CN109852259A - A kind of high temperature resistant waterproof absorbent-type silicate adhesive and preparation method thereof - Google Patents
A kind of high temperature resistant waterproof absorbent-type silicate adhesive and preparation method thereof Download PDFInfo
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- CN109852259A CN109852259A CN201811311567.5A CN201811311567A CN109852259A CN 109852259 A CN109852259 A CN 109852259A CN 201811311567 A CN201811311567 A CN 201811311567A CN 109852259 A CN109852259 A CN 109852259A
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000000853 adhesive Substances 0.000 title claims abstract description 109
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 76
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000007791 liquid phase Substances 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 239000004111 Potassium silicate Substances 0.000 claims abstract description 33
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 32
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052912 lithium silicate Inorganic materials 0.000 claims abstract description 32
- 229910052913 potassium silicate Inorganic materials 0.000 claims abstract description 32
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 32
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 31
- 239000000945 filler Substances 0.000 claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 45
- 238000001354 calcination Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052627 muscovite Inorganic materials 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 12
- 229910021502 aluminium hydroxide Inorganic materials 0.000 abstract 3
- 239000000084 colloidal system Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 9
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 9
- 238000000227 grinding Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000002052 molecular layer Substances 0.000 description 2
- 229910001120 nichrome Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241001089723 Metaphycus omega Species 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention belongs to silicate adhesive technology fields, a kind of high temperature resistant waterproof absorbent-type silicate adhesive and preparation method thereof is provided, the silicate adhesive is by including that following reaction raw materials are prepared: liquid phase silicate mixture, curing agent, inorganic toughening filler；Wherein, liquid phase silicate mixture is the mixed solution of potassium silicate solution and lithium metasilicate solution；Curing agent is by including that the reaction raw materials of aluminium hydroxide and phosphoric acid are prepared；It is in terms of 100% by the total weight of solute in liquid phase silicate mixture, aluminium hydroxide, phosphoric acid solution and inorganic toughening filler, 30~35% liquid phase silicate mixture, 2~3% aluminium hydroxide, the solute in 8~12% phosphoric acid solution, 43~60% inorganic toughening filler；Wherein, liquid phase silicate mixture is the mixed solution of potassium silicate solution and lithium metasilicate solution.Gained silicate adhesive of the invention can be realized preferably water-fast Molecular Adsorption and insulation performance in hot humid environment.
Description
Technical Field
The invention belongs to the technical field of silicate adhesives, and particularly relates to a high-temperature-resistant waterproof adsorption type silicate adhesive and a preparation method thereof.
Background
Under normal conditions, the high modulus ratio silicate colloid and the solid ceramic powder can be cured by heating to form the polycrystalline composite inorganic adhesive with a ceramic structure, which has the characteristics of high temperature resistance (up to 1000-3000 ℃), good insulation, high corrosion resistance, high wear resistance and the like, and can be widely applied to high temperature resistance connection of electronic components and insulation bonding among dissimilar materials.
However, used in special conditionsIn the process (such as high-temperature humid environment), a large amount of active SiO exists on the surface of the colloid after the silicate adhesive is cured2Particles of SiO2The particles can absorb water molecules in the environment on the surface of the colloid through chemical and physical actions to gradually form a water molecular layer; under the action of an applied electric field, the bonded parts (generally metal parts) are communicated with each other through a water molecular layer on the surface of the colloid, so that the insulating property between the colloid and the bonded parts is reduced. In addition, a large number of micro cracks exist on the surface of the cured silicate adhesive, and the water molecules adsorbed on the surface of the cured silicate adhesive can more easily permeate into the colloid through the cracks to dissolve free alkali metal ions in the colloid, so that the adhesive strength of the colloid is greatly reduced, and the phenomena of adhesive failure and the like occur.
Therefore, the above reasons limit the application of silicate adhesives in special working conditions.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant waterproof adsorption type silicate adhesive and a preparation method thereof, aiming at the problems of the existing silicate adhesive.
