CN102603293B

CN102603293B - Preparation method for high-temperature erosion and abrasion resistant LnMgAl11O19-ZrO2 composite ceramic material

Info

Publication number: CN102603293B
Application number: CN201110448103.0A
Authority: CN
Inventors: 房明浩; 闵鑫; 黄朝晖; 刘艳改; 刘凤娇; 唐潮; 胡美羚
Original assignee: China University of Geosciences Beijing
Current assignee: China University of Geosciences Beijing
Priority date: 2011-12-27
Filing date: 2011-12-27
Publication date: 2014-07-16
Anticipated expiration: 2031-12-27
Also published as: CN102603293A

Abstract

The invention discloses a high-temperature erosion and abrasion resistant LnMgAl11O19-ZrO2 composite ceramic material and a preparation method thereof, which belongs to the technical field of special ceramics and high-temperature resistant materials. The preparation method for the material comprises the following steps: adding LnMgAl1O19 (Ln=La, Ce, Pr, Nd, Sm, Eu and Gd) flaky grains in yttria stabilized zirconia; regulating the LnMgAl1O19 flaky grain adding amount to increase the breaking tenacity of the material and improve the high-temperature erosion and abrasion resistance; and obtaining the high-temperature erosion and abrasion resistant LnMgAl11O19-ZrO2 composite ceramic material by the preparation processes of mixing materials, shaping and sintering at high temperature. With the preparation method, the high-temperature gas and solid two-phase flow erosion and abrasion resistance of the prepared material LnMgAl11O19-ZrO2 is superior to that of alumina and zirconia series ceramic, and the ceramic material can replace low carbon steel, heat-resisting alloy steel and hard alloy to apply to the high temperature, erosion and abrasion resistant materials of various easily-abraded components (such as a circulating fluidized bed, a high-temperature smoke material conveying pipeline and the like).

Description

A kind of high temperature resistant erosive wear LnMgAl 11o 19-ZrO 2the preparation method of diphase ceramic material

Technical field

A kind of high temperature resistant erosive wear LnMgAl11O ₁₉-ZrO ₂the preparation method of diphase ceramic material, belongs to special cermacis and high temperature material technical field.

Background technology

Erosive wear is one of principal mode of material damage, accounts for 8% of wear-out failure sum in industrial production, and it refers to that fluid or solids impact according to certain speed and angle the wearing and tearing that caused with loose small-particle to material surface.The High Temperature Gas fixed double phase flow erosive wear phenomenon that exists in industry is more and harm is very large, for example: the erosive wear of fuel-burning power plant coal powder boiler combustion tail gas heat exchanger pipeline and the destruction of causing roughly accounts for 1/3 of pipeline damage; In petroleum chemical plant flue gas generating set, the broken catalyzer powder that high-temperature flue gas is carried secretly can cause serious erosive wear to the turbine vane of recovery overfire air stream energy and relevant flow passage part etc.; The heating surface of the thermal treatment unit of the burning solid such as circular fluid bed, waste solid incinerator material and inner lining material stand the erosive wear of High Temperature Gas fixed double phase flow for a long time, its life-span is seriously shortened, need frequent blowing out maintenance, and some blowing out fault is unpredictalbe, to enterprise, cause larger financial loss, and the supply of electric power of stability and safety and daily life etc. are all brought to serious threat.

For example, circulating fluidized bed boiler systems is the main equipment that stands for a long time the erosive wear of High Temperature Gas fixed double phase flow of a quasi-representative, it drives solid materials to burn in burner hearth by the air-flow of high-speed cruising, through feed separation equipment and recirculation device, material is returned to burner hearth, reach the object of efficient burning.But in fuel unburn to the greatest extent small-particle (mineral of infusibility) and desulfurization with limestone particle with and reactant particle, in the closed circulation of burner hearth, in high temperature circulation ceaselessly, flow, bed material constantly carries out internal recycle along burner hearth wall under action of gravity, and corresponding site refractory materials is carried out to strong erosive wear, can cause the wear out failure of refractory materials and corresponding pipeline to cause blowing out accident.

At present, the recirculation device of circulating fluidized bed is mainly main by soft steel, heat-resisting alloy steel and Wimet, and price is higher, and withstand temp is relatively low simultaneously, and high temperature wear resistant is poor, volatility under parts high temperature, and not resistance to oxidation corrosion, work-ing life is shorter.But because its special combustion system and heating surface long term operation thereof are under the severe environment such as high temperature (1200 ℃ of left and right), solid particulate (2-500 μ m) erosion and flue gas corrosion, very easily produce high temperature wear and abrasion, thereby make tube wall attenuation even worn out, have a strong impact on its operating safety and economic benefit thereof.Mainly adopt in this respect heat-resisting alloy steel and aluminum oxide series pottery both at home and abroad.The former ubiquity the characteristics such as high temperature resistant Abrasion properties is poor, expensive, high temperature (over 1000 ℃) easily softens, thereby causes the defects such as its wear resisting property is poor, work-ing life is shorter; The latter can meet resistant to elevated temperatures requirement, but exist that fragility is large, heat-resistant stable is not good enough and the shortcoming such as poor toughness, thereby cause working the problem such as easily cause bulk to peel off, work-ing life is short under hot environment, all can not meet the requirement of high temperature production and high-temperature technology progress.

