CN109851853A - Not molten ceramic filler of low-temperature sintering high temperature and preparation method thereof - Google Patents

Abstract

The invention discloses not molten ceramic fillers of low-temperature sintering high temperature and preparation method thereof, include: refractory fibre A (15~60) part, refractory fibre B (8~50) part, red phosphorus or phosphate (6~20) part, metal hydrate (1~10) part, metal oxide (2~20) part, low melting point ceramic hotmelt (30~70) part, hydrophobic modified dose or cross-linking covering (0.3~7) part；The filler is at least one of mixture, co-melting body homogeneous substance or eutectic homogeneous substance, in fibrous, powdered or granular at least one；Preparation method includes hydrophobic modified or the modified coating equipment of the stupefied nano combined machine of crosslinking cladding process, the wing.The not molten ceramic powder of the base low-temperature sintered high temperature of high polymer is added respectively in the base-materials such as PA6, PE, PP, product weld point is down to 423 DEG C, and softening point is at 950 DEG C or more；Applicability is wide, simple process, at low cost, and extensive industrialization is feasible in Technological Economy.

Description

Not molten ceramic filler of low-temperature sintering high temperature and preparation method thereof

Technical field

The invention belongs to can ceramic polymer composites materials function powder manufacturing field, and in particular to can make Polymer composites materials can be sintered at a lower temperature and become the one of the hot-face insulation ceramics not softened at relatively high temperatures Kind functional additive technology, i.e., low sintering, insoluble ceramic filler of high temperature and preparation method thereof.

Background technique

It is added to the polymer composites materials of filler, such as composite engineering plastics, coating, adhesive, sealant, elasticity Body and foaming body since its light, easily processed into type, resource is easy to get, inexpensive, and are widely used in skyscraper, aviation The every field such as space flight, submarine ship, rail traffic, electron electric power, information engineering, household electrical appliance, machinery, chemical industry.But by In the inflammability of most high polymers itself, superior function and application thereof is not excavated sufficiently also.In fact, from high poly- From object is born, people are just had been working hard, by being introduced into fire-retardant group on strand or adding in base-material fire retardant Etc. technological means and achieve significant progress to scheme to improve the anti-flammability or fire resistance of high polymer.For example, adding more bromine connection Benzene, polybrominated diphenyl ethers and antimony oxide add aluminium hydroxide, magnesium hydroxide, calcium hydroxide, add ammonium polyphosphate and Ji Wusi The powders such as alcohol, melamine can make the anti-flammability of high polymer meet part B/T2406.2, part B/T 24030, part B/T 5169.16 requirement, or meet the highest flame-retardant standard requirement of UL 94 V0 grade, UL 224, or meet wire and cable most The VW-1 requirement of high fire-retardance standard.

But above-mentioned fire-retardant rank is still difficult to meet modern ultrahigh layer building, aerospace, rail traffic, Study on Submarine The more stringent refractory standard requirement in the fields such as oceangoing ship.For example, the A grade requirement of 30624 refractory design of part B is not achieved, also meet not Heatproof 950 DEG C of at least requirements of 180min in architectural electricity fire safety rules.

For this purpose, before and after 2007, domestic project technical staff expand use Ceramic silicon rubber as high polymer fire prevention, The research of refractory material.

Between 2007~2013 years, there is qualified Ceramic silicon rubber product to emerge, product can be marked by BS 6387 The spray of standard, vibration, fire resistance test, but since the tensile strength of silicon rubber, rigidity are too low and cost is too high, and at porcelain temperature 600 DEG C or more [1], the limitation of application range and market potential is difficult to break through [2,3], so far Ceramic silicon rubber product It is not widely applied listing.

Between 2013~2017 years, people attempt invention vitrification polyene diameter composite material and substitute Ceramic silicon rubber, such as:

A kind of ceramic polyolefin fire-resisting cable material of CN 105348627A；

A kind of ceramic polyolefine material of CN 104558805A and preparation method thereof；

A kind of ceramic cable material of polyolefin of CN 106336563A and preparation method thereof；

A kind of ceramic polyolefin fire-resisting cable material of CN 105778239A；

CN 105367965A fire-resisting cable halogen-free flameproof ceramic cable material of polyolefin and preparation method thereof；

CN 104744794A ceramic fire resisting polyene diameter and preparation method thereof, etc..

