WO2011106988A1 - 提高t91/p91钢在高温水蒸气中抗氧化性能的预处理方法 - Google Patents

提高t91/p91钢在高温水蒸气中抗氧化性能的预处理方法 Download PDF

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WO2011106988A1
WO2011106988A1 PCT/CN2011/000243 CN2011000243W WO2011106988A1 WO 2011106988 A1 WO2011106988 A1 WO 2011106988A1 CN 2011000243 W CN2011000243 W CN 2011000243W WO 2011106988 A1 WO2011106988 A1 WO 2011106988A1
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steel
slurry
rare earth
oxidation resistance
pretreatment method
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PCT/CN2011/000243
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English (en)
French (fr)
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张都清
刘光明
张广成
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山东电力研究院
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Priority to JP2012531232A priority Critical patent/JP5528559B2/ja
Priority to US13/375,654 priority patent/US8367162B2/en
Publication of WO2011106988A1 publication Critical patent/WO2011106988A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat

Definitions

  • the invention relates to a surface pretreatment method for T91/P91 steel, in particular to a pretreatment method for improving the oxidation resistance of T91/P91 steel in water vapor in a high temperature environment (500 ° C ⁇ 750 ° C).
  • a series of ferritic steels containing 9-12% Cr have excellent performance and are used for large-diameter steam pipes P91 (main steam pipes and reheat steam pipes) and small-diameter T91 steam pipes for thermal power generation. (superheater tube and reheater tube). These materials have better mechanical properties than conventional ferritic steels and can therefore be used at higher temperatures and pressures to increase the efficiency of thermal power generation.
  • T91 steel and P91 steel are used in power station boilers due to their high tensile strength, high temperature creep and long-term strength, low thermal expansion, good thermal conductivity, processability and oxidation resistance, and high toughness.
  • Common materials for supercritical units However, they will still work in high temperature and high pressure water vapor after long-term oxidation or higher temperature work.
  • the oxidation rate increases with the increase of temperature at 500 °C ⁇ 750 °C.
  • the oxidation products are Fe 2 O 3 , Fe 3 0 4 and (Fe,C r ) 3 0 4 . Due to the low Cr content in such materials, continuous, dense Cr is not formed in the oxide film formed at different temperatures. 2 0 3 layers, even in the oxide film, no Cr 2 0 3 phase is formed, usually in the form of (Fe,Cr) 3 4 4 solid solution.
  • the thicker oxide film is subjected to larger growth stress and thermal stress, and the plastic deformation of the oxide film is limited. Therefore, such materials have a significant phenomenon of oxide film peeling during service, and in turn, the falling off of the oxide film further accelerates the oxidation rate.
  • T91 and P91 steels are used in steam pipes for thermal power generation. Applying a coating or surface modification on the inner wall is one of the effective ways to improve the oxidation resistance of high temperature ice steam.
  • the coating/coating process is usually complicated in a small-diameter steam pipe.
  • the process of hot-dip aluminizing is relatively simple. The brittle phase of the iron-aluminum intermetallic compound is peeled off during the oxidation process, and the mechanical properties of the pipe are compared. Great impact.
  • T. Sundararajan [T. Sundararajan, et al: Surface and Coatings Technology, 2006, 201, 2124.] [T. Sandra Lajay, Surface and Coating Technology, 2006, 201, 2124] Directly coated on T91 steel After the nano-Ce0 2 was applied, the oxidation behavior of the sample in water vapor at 650 °C was tested. The results showed that the oxidation rate was lower than that of the blank sample, but after 500 h of oxidation, the outer layer of the oxide film was iron oxide, and the inner layer was iron, a mixture of 'chromium and silicon. Oxide film, its resistance to water vapor oxidation is still limited.
  • the object of the present invention is to overcome the deficiencies of the prior art described above, and to provide a simple process, low cost, and high practicability.
  • the utility model has the advantages of long service life, high oxidation resistance to high temperature water vapor, and formation of a chromium oxide-rich chromium oxide film on the surface of the T91/P91 steel to improve the oxidation resistance of the T91/P91 steel in high temperature steam.
  • a pretreatment method for improving the oxidation resistance of T91/P91 steel in high temperature steam comprising the following steps:
  • step 2) Applying the prepared slurry of step 1) to the surface of T91/P91 steel;
  • step 3 Dry, dry the coated T91/P91 steel in step 2) in an oven at 10 ⁇ 30 °C for 1 ⁇ 4 hours, then dry at 70 ⁇ 100 °C for 1 ⁇ 4 hours;
  • T91/P91 steel dried in step 3) is kept at 600-800 °C for 24 to 48 hours in an atmosphere furnace filled with a mixture of inert gas and water vapor; then the furnace is de-energized, T91/P91 The steel is naturally cooled to room temperature in the furnace;
  • T91/P91 steel surface-attached powder which is T91/P91 steel with surface composition containing chromium and rare earth oxide.
