CN1919786A - Manufacture method of ceramic lining composite square steel tube - Google Patents
Manufacture method of ceramic lining composite square steel tube Download PDFInfo
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Abstract
The invention discloses a manufacturing method of ceramic lining composite steel pipe, which comprises the following parts: Fe2O3 powder, Al powder, SiO2 powder and CrO3 powder, wherein these materials are blended evenly to generate the product through toasting, allocating, loading, adding core and igniting; certain shaped core material is added in the middle of square pipe, which reduces quality of thermit to control manufacturing cost; the thermit is added directly in the square steel pipe with external radius less than 35mm to ignite.
Description
Technical Field
The invention relates to the new technical field of steel surface coatings, in particular to a production method of a ceramic lining composite steel pipe.
Background
The ceramic lining composite square steel pipe and its production process utilize the chemical energy inside the reactant to synthesize material. After the reactants are ignited, the combustion reaction can self-sustain, generally without the need for supplemental energy. The whole process is very simple, the energy consumption is low, the production efficiency is high, and the product purity is high.
The technological process of producing ceramic coating with ceramic lining composite square steel pipe includes the following steps: mixing Al powder and Fe with certain granularity2O3The powder is prepared in proportion, mixed by a mixer and filled into a tube to reach a certain density, the square steel tube is vertically placed, and the upper part of the thermite is ignited. Under the action of high reaction heat, the reaction is continuously carried out to generate Al2O3And a melt of Fe, forming a molten pool on top of the thermite. Due to the considerable density difference, the molten pool is subjected to gravity separation, the Fe with high density sinks, and the Al with low density2O3Floating on the upper part of the molten pool. Due to Al2O3Has high melting point, short liquid phase retention time, and Al content falling along with the liquid level2O3The contact part of the melt and the inner wall of the metal pipe isfirstly cooled and solidified and combined with the wall of the metal pipe to form the ceramic coating lining. And forming a continuous ceramic coating on the inner wall of the steel pipe along with the continuous descending of the reaction interface until an inner lining alumina coating with the thickness of 0.7-4 mm is formed on the inner wall of all the steel pipes. And discharging the high-density Fe melt and the redundant ceramic melt together from the lower hole of the steel pipe, and cooling to obtain the composite pipe with the ceramic coating as the lining. The reaction formula is as follows:
the gravity separation ceramic lining composite square steel tube technology is derived from self-propagating high-temperature synthesis, and the required product is obtained by separating the ceramic lining composite square steel tube under the action of gravity. The current method for preparing the composite coating mainly focuses on preparing the round composite steel pipe. The technology for generating the ceramic coating on the inner wall of the non-circular pipe and the plate has wide application prospect, but the prior art is not mature.
Chinese patent CN 1226451C discloses a manufacturing process of ceramic composite steel tube, but mainly focuses on preparing composite round steel tube, and the differences of ceramic lining coating prepared by round tube and square tube are ① proportion, filling density, powder-weight matrix ratio and SiO2And CrO3The influence rules of the factors such as the additive and the like on the square steel pipe and the round steel pipe are basically consistent, but because of the shape difference of the steel pipe base bodies, the square steel pipe has better fluidity when being required to be in a molten state, the preparation of the reagent is different from that of the round steel pipe, ② when the ceramic lining coating of the square pipe is prepared, the coating at four right angles of the square pipe is thicker, and the pipe wall is relatively thinner, if the thickness of the square pipe and the thickness③ if the test tube is not vertical, the thickness of the coating is not uniform for the round tube, the square tube is easy to twist and deform, and the uneven thickness of the coating of each plane generates uneven stress, so that the ceramic coating is easy to fall off.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for producing a ceramic lining composite square steel tube by utilizing a gravity separation self-propagating high-temperature synthesis technology, which meets the working conditions of high temperature, low impact and the like, and obtains a ceramic lining composite plate by cutting the side surface of the steel tube.
