CN108558424B - Thermal shock resistant substrate material and application thereof as solar thermal power generation heat absorption material - Google Patents

Abstract

The invention discloses a thermal shock resistant substrate material and application thereof as a solar thermal power generation heat absorption material, wherein the thermal shock resistant substrate material is prepared from the following raw materials in parts by weight: 35-45 parts of silicon carbide; 8-12 parts of silicon dioxide; 4-8 parts of aluminum oxide; 3-5 parts of aluminum carbide; 1-3 parts of zinc molybdate; 4-6 parts of polyethylene glycol; 0.3-0.5 parts of silicon nitride; 0.4-0.8 parts of cesium oxide; 0.3-0.5 parts of molybdenum trioxide; 0.8-1.2 parts of glass fiber; 0.7-0.9 part of zinc fluosilicate and barium carbide, and the weight part ratio of the zinc fluosilicate to the barium carbide is 6-8: 1. The thermal shock resistant base material provided by the invention has excellent thermal shock resistance, higher strength and refractoriness, and meets the requirements of the current solar thermal power generation heat absorption material. The effect is related to the weight ratio of the zinc fluosilicate to the barium carbide in the raw materials, and when the weight ratio of the zinc fluosilicate to the barium carbide is 6-8: 1, the thermal shock resistance is optimal.

Description

Thermal shock resistant substrate material and application thereof as solar thermal power generation heat absorption material

Technical Field

The invention belongs to the field of materials, and particularly relates to a thermal shock resistant substrate material and application thereof as a solar thermal power generation heat absorption material.

Background

Solar energy as a green energy source has no pollution to the environment, and the source of the solar energy is simple, so that the solar energy is inexhaustible in the life of human beings. Solar energy is not only disposable energy, but also clean energy, has rich resources, is ubiquitous, does not need to be transported, can be used freely, and most importantly, has no pollution to the environment. Solar cells also have many advantages that other power generation methods do not have due to the particularity of solar energy: the method is not limited by regions, does not consume fuel, can be scaled up or down, has high flexibility, no pollution, no noise, safety and reliability, short construction period, simple maintenance and the maximum possibility of large-scale application. Therefore, many experts develop solar energy as an alternative energy source, and hope that the sun can benefit human beings. A large part of the solar energy used today is converted by solar cells. Because the solar cell is sensitive to light, light energy irradiated on the surface of the solar cell can be converted into electric energy. At present, the solar cell has been commercialized and industrialized under the efforts of related experts.

The solar power generation has many types, and the mature solar photovoltaic power generation and the solar thermal power generation exist. Among the numerous solar energy utilization technologies, the solar thermal power generation technology is praised as the most promising technology, and the technology of utilizing solar energy on a large scale is the most possible. The solar thermal power generation is to utilize a condenser to gather solar energy, the solar energy is absorbed by an absorber and then converted into heat energy, and high-temperature steam or gas is generated and enters a steam turbine generator set or a gas turbine generator set to generate electric energy. Solar thermal power generation can be divided into tower type solar thermal power generation, trough type solar thermal power generation and disc type solar thermal power generation according to different light-gathering forms. The tower type solar thermal power generation system is an advanced large-scale solar thermal power generation technology which is researched vigorously in various countries at present because the tower type solar thermal power generation system has the characteristics of high condensation ratio, high thermodynamic cycle temperature, small heat loss, simple system and high efficiency and is valued by various countries in the world. The air heat absorber serving as the core of the tower type solar thermal power generation is made of a high-temperature heat absorber material which plays an important role in receiving solar concentrated light energy, absorbing heat and exchanging heat, and influences the stability and efficiency of the whole thermal power generation system.

The development of a base material resistant to thermal shock is urgent.

Disclosure of Invention

The invention aims to provide a thermal shock resistant substrate material and application thereof as a solar thermal power generation heat absorption material.

The above object of the present invention is achieved by the following technical solutions:

the thermal shock resistant base material is prepared from the following raw materials in parts by weight: 40 parts of silicon carbide; 10 parts of silicon dioxide; 6 parts of aluminum oxide; 4 parts of aluminum carbide; 2 parts of zinc molybdate; 5 parts of polyethylene glycol; 0.4 part of silicon nitride; 0.6 part of cesium oxide; 0.4 part of molybdenum trioxide; 1.0 part of glass fiber; 0.8 part of zinc fluosilicate and 0.8 part of barium carbide, wherein the weight part ratio of the zinc fluosilicate to the barium carbide is 6:1, or the weight part ratio of the zinc fluosilicate to the barium carbide is 8: 1.

