阅读说明：本技术 一种耐腐蚀抗磨耐火材料及其制备方法 (Corrosion-resistant wear-resistant refractory material and preparation method thereof ) 是由 孙玉岩 于 2021-10-14 设计创作，主要内容包括：本发明涉及耐火材料技术领域,提出了一种耐腐蚀抗磨耐火材料及其制备方法,其中耐火材料包括以下重量份组分：100-130份棕刚玉、15-27份氧化铬、0.5-3份氧化钇、2-8份碳化硅、1-7份碳化钨、0.1-1份碳化钛、5-10份酚醛树脂。本发明通过碳化钨、碳化硅、碳化钛之间的协同作用,避免材料内部孔隙的形成,提高材料的耐腐蚀性；通过氧化钇、碳化钨、碳化硅、碳化钛的共同作用,显著提高材料的抗磨性。(The invention relates to the technical field of refractory materials, and provides a corrosion-resistant wear-resistant refractory material and a preparation method thereof, wherein the refractory material comprises the following components in parts by weight: 100 portions of brown corundum 130 portions, 15-27 portions of chromium oxide, 0.5-3 portions of yttrium oxide, 2-8 portions of silicon carbide, 1-7 portions of tungsten carbide, 0.1-1 portion of titanium carbide and 5-10 portions of phenolic resin. According to the invention, through the synergistic effect of tungsten carbide, silicon carbide and titanium carbide, the formation of pores in the material is avoided, and the corrosion resistance of the material is improved; the abrasion resistance of the material is obviously improved through the combined action of yttrium oxide, tungsten carbide, silicon carbide and titanium carbide.)

1. The corrosion-resistant wear-resistant refractory material is characterized by comprising the following components in parts by weight: 100 portions of brown corundum 130 portions, 15-27 portions of chromium oxide, 0.5-3 portions of yttrium oxide, 2-8 portions of silicon carbide, 1-7 portions of tungsten carbide, 0.1-1 portion of titanium carbide and 5-10 portions of phenolic resin.

2. The corrosion-resistant, abrasion-resistant and fire-resistant material according to claim 1, wherein the brown fused alumina comprises 70-80 parts of particles with a particle size of 1-5mm, 20-30 parts of particles with a particle size of 10-50 μm, and 10-20 parts of particles with a particle size of 50-100 nm.

3. The corrosion-resistant, wear-resistant and refractory material of claim 1, wherein the alumina content in the brown corundum is not less than 98%.

4. The corrosion-resistant, abrasion-resistant, and refractory material of claim 1, wherein said chromium oxide has a particle size of 50 μm or less;

the grain size of the yttrium oxide is less than or equal to 50 mu m;

the grain diameter of the silicon carbide is 10-50 mu m;

the particle size of the tungsten carbide is 30-80 nm;

the grain diameter of the titanium carbide is 10-100 nm.

5. The corrosion-resistant, abrasion-resistant and fire-resistant material according to claim 2, comprising the following components in parts by weight: 115 parts of brown fused alumina, 20 parts of chromium oxide, 1.5 parts of yttrium oxide, 5 parts of silicon carbide, 4 parts of tungsten carbide, 0.5 part of titanium carbide and 7 parts of phenolic resin.

6. The corrosion-resistant, wear-resistant and refractory material according to claim 5, wherein the mass ratio of the particle size of the brown corundum to the particle size of 1-5mm, 10-50 μm and 50-100nm is 15:5: 3.

7. The method for preparing a corrosion-resistant, abrasion-resistant and fire-resistant material according to any of claims 1 to 6, comprising the steps of:

(1) mixing part of brown corundum with the grain diameter of 1-5mm with brown corundum with the grain diameter of 10-100nm and yttrium oxide to obtain a mixture 1;

(2) mixing the rest brown corundum with the grain diameter of 1-5mm with the brown corundum with the grain diameter of 10-50 mu m and chromium oxide to obtain a mixture 2;

(3) mixing tungsten carbide and titanium carbide, and heating to obtain a mixture 3;

(4) and fully mixing the mixture 1, the mixture 2, the mixture 3 and the silicon carbide, drying, adding the phenolic resin, uniformly mixing, and keeping the temperature at high temperature to obtain the refractory material.

