CN1442509A - Manufacturing method of ceramic lining composite copper pipe - Google Patents
Manufacturing method of ceramic lining composite copper pipe Download PDFInfo
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- CN1442509A CN1442509A CN 03114615 CN03114615A CN1442509A CN 1442509 A CN1442509 A CN 1442509A CN 03114615 CN03114615 CN 03114615 CN 03114615 A CN03114615 A CN 03114615A CN 1442509 A CN1442509 A CN 1442509A
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Abstract
A copper pipe with internal ceramic liner for the pipe crystallizer is prepared through preparing aluminothermics from Al, CuO, SiO2, CrO3, Na2B4O7, and ZrO2, putting it in the copper pipe fixed to centrifugal machine, turning on the centrifugal machine, igniting said aluminothermics, aluminnothermal reaction to release heat for instantaneously smelting the resultant, and cooling. Said copper pipe has the internal liner of Al2O3 ceramics and the transition layer of Cu. Its advantages are high hardness and antiwear performance, high strength and thermal conductivity, and long service life.
Description
One, belonging to the technical field
The invention belongs to the field of metallurgical equipment manufacturing, relates to a manufacturing method of a composite copper pipe, and particularly relates to a manufacturing method of a ceramic lining composite copper pipe for a pipe blank crystallizer.
Second, background Art
The continuous casting production has the characteristics of energy conservation, high efficiency and the like, is widely applied to steel production, and the domestic continuous casting ratio is over 90 percent at present. The crystallizer is a key spare part on a continuous casting machine, and the quality of the crystallizer directly influences the surface quality of a continuous casting billet, the operation rate of the continuous casting machine and the cost of the continuous casting billet. With the development of high-efficiency continuous casting technology, higher requirements are put on the quality of a crystallizer, high strength and good thermal conductivity are required, high wear resistance and high corrosion resistance are required, and the surface treatment of the crystallizer is an effective means for improving the wear resistance and the corrosion resistance. CN1075512 and CN1101686 respectively report that the Ni-Fe alloy plating method on the surface of a crystallizer copper plate has the plating hardness less than 500Hv and low wear resistance. The chromium plating on the crystallizer surface can obtain a plating layer with the voltage of over 900Hv, but the chromium plating layer has thin thickness, generally less than 0.2mm, large stress and easy cracking and peeling in use. In addition, electroplating production also pollutes the environment. The supersonic spraying technology is applied to crystallizer surface treatment, can obtain a high-hardness coating and has a good effect, but the supersonic spraying technology is only applicable to a slab crystallizer and cannot treat the slab crystallizer. It is therefore of great interest to develop a surface treatment process suitable for a tube billet crystallizer.
Third, the invention
The invention aims to provide a method for manufacturing a ceramic lining composite copper pipe suitable for a pipe blank crystallizer copper pipe.
The technical solution for realizing the above purpose is as follows: a method for manufacturing a ceramic lining composite copper pipe for a pipe blank crystallizer comprises the following steps:
the first step is as follows: firstly, preparing a thermite, wherein the thermite is prepared according to the following formula (weight ratio):
CuO 100-300 meshes 50-70%
Al 100-300 meshes 20-40%
Na2B4O72 to 4 percent of 100 to 300 meshes
The second step is that: adding thermite into the copper pipe, placing the copper pipe on a centrifuge, and starting the centrifuge;
the third step: igniting the thermite to cause the thermite to thermally react, i.e. press The reaction and the heat release, so that the resultant is melted instantly. The molten resultant is separated according to its own density under the action of centrifugal force, and after cooling, Al can be formed2O3Ceramic lining composite copper pipe.
The invention has other characteristics that the inner diameter of the copper pipe is phi 50 mm-phi 600mm, and the length of the copper pipe is 120 mm-3000 mm.
The centrifuge is a horizontal centrifuge, the thermite is ignited after the rotation speed of the centrifuge reaches 520-2600 rpm, the thermite generates thermite combustion reaction, the reaction time lasts for 5-60 s, and the centrifuge is stopped 10-50 min after the thermite combustion reaction is finished.
Compared with the prior art, the ceramic lining composite copper pipe prepared by the invention has the following characteristics:
(1) the process and the equipment are simple, the process flow is short, the production efficiency is high, no pollution is caused, and the environment protection is facilitated;
(2) the power consumption is low, the reaction of CuO and Al is a self-heat-release process, and once the reaction is initiated, the reaction is performed spontaneously without energy supplement, so that the energy is saved;
(3) the main raw material resources for producing the centrifugal ceramic lining composite copper pipe are rich, and the price is low;
(4) the ceramic lining composite copper pipe has excellent performance shown in table 1, and particularly, the ceramic layer has extremely high hardness, so that the wear resistance of the composite copper pipe is improved.