Furthermore, the grain diameter of the silicon carbide is 0.4-0.6 mm.

The preparation method of the thermal shock resistant substrate material comprises the following steps:

step S1, soaking silicon carbide in polyethylene glycol for 24 hours, then heating to 100 ℃, adding silicon dioxide and aluminum oxide, stirring, and uniformly mixing to obtain a material A;

step S2, adding the rest materials into the material A in the step S1 in proportion, uniformly mixing, grinding until the fineness of the material is 300 meshes, and then granulating and pressing;

step S3, drying the green body pressed in the step S2 at the drying temperature of 140 ℃ and firing to obtain a product; the firing conditions are as follows: preserving heat for 30min at 120 ℃, then carrying out temperature programming, reducing the temperature rising rate to 5 ℃/min when the temperature rises to 750 ℃ initially at the temperature rising rate of 12 ℃/min, preserving heat for 30min at 250 ℃ and 480 ℃ respectively in the temperature rising process, preserving heat for 50min at 800 ℃, 1000 ℃, 1200 ℃, 1300 ℃, 1400 ℃ and 1500 ℃ respectively, finally rising the temperature to 1800 ℃ and preserving heat for 2 h.

The thermal shock resistant substrate material is used as a heat absorbing material for solar thermal power generation.

The invention has the advantages that:

the thermal shock resistant base material provided by the invention has excellent thermal shock resistance, higher strength and refractoriness, and meets the requirements of the current solar thermal power generation heat absorption material.

Detailed Description

The following examples are given to further illustrate the essence of the present invention, but should not be construed as limiting the scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention.

Example 1: preparation of thermal shock resistant substrate material

The weight parts of the raw materials are as follows:

40 parts of silicon carbide; 10 parts of silicon dioxide; 6 parts of aluminum oxide; 4 parts of aluminum carbide; 2 parts of zinc molybdate; 5 parts of polyethylene glycol; 0.4 part of silicon nitride; 0.6 part of cesium oxide; 0.4 part of molybdenum trioxide; 1.0 part of glass fiber; 0.8 part of zinc fluosilicate and 0.8 part of barium carbide, wherein the weight part ratio of the zinc fluosilicate to the barium carbide is 7: 1.

The preparation method comprises the following steps:

step S1, soaking silicon carbide in polyethylene glycol for 24 hours, then heating to 100 ℃, adding silicon dioxide and aluminum oxide, stirring, and uniformly mixing to obtain a material A;

step S2, adding the rest materials into the material A in the step S1 in proportion, uniformly mixing, grinding until the fineness of the material is 300 meshes, and then granulating and pressing;

step S3, drying the green body pressed in the step S2 at the drying temperature of 140 ℃ and firing to obtain a product; the firing conditions are as follows: preserving heat for 30min at 120 ℃, then carrying out temperature programming, reducing the temperature rising rate to 5 ℃/min when the temperature rises to 750 ℃ initially at the temperature rising rate of 12 ℃/min, preserving heat for 30min at 250 ℃ and 480 ℃ respectively in the temperature rising process, preserving heat for 50min at 800 ℃, 1000 ℃, 1200 ℃, 1300 ℃, 1400 ℃ and 1500 ℃ respectively, finally rising the temperature to 1800 ℃ and preserving heat for 2 h.

Example 2: preparation of thermal shock resistant substrate material

The weight parts of the raw materials are as follows:

35 parts of silicon carbide; 8 parts of silicon dioxide; 4 parts of aluminum oxide; 3 parts of aluminum carbide; 1 part of zinc molybdate; 4 parts of polyethylene glycol; 0.3 part of silicon nitride; 0.4 part of cesium oxide; 0.3 part of molybdenum trioxide; 0.8 part of glass fiber; 0.7 part of zinc fluosilicate and 0.7 part of barium carbide, wherein the weight part ratio of the zinc fluosilicate to the barium carbide is 6: 1.

The preparation method comprises the following steps:

step S1, soaking silicon carbide in polyethylene glycol for 24 hours, then heating to 100 ℃, adding silicon dioxide and aluminum oxide, stirring, and uniformly mixing to obtain a material A;

step S2, adding the rest materials into the material A in the step S1 in proportion, uniformly mixing, grinding until the fineness of the material is 300 meshes, and then granulating and pressing;

step S3, drying the green body pressed in the step S2 at the drying temperature of 140 ℃ and firing to obtain a product; the firing conditions are as follows: preserving heat for 30min at 120 ℃, then carrying out temperature programming, reducing the temperature rising rate to 5 ℃/min when the temperature rises to 750 ℃ initially at the temperature rising rate of 12 ℃/min, preserving heat for 30min at 250 ℃ and 480 ℃ respectively in the temperature rising process, preserving heat for 50min at 800 ℃, 1000 ℃, 1200 ℃, 1300 ℃, 1400 ℃ and 1500 ℃ respectively, finally rising the temperature to 1800 ℃ and preserving heat for 2 h.