To achieve the above object, the technical solution of the present invention is described as follows:
ceramic liningThe production method of composite square steel pipe is characterized by that its raw material includes Fe2O3Powder, Al powder, SiO2Powder and CrO3The manufacturing process of the powder comprises the steps of drying, proportioning, mixing, charging, core adding and ignition, and is characterized in that the method comprises the following steps:
1) preparing a steel pipe matrix: cutting the square steel pipe for the test to reach the required length, washing away oxide skin on the surfaceby using hydrochloric acid, drying the square steel pipe at a position far away from the electric furnace after cleaning, and polishing the inner wall of the square steel pipe by using abrasive paper after drying;
2) selecting materials: screening the raw materials by a 100-mesh and 300-mesh sieve, then respectively drying the raw materials, and drying Fe by a drying box2O3Powder and SiO2Drying the powder in an electric control thermostat at 140 ℃ for 24 hours, drying the Al powder at 60 ℃, and detecting the absence of moisture for later use;
3) preparing materials: preparing a thermite, wherein the thermite is prepared according to the following formula in percentage by weight; mixing raw materials, and mixing the reagents for 12 hours by using a mixer;
Fe2O3the powder is 100-300 meshes, 65-70%;
20-30% of Al powder with 100-300 meshes;
SiO2powder of 100 meshes to 300 meshes 2 percent to 8 percent;
CrO3the powder is 100-300 meshes and 1-4 percent.
4) Core matching: the square tube with the outer side length larger than 35mm is internally provided with a core material, the core material is a square steel tube, and the outer diameter of the square steel tube depends on a steel tube base body.
5) Charging: uniformly mixing the reaction reagents according to the powder weight matrix ratio of 2-5.5 g/cm3Determining the weight of raw materials according to the principle of (1) and the thickness of the ceramic to be obtained, and uniformly filling a reagent into a gap between the steel pipe and the core body while keeping the vertical state of the steel pipe;
6) igniting a reagent and manufacturing a tube: igniting thermite to make it react, and under the action of high reaction heat making reaction continuously proceedLine of formation of Al2O3And a melt of Fe formed on top of the thermiteA molten pool; and (3) forming a continuous ceramic coating on the inner wall of the steel pipe along with the continuous descending of the reaction interface until an inner lining alumina coating with the thickness of 1-3 mm is formed on the inner wall of all the pipes, and cooling to obtain the ceramic lining composite square steel pipe.
Compared with the prior art, the manufacturing method of the ceramic lining composite square steel pipe has the following novel and creative aspects:
(1) the combustion temperature is extremely high, typically 2000 ℃ to 3000 ℃. The low-melting-point impurities in the raw materials can volatilize and escape during the synthesis reaction, and the purity and the quality of the product are high.
(2) The synthesis process has great temperature gradient, and the product may have concentrated defect phase and non-equilibrium phase, high product activity and capacity of obtaining complex phase and metastable phase.
(3) The method has the advantages of less industrial production procedures, simple required equipment, small field and short production period. The production process is simple, the synthesis reaction process is rapid and is generally finished within several seconds or dozens of seconds, and the process time is saved.
(4) The energy-saving benefit is obvious, and the solid combustion synthesis technology generates compounds by means of chemical reaction between reaction substances and releases a large amount of heat energy. It is different from traditional metallurgical method such as smelting or sintering in furnace, and does not need additional energy source, so that it can save a lot of energy source, and its technological and economic effects are very obvious.
(5) The range of the prepared synthetic materials is very wide, and the method is suitable for manufacturing ceramic lining composite square steel pipes with various pipe diameters and thicknesses.
(6) The synthesized coating realizes mechanical bonding and micro-metallurgical bonding of the ceramic layer and the substrate due to the high-temperature melt and the high-temperature action, and the bonding is tight; the ceramic layer has certain toughness and can bear the action of low impact load. Some highly exothermic reactions form coatings that can produce metallurgical bonds. The prepared ceramic metal composite square steel pipe can greatly improve the high temperature resistance, high wear resistance and high corrosion resistance.
Drawings
FIG. 1 is a schematic diagram of an experimental device for ceramic composite small-section square steel tubes.
FIG. 2 is a schematic diagram of an experimental device for ceramic composite large-section square steel pipes.
