CN116835962A - 0-3 type leadless piezoelectric composite material and synthesis method thereof - Google Patents
0-3 type leadless piezoelectric composite material and synthesis method thereof Download PDFInfo
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- CN116835962A CN116835962A CN202310732421.2A CN202310732421A CN116835962A CN 116835962 A CN116835962 A CN 116835962A CN 202310732421 A CN202310732421 A CN 202310732421A CN 116835962 A CN116835962 A CN 116835962A
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- Prior art keywords
- composite material
- piezoelectric
- piezoelectric composite
- phase
- titanium slag
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- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000001308 synthesis method Methods 0.000 title abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 70
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 68
- 239000002893 slag Substances 0.000 claims abstract description 63
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 24
- 239000010881 fly ash Substances 0.000 claims abstract description 22
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 21
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 10
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 5
- 239000010433 feldspar Substances 0.000 claims abstract description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 48
- 239000002994 raw material Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 36
- 229910052709 silver Inorganic materials 0.000 claims description 36
- 239000004332 silver Substances 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000000498 ball milling Methods 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 12
- 238000007650 screen-printing Methods 0.000 claims description 12
- 229920002545 silicone oil Polymers 0.000 claims description 12
- 159000000009 barium salts Chemical class 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 40
- 239000012071 phase Substances 0.000 description 28
- 238000004321 preservation Methods 0.000 description 26
- 238000005303 weighing Methods 0.000 description 23
- 239000004568 cement Substances 0.000 description 22
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 20
- 230000008569 process Effects 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 11
- 239000011575 calcium Substances 0.000 description 11
- 238000007873 sieving Methods 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 238000005245 sintering Methods 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910017639 MgSi Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052656 albite Inorganic materials 0.000 description 2
- 229910052661 anorthite Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052916 barium silicate Inorganic materials 0.000 description 2
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229910052611 pyroxene Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- LVJIUWYFPCLBIP-UHFFFAOYSA-N [Mg].[Ti].[Fe] Chemical compound [Mg].[Ti].[Fe] LVJIUWYFPCLBIP-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910002115 bismuth titanate Inorganic materials 0.000 description 1
- 235000012215 calcium aluminium silicate Nutrition 0.000 description 1
- 239000000404 calcium aluminium silicate Substances 0.000 description 1
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 description 1
- 229940078583 calcium aluminosilicate Drugs 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/6567—Treatment time
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
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Abstract
The invention discloses a 0-3 type leadless piezoelectric composite material and a synthesis method thereof, belonging to the technical field of piezoelectric composite material preparation, and comprising a piezoelectric phase and an aluminosilicate phase, wherein the piezoelectric phase is perovskite type barium titanate and bismuth ferrite, the aluminosilicate phase is sodium feldspar with a frame-shaped structure, fly ash, molten titanium slag, barium carbonate, bismuth oxide and sodium salt are uniformly mixed according to proportion, and then are roasted under the preset temperature and air atmosphere to prepare the composite material containing bismuth ferrite, barium titanate and aluminosilicate.
Description
Technical Field
The invention mainly relates to the technical field of piezoelectric composite material preparation, in particular to a 0-3 type leadless piezoelectric composite material and a synthesis method thereof.
Background
The Cement-based piezoelectric composite material (CPC) has good compatibility with a concrete structure, and has wide application prospects in the fields of concrete structure health detection, dynamic load Weighing (WIM) and the like. CPC generally takes cement as a matrix, lead zirconate titanate (Lead zirconate titanate, PZT) is used as a functional phase, and the CPC can be divided into 0-3,1-3 and 2-2 types according to different connection modes of the PZT phases, wherein the 0-3 type CPC is prepared by filling PZT powder in a three-dimensional communicated cement matrix, has the advantages of stable performance, good electromechanical coupling, easy regulation and modification and the like, is more suitable for being used as an embedded sensor for intelligent monitoring, however, the traditional synthesis process is long and complicated, the prepared CPC is expensive, especially the firing of cement and the extraction process of titanium element are high in energy consumption and large in emission and amplification.