  • the solid component composed of the aluminum powder and the rare earth oxide in the slurry of the steps 1) and 2) and the aqueous sodium silicate solution are prepared in a ratio of 100 to 60 mL of the aqueous sodium silicate solution per 100 g of the solid component.
  • the rare earth oxide has a purity of 99.00% and a particle size of 30 ⁇ m; the aluminum powder has a purity of 99.00% and a particle size of 0.4 mm.
  • the rare earth oxide is Y 2 O 3 or La 2 0 3 .
  • the slurry in step 2) is applied by hand brushing or dip coating, or the slurry is naturally attached to the inner wall of the steel pipe after being injected into the T91/P91 steel pipe.
  • the inert gas and water vapor mixed gas in the step 4) has a volume ratio of inert gas of 60% to 95% and a water vapor content of 5 to 40%.
  • the inert gas is argon gas having a purity of 99.99% or helium gas having a purity of 99.99%.
  • the cleaning of the surface of the T91/P91 steel in the step 5) can be washed with distilled water.
  • T91/P91 steel is used at a temperature of 500 ° C to 750 ° C and a water vapor content of 5-40% by volume.
  • the invention has the following advantages:
  • the T91 steel and P91 steel pretreated by the invention have excellent high temperature steam oxidation resistance, and can significantly reduce the oxidation rate of such materials in a water vapor atmosphere.
  • the oxidative weight gain of the blank sample was 16.51 mg/cm 2
  • the surface modified sample had an oxidative weight gain of only 0.15 mg/cm 2 .
  • the oxidation weight gain was less than 1/100 of the blank sample, and no surface crack and oxide film peeling were observed on the surface of the surface modified sample.
  • T91 and P91 steels are treated with a mixed gas of high-temperature steam and an inert gas to form a surface rich in chromium and a small amount of rare earth oxide.
  • the preparation process is simple, does not need to be carried out in a vacuum, and is inexpensive.
  • the invention can treat the inner wall of the pipe with small diameter and has wide application range. The invention can improve the oxidation resistance of the T91 and P91 steel in the high temperature steam environment.
  • the coating process of the invention is simple, and can be applied by brushing or dip coating to adjust the viscosity of the slurry to be injected into the inner wall of the steel pipe after being injected into the steel pipe of T91 or P91.
  • Figure 1 is a surface topography of the T91 steel treated by the rare earth-containing mixture of the present invention
  • FIG. 1 is an energy spectrum (EDS) of the T91 steel treated by the rare earth-containing mixture of the present invention
  • Fig. 3 is a cross-sectional view showing the T91 steel of the present invention after being pretreated for 700 hours in water vapor at 700 °C.
  • Example 1 Composition of solid powder mixture: Yttrium oxide (Y 2 0 3 ) purity 99.00%, particle size 30 ⁇ m; aluminum powder purity 99.00%, particle size 0.4 mm.
  • yttrium oxide (Y 2 0 3 ) powder and 0.5% of aluminum powder are first added to 30 mL of an aqueous solution of sodium silicate having a modulus of 2.4 and a density of 1.lg/cm 3 . Stir well to prepare a slurry.
  • the specific data of this embodiment is as follows:
  • the sample size of T91 steel is 10 X 15 X 3 mm, and the surface of the T91 steel sample is coated with the slurry prepared by the above method by dip coating method, and dried in an oven at 30 ° C for 2 hours, Dry at 100 ° C for 1 hour.
  • the dried T91 steel is placed in an atmosphere furnace filled with a volume ratio of 90% argon (purity: 99.99%) and 10% water vapor; heating temperature: 720 ° C; holding time: 48 hours; After the power is turned off, the T91 steel is naturally cooled to room temperature in the furnace; after the furnace is cooled to room temperature, the sample is taken out, and the sample is washed with distilled water to remove the surface solid powder, thereby forming a surface rich in chromium and a small amount of rare earth oxide.
  • T91 steel is used at a temperature of 500 ° C and a water vapor content of 5% (by volume).
  • Figure 1 shows the surface topography and energy spectrum of T91 steel treated by the above process.
  • the surface of the sample is rich in chromium and contains a small amount of .Y.
  • the surface of the sample is observed by scanning electron microscopy. The scratches before polishing are still visible.
  • the surface roughness of the sample is not affected after the treatment.
  • the surface color is slightly dark red.
  • the sample was oxidized in a constant temperature water vapor at 700 ° C for 600 h and the weight gain was only 0.15 mg/cm 2 .
  • the surface of the sample did not undergo significant oxidation, and the surface oxide film did not peel off, and its anti-flaking performance also improved significantly, as shown in Fig. 3. Shown.
  • the oxidation process forms a complete continuous Cr 2 0 3 oxide film with a good adhesion, and the oxide film has a thickness of about 1 ⁇ m, see Figure 2.
  • Example 2 Composition of solid powder mixture: yttrium oxide (Y 2 0 3 ) purity 99.00%, particle size 30 ⁇ m; aluminum powder purity 99.00%, particle size 0.4 mm.