FIG. 3 shows a ceramic lined composite square steel tube that has been successfully prepared.
Fig. 4 is a composite plate obtained by cutting a composite square pipe.
In the figures 1 and 2, 1-magnesium powder 2-square steel tube 3-thermite 4-hardboard 5-base 6-core 7-clamping device
Detailed Description
The present invention is described in further detail below with reference to the attached drawing figures. The invention is realized based on the principle of thermite reaction:
a method for producing a ceramic lining composite square steel tube comprises the following raw materials of Fe2O3Powder, Al powder, SiO2Powder CrO3The manufacturing process of the powder comprises the steps of drying, proportioning, mixing, charging, core adding and ignition, and the method comprises the following steps:
1) preparing a steel pipe matrix: cutting the square steel pipe for the test to reach the required length, washing away oxide skin on the surface by using hydrochloric acid, drying after washing, and polishing the inner wall by using abrasive paper after drying;
2) selecting materials: screening the raw materials by a 100-mesh and 300-mesh sieve, then respectively drying the raw materials, and drying Fe by a drying box2O3Powder and SiO2Drying the powder in an electric control thermostat at 140 ℃ for 24 hours, drying the Al powder at 60 ℃, and detecting the absence of moisture for later use;
3) preparing materials: preparing a thermite, wherein the thermite is prepared according to the following formula in percentage by weight; mixing raw materials, and mixing the reagents for 12 hours by using a mixer;
Fe2O3the powder is 100-300 meshes, 65-70%;
20-30% of Al powder with 100-300 meshes;
SiO2powder of 100 meshes to 300 meshes 2 percent to 8 percent;
CrO3the powder is 100-300 meshes and 1-4 percent.
4) Core matching:
the method is used for preparing the ceramic lining coating of the square tube with the large cross section, the square steel tube with the outer diameter of more than 35mm needs to add a core material with a certain shape in the middle of the square tube, the quality of the thermite is reduced, the heat generated by self-propagating reaction is reduced, the burning leakage of a matrix is prevented, and the production cost is controlled. For the square steel pipe with the outer diameter less than 35mm, the thermite is directly put into the inner cavity of the square steel pipe and ignited. In the experiment, the core material selected was a square steel tube. When square steel or round steel is adopted, the purity of the melt cannot be affected. The ceramic coating can be generated on the surface of the core in the reaction process, but because the difference between the thermal expansion coefficients of iron and ceramic is large, after cooling, a gap of 0.5-1.0 mm can be generated between the ceramic coating and the core material, the coating can completely fall off from the surface of the core after knocking, and the core material can be reused. We studied two shapes of core material, square or round steel tube, with dimensional parameters including length h, and side length C of the external section of the square steel tube1Or the outer radius C of the cylindrical steel tube2. The length h is equal to or slightly greater than the length of the square tube. Parameter C1、C2Calculated from the following equation:
in the formula: a-the outside length of the square tube is cm;
d-wall thickness, cm;
v-volume of matrix, cm3；
Rho-swage Density, g/cm3Usually 1.4-2.5;
α -weight ratio of powder to matrix, and the ratio of the mass of thermite to the volume of steel tube, is usually 2-5.5 g/cm3；
h-square tube length, cm.
The reason for the selection of the core volume of the present invention is as follows:
① the size of the core directly affects the amount of the filling agent, the thicknessof the ceramic coating generated by more agent is large, the thickness of the ceramic coating generated by less agent is small, so the amount of the reagent ② is selected according to the thickness of the ceramic coating expected to be obtained, the powder-to-weight-matrix ratio is 2-5.5 g/cm3。
5) Charging: the even mixing is carried outReacting the reagent according to the ratio of 1.4-2.5g/cm3The filler density of (2) is filled into the steel tube (for the reaction with the guide tube, the guide tube and the asbestos sheet are fixed well), and meanwhile, the vertical state of the steel tube is kept. If a transformer and a resistance wire are adopted for ignition, the resistance wire is embedded at the top end of the reaction reagent, and the output voltage and current of the transformer are adjusted. The diameter of the resistance wire is 0.5mm, the output voltage of the transformer is 24V, the output current is 1-2A, and the ignition delay time is about 30s generally. If the magnesium powder is used for ignition, only a small amount of magnesium powder needs to be scattered in the middle of the reaction reagent, and then the magnesium powder is ignited by a magnesium tape.