8. The method for preparing the corrosion-resistant, wear-resistant and fire-resistant material according to claim 7, wherein the brown corundum with the partial particle size of 1-5mm in the step (1) is half of the total amount of the brown corundum with the particle size of 1-5 mm.

9. The method for preparing a corrosion-resistant, wear-resistant and refractory material according to claim 7, wherein the tungsten carbide and the titanium carbide are heated to 500-600 ℃ in the step (3) and maintained for 30-40 min.

10. The method for preparing corrosion-resistant, abrasion-resistant and fire-resistant material as claimed in claim 7, wherein the drying in step (4) is vacuum drying, drying at 100-120 ℃ for 10-15 h; the high temperature is 1700-1800 ℃ and the temperature is kept for 30-40 min.

Technical Field

The invention relates to the technical field of refractory materials, in particular to a corrosion-resistant and wear-resistant refractory material and a preparation method thereof.

Background

The refractory material is widely applied to various fields of national economy such as steel, nonferrous metals, glass, cement, ceramics, petrifaction, machinery, boilers, light industry, electric power, military industry and the like, is an essential basic material for ensuring the production operation and the technical development of the industries, and plays an irreplaceable important role in the development of high-temperature industrial production. The aluminum-chromium refractory material has the characteristics of high refractoriness, excellent erosion resistance, good thermal shock resistance and high wear resistance, and has wide application prospect.

However, in the conventional aluminum-chromium refractory, sodium, potassium and other unstable phases existing in the form of alkali metal oxides in the raw materials cause expansion of products in the production process, so that the apparent porosity is large, the volume density is reduced, the physical properties are deteriorated, and the normal-temperature compressive strength is low. Patent CN105036715B discloses an aluminum-chromium refractory material, which comprises 80-100 parts of aluminum oxide particles, 25-35 parts of alpha-aluminum oxide powder, 15-20 parts of nano aluminum oxide, 20-35 parts of chromium oxide, 10-20 parts of graphene, 5-10 parts of an additive, 7-12 parts of a binding agent and 5-12 parts of nano silicon carbide. The refractory material disclosed in the patent is internally dense, the volume density is improved, the apparent porosity of the refractory material is reduced, and expansion is prevented. However, the binding agent is a seaweed extract, the preparation method is complex, the thermal stability is poor, the binding property is obviously reduced after the high-temperature firing, and the mechanical property of the final material is influenced.

Disclosure of Invention

The invention provides a corrosion-resistant wear-resistant refractory material and a preparation method thereof, which solve the problem that the aluminum-chromium refractory material in the prior art is easy to generate air holes and corrosion, remarkably improve the strength of the material and further improve the wear resistance of the material.

The technical scheme of the invention is as follows:

the corrosion-resistant wear-resistant refractory material comprises the following components in parts by weight: 100 portions of brown corundum 130 portions, 15-27 portions of chromium oxide, 0.5-3 portions of yttrium oxide, 2-8 portions of silicon carbide, 1-7 portions of tungsten carbide, 0.1-1 portion of titanium carbide and 5-10 portions of phenolic resin.

Furthermore, the brown corundum comprises 70-80 parts of 1-5mm grain diameter, 20-30 parts of 10-50 mu m grain diameter and 10-20 parts of 50-100nm grain diameter.

Furthermore, the content of alumina in the brown corundum is more than or equal to 98 percent.

Furthermore, the grain diameter of the chromium oxide is less than or equal to 50 μm.

Furthermore, the grain diameter of the yttrium oxide is less than or equal to 50 μm.

Further, the particle size of the silicon carbide is 10-50 μm.

Further, the particle size of the tungsten carbide is 30-80 nm.

Further, the particle size of the titanium carbide is 10-100 nm.

