CN1935745A - Method for inhibiting alkali metal volatilization during niobate base lead-free piezoelectric ceramic sintering process - Google Patents
Method for inhibiting alkali metal volatilization during niobate base lead-free piezoelectric ceramic sintering process Download PDFInfo
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- CN1935745A CN1935745A CN 200610112893 CN200610112893A CN1935745A CN 1935745 A CN1935745 A CN 1935745A CN 200610112893 CN200610112893 CN 200610112893 CN 200610112893 A CN200610112893 A CN 200610112893A CN 1935745 A CN1935745 A CN 1935745A
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- 238000000034 method Methods 0.000 title claims abstract description 63
- 238000005245 sintering Methods 0.000 title claims abstract description 48
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 27
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 27
- 239000000919 ceramic Substances 0.000 title claims abstract description 21
- 239000002585 base Substances 0.000 title claims description 20
- 230000002401 inhibitory effect Effects 0.000 title abstract 2
- 239000000843 powder Substances 0.000 claims abstract description 73
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000001272 pressureless sintering Methods 0.000 claims abstract description 18
- 239000010953 base metal Substances 0.000 claims description 61
- 230000010287 polarization Effects 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- 229910010293 ceramic material Inorganic materials 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 229920002545 silicone oil Polymers 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract 3
- 238000000576 coating method Methods 0.000 abstract 3
- 239000011734 sodium Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
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Abstract
The invention discloses a method for effectively inhibiting alkali metal volatilization in the course of sintering leadless columbate piezoelectric ceramic, called double-layer pot method for short: placing an alkali metal columbate inner pot with the component similar to that of the to-be-sintered material into a common alumina ceramic outer pot, and filling alkali metal columbate coating powder around the inner pot; and the concrete method: placing the pressed blank of the prefired alkali metal columbate ceramic into an alkali metal columbate inner pot with the similar component, then burying the inner pot into an outer pot holding alkali metal columbate coating powder with the component similar to that of the to-be-sintered ceramic, and making pressureless sintering in the atmosphere. And it can effectively inhibit the alkali metal volatilization in the sintering course, and obtains high-compactness ceramic block product whose piezoelectric constant is largely increased as compared with the alkali metal columbate ceramic sintered only by the coating powder.
Description
Technical field
The invention belongs to the ceramic material field, particularly a kind of method that suppresses alkali metal volatilization in the columbate leadless piezoceramic material sintering process.
Background technology
The extensive in the market piezoceramic material system of using mainly is the lead base piezoelectric ceramics, plumbous series piezoelectric ceramic has excellent piezoelectric property, and can regulate its performance by doped and substituted, meeting the different needs, but PbO (or Pb in these stupaliths
3O
4) content account for about 7%.Bring serious harm all can for the mankind and ecotope in the treating processes of lead base piezoelectric after producing, use and discarding, be dissolved in the lead in the acid rain, can be by water and animals and plants and direct or indirect invasion human body, the plumbous neural system that mainly influences human body.Therefore the piezoceramic material of researching and developing the novel environmental close friend has become one of focus material of world developed country research and development.
The base metal niobate piezoceramic material belongs to leadless piezoelectric ceramics, NaNbO
3, KNbO
3Deng being perovskite-like type compound crystal, the general formula of this compounds is ABO
3(A is Li, Na, K, and B is Nb, Ta).Than leaded base piezoelectric ceramics such as PZT, the base metal niobate pottery has following characteristics: specific inductivity is little, and frequency constant is big; Density is little; The acoustic velocity height is mainly used on the transverter at present.The base metal niobate pottery is difficult to densified sintering product in sintering process.A reason is because potassium niobate is stable when temperature is lower than 1040 ℃, and sodium columbate is lower than 1140 ℃ to be stablized, so be difficult to carry out high temperature sintering.Non-impurity-doped (K
0.5Na
0.5) NbO
3In pressureless sintering density the highest also be 90～95% (theoretical density 4.51g/cm
3).Up to the present, have only hot-pressing sintering technique and discharge plasma sintering process can prepare high fine and close pottery preferably; But because of potassium oxide, the volatility of sodium oxide can make stoichiometric ratio be difficult to control, and the small change (being in rich potassium district or in rich sodium district) of stoichiometric ratio all can cause the formation of second phase (non-piezoelectric phase), so reduction potassium oxide, the volatility of sodium oxide, stoichiometry realizes that recently the densification pressureless sintering under the comparatively high temps is to press for thereby control more accurately.
