A kind of preparation method of model casting TiAl base alloy shell mould
Technical field
The invention belongs to the precision casting technology field, be specifically related to a kind of preparation method of model casting TiAl base alloy shell mould.
Background technology
TiAl base alloy has high strength; Low-density; High elastic modulus; Advantages such as non-oxidizability and croop property are good are a kind of very potential lightweight high-temperature structural materials, are the one type of alloys [E.A.Loria.Quo vadis gamma titanium aluminide.Intermetallics.2001.9:997-1001] that develops rapidly in the titanium casting field in the last few years.TiAl base alloy is expected to be used for the wing, housing of high temperature resistant component and the super speed vehicle of Aero-Space such as jet engine and turbine, auto industry etc.; Be considered to have most the lightening fire resistant structural material [Li Jinshan of new generation of application potential; Zhang Tiebang, the progress and the development trend of .TiAl base intermetallic compounds such as Chang Hui. Chinese material progress .201029 (3): 1~2; Xinhua Wu.Review of alloy and process development of TiAl alloys.Intermetallics 14 (2006): 1114-1122].
Because TiAl base alloy temperature-room type plasticity is poor, and tangible room temperature fragility is arranged, percentage elongation less than 1% in its drawing process, and crystal grain can sharply be grown up in hot procedure, causes further embrittlement, so machinability is very poor, and its application is met difficulty.
In view of the characteristic of TiAl base alloy, forging molding had obviously not only been required great effort but also waste material, particularly when making some complex-shaped parts, seemed unable to do what one wishes especially.So casting just naturally becomes the processing method that is suitable for TiAl base alloy, particularly near clean formation type technology---precision-investment casting.In the last few years, the type shell material of TiAl alloy precision casting commonly used had: 1. Delanium; 2. refractory metal (powder such as tungsten, molybdenum, niobium); 3. special type fire oxide (ZrO
2With some rare-earth oxides and calcium oxide thereof etc.), using more is the special type fire oxide widely.ZrO
2The ceramic shell thermal conductivity is low, and intensity is high, the titanium alloy casting of pourable high-quality.Its advantage is, for the molten titanium alloy better chemical stability arranged, and particularly through after the appropriate grain size distribution, surface quality of continuous castings significantly improved.Because ZrO
2What had has a superior function, and also maximum to its research now, many researchs have all concentrated on raising ZrO
2On the surface layer shell mould performance.
Summary of the invention
The purpose of this invention is to provide a kind of easy to make, sufficient intensity is arranged and has preparation method than the formwork of high chemical stability for molten condition TiAl base alloy, adopt this method can satisfy the requirement of preparation TiAl base alloy component.
Technical scheme of the present invention is:
The preparation method of the formwork that a kind of model casting TiAl base alloy is used is characterized in that, comprises that step is following:
1) be 300~400 purpose ZrO with granularity
2Powder and zirconium colloidal sol are that to be configured to room temperature flow cup viscosity in 2.5: 1~3.5: 1 be 40~55 seconds slurry by powder liquor ratio g/ml;
2) above-mentioned slurry is coated on the wax-pattern, spreading granularity is 120~180 purpose ZrO
2Sand, drying; Adopt 800~1100 purpose Al
2O
3Sand and silicate hydrolyzate liquid were configured to room temperature flow cup viscosity by weight 2.2: 1~2.4: 1 be 35~55 seconds slurry, applies the 2nd layer, and the stucco granularity is 60~90 purpose Al
2O
3Sand, ammonia is done, drying;
3) slurry coating step 2 then), spreading granularity again is 30~50 purpose Al
2O
3Sand, repetitive coatings slurry and stucco successively prepares the 3rd~4 layer, and ammonia is done, drying; Then coating step 2 again) slurry, spreading granularity is 16~25 purpose Al
2O
3Be coated with extension, and repetitive coatings slurry and stucco prepare the 5th~7 layer successively, ammonia is done, drying; Last coating step 2) slurry, and spread 6~10 purpose Al
2O
3Sand prepares last one deck, immerses hardening agent, drying;
4) dewaxing, sintering.
