CN102352136A - Inorganic activation process of nanometer or submicron PAL material - Google Patents
Inorganic activation process of nanometer or submicron PAL material Download PDFInfo
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Abstract
The invention, relating to the technical field of flame retardant material, especially relates to an inorganic activation process of a nanometer or submicron PAL material, solving the technical problems of insufficient reasonableness existing in the prior art and the like. The process comprises the following steps: A, mechanochemical activation; B, acid activation, and C, thermal activation. Compared with the prior art, the invention has the advantages that: by using united activation comprising acid activation, thermal activation, and mechanical activation as the main part. an acid activation-thermal activation-mechanical activation technical system is established, the product performance of the PAL material, the power for self-assembly and guidance function are provided for realizing self-assembly of the inorganic supermolecule intercalation of the PAL material, the accumulation of energy and guidance function to space and direction are provided for realizing the organizing of inorganic supermolecule intercalation assembly chemical technique, and more importantly, the high performance assistant material is provided for building material, high-molecular polymer and other wide fields.
Description
Technical field
The present invention relates to the fire retardant material technical field, especially relate to a kind of inorganic activation technology of nanometer submicron PAL material.
Background technology
Fire-retardant essential for human beings'health and safety, The development in society and economy, its significance is self-evident.In self the fire-fighting demand in fields such as building, chemical industry, military affairs and traffic and the field of tool inflammableness macromolecular material, fire retardant material is reducing ratio aspect the fire hazard up to more than 70%.Facts have proved that fire retardant material is avoided heavy economic losses and the aspect of preserving the ecological environment reducing the fire loss of life and personal injury; All bring into play big emphatically effect; Thereby, the research of fire retardant and fire retardant material, production and application, significant for socio-economic development " mankind and environment ".At present, common fire retardant mainly contains halogenated flame retardant, silicon-series five-retardant, phosphorus flame retardant, triazine flame retardant and inorganic combustion inhibitor.China is main with halogen containing flame-retardants such as bromine system, chlorine systems; Though the Halogen fire retardant material has good flame-retardant effect; But can discharge a large amount of smog and poisonous, harmful corrosive gases during general Halogen fire retardant material presence of fire, personnel and precision instrument are brought very big infringement.Strictness along with the global environment rules; China requires the reinforcement of dynamics to flame-retarded technology; People require increasingly high to fire safety and goods fire-retardant, Halogen, low cigarette, low toxicity, high-performance environment protection type flame-proof agent have become the target of socio-economic development and the harmonious pursuit of environment.
The PAL material is the green flame retardant of excellent performance, disturbs intercalation, peel ply, the chain flame retarding construction function of supporting component of combustion but have, and contains multiple ignition-proof element (Si, P, S, B) and press down cigarette element (Mo, Fe, Mg, Zn, Cn).The structure construction of PAL material is the structure of layer, chain, fibrous crystalline structure and nano level hole passage.It is an oblique system, and crystalline structure belongs to 2:1 type non-metallic minerals, promptly two-layer silicon-oxy tetrahedron folder one deck magnesium (aluminium) octahedron, and its tetrahedron and octahedral arrangement mode are laminate structure.In each 2.1 layers, the tetrahedron corner is pushed up at a certain distance direction and is put upside down form layers, chain combination characteristic.Form parallel at tetrahedron bar interband with chain; The passage that runs through skeleton; Channel cross-section is about 0.37nm * 0.63nm; Passage is that water molecules is filled, for the zeolite water (H2O) that is parallel to fiber and with mg ion coordinate crystal water (OH2), have surface adsorption water (H2O) and with octahedral cations coordinate water of constitution (OH).Its crystalline structure is a needle-like, is made up of elongated hollow tube.The unevenness on PAL material surface micromorphology performance structure surface rises and falls, and especially cleavage surface is very coarse, has the step of 1-2nm to occur, and presents the complicated micromorphology of distortion and spiral.Parallel fibers tunnel hole accounts for more than 1/2 of fiber volume, and interior external surface area is considerable, and the duct effect is remarkable.Combine with molecular linkage between the PAL material layer, even K+, Na+ are arranged, K-O, also much smaller than the linkage force of Si-O or Mg-O, water molecules, atoms metal, organic molecule can get into interlayer to the bonding force of Na-O key, make interfloor distance (interlamination region) that mutability arranged.The PAL material has unique layer, chain crystalline structure, has given PAL material particular performances.