Further, the corrosion-resistant, wear-resistant and fireproof material comprises the following components in parts by weight: 115 parts of brown fused alumina, 20 parts of chromium oxide, 1.5 parts of yttrium oxide, 5 parts of silicon carbide, 4 parts of tungsten carbide, 0.5 part of titanium carbide and 7 parts of phenolic resin.

Furthermore, the mass ratio of the particle size of the brown fused alumina to the particle size of 1-5mm, 10-50 μm and 50-100nm is 15:5: 3.

The invention further provides a preparation method of the corrosion-resistant wear-resistant refractory material, which comprises the following steps:

(1) mixing part of brown corundum with the grain diameter of 1-5mm with brown corundum with the grain diameter of 10-100nm and yttrium oxide to obtain a mixture 1;

(2) mixing the rest brown corundum with the grain diameter of 1-5mm with the brown corundum with the grain diameter of 10-50 mu m and chromium oxide to obtain a mixture 2;

(3) mixing tungsten carbide and titanium carbide, and heating to obtain a mixture 3;

(4) and fully mixing the mixture 1, the mixture 2, the mixture 3 and the silicon carbide, drying, adding the phenolic resin, uniformly mixing, and keeping the temperature at high temperature to obtain the refractory material.

Furthermore, part of the brown corundum with the grain diameter of 1-5mm in the step (1) is specifically half of the total amount of the brown corundum with the grain diameter of 1-5 mm.

Further, in the step (3), the tungsten carbide and the titanium carbide are heated to 500-600 ℃ and kept for 30-40 min.

Further, the drying in the step (4) is vacuum drying, and the drying is carried out at the temperature of 100 ℃ and 120 ℃ for 10-15 h.

Further, the temperature in the step (4) is maintained at 1700-1800 ℃ for 30-40 min.

The invention has the beneficial effects that:

1. the addition of the yttrium oxide, the tungsten carbide, the silicon carbide and the titanium carbide can enhance the strength of the refractory material and obviously improve the wear resistance of the material. Wherein, the tungsten carbide is fragile, but the brittleness of the tungsten carbide can be reduced by heating treatment after the tungsten carbide is mixed with the titanium carbide, and the abrasion resistance of the material is obviously improved; the yttrium oxide and the main component aluminum oxide in the brown fused alumina form yttrium aluminum garnet at high temperature, and the rare earth binding phase can jointly enhance the wear resistance of the refractory material with tungsten carbide, silicon carbide and titanium carbide.

2. The unstable phase existing in the form of sodium, potassium and other alkali metal oxides in the brown corundum raw material enables the product to expand in the production process, so that the material is easy to generate pores, and the silicon carbide can continuously form SiO gas in the sintering process and also can cause fine pores to be generated in the material, so that aggressive gas or slag can enter the silicon carbide, and finally the material is easy to corrode.

3. The invention carries out gradation on the brown fused alumina with different grain diameters when preparing the refractory material, so that the material obtains a matrix with a more compact structure, and the abrasion resistance and the corrosion resistance of the material are improved.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, are intended to be within the scope of the present invention.

Example 1

The corrosion-resistant wear-resistant refractory material comprises the following components in parts by weight: 115 parts of brown corundum (wherein the brown corundum with the particle size of 1-5mm is 75 parts, 25 parts of 10-50 mu m and 15 parts of 50-100 nm), 20 parts of chromium oxide (the particle size is less than or equal to 50 mu m), 1.5 parts of yttrium oxide (the particle size is less than or equal to 50 mu m), 5 parts of silicon carbide (the particle size is 10-50 mu m), 4 parts of tungsten carbide (the particle size is 30-80nm), 0.5 part of titanium carbide (the particle size is 10-100nm) and 7 parts of phenolic resin.

Wherein, the alumina content in the brown corundum is more than or equal to 98 percent.