6) Igniting a reagent and manufacturing a tube: igniting the thermite in accordance with The reaction is carried out, and the reaction is continuously carried out under the action of high reaction heat to generate Al2O3And a melt of Fe, forming a molten pool on top of the thermite. Due to the considerable density difference, the molten pool is subjected to gravity separation, the Fe with high density sinks, and the Al with low density2O3Floating on the upper part of the molten pool. Due to Al2O3Has high melting point, short liquid phase retention time, and Al content falling along with the liquid level2O3The contact part of the melt and the inner wall of the metal pipe is firstly cooled and solidified and combined with the wall of the metal pipe to form the ceramic coating lining. And forming a continuous ceramic coating on the inner wall of the steel pipe along with the continuous descending of the reaction interface until an inner lining alumina coating with the thickness of 1-3 mm is formed on the inner wall of all the steel pipes. And discharging the high-density Fe melt and the redundant ceramic melt together from the lower hole of the steel pipe, and cooling to obtain the ceramic lining composite square steel pipe.
The ceramic lining composite square steel tube is manufactured on a series of square steel tubes with the outer side length of 20-60mm, the wall thickness of 1.5-4mm and the length of 70-350mm by the method. The thickness of the ceramic layer is 0.8-3.5 mm.
The surface of the generated ceramic lining layer is uniform and smooth, and no obvious visible air holes, cracks and bulges exist. The composite ceramic coating sample has the structure that the outer layer is a metal matrix layer, and the inner layer is a prepared lining coating. The lining obviously contains two kinds of substances, one kind of white metal in granular or agglomerated form is metal or intermetallicThe composite phase and the other phase are gray and have no metallic luster, and are ceramic phases, the alumina ceramic and the molten iron melt cannot form metallurgical bonding, the ceramic and the metal matrix mainly adopt a clamping type mechanical bonding mode, the hardness value is more than 1200-1400 (HV0.2), and the ceramic layer structure mainly comprises α -Al2O3Matrix phase and FeO. Al2O3Formed of spinel phase, SiO2In ceramics there is mainly a spinel quartz phase structure.
The following are specific examples given by the inventors, and the present invention is not limited to these examples.
Example 1:
the matrix is a square steel tube with the length of 30mm multiplied by 1.5mm and the length is 200 mm.
Al powder with the granularity of 200 +/-20 meshes and Fe2O3SiO with a particle size of 150-250 mesh2The granularity is 200 plus or minus 20 meshes, and the filler density is 1.5-2.0 g/cm3The powder weight matrix ratio is 3.0-5.5 g/cm3The ratio of the reagents is Al to Fe2O3∶SiO2＝24.2％∶71.8％∶4％。
Reacting at normal temperature, and naturally cooling to obtain ceramic with uniform thickness, smooth surface and thickness of 1.5-2.5mm, wherein the average hardness value is 1200-1400 (HV0.2), and the maximum hardness value can be 1415(HV 0.2). The ceramic and the metal substrate are firmly combined and are not easy to fall off.
Example 2:
the matrix is a square steel tube with the length of 30mm multiplied by 1.5mm and the length is 200 mm.
The Al powder with the granularity of 100-200 meshes and Fe2O3SiO with a particle size of 100-200 meshes2Particle size of 100-200 mesh CrO3The powder particle size is 100-200 meshes, and the filler density is 1.5-2.0 g/cm3The powder weight matrix ratio is 3.0-5.5 g/cm3The ratio of the reagents is Al to Fe2O3∶SiO2∶CrO3＝26％∶68％∶4％∶2％。
Reacting at normal temperature, and naturally cooling to obtain ceramic with uniform thickness, smooth surface and thickness of 1.5-2.5mm, wherein the average hardness value is 1200-1400 (HV0.2), and the maximum hardness value can be 1415(HV 0.2). The ceramic and themetal substrate are firmly combined and are not easy to fall off.
