A free radical polymerization method of high polymerization degree high temperature resistant inorganic material

Abstract

The application relates to a free radical polymerization method of high-polymerization-degree high-temperature-resistant inorganic materials, and the technical scheme is as follows: iron oxide powder, aluminum oxide powder, silicon dioxide powder and calcium oxide powder are uniformly mixed according to the mass ratio of 0.1-4:1 to prepare oxide mixed powder; the oxide mixed powder is filled into a platinum gold crucible and heated to complete melting under a protective atmosphere; after being kept stable for 3-10 minutes under the protective atmosphere or an oxidation atmosphere, polymerization monomer powder is added into active oxide melt containing free radicals according to the mass ratio of 0.1-1:1, chain-type chain polymerization is carried out under the protective atmosphere for 5-30 minutes, the temperature is reduced to room temperature at a speed of 50-1000 DEG C / s, and high-polymerization-degree inorganic materials are obtained. The application has the advantages of simple preparation process, short cycle, high polymerization degree of the prepared high-temperature-resistant inorganic materials, excellent high-temperature service performance, and the like, and can significantly improve the strength and toughness of high-temperature ceramic materials.

Description

Technical Field

[0001] The invention belongs to the field of high-temperature inorganic material preparation, and particularly relates to a free radical polymerization method for high-polymerization-degree inorganic materials. Background Art

[0002] High-temperature inorganic materials, such as refractories, are fundamental to high-temperature process industries such as metallurgy, electricity, building materials, and aerospace. High-temperature inorganic materials operate in harsh environments and require excellent thermomechanical and thermochemical properties. Traditional high-temperature inorganic material synthesis processes require the addition of sintering promoters to the material matrix and long-term sintering at high temperatures to meet the requirements of extreme environments above 1000°C. However, the uniformity of the materials prepared in this way depends on the amount of sintering promoter added and the heat treatment time, resulting in high energy consumption, a low degree of polymerization, and poor toughness.

[0003] Through acid-base excitation, [SiO4] and [AlO4] tetrahedra can be linked by bridging oxygen to form a three-dimensional network structure, thereby producing an inorganic polymer with a certain degree of polymerization. However, this synthesis method requires a large amount of acid-base exciters, and the resulting material has a low degree of polymerization and a low service temperature. In summary, the shortcomings of the existing technology are that the preparation of high-temperature-resistant inorganic materials requires a long cycle and complex process, and the material has a low degree of polymerization and a low service temperature. Summary of the Invention

[0004] The purpose of the present invention is to provide a free radical polymerization method for a high-polymerization, high-temperature resistant inorganic material with low energy consumption and short preparation cycle. The method has a short preparation cycle and a simple process, and the prepared high-temperature resistant inorganic material has a high polymerization degree.

[0005] To achieve the above object, the specific steps of the technical solution adopted by the present invention are:

[0006] Step 1: Mix iron oxide powder and (aluminum oxide powder + silicon dioxide powder + calcium oxide powder) in a mass ratio of 0.1 to 4:1 to obtain an oxide mixed powder;

[0007] Step 2: Filling the oxide mixed powder into a platinum crucible, heating it to a completely molten state under a protective atmosphere, and keeping it stable for 3 to 10 minutes under a protective atmosphere or an oxidizing atmosphere to obtain an active oxide melt containing free radicals;

[0008] Step 3: adding the polymerized monomer powder to the active oxide melt at a mass ratio of 0.1-1:1, reacting for 5-30 minutes under a protective atmosphere, and then cooling to room temperature at a rate of 50-1000°C / s to obtain a high-polymerization-degree inorganic material.

[0009] Furthermore, the liquid phase accounts for ≥50% in the completely melted state.

[0010] Furthermore, the protective atmosphere is argon or nitrogen atmosphere.

[0011] Furthermore, during the heat preservation process, the oxide mixed powder can be irradiated with a continuous or pulsed laser having a wavelength of 355 nm, 532 nm or 1064 nm.

[0012] Furthermore, the volume fraction of O2 in the oxidizing atmosphere is 20% to 80%;

[0013] Furthermore, the polymer monomer powder is one or a mixture of elemental silicon, aluminum silicon alloy, aluminum nitride, calcium nitride, aluminum diboride, iron boride, iron disilicide, titanium silicide, gallium phosphide, zirconium sulfide, tungsten sulfide, chromium oxide, tantalum oxide and niobium oxide, and their compounds.

