Nano-composite sol with high-strength ionic bond structure chain for inhibiting high-temperature bursting and collapsing and preparation method of nano-composite sol

Abstract

The invention provides nano-composite sol with a high-strength ionic bond structure chain for inhibiting high-temperature explosion and collapse and a preparation method of the nano-composite sol, and belongs to the technical field of high-temperature infiltration fire tracing materials and surface high-temperature repair coating. The nano-composite sol with the high-strength ionic bond structure chain for inhibiting high-temperature explosion and collapse is used for infiltrating refractory materials at ultrahigh temperature and repairing coating liquid on the surface at high temperature, can resist extremely cold and hot high and low temperatures, can resist acid and alkali corrosion, has better mutual impregnation property with a resin matrix after surface heat treatment, and has higher strength after curing. In order to prepare a coating liquid applied to ultrahigh-temperature infiltrating refractory materials and surface high-temperature repair, a set of process for large-scale production of the nano-composite sol with high-strength ionic bond structure chains is researched and developed, and the nano-composite sol is short in processing and manufacturing period, low in production cost and high in year-on-year purity, so that the nano-composite sol shows a relatively high additional value and has a relatively long-range industrial value.

Description

A nanocomposite sol with high-strength ionic bond structure that inhibits high-temperature cracking and collapse and its preparation method. Technical Field

[0001] This invention belongs to the field of high-temperature wetting flammable materials and surface high-temperature repair coating technology, and relates to a nanocomposite sol with a high-strength ionic bond structure chain that inhibits high-temperature cracking and collapse and its preparation method. Background Technology

[0002] In the high-temperature resistant aluminum-silicon composite long fibers currently produced by enterprises, after the filaments are dispersed, a microscope reveals that the surface of the filaments is micro-wrinkled, not smooth, and has micro-cracks in some areas. These surface defects significantly affect their performance, including subsequent twisting or weaving processes. To address these defects, a film is applied to the surface of the fiber filaments to modify and compensate for them. Considering that the original fiber filaments have been calcined at nearly 1000 degrees Celsius, after applying the film, the entire filament bundle needs to be calcined again in a high-temperature furnace. This surface treatment results in fibers with extremely high gloss and a generally rounded outer shape, greatly facilitating the three-strand twisting and subsequent warp and weft weaving. Furthermore, the instantaneous temperature fluctuations from room temperature to over 1000 degrees Celsius do not affect its overall performance and can even improve its overall high-temperature resistance. The surface, after high-temperature calcination, forms a zirconium-based framework with a high-strength ionic bond structure containing yttrium aluminum to compensate for intergranular gaps. In addition, the composite material can withstand extreme cold and heat, as well as acid and alkali corrosion. After surface heat treatment, it has good interpenetration with the resin matrix and has high strength after curing. Summary of the Invention

[0003] The first objective of this invention is to address the aforementioned problems in existing technologies by proposing a nanocomposite sol with a high-strength ionic bond structure that inhibits high-temperature cracking and collapse. This invention is intended for use in ultra-high temperature impregnation of refractory materials and surface high-temperature repair coating liquids. It has a high-strength ionic bond structure that inhibits high-temperature cracking and collapse, can withstand extreme cold and heat, and is resistant to acid and alkali corrosion. Furthermore, after surface heat treatment, it has good interpenetration with the resin matrix and high strength after curing.

[0004] The first objective of this invention can be achieved through the following technical solutions:

[0005] A nanocomposite sol with a high-strength ionic bond structure that inhibits high-temperature cracking and collapse, characterized in that the nanocomposite sol is composed of Al(OH)₂. 3、 The three oxides Y(OH)3 and Zr(OH)4 are obtained by high-temperature calcination, and their molecular chain structures are as follows:

[0006] .

[0007] An application of a nanocomposite sol with a high-strength ionic bond structure that inhibits high-temperature cracking and collapse is characterized by its use as an ultra-high temperature impregnation liquid for refractory materials and a high-temperature surface repair coating.

[0008] The second objective of this invention is to prepare a nanocomposite sol with a high-strength ionic bond structure that inhibits high-temperature cracking and collapse, and a method for preparing such a nanocomposite sol is proposed.