Summary of the invention
The object of the present invention is to provide a kind of method that can effectively suppress alkali metal volatilization in the niobate piezoelectric ceramic material sintering process, described niobate piezoelectric ceramic material is pressed compound general formula (Li
xK
zNa
1-x-z) (Nb
1-yTa
y) O
3, x wherein, y, z are molar weight; 0≤x＜0.1,0≤y＜0.5,0＜z≤0.5; The preparation of employing pressureless sintering method is characterized in that the method for alkali metal volatilization adopts the double crucible pressureless sintering method in the described inhibition niobate piezoelectric ceramic material sintering process, and concrete implementing process is as follows:
(1) preparation base metal niobate based leadless piezoelectric ceramic pre-burning powder: with required Li, K, the carbonate powder of Na, and Nb, the oxide powder of Ta is by (Li
xK
zNa
1-x-z) (Nb
1-yTa
y) O
3, the stoichiometric ratio that formula is represented takes by weighing batching, x wherein, and y, z are molar weight; 0≤x＜0.1,0≤y＜0.5,0＜z≤0.5; It is in the ball grinder of medium that confected materials joins with the dehydrated alcohol, uses planetary ball mill batch mixing 4～24 hours, gets the compound powder after the oven dry; With the roasting in air, in 750～900 ℃ of compound powder, be incubated 2～10 hours, the synthetic alkali metal niobate; After coldmoulding under 50～90MPa, isostatic cool pressing under 200MPa obtains base metal niobate presintered compact system product with the base metal niobate powder after synthetic.
(2) preparation of crucible in the base metal niobate in the double crucible: with the base metal niobate powder after the pre-burning in the step (1) or with the similar pre-burning of its composition after the base metal niobate powder, slotted base metal niobate crucible in the middle of compacting is suppressed a base metal niobate loam cake of base metal niobate crucible base substrate identical component therewith simultaneously.
(3) double-deck crucible method sintering prepares the base metal niobate leadless piezoelectric material material: the base metal niobate presintered compact system product in the step (1) after the isostatic cool pressing are put into the groove of the base metal niobate crucible of step (2) preparation, and cover loam cake, again it is imbedded in the outer crucible with the burying in the powder of ceramic similar component to be sintered; Under air atmosphere, 1000～1200 ℃ are carried out pressureless sintering, are incubated 1～3 hour, make base metal niobate lead-free piezoceramic material goods.
(4) following process and detection: with the density of Archimedes's method working sample; Goods behind the sintering are coated with roasting silver electrode, in silicone oil, polarize,, kept 10～60 minutes, cool to room temperature again, finish polarization 80～120 ℃ of polarizing voltages that apply 1～4kV/mm; Polarization is finished to place and is measured piezoelectric constant d after one day
33
The invention has the beneficial effects as follows with the existing common powder sintering technology of burying and compare that the present invention has (1) and obtains not reducing the piezoelectric property of goods in the high dense product under higher sintering temperature; (2) can obtain uniform tissue, and the abnormal grain that can effectively suppress to occur easily in the high-temperature sintering process is grown up; (3) effectively suppress alkali metal volatilization in the high-temperature sintering process, control the sintering component concentration comparatively accurately.
Description of drawings
Fig. 1. double crucible method sintering structure synoptic diagram.
(the Li of Fig. 2 .800 ℃ pre-burning after 5 hours
0.04K
0.44Na
0.52) (Nb
0.85Ta
0.15) O
3The X ray diffracting spectrum of powder.
Fig. 3. the X ray diffracting spectrum of 1110 ℃ of agglomerating goods of same sintering temperature under the different sfgd.s.
Fig. 4. two kinds of differences are buried the surface heat erosion profile of the goods that obtain under the powder mode.