[0014] Due to the adoption of the above technical solution, the present invention has the following positive effects compared with the prior art:

[0015] (1) The present invention uses conventional oxide powders, which are low in cost, and the polymerized monomer powders used are stable in composition and easy to store and transport safely;

[0016] (2) The high-polymerization inorganic material prepared by the present invention has a simple synthesis process, a short preparation cycle, and the production process does not cause harm to the human body and the environment.

[0017] (3) The present invention utilizes free radical active components such as superoxide radicals in active inorganic oxide melts, combined with high-temperature resistant polymer monomer powders, to prepare high-polymerization-degree two-dimensional materials through chain polymerization reactions. The material synthesis path is simple and the preparation cost is low. The prepared material has the properties of high-temperature resistance, high polymerization degree, and excellent mechanical properties, and can be used under high-temperature conditions above 1300°C.

[0018] (4) The high-polymerization inorganic material prepared by the present invention has rich main chain components and strong scalability, and can be further organically modified to prepare composite framework materials.

[0019] (5) The high-polymerization inorganic material prepared by the present invention has high viscosity and can be used for sealing, filling, coating, repairing and bonding of metal-based and ceramic-based high-temperature equipment in high-temperature environments above 1300°C. It can also be used as a binder for high-temperature ceramics and refractory materials to enhance the interface bonding strength between their aggregates and matrix.

[0020] Therefore, the present invention has a short cycle and a simple process, and the prepared high-temperature resistant inorganic material has the characteristics of high polymerization degree, high viscosity, low conductivity, good high-temperature resistance and excellent mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1This is a microstructure of a high-polymerization, high-temperature-resistant inorganic material prepared in Example 1 of the present invention;

[0022] Figure 2 This is a microstructure of a high-polymerization, high-temperature-resistant inorganic material prepared in Example 5 of the present invention;

[0023] Figure 3 This is a microstructure of a high-polymerization, high-temperature-resistant inorganic material prepared in Example 10 of the present invention; DETAILED DESCRIPTION

[0024] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, which does not limit the scope of protection thereof.

[0025] A free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material comprises the following steps:

[0026] Step 1: Mix the iron oxide powder and (aluminum oxide powder + silicon dioxide powder + calcium oxide powder) in a mass ratio of 0.1 to 4:1 to obtain an oxide mixed powder; the ratio of aluminum oxide powder, silicon dioxide powder and calcium oxide powder can be adjusted as long as the total mass and the ratio of iron oxide powder meet the above requirements.

[0027] Step 2: Place the above-mentioned oxide powder mixture into a platinum crucible and heat it under a protective atmosphere until it is completely melted, with the liquid phase accounting for ≥50% of the melt. Specifically, the liquid phase volume of the powder components at various temperatures is calculated using Factsage thermodynamic software. Hold the mixture at a stable temperature for 3-10 minutes under a protective or oxidizing atmosphere, where the protective atmosphere is argon or nitrogen, and the O2 volume fraction in the oxidizing atmosphere is 20%-80%. During the holding process, a continuous or pulsed laser with a wavelength of 355nm, 532nm, or 1064nm can be applied to obtain an active oxide melt containing free radicals. Light is used to excite the generation of free radicals. Short-wavelength lasers have high energy and are more likely to excite a large number of free radicals on the melt surface, while long-wavelength lasers help stimulate the formation of free radicals deep within the melt.

[0028] Step 3: Add the polymerized monomer powder to the above-mentioned active oxide melt at a mass ratio of 0.1 to 1:1. After reacting for 5 to 30 minutes under a protective atmosphere, cool the temperature to room temperature at a rate of 50 to 1000°C / s to obtain a high-polymerization-degree inorganic material. The polymerized monomer powder can be one or a mixture of silicon, aluminum-silicon alloy, aluminum nitride, calcium nitride, aluminum diboride, iron boride, iron disilicide, titanium silicide, gallium phosphide, zirconium sulfide, tungsten sulfide, chromium oxide, tantalum oxide, and niobium oxide, or any combination thereof.

[0029] Example 1

[0030] A free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material. The free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material described in this embodiment is as follows:

[0031] Step 1: Mix iron oxide powder and (aluminum oxide powder + silicon dioxide powder + calcium oxide powder) in a mass ratio of 0.1:1 to obtain an inorganic oxide mixed powder;

[0032] Step 2: The inorganic oxide mixed powder is placed in a platinum crucible and heated to 1500°C in an argon atmosphere to achieve a completely molten state, wherein the liquid phase accounts for 50% of the completely molten state. The mixture is then kept stable for 3 minutes in an oxidizing atmosphere with an O2 volume fraction of 20%, thereby obtaining an active inorganic oxide melt containing structures such as superoxide radicals.