With the zirconium white (YSZ) of 3mol% stabilized with yttrium oxide have that fusing point is high, hardness is high, intensity and toughness is higher, thermal conductivity is low, thermal expansivity and the feature such as superalloy is very approaching, in fields such as aero-gas turbines, obtained good effect.But because zirconia ceramics transformation toughening under hot conditions lost efficacy, there is the especially decline of fracture toughness property and the service life cycle shortcoming such as shorten of mechanical property in the YSZ pottery causing.Therefore, the present invention is on the basis of the newest research results of zirconia ceramics, by adding LnMgAl ₁₁o ₁₉(Ln=La, Ce, Pr, Nd, Sm, Eu, Gd) platy shaped particle, improve toughness and the high temperature resistant Erosive Properties of zirconia ceramics material, can, as the high temperature wear resistant parts of circular fluid bed and pulverized coal boiler, be a kind of novel high temperature resistant Dual-Phrase Distribution of Gas olid erosive wear protective material.

Summary of the invention

The present invention proposes in the zirconium white of stabilized with yttrium oxide and add LnMgAl ₁₁o ₁₉the preparation of (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd) platy shaped particle has the LnMgAl of high high temperature resistant erosive wear ₁₁o ₁₉-ZrO ₂the preparation method of diphase ceramic material.By adjusting LnMgAl ₁₁o ₁₉the add-on of platy shaped particle, the toughening effect having produced, improves its high temperature resistant Erosive Properties.

A kind of high temperature resistant erosive wear LnMgAl ₁₁o ₁₉-ZrO ₂the preparation method of diphase ceramic material, is characterized in that: LnMgAl ₁₁o ₁₉-ZrO ₂the Application Areas of material is high-temperature erosion abrasion field, and its composition consists of (1-x) ZrO2-xLnMgAlllO19,0.2wt%≤x≤15wt% wherein, Ln=La, Ce, Pr, Nd, Sm, Eu, Gd.

According to a kind of high temperature resistant erosive wear LnMgAl described in claims 1 ₁₁o ₁₉-ZrO ₂the preparation method of diphase ceramic material, is characterized in that: with LnMgAl ₁₁o ₁₉the zirconium white of (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd) platy shaped particle and 2-5mol% stabilized with yttrium oxide is raw material, by the LnMgAl of 0.2-15wt% ₁₁o ₁₉the zirconium white of platy shaped particle and stabilized with yttrium oxide is prepared burden, then ball milling 3h-48h, ball milling obtains powder by drying treatment, adopt dry-pressing or slip casting to obtain base substrate, through 100-300MPa isostatic cool pressing, processing and obtaining green compact again, green compact carry out sintering in 1-80 hour 1500 ℃-1700 ℃ insulations, naturally cool to room temperature, obtain the LnMgAl of high temperature resistant erosive wear ₁₁o ₁₉-ZrO ₂diphase ceramic material.

According to a kind of high temperature resistant erosive wear LnMgAl claimed in claim 2 ₁₁o ₁₉-ZrO ₂the preparation method of diphase ceramic material, is characterized in that: with Mg (OH) ₂, Al (OH) ₃and rare earth oxide (La ₂o ₃, Ce ₂o ₃, Pr ₂o ₃, Nd ₂o ₃, Sm ₂o ₃, Eu ₂o ₃and Gd ₂o ₃) be raw material (being chemical analysis pure), according to stoichiometric ratio, prepare burden, carry out ball milling mixing 3h-48h, by the mixture after ball milling after drying, after 1400 ℃-1650 ℃ insulation 1h-20h, by synthetic powder pulverizing and jevigating, obtain LnMgAl ₁₁o ₁₉platy shaped particle.

The LnMgAl that adopts the present invention to prepare ₁₁o ₁₉-ZrO ₂diphase ceramic material bending strength reaches as high as 850MPa, and fracture toughness property reaches as high as 14.0MPam ^1/2it is high temperature resistant, and Dual-Phrase Distribution of Gas olid Erosive Properties is all better than aluminum oxide and zirconium white series ceramic, can replace soft steel, heat-resisting alloy steel and Wimet to be applied to the high temperature resistant erosive wear material of various easy-abrasion parts (as circulating fluidized bed, high-temperature flue gas material conveying pipe etc.).

Embodiment

Embodiment 1:

With analytically pure Al (OH) ₃, Mg (OH) ₂, La ₂o ₃as experimental raw, by LaMgAl ₁₁o ₁₉stoichiometric ratio design batching, rear ball milling 12h takes out and is dried, under 1650 ℃ of conditions, is incubated 5h respectively, calcining synthetic powder, the powder after synthesizing makes LaMgAl through pulverizing to grind ₁₁o ₁₉platy shaped particle.