Wherein, Al
2O
3Be electric smelting Al through calcining
2O
3The composition of silicate hydrolyzate liquid is the mixed liquor of ethyl orthosilicate, water, absolute ethyl alcohol, hydrochloric acid and boric acid, and it uses magnitude relation to be ethyl orthosilicate ml: water ml: absolute ethyl alcohol ml: concentrated hydrochloric acid g: boric acid g is (800-1200): (150-180): (600-650): (8-10): (3-4); The composition of hardening agent is the mixed liquor of ethyl orthosilicate, water, absolute ethyl alcohol and hydrochloric acid, and it uses magnitude relation to be ethyl orthosilicate ml: water ml: absolute ethyl alcohol ml: concentrated hydrochloric acid g is (800-1200): (150-180): (600-650): (4-6).
Also add wetting agent, antifoaming agent in the said pulp preparation process of step 1), wherein to account for the weight percentage of slurry be 1~3 ‰ to wetting agent, and the percentage by weight that antifoaming agent accounts for slurry is 3~5 ‰, and wherein wetting agent is a n-octyl alcohol; Zirconium colloidal sol limit is stirred with ZrO in the limit
2Powder adds, and then adds wetting agent, antifoaming agent successively, stirs more than 2 hours, but places coating after 12 hours.
Step 2) and 3) concrete steps be preferably: wax-pattern is immersed in the above-mentioned slurry, soaked 5~10 seconds, during rotate wax-pattern in case coating to cover type even, take out the wax-pattern rear overhang and put 3~5 seconds, the unnecessary coating that pours off spreads the ZrO that granularity is 120~180 order numbers
2Sand is 25~27 ℃ in temperature, and humidity is that 50~70% environment is dry down more than 12 hours, constitutes surface layer; Al with 800~1100 order numbers
2O
3Sand and silicate hydrolyzate liquid were configured to room temperature flow cup viscosity by weight 2.2: 1~2.4: 1 be 35~55 seconds slurry, is coated with to hang the 2nd layer, and mode is with to be coated with the extension ground floor similar, and spreading granularity is 60~90 purpose Al
2O
3Sand is 25~27 ℃ in temperature, and humidity is 50~70% environment air dried 15~30 minutes, then the shell mould is put into enclosed environment, places ammoniacal liquor, and ammonia concn is 40%, preferred every 1m
3Corresponding 10ml ammoniacal liquor carries out ammonia and did 15~45 minutes, and purpose is to make the shell quick-hardening; After ammonia was done, being placed on temperature again was 25~27 ℃, and humidity is 50~70% ventilated environment dry 15~20 minutes down; Adopt identical method then, apply 800~1100 purpose Al
2O
3The slurry that sand and silicate hydrolyzate liquid are formed, spreading granularity is 35~45 purpose Al
2O
3Sand is coated with hangs the 3rd~4 layer, drying, and ammonia is done, drying; Spreading granularity is 20~30 purpose Al
2O
3Be coated with and hang the 5th~7 layer, drying, ammonia is done, and is dry again; Spreading granularity at last is the electric smelting Al after the calcining of 6~10 purposes
2O
3Sand, drying, ammonia is done, and in hardening agent, soaks the shell mould 2~3 minutes then, puts in the ventilation 7~12 hours.
Step 3); Shell mould after steam dewaxing or the warm water dewaxing is placed after 1~2 hour and is carried out sintering; Sintering process is for being heated to 400~500 ℃ of insulations 1~1.5 hour; Be heated to 700~800 ℃ of insulations 1~1.5 hour again, be heated to 900~1100 ℃ of insulations 1~2 hour at last, can take out after being cooled to room temperature.
Advantage of the present invention:
1, the ZrO of the present invention's employing
2As surface material, ZrO
2Have heat endurance and chemical stability preferably with respect to molten state TiAl base alloy, the foundry goods that casts out has high surface quality and surface smoothness.