In order to achieve the purpose, the invention provides a high-temperature-resistant waterproof adsorption type silicate adhesive which is prepared from the following reaction raw materials: liquid phase silicate mixture, curing agent and inorganic toughening filler; wherein,
the liquid phase silicate mixture is a mixed solution of a potassium silicate solution and a lithium silicate solution;
the curing agent is obtained by contacting a suspension of aluminum hydroxide in water with a phosphoric acid solution for reaction, dehydrating, drying and calcining the obtained reaction product at 350-450 ℃, and then heating to 750-800 ℃ for calcination polymerization;
based on the total weight of the solute and the inorganic toughening filler in the liquid phase silicate mixture, the aluminum hydroxide and the phosphoric acid solution as 100 wt%,
according to the high-temperature-resistant waterproof adsorption type silicate adhesive provided by the invention, preferably, in the mixed solution, the ratio of potassium silicate: the mass ratio of the lithium silicate is 2-2.5: 1;
more preferably, the modulus ratio of the potassium silicate is SiO2/K2O is 3.0 to 5.0, and the mass concentration of the potassium silicate solution is 30 to 40 percent; the modulus ratio of the lithium silicate is SiO2/Li2O is 5.0 to 9.0, and the mass concentration of the lithium silicate solution is 30 to 40%. As will be appreciated by those skilled in the art, the modulus ratio of the potassium silicate described herein is SiO2/K2O is SiO in potassium silicate2And K2The ratio of the amount of substance of O; the modulus ratio of the lithium silicate is SiO2/Li2O is SiO in lithium silicate2With Li2The ratio of the amount of substance of O.
According to the high-temperature-resistant waterproof adsorption type silicate adhesive provided by the invention, preferably, P in the phosphoric acid solution2O5The mass concentration of (A) is 50-55%.
According to the high-temperature-resistant waterproof adsorption-type silicate adhesive provided by the invention, preferably, the inorganic toughening filler comprises: silicon dioxide powder, flaky muscovite, potassium hexatitanate inorganic crystal whisker and alumina powder; based on the total weight of the solute and the inorganic toughening filler in the liquid phase silicate mixture, the aluminum hydroxide and the phosphoric acid solution as 100 wt%,
more preferably, the silica powder is a mixture of silicas of different particle sizes; the mass ratio of the silicon dioxide with different particle diameters is 10 nanometers: 1000 meshes: 600 meshes: 400 meshes: 1 for 200 meshes: (1-2): (2.5-3): (2.5-3): 2.
using SiO of different particle sizes2The powder can be mixed with flaky muscovite as filler to make SiO2When the powder is more finely surrounded in the gaps of the flaky muscovite, a good sealing effect is obtained; meanwhile, the flaky dolomite matrix material not only improves the compactness of the colloid, but also plays an excellent shielding role and blocks a permeation line of a liquid-phase medium; in addition, the potassium hexatitanate inorganic whisker is used as a modified filler, so that the overall bonding strength and the water resistance of the adhesive are improved, the toughness is enhanced, and the adhesive has good heat resistance.
Another object of the present invention is to provide a method for preparing the above high temperature resistant waterproof adsorption type silicate adhesive, which comprises the following steps:
1) preparation of a liquid phase silicate mixture: contacting and mixing a potassium silicate solution and a lithium silicate solution according to the mass ratio to obtain a liquid phase silicate mixture;
2) preparation of the curing agent: contacting a suspension of aluminum hydroxide in water with a phosphoric acid solution according to a mass ratio to react; dehydrating, drying and calcining the obtained reaction product at 350-450 ℃, and then heating to 750-800 ℃ for calcining polymerization to obtain the curing agent;
3) preparing and curing the silicate adhesive: and mixing the prepared liquid phase silicate mixture, the inorganic toughening filler and the prepared curing agent according to a mass ratio, uniformly stirring, and bonding and packaging to obtain the silicate adhesive.
According to the preparation method provided by the invention, preferably, in the step 1), the reaction process conditions of the potassium silicate solution and the lithium silicate solution comprise: the stirring speed is 1200-1500 rpm, the reaction temperature is 35-45 ℃, and the reaction time is 1-2 h.
According to the preparation method provided by the invention, preferably, in the step 2), the phosphoric acid solution and the aluminum hydroxide suspension are uniformly stirred at 50-60 ℃, and then the temperature is continuously increased to 85-95 ℃ for full reaction; the reaction time is 1-1.5 h.
More preferably, in the step 2), the curing agent obtained by calcining, calcining and polymerizing is cooled and then pulverized and ground, and the number of grinding meshes is 400 to 600 meshes.
More preferably, the calcination time is 2.5-3 h, and the calcination polymerization time is 2.5-3.5 h.
According to the preparation method provided by the invention, preferably, the preparation method further comprises the following steps: curing and heat-treating the silicate adhesive obtained in the step 3).