  • yttrium oxide (Y 2 0 3 ) powder and 15% of aluminum powder are first added to 10 mL of an aqueous solution of sodium silicate having a modulus of 2.6 and a density of 1.3 g/cm 3 and stirred.
  • the slurry is prepared uniformly.
  • P91 steel sample size is 10 X 15 X 3 mm, using Dip coating method, P91 steel sample table
  • the slurry prepared by the above method was applied to the slurry in an oven at 4 ° C for 4 hours and then dried at 70 ° C for 4 hours.
  • the dried P91 steel is placed in an atmosphere furnace filled with a mixture of 95% argon (purity: 99.99%) and 5% steam; heating temperature: 600 ° C; holding time: 45 hours; After the power is turned off, the P91 steel is naturally cooled to room temperature in the furnace; after the furnace is cooled to room temperature, the sample is taken out, and the sample is washed with distilled water to remove the surface solid powder, thereby forming a surface rich in chromium and a small amount of rare earth oxide.
  • P91 steel is used at a temperature of 600 ° C and a water vapor content of 25% by volume.
  • Example 3 Composition of solid powder mixture: yttrium oxide (Y 2 0 3 ) purity 99.00%, particle size 30 ⁇ m; aluminum powder purity 99.00%, particle size 0.4 mm.
  • the specific data of this embodiment is: T91 steel pipe sample, the slurry is naturally attached to the inner wall of the steel pipe after being injected into the T91 steel pipe. After drying at 20 ° C for 1 hour in an oven, it was dried at 85 ° C for 2.5 hours.
  • the dried T91 steel pipe is placed in an atmosphere furnace filled with a volume ratio of 60% helium (purity 99.99%) and 40% steam mixed gas; heating temperature: 800 ° C; heat preservation time: 24 hours; After the power is turned off, the T91 steel pipe is naturally cooled to room temperature in the furnace; after the furnace is cooled to room temperature, the sample is taken out, and the sample is washed with distilled water to remove the surface solid powder, thereby forming a surface rich in chromium and a small amount of rare earth oxide.
  • T91 steel is used at a temperature of 750 ° C and a water vapor content of 40% by volume.
  • Example 4 Composition of solid powder mixture: Yttrium oxide (Y 2 0 3 ) purity 99.00%, particle size 30 ⁇ m; aluminum powder purity 99.00%, particle size 0.4 mm.
  • yttrium oxide (Y 2 0 3 ) powder and 30% of aluminum powder For the preparation of the material, first add 100g of 70% by weight of yttrium oxide (Y 2 0 3 ) powder and 30% of aluminum powder to 20mL of sodium silicate aqueous solution with a modulus of 2.8 and a density of 1.2g/cm 3 and stir evenly. Prepared into a slurry.
  • the specific data of this embodiment is as follows:
  • the sample size of P91 steel is 10 ⁇ 15 ⁇ 3 mm.
  • the surface of the sample of P91 steel is coated with the slurry prepared by the above method by hand brushing method, and dried at 25 ° C for 3 hours in the oven at 90 ° C. Dry at 2 hours under temperature.
  • the dried P91 steel is placed in an atmosphere furnace filled with a volume ratio of 85% argon (purity: 99.99%) and 15% water vapor; heating temperature: 780 ° C; holding time: 30 hours; After the power is turned off, the P91 steel is naturally cooled to room temperature in the furnace; after the furnace is cooled to room temperature, the sample is taken out, and the sample is washed with distilled water to remove the surface solid powder, thereby forming a surface rich in chromium and a small amount of rare earth oxide.
  • P91 steel is used at a temperature of 600 ° C and a water vapor content of 25% by volume.
  • Example 5 Composition of solid powder mixture: lanthanum oxide (La 2 0 3 ) purity 99.00%, particle size 30 ⁇ m; aluminum powder purity 99.00%, particle size 0.4 mm.
  • lanthanum oxide (La 2 0 3 ) powder and 1% of aluminum powder are first added to 50 mL of an aqueous solution of sodium silicate having a modulus of 2.6 and a density of 1.3 g/cm 3 and stirred.
  • the slurry is prepared uniformly.
  • T91 steel sample size is 10X15X3 mm, using manual brushing method, T91 steel
  • the surface of the sample was coated with the slurry prepared by the above method, and then dried in an oven at 30 ° C for 1 hour and then at 100 ° C for 2 hours.
  • the dried T91 steel was placed in an atmosphere furnace filled with a mixture of 95% argon (purity 99.99%) and 10% steam; heating temperature: 690 ° C; holding time: 40 hours.
  • the atmosphere furnace is de-energized, and the T91 steel is naturally cooled to room temperature in the furnace; after the furnace is cooled to room temperature, the sample is taken out, and the sample is washed with distilled water to remove surface solid powder, thereby forming a surface of T91 steel rich in chromium and a small amount of rare earth oxide.
  • T91 steel is used at a temperature of 500 ° C and a water vapor content of 5% (by volume).
  • Example 6 Composition of solid powder mixture: yttrium oxide (La 2 0 3 ) purity 99.00%, particle size 30 ⁇ m; aluminum powder purity 99.00%, particle size 0.4 mm.
