thing with the purification sepiolite of the 3rd coupling modification that make of step; After 20 mesh sieves sieve, carry out the supersonic airstream degree of depth and separate bundle with fluidized bed counter jet mill; Stream pressure is 0.6MPa; The grading wheel rotating speed is 2500r/min, separates bundle processing 10min through under the effect of supersonic airstream, carrying out the degree of depth, makes the nano mineral fiber product.
Fig. 3 is the scanning electron microscope diagram sheet of the nano mineral fiber product that makes through the present embodiment that sem photography obtains, and its shows that the nano mineral fiber product mean diameter that present embodiment makes is 70～90nm, and length is 3～8 μ m.
The fluffy softness of this nano mineral fiber can be observed its not sedimentation in water, and good dispersiveness and stability are arranged in ethanol.
Comparative Examples 1
The first step is purified
It is in the 3L water of packing in the beaker of 5L that the 500g scpiolitc is immersed in volume; The purificant hydrochloric acid of scpiolitc weight 3% is counted in adding by pure acid; Through stirring 2 hours, washing and centrifugal settling; The sepiolite slurry that obtains purifying, used hydrochloric acid is the commercially available chemical reagent hydrochloric acid after diluting with 1 times of water;
Second step, drying and screening
It is in the vacuum drying oven of 130Pa with vacuum tightness that the purification sepiolite slurry that the first step is made places temperature to be 60 ℃; All remove to moisture content; Make the dry thing of purification sepiolite, the sepiolite fibre sample obtains purifying after the dry thing that will obtain again sieves with 20 mesh sieves.
Fig. 4 is the scanning electron microscope diagram sheet of the purification sepiolite fibre of this Comparative Examples preparation of obtaining through sem photography, shows that this sample appearance is hard and closely knit, and this average fibre diameter is 3.5 μ m.
Embodiment 2
The first step is purified
It is in the 3L water of being adorned in the beaker of 5L that the 500g scpiolitc is immersed in volume; The purificant sulfuric acid of scpiolitc weight 2% is counted in adding by pure acid; Through stirring 1.5 hours, washing, sedimentation and drying; The sepiolite 350g that obtains purifying, the yield of purification is 70%, used sulfuric acid is for 20 times of water-reducible commercially available chemical reagent sulfuric acid;
Second step, high-speed stirring and coupling modification
Getting purification sepiolite that the first step makes, to put into volume be the 3L polarizable medium ethanol that the beaker of 5L is adorned; Be made into weight percent and be 5% slurries,, stir at slurries and to heat to 90 ℃ and keep constant temperature simultaneously with the speed dispersed with stirring of 2500r/min 1.5 hours; Be incorporated as three Triple Pressed Stearic Acid iso-butyl titanates of purification sepiolite weight 10% then; Reacted 4 hours, and stopped to stir, make the purification sepiolite slurry of coupling modification;
The 3rd step, drying
The purification sepiolite slurry that second step was made the coupling modification all removes to moisture 150 ℃ of following spraying dryings, makes the dry thing of the purification sepiolite of coupling modification;
In the 4th step, the supersonic airstream degree of depth is separated bundle
Dry thing with the purification sepiolite of the 3rd coupling modification that make of step; After 20 mesh sieves sieve, carry out the supersonic airstream degree of depth and separate bundle with flat airflow milling; Stream pressure is 0.8MPa; The grading wheel rotating speed is 2800r/min, separates bundle processing 2min through under the effect of supersonic airstream, carrying out the degree of depth, makes the nano mineral fiber product.
Obtain the scanning electron microscope diagram sheet of this nano mineral fiber product through sem photography, this picture shows that its mean diameter is 70～90nm, and length is 3～8 μ m.
The fluffy softness of this nano mineral fiber can be observed its not sedimentation in water, and good dispersiveness and stability are arranged in ethanol.