Example 3: preparation of thermal shock resistant substrate material

The weight parts of the raw materials are as follows:

45 parts of silicon carbide; 12 parts of silicon dioxide; 8 parts of aluminum oxide; 5 parts of aluminum carbide; 3 parts of zinc molybdate; 6 parts of polyethylene glycol; 0.5 part of silicon nitride; 0.8 part of cesium oxide; 0.5 part of molybdenum trioxide; 1.2 parts of glass fiber; 0.9 part of zinc fluosilicate and 0.9 part of barium carbide, wherein the weight part ratio of the zinc fluosilicate to the barium carbide is 8: 1.

The preparation method comprises the following steps:

step S1, soaking silicon carbide in polyethylene glycol for 24 hours, then heating to 100 ℃, adding silicon dioxide and aluminum oxide, stirring, and uniformly mixing to obtain a material A;

step S2, adding the rest materials into the material A in the step S1 in proportion, uniformly mixing, grinding until the fineness of the material is 300 meshes, and then granulating and pressing;

step S3, drying the green body pressed in the step S2 at the drying temperature of 140 ℃ and firing to obtain a product; the firing conditions are as follows: preserving heat for 30min at 120 ℃, then carrying out temperature programming, reducing the temperature rising rate to 5 ℃/min when the temperature rises to 750 ℃ initially at the temperature rising rate of 12 ℃/min, preserving heat for 30min at 250 ℃ and 480 ℃ respectively in the temperature rising process, preserving heat for 50min at 800 ℃, 1000 ℃, 1200 ℃, 1300 ℃, 1400 ℃ and 1500 ℃ respectively, finally rising the temperature to 1800 ℃ and preserving heat for 2 h.

Example 4: preparation of thermal shock resistant substrate material

The weight parts of the raw materials are as follows:

40 parts of silicon carbide; 10 parts of silicon dioxide; 6 parts of aluminum oxide; 4 parts of aluminum carbide; 2 parts of zinc molybdate; 5 parts of polyethylene glycol; 0.4 part of silicon nitride; 0.6 part of cesium oxide; 0.4 part of molybdenum trioxide; 1.0 part of glass fiber; 0.8 part of zinc fluosilicate and 0.8 part of barium carbide, wherein the weight part ratio of the zinc fluosilicate to the barium carbide is 6: 1.

The preparation method comprises the following steps:

step S1, soaking silicon carbide in polyethylene glycol for 24 hours, then heating to 100 ℃, adding silicon dioxide and aluminum oxide, stirring, and uniformly mixing to obtain a material A;

step S2, adding the rest materials into the material A in the step S1 in proportion, uniformly mixing, grinding until the fineness of the material is 300 meshes, and then granulating and pressing;

step S3, drying the green body pressed in the step S2 at the drying temperature of 140 ℃ and firing to obtain a product; the firing conditions are as follows: preserving heat for 30min at 120 ℃, then carrying out temperature programming, reducing the temperature rising rate to 5 ℃/min when the temperature rises to 750 ℃ initially at the temperature rising rate of 12 ℃/min, preserving heat for 30min at 250 ℃ and 480 ℃ respectively in the temperature rising process, preserving heat for 50min at 800 ℃, 1000 ℃, 1200 ℃, 1300 ℃, 1400 ℃ and 1500 ℃ respectively, finally rising the temperature to 1800 ℃ and preserving heat for 2 h.

Example 5: preparation of thermal shock resistant substrate material

The weight parts of the raw materials are as follows:

40 parts of silicon carbide; 10 parts of silicon dioxide; 6 parts of aluminum oxide; 4 parts of aluminum carbide; 2 parts of zinc molybdate; 5 parts of polyethylene glycol; 0.4 part of silicon nitride; 0.6 part of cesium oxide; 0.4 part of molybdenum trioxide; 1.0 part of glass fiber; 0.8 part of zinc fluosilicate and 0.8 part of barium carbide, wherein the weight part ratio of the zinc fluosilicate to the barium carbide is 8: 1.