Although above-mentioned patent application discloses following technical characteristic:

A) polyolefin used in includes EVA, PE, PP, PS, PVC, the ethene-alpha-olefin copolymer (α-the third of low oxygen-containing group Alkene, alpha-butylene, α-hexene, α-octene)；

B) porcelain material used in include Vitrified powder A, Vitrified powder B, Vitrified powder C, white bole, talcum powder, mica powder, pyrophillite, Boromagnesite, datolite, calcite, wollastonite, spodumene, clay, montmorillonite, clay；

C) fire retardant used in includes Sb2O3, Al (0H) 3, M parts of (0H) 2, basic magnesium carbonate, kaolin, zinc borate, boric acid Ammonium, borax, boric anhydride, APP, red phosphorus；

D) adjuvant used includes platinum element catalyst or peroxide initiator；

E) wherein Vitrified powder A includes attapulgite, bentonite, montmorillonite, mica, glass, alumina nano tube, silicic acid Calcium, wollastonite, calcium carbonate crystal whisker, calcium sulfate crystal whiskers, aluminium borate whisker, SiO2, Al2O3, iron oxide, M part O, ZnO, BaO, CaO, carbon black, shepardite, waste ceramic, forsterite, sn-bi alloy, bone meal；

F) wherein Vitrified powder B, undisclosed ingredient；

G) wherein Vitrified powder C, undisclosed ingredient；

H) wherein high softening-point glass is known as (700~800) DEG C, including silicate glass powder, borate glass powder, oxygen Change lime glass powder, bismuth oxide glass powder, undisclosed proportioning components；

I) it includes silicate glass powder, borate glass powder, oxidation that wherein lowization point glass, which is known as (400~600) DEG C, Lime glass powder, phosphate glass powder, undisclosed proportioning components.

But found after the further investigation test of the author team, the above patent application exist market be difficult to tolerate it is following Defect:

Defect one

It may be only available for simple hydro carbons base-material, be not applied for the high polymer of wide spectrum, such as be unsuitable for high oxygen-containing group PA, PU, PET, PBT, PAA.

Defect two

500 DEG C are above at porcelain temperature, causes combustion product dusting without at porcelain.

Defect three

Ceramic polyolefin is below 3H, even lower than 2H at porcelain pencil hardness, and engineering application value is low.

Defect four

Water imbibition is water-soluble too strong, is unfavorable for that outdoor environment should can not be suitable in electron electric power insulation applications.

Defect five

It is burnt in high polymer into ceramic conversion process, is easy the molten original-shape for collapsing, not being able to maintain product of liquefaction.

Further research it is also shown why above-mentioned patent application on Functional Design exist five big defects, ceramic gather Olefin product do not obtain in test the approval of Consensus of experts and client yet, lack market practicability and so far can not industrialization throw It produces, is because of " both ends " that ceramic filler used lacks sufficient amount, softening point is lower than 500 DEG C and fusing point is at 950 DEG C or more Crucial important component --- low temperature sintering hotmelt and superhigh temperature burn the skeleton not collapsed.

Therefore, it is necessary to invent it is a kind of for wide spectrum polymer composites materials, weld point lower than 500 DEG C and 950 DEG C Infusible functional material below becomes high polymer base-material and realizes the indispensable key of ceramic, important component, must ensure height Polymers base reaches 4H or more at porcelain pencil hardness, and is suitable for electron electric power insulation applications, is suitable for outdoor environment, in fire The shape that product can be kept original under calamity environment is collapsed without molten.

Bibliography

[1] Xie Zhonglin Ceramic silicon rubber rubber industry, 2013 volume 60,2013-07-24

[2] ALexander parts of .Chen parts of YB, Burford RP, etal.Fire Resistant Silicone Polymer

Compositions[P]US:USP 7652090B2,2010-01-26

[3] Shao Haibin, Zhang Qishi, Wu Li etc. can the resistance to silicon rubber of ceramic preparation and performance [J] Nanjing University of Technology learn Report is (natural

Scientific version), 2011.33 (1): 48-51

Summary of the invention

The purpose of the present invention is to provide it is a kind of for wide spectrum polymer composites materials, make polymer composites materials Weld point be lower than 500 DEG C and 950 DEG C or less infusible functional materials, become high polymer base-material realization ceramic it is indispensable Crucial important component, reach 4H or more at porcelain pencil hardness with ensure high polymer base, and be suitable for electron electric power and insulate Field is collapsed suitable for outdoor environment, the shape that product can be kept original under fire hazard environment without molten.