The preparation method of the corrosion-resistant wear-resistant refractory material comprises the following steps:

(1) mixing half of the brown corundum with the grain diameter of 1-5mm with the brown corundum with the grain diameter of 10-100nm and yttrium oxide to obtain a mixture 1;

(2) mixing the rest brown corundum with the grain diameter of 1-5mm with the brown corundum with the grain diameter of 10-50 mu m and chromium oxide to obtain a mixture 2;

(3) mixing tungsten carbide and titanium carbide, heating to 550 ℃, and keeping the temperature for 35min to obtain a mixture 3;

(4) and (3) fully mixing the mixture 1, the mixture 2, the mixture 3 and the silicon carbide, performing vacuum drying at 110 ℃ for 12h, adding phenolic resin, uniformly mixing, and performing heat preservation at 1750 ℃ for 35min to obtain the refractory material.

Example 2

The corrosion-resistant wear-resistant refractory material comprises the following components in parts by weight: 100 parts of brown corundum (wherein the brown corundum with the grain diameter of 1-5mm is 70, 20 parts of 10-50 mu m and 10 parts of 50-100 nm), 15 parts of chromium oxide (the grain diameter is less than or equal to 50 mu m), 0.5 part of yttrium oxide (the grain diameter is less than or equal to 50 mu m), 8 parts of silicon carbide (the grain diameter is 10-50 mu m), 7 parts of tungsten carbide (the grain diameter is 30-80nm), 1 part of titanium carbide (the grain diameter is 10-100nm) and 5 parts of phenolic resin.

Wherein, the alumina content in the brown corundum is more than or equal to 98 percent.

The preparation method of the corrosion-resistant wear-resistant refractory material comprises the following steps:

(1) mixing half of the brown corundum with the grain diameter of 1-5mm with the brown corundum with the grain diameter of 10-100nm and yttrium oxide to obtain a mixture 1;

(2) mixing the rest brown corundum with the grain diameter of 1-5mm with the brown corundum with the grain diameter of 10-50 mu m and chromium oxide to obtain a mixture 2;

(3) mixing tungsten carbide and titanium carbide, heating to 500 ℃, and keeping the temperature for 40min to obtain a mixture 3;

(4) and (3) fully mixing the mixture 1, the mixture 2, the mixture 3 and the silicon carbide, then carrying out vacuum drying for 15h at 100 ℃, adding phenolic resin, uniformly mixing, and carrying out heat preservation for 30min at 1800 ℃ to obtain the refractory material.

Example 3

The corrosion-resistant wear-resistant refractory material comprises the following components in parts by weight: 130 parts of brown corundum (wherein the brown corundum with the grain diameter of 1-5mm is 80 parts, 30 parts of 10-50 mu m and 20 parts of 50-100 nm), 27 parts of chromium oxide (the grain diameter is less than or equal to 50 mu m), 3 parts of yttrium oxide (the grain diameter is less than or equal to 50 mu m), 2 parts of silicon carbide (the grain diameter is 10-50 mu m), 1 part of tungsten carbide (the grain diameter is 30-80nm), 0.1 part of titanium carbide (the grain diameter is 10-100nm) and 10 parts of phenolic resin.

Wherein, the alumina content in the brown corundum is more than or equal to 98 percent.

The preparation method of the corrosion-resistant wear-resistant refractory material comprises the following steps:

(1) mixing half of the brown corundum with the grain diameter of 1-5mm with the brown corundum with the grain diameter of 10-100nm and yttrium oxide to obtain a mixture 1;

(2) mixing the rest brown corundum with the grain diameter of 1-5mm with the brown corundum with the grain diameter of 10-50 mu m and chromium oxide to obtain a mixture 2;

(3) mixing tungsten carbide and titanium carbide, heating to 600 ℃, and keeping the temperature for 30min to obtain a mixture 3;

(4) and (3) fully mixing the mixture 1, the mixture 2, the mixture 3 and the silicon carbide, then drying in vacuum at 120 ℃ for 10h, adding phenolic resin, uniformly mixing, and preserving heat at 1700 ℃ for 40min to obtain the refractory material.

Comparative example 1

The same procedure as in example 1 was repeated except that lanthanum oxide was used in place of yttrium oxide.