Fig. 5 is dispersed in the scanning electron microscope diagram sheet in the epoxy resin through the nano mineral fiber product that the present embodiment that the sem photography obtains makes; Show that this nano mineral fiber directly mixes with epoxy resin, can be dispersed in the epoxy resin-base with the nano unit yardstick.
Comparative Examples 2
The first step is purified
It is in the 3L water of being adorned in the beaker of 5L that the 500g scpiolitc is immersed in volume; The purificant sulfuric acid of scpiolitc weight 2% is counted in adding by pure acid; Through stirring 1.5 hours, washing and centrifugal settling; The sepiolite slurry that obtains purifying, used sulfuric acid is for 20 times of water-reducible commercially available chemical reagent sulfuric acid;
Second step, drying and screening
The purification sepiolite slurry that the first step is made is 150 ℃ of following spraying dryings, all removes to moisture, makes the dry thing of purification sepiolite, and the sepiolite fibre sample obtains purifying after the dry thing that will obtain again sieves with 20 mesh sieves.
Fig. 6 is dispersed in the scanning electron microscope diagram sheet in the epoxy resin through the purification sepiolite fibre that this Comparative Examples that the sem photography obtains prepares, and can not be dispersed in the epoxy resin-base with the nano unit yardstick after showing this sample and epoxy resin mixing.
Embodiment 3
The first step is purified
It is in the 3L water of being adorned in the beaker of 5L that 500g attapulgite mineral are immersed in volume; The purificant nitric acid of attapulgite mineral weight 10% is counted in adding by pure acid; Through stirring 2.5 hours, washing, sedimentation and drying; The attapulgite mineral 335g that obtains purifying, the yield of purification is 67%, used nitric acid is for 10 times of water-reducible commercially available chemical reagent nitric acid;
Second step, high-speed stirring and coupling modification
Getting purification attapulgite mineral that the first step makes, to put into volume be the 0.5L polarizable medium Virahol that the beaker of 2L is adorned; Be made into weight percent and be 35% slurries,, stir at slurries and to heat to 70 ℃ and keep constant temperature simultaneously with the speed dispersed with stirring of 2800r/min 2.5 hours; Be incorporated as the distearyl acyl-oxygen aluminum isopropoxide acid esters of purification attapulgite mineral weight 50% then; Reacted 8 hours, and stopped to stir, make the purification attapulgite mineral slurries of coupling modification;
The 3rd step, drying
The purification attapulgite mineral slurries that second step was made the coupling modification all removes to moisture at 75 ℃ of following fluidized dryings, makes the dry thing of the purification attapulgite mineral of coupling modification;
In the 4th step, the supersonic airstream degree of depth is separated bundle
Dry thing with the purification attapulgite mineral of the 3rd coupling modification that make of step; After 20 mesh sieves sieve, carry out the supersonic airstream degree of depth and separate bundle with the Cyclonic airflow milling; Stream pressure is 1.0MPa; The grading wheel rotating speed is 3000r/min, separates bundle processing 5min through under the effect of supersonic airstream, carrying out the degree of depth, makes the nano mineral fiber product.
Obtain the scanning electron microscope diagram sheet of this nano mineral fiber product through sem photography, this picture shows that its mean diameter is 60～70m, and length is 2～4 μ m.
This nano mineral fiber is fluffy, soft, can observe its not sedimentation in water, and good dispersiveness and stability are arranged in ethanol.