[0033] Step 3: Add polymerized monomer ceramic powder to the above active inorganic oxide melt at a mass ratio of elemental silicon to active inorganic oxide melt of 0.1:1. After reacting for 5 minutes under an argon atmosphere, cool to room temperature at a rate of 50°C / s to obtain a high-polymerization inorganic material.

[0034] Example 2

[0035] A free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material. The free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material described in this embodiment is as follows:

[0036] Step 1: Mixing the iron oxide powder and (aluminum oxide powder + silicon dioxide powder + calcium oxide powder) in a mass ratio of 2:1 to obtain an inorganic oxide mixed powder;

[0037] Step 2: Fill the inorganic oxide mixed powder into a platinum crucible and heat it to 1575° C. under an argon atmosphere to reach a completely molten state, wherein the liquid phase accounts for 70% in the completely molten state, and keep it stable for 6.5 minutes in an oxidizing atmosphere with an O2 volume fraction of 50%, thereby obtaining an active inorganic oxide melt containing structures such as superoxide free radicals;

[0038] Step 3: adding polymerized monomer ceramic powder to the active inorganic oxide melt at a mass ratio of elemental silicon to active inorganic oxide melt of 0.5:1, reacting for 17.5 minutes under an argon atmosphere, and then cooling to room temperature at a rate of 525°C / s to obtain a high-polymerization inorganic material.

[0039] Example 3

[0040] A free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material. The free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material described in this embodiment is as follows:

[0041] Step 1: Mixing the iron oxide powder and (aluminum oxide powder + silicon dioxide powder + calcium oxide powder) in a mass ratio of 4:1 to obtain an inorganic oxide mixed powder;

[0042] Step 2: Fill the inorganic oxide mixed powder into a platinum crucible and heat it to 1650° C. under an argon atmosphere to reach a completely molten state, wherein the liquid phase accounts for 100% in the completely molten state, and keep it stable for 10 minutes in an oxidizing atmosphere with an O2 volume fraction of 80%, thereby obtaining an active inorganic oxide melt containing structures such as superoxide free radicals;

[0043] Step 3: Add the polymerized monomer ceramic powder to the active inorganic oxide melt at a mass ratio of 1:1, react for 30 minutes under an argon atmosphere, and then cool to room temperature at a rate of 1000°C / s to obtain a high-polymerization-degree inorganic material.

[0044] Example 4

[0045] A free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material. The free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material described in this embodiment is as follows:

[0046] Step 1: mixing the iron oxide powder and (aluminum oxide powder + silicon dioxide powder + calcium oxide powder) in a mass ratio of 0.1:1 to obtain an inorganic oxide mixed powder;

[0047] Step 2: Fill the inorganic oxide mixed powder into a platinum crucible and heat it to 1500° C. under a nitrogen atmosphere to reach a completely molten state, wherein the liquid phase accounts for 50% of the completely molten state, and keep it stable for 3 minutes in an oxidizing atmosphere to obtain an active inorganic oxide melt containing structures such as superoxide free radicals;

[0048] Step 3: Add polymerized monomer ceramic powder to the active inorganic oxide melt at a mass ratio of 0.1:1 of elemental silicon and eutectic aluminum-silicon alloy mixed powder to the active inorganic oxide melt, react for 5 minutes under a nitrogen atmosphere, and then cool to room temperature at a rate of 50°C / s to obtain a high-polymerization inorganic material.

[0049] Example 5

[0050] A free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material. The free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material described in this embodiment is as follows:

[0051] Step 1: Mixing the iron oxide powder and (aluminum oxide powder + silicon dioxide powder + calcium oxide powder) in a mass ratio of 2:1 to obtain an inorganic oxide mixed powder;

[0052] Step 2: Fill the inorganic oxide mixed powder into a platinum crucible and heat it to 1575° C. under a nitrogen atmosphere to reach a completely melted state, wherein the liquid phase accounts for 70% of the complete melt, and keep it stable for 6.5 minutes in an oxidizing atmosphere with an O2 volume fraction of 50%, thereby obtaining an active inorganic oxide melt containing structures such as superoxide free radicals;

[0053] Step 3: Add polymerized monomer ceramic powder to the active inorganic oxide melt at a mass ratio of elemental silicon and eutectic aluminum-silicon alloy mixed powder to the active inorganic oxide melt of 0.5:1, react under a nitrogen atmosphere for 17.5 minutes, and then cool to room temperature at a rate of 525°C / s to obtain a high-polymerization inorganic material.