One of for the above-mentioned purpose, low-temperature sintering high temperature of the invention does not melt ceramic filler, comprising: according to the mass fraction The formula composition of amount have refractory fibre A (15~60) part, refractory fibre B (8~50) part, red phosphorus or phosphate (6~20) part, Metal hydrate (1~10) part, metal oxide (2~20) part, low melting point ceramic hotmelt (30~70) part, hydrophobic Modifying agent or cross-linking covering (0.3~7) part；The formula composition is that mixture, co-melting body homogeneous substance or eutectic are equal At least one of metallic substance, in fibrous, powdered or granular at least one.

Further, the refractory fibre A includes: the draw ratio of particle in (4~30) times and diameter is in (0.3~30) μm Bulk composition in range is silicon nitride, aluminium oxide, silicon carbide, magnesium silicate, calcium silicates, alumina silicate, magnesium phosphate, calcium phosphate, phosphorus At least one of sour aluminium and mineral wool；The bulk composition is that maximum chemical component of mass content in homogeneous substance.

Further, institute's refractory fibre states that B includes: the draw ratio of particle in (2~15) times and diameter is in (0.1~5) μm In range and bulk composition is silicon nitride, aluminium oxide, silicon carbide, magnesium silicate, calcium silicates, alumina silicate, magnesium phosphate, calcium phosphate, phosphorus At least one of sour aluminium and mineral wool；The bulk composition is that maximum chemical component of mass content in homogeneous substance.

Further, the red phosphorus include: it is powder covered with organic or inorganic substances cladding any one, and partial size exists In (3~35) μ m.Further, the phosphate includes: first group phosphate, the phosphatic at least one set of second group；It is described First group phosphate has by sodium ion, potassium ion, magnesium ion, calcium ion, aluminium ion, zinc ion, organic or inorganic ammonium ion At least one at least one production being bound up with phosphate radical, pyrophosphate, metaphosphoric acid radical, hypophosphorous acid root and orthophosphite Object；The second group phosphate has by sodium ion, potassium ion, magnesium ion, calcium ion, aluminium ion, zinc ion, organic or inorganic ammonium The product that polyphosphoric acid root of at least one and the degree of polymerization of ion in (2~2000) range is bound up.

Further, the metal hydrate include: calcium hydroxide, aluminium hydroxide, magnesium hydroxide, Basic Magnesium Aluminum Carbonate, At least one of basic zinc carbonate, basic copper carbonate.

Further, the metal oxide includes: lithium, sodium, potassium, magnesium, calcium, aluminium, zinc, barium, iron, copper, antimony element oxidation At least one of object.

Further, the low melting point ceramic hotmelt includes: the A type formula and Type B measured according to the mass fraction Formula；The A type formula is measured by raw material additive amount, has silicate (1~50) part, borate (5~70) part, carbonate (0.1~44) part, phosphate (0.1~70) part and halide (1~30) part；The Type B formula is by low melting point ceramic material The chemical composition analysis result of material hotmelt finished product is measured, and has (2.4~28.4) % in terms of silica, with three oxygen Change two boron meter (11.9~39.8) %, (48.6~61.4) % in terms of metal oxide, in terms of phosphorus pentoxide (0.01~ 28.4) %, (2.9~19.3) % in terms of content of halogen；The A type formula and Type B formula have mixture, co-melting body homogeneous object Matter is powdered or granular at least one.

Further, described hydrophobic modified dose or cross-linking covering include: cocinic acid, zinc laurate, linolenic acid, Ethyl orthosilicate, dodecyl benzene sulfonic acid, ethylmaltol, benzotriazole, glyceryl monolaurate, to methylphenyl acetic acid, Stearic acid, zinc stearate, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy Base silane, Triethoxyvinylsilane, vinyltrimethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, ten At least one of six alkyl trimethoxysilanes, hexamethyldisilazane.