Description of the drawings
FIG. 1 is a schematic diagram of the manufacture of the ceramic lined composite copper pipe of the present invention, wherein (a) is a cross-sectional view and (b) is a left side view of (a).
Fifth, detailed description of theinvention
The invention is described in further detail below with reference to the drawings and the embodiments given by the inventor.
The invention is realized based on the following thermite reaction principle:
the thermite is prepared according to the following formula (weight ratio):
CuO 100-300 meshes 50-70%
Al 100-300 meshes 20-40%
Na2B4O72 to 4 percent of 100 to 300 meshes
Putting thermit (figure 1) prepared by CuO and Al into a copper pipe in advance, putting the copper pipe on a centrifuge, starting the centrifuge, igniting the thermit, generating thermit reaction shown in formula (1), wherein the reaction shown in formula (1) releases huge heat, the combustion temperature reaches 2844K and is higher than that of the product Al2O3And the melting point of Cu, so that the resultant is instantaneously melted. The molten products are separated from each other by centrifugal force according to their densities, and the density of Cu is 87220N/m3) Specific to Al2O3Density (38906N/m)3) Large so that Cu abuts against the surface of the copper pipe, and Al2O3In the innermost layer, Al is formed after cooling2O3The ceramic lining is a composite copper pipe, and Cu forms a transition layer.
The main technical key of the invention is to control centrifugal force and ensure Al2O3And the separation of Cu, and simultaneously the compactness of a ceramic layer, the toughness of the ceramic and the bonding strength of the ceramic and the copper pipe matrix are improved.
The object of the invention can be achieved by the following measures:
the invention is realized on a horizontal centrifuge with the speed regulation range of 520 rpm-2600 rpm, the inner diameter size phi of the copper pipe is 50 mm-600 mm, and the length of the copper pipe is 120 mm-3000 mm. In the thermite, 100-300 meshes of CuO powder and 100-300 meshes of aluminum powder are added, the CuO and the Al are proportioned according to the stoichiometric proportion, and SiO accounting for 2-8 percent of the total amount of the materials is added2CrO accounting for 1-5% of the total material3Na accounting for 2-4% of the total weight of the materials2B4O7And ZrO accounting for 2-8% of the total material2After being mixed evenly, the mixture is put into a copper pipe, the copper pipe filled with the materials is clamped on a centrifuge, the thermite is ignited after the revolution of the centrifuge reaches 520rpm to 2600rpm,al and CuO react in the formula (1). The combustion reaction lasts for 5-60 s, and the machine is stopped after 10-50 min, so that the lining ceramic composite copper pipe can be obtained.
The reasons for the determination of the number of revolutions of the centrifuge and the selection and amount of additives in the thermite in the present invention are as follows:
according to the ceramic solidification characteristics, the rotation number of the centrifuge is determined by adopting a Constantinenuf formula, wherein the formula is as follows:
in the formula: n-number of mold revolutions (rpm);
r-inner radius (cm) of copper tube;
density (g/cm) of gamma-ceramic liquid3)；
β -adjustment coefficient, the ceramic lining composite tube β is 1.0-1.5.
The centrifuge revolution number can be determined from the equation (2) to be 520 to 2600 rpm. The centrifugal force mainly acts on:
(1) is favorable to Cu and Al2O3And (5) layering. The greater the difference in density of the reaction products under the action of centrifugal force, the easier the demixing. The greater the centrifugal force, the more thorough the delamination. But the centrifugal force is too large, so that the reduced copper liquid and the ceramic liquid mold are completely separated, and a gap is generated between the reduced copper liquid and the ceramic liquid mold, so that the interlayer bonding force is reduced,the uniformity of the ceramic lining layer is deteriorated, and the bonding strength between the ceramic layer and the copper layer is affected.
(2) Is favorable for improving the density of the ceramic. In the combustion process, a large amount of gas is generated due to volatilization of moisture and low-melting-point impurities in reactants, so that the performance of the ceramic layer is greatly influenced. The existence of a certain centrifugal force is beneficial to the separation of liquid phase products and gas phase products, the escape of gas is accelerated, and the density of the ceramic layer is improved.