[0054] Example 6

[0055] A free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material. The free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material described in this embodiment is as follows:

[0056] Step 1: Mixing the iron oxide powder and (aluminum oxide powder + silicon dioxide powder + calcium oxide powder) in a mass ratio of 4:1 to obtain an inorganic oxide mixed powder;

[0057] Step 2: Fill the inorganic oxide mixed powder into a platinum crucible and heat it to 1650°C in a nitrogen atmosphere to reach a completely molten state, wherein the liquid phase accounts for 100% in the completely molten state, and keep it stable for 10 minutes in an oxidizing atmosphere with an O2 volume fraction of 80%, thereby obtaining an active inorganic oxide melt containing structures such as superoxide free radicals;

[0058] Step 3: Add polymerized monomer ceramic powder to the active inorganic oxide melt at a mass ratio of 1:1 of elemental silicon and eutectic aluminum-silicon alloy mixed powder to the active inorganic oxide melt, react for 30 minutes under a nitrogen atmosphere, and then cool to room temperature at a rate of 1000°C / s to obtain a high-polymerization inorganic material.

[0059] Example 7

[0060] A free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material. The free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material described in this embodiment is as follows:

[0061] Step 1: Mix the iron oxide powder and (aluminum oxide powder + silicon dioxide powder + calcium oxide powder) in a mass ratio of 2:1 to obtain an oxide mixed powder;

[0062] Step 2: Fill the oxide mixed powder into a platinum crucible and heat it under an argon atmosphere until it is completely melted, wherein the liquid phase accounts for 70% of the completely melted state. Keep the temperature stable for 3 minutes under the argon atmosphere while applying a pulsed laser with a wavelength of 355 nm to obtain an active oxide melt containing free radicals;

[0063] Step 3: adding polymerizable monomer powder to the active oxide melt at a mass ratio of chromium oxide and tantalum oxide compounds to the active oxide melt of 0.1:1, reacting for 17.5 minutes under a protective atmosphere, and then cooling to room temperature at a rate of 525°C / s to obtain a high-polymerization inorganic material.

[0064] Example 8

[0065] A free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material. The free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material described in this embodiment is as follows:

[0066] Step 1: mixing iron oxide powder and (aluminum oxide powder + silicon dioxide powder + calcium oxide powder) in a mass ratio of 0.1:1 to obtain an oxide mixed powder;

[0067] Step 2: Fill the oxide mixed powder into a platinum crucible and heat it under an argon atmosphere until it is completely melted, wherein the liquid phase accounts for 70% of the completely melted state. Keep the temperature stable for 3 minutes under the argon atmosphere, and apply a pulsed laser with a wavelength of 532 nm to obtain an active oxide melt containing free radicals;

[0068] Step 3: adding polymerizable monomer powder to the active oxide melt at a mass ratio of chromium oxide and tantalum oxide compounds to the active oxide melt of 0.5:1, reacting for 5 minutes under a protective atmosphere, and then cooling to room temperature at a rate of 50°C / s to obtain a high-polymerization inorganic material.

[0069] Example 9

[0070] A free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material. The free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material described in this embodiment is as follows:

[0071] Step 1: Mixing the iron oxide powder and (aluminum oxide powder + silicon dioxide powder + calcium oxide powder) in a mass ratio of 4:1 to obtain an inorganic oxide mixed powder;

[0072] Step 2: Filling the inorganic oxide mixed powder into a platinum crucible, heating it to 1650° C. under a protective atmosphere to reach a completely molten state, wherein the liquid phase accounts for 100% of the completely molten state, and keeping it stable for 10 minutes under an argon atmosphere. Applying a pulsed laser with a wavelength of 1046 nm to obtain an active inorganic oxide melt containing structures such as superoxide free radicals;

[0073] Step 3: Add polymerized monomer ceramic powder to the active inorganic oxide melt at a mass ratio of chromium oxide and tantalum oxide compounds to the active inorganic oxide melt of 1:1, react for 30 minutes under an argon atmosphere, and then cool to room temperature at a rate of 1000°C / s to obtain a high-polymerization inorganic material.