Embodiment
The invention provides a kind of method that can effectively suppress alkali metal volatilization in the niobate piezoelectric ceramic material sintering process.The method of alkali metal volatilization adopts the double crucible pressureless sintering method in the described inhibition niobate piezoelectric ceramic material sintering process.The concrete implementing process that effectively suppresses the alkali metal volatilization in the high-temperature sintering process is as follows:
(1) preparation base metal niobate based leadless piezoelectric ceramic pre-burning powder: press compound general formula (Li
xK
zNa
1-x-z) (Nb
1-yTa
y) O
3Stoichiometric ratio take by weighing batching, x wherein, y, z are molar weight; 0≤x＜0.1,0≤y＜0.5,0＜z≤0.5; With required Li, K, it is in the ball grinder of medium that the carbonate powder of Na, and Nb, the oxidate powder powder stock of Ta join with the dehydrated alcohol, uses planetary ball mill batch mixing 4～24 hours, gets the compound powder after the oven dry; With the roasting in air, in 750～900 ℃ of compound powder, be incubated 2～10 hours, the synthetic alkali metal niobate; After coldmoulding under 50～90MPa, isostatic cool pressing under 200MPa obtains base metal niobate presintered compact system product with the base metal niobate powder after synthetic.
(2) preparation of crucible in the base metal niobate in the double crucible: with the base metal niobate powder after the pre-burning in the step (1) or with the similar pre-burning of its composition after the base metal niobate powder, crucible 4 in the base metal niobate of groove 5 is arranged in the middle of compacting, suppress a base metal niobate loam cake 3 (as shown in Figure 1) of base metal niobate crucible base substrate identical component therewith simultaneously.
(3) double-deck crucible method sintering prepares the base metal niobate block materials: base metal niobate presintered compact system product are put into 5 li of grooves with the base metal niobate crucible 4 of step (2) preparation, and cover loam cake 3, again it is imbedded the base metal niobate that fills with ceramic 6 similar components to be sintered and bury in the alumina outer crucible 1 of powder 7, closed the lid then for 2 (as shown in Figure 1).In atmosphere, 1000～1200 ℃ are carried out sintering, are incubated 1～3 hour, make base metal niobate lead-free piezoceramic material goods 5.In order to compare, only with the common powder sintering that buries, other all adopts above-mentioned same processing parameter also to prepare the base metal niobate goods.
(4) following process and detection: a. Archimedes's method, the density of working sample in room temperature, pure water; B. the goods behind the sintering are coated with roasting silver electrode, in silicone oil, polarize,, kept 10～60 minutes, cool to room temperature again, finish polarization 80～120 ℃ of polarizing voltages that apply 1～4kV/mm; C. polarization is finished to place and is measured piezoelectric constant d after one day
33
Lifting specific embodiment is below further specified:
Embodiment 1 (the double crucible legal system is equipped with the base metal niobate goods):
1. according to chemical formula (Li
0.04K
0.44Na
0.52) (Nb
0.85Ta
0.15) O
3Prepare burden, total mass is 20g;
2. confected materials adds dehydrated alcohol as medium, uses planetary ball mill ball milling 12 hours, and ball milling speed is 250 rev/mins, and the powder behind the ball milling is dried down at 70 ℃ and obtained dry powder.
3. with the dry powder roasting, 800 ℃ of maturing temperatures are incubated 5 hours, carry out the synthetic of niobate.Fig. 2 represents the X-ray diffractogram of the niobate material powder after the roasting, illustrates to have finished the synthetic of niobate this moment.
4. the niobate material powder after will synthesizing is after 90MPa coldmoulding, and isostatic cool pressing under the 200MPa makes base substrate;
5. pressureless sintering in the inherent air of the double crucible of base substrate being packed into, temperature is 1110 ℃, and 10 ℃/min of temperature rise rate is incubated 2 hours, and furnace cooling can make the base metal niobate goods;
6. the density with Archimedes's method working sample is 96.9%; Goods behind the sintering are coated with roasting silver electrode, in silicone oil, polarize,, kept 30 minutes, cool to room temperature again, finish polarization 120 ℃ of polarizing voltages that apply 3kV/mm; Polarization is finished to place and is measured piezoelectric constant d after one day
33=196pc/N.
Embodiment 2 (the double crucible legal system is equipped with the base metal niobate goods):
1. according to chemical formula (Li
0.02K
0.48Na
0.5) (Nb
0.8Ta
0.2) O
3Prepare burden, total mass is 20g;
2. confected materials adds dehydrated alcohol as medium, uses planetary ball mill ball milling 12 hours, and ball milling speed is 250 rev/mins, and the powder behind the ball milling is dried down at 70 ℃ and obtained dry powder.
