CN102531566A - Method for improving thermal shock resistance of phosphate ceramic material - Google Patents
Method for improving thermal shock resistance of phosphate ceramic material Download PDFInfo
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- CN102531566A CN102531566A CN2012100541501A CN201210054150A CN102531566A CN 102531566 A CN102531566 A CN 102531566A CN 2012100541501 A CN2012100541501 A CN 2012100541501A CN 201210054150 A CN201210054150 A CN 201210054150A CN 102531566 A CN102531566 A CN 102531566A
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000035939 shock Effects 0.000 title abstract description 18
- 229910010293 ceramic material Inorganic materials 0.000 title abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 title abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title abstract description 6
- 239000010452 phosphate Substances 0.000 title abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 238000000975 co-precipitation Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 32
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 8
- 235000019353 potassium silicate Nutrition 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000003916 acid precipitation Methods 0.000 claims description 7
- 235000015895 biscuits Nutrition 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 11
- 239000000919 ceramic Substances 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 5
- 108010053481 Antifreeze Proteins Proteins 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
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Abstract
The invention relates to near zero expansion constitution Ca0.85Ba0.15Zr4(PO4)6 in the NZP group phosphate ceramic material Ca1-xBaxZr4(PO4)6 (x is more than or equal to 0 and less than or equal to 1, short for CBZP) series, and belongs to the field of fine ceramic materials. When the ceramic material is prepared by a coprecipitation method, the thermal expansion coefficient of the Ca0.85Ba-0.15Zr4(PO4)6 obtained by only adding 3 percent of ZnO sintering aid is near zero (TEC is equal to 0.6*10<-6>/DEG C), but the thermal expansion anisotropy is high and the thermal shock resistance is not ideal (the material is broken after subjected to only two times of temperature difference of 900 DEG C); and the 3 percent of ZnO sintering aid and 1 percent of active SiO2 added, so the thermal shock resistance of the CBZP ceramic can be effectively improved and the sample is not broken after subjected to 5 times of temperature difference of 900 DEG C. The action mechanism is that the active SiO2 can inhibit growth of crystal grains, so that an effective route of improving the thermal shock resistance is achieved.
Description
Technical field
The present invention relates to the phosphate ceramic material Ca of NZP family
1-xBa
xZr
4(PO
4)
6(0≤
x≤1, being called for short CBZP) near-zero thermal expansion is formed Ca in the series
0. 85Ba
-0.15Zr
4(PO
4)
6, purpose is further to improve its resistance to sudden heating, belongs to the fine ceramics material field.
Background technology
NZP family phosphate ceramic material has good low-thermal-expansion and thermal shock resistance; Can be widely used in aerospace, automotive industry, military field high temperature guided missile, little type heat exchanger, support of the catalyst etc., its important use value receives highly visible just day by day.
Yet most NZP type compounds have thermal expansion anisotropy, elongation when promptly unit cell parameters a and c are with temperature variation, a shortening.Like this when sintered compact when sintering temperature cools down; Because single crystal grain expands on a crystallographic axis and on another crystallographic axis, shrinks; Caused difference makes and has produced thermal stresses in the polycrystalline ceramics, possibly surpass the tensile strength of crystal grain or crystal boundary at some some place, produces cracking when further cooling off; In polycrystal, form tiny crack, this has just reduced anti-thermal shock (heat shock resistance) property of material.The grain size of generation and sintered compact of finding tiny crack after deliberation is closely related, when grain size surpasses certain particle size values, just produces tiny crack, and this particle size values is called critical particle diameter G
Cr
According to the Cleveland relational expression:
G
cr=1.44γ
f/(E△α
max 2△T
2)
γ
f-fracture surface energy
The Young's modulus of E-single crystal grain
△ α
Max-single crystal grain axis expansible maximum difference
It is thus clear that the anisotropy of critical particle diameter and crystal thermal expansion size △ α
MaxSquare be inversely proportional to, promptly anisotropy is big more, critical particle diameter is more little, tiny crack is easy to generate more.