The preparation method comprises the following steps:

step S1, soaking silicon carbide in polyethylene glycol for 24 hours, then heating to 100 ℃, adding silicon dioxide and aluminum oxide, stirring, and uniformly mixing to obtain a material A;

step S2, adding the rest materials into the material A in the step S1 in proportion, uniformly mixing, grinding until the fineness of the material is 300 meshes, and then granulating and pressing;

step S3, drying the green body pressed in the step S2 at the drying temperature of 140 ℃ and firing to obtain a product; the firing conditions are as follows: preserving heat for 30min at 120 ℃, then carrying out temperature programming, reducing the temperature rising rate to 5 ℃/min when the temperature rises to 750 ℃ initially at the temperature rising rate of 12 ℃/min, preserving heat for 30min at 250 ℃ and 480 ℃ respectively in the temperature rising process, preserving heat for 50min at 800 ℃, 1000 ℃, 1200 ℃, 1300 ℃, 1400 ℃ and 1500 ℃ respectively, finally rising the temperature to 1800 ℃ and preserving heat for 2 h.

Example 6: comparative example, the weight ratio of zinc fluorosilicate to barium Dicarbide was 5:1

The weight parts of the raw materials are as follows:

40 parts of silicon carbide; 10 parts of silicon dioxide; 6 parts of aluminum oxide; 4 parts of aluminum carbide; 2 parts of zinc molybdate; 5 parts of polyethylene glycol; 0.4 part of silicon nitride; 0.6 part of cesium oxide; 0.4 part of molybdenum trioxide; 1.0 part of glass fiber; 0.8 part of zinc fluosilicate and 0.8 part of barium carbide, wherein the weight part ratio of the zinc fluosilicate to the barium carbide is 5: 1.

The preparation method comprises the following steps:

step S1, soaking silicon carbide in polyethylene glycol for 24 hours, then heating to 100 ℃, adding silicon dioxide and aluminum oxide, stirring, and uniformly mixing to obtain a material A;

step S2, adding the rest materials into the material A in the step S1 in proportion, uniformly mixing, grinding until the fineness of the material is 300 meshes, and then granulating and pressing;

step S3, drying the green body pressed in the step S2 at the drying temperature of 140 ℃ and firing to obtain a product; the firing conditions are as follows: preserving heat for 30min at 120 ℃, then carrying out temperature programming, reducing the temperature rising rate to 5 ℃/min when the temperature rises to 750 ℃ initially at the temperature rising rate of 12 ℃/min, preserving heat for 30min at 250 ℃ and 480 ℃ respectively in the temperature rising process, preserving heat for 50min at 800 ℃, 1000 ℃, 1200 ℃, 1300 ℃, 1400 ℃ and 1500 ℃ respectively, finally rising the temperature to 1800 ℃ and preserving heat for 2 h.

Example 7: comparative example, the weight ratio of zinc fluorosilicate to barium Dicarbide was 9:1

The weight parts of the raw materials are as follows:

40 parts of silicon carbide; 10 parts of silicon dioxide; 6 parts of aluminum oxide; 4 parts of aluminum carbide; 2 parts of zinc molybdate; 5 parts of polyethylene glycol; 0.4 part of silicon nitride; 0.6 part of cesium oxide; 0.4 part of molybdenum trioxide; 1.0 part of glass fiber; 0.8 part of zinc fluosilicate and 0.8 part of barium carbide, wherein the weight part ratio of the zinc fluosilicate to the barium carbide is 9: 1.

The preparation method comprises the following steps:

step S1, soaking silicon carbide in polyethylene glycol for 24 hours, then heating to 100 ℃, adding silicon dioxide and aluminum oxide, stirring, and uniformly mixing to obtain a material A;

step S2, adding the rest materials into the material A in the step S1 in proportion, uniformly mixing, grinding until the fineness of the material is 300 meshes, and then granulating and pressing;

step S3, drying the green body pressed in the step S2 at the drying temperature of 140 ℃ and firing to obtain a product; the firing conditions are as follows: preserving heat for 30min at 120 ℃, then carrying out temperature programming, reducing the temperature rising rate to 5 ℃/min when the temperature rises to 750 ℃ initially at the temperature rising rate of 12 ℃/min, preserving heat for 30min at 250 ℃ and 480 ℃ respectively in the temperature rising process, preserving heat for 50min at 800 ℃, 1000 ℃, 1200 ℃, 1300 ℃, 1400 ℃ and 1500 ℃ respectively, finally rising the temperature to 1800 ℃ and preserving heat for 2 h.