More preferably, the curing process performed on the obtained silicate adhesive is: standing the obtained silicate adhesive at room temperature for 20-24 h, and then, keeping the temperature at 80-90 ℃ for drying for 2-2.5 h; and then heating to 140-160 ℃ for curing for 1-1.5 h, and cooling to obtain the cured silicate adhesive.
More preferably, the heat treatment process of the cured silicate adhesive is as follows: and (3) carrying out heat treatment on the cured silicate adhesive at 400-800 ℃ for 1.5-2 h, and then cooling to obtain the high-temperature-resistant waterproof adsorption type silicate adhesive. After the adhesive sample is subjected to heat treatment at 400 ℃ or above, SiO on the surface of the colloid can be formed2The structure of the active group on the colloidal particle is changed, so that the adsorption function of the colloidal particle on water molecules is lost, and the insulating property of an adhesive sample is greatly improved. In addition, as the heat treatment temperature rises, the phosphate double salt, silicate and SiO in the colloid2The self-healing phenomenon of the microcracks is more obvious along with the rise of the heat treatment temperature, so that the overall mechanical property of the adhesive sample is improved.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1) the lithium silicate in the liquid-phase silicate mixture has good waterproofness, but the price is high, the bonding strength is low, and a certain amount of potassium silicate is mixed, so that the bonding strength of the adhesive is enhanced, and the cost of the adhesive is reduced;
2) the curing agent prepared by adopting the aluminum hydroxide and the phosphoric acid can be slowly hydrolyzed in an alkaline solution, and H is released+Promoting the gelatinization of silicate (i.e. the formation of silica gel particles); as the water in the colloid evaporates, the colloidal silica particles are condensed into a net-shaped coating film of "-Si-O-Si-", and simultaneously, alkali metal ions in the silicate release protons (namely H)+) The condensed phosphate generates a water-insoluble double salt which is fixed in a net structure, so that the water resistance of the adhesive is greatly improved;
3) after the adhesive sample is subjected to heat treatment, the insulating property of the adhesive sample can be greatly improved; in addition, the overall mechanical property of the adhesive sample is improved along with the rise of the heat treatment temperature to a certain value;
4) using SiO of different particle sizes2The powder and the flaky muscovite are mixed to be used as the filler, so that the compactness of the colloid can be improved, an excellent shielding effect can be achieved, and a permeation line of a liquid-phase medium in the colloid is blocked; in addition, the potassium hexatitanate inorganic whisker is used as a modified filler, so that the overall bonding strength, toughness and heat resistance of the adhesive can be improved, the number of microcracks generated on the surface of a colloid due to thermal stress is reduced in a subsequent high-temperature heat treatment process, and the waterproof performance of the adhesive after heat treatment is improved.
Drawings
Fig. 1 is a schematic view of an electronic device filled with a silicate adhesive as an insulating material.
The numbers in the above figures are illustrated as follows:
1-stainless steel sleeve; 2-alloy wire; 3-a filler of a silicate adhesive.
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
The high-temperature-resistant waterproof adsorption type silicate adhesive is prepared from the following reaction raw materials: liquid phase silicate mixture, curing agent and inorganic toughening filler; wherein,
the liquid phase silicate mixture is a mixed solution of a potassium silicate solution and a lithium silicate solution;
the curing agent is obtained by contacting a suspension of aluminum hydroxide in water with a phosphoric acid solution for reaction, dehydrating, drying and calcining the obtained reaction product at 350-450 ℃, and then heating to 750-800 ℃ for calcination polymerization;
based on the total weight of the solute and the inorganic toughening filler in the liquid phase silicate mixture, the aluminum hydroxide and the phosphoric acid solution as 100 wt%,
30-35 wt% of liquid phase silicate mixture,
e.g., 32 wt%, 34 wt%;
2 to 3 wt% of aluminum hydroxide,
for example, 2.5 wt%;
8-12 wt% of solute in the phosphoric acid solution,
for example, 9 wt%, 10 wt%, 11 wt%;
43-60 wt% of inorganic toughening filler,
for example, 45 wt%, 50 wt%, 55 wt%.
In a preferred embodiment, in the mixed solution, the ratio of the solute potassium silicate: the mass ratio of solute lithium silicate is 2-2.5: 1, e.g., 2.3: 1;
more preferably, the modulus ratio of the potassium silicate is SiO2/K2O is 3.0 to 5.0, and the mass concentration of the potassium silicate solution is 30 to 40 percent; the modulus ratio of the lithium silicate is SiO2/Li2O is 5.0 to 9.0, and the mass concentration of the lithium silicate solution is 30 to 40%.