Though the generation of tiny crack has reduced thermal expansivity, the thermal shock resistance of material is descended, therefore controlling the anisotropy of thermal expansion and the grain size of sintered compact is two important means of exploitation expansion ceramic material.
Reducing thermal expansion anisotropy is an important channel of improving its resistance to sudden heating, the existing both at home and abroad report of the research of this respect, and a series of researchs were also done by this seminar, and had successfully synthesized Ca
1-xBa
xZr
4(PO
4)
6
(x=0,0.15,0.25,0.5,0.75,1.0) and K
xSr
(1-x)/2Zr
2(PO
4)
3The NZP family material of (x=0,0.25,0.5,0.75,1.0) two series.
In addition, because NZP is the single-phase polycrystalline material, crystal grain is big more, and boundary stress is also big more, even can make big crystal grain fracture occur running through.And grained material crystal boundary ratio is big, and during along intercrystalline failure, the expansion of crackle will be walked full of twists and turns road; Crystal grain is thin more, and the crack propagation road is longer, and intensity is high more; Therefore crystal grain thinning is another effective means that improves the stupalith resistance to sudden heating, and the present invention intends with adding active SiO
2With the method for control sintering condition, promptly with stable hetero atom insert crystal boundary or crystal boundary form ultra tiny stablize second suppress crystal grain mutually growth, reach crystal grain thinning, improve the purpose of its thermal shock resistance.
Up to now, disclosed the halfway relevant research report, do not find the open source literature report identical as yet with the present invention except that what applicant of the present invention delivered.
Summary of the invention:
The objective of the invention is to through adding active SiO
2Method with the control sintering condition makes grain refining, with further raising near-zero thermal expansion phosphate ceramic material Ca
0. 85Ba
-0.15Zr
4(PO
4)
6Thermal shock resistance.
The present invention adopts first and adds active SiO
2Method, more efficiently improved the thermal shock resistance of CBZP pottery.Specifically comprise and be prepared as follows step:
(1) coprecipitation method prepares Ca
0. 85Ba
0.15Zr
4(PO
4)
6Superfine powder: according to Ca
0.85Ba
0.15Zr
4(PO
4)
6The proportioning of molecular formula takes by weighing CaCO
3And BaCO
3The ZrOCl that is dissolved in
2In the solution, under stirring condition, according to Ca
0.85Ba
0.15Zr
4(PO
4)
6With (NH
4)
2HPO
4Mol ratio 0.95～1:6～6.5, with Ca
0.85Ba
0.15Zr
4(PO
4)
6Drips of solution is added to (NH
4)
2HPO
4In the solution; The throw out that is generated adds the ethanol of 3～5 times of throw out quality after centrifuging, in stir speed (S.S.) be to stir 30～40 minutes under the condition of 200～450rpm; Promptly carry out dispersion treatment; Place the ebullient water-bath to heat in beaker then, and constantly stir beaker inner suspension liquid, up to evaporate to dryness; Through 850 ℃～950 ℃ calcinings 1～2 hour, calcining finished and grinds behind the naturally cooling, obtains the superfine powder that median size is the CBZP of 8.12～9.12 μ m again;
(2) the acid precipitation legal system is equipped with active SiO
2: water glass and hydrochloric acid are got in ratio 1:1.85～2 by mole number, under the condition of stir speed (S.S.) 400～800rpm, with its mixing, and add the dilution of volume fraction 10%～25% water, and keeping the PH of reaction solution is between 6.5～7.5, makes SiO
2The condensation sedimentation speed be maximum, deposition through centrifuging, and with distilled water wash 2～5 times after, calcined 1～2.5 hour down at 850 ℃～1000 ℃, obtaining median size after the grinding is the active SiO of 13.8～15.8 μ m
2
(3) at first in the superfine powder of the CBZP that step (1) obtains, add massfraction 3% sintering aid ZnO, again with the SiO that obtains in the step (2)
2Add according to massfraction 1～4%,, even with ground and mixed, with powder dry-pressing formed under 80MPa be the right cylinder biscuit of φ 5 * 20mm, obtained the CBZP pottery then at 1050 ℃～1200 ℃ times normal pressure-sintered 1.5～2.5 hours.