  • lanthanum oxide (La 2 0 3 ) powder and 0.5% of aluminum powder are first added to 60 mL of an aqueous solution of sodium silicate having a modulus of 2.4 and a density of 1.1 g/cm 3 and stirred. It is uniformly prepared into a slurry.
  • the specific data of this embodiment is as follows:
  • the sample size of P91 steel is 10 ⁇ 15 ⁇ 3 mm, and the surface of the sample of P91 steel is coated with the paddle prepared by the above method by dip coating method, and then dried in an oven at 10° C. for 4 hours and then at 70°. Dry under C for 4 hours.
  • the dried P91 steel was placed in an atmosphere furnace filled with a volume ratio of 80% helium (purity 99.99%) and 20% steam mixed gas; heating temperature: 600 ° C ; holding time: 48 hours.
  • the atmosphere furnace is de-energized, and the P91 steel is naturally cooled to room temperature in the furnace; _ After the furnace is cooled to room temperature, the sample is taken out, and the sample is washed with distilled water to remove the surface solid powder, thereby forming a surface of P91 steel rich in chromium and a small amount of rare earth oxide. .
  • P91 steel is used at a temperature of 600 ° C and a water vapor content of 25% by volume.
  • Example 7 Composition of solid powder mixture: lanthanum oxide (La 2 0 3 ) purity 99.00%, particle size 30 ⁇ m; aluminum powder purity 99.00%, particle size 0.4 mm.
  • lanthanum oxide (La 2 0 3 ) powder and 35% of aluminum powder are first added to 10 mL of an aqueous solution of sodium silicate having a modulus of 2.9 and a density of 1.5 g/cm 3 and stirred. It is uniformly prepared into a slurry.
  • the specific data of this embodiment is: T91 steel pipe sample, the slurry is naturally attached to the inner wall of the steel pipe after being injected into the T91 steel pipe. After 1 hour in an oven at 20 ° C, dried for 2.5 hours at 85 D C temperature. The dried T91 steel pipe is placed in an atmosphere furnace filled with a volume ratio of 60% helium (purity 99.99%) and 40% steam mixed gas; heating temperature: 800 ° C; holding time: 24 hours; Electric, T91 steel pipe is naturally cooled to room temperature in the furnace; after the furnace is cooled to room temperature, the sample is taken out, and the sample is washed with distilled water to remove the surface solid powder, thereby forming a surface rich in chromium and a small amount of rare earth oxide.
  • T91 steel is used at a temperature of 750 ° C and a water vapor content of 40% by volume.
  • Example 8 Composition of solid powder mixture: lanthanum oxide (La 2 0 3 ) purity 99.00%, particle size 30 ⁇ m; aluminum powder purity 99.00%, particle size 0.4 mm.
  • lanthanum oxide (La 2 0 3 ) powder and 25% of aluminum powder are first added to 45 mL of an aqueous solution of sodium silicate having a modulus of 2.5 and a density of 1.4 g/cm 3 and stirred. It is uniformly prepared into a slurry.
  • T91 steel sample size is 10X15X3 mm, using manual brushing method, T91 steel
  • the surface of the sample was coated with the slurry prepared by the above method, and then dried in an oven at 25 ° C for 3 hours and then at 90 ° C for 3 hours. After drying, the T91 steel was placed in an atmosphere furnace filled with a volume ratio of 78% argon (purity: 99.99%) and 22% steam; heating temperature: 750 ° C ; holding time: 35 hours.
  • the atmosphere furnace is de-energized, and the T91 steel is naturally cooled to room temperature in the furnace; after the furnace is cooled to room temperature, the sample is taken out, and the sample is washed with distilled water to remove surface solid powder, thereby forming a surface of T91 steel rich in chromium and a small amount of rare earth oxide.
  • T91 steel is used at a temperature of 650 ° C and a water vapor content of 38% by volume.