[0009] The second objective of this invention can be achieved through the following technical solutions:

[0010] A method for preparing a nanocomposite sol with a high-strength ionic bond structure that inhibits high-temperature cracking and collapse is characterized by the following steps performed in a strictly temperature- and humidity-controlled workshop:

[0011] (1) In the spray atomization fresh air supply environment, industrial pure aluminum ingots are side-cut into 1mm thin aluminum sheets using a vertical gantry shearing machine (because aluminum ingots are soft, it is very easy to cut into thin sheets). Industrial ultrapure water and industrial pure zirconium oxynitrate are mixed and poured into a high-pressure reactor. Under the drive of ultrasonic oscillation, the PTFE sealed stirring paddle is turned on at the same time to increase the temperature of the reactor jacket. At the same time, the condensation reflux is turned on to obtain nanocomposite polymer a. The sample is placed in a transparent glass beaker and the Tyndall effect can be generated more obviously when irradiated with a strong flashlight.

[0012] (2) In the spray atomization fresh air supply environment, industrial pure aluminum ingots are side-cut into 1mm thin aluminum sheets using a vertical gantry shearing machine (because aluminum ingots are soft, it is very easy to cut into thin sheets). Industrial ultrapure water and industrial pure yttrium nitrate are mixed and poured into a high-pressure reactor. Under the drive of ultrasonic oscillation, the PTFE sealed stirring paddle is turned on at the same time to increase the temperature of the reactor jacket. At the same time, the condenser reflux is turned on to obtain nanocomposite polymer b. The sample is placed in a transparent glass beaker and the Tyndall effect can be produced more obviously when irradiated with a strong flashlight.

[0013] (3) Under constant temperature (lower) and constant humidity (higher) workshop conditions, pour nanocomposite polymer b into nanocomposite polymer a according to a suitable molar ratio, and store it separately. At the same time, measure an appropriate amount of material and adjust it to a reasonable concentration with the assistance of a screw vacuum pump to obtain a long-chain composite polymer c with a stability of one year.

[0014] (4) Under constant temperature (lower) and constant humidity (higher) workshop conditions, the composite polymer c is subjected to ion exchange. The free nitrate ions in the sol are replaced by ion exchange resin to obtain a weakly acidic nanocomposite sol with a pH of 4.5.

[0015] Furthermore, the reaction formula for preparing composite polymer a is:

[0016] .

[0017] Furthermore, the reaction formula for preparing composite polymer b is as follows:

[0018] .

[0019] Furthermore, the resulting composite polymer c after mixing includes Al(OH)₂. 3、 Three oxides: Y(OH)3 and Zr(OH)4.

[0020] Furthermore, the production environment is a constant temperature and humidity workshop, with humidity of 50%-80% and temperature of 15-25℃.

[0021] Furthermore, it features a brand-new air delivery mode and a million-level filtration purification system.

[0022] Furthermore, the weighing of materials must be carried out in a spray-atomized atmosphere, and the workshop humidification adopts an ultrapure water electric heating mode.

[0023] Furthermore, the raw materials selected are for large-scale industrial preparation: industrial pure aluminum ingots, industrial ultrapure water, industrial pure nitric acid, industrial pure zirconium oxynitrate, and industrial pure yttrium nitrate.

[0024] Furthermore, the above materials are mixed and pumped into the enamel-lined reactor. This must be done in a spray atomization environment, with ultrapure water as the atomization water source.

[0025] Furthermore, the mixing and stirring of materials must be driven by ultrasonic oscillation. To prevent other impurities from being mixed in during stirring, a fully PTFE-sealed stirring paddle must be used.

[0026] Furthermore, heat transfer oil must be used as the heat exchange medium inside the jacket of the stirred tank.

[0027] Furthermore, to obtain a weakly acidic, high-purity aluminum zirconium yttrium long-chain polymer sol d with a pH of 4.5 from the composite polymer c via ion exchange resin, it is essential to completely exchange all free nitrate ions.