In a preferred embodiment, P is present in the phosphoric acid solution2O5The mass concentration of (A) is 50-55%.
In a preferred embodiment, the inorganic toughening filler comprises: silicon dioxide powder, flaky muscovite, potassium hexatitanate inorganic crystal whisker and alumina powder; based on the total weight of the solute and the inorganic toughening filler in the liquid phase silicate mixture, the aluminum hydroxide and the phosphoric acid solution as 100 wt%,
20-25 wt% of silicon dioxide powder,
e.g., 22 wt%, 24 wt%;
10-15 wt% of flaky muscovite,
e.g., 11 wt%, 13 wt%;
8-10 wt% of potassium hexatitanate inorganic whisker,
for example, 9 wt%;
5-10 wt% of alumina powder,
e.g., 6 wt%, 8 wt%;
more preferably, the silica powder is a mixture of silicas of different particle sizes; the mass ratio of the silicon dioxide with different particle diameters is 10 nanometers: 1000 meshes: 600 meshes: 400 meshes: 1 for 200 meshes: (1-2): (2.5-3): (2.5-3): 2, e.g., 1:1.5:2.5:2.5:2, 1:1.5:2.8:2.8: 2.
In the invention, the preparation method of the high-temperature-resistant waterproof adsorption type silicate adhesive comprises the following steps:
1) preparation of a liquid phase silicate mixture: contacting and mixing a potassium silicate solution and a lithium silicate solution according to the mass ratio to obtain a liquid phase silicate mixture;
2) preparation of the curing agent: contacting a suspension of aluminum hydroxide in water with a phosphoric acid solution according to a mass ratio to react; dehydrating, drying and calcining the obtained reaction product at 350-450 ℃, and then heating to 750-800 ℃ for calcining polymerization to obtain the curing agent;
3) preparing and curing the silicate adhesive: and mixing the prepared liquid phase silicate mixture, the inorganic toughening filler and the prepared curing agent according to a mass ratio, uniformly stirring, and bonding and packaging to obtain the silicate adhesive.
In a preferred embodiment, in step 1), the reaction process conditions of the potassium silicate solution and the lithium silicate solution include: the stirring speed is 1200-1500 rpm, the reaction temperature is 35-45 ℃, and the reaction time is 1-2 h.
In a preferred embodiment, in the step 2), the phosphoric acid solution and the aluminum hydroxide suspension are uniformly stirred at 50-60 ℃, and then the temperature is continuously increased to 85-95 ℃ for full reaction; the reaction time is 1-1.5 h. Here, the mass concentration of the aluminum hydroxide suspension may be 40 to 50%, for example, 50%.
More preferably, in the step 2), the curing agent obtained by calcining, calcining and polymerizing is cooled and then pulverized and ground, and the number of grinding meshes is 400 to 600 meshes.
More preferably, the calcination time is 2.5-3 h, and the calcination polymerization time is 2.5-3.5 h.
In a preferred embodiment, the preparation method further comprises: curing and heat-treating the silicate adhesive obtained in the step 3).
More preferably, the curing process performed on the obtained silicate adhesive is: standing the obtained silicate adhesive at room temperature for 20-24 h, and then, keeping the temperature at 80-90 ℃ for drying for 2-2.5 h; and then heating to 140-160 ℃ for curing for 1-1.5 h, and cooling to obtain the cured silicate adhesive.
More preferably, the heat treatment process of the cured silicate adhesive is as follows: and (3) carrying out heat treatment on the cured silicate adhesive at 400-800 ℃ (for example, 500 ℃, 600 ℃ and 700 ℃) for 1.5-2 h, and then cooling to obtain the high-temperature-resistant waterproof adsorption type silicate adhesive.