The centrifugal SHS ceramic lining composite copper tube ceramic layer generally has more pores, which seriously affects the corrosion resistance, heat resistance and wear resistance of the composite copper tube. In order to improve the compactness of the ceramic layer, SiO is added into Al-CuO thermite2、CrO3The density of the ceramic layer can be obviously improved from SiO2-Al2O3The binary phase diagram of (A) shows that SiO is not added2Pure Al of (2)2O3The starting point and the final point of crystallization are 2054 ℃ and SiO2Not only add Al2O3The initial precipitation temperature of primary crystals is reduced and the crystallization end point is reduced to 1828 ℃, so that the reaction product Al is obtained2O3The time of high temperature liquid state is prolonged, the gas adsorbed in the powder and the gas evaporated in the SHS reaction process have more time to escape, and the ceramic layer can be improvedAnd (5) compactness. But SiO2Obviously reduces the microhardness of the ceramic layer and is SiO2The effect is larger as the addition amount is larger. CrO3The density of the ceramic layer can be obviously improved, but the hardness of the ceramic layer can not be reduced. CrO3The main reason for improving the compactness of the ceramic is CrO3And Al, the reaction is carried out according to the formula (3), the reaction temperature of the system is up to 5800K, and therefore CrO is added into a CuO + Al system3Greatly increases the reaction temperature of the system, thereby prolonging the gas escape time and promoting the densification of the ceramic layer.
The capability of the ceramic lining composite copper pipe for bearing mechanical impact and thermal impact is closely related to the bonding strength of the ceramic layer, and the ceramic lining composite copper pipe is usually pressedShear strength is used to characterize the bond strength. Adding NaB into thermite4O7The compression shear strength of the ceramic lining composite copper pipe can be obviously improved. With NaB4O7The addition amount is increased, the compression shear strength is obviously improved, when NaB is added4O7When the addition amount exceeds 4%, the increase of the press-shear strength is retarded. This is because the molten product Al after the thermite reaction2O3And Cu realizes two-phase separation under the action of centrifugal force, and Al2O3The bonding condition after separation from Cu depends on the wettability between the ceramic layer and the copper layer, because the ceramic layer and the copper layer are bonded together by mechanical engagement, improving Al2O3And Cu is favorable for improving the bonding strength between the two. Al (Al)2O3And the Cu wettability is poor, so that the bonding strength of the common ceramic composite copper pipe is low. Adding NaB4O7Thereafter, it decomposes at elevated temperature to form B2O3Its surface tension is only 0.08N/m, it can obviously reduce Al2O3And surface tension between Cu, solid Al after separation2O3And liquid Cu, thereby promoting an increase in bonding strength.
The composite copper pipe ceramic layer has large brittleness, cannot bear large mechanical impact and seriously influences the application of the composite copper pipe ceramic layer on a pipe blank crystallizer. The toughness of the ceramic layer is increased, and the working reliability of the ceramic layer can be improved. Adding proper amount of ZrO into thermite2Has the function of refining the grains of the ceramic coating, can obviously improve the toughness of the ceramic layer and ZrO2When the addition amount is less than 2%, the fracture toughness is not obviously increased, and ZrO2The addition amount is within the range of 2-8%, and the fracture toughness is obviously increased. When ZrO2At 8% addition, the highest fracture toughness value was obtained, more than twice as high as the original coating. When ZrO2When the amount exceeds 8%, the fracture toughness tends to be lowered due to the large amount of ZrO2The heat is absorbed when the coating enters a self-propagating high-temperature synthesis reaction system, so that the reaction temperature of the system is reduced, the density of the coating is reduced, and the toughness of the coating is influenced.
TABLE 1 ceramicsPerformance of lining composite copper pipe
Note:*the mechanical impact resistance refers to the impact frequency of the ceramic coating when cracks are generated under 50J impact;
| Material | Thickness of ceramic mm | Porosity of ％ | Crushing strength σp，MPa | Compressive shear strength σs，MPa |
| Copper pipe | - | - | 327 | - |
| Composite copper pipe | 1.5～8.0 | 1.2～3.0 | 320～380 | 18～25 |
| Material | Microhardness Hv | Fracture toughness K1c，Mpa.m1/2 | The resistance to mechanical impact is improved, and the performance of the rubber, next time* | The heat shock resistance of the composite material is improved, next time** |
| Copper pipe | 67 | - | - | - |
| Composite copper pipe | 1200～1500 | 2.5～4.2 | 20～30 | 30～45 |
**the thermal shock resistance refers to the number of times when the ceramic coating has a crack length exceeding 5mm when cooled by cyclic heating.
The following are examples given by the inventors, and the present invention is not limited to these examples.