Example 8: effects of the embodiment

Thermal shock resistance, which is reflected in the ability of a material to withstand rapid changes in temperature without failure, is one of the most critical parameters that determine the useful life of the material. The experimental procedure was as follows: and (3) putting the sample into a high-temperature furnace, heating to 1100 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 60min, taking out the sample, naturally cooling the sample in room-temperature air, putting the sample prepared according to the formula of the embodiment 1-7 into a high-temperature resistance furnace, and carrying out thermal shock for 60 times. The samples were taken after 10 th, 20 th, 30 th, 40 th, 50 th and 60 th thermal shock resistance, respectively, to test the breaking strength, calculate the strength loss rate and describe the appearance of the wafer samples, and the results are shown in the following table.

The thermal conductivity of the samples of the formulations of examples 1 to 7 was measured by using a laser thermal constant tester TC-7000H, manufactured by Nippon vacuum physic corporation, and the results are shown in the following table.

The oxidation resistance test adopts a discontinuous weighing method, and the sample is put into a box type silicon key resistance furnace with good air flowing state and is insulated for 3 hours at 1300 ℃. The sample was taken out of the furnace, slowly cooled in the air, and then the mass of the sample was weighed by an electronic balance, and the amount of change before and after the change was recorded, and the oxidation resistance was calculated from the amount of change as compared with the mass of the sample before the oxidation, and the results are shown in the following table.

	Number of thermal shocks with cracks	Flexural strength/MPa	Thermal conductivity W/(m.k)	Oxidation resistance%
					Example 1	60 times without cracks	110	33.5	0.35
Example 4	60 times without cracks	103	31.8	0.38
					Example 5	60 times without cracks	105	32.3	0.39
Example 6	30 times (twice)	55	15.4	1.45
					Example 7	30 times (twice)	53	15.1	1.49

The test results of examples 2 and 3 are substantially the same as those of examples 4 and 5.

The results show that the thermal shock resistant base material provided by the invention has excellent thermal shock resistance, higher strength and refractoriness, and meets the requirements of the current solar thermal power generation heat absorption material. The effect is related to the weight ratio of the zinc fluosilicate to the barium carbide in the raw materials, and when the weight ratio of the zinc fluosilicate to the barium carbide is 6-8: 1, the thermal shock resistance is optimal.

The above-described embodiments are intended to illustrate the substance of the present invention, but are not intended to limit the scope of the present invention. It will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true spirit and scope of the invention.

Claims (3)

1. The thermal shock resistant substrate material is characterized by being prepared from the following raw materials in parts by weight: 40 parts of silicon carbide; 10 parts of silicon dioxide; 6 parts of aluminum oxide; 4 parts of aluminum carbide; 2 parts of zinc molybdate; 5 parts of polyethylene glycol; 0.4 part of silicon nitride; 0.6 part of cesium oxide; 0.4 part of molybdenum trioxide; 1.0 part of glass fiber; 0.8 part of zinc fluosilicate and 0.8 part of barium carbide, wherein the weight part ratio of the zinc fluosilicate to the barium carbide is 6:1, or the weight part ratio of the zinc fluosilicate to the barium carbide is 8: 1; the grain size of the silicon carbide is 0.4-0.6 mm.

2. A method of preparing a thermal shock resistant base material according to claim 1 comprising the steps of:

step S1, soaking silicon carbide in polyethylene glycol for 24 hours, then heating to 100 ℃, adding silicon dioxide and aluminum oxide, stirring, and uniformly mixing to obtain a material A;

step S2, adding the rest materials into the material A in the step S1 in proportion, uniformly mixing, grinding until the fineness of the material is 300 meshes, and then granulating and pressing;

step S3, drying the green body pressed in the step S2 at the drying temperature of 140 ℃ and firing to obtain a product; the firing conditions are as follows: preserving heat for 30min at 120 ℃, then carrying out temperature programming, reducing the temperature rising rate to 5 ℃/min when the temperature rises to 750 ℃ initially at the temperature rising rate of 12 ℃/min, preserving heat for 30min at 250 ℃ and 480 ℃ respectively in the temperature rising process, preserving heat for 50min at 800 ℃, 1000 ℃, 1200 ℃, 1300 ℃, 1400 ℃ and 1500 ℃ respectively, finally rising the temperature to 1800 ℃ and preserving heat for 2 h.

3. Use of the thermal shock resistant base material of claim 1 as a solar thermal power generation heat sink material.