High-purity micro-nano PAL material is polarity " hydrophilic " material; Homodisperse in polymeric matrix, and be separated into sheet, stratiform monomer, realize obstruct to heat; Reach fire-retardant purpose; Must implement " organising " and be modified as " oleophylic ", " hydrophobic ", and fully compatible with polymeric matrix, activation is its forerunner's condition that " organises ".Its principle is: " organising " is inorganic supermolecular intercalation crackle chemical process, be molecule and molecule under certain condition, rely on non-covalent Intermolecular Forces, spontaneously connect into the process that constitutionally stable molecule splits collective.Self assembling process takes place, and needs power and two conditions of guide effect of self-assembly.Because " activation " to material; Produced the interior external surface area of material structure and promoted significantly, interfacial activity center and group are grown, and free energy improves; For providing of self-assembly the space and the direction of molecular transposition; And the intermolecular synergistic power that provides by interfacial activity, high free energy, so be gordian technique, also be critical process link to " activation " of PAL material.
With regard to the inorganic non-metallic field; The technical matters of " activation " mainly contains methods such as medium activation, heat, electricity, microwave, ultrasonic, radiation; But more employings is technology comparatively simple, lower-cost " acid activation " and " thermal activation " technical matters; But the former is prone to produce the handling problem of " acidifying " waste water, and the latter has the defective of highly energy-consuming.The proposition of relevant " mechanical force and chemical activation " comes from " mechanochemistry " of the German scholar Ostwald twenties in 20th century; And use till today; Refer to the mechanical force induced chemical reaction; Expert after nineteen ninety research is thought: mechanochemistry essence be solid particulate under the effect of mechanical energy, cause the variation of aspects such as the structure of matter, physical and chemical performance and chemically reactive owing to deformation, defective and dissociating etc.
Summary of the invention
The objective of the invention is provides a kind of easy to implement to the problems referred to above, can effectively promote the inorganic activation technology of the nanometer submicron PAL material of PAL material property.
For achieving the above object, the present invention has adopted following technical proposal: the inorganic activation technology of Ben Nami submicron PAL material is characterized in that this technology comprises the steps:
A, mechanical force and chemical activation: nanometer submicron PAL material material is received violent impact under strong mechanical force; In the ruined while of crystalline structure; The part also can produce plasma body, reduces the temperature of reaction and the activation energy of system, thus the reaction between evocating substance;
B, acid activation: the impurity of nanometer submicron PAL material is removed in dissolving, thereby increases specific surface area; Utilize the H of minor radius
+The positively charged ion of exchange PAL material crystals interlayer, thus the duct formed; The Al of part in the dissolving PAL material octahedron
3+Fe
2+, Fe
3+And Mg
2+Ion increases duct angle increase, specific surface area increase, the diameter of crystal end-face;
C, thermal activation: through to nanometer submicron PAL material type of heating, remove the water of four kinds of states of its existence, promptly outside surface planar water, duct planar water, be present in water of constitution and crystal water in the crystal.