ZrOCl in the said step (1)
2The concentration of solution is 0.48～0.52M, (NH
4)
2HPO
4The concentration of solution is 0.95～1.05M.
Said ethanol is the analytical pure absolute ethyl alcohol.
Said water glass and hydrochloric acid are analytical pure.
Said sintering aid ZnO is 99.5% analytical pure, and particle diameter 12.605 μ m are common commercially available.
Advantage of the present invention and beneficial effect:
The present invention uses coprecipitation method and prepares zero thermal expansion stupalith Ca
0. 85Ba
0.15Zr
4(PO
4)
6The time, when adding sintering aid 3%ZnO, add 1% active SiO again
2Can more efficiently improve the resistance to sudden heating of CBZP pottery; The thermal shocking that sample has experienced 5 900 ℃ of temperature difference is not ruptured yet; Than the sample (fracture has just taken place in the thermal shocking of only having experienced 2 900 ℃ of temperature difference) that originally only adds the 3%ZnO sintering aid; Resistance to sudden heating significantly improves, and this method has that technology is simple, product purity is high, is easy to realize the advantage of suitability for industrialized production.
Description of drawings:
Fig. 1 is SiO
2 Addition 0% time CBZP pottery the thermal expansion curve;
Fig. 2 is SiO
2Addition 1% time CBZP pottery the thermal expansion curve;
Fig. 3 is SiO
2Addition 2% time CBZP pottery the thermal expansion curve;
Fig. 4 is SiO
2Addition 3% time CBZP pottery the thermal expansion curve;
Fig. 5 is SiO
2Addition 4% time CBZP pottery the thermal expansion curve.
Embodiment:
Below in conjunction with embodiment and accompanying drawing to the present invention to further specifying, but the invention is not restricted to the following stated scope.
Comparative Examples:
(1) coprecipitation method prepares Ca
0. 85Ba
0.15Zr
4(PO
4)
6Superfine powder: according to Ca
0.85Ba
0.15Zr
4(PO
4)
6The proportioning of molecular formula takes by weighing CaCO
3And BaCO
3Be dissolved in the ZrOCl that concentration is 0.48M
2In the solution, under stirring condition, according to Ca
0.85Ba
0.15Zr
4(PO
4)
6With (NH
4)
2HPO
4Mol ratio 0.95:6.5, with Ca
0.85Ba
0.15Zr
4(PO
4)
6Drips of solution is added to the (NH that concentration is 0.95M
4)
2HPO
4In the solution, the throw out that is generated adds the ethanol of 3 times of throw out quality after centrifuging; Be to stir 35 minutes under the condition of 200rpm in stir speed (S.S.), promptly carry out dispersion treatment, place the ebullient water-bath to heat in beaker then; And constantly stir beaker inner suspension liquid, up to evaporate to dryness; Through 850 ℃ of calcinings 2 hours, calcining finished and grinds behind the naturally cooling, obtains the superfine powder that median size is the CBZP of 8.12 μ m again;
(2) the acid precipitation legal system is equipped with active SiO
2: the ratio 1:1.85 by mole number gets water glass and hydrochloric acid; Under the condition of stir speed (S.S.) 400rpm with its mixing; And add the dilution of volume fraction 10% water, keeping the PH of reaction solution is 6.5, deposition through centrifuging, and with distilled water wash 4 times after; Calcined 1 hour down at 850 ℃, obtaining median size after the grinding is the active SiO of 15.8 μ m
2
(3) (knot auxiliary agent ZnO's is analytical pure at first in the superfine powder of the CBZP that step (1) obtains, to add massfraction 3% sintering aid ZnO; Particle diameter 12.605 μ m); Even with ground and mixed; With powder dry-pressing formed under 80MPa be the right cylinder biscuit of φ 5 * 20mm, obtained down the CBZP pottery in normal pressure-sintered 1.5 hours at 1050 ℃ then.(experimental result is shown in Fig. 1)