The raw material sources are as follows:
potassium silicate solution (Qingdao Bidao silicide Co., Ltd., type 1-technical grade),
lithium silicate solution (Zhengzhou Zhi Yuan chemical products Co., Ltd., industrial grade),
aluminum hydroxide (Shenyang Zhongtian Hai Hua environmental protection science and technology Co., Ltd., chemical purity),
phosphoric acid solution (Tianjin Rong Macro chemical Co., Ltd., chemical purity),
silica powders of different particle sizes (Weifang Ming Chengxi New Material Co., Ltd., Industrial grade),
flake muscovite (Cisco county Huayuan mica Co., Ltd., technical grade),
potassium hexatitanate inorganic whisker (Nantong ao New electronic technology Co., Ltd., chemical purity),
alumina powder (Zibose Mill materials Co., Ltd., industrial grade),
conventional curing agent (Zinc oxide/magnesium oxide, Henan sublimation chemical products Co., Ltd./Weifang Hai)
Rilongmagne industries, ltd).
Example 1
The preparation method of the high-temperature-resistant waterproof adsorption type silicate adhesive and the heat treatment method thereof comprise the following specific steps of taking the total weight of solutes and inorganic toughening fillers in a liquid phase silicate mixture, aluminum hydroxide and phosphoric acid solution as 100 wt%:
1) preparation of a liquid phase silicate mixture: firstly, pouring 23.4 wt% of potassium silicate solution (the mass concentration of the potassium silicate solution is 30% and the modulus ratio is 5.0) into a reaction vessel provided with a constant-temperature magnetic stirrer, dropwise adding 11.6 wt% of lithium silicate solution (the mass concentration of the lithium silicate solution is 30% and the modulus ratio is 9.0) under the high-speed stirring of 1500rpm, and then heating the system to 45 ℃ and stirring for 1h to obtain a liquid phase silicate mixture;
2) preparation of the curing agent: 2.5 wt% of aluminum hydroxide and deionized water were made into a suspension, and then a 20 wt% phosphoric acid solution (P in solution) was added2O550%) is added into a reaction kettle and slowly poured with aluminum hydroxide suspension; heating the reaction kettle to 60 ℃, keeping the temperature constant, continuously stirring, continuously heating to 90 ℃ to fully react for 1h, and then cooling to room temperature; putting the obtained reaction product into an oven for dehydration, drying to constant weight, calcining for 2.5h at 450 ℃ in a muffle furnace, heating to 800 ℃ for calcining and polymerizing for 2.5h to obtain the curing agent, cooling, and crushing and grinding the blocks by using a ball mill pulverizer, wherein the grinding mesh number is 400 meshes;
3) preparing and curing the silicate adhesive: sequentially adding 20 wt% of silicon dioxide powder (the mass ratio of the particle diameter is 10 nanometers: 1000 meshes: 600 meshes: 400 meshes: 200 meshes: 1: 2: 2.5:2.5: 2), 15 wt% of sheet muscovite and 10 wt% of potassium hexatitanate inorganic crystal whisker into the prepared liquid phase silicate mixture, stirring for 30min, adding 7.5 wt% of alumina powder and the ground curing agent, and uniformly stirring to bond or encapsulate the base material;
4) placing the bonded and packaged adhesive sample at room temperature for 24h, placing the sample in a drying oven, keeping the temperature at 80 ℃ for 2.5h, then heating to 150 ℃, placing the sample for 1.5h for curing, and then cooling the sample along with the oven to obtain a cured adhesive sample;
5) and (3) putting the cured silicate adhesive sample into a muffle furnace, heating to 400 ℃, keeping the temperature for 2 hours, and cooling along with the furnace, wherein the heating rate is 10-20 ℃/min.
Example 2
The preparation and curing of the high-temperature-resistant waterproof adsorption type silicate adhesive are as in example 1, except that the cured silicate adhesive sample is put into a muffle furnace to be heated to 600 ℃, the heating rate is 10-20 ℃/min, the temperature is kept for 1.5h, and then the silicate adhesive is cooled along with the furnace.