2, the backing layer type shell material of the present invention's employing is Al
2O
3Sand, the emergy low price, fusing point is high, good heat conductivity, thermal coefficient of expansion is little.
3, the backing layer binding agent that the present invention adopted is homemade silicate hydrolyzate liquid, and this hydrolyzate is easy to make, and the holding time is long, and is nontoxic, and the formwork after the making has enough intensity.
4, the used surface layer refractory material of the present invention granularity that sands is 120~180 purpose ZrO
2Fine sand forms the highly polished surface layer of compact surfaces, can play promptly to reinforce surface layer and can prevent that again big sand grains from penetrating surface layer slurry and causing mo(U)ld face coarse.
5, the present invention adds the dried dry run of ammonia between the shell dry period, and shortened drying time greatly, has improved system shell efficient.
The specific embodiment
Ethyl orthosilicate is (with SiO in following examples
2Meter) the 28% zirconium colloidal sol place of production: this promise chemistry new material science and technology Co., Ltd of Dalian, room temperature is 25 ℃.
Embodiment 1
1) be 325 purpose ZrO with granularity under the room temperature
2With zirconium colloidal sol 3: 1 (g/ml) proportional arrangement form slurry of pressing the powder liquor ratio, add n-octyl alcohol and antifoaming agent then, the percentage by weight of two kinds of additives is respectively 3 ‰, 5 ‰, promptly in zirconium colloidal sol whipping process, adds ZrO
2Powder, n-octyl alcohol, antifoaming agent (commercialization) stirred 1.5 hours then, left standstill 24 hours, and at this moment the viscosity of slurry is flow cup viscosity 49 seconds.
2) wax-pattern was immersed in coating 8 seconds and fine rotation, make slurry cover wax-pattern fully, take out wax-pattern, vacant 5 seconds, unnecessary slurry is flowed away, and guarantee that last slurry evenly covers wax-pattern on the wax-pattern, spreading granularity is 120 purpose ZrO
2Sand is 25 ℃ in temperature as surface layer then, and humidity is 65% non-negotiable environment held 12 hours.Using granularity is the electric smelting Al after the calcining of 800 purposes
2O
3By pouring silicate hydrolyzate liquid and continuous stirring 1.5 hours in stirring at 2.2: 1 with silicate hydrolyzate liquid weight ratio, stirring back flow cup viscosity is 43 seconds; Immerse shell in the slurry, placed 8 seconds, and slight rotation, take out shell, vacant 2 seconds, spreading granularity was the electric smelting Al after the calcining of 70 purposes
2O
3Sand, being placed on temperature then is 25 ℃, humidity is little ventilation of 65% 20 minutes; Put into that to contain ammonia concn be 40% airtight cabinet 15 minutes; Be placed into the place 10 minutes of ventilation, this is the 2nd layer; Spreading granularity then is the electric smelting Al after the calcining of 40 purposes
2O
3Sand, and under above same steps as, be coated with and hang 3~4 layers; Spreading granularity is the electric smelting Al after the calcining of 20 purposes
2O
3Sand repeats identical coating step, is coated with to hang 5~7 layers, and spreading granularity at last is the electric smelting Al after the calcining of 5 purposes
2O
3Sand after the repetition same steps as, soaked 3 minutes in hardening agent at last again, dry 12 hours then
Be put into model and be heated to 150 ℃ in the heating furnace, after the dewaxing, placed 2 hours, carry out sintering then, sintering method is 450 ℃ of insulations 1.5 hours, and 780 ℃ of insulations 1.5 hours are at last 980 ℃ of insulations 2 hours., takes out by stove shell when being as cold as room temperature.The shell inner surface is smooth, and intensity is enough.Cast back TiAl base alloy-steel casting and formwork reaction are little, have high surface quality.