[0028] Compared with existing technologies, the nanocomposite sol with high-strength ionic bond structure that inhibits high-temperature cracking and collapse, and its preparation method, have the following advantages:

[0029] 1. The nanocomposite sol of the present invention has a high-strength ionic bond structure chain that inhibits high-temperature cracking and collapse. It is used for ultra-high temperature impregnation of refractory materials and surface high-temperature repair coating liquid. It has a high-strength ionic bond structure chain that inhibits high-temperature cracking and collapse. It can withstand extreme cold and heat, as well as acid and alkali corrosion. After surface heat treatment, it has good interpenetration with the resin base and has high strength after curing.

[0030] 2. In order to prepare liquids for ultra-high temperature impregnation of refractory materials and high temperature surface repair coatings, this invention has developed a process for large-scale production of nanocomposite sols with high-strength ionic bond structure chains. The process has a short production cycle, low production cost, and high purity compared to other materials, thus showing its high added value and greater potential industrial value. Attached Figure Description

[0031] Figure 1 shows the particle size of polymer a (127 nm) measured using a Bruker laser particle size analyzer in an embodiment of the present invention.

[0032] Figure 2 shows the particle size of polymer C (1196 nm) measured using a Bruker laser particle size analyzer in an embodiment of the present invention.

[0033] Figure 3 is a crystal structure diagram of α-stable phase alumina in an embodiment of the present invention.

[0034] Figure 4 is a crystal structure diagram of yttrium oxide in an embodiment of the present invention.

[0035] Figure 5 shows three crystal structures of zirconium oxide as a function of temperature in the embodiments of the present invention.

[0036] Figure 6 is a microscopic view of the state of the fiber bundles before treatment in an embodiment of the present invention.

[0037] Figure 7 is a microscopic observation of the state of the fiber bundle after treatment in an embodiment of the present invention. Detailed Implementation

[0038] The following are specific embodiments of the present invention, which are described in conjunction with the accompanying drawings to further illustrate the technical solutions of the present invention. However, the present invention is not limited to these embodiments.

[0039] This embodiment provides a method for preparing a nanocomposite sol with a high-strength ionic bond structure that inhibits high-temperature cracking and collapse. The specific implementation process is as follows:

[0040] (1) Production and material preparation environment conditions in the workshop: The production workshop is a fully enclosed cleanroom with an external million-level cleanroom air conditioning supply and return air system with constant temperature and humidity. Ultrapure water heating is used for humidity compensation in the workshop. The temperature is controlled at 15℃ and the humidity at 80%.

[0041] (2) Selection of raw materials:

[0042] The water source is industrial ultrapure water with a pH of 7 and a resistance of 18 megohms.

[0043] Zirconium oxynitrate trihydrate, industrial purity 99.99%.

[0044] Yttrium nitrate hexahydrate, industrial purity 99.99%.

[0045] Industrial-grade pure nitric acid, 68%.

[0046] Industrial pure aluminum ingots, 99.99%.

[0047] (3) Industrial production equipment: industrial ultrapure water generator, enamel glass reactor, PTFE packing agitator, high frequency ultrasonic oscillation shaft, constant temperature hot water heater, double funnel dry mixing tank (all plastic), negative pressure spray tower system, positive pressure spray atomization system, vibrating tank with four eccentric vibration motors, screw vacuum negative pressure system, Bruker nano laser particle size and Zeta potential meter, high precision peristaltic pump, shearing machine.

[0048] Step 1: Preparation of composite polymer a

[0049] According to the reaction equation:

[0050] (1) Clean the mixing vessel with ultrapure water. In a strictly constant temperature and humidity workshop, the air supply is fresh air, the temperature is 20℃ and the humidity is 70%. In a spray atomization environment, weigh 27 kg of industrial pure aluminum ingots according to the proportion, cut the aluminum ingots into thin slices with a shearing machine, add 1000 kg of ultrapure water and 141 kg of zirconium oxynitrate trihydrate into the mixing vessel in small and even amounts.

[0051] (2) After observing that the mixture is evenly stirred, turn on the vacuum screw pump and pour the mixed material into the enamel reactor.

[0052] (3) Turn on the PTFE agitator and control the stirring speed to 150 r / min, adding the PTFE while stirring.

[0053] (4) Turn on the heat transfer oil temperature of the mixing vessel jacket and adjust the oil temperature to 90℃.