Example 3
The preparation method of the high-temperature-resistant waterproof adsorption type silicate adhesive and the heat treatment method thereof comprise the following specific steps of taking the total weight of solutes and inorganic toughening fillers in a liquid phase silicate mixture, aluminum hydroxide and phosphoric acid solution as 100 wt%:
1) preparation of a liquid phase silicate mixture: firstly, pouring 25 wt% of potassium silicate solution (the mass concentration of the potassium silicate solution is 35% and the modulus ratio is 4.0) into a reaction container provided with a constant-temperature magnetic stirrer, dropwise adding 10 wt% of lithium silicate solution (the mass concentration of the lithium silicate solution is 35% and the modulus ratio is 6.0) under the high-speed stirring of 1500rpm, raising the temperature of the system to 45 ℃, and stirring for 1 hour to obtain a liquid-phase silicate mixture;
2) preparation of the curing agent: 2.5 wt% of aluminum hydroxide and deionized water were made into a suspension, and then a 20 wt% phosphoric acid solution (P in solution) was added2O550%) is added into a reaction kettle and slowly poured with aluminum hydroxide suspension; heating the reaction kettle to 60 ℃, keeping the temperature constant, continuously stirring, continuously heating to 90 ℃ to fully react for 1h, and then cooling to room temperature; putting the obtained reaction product into a baking ovenDehydrating in a box, drying to constant weight, calcining in a muffle furnace at 450 ℃ for 2.5h, heating to 800 ℃ for calcining and polymerizing for 2.5h to obtain the curing agent, cooling, and crushing and grinding the blocks by using a ball mill pulverizer, wherein the grinding mesh number is 400 meshes;
3) preparing and curing the silicate adhesive: sequentially adding 20 wt% of silicon dioxide powder (the mass ratio of the particle diameter is 10 nanometers: 1000 meshes: 600 meshes: 400 meshes: 200 meshes: 1: 2: 2.5:2.5: 2), 15 wt% of sheet muscovite and 10 wt% of potassium hexatitanate inorganic crystal whisker into the prepared liquid phase silicate mixture, stirring for 30min, adding 7.5 wt% of alumina powder and the ground curing agent, and uniformly stirring to bond or encapsulate the base material;
4) placing the bonded and packaged adhesive sample at room temperature for 24h, placing the sample in a drying oven, keeping the temperature at 80 ℃ for 2.5h, then heating to 160 ℃, placing the sample for 1h for curing, and then cooling the sample along with the oven to obtain a cured adhesive sample;
5) and (3) putting the cured silicate adhesive sample into a muffle furnace, heating to 800 ℃, wherein the heating rate is 10-20 ℃/min, and carrying out heat preservation for 1.5h and then cooling along with the furnace.
Example 4
The preparation method of the high-temperature-resistant waterproof adsorption type silicate adhesive and the heat treatment method thereof comprise the following specific steps of taking the total weight of solutes and inorganic toughening fillers in a liquid phase silicate mixture, aluminum hydroxide and phosphoric acid solution as 100 wt%:
1) preparation of a liquid phase silicate mixture: firstly, pouring 22 wt% of potassium silicate solution (the mass concentration of the potassium silicate solution is 40% and the modulus ratio of the potassium silicate solution is 3.0) into a reaction vessel provided with a constant-temperature magnetic stirrer, dropwise adding 10 wt% of lithium silicate solution (the mass concentration of the lithium silicate solution is 30% and the modulus ratio of the lithium silicate solution is 8.0) under the high-speed stirring of 1400rpm, raising the temperature of the system to 40 ℃, and stirring for 1 hour to obtain a liquid-phase silicate mixture;
2) preparation of the curing agent: 3 wt% of aluminum hydroxide and deionized water are prepared into suspensionThen, 18 wt% phosphoric acid solution (P) was added2O550%) was added to the reaction vessel and the aluminum hydroxide suspension was poured slowly; heating the reaction kettle to 55 ℃, keeping the temperature constant, continuously stirring, continuously heating to 85 ℃ to fully react for 1.5h, and then cooling to room temperature; putting the obtained reaction product into an oven for dehydration, drying to constant weight, calcining for 2.5h at 400 ℃ in a muffle furnace, heating to 780 ℃ for calcining and polymerizing for 2.5h to obtain the curing agent, cooling, and crushing and grinding the blocks by using a ball mill pulverizer, wherein the grinding mesh number is 500 meshes;
3) preparing and curing the silicate adhesive: sequentially adding 24 wt% of silicon dioxide powder (the mass ratio of the particle diameter is 10 nanometers: 1000 meshes: 600 meshes: 400 meshes: 200 meshes: 1: 3: 3: 2), 12 wt% of flaky muscovite and 10 wt% of potassium hexatitanate inorganic crystal whisker into the prepared liquid phase silicate mixture, stirring for 30min, adding 10 wt% of alumina powder and the ground curing agent, stirring uniformly, and bonding or packaging the base material;
4) placing the bonded and packaged adhesive sample at room temperature for 24h, placing the sample in a drying oven for heat preservation at 90 ℃ for 2.5h, then heating to 160 ℃ and placing for 1h for curing, and then cooling along with the oven to obtain a cured adhesive sample;
5) and (3) putting the cured silicate adhesive sample into a muffle furnace, heating to 600 ℃, keeping the temperature for 2 hours, and cooling along with the furnace, wherein the heating rate is 10-20 ℃/min.