Example 3: :
the substrate is a square steel tube with the length of 100mm and the material quality of Q235, and the square steel tube is 60 multiplied by 4 mm.
The Al powder with the granularity of 100-200 meshes and Fe2O3SiO with a particle size of 100-200 meshes2A particle size of 100-200 meshes, a filler density of 1.4-1.8 g/cm3The powder weight matrix ratio is 3.0-5.5 g/cm3The ratio of the reagents is Al to Fe2O3∶SiO2＝30％∶66％∶4％。
In the experiment for preparing the large-section ceramic composite square tube, in order to improve the compactness of the ceramic layer, SiO is added into the thermite2Since it has a dual effect on coating quality, we have determined reasonable SiO2The addition amount is 4%. The core is a round steel tube with the diameter of phi 30mm, and the reaction is carried out at normal temperature and the natural cooling is carried out. The ceramic composite square tube sample with smooth surface and uniform coating thickness is prepared and can be directly used; can also be cut into a ceramic composite steel plate, and is a new effective method for preparing the ceramic composite coating on the surface of the steel plate.
The composite material comprises three layers, namely an outer steel pipe layer, a middle transition layer and an inner ceramic layer, wherein the middle transition layer and the inner ceramic layer are mainly made of iron particles, the thickness of a lining layer (consisting of the middle transition layer and the ceramic layer) is 1.0-3.5 mm, no obvious bonding interface exists between the transition layer and a base layer, and the bonding interface with the ceramic is clear. The alumina ceramic and the iron liquid melt can not form metallurgical bonding and can not generate wetting reaction, thereby forming a bonding mode mainly based on mechanical clamping.
After a plurality of tests, the invention can use a plurality of examples according to the formula, and the invention does not list one by one, as long as the ceramic lining composite square steel pipe can be prepared within the range of the invention.
Claims (6)
1. A method for producing a ceramic lining composite square steel tube comprises the following raw materials of Fe2O3Powder, Al powder, SiO2Powder and CrO3The powder is produced through the processes of drying, compounding, mixing, charging, filling and igniting, and features thatThe method comprises the following steps:
1) preparing a steel pipe matrix: cutting the square steel pipe for the test to reach the required length, washing away oxide skin on the surface by using hydrochloric acid, drying the square steel pipe at a position far away from the electric furnace after cleaning, and polishing the inner wall of the square steel pipe by using abrasive paper after drying;
2) selecting materials: screening the raw materials by a 100-mesh and 300-mesh sieve, then respectively drying the raw materials, and drying Fe by a drying box2O3Powder and SiO2Drying the powder in an electric control thermostat at 140 ℃ for 24 hours, drying the Al powder at 60 ℃, and detecting the absence of moisture for later use;
3) preparing materials: preparing a thermite, wherein the thermite is prepared according to the following formula in percentage by weight; mixing raw materials, and mixing the reagents for 12 hours by using a mixer;
Fe2O3the powder is 100-300 meshes, 65-70%;
20-30% of Al powder with 100-300 meshes;
SiO2powder of 100 meshes to 300 meshes 2 percent to 8 percent;
CrO3the powder is 100-300 meshes and 1-4 percent.
4) Core matching: the square tube with the outer side length larger than 35mm is internally provided with a core material, the core material is a square steel tube, and the outer diameter of the square steel tube depends on a steel tube base body.
5) Charging: uniformly mixing the reaction reagents according to the powder weight matrix ratio of 2-5.5 g/cm3Determining the weight of raw materials according to the principle of (1) and the thickness of the ceramic to be obtained, and uniformly filling a reagent into a gap between the steel pipe and the core body while keeping the vertical state of the steel pipe;
6) igniting a reagent and manufacturing a tube: igniting thermite to react, and generating Al under the action of high reaction heat2O3And a melt of Fe, forming a molten pool on top of the thermite; and (3) forming a continuous ceramic coating on the inner wall of the steel pipe along with the continuous descending of the reaction interface until an inner lining alumina coating with the thickness of 1-3 mm is formed on the inner wall of all the pipes, and cooling to obtain the ceramic lining composite square steel pipe.