[0054] (5) Wait for the reaction time to be about 2 hours, then stop heating the oil.

[0055] (6) After 8 hours, when the material temperature drops to around 35-40℃, start releasing the composite polymer a.

[0056] As shown in Figure 1, samples were taken, and the particle size of the material was tested using a Bruker laser particle size analyzer. The average value was 127 nm, which met the initial preparation target.

[0057] Step 2: Preparation of composite polymer b

[0058] According to the reaction equation:

[0059] (1) Clean the mixing vessel with ultrapure water. In a strictly constant temperature and humidity workshop, the air supply is fresh air, the temperature is 20℃ and the humidity is 70%. In a spray atomization environment, weigh 27 kg of industrial pure aluminum ingots according to the proportion, cut the aluminum ingots into thin slices with a shearing machine, add 1000 kg of ultrapure water and 190 kg of yttrium nitrate hexahydrate into the mixing vessel in small and even amounts.

[0060] (2) After observing that the mixture is evenly stirred, turn on the vacuum screw pump and pour the mixed material into the enamel reactor.

[0061] (3) Turn on the PTFE agitator and control the stirring speed to 150 r / min. Add the agitator while stirring.

[0062] (4) Turn on the heat transfer oil temperature of the mixing vessel jacket and adjust the oil temperature to 90℃.

[0063] (5) Wait for the reaction time to be about 2 hours, then stop heating the oil.

[0064] (6) After 8 hours, when the material temperature drops to around 35-40℃, start feeding the composite polymer b.

[0065] Step 3: Preparation of composite polymer C

[0066] Materials b and a are mixed and stirred in a certain proportion to obtain polymer c.

[0067] As shown in Figure 2, samples were taken, and the particle size of the material was tested using a Bruker laser particle size analyzer. The average value was 1196 nm, which met the initial preparation target.

[0068] Step 4: Preparation of nanocomposite sol

[0069] Then, through ion exchange: the material contains some nitrate ions, which need to be replaced by ion exchange resin to obtain nanocomposite sol d.

[0070] Step 5: Preparation of high-strength fiber bundles

[0071] Then, d is vacuum concentrated to a certain Newtonian fluid viscosity. The pre-prepared high-temperature calcined silicon-aluminum composite nanofibers are immersed in d sol, dried, and calcined again to obtain a fiber bundle with a very smooth fiber surface. Based on the destructive ionic bond after high-temperature treatment, the material on the fiber surface naturally has special resistance to acid and alkali corrosion, resistance to high temperature and rapid cooling, and resistance to ultraviolet aging.

[0072] The specific process is as follows:

[0073]

[0074] ⇓高温煅烧（高温高压热解再生长）

[0075]

[0076] As shown in Figures 3-5, a zirconia matrix is ​​used, with the addition of alumina and yttrium oxide. The monoclinic phase density of zirconia is 5.65 g / cm³, the tetragonal phase density is 6.10 g / cm³, and the cubic phase density is 6.27 g / cm³. As the temperature rises, the volume decreases. The addition of alumina and yttrium oxide fills the gaps after the lattice expansion, thus ensuring that the material volume remains unchanged when the temperature fluctuates drastically. As a coating layer on the material surface, it ensures the high-temperature resistance of the matrix fiber.

[0077] As shown in Figure 6, the state of the fiber bundles under a microscope before treatment is evident. The surface of the fiber bundles is extremely rough, which will significantly reduce the complexity of subsequent processes such as weaving and twisting.

[0078] As shown in Figure 7, the state of the fiber bundle after treatment under a microscope can be seen that after coating the surface of the fiber bundle with a zirconium-containing matrix film and then treating it at high temperature again, the surface is very smooth and without any defects, which greatly facilitates the post-processing of the fiber.

[0079] The specific embodiments described herein are merely illustrative of the spirit of the invention. Those skilled in the art to which this invention pertains may make various modifications or additions to the described specific embodiments or use similar methods to substitute them, without departing from the spirit of the invention or exceeding the scope defined by the appended claims.