Embodiment 1:
(1) coprecipitation method prepares Ca
0. 85Ba
0.15Zr
4(PO
4)
6Superfine powder: according to Ca
0.85Ba
0.15Zr
4(PO
4)
6The proportioning of molecular formula takes by weighing CaCO
3And BaCO
3Be dissolved in the ZrOCl that concentration is 0.5M
2In the solution, under stirring condition, according to Ca
0.85Ba
0.15Zr
4(PO
4)
6With (NH
4)
2HPO
4Mol ratio 0.98:6, with Ca
0.85Ba
0.15Zr
4(PO
4)
6Drips of solution is added to the (NH that concentration is 1M
4)
2HPO
4In the solution, the throw out that is generated adds the ethanol of 4 times of throw out quality after centrifuging; Be to stir 30 minutes under the condition of 300rpm in stir speed (S.S.), promptly carry out dispersion treatment, place the ebullient water-bath to heat in beaker then; And constantly stir beaker inner suspension liquid, up to evaporate to dryness; Through 900 ℃ of calcinings 1 hour, calcining finished and grinds behind the naturally cooling, obtains the superfine powder that median size is the CBZP of 9.1 μ m again;
(2) the acid precipitation legal system is equipped with active SiO
2: the ratio 1:1.90 by mole number gets water glass and hydrochloric acid; Under the condition of stir speed (S.S.) 600rpm with its mixing; And add the dilution of volume fraction 21% water, keeping the PH of reaction solution is between 7.5, deposition through centrifuging, and with distilled water wash 2 times after; Calcined 2.5 hours down at 900 ℃, obtaining median size after the grinding is the active SiO of 14.8 μ m
2
(3) at first in the superfine powder of the CBZP that step (1) obtains, add massfraction 3% sintering aid ZnO (knot auxiliary agent ZnO's is analytical pure, particle diameter 12.605 μ m), again with the SiO that obtains in the step (2)
2Add according to massfraction 1% in the superfine powder of CBZP, even with ground and mixed, with powder dry-pressing formed under 80MPa be the right cylinder biscuit of φ 5 * 20mm, obtained the CBZP pottery then at 1100 ℃ times normal pressure-sintered 2 hours.(experimental result is as shown in Figure 2)
Embodiment 2:
(1) coprecipitation method prepares Ca
0. 85Ba
0.15Zr
4(PO
4)
6Superfine powder: according to Ca
0.85Ba
0.15Zr
4(PO
4)
6The proportioning of molecular formula takes by weighing CaCO
3And BaCO
3Be dissolved in the ZrOCl that concentration is 0.52M
2In the solution, under stirring condition, according to Ca
0.85Ba
0.15Zr
4(PO
4)
6With (NH
4)
2HPO
4Mol ratio 1:6.2, with Ca
0.85Ba
0.15Zr
4(PO
4)
6Drips of solution is added to the (NH that concentration is 1.05M
4)
2HPO
4In the solution, the throw out that is generated adds the ethanol of 5 times of throw out quality after centrifuging; Be to stir 40 minutes under the condition of 450rpm in stir speed (S.S.), promptly carry out dispersion treatment, place the ebullient water-bath to heat in beaker then; And constantly stir beaker inner suspension liquid, up to evaporate to dryness; Through 950 ℃ of calcinings 1.5 hours, calcining finished and grinds behind the naturally cooling, obtains the superfine powder that median size is the CBZP of 9.12 μ m again;
(2) the acid precipitation legal system is equipped with active SiO
2: the ratio 1:1.90 by mole number gets water glass and hydrochloric acid; Under the condition of stir speed (S.S.) 600rpm with its mixing; And add the dilution of volume fraction 21% water, keeping the PH of reaction solution is 7.5, deposition through centrifuging, and with distilled water wash 2 times after; Calcined 2.5 hours down at 900 ℃, obtaining median size after the grinding is the active SiO of 14.8 μ m