2. The method for producing a ceramic-lined composite square steel pipe as claimed in claim 1, wherein the step 4) is omitted when the ceramic composite small-section square steel pipe is produced.
3. The method for producing a ceramic-lined composite square steel pipe as claimed in claim 1 or 2, wherein Al powder with a particle size of 200 ± 20 meshes and Fe is used2O3SiO with a particle size of 150-250 mesh2The granularity is 200 plus or minus 20 meshes, and the filler density is 1.5-2.0 g/cm3The powder weight matrix ratio is 3.0-5.5 g/cm3The ratio of the reagents is Al to Fe2O3∶SiO2＝24.2％∶71.8％∶4％。
4. The method for producing a ceramic-lined composite square steel pipe as claimed in claim 1 or 2, wherein the Al powder has a particle size of 100-200 mesh and Fe2O3SiO with a particle size of 100-200 meshes2Particle size of 100-200 mesh CrO3The powder particle size is 100-200 meshes, and the filler density is 1.5-2.0 g/cm3The powder weight matrix ratio is 3.0-5.5 g/cm3The ratio of the reagents is Al to Fe2O3∶SiO2∶CrO3＝26％∶68％∶4％∶2％。
5. The method for producing a ceramic-lined composite square steel pipe as claimed in claim 1 or 2, wherein the Al powder has a particle size of 100-200 mesh and Fe2O3SiO with a particle size of 100-200 meshes2A particle size of 100-200 meshes, a filler density of 1.4-1.8 g/cm3The powder weight matrix ratio is 3.0-5.5 g/cm3The ratio of the reagents is Al to Fe2O3∶SiO2＝30％∶66％∶4％。
6. A ceramic lined composite square steel tube manufactured by the method of claim 1, 2, 3, 4 or 5, wherein the ceramic lined composite square steel tube is manufactured by the above method on a series of square steel tubes having an outer side length of 20 to 60mm, a wall thicknessof 1.5 to 4mm and a length of 70 to 350mm, and the ceramic layer has a thickness of 0.8 to 3.5 mm.
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| CN102320842A (en) * | 2011-06-15 | 2012-01-18 | 新兴铸管股份有限公司 | Method for preparing ceramic coating for replacing refractory coating prepared with centrifugal cast-steel pipe thermal mold method |
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| CN102505117A (en) * | 2011-09-09 | 2012-06-20 | 内蒙古科技大学 | Manufacturing method for ceramic-lined composite steel pipe |
| CN102610288A (en) * | 2011-12-02 | 2012-07-25 | 中国人民解放军63653部队 | Curing process method for radioactive nuclide polluted sandy soil |
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| CN109232002A (en) * | 2018-10-17 | 2019-01-18 | 杨松 | It is a kind of to prepare the dedicated lining brick of hydrogen fluoride recirculating fluidized bed reacting furnace |
| CN109232002B (en) * | 2018-10-17 | 2021-08-20 | 戴志刚 | Special lining brick for preparing hydrogen fluoride circulating fluidized bed reaction furnace |
| CN109822209A (en) * | 2019-03-05 | 2019-05-31 | 郑州机械研究所有限公司 | A kind of clad steel plate preparation method based on thermit reaction |
| CN109822209B (en) * | 2019-03-05 | 2023-04-28 | 郑州机械研究所有限公司 | Preparation method of composite steel plate based on thermite reaction |
| CN110280773A (en) * | 2019-07-22 | 2019-09-27 | 中国航发北京航空材料研究院 | A kind of preparation method of low-temperature self-propagating composite material |
| CN114908309A (en) * | 2022-04-02 | 2022-08-16 | 北方民族大学 | Corrosion-resistant and wear-resistant composite coating and process for forming coating on inner surface of steel pipe |
| CN114908309B (en) * | 2022-04-02 | 2024-01-19 | 北方民族大学 | Corrosion-resistant wear-resistant composite coating and process for forming coating on inner surface of steel pipe by using same |
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