Comparative example 1
The preparation and curing of the high-temperature-resistant waterproof adsorption type silicate adhesive are as in example 4, except that the adhesive sample cured in the step (4) is not placed in a muffle furnace for a subsequent heat treatment process.
Comparative example 2
Preparation and curing of the high temperature resistant waterproof adsorption type silicate adhesive are as in example 4, except that the curing agent is replaced by zinc oxide/magnesium oxide (zinc oxide: magnesium oxide is 1:1, and the amount of the curing agent accounts for 12 wt% of the total amount of the components).
Comparative example 3
The preparation and curing of the high temperature resistant waterproof adsorption type silicate adhesive was as in example 4 except that the liquid phase silicate used was a single potassium silicate solution (in an amount of 32 wt% based on the total weight of the components).
Comparative example 4
The preparation and curing of the high temperature resistant waterproof adsorption type silicate adhesive are as in example 4, except that the inorganic toughening filler is single 400-mesh SiO2Solid powder (accounting for 56 wt% of the formula).
Application examples of silicate adhesives:
an electronic device is shown in figure 1, wherein the shell is a stainless steel sleeve, and the silicate adhesive prepared in each example and comparative example is filled in the shell. A nichrome wire is inserted into the centers of two ends of the sleeve respectively, and the sleeve and the nichrome wire are filled and insulated by silicate adhesive. The device is placed in a high-temperature and humid environment for use, and the adsorption of the surface of the adhesive to moisture is observed, and the insulating property of the device is tested.
And (3) testing the insulation performance of the device: the outer lead wires are connected to the alloy wires at two ends of the sleeve, the single-hole quartz sleeve is sleeved outside the sleeve for insulation protection, the silicate adhesives prepared in each embodiment and each comparative example are respectively placed in a room-temperature constant-humidity test box, and are respectively placed in environments with humidity of 50%, 60%, 70%, 80% and 90% for 6 hours, and then the insulation resistance values of the outer lead wires are measured by using an insulation resistance meter, and the table 1 shows.
TABLE 1 insulation resistance (/ M.OMEGA.) of test specimens
① shows insulation failure under insulation resistance meter measurement
Due to the adsorption effect of the surfaces (exposed parts at two ends of the sleeve) of the adhesives prepared in each proportion on water molecules, water molecule layers are gradually formed, and the alloy wires and the stainless steel sleeve are communicated through the water molecule layers on the surfaces of the adhesives, so that the insulation failure or poor insulation performance of the device is caused. In the technical scheme, the adhesive prepared by each embodiment has higher water-resistant adsorbability, and the water molecule layer forming capability of the exposed part of the adhesive is lower, so that the insulating property of a device is better.
As can be seen from the comparison between the experimental results of example 4 and comparative example 1, the insulating property of the adhesive after heat treatment is improved by times compared with the adhesive sample after curing without performing the subsequent heat treatment process. Compared with the conventional curing agent, the curing agent prepared from aluminum hydroxide and phosphoric acid promotes the gelatinization of silicate (i.e., silica gel particles are generated), so that the water resistance of the adhesive is greatly improved, and the insulating property of the device is better. Compared with the experimental results of the comparative example 3 and the example 4, the lithium silicate in the liquid phase silicate mixture has better water resistance, can enhance the bonding strength of the adhesive and has higher water-resistant adsorption compared with the single potassium silicate. From the comparison of the experimental results of example 4 and comparative example 4, it can be seen that SiO is added singly2In contrast, SiO with different particle sizes is used2The powder and the flaky muscovite are mixed to be used as the filler, so that the compactness of the colloid is improved, and the permeation line of the liquid-phase medium in the colloid is blocked; in addition, the potassium hexatitanate inorganic whisker is used as a modified filler, so that the overall bonding strength, toughness and heat resistance of the adhesive can be improved, the number of microcracks generated on the surface of a colloid due to thermal stress is reduced in a subsequent high-temperature heat treatment process, and the waterproof performance of the adhesive after heat treatment is improved.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. The high-temperature-resistant waterproof adsorption type silicate adhesive is characterized by being prepared from the following reaction raw materials: liquid phase silicate mixture, curing agent and inorganic toughening filler; wherein,
the liquid phase silicate mixture is a mixed solution of a potassium silicate solution and a lithium silicate solution;
the curing agent is obtained by contacting a suspension of aluminum hydroxide in water with a phosphoric acid solution for reaction, dehydrating, drying and calcining the obtained reaction product at 350-450 ℃, and then heating to 750-800 ℃ for calcination polymerization;
based on the total weight of the solute and the inorganic toughening filler in the liquid phase silicate mixture, the aluminum hydroxide and the phosphoric acid solution as 100 wt%,
2. the high-temperature-resistant waterproof adsorption-type silicate adhesive according to claim 1, wherein in the mixed solution, the ratio of potassium silicate: the mass ratio of the lithium silicate is 2-2.5: 1;
preferably, the modulus ratio of the potassium silicate is SiO2/K2O is 3.0 to 5.0, and the mass concentration of the potassium silicate solution is 30 to 40 percent; the modulus ratio of the lithium silicate is SiO2/Li2O is 5.0 to 9.0, and the mass concentration of the lithium silicate solution is 30 to 40%.