Further, the silicate include: by sodium, potassium, magnesium, calcium, barium, aluminium, zinc ion or element at least one with The product that silicic acid and/or silica are bound up.

Further, the borate include: by ammonium, sodium, potassium, zinc ion or element at least one with metaboric acid root, Borate, more borates, diboron trioxide at least one product being bound up.

Further, the carbonate include: lithium carbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, barium carbonate, zinc carbonate, At least one of ferrous carbonate, carbon formula copper carbonate.

Further, the halide include: by magnesium, calcium, aluminium, copper, zinc, chromium, iron, cobalt, tin, silver, gadolinium, gallium ion or The product that at least one and halogen of element is combined into；The halogen has fluorine, chlorine, bromine, the ion of iodine or element at least It is a kind of.

For the above-mentioned purpose two, the preparation method of the not molten ceramic filler of low-temperature sintering high temperature of the invention, comprising: pre- It is dry, hydrophobic modified or crosslinking cladding, re-dry processing step, if the mass fraction of feed moisture content 1.0% or with Under then pre-drying process step can be default；Described hydrophobic modified or crosslinking cladding process step stirs machine, rake using bee slot mill, height The formula composition material is placed in by at least one of the stupefied nano combined machine of formula mixing machine, pants type mixing machine, the wing in advance or continuously In modified coating equipment, hydrophobic modified dose or cross-linking covering are added in advance or are continuously added dropwise/are sprayed at the formula group At in material, opens modified coating equipment and to maintain the temperature (65~130) DEG C of formula composition material to continue 15 minutes to 2.5 small Shi Hou is transferred to re-dry processing step to remove hydrophobic modified dose or cross-linking covering and formula composition material because of chemical reaction Moisture, alcohol or the ammonia lower-molecular substance of generation.

Further, the construction of the stupefied nano combined machine of the wing includes the stupefied type stator of the wing and the stupefied type rotor of the wing, the stator and Rotor use is coaxial, layering, replaces, is nested against one another in concentric shafts, such as by " given layer-turns layer-given layer-and turns layer " or " turns layer- Given layer-turns layer ", any one coaxial regional model of " given layer-turns layer-given layer ", " given layer-turns layer ", the stator and adjacent one Layer rotor can mutually rotate；The number of plies of the stator is at least one layer of, the rotor number of plies is at least one layer of or total number of plies of stator is big In 1, rotor total number of plies be greater than 1 and stator total number of plies and rotor total number of plies difference be 1 or 0.

Wherein, it is to be respectively provided with the fin parallel with axis on the interior outer cylinder of stator and/or rotor that the wing is stupefied Or stupefied muscle, within the scope of (0.1~1.5) mm, every layer of stator and/or every layer turn the stupefied blade distance of the wing between the stator and rotor It is provided at least one radial through-hole in gap between each pair of adjacent foil of son is stupefied, the shape of through-hole is arbitrary, to process just Benefit and it is preferred that one kind of rectangle, circle, kidney-shaped；Parallel distance between the wing of the stator or rotor is stupefied is in (1~25) mm model In enclosing；The stupefied blade radius of curvature of the wing is within the scope of (0.05~2) mm.

Further, the re-dry processing step includes: the static drying of baking oven layering, fluidized bed is continuous drying or flashes The continuous drying at least one of tower；Drying temperature control is in (65~130) DEG C, and static drying layer thickness is in 200mm or less, drying The drying time of time (2~4) h, fluidized bed or flash column is (2~130) s.

Not molten ceramic filler of low-temperature sintering high temperature of the invention and preparation method thereof, advantageous effects are:

1. the weld point of ceramic filler is at 500 DEG C hereinafter, softening point is at 950 DEG C or more；

It, can be by PA, PU, PET, PBT, PAA, EVA, PE, PP, PS, PVC whole ceramic 2. applicability is wide；

3. simple process can put up with and stir machine, rake mixing machine, pants type mixing machine technological equipment using existing bee slot mill, height；

4. raw material is easy to get with resource, is at low cost, extensive industrialization is feasible in Technological Economy.