In the technology of the present lead-free piezoelectric composite material, for example, the application publication No. 202010401284.0, a carbon-enhanced lead-free cement-based piezoelectric composite material, a preparation method and application thereof are disclosed, the method comprises uniformly mixing carbon, lead-free piezoelectric ceramic, cement and water, and aging to obtain the lead-free cement-based piezoelectric composite material, wherein the lead-free piezoelectric ceramic comprises barium titanate (BaTiO 3 ) Bismuth ferrite (BiFeO) 3 ) Bismuth titanate (BiTiO) 3 ) Sodium niobate (NaNbO) 3 ) Etc., however, the synthetic raw materials of the above CPC are still based on pure reagents, such as expensive TiO 2 Etc. belong to the traditional synthesis method, the firing of cement in raw materials needs to consume a large amount of energy and is accompanied by a large amount of CO 2 Is a typical high energy consumption, high emission process.
For example, in the art of application No. 202110471834.0, a method for preparing a gelled composite material having piezoelectric properties, which comprises reacting titanium-containing blast furnace slag with PbO, zrO, and a gelled composite material and the use thereof are disclosed 2 Uniformly mixing and roasting to obtain the gel composite material with piezoelectricity, wherein the piezoelectric phase in the composite material is PZT, and the gel phase is Ca 2 MgSi 2 O 7 In order to promote Pb and Zr to be enriched in perovskite, the method adopts a harsher heat system (heat preservation at 600-768 ℃ for 0.5-1.5 h and heat preservation at 600-768 ℃ for 1.5-2.5 h) and the gelation active phase in the prepared CPC is Ca 2 MgSi 2 O 7 It is well known that the gelling process of cement relies on hydration of dicalcium silicate, tricalcium silicate or tricalcium aluminate, whereas anorthite phase (Ca 2 MgSi 2 O 7 ) After CPC prepared by the method is pressed and molded, an aging experiment is carried out for 28 days under the conditions of constant temperature and constant humidity, and the result shows that the aged CPC has low mechanical strength, is easy to pulverize, can not meet the requirement of an actual use scene on the mechanical property of a material, and has sensitivity to roasting temperature and Ca 2 MgSi 2 O 7 The formation of the three-dimensional communication structure needs to be insulated above the melting starting temperature>1200 c), however at this temperature Pb will preferentially react with SiO 4 Tetrahedral bonding inhibits the formation of PZT phases, in other words, there is a significant paradox to the basic principle of the above method, namely that the synthesized CPC cannot achieve both mechanical and piezoelectric properties, and in addition, the synthesized CPC is a lead-containing material, which has a potential threat to the environment.
The traditional CPC synthesis method usually takes pure reagent as raw material, the prepared CPC is expensive, the traditional synthesis process is long in flow, the titanium extraction and cement firing processes are both high-energy consumption and high-emission processes, about 0.1 ton of standard coal is required to be consumed for each 1 ton of cement clinker produced, about 1 ton of CO2 is discharged, at least 0.67 ton of chloride slag is discharged for each 1 ton of TiO2 produced, attempts to synthesize CPC from titanium-containing blast furnace slag have been reported, but the mineral phase reconstruction process cannot reconcile the piezoelectric performance and the mechanical performance of the material, the prepared CPC cannot meet the actual use requirements, and is a lead-containing material and has potential threat to the environment.
The application of CPC in civil engineering is faced with long-term impact of dynamic load, besides piezoelectric performance, the CPC has to have good mechanical properties, and meanwhile, the complex natural environment functions, such as acid rain erosion, rain leaching and the like, require the CPC to have environmental friendliness and structural stability, and large-scale application, such as an array sensor in a roadbed sensing system and the like, and also require the price of the CPC to be low enough, so that a green process for synthesizing a lead-free piezoelectric composite material with low cost is needed at present.
Disclosure of Invention
Aiming at the technical problem that the prior art solution is too single, the technical scheme of the invention is obviously different from the prior art solution, and particularly the invention mainly provides a 0-3 type leadless piezoelectric composite material and a synthesis method thereof, which are used for solving the technical problems that the prior CPC synthesis method provided in the prior art is high in price and long in synthesis process flow, wherein the extraction and cement firing processes of titanium are both high-energy consumption and high-emission processes, the mineral phase reconstruction process can not be used for harmonizing the piezoelectric property and the mechanical property of the material, the prepared CPC can not meet the actual use requirement, is a lead-containing material and has potential threat to the environment.