3. The high-temperature-resistant waterproof adsorption-type silicate adhesive as claimed in claim 2, wherein P in the phosphoric acid solution is2O5The mass concentration of (A) is 50-55%.
4. The high-temperature-resistant waterproof adsorption-type silicate adhesive according to claim 1, wherein the inorganic toughening filler comprises: silicon dioxide powder, flaky muscovite, potassium hexatitanate inorganic crystal whisker and alumina powder; based on the total weight of the solute and the inorganic toughening filler in the liquid phase silicate mixture, the aluminum hydroxide and the phosphoric acid solution as 100 wt%,
preferably, the silicon dioxide powder is a mixture of silicon dioxide with different particle sizes; the mass ratio of the silicon dioxide with different particle diameters is 10 nanometers: 1000 meshes: 600 meshes: 400 meshes: 1 for 200 meshes: (1-2): (2.5-3): (2.5-3): 2.
5. a preparation method of the high-temperature-resistant waterproof adsorption type silicate adhesive as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
1) preparation of a liquid phase silicate mixture: contacting and mixing a potassium silicate solution and a lithium silicate solution according to the mass ratio to obtain a liquid phase silicate mixture;
2) preparation of the curing agent: contacting a suspension of aluminum hydroxide in water with a phosphoric acid solution according to a mass ratio to react; dehydrating, drying and calcining the obtained reaction product at 350-450 ℃, and then heating to 750-800 ℃ for calcining polymerization to obtain the curing agent;
3) preparing and curing the silicate adhesive: and mixing the prepared liquid phase silicate mixture, the inorganic toughening filler and the prepared curing agent according to a mass ratio, uniformly stirring, and bonding and packaging to obtain the silicate adhesive.
6. The method for preparing the lithium silicate solution according to claim 5, wherein the reaction process conditions of the potassium silicate solution and the lithium silicate solution in the step 1) comprise: the stirring speed is 1200-1500 rpm, the reaction temperature is 35-45 ℃, and the reaction time is 1-2 h.
7. The preparation method according to claim 5, wherein in the step 2), the phosphoric acid solution and the aluminum hydroxide suspension are uniformly stirred at 50-60 ℃, and then the temperature is continuously increased to 85-95 ℃ for full reaction; the reaction time is 1-1.5 h.
8. The method according to claim 7, wherein in the step 2), the curing agent obtained by calcining, calcining and polymerizing is cooled and then ground, and the number of the ground meshes is 400 to 600.
9. The preparation method of claim 7, wherein in the step 2), the calcination time is 2.5-3 h, and the calcination polymerization time is 2.5-3.5 h.
10. The production method according to any one of claims 5 to 9, characterized by further comprising: curing and heat-treating the silicate adhesive obtained in the step 3);
preferably, the curing process performed on the obtained silicate adhesive is as follows: standing the obtained silicate adhesive at room temperature for 20-24 h, and then, keeping the temperature at 80-90 ℃ for drying for 2-2.5 h; heating to 140-160 ℃ again, curing for 1-1.5 h, and cooling to obtain a cured silicate adhesive;
preferably, the heat treatment process of the cured silicate adhesive is as follows: and (3) carrying out heat treatment on the cured silicate adhesive at 400-800 ℃ for 1.5-2 h, and then cooling to obtain the high-temperature-resistant waterproof adsorption type silicate adhesive.
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Application publication date: 20190607 |