Example 1:
the thermite 3 is placed in a copper tube 2 with an internal diameter of 150mm and a length of 1000 mm. In the thermite, CuO powder is 120 meshes, aluminum powder is 150 meshes, CuO and Al are respectively mixed according to 60 percent and 30 percent, and SiO accounting for 2.5 percent of the total amount of the materials is added2CrO accounting for 2 percent of the total amount of the materials3Na accounting for 2.5 percent of the total amount of the materials2B4O7ZrO accounting for 3 percent of the total material2And after the mixture is uniformly mixed, putting the mixture into a copper pipe, clamping the copper pipe filled with the material on a centrifugal machine 1, igniting the material after the revolution of the centrifugal machine reaches 1220rpm, and reacting Al and CuO in a formula (1). Combustion reaction product Al2O3And the Cu is layered under the action of centrifugal force, the combustion reaction lasts for 12 seconds, and the machine is stopped after 15 minutes, so that the Al-containing material can be obtained2O3The properties of the ceramic-lined composite copper pipe of ceramic 5 and transition layer Cu4 are shown in Table 2.
Example 2:
the thermite 3 is placed in a copper tube 2 with an inner diameter of 120mm and a length of 800 mm. In the thermite, CuO powder is 150 meshes, aluminum powder is 150 meshes, CuO and Al are respectively mixed according to the proportion of 52 percent and 32.5 percent, and SiO accounting for 4 percent of the total amount of the materials is added2CrO accounting for 4 percent of the total material3Na accounting for 2.5 percent of the total amount of the materials2B4O7ZrO accounting for 5 percent of the total material2After mixing uniformlyGo into the copper pipe, the copper pipe clamping that is equipped with the materialOn the centrifuge 1, after the rotation speed of the centrifuge reaches 1350rpm, the materials are ignited, and Al and CuO react in the formula (1). Combustion reaction product Al2O3And the Cu is layered under the action of centrifugal force, the combustion reaction lasts for 11 seconds, and the machine is stopped after 14 minutes to obtain the Al-containing material2O3The properties of the ceramic-lined composite copper pipe with ceramic 5 and the transition layer Cu4 are shown in Table 3.
TABLE 2 ceramic liner composite copper pipe Properties
Note:*the mechanical impact resistance refers to the impact frequency of the ceramic coating when cracks are generated under 50J impact;
| Material | Thickness of ceramic mm | Porosity of ％ | Crushing strength σp，MPa | Compressive shear strength σs，MPa |
| Copper pipe | - | - | 327 | - |
| Composite copper pipe | 4.5 | 1.73 | 336 | 22.3 |
| Material | Microhardness Hv | Fracture toughness K1c，Mpa.m1/2 | Resistance to mechanical impact Next time* | Resistance to thermal shock Next time** |
| Copper pipe | 67 | - | - | - |
| Composite copper pipe | 1412 | 3.87 | 26 | 41 |
**the thermal shock resistance refers to the number of times when the ceramic coating has a crack length exceeding 5mm when cooled by cyclic heating.
TABLE 3 ceramic liner composite copper pipe Properties
Note:*the mechanical impact resistance refers to the impact frequency of the ceramic coating when cracks are generated under 50J impact;
| Material | Thickness of ceramic mm | Porosity of ％ | Crushing strength σp，MPa | Compressive shear strength σs，MPa |
| Copper pipe | - | - | 327 | - |
| Composite copper pipe | 4.2 | 1.24 | 357 | 23.5 |
| Material | Microhardness Hv | Fracture toughness K1c，Mpa.m1/2 | Resistance to mechanical impact Next time* | Resistance to thermal shock Next time** |
| Copper pipe | 67 | - | - | - |
| Composite copper pipe | 1385 | 4.11 | 28 | 44 |
**the thermal shock resistance refers to the crack length of the ceramic coating exceeding 5mm when the ceramic coating is heated and cooled circularlyThe number of times.
The above formula can be many, the invention is not limited to the above formula, and the ceramic lining composite copper pipe can be prepared within the range of the invention.
The ceramic lining composite copper pipe prepared by the method is loaded on a pipe blank crystallizer for use, and the result shows that a ceramic lining layer of the composite copper pipe is high in hardness, good in wear resistance, free of cracking and peeling in use, uniform in ceramic wear, high in strength, good in heat conductivity, free of deformation in use, free of special requirements for cooling water, and capable of prolonging the service life by 50% -80% compared with that of a chromium-plated copper pipe, and the service life of the composite copper pipe reaches 2.5-3. O times of that of a common copper pipe.