It is " acid activation, thermal activation, mechanical force and chemical activation " technical system of major technique approach that the present invention has constructed with the mechanical force and chemical activating technology; For the PAL material has been optimized performance as stand-alone product; Realize the self assembling process of inorganic supermolecular intercalation assembling chemical technological " organising " for the PAL material, the power and the guiding condition of self-assembly is provided.The essence of mechanical force and chemical activating technology is the modification of the physical-chemical of micro-nano split; The process of acid activation, thermal activation is also comprising the performance optimization process of physical-chemical.Through the physical-chemical effect of mechanical force and chemical, PAL material powder is carried out activation modification handle, efficiently disperse PAL material powder, obtain best PAL material powder characteristic.In this course; The PAL material granule produces like physical influence and chemical effects such as heat effect, crystal conversion, electrically change, plasma chemicals; Thereby bring out the chemical physics effect of properties-correcting agent; Reach the identification of molecular recognition and position, realize organic modification, reach highly compatible and homodisperse with matrix (organic polymer-based or inorganic based).The thermodynamics and kinetics characteristic of mechanical force and chemical reaction mechanism, reaction is all distinguished with the chemical reaction of routine to some extent.
Mechanical force and chemical can produce multiple effect:
1, crystal habit changes.Material is in crushing process, and crystalline structure has experienced from thing and become (grain-size diminishes, specific surface area increase etc.) process to qualitative change (grain surface or the inner defective that produces, decrystallized and disordering etc.).Wherein be mainly: 1. lattice distortion: the mechanical force and chemical effect, lattice dot matrix particulate aligning part is lost periodically, and cause spacing to change, form lattice imperfection, grain-size diminishes etc.2. crystal grain is decrystallized: under mechanical force, orderly crystalline network is destroyed, and plane of crystal produces many defectives, makes the crystalline structure disordering, and after mechanical load removes, can not recover.Because the effect of mechanical force, the crystal structure of crystal surface is damaged and forms non-crystalline state; 3. crystal conversion: mechanical force is brought out material and is not changed chemical constitution, and forms such as amorphization, middle junction crystalline phase occur, forms unstable phase; 4. crystal structure one-piece construction distortion: for the mineral substance of this laminate structure of PAL material; Under mechanical force and since interlayer particle bonding force a little less than, under shear action; Generally all open along aspect or the splitting abreast of atomic thin cleavage; Become the lower structure of percent crystallinity,, progressively accomplish one-piece construction and change if continue to impose mechanical force.Layered silicate (PAL material feedstock) is sloughed hydroxyl and bond energy to some extent and is descended under the mechanical activation effect, lost crystalline structure and amorphization.
2, physicochemical property change.1. grain refine: promptly particle diameter diminishes, corresponding specific surface area increases.2. produce many fresh surfaces: fresh surface is the cleaning face, and unsaturated link(age) is arranged, and can produce very high activity.It is the result who removes PAL material surface hydroxyl planar water.3. density reduces: under the effect of mechanical force, caused the change of crystalline structure, crystal is tending towards that disordering, structure are loose relatively, density reduces; 4. electrically change: mechanical force changes micro-nano granules electroconductibility and semiconductor property.Under usual conditions, impose mechanical force like the former powder of sintering barium titanate again, its specific inductivity at room temperature improves 2-3 times.2. surface adsorption ability and ion-exchange capacity strengthen: under the mechanical force, particle is pulverized, and unsaturated link(age) and charged structural unit on surface of fracture, occur, makes particle be in unsettled high-energy state, thus enhanced activity, its surface adsorption ability that improves.Simultaneously, cause the surface to be rich in the activated sites of unsaturated link(age) and residual charge, promoted the raising of ion-exchange capacity or replacing power; 6. solubleness improves: various silicate mineralss, because mechanical force activating can both significantly improve its solubleness and dissolution rate.
3, induced chemical reaction.Mechanical force is the same with form energies such as light, electricity, magnetic, heat, radiation, also can cause the chemical reaction of material.1. mechanical force induced chemical reaction type: under the mechanical force, free energy rising, increased activity, reaction activity reduce, and the reaction of bringing out is divided into according to state of matter: solid-, solid-liquid, consolidate-the gas three major types.2. mechanical force and chemical reaction mechanism: compare with thermodynamics; The mechanical force and chemical reaction has its characteristics; Not necessarily meet the law of thermodynamics, reaction product also maybe be different with thermal chemical reaction, and its reaction mechanism is generally: surface reaction mechanism, self propagating high temperature synthesis mechanism and solid solution-decomposition mechanism.