2
(3) at first in the superfine powder of the CBZP that step (1) obtains, add massfraction 3% sintering aid ZnO (knot auxiliary agent ZnO's is analytical pure, particle diameter 12.605 μ m), again with the SiO that obtains in the step (2)
2Add according to massfraction 2% in the superfine powder of CBZP, even with ground and mixed, with powder dry-pressing formed under 80MPa be the right cylinder biscuit of φ 5 * 20mm, obtained the CBZP pottery then at 1100 ℃ times normal pressure-sintered 2 hours.(experimental result is as shown in Figure 3)
Embodiment 3:
(1) coprecipitation method prepares Ca
0. 85Ba
0.15Zr
4(PO
4)
6Superfine powder: according to Ca
0.85Ba
0.15Zr
4(PO
4)
6The proportioning of molecular formula takes by weighing CaCO
3And BaCO
3Be dissolved in the ZrOCl that concentration is 0.51M
2In the solution, under stirring condition, according to Ca
0.85Ba
0.15Zr
4(PO
4)
6With (NH
4)
2HPO
4Mol ratio 0.96:6.3, with Ca
0.85Ba
0.15Zr
4(PO
4)
6Drips of solution is added to the (NH that concentration is 0.98M
4)
2HPO
4In the solution, the throw out that is generated adds the ethanol of 5 times of throw out quality after centrifuging; Be to stir 38 minutes under the condition of 450rpm in stir speed (S.S.), promptly carry out dispersion treatment, place the ebullient water-bath to heat in beaker then; And constantly stir beaker inner suspension liquid, up to evaporate to dryness; Through 950 ℃ of calcinings 1.6 hours, calcining finished and grinds behind the naturally cooling, obtains the superfine powder that median size is the CBZP of 8.60 μ m again;
(2) the acid precipitation legal system is equipped with active SiO
2: the ratio 1:2 by mole number gets water glass and hydrochloric acid; Under the condition of stir speed (S.S.) 800rpm with its mixing; And add the dilution of volume fraction 25% water, keeping the PH of reaction solution is 7, deposition through centrifuging, and with distilled water wash 5 times after; Calcined 2 hours down at 1000 ℃, obtaining median size after the grinding is the active SiO of 13.8 μ m
2
(3) at first in the superfine powder of the CBZP that step (1) obtains, add massfraction 3% sintering aid ZnO (knot auxiliary agent ZnO's is analytical pure, particle diameter 12.605 μ m), again with the SiO that obtains in the step (2)
2Add according to massfraction 3% in the superfine powder of CBZP, even with ground and mixed, with powder dry-pressing formed under 80MPa be the right cylinder biscuit of φ 5 * 20mm, obtained the CBZP pottery then at 1200 ℃ times normal pressure-sintered 2.5 hours.(experimental result is as shown in Figure 4)
Embodiment 4:
(1) coprecipitation method prepares Ca
0. 85Ba
0.15Zr
4(PO
4)
6Superfine powder: according to Ca
0.85Ba
0.15Zr
4(PO
4)
6The proportioning of molecular formula takes by weighing CaCO
3And BaCO
3Be dissolved in the ZrOCl that concentration is 0.48M
2In the solution, under stirring condition, according to Ca
0.85Ba
0.15Zr
4(PO
4)
6With (NH
4)
2HPO
4Mol ratio 0.95:6.5, with Ca
0.85Ba
0.15Zr
4(PO
4)
6Drips of solution is added to the (NH that concentration is 0.95M
4)
2HPO
4In the solution, the throw out that is generated adds the ethanol of 3 times of throw out quality after centrifuging; Be to stir 35 minutes under the condition of 200rpm in stir speed (S.S.), promptly carry out dispersion treatment, place the ebullient water-bath to heat in beaker then; And constantly stir beaker inner suspension liquid, up to evaporate to dryness; Through 850 ℃ of calcinings 2 hours, calcining finished and grinds behind the naturally cooling, obtains the superfine powder that median size is the CBZP of 8.12 μ m again;