Specific embodiment

By not molten ceramic filler of the present invention will be described in detail low-temperature sintering high temperature and preparation method thereof technology contents, reality Existing purpose and effect, further illustrate with reference to embodiments.

It is preferred that the formula of six embodiments of the not molten ceramic filler of low-temperature sintering high temperature, is shown in Table 1.

Wherein, composition of raw materials includes ca silicate fibre A, ca silicate fibre B, ammonium polyphosphate, hypo-aluminum orthophosphate, hexa metaphosphoric acid Sodium, aluminium hydroxide, magnesium hydroxide, zinc oxide, self-control low melting point ceramic hotmelt, are powder morphology, respective partial size 1 is shown in Table with mass fraction.

Wherein, the average aspect ratio of ca silicate fibre A is 27, and the average aspect ratio of ca silicate fibre B is 8.

Wherein, the nominal degree of polymerization of ammonium polyphosphate is 1000.

Wherein, low melting point ceramic hotmelt is self-control, and the surveyed softening point of cooling curve method is 423 DEG C.

Wherein, hydrophobic modified dose be 0.8 part of hexadecyl trimethoxy silane, cross-linking covering is ethyl orthosilicate 3.0 part.

The low-temperature sintering high temperature of this group of embodiment not melt ceramic filler preparation method, include: predrying, it is hydrophobic modified or Crosslinking cladding, the processing step of re-dry；It is hydrophobic modified to use the stupefied nano combined machine of the homemade wing with crosslinking cladding process step, 1 formula composition material of table and hydrophobic modified dose, cross-linking covering are added in advance in 1 formula composition material of table, unlatching changes After property coating equipment is allowed to operate and maintains 120 DEG C of temperature of formula composition material material to continue 45 minutes, it is transferred to re-dry technique Step is to remove hydrophobic modified dose or cross-linking covering and powder because chemical reaction generates methanol and ethyl alcohol.

Wherein, the stupefied nano combined machine of the wing includes that the stator with parallel fin on an inner periphery, band is flat on an excircle The rotor of row fin；Gap between stator and the fin of rotor is 0.15mm；Between stator or the fin of rotor it is parallel away from From being 15mm；Blade radius of curvature is 0.8mm.

Wherein, re-dry processing step selects baking oven layering static dry；Drying temperature control is in (120 ± 2) DEG C, static state Drying layer thickness is in (10~13) mm, drying time 2h.

Later, solubility is tested to the not molten ceramic powder finished product of the base low-temperature sintered high temperature of high polymer and comparative example, seen Table 2.

See from table 2, it is breakthrough that the solubility of six embodiments decline volume compared with comparative example, which is greater than 90%, One of.

Later, the not molten ceramic powder of the base low-temperature sintered high temperature of high polymer is added respectively in PA6, PE, PP finished product and right Ratio test polymer composites materials at porcelain temperature and at porcelain pencil hardness, be shown in Table 3.

See from table 3, six embodiments at porcelain temperature, decline volume is greater than compared with commercially available ceramic powder comparative example 130 DEG C, be one of breakthrough；Six embodiments of the calcination at 600 DEG C at porcelain pencil hardness in 4H or more, 1200 DEG C It is not molten to collapse, and comparative example at porcelain pencil hardness in 3H hereinafter, and molten collapsing at 820 DEG C.

Not molten ceramic filler of low-temperature sintering high temperature of the invention and preparation method thereof, advantageous effects are:

1. the weld point of ceramic powder, at 500 DEG C or less and can be down to 423 DEG C, softening point be at 950 DEG C or more；

2. applicability is wide, 423 DEG C can be by PA, PU, PET, PBT, PAA, EVA, PE, PP, PS, PVC whole ceramic；

3. simple process can put up with and stir machine, rake mixing machine technological equipment production line using existing bee slot mill, height；

4. raw material is easy to get with resource, is at low cost, extensive industrialization is feasible in Technological Economy.