The purpose of acid activation be for the specific surface area that increases the PAL material with increase surfactivity, realize in the following manner: 1. dissolve partial impurities: disperse to mix living micro-chlorite, illite, feldspar and calcite etc. in purifying with separating in depolymerization; 2. use H
+The Ca of displacement interchangeability
2+3. dissolve a certain amount of Al that is present in the tetrahedron
3+With some Fe
2+, Fe
3+And be present in the Fe in the octahedron
3+(Fe
2+), Al
3+And Mg
2+
The mechanism of PAL material acid activation: 1. the impurity of PAL material has been removed in dissolving, has increased specific surface area (inside and outside surface-area) and avtive spot is provided; 2. the H of minor radius
+The positively charged ion of exchange PAL material crystals interlayer forms the duct; 3. dissolve the Al of part in the octahedron
3+Fe
2+, Fe
3+And Mg
2+Plasma increases duct angle increase, specific surface area increase, the diameter of crystal end-face, and acidifying is complete, and the duct value is bigger; 4. the PAL material after the activation has caused as the same exposure surface of solid acid effect along with cationic taking out of in the octahedron, is linked to each other by hydrogen bond.Activation causes osmosis enhancing, structure to be launched, the duct is open and enlarged-diameter, and surface-area is by 80m
2/ g increases to 200m
2/ g, active site and position also obtain increasing simultaneously.
The PAL material heat treatment is thermal activation, and purpose is improved the physicochemical property of PAL material, and target is to remove the water of four kinds of states of its existence, and these four kinds of water are respectively outside surface planar water (H
2O), duct planar water (H
2O), be present in water of constitution (OH) and crystal water (OH in the crystal
2).DTA (DTA), pine for analyzing (TGA) and show that the first heat absorption paddy belongs to the planar water dehydration effect of outside surface at 65 ℃; The second heat absorption paddy is at 98 ℃, the heat effect (quality of outside surface planar water and duct planar water is 5.87%) of deviating from for the duct planar water; The 3rd heat absorption paddy is equivalent to the endothermic effect that partial crystallization water is deviate to produce at 230 ℃, and heat absorption paddy is less, and wide (WL 3.12%); The 4th heat absorption paddy is at 481 ℃, also broad, and what be equivalent to the second section crystal water deviates from heat effect (dehydrating amount 3.7%); The 5th heat absorption paddy is 595 ℃, corresponding to deviate from (dehydration 5.3%) of water of constitution.Preceding 5 are heat absorption paddy, and exothermic effect only has 1, at 827 ℃, for decomposing due to the crystallization of new thing phase.
In the PAL material thermal activation process, the structure of PAL material, variation has but taken place in pattern and physicochemical property, and the variation of structure and pattern is reflected in the variation of physicochemical property, and for physicochemical property changes theory support is provided.It is generally acknowledged that 400 ℃ of thermal activations have deviate from the planar water of PAL material, partial crystallization water, vacateed space, duct and active site that water molecules occupies, more help the absorption of polarity small molecules.This is the actual purpose of thermal activation (processing), and better temperature is about 252 ℃, and this moment, PAL material specific surface area was maximum.
Because the PAL material is micro-nano crystalline material, external surface area is bigger, not only has physical adsorption, and has exhibiting high surface scission of link combination water, and this bonding water is more firm, deviates to need comparatively high temps.Thermogravimetric analysis shows that the water of constitution dehydrating amount obviously exceeds PAL material structure water theory content.Deviating from of surface tissue water changed PAL material surface character, and the selectivity of molecular adsorption has been had very big variation, just to the contribution of " organising " modification.