[0074] Example 10

[0075] A free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material. The free radical polymerization method for a high-polymerization-degree, high-temperature-resistant inorganic material described in this embodiment is as follows:

[0076] Step 1: mixing iron oxide powder and (aluminum oxide powder + silicon dioxide powder + calcium oxide powder) in a mass ratio of 0.1:1 to obtain an oxide mixed powder;

[0077] Step 2: Fill the oxide mixed powder into a platinum crucible and heat it to a completely molten state under a protective atmosphere, wherein the completely molten state is a state where the liquid phase accounts for 70%. The mixture is kept stable for 3 minutes in an oxidizing atmosphere with an O2 volume fraction of 50%, and a continuous laser with a wavelength of 532 nm is applied to obtain an active oxide melt containing free radicals.

[0078] Step 3: adding polymerizable monomer powder to the active oxide melt at a mass ratio of chromium oxide and tantalum oxide compounds to the active oxide melt of 0.5:1, reacting for 5 minutes under a protective atmosphere, and then cooling to room temperature at a rate of 50°C / s to obtain a high-polymerization inorganic material.

[0079] Compared with the prior art, the present invention has the following positive effects:

[0080] (1) The present invention uses conventional oxide powders, which are low in cost, and the polymerized monomer powders used are stable in composition and easy to store and transport safely;

[0081] (2) The high-polymerization inorganic material prepared by the present invention has a simple synthesis process, a short preparation cycle, and the production process does not cause harm to the human body and the environment.

[0082] (3) The present invention utilizes free radical active components such as superoxide radicals in active inorganic oxide melts, combined with high-temperature resistant polymer monomer powders, to prepare high-polymerization-degree two-dimensional materials through chain polymerization reactions. The material synthesis path is simple and the preparation cost is low. The prepared material has the properties of high-temperature resistance, high polymerization degree, and excellent mechanical properties, and can be used under high-temperature conditions above 1300°C.

[0083] (4) The high-polymerization inorganic material prepared by the present invention has rich main chain components and strong scalability, and can be further organically modified to prepare composite framework materials.

[0084] (5) The high-polymerization inorganic material prepared by the present invention has high viscosity and can be used for sealing, filling, coating, repairing and bonding metal-based and ceramic-based high-temperature equipment in high-temperature environments above 1300°C. It can also be used as a binder for high-temperature ceramics and refractory materials to enhance the interface bonding strength between their aggregates and matrix.

[0085] Therefore, the present invention has a short cycle and a simple process, and the prepared high-temperature resistant inorganic material has the characteristics of high polymerization degree, high viscosity, low conductivity, good high-temperature resistance and excellent mechanical properties.

[0086] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made by using the contents of the present invention description and drawings under the concept of the present invention, or direct / indirect application in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A free radical polymerization method for high-polymerization-degree high-temperature resistant inorganic materials, characterized in that: The specific steps include: Step 1: Mix iron oxide powder and (aluminum oxide powder + silicon dioxide powder + calcium oxide powder) in a mass ratio of 0.1 to 4:1 to obtain an oxide mixed powder; Step 2: Filling the oxide mixed powder into a platinum crucible, heating it to a completely molten state under a protective atmosphere, and keeping it stable for 3 to 10 minutes under a protective atmosphere or an oxidizing atmosphere to obtain an active oxide melt containing free radicals; Step 3: adding the polymerized monomer powder to the active oxide melt at a mass ratio of 0.1 to 1:1, reacting for 5 to 30 minutes under a protective atmosphere, and then cooling to room temperature at a rate of 50 to 1000°C / s to obtain a high-polymerization-degree inorganic material; The polymer monomer powder is one or a mixture of elemental silicon, aluminum silicon alloy, aluminum nitride, calcium nitride, aluminum diboride, iron boride, iron disilicide, titanium silicide, gallium phosphide, zirconium sulfide, tungsten sulfide, chromium oxide, tantalum oxide or niobium oxide.

2. The free radical polymerization method of a high-polymerization-degree high-temperature-resistant inorganic material according to claim 1, characterized in that: The liquid phase accounts for ≥50% in the completely melted state.

3. The free radical polymerization method of a high-polymerization-degree high-temperature-resistant inorganic material according to claim 1, characterized in that: The protective atmosphere is argon or nitrogen atmosphere.

4. The free radical polymerization method of a high-polymerization-degree high-temperature-resistant inorganic material according to claim 1, characterized in that: During the heat preservation process after melting, the oxide mixed powder is subjected to continuous or pulsed laser with a wavelength of 355 nm, 532 nm or 1064 nm.

5. The free radical polymerization method of a high-polymerization-degree high-temperature-resistant inorganic material according to claim 1, characterized in that: The volume fraction of O2 in the oxidizing atmosphere is 20% to 80%.

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