The technical scheme adopted for solving the technical problems is as follows:
a0-3 type leadless piezoelectric composite material comprises piezoelectric phase and aluminosilicate phase, wherein the piezoelectric phase is perovskite type barium titanate and bismuth ferrite, and the chemical formula is BaTiO 3 With BiFeO 3 Ba and Bi are respectively positioned at A position of perovskite structure, ti and Fe are respectively positioned at B position, baTiO 3 With BiFeO 3 The solid solution perovskite structure has a quasi-homotype phase boundary, gives the material good piezoelectric performance, and the aluminosilicate phase is sodium feldspar with a frame-shaped structure and has a chemical formula of Na 2 (Mg,Al)(Al,Si) 2 O 7 Wherein Na is positioned in the center of the polyhedron, mg and Si are respectively positioned in the center of the octahedron and the center of the tetrahedron, al is positioned in the center of the octahedron or the center of the tetrahedron, and the partial substitution of Mg or Si is performed, the volume fraction of the piezoelectric phase in the composite material is 45.0-77.0%, wherein BaTiO 3 Volume fraction of 19-39%, biFeO 3 The volume fraction of (2) is 17-34%; silicate phase accounts for 23.0-55.0%.
Preferably, the mass fraction of Ba in the piezoelectric phase is 17-32%, the mass fraction of Ti is 6-17%, the mass fraction of Bi is 15-34%, and the mass fraction of Fe is 3-9%.
Preferably, the piezoelectric coefficient d of the piezoelectric composite material 33 The pressure resistance is 62-74 MPa, the bending resistance is 117-130 MPa, and the Vickers hardness is 510HV 2/20-1870 HV2/20.
The synthesis method of the 0-3 type leadless piezoelectric composite material comprises the following steps of: crushing and ball milling molten titanium slag, mixing the crushed and ball milled titanium slag with fly ash, barium salt, bismuth oxide and sodium salt, fully mixing the mixture, pressing the mixture to form, heating the mixture to 800-950 ℃ under an air atmosphere, preserving heat for 0.5-2 h, then heating the mixture to 1050-1200 ℃, preserving heat for 0.5-2 h, cooling the sample along with a furnace to room temperature, polishing the sintered block sample to be flat on two sides, coating conductive silver paste on two sides of a wafer through a screen printing template, putting the wafer into a muffle furnace for silver firing, wherein the silver firing temperature is 600 ℃, the preserving heat time is 30min, polarizing the wafer in silicone oil under the direct current voltage of 6kV after the silver firing is finished, and the polarizing temperature is 90-120 ℃ and the polarizing time is 20-40 min, thus obtaining the piezoelectric composite material;
the method comprises the steps of taking melted titanium slag (Titaniferous slag, TS) and fly ash (Pulverized fuel ash, PFA) as main raw materials (typical components of the two are shown in table 1), adding barium salt, bismuth oxide and sodium salt, uniformly mixing, pressing and forming, roasting at a preset temperature to reconstruct mineral phases, and converting titanium-magnesium iron ore, glass bodies, mullite and quartz in the raw materials into perovskite and albite, wherein the mineral phase reconstruction mechanism is shown in figure 1.
TABLE 1 melting titanium slag and fly ash main chemical composition
Preferably, the sodium salt is NaOH or Na 2 CO 3 The mass of the sodium salt accounts for 1.7-4.1% of the total weight of the raw materials.
Preferably, the titanium content in the molten titanium slag is 42.4-60.0%, the iron content is 20.8-39.6%, the mass ratio of the fly ash to the molten titanium slag is 20-40%, and the calcium content is less than 5% (calculated by CaO);
PFA is low-calcium fly ash, the calcium content is less than 5%, and Ca ions are easy to combine with TiO 6 Octahedron incorporation into CaTiO 3 Inhibition of BaTiO 3 Therefore, the calcium content of the raw material is not excessively high.
Preferably, the barium salt is BaCO 3 The mass ratio of the barium salt to the total amount of the raw materials is 29.2-40.1%.
Preferably, the bismuth oxide is Bi 2 O 3 The mass proportion of bismuth oxide is 16.5-32.3% of the total amount of the raw materials.