The composition of above-mentioned silicate hydrolyzate liquid is the mixed liquor of ethyl orthosilicate, water, absolute ethyl alcohol, hydrochloric acid and boric acid, and it uses magnitude relation to be ethyl orthosilicate ml: water ml: absolute ethyl alcohol ml: concentrated hydrochloric acid g: boric acid g is 800: 160: 600: 8: 4; The composition of hardening agent is the mixed liquor of ethyl orthosilicate, water, absolute ethyl alcohol and hydrochloric acid, and it uses magnitude relation to be ethyl orthosilicate ml: water ml: absolute ethyl alcohol ml: concentrated hydrochloric acid g is 900: 180: 650: 4.
Formwork with method for preparing is carried out the casting experiment of TiAl alloy, and gained casting pouring surface quality is high, no scab phenomenon, and the shell collapsibility is good, intensity 3.5MPa.
Embodiment 2
3) be 400 purpose ZrO with granularity
2With zirconium colloidal sol 2.8: 1 (g/ml) proportional arrangement form slurry of pressing the powder liquor ratio, add n-octyl alcohol and antifoaming agent then, the percentage by weight of two kinds of additives is respectively 1 ‰, 3 ‰, in zirconium colloidal sol whipping process, adds ZrO
2Powder, n-octyl alcohol, antifoaming agent stirred 1 hour then, left standstill 24 hours, and at this moment the viscosity of slurry is flow cup viscosity 58 seconds.
4) wax-pattern was immersed in coating 8 seconds and fine rotation, make slurry cover wax-pattern fully, take out wax-pattern, vacant 5 seconds, unnecessary slurry is flowed away, and guarantee that last slurry evenly covers wax-pattern on the wax-pattern, spreading granularity is 100 purpose ZrO
2Sand is 28 ℃ in temperature as surface layer then, and humidity is 70% non-negotiable environment held 12 hours.Using granularity is the electric smelting Al after the calcining of 1100 purposes
2O
3By pouring silicate hydrolyzate liquid and continuous stirring 1 hour in stirring at 2.4: 1 with silicate hydrolyzate liquid weight ratio, stirring back flow cup viscosity is 38 seconds; Immerse shell in the slurry, placed 5 seconds, and slight rotation, take out shell, vacant 2 seconds, spreading granularity was the electric smelting Al after the calcining of 80 purposes
2O
3Sand, being placed on temperature then is 28 ℃, humidity is little ventilation of 70% 15 minutes; Put into that to contain ammonia concn be 40% airtight cabinet 15 minutes; Be placed into the place 15 minutes of ventilation, this is the 2nd layer; Spreading granularity then is the electric smelting Al after the calcining of 50 purposes
2O
3Sand, and under above same steps as, be coated with and hang 3~4 layers; Spreading granularity is the electric smelting Al after the calcining of 30 purposes
2O
3Sand repeats same steps as, is coated with and hangs 5~7 layers, and spreading granularity at last is the electric smelting Al after the calcining of 4 purposes
2O
3Sand after the repetition same steps as, soaked 2 minutes in hardening agent at last again, dry 12 hours then
5) be put into model and be heated to 150 ℃ in the heating furnace, after the dewaxing, placed 2 hours, carry out sintering then, sintering method is 400 ℃ of insulations 2 hours, and 800 ℃ of insulations 2 hours are at last 900 ℃ of insulations 2 hours., takes out by stove shell when being as cold as room temperature.The shell inner surface is smooth, and intensity enough is 4.0MPa.
The composition of silicate hydrolyzate liquid is the mixed liquor of ethyl orthosilicate, water, absolute ethyl alcohol, hydrochloric acid and boric acid, and it uses magnitude relation to be ethyl orthosilicate ml: water ml: absolute ethyl alcohol ml: concentrated hydrochloric acid g: boric acid g is 1000: 170: 630: 10: 3.5; The composition of hardening agent is the mixed liquor of ethyl orthosilicate, water, absolute ethyl alcohol and hydrochloric acid, and it uses magnitude relation to be ethyl orthosilicate ml: water ml: absolute ethyl alcohol ml: concentrated hydrochloric acid g is 1100: 165: 645: 5.The formwork inner surface quality is good, and cast back TiAl base alloy-steel casting and formwork reaction are little, have high surface quality.