3. with the dry powder roasting, 850 ℃ of maturing temperatures are incubated 4 hours, carry out the synthetic of niobate.Fig. 2 represents the X-ray diffractogram of the niobate material powder after the roasting, illustrates to have finished the synthetic of niobate this moment.
4. the niobate material powder after will synthesizing is after 90MPa coldmoulding, and isostatic cool pressing under the 200MPa makes base substrate;
5. pressureless sintering in the inherent air of the double crucible of base substrate being packed into, temperature is 1120 ℃, and 10 ℃/min of temperature rise rate is incubated 2 hours, and furnace cooling can make the base metal niobate goods;
6. the density with Archimedes's method working sample is 97%; Goods behind the sintering are coated with roasting silver electrode, in silicone oil, polarize,, kept 30 minutes, cool to room temperature again, finish polarization 120 ℃ of polarizing voltages that apply 3kV/mm; Polarization is finished to place and is measured piezoelectric constant d after one day
33=190pC/N.
Embodiment 3 (the double crucible legal system is equipped with the base metal niobate goods):
1. with embodiment 1 step 1;
2. with embodiment 1 step 2;
3. with the dry powder roasting, 750 ℃ of maturing temperatures are incubated 5 hours, carry out the synthetic of niobate.
4. the niobate material powder after will synthesizing is after 90MPa coldmoulding, and isostatic cool pressing under the 200MPa makes base substrate;
5. pressureless sintering in the inherent air of the double crucible of base substrate being packed into, temperature is 1060 ℃, and 10 ℃/min of temperature rise rate is incubated 2 hours, and furnace cooling can make the base metal niobate goods;
6. the density with Archimedes's method working sample is 86.5%; Goods behind the sintering are coated with roasting silver electrode, in silicone oil, polarize,, kept 30 minutes, cool to room temperature again, finish polarization 120 ℃ of polarizing voltages that apply 3kV/mm; Polarization is finished to place and is measured piezoelectric constant d after one day
33=180pC/N.
Embodiment 4 (the double crucible legal system is equipped with the base metal niobate goods):
1. with embodiment 2 steps 1;
2. with embodiment 2 steps 2;
3. with the dry powder roasting, 900 ℃ of maturing temperatures are incubated 5 hours, carry out the synthetic of niobate.Fig. 2 represents the X-ray diffractogram of the niobate material powder after the roasting, illustrates to have finished the synthetic of niobate this moment.
4. the niobate material powder after will synthesizing is after 90MPa coldmoulding, and isostatic cool pressing under the 200MPa makes base substrate;
5. pressureless sintering in the inherent air of the double crucible of base substrate being packed into, temperature is 1160 ℃, and 10 ℃/min of temperature rise rate is incubated 2 hours, and furnace cooling can make the base metal niobate goods;
6. the density with Archimedes's method working sample is 98.1%; Goods behind the sintering are coated with roasting silver electrode, in silicone oil, polarize,, kept 30 minutes, cool to room temperature again, finish polarization 120 ℃ of polarizing voltages that apply 3kV/mm; Polarization is finished to place and is measured piezoelectric constant d after one day
33=115pC/N.
Comparing embodiment
Commonly bury the preparation process that the powder legal system is equipped with the base metal niobate goods:
1. according to chemical formula (Li
0.04K
0.44Na
0.52) (Nb
0.85Ta
0.15) O
3Prepare burden, total mass is 20g;
2. confected materials adds dehydrated alcohol as medium, uses planetary ball mill ball milling 12 hours, and ball milling speed is 250 rev/mins, and the powder behind the ball milling is dried down at 70 ℃ and obtained dry powder.
3. with the dry powder roasting, 800 ℃ of maturing temperatures are incubated 5 hours, carry out the synthetic of niobate.