Claims

1. A nanocomposite sol with a high-strength ionic bond structure that inhibits high-temperature cracking and collapse, characterized in that, This nanocomposite sol is composed of Al(OH)₂ 3、 The three oxides Y(OH)3 and Zr(OH)4 are obtained by high-temperature calcination, and their molecular chain structures are as follows: 。 2. An application of a nanocomposite sol with a high-strength ionic bond structure that inhibits high-temperature cracking and collapse, characterized in that, Liquid used for ultra-high temperature impregnation of refractory materials and high temperature surface repair coating.

3. A method for preparing a nanocomposite sol with a high-strength ionic bond structure that inhibits high-temperature cracking and collapse, used to prepare the nanocomposite sol with a high-strength ionic bond structure that inhibits high-temperature cracking and collapse as described in claim 1, characterized in that, In a strictly controlled temperature and humidity workshop, the following steps are achieved: (1) Under the spray atomization fresh air supply environment, industrial pure aluminum ingots are laterally cut into 1mm thin aluminum sheets using a vertical gantry shearing machine. Industrial ultrapure water and industrial pure yttrium nitrate are mixed and poured into a high-pressure reactor. Under the drive of ultrasonic oscillation, the PTFE sealed stirring paddle is turned on to raise the temperature of the reactor jacket. At the same time, the condenser reflux is turned on to obtain nanocomposite polymer a. A sample is placed in a transparent glass beaker and irradiated with a strong flashlight. The Tyndall effect can be produced more obviously. (2) Under the spray atomization fresh air supply environment, industrial pure aluminum ingots are laterally cut into 1mm thin aluminum sheets using a vertical gantry shearing machine. Industrial ultrapure water and industrial pure yttrium nitrate are mixed and poured into a high-pressure reactor. Under the drive of ultrasonic oscillation, the PTFE sealed stirring paddle is turned on to raise the temperature of the reactor jacket. At the same time, the condenser reflux is turned on to obtain nanocomposite polymer a. The sample is placed in a transparent glass beaker and irradiated with a strong flashlight. The Tyndall effect can be produced more obviously. Start the PTFE sealed stirring paddle, increase the temperature of the reactor jacket, and simultaneously start the reflux condenser to obtain nanocomposite polymer b. Take a sample and put it into a transparent glass beaker. Irradiate it with a strong flashlight, and the Tyndall effect can be generated more obviously. (3) Under constant temperature (lower) and constant humidity (higher) workshop conditions, pour nanocomposite polymer b into nanocomposite polymer a according to a suitable molar ratio, and store it separately. At the same time, measure an appropriate amount of material and adjust it to a reasonable concentration with the assistance of a screw vacuum pump to obtain a long-chain composite polymer c with a stability of one year. (4) Under constant temperature (lower) and constant humidity (higher) workshop conditions, perform ion exchange on the composite polymer c. Replace the free nitrate ions in the sol with ion exchange resin to obtain a weakly acidic nanocomposite sol d with a pH value of 4.

5.

4. The advanced industrial preparation method for the progressively grown aluminum zirconium yttrium chain polymer according to claim 3, characterized in that, The reaction formula for preparing composite polymer a is: 。 5. The advanced industrial preparation method for the progressively grown aluminum-zirconium yttrium chain polymer according to claim 3, characterized in that, The reaction formula for preparing composite polymer b is: 。 6. The advanced industrial preparation method for the progressively grown aluminum-zirconium yttrium chain polymer according to claim 3, characterized in that, The resulting composite polymer C after mixing includes Al(OH) 3、 Three oxides: Y(OH)3 and Zr(OH)4.

7. The advanced industrial preparation method for the progressively grown aluminum zirconium yttrium chain polymer according to claim 3, characterized in that, The raw materials selected are those used for large-scale industrial preparation: industrial pure aluminum ingots, industrial ultrapure water, industrial pure nitric acid, industrial pure zirconium oxynitrate, and industrial pure yttrium nitrate.

8. The advanced industrial preparation method for the progressive growth of aluminum zirconium yttrium chain polymers according to claim 3, characterized in that, To obtain a weakly acidic, high-purity aluminum zirconium yttrium long-chain polymer sol d with a pH of 4.5 from the composite polymer c through an ion exchange resin, it is essential to completely exchange all free nitrate ions.

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