Six Example formulations tables of the not molten ceramic filler of 1 low-temperature sintering high temperature of table

The solubility of table 2 six embodiments (1~6) and comparative example

3 six embodiments (7~12) of table are with comparative example at porcelain temperature and pencil hardness

Claims (17)

1. low-temperature sintering high temperature does not melt ceramic filler, characterized by comprising: the formula composition measured according to the mass fraction has Refractory fibre A (15~60) part, refractory fibre B (8~50) part, red phosphorus or phosphate (6~20) part, metal hydrate (1~ 10) part, metal oxide (2~20) part, low melting point ceramic hotmelt (30~70) part, hydrophobic modified dose or cross-linking Covering (0.3~7) part；The formula composition is at least the one of mixture, co-melting body homogeneous substance or eutectic homogeneous substance Kind, in fibrous, powdered or granular at least one.

2. ceramic filler according to claim 1, it is characterised in that the refractory fibre A includes: the draw ratio of particle In (4~30) times and diameter in (0.3~30) μ m and bulk composition be silicon nitride, aluminium oxide, silicon carbide, magnesium silicate, At least one of calcium silicates, alumina silicate, magnesium phosphate, calcium phosphate, aluminum phosphate and mineral wool；The bulk composition is in homogeneous substance That maximum chemical component of middle mass content.

3. ceramic filler according to claim 1, it is characterised in that institute's refractory fibre states the draw ratio that B includes: particle In (2~15) times and diameter is in (0.1~5) μ m and bulk composition is silicon nitride, aluminium oxide, silicon carbide, magnesium silicate, silicon At least one of sour calcium, alumina silicate, magnesium phosphate, calcium phosphate, aluminum phosphate and mineral wool；The bulk composition is in homogeneous substance That maximum chemical component of mass content.

4. ceramic filler according to claim 1, it is characterised in that the red phosphorus include: powder covered with organic or nothing Any one of machine substance cladding, and partial size is in (3~35) μ m.

5. ceramic filler according to claim 1, it is characterised in that the phosphate includes: first group phosphate, second group Phosphatic at least one set or first group phosphate and the phosphatic mixture of second group；The first group phosphate have by sodium, potassium, Magnesium, calcium, aluminium, zinc, organic or inorganic ammonium ion at least one with phosphate radical, pyrophosphate, metaphosphoric acid radical, hypophosphorous acid root and At least one product being combined into of orthophosphite；The second group phosphate has by sodium, potassium, magnesium, calcium, aluminium, zinc, You Jihuo Product made of at least one and the degree of polymerization of the ion of Inorganic Ammonium are closed in the polyphosphoric acid root knot in (2~2000) range.

6. ceramic filler according to claim 1, it is characterised in that the metal hydrate includes: calcium hydroxide, hydrogen Aluminium oxide, magnesium hydroxide, Basic Magnesium Aluminum Carbonate, at least one of basic zinc carbonate, basic copper carbonate.

7. ceramic filler according to claim 1, it is characterised in that the metal oxide include: lithium, sodium, potassium, magnesium, At least one of calcium, aluminium, zinc, barium, iron, copper, antimony element oxide.

8. ceramic filler according to claim 1, it is characterised in that the low melting point ceramic hotmelt includes: The A type formula and Type B formula measured according to the mass fraction；The A type formula be by raw material additive amount measure, have silicate (1~ 50) part, borate (5~70) part, carbonate (0.1~44) part, phosphate (0.1~70) part and halide (1~30) part；Institute Stating Type B formula is measured by the chemical composition analysis result of low melting point ceramic material hotmelt finished product, is had with two Silica meter (2.4~28.4) %, (11.9~39.8) % in terms of diboron trioxide, in terms of metal oxide (48.6~ 61.4) %, (0.01~28.4) %, (2.9~19.3) % in terms of content of halogen in terms of phosphorus pentoxide；The A type formula and B Type formula has mixture, co-melting body homogeneous substance powdered or granular at least one.

9. ceramic filler according to claim 1, it is characterised in that described hydrophobic modified dose or cross-linking covering packet It includes: cocinic acid, zinc laurate, linolenic acid, ethyl orthosilicate, dodecyl benzene sulfonic acid, ethylmaltol, three nitrogen of benzo Azoles, glyceryl monolaurate, to methylphenyl acetic acid, stearic acid, zinc stearate, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy Silane, γ-methacryloxypropyl trimethoxy silane, Triethoxyvinylsilane, vinyltrimethoxysilane, Vinyl three ('beta '-methoxy ethyoxyl) silane, hexadecyl trimethoxy silane, hexamethyldisilazane at least one.