(2) the acid precipitation legal system is equipped with active SiO
2: the ratio 1:1.85 by mole number gets water glass and hydrochloric acid; Under the condition of stir speed (S.S.) 400rpm with its mixing; And add the dilution of volume fraction 10% water, keeping the PH of reaction solution is 6.5, deposition through centrifuging, and with distilled water wash 4 times after; Calcined 1 hour down at 850 ℃, obtaining median size after the grinding is the active SiO of 15.8 μ m
2
(3) at first in the superfine powder of the CBZP that step (1) obtains, add massfraction 3% sintering aid ZnO (knot auxiliary agent ZnO's is analytical pure, particle diameter 12.605 μ m), again with the SiO that obtains in the step (2)
2Add according to massfraction 4% in the superfine powder of CBZP, even with ground and mixed, with powder dry-pressing formed under 80MPa be the right cylinder biscuit of φ 5 * 20mm, obtained the CBZP pottery then at 1200 ℃ times normal pressure-sintered 2.5 hours.(experimental result is as shown in Figure 5)
The testing tool of experimental result is the Japanese Thermdflex of Rigaku Denki Co., Ltd apparatus for thermal analysis.Measuring method is thermo-mechanical analysis (TMA) compression method, and on-load pressure is 5g, and the thermal expansion curve is also measured with same set of device.With the thermo-mechanical analysis compression method it has been carried out the test of mean coefficient of linear thermal expansion and thermal expansion curve; Resistance to sudden heating with the big or small exosyndrome material of hysteresis loop on the thermal expansion curve; Simultaneously with sample thermal shocking repeatedly under 900 ℃ of temperature difference, up to the checking that experimentizes of thermal shocking number of times that eyes can observed tiny crack experiences occurring.
Because polycrystalline ceramics inside has the cause of tiny crack, when sample when room temperature heats, the thermal expansion of generation at first is used for closed tiny crack; Make polycrystal show low-down thermal expansivity, tiny crack is many more, and then the coefficient of expansion is low more; Along with the rising of Heating temperature, the crackle width reduces linearity, will reconfigure again during to certain temperature; As long as the magnetism (being London-Vander Walls Force) of this moment is even as big as closed crackle, sample begins again to expand so, and sample interior will crack again in the time of refrigerative; So just cause hysteresis phenomenon, promptly on heating-refrigerative thermal expansion curve, hysteresis loop occurred.If the area that hysteresis loop surrounds is big more, explain that the thermal expansion anisotropy of this sample is also big more, then be easy to generate tiny crack more, and the formation of tiny crack will cause mechanical strength to descend, the thermal shock resistance variation.Therefore, can use the quality of the size reflection resistance to sudden heating of hysteresis loop.
Add active SiO
2Amount and its average coefficient of linear expansion (Thermal Expansion Coefficient is called for short TEC) in 20～1000 ℃ between relation as shown in table 1 below.
The thermal expansivity of CBZP pottery during the different addition of table 1
| Add SiO 2Amount/% 0 1 2 3 4 |
| TEC ×10 -6/ ℃ -1 0.6 1.6 1.4 2.6 1.6 |
Visible by last table, active SiO
2Interpolation the mean thermal expansion coefficients of CBZP pottery is raise to some extent, this possibly be since second generate mutually cause, but satisfy low-thermal-expansion α basically<2 * 10
-6/ ℃ requirement.