Embodiment 4
The first step is purified
It is in the 3L water of being adorned in the beaker of 5L that 500g polygorskite mineral are immersed in volume; The purificant hydrochloric acid of polygorskite mineral weight 20% is counted in adding by pure acid; Through stirring 2.5 hours, washing, sedimentation and drying; The polygorskite mineral 355g that obtains purifying, the yield of purification is 71%, used hydrochloric acid is for 10 times of water-reducible commercially available chemical reagent hydrochloric acid;
Second step, high-speed stirring and coupling modification
Getting purification polygorskite mineral that the first step makes, to put into volume be the 0.8L Virahol that the beaker of 5L is adorned; Be made into weight percent and be 20% slurries,, stir at slurries and to heat to 70 ℃ and keep constant temperature simultaneously with the speed dispersed with stirring of 2900r/min 2 hours; Be incorporated as the distearyl acyl-oxygen aluminum isopropoxide acid esters of purification polygorskite mineral weight 50% then; Reacted 0.5 hour, and stopped to stir, make the purification polygorskite mineral slurries of coupling modification;
The 3rd step, drying
The purification polygorskite mineral slurries that second step was made the coupling modification all removes to moisture at 75 ℃ of following fluidized dryings, makes the dry thing of the purification polygorskite mineral of coupling modification;
In the 4th step, the supersonic airstream degree of depth is separated bundle
Dry thing with the purification polygorskite mineral of the 3rd coupling modification that make of step; After 20 mesh sieves sieve, carry out the supersonic airstream degree of depth and separate bundle with the Cyclonic airflow milling; Stream pressure is 1.0MPa; The grading wheel rotating speed is 3000r/min, separates bundle processing 30min through under the effect of supersonic airstream, carrying out the degree of depth, makes the nano mineral fiber product.
Obtain the scanning electron microscope diagram sheet of this nano mineral fiber product through sem photography, this picture shows that its mean diameter is 70～80nm, and length is 3～5 μ m.
This nano mineral fiber is fluffy, soft, can observe its not sedimentation in water, and good dispersiveness and stability are arranged in ethanol.
Claims (3)
1. method for preparing nano mineral fiber is characterized in that step is:
The first step is purified
Natural fiber pencil silicate is immersed in the water; Add purificant; Through stirring 1.5～2.5 hours, washing, sedimentation and drying; The natural fiber pencil silicate that obtains purifying, said purificant is a mineral acid: hydrochloric acid, sulfuric acid or nitric acid, its consumption is counted 0.5%～20% of natural fiber pencil silicate weight by pure acid;
Second step, high-speed stirring and coupling modification
The purification natural fiber pencil silicate that the first step is made places polarizable medium: water, ethanol or Virahol; The amount of this fiber bundle-like silicate shared weight percent in this overall mixture is 5%～35%; With the speed dispersed with stirring of 2500～3000r/min 1.5～2.5 hours; Stir in this mix slurry and to heat to 50～90 ℃ and keep constant temperature simultaneously; Add coupling agent then: vinyltriethoxysilane, three Triple Pressed Stearic Acid iso-butyl titanates or distearyl acyl-oxygen aluminum isopropoxide acid esters, reacted 0.5～8 hour, stop to stir; Make the purification natural fiber pencil silicate slurry of coupling modification, the coupling agent consumption is 3%～60% of a purification fiber bundle-like silicate weight;
The 3rd step, drying
The purification natural fiber pencil silicate slurry that second step was made the coupling modification carries out vacuum-drying, fluidized drying or spraying drying under 60～150 ℃, all remove to the polarity medium, makes the dry thing of the purification natural fiber pencil silicate of coupling modification;
In the 4th step, the supersonic airstream degree of depth is separated bundle
Dry thing with the purification natural fiber pencil silicate of the 3rd coupling modification that make of step; After 20 mesh sieves sieve, carry out the supersonic airstream degree of depth and separate bundle with flat airflow milling, fluidized bed jet mill or cyclonic air flow mill; Stream pressure is 0.6～1.0MPa, and the grading wheel rotating speed is 2500～3000r/min, separates bundle processing 2min-30min through under the effect of supersonic airstream, carrying out the degree of depth; Making mean diameter is 60～90nm, and length is the nano mineral fiber product of 2～8 μ m.
2. a kind of method for preparing nano mineral fiber according to claim 1 is characterized in that: the natural fiber pencil silicate described in the first step is any one in sepiolite, attapulgite or the polygorskite.
3. a kind of method for preparing nano mineral fiber according to claim 1 is characterized in that: mineral acid described in the first step is the commercially available chemical reagent mineral acid after diluting with 1～20 times of water.
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