Preferably, ba ions and SiO 4 The tetrahedral bonding force is strong, and barium-containing silicate is preferentially formed instead of BaTiO 3 After the sodium salt is introduced, siO 4 Tetrahedra preferentially bind to Na ions, as shown in fig. 2, promoting BaTiO 3 On the other hand, the low-calcium fly ash has high melting point>1500 ℃, the sodium salt can be used as a fluxing agent to reduce the melting point of the mixture, improve the dynamic conditions of the reaction between solid phases and promote the transformation of glass phase, mullite, quartz and pyroxene phase to feldspar phase (the sodium salt can be used with SiO) 2 、Al 2 O 3 And pyroxene phase reaction to generate a composite structure of albite and anorthite solid solution);
as can be seen from FIG. 2, baCO is a catalyst that when the temperature is greater than 425 degrees 3 Can spontaneously and SiO 2 The reaction to form barium silicate means that barium salt can combine with silicon oxygen tetrahedron during mineral phase reconstruction, thus inhibiting the formation of barium titanate, when NaOH exists in the system, the barium silicate can spontaneously react with magnesium titanate at a temperature ranging from 0 to 1200 ℃ to form sodium silicate and barium titanate, as shown by the lowest curve in fig. 2, which shows that sodium salt can inhibit the combination of barium salt and silicon oxygen tetrahedron, and promote the formation of barium titanate.
Preferably, the roasting process in the synthesis method adopts a two-step method, namely heating to 800-950 ℃ under the air atmosphere, preserving heat for 0.5-2 h, then heating to 1050-1200 ℃ and preserving heat for 0.5-2 h, because bismuth oxide is prepared at high temperature>950 ℃ is easy to volatilize, and the mixture is firstly kept at the temperature of 800-950 ℃ during roasting, while the BaTiO 3 The generation temperature of the catalyst is relatively high, the mixture is heated to over 1050 ℃ for heat preservation after the heat preservation in the first stage is finished, and the main purpose of two-stage roasting is to avoid volatilization of bismuth oxide.
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with the traditional cement-based piezoelectric composite material, the main mineral phases in the traditional 0-3 cement-based piezoelectric composite material are piezoelectric ceramic and calcium aluminosilicate, obvious phase interfaces and pores exist between piezoelectric ceramic particles and aluminosilicate through cement aging molding, and the mechanical property of the material is relatively low.
(2) Compared with the traditional synthesis method, the traditional CPC synthesis method generally takes pure reagent as raw materials, piezoelectric ceramics and fired cement are prepared respectively, then the piezoelectric ceramics and the fired cement are fully and uniformly mixed and then aged and formed, as shown in figure 3, the traditional process is complex, the flow is long, pollution is heavy, the titanium extraction and cement firing processes are high in energy consumption and large in emission, the synthesis process directly prepares the leadless piezoelectric composite material by taking molten titanium slag and coal ash as raw materials through mineral phase reconstruction, the titanium extraction and cement firing processes are not needed, the process flow is short, solid waste emission is avoided, and compared with the traditional synthesis method, each 1 ton of leadless CPC is produced, the method can reduce the emission of 0.62 ton of carbon dioxide, reduce the emission of 0.38 ton of solid waste, reduce 90% of energy consumption, lead-free CPC shows wide application prospects in the field of civil engineering, such as concrete structure health detection, roadbed sensing and the like, however, the large-scale use of CPC is still limited by adverse factors of high cost, and compared with the traditional method, the cost of the preparation method is reduced by about 1700 yuan/ton.
The invention will be explained in detail below with reference to the drawings and specific embodiments.
Drawings
FIG. 1 is a schematic diagram of a mineral phase reconstruction mechanism in the preparation process of the piezoelectric composite material of the invention;
FIG. 2 is a graph showing the standard Gibbs free energy curve of a chemical reaction during mineral phase reconstitution according to the present invention;
FIG. 3 is a comparative diagram of the conventional synthetic process route for CPC of the present invention and the process route of the present invention;
FIG. 4 is a schematic view of a built-in piezoelectric sensor cement-based weighing beam of the present invention;
fig. 5 is a schematic diagram of a dynamic load weighing system of the present invention.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will be rendered by reference to the appended drawings, in which several embodiments of the invention are illustrated, but which may be embodied in different forms and are not limited to the embodiments described herein, which are, on the contrary, provided to provide a more thorough and complete disclosure of the invention.