Comparative example 2

The rest of the process is the same as example 1 except that silicon powder is used instead of tungsten carbide.

Comparative example 3

When the refractory material is prepared, brown corundum with different grain sizes is directly mixed without grading, and the rest of the method is the same as that in example 1 and specifically comprises the following steps:

(1) mixing brown corundum, yttrium oxide and chromium oxide with different grain diameters to obtain a mixture 1;

(2) mixing tungsten carbide and titanium carbide, heating to 550 ℃, and keeping the temperature for 35min to obtain a mixture 2;

(3) and (3) fully mixing the mixture 1, the mixture 2 and the silicon carbide, performing vacuum drying at 110 ℃ for 12h, adding phenolic resin, uniformly mixing, and keeping the temperature at 1750 ℃ for 35min to obtain the refractory material.

Comparative example 4

The same amount of titanium carbide was used instead of tungsten carbide, as in example 1.

Comparative example 5

The same amount of silicon carbide was used instead of tungsten carbide, as in example 1.

Experimental examples study on the Properties of various refractory materials

1. The abrasion resistance of the refractory material is tested according to the relevant regulations in the test method of the normal temperature abrasion resistance of the GB/T18301-.

2. And (3) crucible corrosion test: a test piece of 115X 50X 65mm was drilled with a hole of 26mm in inner diameter and 20mm in depth by a drill, and 15g of each corrosive agent was put into the hole and sealed with mortar to prevent oxidation of the corrosive agent, and the test piece was left at 1730 ℃ for 6 hours and then cut after cooling to determine the permeation thickness of the corrosive agent. The smaller the penetration thickness, the better the result.

Wherein, corrosive agent chooses respectively:

the mixture of the steel and the slag with the mass ratio of 6:4, wherein the alkalinity CaO/SiO of the slag₂＝3；

② the copper refining slag, when the corrosive is selected, the slag is placed at 1500 ℃ for 2h for corrosion experiment;

③ the metal (the main component is essentially iron) produced in the ash fusion furnace.

TABLE 1 abrasion and Corrosion resistance of different refractory materials

As can be seen from the data in Table 1, the refractory materials prepared in examples 1-3 of the present invention have a small wear amount and a small thickness to be corroded, and have good abrasion resistance and corrosion resistance. Comparative example 1, yttrium oxide is replaced by lanthanum oxide, the lanthanum oxide is similar to the yttrium oxide and has the function of grain refinement, but the lanthanum oxide cannot form a new rare earth bonding phase with alumina in brown alumina, so that the abrasion resistance of the refractory material cannot be effectively improved, and after an abrasion test, the abrasion amount reaches 12.34cm³Meanwhile, lanthanum oxide, silicon carbide, titanium carbide and tungsten carbide cannot form a synergistic effect, so that the corrosion resistance of the material is reduced to a certain extent. Comparative example 2 adopts silica flour to replace tungsten carbide, and silica flour can also fill up the hole that forms in the carborundum in the high-temperature firing process of carborundum, avoids carborundum to be corroded by the slag, but the hole that forms is only filled up to carborundum to silicon oxide, does not have good filling effect to the hole that other raw materials formed, therefore the overall corrosion resistance of refractory material is not high, easily corrodes by the slag and destroys. At the same time, the overall abrasion resistance of the refractory is also reduced due to the formation of internal pores. Comparative example 3 in the preparation of the refractory, no difference was madeThe brown corundum with the grain diameter is graded and directly mixed, the internal structure of the material is unevenly distributed, and pores are easy to appear, so that the abrasion resistance and the corrosion resistance of the refractory material are obviously reduced. Comparative examples 4 and 5 use titanium carbide and silicon carbide instead of tungsten carbide, respectively, and although titanium carbide and silicon carbide also have higher strength, the synergistic effects among tungsten carbide, titanium carbide and silicon carbide are lost in comparative examples 4 and 5, so that the wear resistance and corrosion resistance of the final material are reduced.

The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.