The analysis of experimental result: active SiO
2Addition to the influence of CBZP pottery resistance to sudden heating
Accompanying drawing is that the CBZP powder is added 0,1%, 2%, 3%, 4% active SiO respectively again when adding 3%ZnO
2Five kinds of CBZP ceramic samples that obtain at 1100 ℃ of following sintering 2h; Be heated to the intensification-temperature lowering curve that is cooled to 100 ℃ after 1000 ℃ again from room temperature, temperature rate is controlled at 10 ℃/min, and ordinate zou △ L/Lso representes relative linear expansivity among the figure; Lso is a sample length at room temperature, and △ L is the absolute expansion amount.
Can find out by accompanying drawing 1～5, not add SiO
2Sample (Fig. 1), have bigger thermal hysteresis ring on the thermal expansion curve, explain that still there is bigger thermal expansion anisotropy in its single crystal; There is tangible tiny crack polycrystal pottery inside; The poor thermal shock resistance of sample, this is because sintering aid ZnO when promoting densification, has also greatly promoted grain growing; Make size of microcrystal might surpass produce the critical particle diameter of tiny crack, cause a large amount of tiny cracks occurring in the sintered compact and weakened its resistance to sudden heating.
When adding ZnO, add active SiO
2Sample in, (Fig. 2), (Fig. 3), (Fig. 4), (Fig. 5) hysteresis loop do not add active SiO on the thermal expansion curve
2Sample (Fig. 1) thermal hysteresis ring obviously reduce, the result shows, if when adding sintering aids, add grain growth inhibitor SiO
2, utilize the second phase pinning crystal boundary, suitably control grain growing, particle diameter is remained on below the critical particle diameter that produces tiny crack, then might avoid the generation of tiny crack, this is the effective way that improves CBZP series ceramic material resistance to sudden heating.
Through relatively add 1%, 2%,, 3%, 4% active SiO
2The size of hysteresis loop is found on the resulting thermal expansion curve, (Fig. 2) the middle 1% active SiO that adds
2The thermal hysteresis ring of sample minimum, be 3%, 2% secondly, show the better heat-resisting impact.
The thermal shock resistance of CBZP pottery
Most of potteries produce with use in all be in the condition of high temperature, so can receive temperature variation and cause the member Cracking Failure.Material withstand temp cataclysm and non-destructive ability is heat-shock resistance.The material anti-thermal shock is destroyed and can be divided into two big types: one, and instantaneous fracture is referred to as (thermal shocking) thermal shock fatigue; Two, under the heat shock cycling effect, material occurs cracking earlier, peels off, and is cracked then and rotten, destroys to whole eventually, is referred to as the thermal shock damage.
In order further to verify above-mentioned conclusion, the sample that this is serial is chilling under 900 ℃ of temperature difference, and the thermal shocking number of times that ceramics sample experienced is as shown in table 2.
Table 2 adds active SiO
2
Amount and the thermal shocking number of times of its experience
| Add active SiO 2Amount/% | 0 | 1 | 2% | 3％ | 4% |
| The thermal shocking number of times that receives | 2 times | 5 times | 4 times | 4 times | 3 times |
| Whether rupture | Rupture | Fracture not yet | Rupture | Rupture | Rupture |
Find not add SiO
2The thermal shocking that the sample that only adds 3%ZnO has only experienced 2 900 ℃ of temperature difference has just been ruptured, and all the other samples have all added SiO on the basis of interpolation 3%ZnO
2, add 2% and 3% SiO
2The sample thermal shocking of having experienced 4 900 ℃ of temperature difference all rupture, added 4%SiO
2The sample thermal shocking of having experienced 3 900 ℃ of temperature difference just rupture, and added 1%SiO
2The sample thermal shocking of having experienced 5 900 ℃ of temperature difference do not rupture yet, showed good resistance to sudden heating, this with Fig. 1 thermal expansion curve on situation about being reflected conform to.