4. the niobate material powder after will synthesizing is after 90MPa coldmoulding, and isostatic cool pressing under the 200MPa makes base substrate;
5. the base metal niobate that fills with ceramic similar component to be sintered of base substrate being packed into buries in the alumina crucible of powder, pressureless sintering in air, and temperature is 1110 ℃, and 10 ℃/min of temperature rise rate is incubated 2 hours, and furnace cooling can make the base metal niobate goods;
6. use the density 97.8% of Archimedes's method working sample; Goods behind the sintering are coated with roasting silver electrode, in silicone oil, polarize,, kept 30 minutes, cool to room temperature again, finish polarization 120 ℃ of polarizing voltages that apply 3kV/mm; Polarization is finished to place and is measured piezoelectric constant d after one day
33=155pC/N.
Table 1 is depicted as the method protection of mensuration double crucible and only uses extrudate density and the piezoelectric constant d that buries after powder is protected sintering
33, under the double crucible method sfgd. density of agglomerating goods with only be more or less the same but piezoelectric constant d with the density of burying the goods that powder sintering obtains
33Than only the raising of higher amplitude but being arranged with burying goods that powder sintering obtains.
Fig. 3 represents the X-ray diffractogram of the sintered article under the different sfgd.s; the main peak position of only burying the goods of powder protection as can be seen all is offset left than the peak position that has double crucible to add to bury the goods of powder protection; this has proved and has had comparatively serious alkali metal volatilization in the goods that only bury the powder protection that double crucible method protection agglomerating preparation method has then effectively suppressed alkali-metal volatilization.
Fig. 4 has compared two kinds of surface heat erosion profile that difference is buried the sample that obtains under the powder mode.(a) double crucible method sintering (b) only buries powder sintering, and the condition of thermal etching is 1050 ℃ and is incubated half an hour.As can be seen, use the homogeneous grain size of the sample that double crucible method sintering obtains, and only protecting and occurred the crystal grain phenomenon of growing up unusually in the agglomerating sample with burying powder.Common bury the powder method and also can prepare highdensity base metal niobate based leadless piezoelectric ceramic although utilize, but because the composition volatilization can not effectively be restrained, can occur too much liquid phase in the sintering process and make that part crystal grain takes place to grow up unusually, the piezoelectric property of resulting product is also low.
The density and the d of the goods of 1110 ℃ of pressureless sinterings under the different sfgd.s of table 1.
33
| Sfgd. | Density (%) | d 33 (pC/N) |
| Double crucible+bury powder | 96.9 | 196 |
| Bury powder | 97.8 | 155 |
Claims (5)
1. method that suppresses alkali metal volatilization in the niobate piezoelectric ceramic material sintering process, described niobate piezoelectric ceramic material is pressed compound general formula (Li
xK
zNa
1-x-z) (Nb
1-yTa
y) O
3, batching, wherein 0≤x＜0.1,0≤y≤0.5,0＜z≤0.5; Its x, y, z is a molar weight, it is characterized in that this material adopts double crucible pressureless sintering method sintering, be about to obtain the base metal niobate powder after this ceramic batch pre-burning, be pressed into base substrate, put into the base metal niobate crucible similar to its composition, again it is imbedded the base metal niobate that fills with ceramic similar component to be sintered and bury in the outer crucible of powder, in atmosphere, carry out pressureless sintering, obtain the niobate piezoelectric ceramic material.