10. ceramic filler according to claim 8, it is characterised in that the silicate include: by sodium, potassium, magnesium, calcium, Barium, aluminium, zinc ion or element the product that is bound up of at least one and silicic acid and/or silica.

11. ceramic filler according to claim 8, it is characterised in that the borate include: by ammonium, sodium, potassium, zinc from At least one production being bound up of at least one and metaboric acid root, borate, more borates, diboron trioxide of son or element Object.

12. ceramic filler according to claim 8, it is characterised in that the carbonate include: lithium carbonate, sodium carbonate, At least one of sodium bicarbonate, potassium carbonate, barium carbonate, zinc carbonate, ferrous carbonate, carbon formula copper carbonate.

13. ceramic filler according to claim 8, it is characterised in that the halide include: by magnesium, calcium, aluminium, copper, Zinc, chromium, iron, cobalt, tin, silver, gadolinium, the ion of gallium or element the product that is combined into of at least one and halogen；The halogen tool There is at least one of fluorine, chlorine, bromine, the ion of iodine or element.

14. the preparation method of the not molten ceramic filler of low-temperature sintering high temperature, it is characterised in that include: predrying, it is hydrophobic modified or Crosslinking cladding, the processing step of re-dry, if the mass fraction of feed moisture content, pre-drying process is walked if 1.0% or less It suddenly can be default；Described hydrophobic modified or crosslinking cladding process step is stirred machine, rake mixing machine, pants type using bee slot mill, height and is mixed The formula composition material is placed in modified coating equipment by at least one of the stupefied nano combined machine of conjunction machine, the wing in advance or continuously, Hydrophobic modified dose or cross-linking covering are added in advance or is continuously added dropwise/is sprayed in the formula composition material, unlatching changes Property coating equipment and after maintaining the temperature (65~130) DEG C of formula composition material to continue 15 minutes to 2.5 hours, is transferred to re-dry Processing step with remove moisture, alcohol that hydrophobic modified dose or cross-linking covering and formula composition material are generated by chemical reaction or Ammonia lower-molecular substance.

15. ceramic filler according to claim 14, it is characterised in that the construction of the stupefied nano combined machine of the wing includes The stupefied type stator of the wing and the stupefied type rotor of the wing, the stator and rotor use are coaxial, layering, replace, is nested against one another in concentric shafts, such as By " given layer-turns layer-given layer-and turns layer " or " turn layer-given layer-and turn layer ", " given layer-turns layer-given layer ", " given layer-turns layer " it is any A kind of coaxial regional model, the stator and adjacent one layer of rotor can mutually rotate；The number of plies at least one layer of the stator, rotor The number of plies is at least one layer of or total number of plies of stator be greater than 1, rotor total number of plies be greater than 1 and stator total number of plies and rotor it is total The difference of the number of plies is 1 or 0.

16. ceramic filler according to claim 15, it is characterised in that the stupefied wing is in stator and/or rotor The fin or stupefied muscle parallel with axis are respectively provided on outer cylinder, the stupefied blade distance of the wing between the stator and rotor is (0.1 ~1.5) within the scope of mm, at least one diameter is provided in the gap between each pair of adjacent foil of every layer of stator and/or every layer of rotor is stupefied To through-hole, the shape of through-hole is arbitrary, for processing convenience it is preferred that one kind of rectangle, circle, kidney-shaped；The stator or rotor The wing it is stupefied between parallel distance within the scope of (1~25) mm；The stupefied blade radius of curvature of the wing is in (0.05~2) mm range It is interior.

17. ceramic filler according to claim 14, it is characterised in that the re-dry processing step includes: baking oven point Layer static drying, at least one that fluidized bed is continuous drying or flash column is continuous drying；Drying temperature is controlled in (65~130) DEG C, static drying layer thickness in 200mm or less, drying time (2~4) h, the drying time of fluidized bed or flash column be (2~ 130)s。