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Description

提高 T91/P91钢在高温水蒸气中抗氧化性能的预処理方法 技术领域
本发明涉及一种 T91/P91钢表面预处理方法， 尤其是一种提高 T91/P91钢在高温环境中 (500°C〜750 °C) 抗水蒸汽中氧化的预处理方法。
背景技术
目前， 含 Cr量为 9-12%的系列铁素体钢由于具有优良的性能而用于火力发电的大口径的 蒸汽管道 P91 (主蒸汽管道和再热蒸汽管道） 及小口径的 T91蒸汽管道 （过热器管和再热器 管）。 这类材料比传统的铁素体钢有更好的力学性能， 因此可以在更高温度和压力下使用， 从 而提高火力发电的效率。 其中 T91钢和说 P91钢以其较高的抗拉强度、 高温蠕变和持久强度， 低的热膨胀性， 良好的导热性、 加工性和抗氧化性能， 高的韧性， 成为目前电站锅炉用于超 临界机组的常用材料。 但它们在高温高压的水蒸气中经过长期氧化或更高温度下工作时仍会
书
受到较严重的氧化。
T91钢和 P91钢在水蒸气气氛中， 在 500°C〜750 °C下随温度升高， 氧化速度明显增大。 氧化产物为 Fe203、 Fe304和 (Fe,Cr)304, 由于这类材料中 Cr含量低， 因此在不同温度下生成 的氧化膜中均未形成连续、致密的 Cr203层， 甚至在氧化膜中未生成 Cr203相， 通常情况下是 以 (Fe,Cr)304固溶形式存在。 随着氧化速度增长和温度的变化， 较厚的氧化膜受到较大的生长 应力和热应力， 而氧化膜的塑性变形有限。 因此， 这类材料在服役过程中有明显氧化膜剥落 的现象， 反过来， 氧化膜的脱落又进一步加快了氧化速度。
T91和 P91钢用于火力发电的蒸汽管道， 在其内壁施加涂层或进行表面改性是提高其抗 高温氷蒸汽氧化的有效途径之一。而通常在小口径蒸气管道内施加涂 /镀层施工工艺复杂， 其 中工艺较简单的热浸镀铝由于生成了铁铝金属间化合物的脆相在氧化过程中镀层剥落， 同时 对管道力学性能有较大影响。
T. Sundararajan [T. Sundararajan, et al: Surface and Coatings Technology, 2006, 201, 2124.] [T. 桑德拉拉简， 表面和涂层技术， 2006, 201, 2124] 直接在 T91钢表面涂敷纳米 Ce02后测试了 样品在 650°C水蒸汽中氧化行为， 结果表明氧化速率较空白样品降低， 但氧化 500h后氧化膜 外层为氧化铁， 内层为铁、'铬和硅的混合氧化物膜， 其抗水蒸汽氧化性能仍有限。
李辛庚， 王学刚 [李辛庚， 王学刚,腐蚀科学与防护技术 2008, 20(3) 157-161.]研宄了 Cr 含量为 9%Fe-Cr合金表面沉积 Ce02薄膜在 600DC~770°C水蒸气中的氧化行为， 结果表明， 沉积稀土薄膜并没有改变氧化膜结构和未明显降低氧化速率。
发明 容
本发明的目的是为克服上述现有技术的不足， 提供一种工艺简单、成本低廉、 实用性强、
-1- 确认本 使用寿命长、 抗高温水蒸汽氧化性能强、 在 T91/P91钢的表面形成富三氧化二铬氧化物薄膜 的提高 T91/P91钢在高温水蒸汽中抗氧化的预处理方法。
为实现上述目的， 本发明釆用下述技术方案：
一种提高 T91/P91钢在高温水蒸汽中抗氧化的预处理方法， 包括以下步骤：
1 ) .制备浆料， 将按重量百分比为 0.5〜35%的铝粉和 65-99.5%稀土氧化物中加入模数为 2.4-2.9, 密度为 l . l~1.5g/cm3的硅酸钠水溶液， 搅拌均匀制备成料浆；
2 ) .将步骤 1 ) 制备好的料浆涂敷于 T91/P91钢表面；
3 ) .干燥， 将步骤 2 ) 中涂敷完毕的 T91/P91钢在 10〜30 °C的烘箱中干燥 1〜4小时， 然 后在 70〜100 °C下千燥 1〜4小时；
4 ) 将步骤 3 ) 中干燥后的 T91/P91 钢在充入惰性气体和水蒸汽混合气体的气氛炉中于 600-800 °C下保温 24-48小时； 然后气氛炉断电， T91/P91钢于该炉中自然冷却至室温；
5 ) .清除 T91/P91钢表面附着粉末， 即得表面成份含铬和稀土氧化物的 T91/P91钢。 所述步骤 1 )和 2 )的浆料中的铝粉和稀土氧化物组成的固体组分与硅酸钠水溶液按照每 100g固体组分： 10〜60mL硅酸钠水溶液比例配制。
所述稀土氧化物纯度 99.00%， 粒度 30微米； 铝粉纯度 99.00%、 粒度 0.4毫米。 所述稀土氧化物为 Y203或 La203。