Claims (5)
1. A method for manufacturing a ceramic lining composite copper pipe for a pipe blank crystallizer is characterized by comprising the following steps:
the first step is as follows: firstly, preparing a thermite, wherein the thermite is prepared according to the following formula (weight ratio):
CuO 100-300 meshes 50-70%
Al 100-300 meshes 20-40%
SiO22 to 8 percent of 100 to 300 meshes
CrO31 to 5 percent of 100 to 300 meshes
Na2B4O72 to 4 percent of 100 to 300 meshes
ZrO22 to 8 percent of 100 to 300 meshes
The second step is that: adding thermite into the copper pipe, placing the copper pipe on a centrifuge, and starting the centrifuge;
the third step: igniting the thermite to cause the thermite to have a thermite reaction, i.e. pressing Reacting and releasing heat to instantly melt the resultant; the molten resultant is separated according to its own density under the action of centrifugal force, and after cooling, Al can be formed2O3Ceramic lining composite copper pipe.
2. The method for manufacturing a ceramic-lined composite copper tube for a tube blank crystallizer as claimed in claim 1, wherein the inner diameter of the copper tube is from phi 50mm to phi 600mm, and the length of the copper tube is from 120mm to 3000 mm.
3. The method for manufacturing the ceramic lining composite copper pipe for the pipe blank crystallizer as claimed in any one of claims 1 and 2, wherein the centrifuge is a horizontal centrifuge, the thermite is ignited after the revolution number of the centrifuge reaches 520-2600 rpm, so that the thermite generates thermite combustion reaction, the reaction time lasts for 5-60 s, and the machine is stopped 10-50 min after the thermite combustion reaction is finished.
4. The method for manufacturing the ceramic lining composite copper pipe for the pipe blank crystallizer according to claim 1, wherein the thermite is prepared according to the following formula (weight ratio):
CuO 100-300 mesh 60%
Al100-300 meshes and 30%
SiO22.5 percent of 100 meshes to 300 meshes
CrO3100 to 300 meshes and 2 percent
Na2B4O72.5 percent of 100 meshes to 300 meshes
ZrO2100 to 300 meshes and 3 percent
5. The method for manufacturing the ceramic lining composite copper pipe for the pipe blank crystallizer according to claim 1, wherein the thermite is prepared according to the following formula (weight ratio):
CuO 100-300 mesh 52%
Al 100-300 meshes 32.5%
SiO2100 to 300 meshes 4％
CrO3100 to 300 meshes and 4 percent
Na2B4O72.5 percent of 100 meshes to 300 meshes
ZrO2100 to 300 meshes and 5 percent
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101080525B (en) * | 2004-12-17 | 2011-05-11 | 纳幕尔杜邦公司 | Flash spun web containing sub-micron filaments and process for forming same |
| CN102278545A (en) * | 2010-06-10 | 2011-12-14 | 扬州恒鑫特种钢管有限公司 | Self-propagating sintering process for ceramic composite steel pipe |
| CN101745756B (en) * | 2009-12-18 | 2012-08-22 | 西安杰邦科技有限公司 | Molecular environment-friendly heat-release welding agent applicable to welding of copper conductor |
| CN104975253A (en) * | 2015-06-10 | 2015-10-14 | 陈新棠 | Thermite for composite copper pipe |
| CN112573904A (en) * | 2020-12-25 | 2021-03-30 | 西安建筑科技大学 | Based on Al2O3-SiO2-ZrO2Steel pipe with ceramic lining and preparation method thereof |
-
2003
- 2003-04-08 CN CN 03114615 patent/CN1200140C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101080525B (en) * | 2004-12-17 | 2011-05-11 | 纳幕尔杜邦公司 | Flash spun web containing sub-micron filaments and process for forming same |
| CN101745756B (en) * | 2009-12-18 | 2012-08-22 | 西安杰邦科技有限公司 | Molecular environment-friendly heat-release welding agent applicable to welding of copper conductor |
| CN102278545A (en) * | 2010-06-10 | 2011-12-14 | 扬州恒鑫特种钢管有限公司 | Self-propagating sintering process for ceramic composite steel pipe |
| CN104975253A (en) * | 2015-06-10 | 2015-10-14 | 陈新棠 | Thermite for composite copper pipe |
| CN112573904A (en) * | 2020-12-25 | 2021-03-30 | 西安建筑科技大学 | Based on Al2O3-SiO2-ZrO2Steel pipe with ceramic lining and preparation method thereof |
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| CN1200140C (en) | 2005-05-04 |
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