By the LaMgAl preparing ₁₁o ₁₉platy shaped particle and 3mol%Y ₂o ₃stable ZrO ₂powder is that raw material is according to LaMgAl ₁₁o ₁₉platy shaped particle 2wt%, 3mol%Y ₂o ₃stable ZrO ₂powder 98wt% prepares burden, ball milling 6h, it is dry-pressing formed under 60MPa condition that ball milling mixing obtains powder by drying treatment, through 250MPa isostatic cool pressing, processing and obtaining green compact, green compact are being incubated 3h pressureless sintering the condition of 1550 ℃, naturally cool to room temperature, can obtain the LaMgAl of high temperature resistant erosive wear ₁₁o ₁₉-ZrO ₂diphase ceramic material.

Prepared LaMgAl ₁₁o ₁₉-ZrO ₂the main performance index bending strength 800MPa of diphase ceramic material, fracture toughness property reaches as high as 13.5MPam ^1/2, High Temperature Gas fixed double phase flow erosive wear rate is than not adding LaMgAl at its 1400 ℃ ₁₁o ₁₉the 3mol%Y of platy shaped particle ₂o ₃stable ZrO ₂pottery is low by 40%.

Embodiment 2:

With analytically pure Al (OH) ₃, Mg (OH) ₂, Nd ₂o ₃as experimental raw, by NdMgAl ₁₁o ₁₉stoichiometric ratio design batching, rear ball milling 24h takes out and is dried, under 1600 ℃ of conditions, is incubated 15h respectively, calcining synthetic powder, the powder after synthesizing makes NdMgAl through pulverizing to grind ₁₁o ₁₉platy shaped particle.

By the NdMgAl preparing ₁₁o ₁₉platy shaped particle and 5mol%Y ₂o ₃stable ZrO ₂powder is that raw material is according to LaMgAl ₁₁o ₁₉platy shaped particle 6wt%, 5mol%Y ₂o ₃stable ZrO ₂powder 94wt% prepares burden, ball milling 12h, and ball milling mixing obtains powder injection forming by drying treatment, through 250MPa isostatic cool pressing, processing and obtaining green compact, green compact in insulation 50h pressureless sintering, naturally cool to room temperature the condition of 1600 ℃, can obtain the NdMgAl of high temperature resistant erosive wear ₁₁o ₁₉-ZrO ₂diphase ceramic material.

Prepared NdMgAl ₁₁o ₁₉-ZrO ₂the main performance index bending strength 780MPa of diphase ceramic material, fracture toughness property reaches as high as 14.0MPam ^1/2, High Temperature Gas fixed double phase flow erosive wear rate is than not adding NdMgAl at its 1400 ℃ ₁₁o ₁₉the 5mol%Y of platy shaped particle ₂o ₃stable ZrO ₂pottery is low by 42%.

Claims

1. a high temperature resistant erosive wear LnMgAl ₁₁o ₁₉-ZrO ₂diphase ceramic material, is characterized in that: composition consists of (1-x) ZrO ₂-xLnMgAl ₁₁o ₁₉, 0.2wt%≤x≤15wt% wherein, Ln=Ce, Pr, Nd, Sm, Eu, Gd;

Above-mentioned high temperature resistant erosive wear LnMgAl ₁₁o ₁₉-ZrO ₂the preparation method of diphase ceramic material is: with LnMgAl ₁₁o ₁₉the zirconium white of platy shaped particle and 2-5mol% stabilized with yttrium oxide is raw material, by the LnMgAl of 0.2-15wt% ₁₁o ₁₉the zirconium white of platy shaped particle and stabilized with yttrium oxide is prepared burden, then ball milling 3h-48h, ball milling obtains powder by drying treatment, adopt dry-pressing or slip casting to obtain base substrate, through 100-300MPa isostatic cool pressing, process and obtain green compact again, green compact carry out sintering in 1-80 hour 1500 ℃-1700 ℃ insulations, naturally cool to room temperature, obtain the LnMgAl of high temperature resistant erosive wear ₁₁o ₁₉-ZrO ₂diphase ceramic material.

2. a kind of high temperature resistant erosive wear LnMgAl according to claim 1 ₁₁o ₁₉-ZrO ₂diphase ceramic material, is characterized in that: with Mg (OH) ₂, Al (OH) ₃with rare earth oxide Ce ₂o ₃, Pr ₂o ₃, Nd ₂o ₃, Sm ₂o ₃, Eu ₂o ₃or Gd ₂o ₃for raw material, it is pure that above raw material is chemical analysis, according to stoichiometric ratio, prepares burden, and ball milling mixing 3h-48h, by drying treatment, at 1400 ℃-1650 ℃ insulation 1h-20h, obtains LnMgAl by synthetic powder pulverizing and jevigating ₁₁o ₁₉platy shaped particle.