It is mechanical force activating, acid activation, the thermal activation associating activation of main body that the present invention adopts with the mechanical force activating, and follows the science and the principle of reasonableness of technical process, has set up acid activation-thermal activation-mechanical force activating technical system.Optimized PAL material product performance, realized the self assembling process of inorganic supermolecular intercalation for the PAL material power and the guide effect of self-assembly is provided.Self-assembly power refers to the synergy of intermolecular interaction force, and it provides energy for the molecule self-assembly; The guide effect of self-assembly refers to the molecule self-assembly and takes place just must on spatial size and direction, reach the molecular transposition requirement.With the mechanical force activating is the activating technology system of major technique approach, through the activation to the PAL material, for realizing inorganic supermolecular intercalation assembling chemical technology " organising " savings of energy and the guide effect of space and direction is provided.What is more important building materials, high molecular polymer etc. more wide spectrum the high performance adjuvant material is provided.
In the inorganic activation technology of above-mentioned nanometer submicron PAL material, in above-mentioned steps A, adopting at a high speed, electricity stone roller device is impacted nanometer submicron PAL material material.
Compared with prior art; The advantage of the inorganic activation technology of this nanometer submicron PAL material is: the mechanical force activating, acid activation, the thermal activation associating activation that with the mechanical force activating are main body; Set up acid activation-thermal activation-mechanical force activating technical system; Optimized PAL material product performance, realized the self assembling process of inorganic supermolecular intercalation for the PAL material power and the guide effect of self-assembly is provided.For realizing that inorganic supermolecular intercalation assembling chemical technology " organising " provides the savings of energy and the guide effect of space and direction.What is more important building materials, high molecular polymer etc. more wide spectrum the high performance adjuvant material is provided.
Embodiment
The inorganic activation technology of this nanometer submicron PAL material comprises the steps:
A, mechanical force and chemical activation: nanometer submicron PAL material material is received violent impact under strong mechanical force; In the ruined while of crystalline structure; The part also can produce plasma body, reduces the temperature of reaction and the activation energy of system, thus the reaction between evocating substance.In the present embodiment, adopting at a high speed, electricity stone roller device is impacted nanometer submicron PAL material material.
B, acid activation: the impurity of nanometer submicron PAL material is removed in dissolving, thereby increases specific surface area; Utilize the H of minor radius
+The positively charged ion of exchange PAL material crystals interlayer, thus the duct formed; The Al of part in the dissolving PAL material octahedron
3+Fe
2+, Fe
3+And Mg
2+Ion increases duct angle increase, specific surface area increase, the diameter of crystal end-face;
C, thermal activation: through to nanometer submicron PAL material type of heating, remove the water of four kinds of states of its existence, promptly outside surface planar water, duct planar water, be present in water of constitution and crystal water in the crystal.
It is " acid activation, thermal activation, mechanical force and chemical activation " technical system of major technique approach that the present invention has constructed with the mechanical force and chemical activating technology; For the PAL material has been optimized performance as stand-alone product; Realize the self assembling process of inorganic supermolecular intercalation assembling chemical technological " organising " for the PAL material, the power and the guiding condition of self-assembly is provided.
The essence of mechanical force and chemical activating technology is the modification of the physical-chemical of micro-nano split; The process of acid activation, thermal activation is also comprising the performance optimization process of physical-chemical.Through the physical-chemical effect of mechanical force and chemical, PAL material powder is carried out activation modification handle, efficiently disperse PAL material powder, obtain best PAL material powder characteristic.In this course; The PAL material granule produces like physical influence and chemical effects such as heat effect, crystal conversion, electrically change, plasma chemicals; Thereby bring out the chemical physics effect of properties-correcting agent; Reach the identification of molecular recognition and position, realize organic modification, reach highly compatible and homodisperse with matrix (organic polymer-based or inorganic based).The thermodynamics and kinetics characteristic of mechanical force and chemical reaction mechanism, reaction is all distinguished with the chemical reaction of routine to some extent.