述步骤 2 ) 中的料浆涂敷为手工刷涂或浸涂方式， 或将料桨注入 T91/P91钢管后自然 附着在钢管内壁。
所述步骤 4) 中的惰性气体和水蒸汽混合气体中按体积比惰性气体含量为 60%-95%， 水 蒸汽含量为 5-40%。
所述惰性气体为纯度 ^99.99%的氩气或纯度 ^99.99%的氦气。
所述步骤 5 ) 中的清除 T91/P91钢表面附着粉末采用蒸馏水冲洗干净即可。
T91/P91钢的使用环境为：温度在 500°C〜750 °C,水蒸汽的含量为 5-40% (体积百分比）。 本发明具有如下优点：
1. 采用本发明预处理的 T91钢和 P91钢具有优良的抗高温水蒸汽氧化性能，能显著地降 低这类材料在水蒸汽气氛中的氧化速度。 在 700QC水蒸汽环境中恒温氧化 600小时后， 空白 样品的氧化增重达 16.51mg/cm2， 而表面改性后的样品的氧化增重只有 0.15mg/cm2。 氧化增 重不到空白样品的 1/100, 同时经表面改性的样品表面未发现表面裂纹和氧化膜剥落。
2. 本发明含稀土混合物处理 T91和 P91钢， 经高温水蒸汽和惰性气体的混合气体处理， 即形成富含铬和少量稀土氧化物表面。 制备过程简单， 不用在真空中进行， 并且成本低廉。
3. 样品预处理后用蒸馏水清洗表面去除表面残留的固体粉末，样品表面处理不改变样品 表面粗糙度。 4. 采用本发明能处理口径较小的管道内壁，应用范围广， 应用本发明可提高 T91和 P91 钢在高温水蒸汽环境中的抗氧化能力。
5. 本发明的涂敷工艺简单， 可以刷涂、浸涂也可以调节料浆粘度注入 T91或 P91钢管后 自然附着在钢管内壁。
附图说明
图 1为本发明 T91钢经含稀土混合物处理后表面形貌；
图 2为本发明 T91钢经含稀土混合物处理后能谱图 （EDS );
图 3为本发明 T91钢经预处理后在 700°C水蒸汽中氧化 600h后的截面形貌图。
具体实施方式
下面结合附图和实施例对本发明进一步说明。
实施例 1 : 固体粉末混合物的组成： 氧化钇 （Y203 ) 纯度 99.00%、 粒度 30微米； 铝 粉纯度 99.00%、 粒度 0.4毫米。
浆料的制备， 先将 100g按重量百分比为 99.5 %氧化钇（Y203)粉和 0.5 %铝粉加入 30mL 模数为 2.4， 密度为 l.lg/cm3的硅酸钠水溶液中， 搅拌均匀制备成料浆。
本实施例具体数据为： T91钢样品尺寸为 10 X 15 X 3毫米， 采用浸涂法， 将 T91钢样品 表面涂敷上述方法制备的料浆， 于烘箱中 30°C下 2小时后， 在 100°C温度下 1小时烘干。干 燥后的 T91钢放入充入体积比为 90%氩气（纯度 ^99.99%)和 10%水蒸汽混合气体的气氛炉 中； 加热温度： 720°C; 保温时间： 48小时； 然后气氛炉断电， T91钢于该炉中自然冷却至室 温； 炉冷至室温后取出试样， 用蒸馏水清洗样品除去表面固体粉末， 即形成富含铬和少量稀 土氧化物的表面。
T91钢的使用环境为： 温度在 500°C， 水蒸汽的含量为 5% (体积百分比）。
图 1为采用经上述工艺处理的 T91钢表面形貌图和能谱图。 处理后样品表面富铬且含有 少量 .Y, 用扫描电子显微镜观察表面试样预处理前抛光的划痕依然可见， 处理后不影响样品 表面粗糙度， 表面颜色略微呈暗红色； 经过预处理后， 样品在 700°C空气中恒温水蒸汽中氧 化 600h增重仅 0.15 mg/cm2, 样品表面基本上未发生明显氧化， 表面氧化膜未出现剥落， 其 抗剥落性能也有明显改善， 如图 3所示。 氧化过程形成了完整连续且结合力良好的富 Cr203 氧化膜， 氧化膜厚度约 1微米， 参见图 2。
实施例 2: 固体粉末混合物的组成： 氧化钇 （Y203) 纯度 99.00%、 粒度 30微米； 铝 粉纯度 99.00%、 粒度 0.4毫米。
浆料的制备， 先将 100g按重量百分比为 85 %氧化钇 （Y203 ) 粉和 15 %铝粉加入 10mL 模数为 2.6， 密度为 1.3g/cm3的硅酸钠水溶液中， 搅拌均匀制备成料桨。
本实施例具体数据为： P91钢样品尺寸为 10 X 15 X 3毫米， 采用浸涂法， 将 P91钢样品表 面涂敷上述方法制备的料浆， 于烘箱中 10°C下 4小时后， 在 70°C温度下 4小时干燥。 干燥 后的 P91钢放入充入体积比为 95%氩气（纯度 ^99.99%)和 5%水蒸汽混合气体的气氛炉中； 加热温度： 600°C; 保温时间： 45小时； 然后气氛炉断电， P91钢于该炉中自然冷却至室温； 炉冷至室温后取出试样， 用蒸馏水清洗样品除去表面固体粉末， 即形成富含铬和少量稀土氧 化物的表面。