Claims (3)
1. one kind is improved Ca
0.85Ba
0.15Zr
4(PO
4)
6The method of stupalith resistance to sudden heating is characterized in that comprising following concrete steps:
(1) coprecipitation method prepares Ca
0. 85Ba
0.15Zr
4(PO
4)
6Superfine powder: according to Ca
0.85Ba
0.15Zr
4(PO
4)
6The proportioning of molecular formula takes by weighing CaCO
3And BaCO
3The ZrOCl that is dissolved in
2In the solution, under stirring condition, according to Ca
0.85Ba
0.15Zr
4(PO
4)
6With (NH
4)
2HPO
4Mol ratio 0.95～1:6～6.5, with Ca
0.85Ba
0.15Zr
4(PO
4)
6Drips of solution is added to (NH
4)
2HPO
4In the solution; The throw out that is generated adds the ethanol of 3～5 times of throw out quality after centrifuging, in stir speed (S.S.) be to stir 30～40 minutes under the condition of 200～450rpm; Promptly carry out dispersion treatment; Place the ebullient water-bath to heat in beaker then, and constantly stir beaker inner suspension liquid, up to evaporate to dryness; Through 850 ℃～950 ℃ calcinings 1～2 hour, calcining finished and grinds behind the naturally cooling, obtains the superfine powder that median size is the CBZP of 8.12～9.12 μ m again;
(2) the acid precipitation legal system is equipped with active SiO
2: water glass and hydrochloric acid are got in ratio 1:1.85～2 by mole number; Under the condition of stir speed (S.S.) 400～800rpm with its mixing; And add the dilution of volume fraction 10%～25% water, keeping the PH of reaction solution is between 6.5～7.5, deposition through centrifuging, and with distilled water wash 2～5 times after; Calcined 1～2.5 hour down at 850 ℃～1000 ℃, obtaining median size after the grinding is the active SiO of 13.8～15.8 μ m
2
(3) at first in the superfine powder of the CBZP that step (1) obtains, add sintering aid, again with the SiO that obtains in the step (2)
2Add in the superfine powder of CBZP according to massfraction 1～4%, even with ground and mixed, the powder dry-pressing is become biscuit, then at 1050 ℃～1200 ℃ resistance to sudden heating CBZP potteries that were improved in normal pressure-sintered 1.5～2.5 hours down.
2. according to claims 1 described raising Ca
0.85Ba
0.15Zr
4(PO
4)
6The method of stupalith resistance to sudden heating is characterized in that: ZrOCl in the said step (1)
2The concentration of solution is 0.48～0.52M, (NH
4)
2HPO
4The concentration of solution is 0.95～1.05M.
3. according to claims 1 described raising Ca
0.85Ba
0.15Zr
4(PO
4)
6The method of stupalith resistance to sudden heating is characterized in that: said sintering aid is ZnO, analytical pure, and particle diameter 12.605 μ m, addition are 3% of CBZP superfine powder massfraction.
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Cited By (2)
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| CN108164262A (en) * | 2016-12-07 | 2018-06-15 | 辽宁法库陶瓷工程技术研究中心 | The preparation method of NZP races ceramics that a kind of coefficient of thermal expansion is continuously adjusted |
| CN111848156A (en) * | 2019-04-25 | 2020-10-30 | 比亚迪股份有限公司 | Ceramic composition, ceramic and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164262A (en) * | 2016-12-07 | 2018-06-15 | 辽宁法库陶瓷工程技术研究中心 | The preparation method of NZP races ceramics that a kind of coefficient of thermal expansion is continuously adjusted |
| CN111848156A (en) * | 2019-04-25 | 2020-10-30 | 比亚迪股份有限公司 | Ceramic composition, ceramic and preparation method thereof |
| CN111848156B (en) * | 2019-04-25 | 2021-11-12 | 比亚迪股份有限公司 | Ceramic composition, ceramic and preparation method thereof |
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