Mechanical force and chemical can produce multiple effect:
1, crystal habit changes.Material is in crushing process, and crystalline structure has experienced from thing and become (grain-size diminishes, specific surface area increase etc.) process to qualitative change (grain surface or the inner defective that produces, decrystallized and disordering etc.).Wherein be mainly: 1. lattice distortion: the mechanical force and chemical effect, lattice dot matrix particulate aligning part is lost periodically, and cause spacing to change, form lattice imperfection, grain-size diminishes etc.2. crystal grain is decrystallized: under mechanical force, orderly crystalline network is destroyed, and plane of crystal produces many defectives, makes the crystalline structure disordering, and after mechanical load removes, can not recover.Because the effect of mechanical force, the crystal structure of crystal surface is damaged and forms non-crystalline state; 3. crystal conversion: mechanical force is brought out material and is not changed chemical constitution, and forms such as amorphization, middle junction crystalline phase occur, forms unstable phase; 4. crystal structure one-piece construction distortion: for the mineral substance of this laminate structure of PAL material; Under mechanical force and since interlayer particle bonding force a little less than, under shear action; Generally all open along aspect or the splitting abreast of atomic thin cleavage; Become the lower structure of percent crystallinity,, progressively accomplish one-piece construction and change if continue to impose mechanical force.Layered silicate (PAL material feedstock) is sloughed hydroxyl and bond energy to some extent and is descended under the mechanical activation effect, lost crystalline structure and amorphization.
2, physicochemical property change.1. grain refine: promptly particle diameter diminishes, corresponding specific surface area increases.2. produce many fresh surfaces: fresh surface is the cleaning face, and unsaturated link(age) is arranged, and can produce very high activity.It is the result who removes PAL material surface hydroxyl planar water.3. density reduces: under the effect of mechanical force, caused the change of crystalline structure, crystal is tending towards that disordering, structure are loose relatively, density reduces; 4. electrically change: mechanical force changes micro-nano granules electroconductibility and semiconductor property.Under usual conditions, impose mechanical force like the former powder of sintering barium titanate again, its specific inductivity at room temperature improves 2-3 doubly.5. surface adsorption ability and ion-exchange capacity strengthen: under the mechanical force, particle is pulverized, and unsaturated link(age) and charged structural unit on surface of fracture, occur, makes particle be in unsettled high-energy state, thus enhanced activity, its surface adsorption ability that improves.Simultaneously, cause the surface to be rich in the activated sites of unsaturated link(age) and residual charge, promoted the raising of ion-exchange capacity or replacing power; 6. solubleness improves: various silicate mineralss, because mechanical force activating can both significantly improve its solubleness and dissolution rate.
3, induced chemical reaction.Mechanical force is the same with form energies such as light, electricity, magnetic, heat, radiation, also can cause the chemical reaction of material.1. mechanical force induced chemical reaction type: under the mechanical force, free energy rising, increased activity, reaction activity reduce, and the reaction of bringing out is divided into according to state of matter: solid-, solid-liquid, consolidate-the gas three major types.2. mechanical force and chemical reaction mechanism: compare with thermodynamics; The mechanical force and chemical reaction has its characteristics; Not necessarily meet the law of thermodynamics, reaction product also maybe be different with thermal chemical reaction, and its reaction mechanism is generally: surface reaction mechanism, self propagating high temperature synthesis mechanism and solid solution-decomposition mechanism.