P91钢的使用环境为： 温度在 600°C， 水蒸汽的含量为 25% (体积百分比）。
实施例 3: 固体粉末混合物的组成： 氧化钇 （Y203) 纯度 99.00%、 粒度 30微米； 铝 粉纯度 99.00%、 粒度 0.4毫米。
浆料的制备， 先将 100g按重量百分比为 65%氧化钇 （Y203) 粉和 35%铝粉加入 60mL 模数 ¾ 2.9， 密度为 1.5g/Cm3的硅酸钠水溶液中， 搅拌均匀制备成料浆。
本实施例具体数据为： T91钢管样品， 将料浆注入 T91钢管后自然附着在钢管内壁。 于烘 箱中 20°C下 1小时后， 在 85°C温度下 2.5小时烘干。 干燥后的 T91钢管放入充入体积比为 60%氦气（纯度 99.99%)和 40%水蒸汽混合气体的气氛炉中； 加热温度： 800°C; 保温吋间： 24小时； 然后气氛炉断电， T91钢管于该炉中自然冷却至室温； 炉冷至室温后取出试样， 用 蒸馏水清洗样品除去表面固体粉末， 即形成富含铬和少量稀土氧化物的表面。
T91钢的使用环境为： 温度在 750°C， 水蒸汽的含量为 40% (体积百分比）。
实施例 4: 固体粉末混合物的组成： 氧化钇 （Y203) 纯度 99.00%、 粒度 30微米； 铝 粉纯度 99.00%、 粒度 0.4毫米。
料的制备， 先将 100g按重量百分比为 70%氧化钇 （Y203) 粉和 30%铝粉加入 20mL 模数为 2.8， 密度为 1.2g/cm3的硅酸钠水溶液中， 搅拌均匀制备成料浆。
本实施例具体数据为： P91钢样品尺寸为 10X15X3毫米， 采用手工刷涂法， 将 P91钢样 品表面涂敷上述方法制备的料浆， 于烘箱中 25°C下 3小时后， 在 90°C温度下 2小时烘干。 干燥后的 P91钢放入充入体积比为 85%氩气（纯度 ^99.99%)和 15%水蒸汽混合气体的气氛 炉中； 加热温度： 780°C; 保温时间： 30小时； 然后气氛炉断电， P91钢于该炉中自然冷却至 室温； 炉冷至室温后取出试样， 用蒸馏水清洗样品除去表面固体粉末， 即形成富含铬和少量 稀土氧化物的表面。
P91钢的使用环境为： 温度在 600°C， 水蒸汽的含量为 25% (体积百分比）。
实施例 5: 固体粉末混合物的组成： 氧化镧 （La203) 纯度 99.00%、 粒度 30微米； 铝 粉纯度 99.00%、 粒度 0.4毫米。
浆料的制备， 先将 100g按重量百分比为 99%氧化镧 （La203) 粉和 1%铝粉加入 50mL 模数为 2.6， 密度为 1.3g/cm3的硅酸钠水溶液中， 搅拌均匀制备成料桨。
本实施例具体数据为： T91钢样品尺寸为 10X15X3毫米， 采用手工刷涂方式， 将 T91钢 样品表面涂敷上述方法制备的料浆， 然后于烘箱中 30°C下 1小时后， 再于 100°C下 2小时烘 干。 干燥后的 T91钢放入充入体积比为 95%氩气（纯度 99.99%)和 10%水蒸汽混合气体的 气氛炉中； 加热温度： 690°C; 保温时间： 40小时。 然后气氛炉断电， T91钢于该炉中自然冷 却至室温； 炉冷至室温后取出试样， 用蒸馏水清洗样品除去表面固体粉末， 即形成富含铬和 少量稀土氧化物的 T91钢表面。
T91钢的使用环境为： 温度在 500°C， 水蒸汽的含量为 5% (体积百分比）。
实施例 6: 固体粉末混合物的组成： 氧化镧（La203)纯度 99.00%、 粒度 30微米； 铝 粉纯度 99.00%、 粒度 0.4毫米。
浆料的制备，先将 100g按重量百分比为 99.5%氧化镧（La203)粉和 0.5%铝粉加入 60mL 模数为 2.4， 密度为 1.1 g/cm3的硅酸钠水溶液中， 搅拌均匀制备成料浆。
本实施例具体数据为： P91钢样品尺寸为 10X15X3毫米， 采用浸涂方式， 将 P91钢样品 表面涂敷上述方法制备的料桨， 然后于烘箱中 10°C下 4小时后， 再于 70°C下 4小时烘干。 干燥后的 P91钢放入充入体积比为 80%氦气（纯度 99.99%)和 20%水蒸汽混合气体的气氛 炉中； 加热温度： 600°C; 保温时间： 48小时。 然后气氛炉断电， P91钢于该炉中自然冷却至 室温; _ 炉冷至室温后取出试样， 用蒸馏水清洗样品除去表面固体粉末， 即形成富含铬和少量 稀土氧化物的 P91钢表面。
P91钢的使用环境为： 温度在 600°C， 水蒸汽的含量为 25% (体积百分比）。
实施例 7: 固体粉末混合物的组成： 氧化镧 （La203) 纯度 99.00%、 粒度 30微米； 铝 粉纯度 99.00%、 粒度 0.4毫米。