2. suppress the method for alkali metal volatilization in the niobate piezoelectric ceramic material sintering process according to claim 1, it is characterized in that the concrete technology of described double crucible pressureless sintering method is as follows:
(1) preparation base metal niobate based leadless piezoelectric ceramic pre-burning powder: with required Li, K, the carbonate powder of Na, and Nb, the oxide powder of Ta are pressed compound general formula (Li
xK
zNa
1-x-z) (Nb
1-yTa
y) O
3Stoichiometric ratio take by weighing batching; X wherein, y, z are molar weight; 0≤x＜0.1,0≤y＜0.5,0＜z≤0.5; It is in the ball grinder of medium that confected materials joins with the dehydrated alcohol, uses planetary ball mill batch mixing 4～24 hours, gets the compound powder after the oven dry; With the roasting in air, in 750～900 ℃ of compound powder, be incubated 2～10 hours, the synthetic alkali metal niobate; After coldmoulding under 50～90MPa, isostatic cool pressing under 200MPa obtains base metal niobate presintered compact system product with the base metal niobate powder after synthetic;
(2) preparation of crucible in the base metal niobate in the double crucible: with the base metal niobate powder after the pre-burning in the step (1) or with the similar pre-burning of its composition after the base metal niobate powder, slotted base metal niobate crucible in the middle of compacting is suppressed a base metal niobate loam cake of base metal niobate crucible base substrate identical component therewith simultaneously;
(3) double-deck crucible method sintering prepares the base metal niobate leadless piezoelectric material material: the base metal niobate presintered compact system product in the step (1) after the isostatic cool pressing are put into the groove of the base metal niobate crucible of step (2) preparation, and cover loam cake, again it is imbedded in the outer crucible with the burying in the powder of ceramic similar component to be sintered; Under air atmosphere, 1000～1200 ℃ are carried out pressureless sintering, are incubated 1～3 hour, make base metal niobate lead-free piezoceramic material goods;
(4) following process and detection: with the density of Archimedes's method working sample; Goods behind the sintering are coated with roasting silver electrode, in silicone oil, polarize,, kept 10～60 minutes, cool to room temperature again, finish polarization 80～120 ℃ of polarizing voltages that apply 1～4kV/mm; Polarization is finished to place and is measured piezoelectric constant d after one day
33
3. suppress the method for alkali metal volatilization in the niobate piezoelectric ceramic material sintering process according to claim 1, it is characterized in that, the preparation of described niobate piezoelectric ceramic material is,
(1) according to chemical formula (Li
0.04K
0.44Na
0.52) (Nb
0.85Ta
0.15) O
3Prepare burden, total mass is 20g;
(2) confected materials adds dehydrated alcohol as medium, uses planetary ball mill ball milling 12 hours, and ball milling speed is 250 rev/mins, and the powder behind the ball milling is dried down at 70 ℃ and obtained mixed powder;
(3), be incubated 5 hours, synthetic niobate material powder with 800 ℃ of mixed powder roastings;
(4) the niobate material powder after will synthesizing is after 90MPa coldmoulding, and isostatic cool pressing under the 200MPa makes niobate presintered compact system product;
(5) base substrate is packed into pressureless sintering in the inherent air of double crucible, temperature is 1110 ℃, and 10 ℃/min of temperature rise rate is incubated 2 hours, and furnace cooling makes base metal niobate piezoceramic material goods.
4. suppress the method for alkali metal volatilization in the niobate piezoelectric ceramic material sintering process according to claim 1, it is characterized in that, described interior crucible is circular or square.
5. suppress the method for alkali metal volatilization in the niobate piezoelectric ceramic material sintering process according to claim 1, it is characterized in that, crucible intermediary groove is circular or square in the described base metal niobate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553605A (en) * | 2013-10-15 | 2014-02-05 | 陕西科技大学 | KNN-BF leadless piezoelectric ceramic and preparation method thereof |
| CN110994009A (en) * | 2019-12-20 | 2020-04-10 | 云南大学 | Sintering device and sintering method for preparing solid electrolyte material |
| CN111121454A (en) * | 2019-12-23 | 2020-05-08 | 武汉科技大学 | High-temperature sintering structure with double-layer nested structure |
| CN112194464A (en) * | 2020-10-28 | 2021-01-08 | 中科传感技术(青岛)研究院 | Sintering method for lead-containing piezoelectric ceramic product |
| CN116813336A (en) * | 2023-06-30 | 2023-09-29 | 北京邮电大学 | Method for optimizing PZT-based piezoelectric ceramic solid-phase sintering process |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553605A (en) * | 2013-10-15 | 2014-02-05 | 陕西科技大学 | KNN-BF leadless piezoelectric ceramic and preparation method thereof |
| CN110994009A (en) * | 2019-12-20 | 2020-04-10 | 云南大学 | Sintering device and sintering method for preparing solid electrolyte material |
| CN111121454A (en) * | 2019-12-23 | 2020-05-08 | 武汉科技大学 | High-temperature sintering structure with double-layer nested structure |
| CN112194464A (en) * | 2020-10-28 | 2021-01-08 | 中科传感技术(青岛)研究院 | Sintering method for lead-containing piezoelectric ceramic product |
| CN116813336A (en) * | 2023-06-30 | 2023-09-29 | 北京邮电大学 | Method for optimizing PZT-based piezoelectric ceramic solid-phase sintering process |
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