The purpose of acid activation be for the specific surface area that increases the PAL material with increase surfactivity, realize in the following manner: 1. dissolve partial impurities: disperse to mix living micro-chlorite, illite, feldspar and calcite etc. in purifying with separating in depolymerization; 2. use H
+The Ca of displacement interchangeability
2+3. dissolve a certain amount of Al that is present in the tetrahedron
3+With some Fe
2+, Fe
3+And be present in the Fe in the octahedron
3+(Fe
2+), Al
3+And Mg
2+
The mechanism of PAL material acid activation: 1. the impurity of PAL material has been removed in dissolving, has increased specific surface area (inside and outside surface-area) and avtive spot is provided; 2. the H of minor radius
+The positively charged ion of exchange PAL material crystals interlayer forms the duct; 3. dissolve the Al of part in the octahedron
3+Fe
2+, Fe
3+And Mg
2+Plasma increases duct angle increase, specific surface area increase, the diameter of crystal end-face, and acidifying is complete, and the duct value is bigger; 4. the PAL material after the activation has caused as the same exposure surface of solid acid effect along with cationic taking out of in the octahedron, is linked to each other by hydrogen bond.Activation causes osmosis enhancing, structure to be launched, the duct is open and enlarged-diameter, and surface-area is by 80m
2/ g increases to 200m
2/ g, active site and position also obtain increasing simultaneously.
The PAL material heat treatment is thermal activation, and purpose is improved the physicochemical property of PAL material, and target is to remove the water of four kinds of states of its existence, and these four kinds of water are respectively outside surface planar water (H
2O), duct planar water (H
2O), be present in water of constitution (OH) and crystal water (OH in the crystal
2).DTA (DTA), pine for analyzing (TGA) and show that the first heat absorption paddy belongs to the planar water dehydration effect of outside surface at 65 ℃; The second heat absorption paddy is at 98 ℃, the heat effect (quality of outside surface planar water and duct planar water is 5.87%) of deviating from for the duct planar water; The 3rd heat absorption paddy is equivalent to the endothermic effect that partial crystallization water is deviate to produce at 230 ℃, and heat absorption paddy is less, and wide (WL 3.12%); The 4th heat absorption paddy is at 481 ℃, also broad, and what be equivalent to the second section crystal water deviates from heat effect (dehydrating amount 3.7%); The 5th heat absorption paddy is 595 ℃, corresponding to deviate from (dehydration 5.3%) of water of constitution.Preceding 5 are heat absorption paddy, and exothermic effect only has 1, at 827 ℃, for decomposing due to the crystallization of new thing phase.
In the PAL material thermal activation process, the structure of PAL material, variation has but taken place in pattern and physicochemical property, and the variation of structure and pattern is reflected in the variation of physicochemical property, and for physicochemical property changes theory support is provided.It is generally acknowledged that 400 ℃ of thermal activations have deviate from the planar water of PAL material, partial crystallization water, vacateed space, duct and active site that water molecules occupies, more help the absorption of polarity small molecules.This is the actual purpose of thermal activation (processing), and better temperature is about 252 ℃, and this moment, PAL material specific surface area was maximum.
Because the PAL material is micro-nano crystalline material, external surface area is bigger, not only has physical adsorption, and has exhibiting high surface scission of link combination water, and this bonding water is more firm, deviates to need comparatively high temps.Thermogravimetric analysis shows that the water of constitution dehydrating amount obviously exceeds PAL material structure water theory content.Deviating from of surface tissue water changed PAL material surface character, and the selectivity of molecular adsorption has been had very big variation, just to the contribution of " organising " modification.
It is mechanical force activating, acid activation, the thermal activation associating activation of main body that the present invention adopts with the mechanical force activating, and follows the science and the principle of reasonableness of technical process, has set up acid activation-thermal activation-mechanical force activating technical system.Optimized PAL material product performance, realized the self assembling process of inorganic supermolecular intercalation for the PAL material power and the guide effect of self-assembly is provided.Self-assembly power refers to the synergy of intermolecular interaction force, and it provides energy for the molecule self-assembly; The guide effect of self-assembly refers to the molecule self-assembly and takes place just must on spatial size and direction, reach the molecular transposition requirement.With the mechanical force activating is the activating technology system of major technique approach, through the activation to the PAL material, for realizing inorganic supermolecular intercalation assembling chemical technology " organising " savings of energy and the guide effect of space and direction is provided.What is more important building materials, high molecular polymer etc. more wide spectrum the high performance adjuvant material is provided.Specific embodiment described herein only is that the present invention's spirit is illustrated.Person of ordinary skill in the field of the present invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although this paper has used term morely, do not get rid of the possibility of using other term.Using these terms only is in order to describe and explain essence of the present invention more easily; It all is contrary with spirit of the present invention being construed to any additional restriction to them.