浆料的制备， 先将 100g按重量百分比为 65%氧化镧 （La203) 粉和 35%铝粉加入 10mL 模数为 2.9， 密度为 1.5g/cm3的硅酸钠水溶液中， 搅拌均匀制备成料浆。
本实施例具体数据为： T91钢管样品， 将料浆注入 T91钢管后自然附着在钢管内壁。 于烘 箱中 20°C下 1小时后， 在 85DC温度下 2.5小时烘干。 干燥后的 T91钢管放入充入体积比为 60%氦气（纯度 99.99%)和 40%水蒸汽混合气体的气氛炉中； 加热温度： 800°C; 保温时间： 24小时； 然后气氛炉断电， T91钢管于该炉中自然冷却至室温； 炉冷至室温后取出试样， 用 蒸馏水清洗样品除去表面固体粉末， 即形成富含铬和少量稀土氧化物的表面。
T91钢的使用环境为： 温度在 750°C， 水蒸汽的含量为 40% (体积百分比）。
实施例 8: 固体粉末混合物的组成： 氧化镧 （La203) 纯度 99.00%、 粒度 30微米； 铝 粉纯度 99.00%、 粒度 0.4毫米。
浆料的制备， 先将 100g按重量百分比为 75%氧化镧 （La203) 粉和 25%铝粉加入 45mL 模数为 2.5， 密度为 1.4g/cm3的硅酸钠水溶液中， 搅拌均匀制备成料浆。
本实施例具体数据为： T91钢样品尺寸为 10X15X3毫米， 采用手工刷涂方式， 将 T91钢 样品表面涂敷上述方法制备的料浆， 然后于烘箱中 25°C下 3小时后， 再于 90°C下 3小时烘 干。 午燥后的 T91钢放入充入体积比为 78%氩气 （纯度 ^99.99%)和 22%水蒸汽混合气体的 气氛炉中； 加热温度： 750°C; 保温时间： 35小时。 然后气氛炉断电， T91钢于该炉中自然冷 却至室温； 炉冷至室温后取出试样， 用蒸馏水清洗样品除去表面固体粉末， 即形成富含铬和 少量稀土氧化物的 T91钢表面。
T91钢的使用环境为： 温度在 650°C， 水蒸汽的含量为 38% (体积百分比）。

Claims

权 利 要 求 书
1. 一种提高 T91/P91钢在高温水蒸汽中抗氧化的预处理方法， 其特征在于， 包括以下步 骤：
1 ) .制备浆料， 将按重量百分比为 0.5〜35%的铝粉和 65-99.5%稀土氧化物中加入模数为 2.4-2.9, 密度为 l . l〜L5g/cm3的硅酸钠水溶液， 搅拌均匀制备成料浆；
2) .将步骤 1 ) 制备好的料浆涂敷于 T91/P91钢表面；
3 ) .干燥， 将步骤 2 ) 中涂敷完毕的 T91/P91钢在 10〜30 °C的烘箱中干燥 1〜4小时， 然 后在 70〜100 °C下干燥 1〜4小时；
4) .将步骤 3 ) 中干燥后的 T91/P91 钢在充入惰性气体和水蒸汽混合气体的气氛炉中于 600-800 °C下保温 24-48小时； 然后气氛炉断电， T91/P91钢于该炉中自然冷却至室温；
5 ) .清除 T91/P91钢表面附着粉末， 即得表面成份含铬和稀土氧化物的 T91/P91钢。
2.根据权利要求 1所述的提高 T91/P91钢在高温水蒸汽中抗氧化的预处理方法， 其特征 在于： 所述步骤 1 )和 2 )的浆料中的铝粉和稀土氧化物组成的固体组分与硅酸钠水溶液按照 每 100g固体组分： 10〜60mL硅酸钠水溶液比例配制。
3.根据权利要求 1或 2所述的提高 T91/P91钢在高温水蒸汽中抗氧化的预处理方法， 其 特征在于： 所述稀土氧化物纯度 99.00%， 粒度 30 微米； 铝粉纯度 99.00%、 粒度 0，4
4.根据权利要求 3所述的提高 T91/P91钢在高温水蒸汽中抗氧化的预处理方法， 其特征 在于： 所述稀土氧化物为 Y203或 La203。
5.根据权利要求 1所述的提高 T91/P91钢在高温水蒸汽中抗氧化的预处理方法， 其特征 在于： 所述步骤 2 ) 中的料浆涂敷为手工刷涂或浸涂方式， 或将料浆注入 T91/P91钢管后自 然附着在钢管内壁。
6.根据权利要求 1所述的提高 T91/P91钢在高温水蒸汽中抗氧化的预处理方法， 其特征 在于： 所述步骤 4) 中的惰性气体和水蒸汽混合气体中按体积比惰性气体含量为 60%-95%， 水蒸汽含量为 5-40%。
7.根据权利要求 1或 6所述的提高 T91/P91钢在高温水蒸汽中抗氧化的预处理方法， 其 特征在于： 所述惰性气体为纯度 99.99%的氩气或纯度 ^99.99%的氦气。
8.根据权利要求 1所述的提高 T91/P91钢在高温水蒸汽中抗氧化的预处理方法， 其特征 在于： 所述步骤 5 ) 中的清除 T91/P91钢表面附着粉末采用蒸馏水冲洗干净即可。
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