Claims (2)
1. the inorganic activation technology of a nanometer submicron PAL material is characterized in that this technology comprises the steps:
A, mechanical force and chemical activation: nanometer submicron PAL material material is received violent impact under strong mechanical force; In the ruined while of crystalline structure; The part also can produce plasma body, reduces the temperature of reaction and the activation energy of system, thus the reaction between evocating substance;
B, acid activation: the impurity of nanometer submicron PAL material is removed in dissolving, thereby increases specific surface area; Utilize the H of minor radius
+The positively charged ion of exchange PAL material crystals interlayer, thus the duct formed; The Al of part in the dissolving PAL material octahedron
3+Fe
2+, Fe
3+And Mg
2+Ion increases duct angle increase, specific surface area increase, the diameter of crystal end-face;
C, thermal activation: through to nanometer submicron PAL material type of heating, remove the water of four kinds of states of its existence, promptly outside surface planar water, duct planar water, be present in water of constitution and crystal water in the crystal.
2. the inorganic activation technology of nanometer submicron PAL material according to claim 1 is characterized in that, in above-mentioned steps A, adopting at a high speed, electricity stone roller device is impacted nanometer submicron PAL material material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102321397A (en) * | 2011-06-02 | 2012-01-18 | 杭州正博新型建筑材料有限公司 | Preparation process for high-performance environmentally-friendly PAL (Phenylalanine Ammonia-Lyase) flame-retardant material |
| CN103785337A (en) * | 2013-12-11 | 2014-05-14 | 甘肃金宇生态环境工程有限公司 | Activation method of natural micro-nano nonmetal PAL material |
| CN106145131A (en) * | 2016-07-03 | 2016-11-23 | 河北工业大学 | A kind of preparation method of porous mineral nanometer rods |
| CN108950603A (en) * | 2018-08-31 | 2018-12-07 | 营口忠旺铝业有限公司 | A kind of method for electrolyzing aluminum improving electrolyte dissolution degree |
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|---|---|---|---|---|
| CN1978396A (en) * | 2005-12-06 | 2007-06-13 | 甘肃凯西生态环境工程有限公司 | PAL material slow-release nitrogen fertilizer |
| CN101870871A (en) * | 2010-04-23 | 2010-10-27 | 杭州贝洋科技有限公司 | Preparation method for novel layered nano PAL flame-retardant material |
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2011
- 2011-06-02 CN CN2011101494823A patent/CN102352136A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978396A (en) * | 2005-12-06 | 2007-06-13 | 甘肃凯西生态环境工程有限公司 | PAL material slow-release nitrogen fertilizer |
| CN101870871A (en) * | 2010-04-23 | 2010-10-27 | 杭州贝洋科技有限公司 | Preparation method for novel layered nano PAL flame-retardant material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321397A (en) * | 2011-06-02 | 2012-01-18 | 杭州正博新型建筑材料有限公司 | Preparation process for high-performance environmentally-friendly PAL (Phenylalanine Ammonia-Lyase) flame-retardant material |
| CN103785337A (en) * | 2013-12-11 | 2014-05-14 | 甘肃金宇生态环境工程有限公司 | Activation method of natural micro-nano nonmetal PAL material |
| CN106145131A (en) * | 2016-07-03 | 2016-11-23 | 河北工业大学 | A kind of preparation method of porous mineral nanometer rods |
| CN108950603A (en) * | 2018-08-31 | 2018-12-07 | 营口忠旺铝业有限公司 | A kind of method for electrolyzing aluminum improving electrolyte dissolution degree |
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