It will be understood that when an element is referred to as being "mounted" on another element, it can be directly on the other element or intervening elements may be present, and when an element is referred to as being "connected" to the other element, it may be directly connected to the other element or intervening elements may also be present, the terms "vertical", "horizontal", "left", "right" and the like are used herein for the purpose of illustration only.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly connected to one of ordinary skill in the art to which this invention belongs, and the knowledge of terms used in the description of this invention herein for the purpose of describing particular embodiments is not intended to limit the invention, and the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The synthesis method of the 0-3 type leadless piezoelectric composite material comprises the following specific steps:
(1) And crushing and ball milling the molten titanium slag, and sieving the crushed and ball milled titanium slag with a 200-mesh sieve to obtain molten titanium slag powder.
(2) 10.0g of molten titanium slag powder, 2.5g of fly ash, 11.1g of barium carbonate, 10.7g of bismuth oxide and 2.0g of sodium hydroxide are respectively weighed and fully mixed.
(3) The mixture was pressed into a block sample at a pressure of 3MPa and dwell time was 20min.
(4) The above block was heated to 850℃under an air atmosphere and incubated for 1 hour.
(5) After the first-stage heat preservation is finished, the temperature is continuously raised to 1050 ℃, and the heat preservation is carried out for 1 hour.
(6) And after the heat preservation is finished, cooling the sample to room temperature along with a furnace to obtain the 0-3 type leadless piezoelectric composite material.
Reference is made to example 1:
taking 100g of the product of the invention as an example, the raw material components used are used in the mass ratios shown in Table 2.
TABLE 2 raw material composition to mass ratio
TiO in the melted titanium slag 2 The content is 42.4 percent, fe 2 O 3 The content is 39.6%, siO 2 6.4% MgO, 5.4% Al 2 O 3 The content was 3.4%.
The CaO content in the fly ash is less than 5.0%, wherein SiO 2 The content is 49.1 percent, al 2 O 3 The content was 40.8%.
The sodium salt is sodium hydroxide.
(1) Crushing and ball milling molten titanium slag, sieving with a 200-mesh sieve to obtain molten titanium slag powder, weighing molten titanium slag, barium carbonate and bismuth oxide according to the proportion in the table, fully mixing, weighing sodium hydroxide, adding the mixture, fully mixing again, pressing the mixture into a block sample under the pressure of 3MPa, and keeping the pressure for 20min.
(2) Heating the block sample to 850 ℃ under the air atmosphere, preserving heat for 1 hour, then continuously heating to 1050 ℃, preserving heat for 1 hour, and cooling the sample to room temperature along with a furnace after the heat preservation is finished.
(3) Polishing the block sample after high-temperature sintering until two surfaces are smooth, coating conductive silver paste on two sides of the wafer through screen printing templates, then placing the wafer into a muffle furnace for silver burning, wherein the silver burning temperature is 600 ℃, the heat preservation time is 30min, and polarizing the wafer in silicone oil under 6kV direct current voltage after silver burning is finished, wherein the polarizing temperature is 120 ℃, and the polarizing time is 30min, so that the piezoelectric composite material is obtained.
Reference is made to example 2:
taking 100g of the product of the invention as an example, the raw material components used are used in the mass ratios shown in Table 3.
TABLE 3 raw material composition to mass ratio
TiO in the melted titanium slag 2 The content is 45.0 percent, fe 2 O 3 The content is 36.8 percent, siO 2 6.4% MgO, 5.5% Al 2 O 3 The content was 3.4%.
The CaO content in the fly ash is less than 5.0%, wherein SiO 2 The content is 49.1 percent, al 2 O 3 The content was 40.8%.
The sodium salt is sodium hydroxide.
(1) Crushing and ball milling molten titanium slag, sieving with a 150-mesh sieve to obtain molten titanium slag powder, weighing molten titanium slag, barium carbonate and bismuth oxide according to the proportion in the table, fully mixing, weighing sodium hydroxide, adding the mixture, fully mixing again, pressing the mixture into a block sample under the pressure of 4MPa, and keeping the pressure for 15min.
(2) Heating the block sample to 800 ℃ in an air atmosphere, preserving heat for 1 hour, then continuously heating to 1000 ℃, preserving heat for 1 hour, and cooling the sample to room temperature along with a furnace after the heat preservation is finished.
(3) Polishing the block sample after high-temperature sintering until two surfaces are smooth, coating conductive silver paste on two sides of the wafer through screen printing templates, and then placing the wafer into a muffle furnace to burn silver, wherein the silver burning temperature is 600 ℃, and the heat preservation time is 30min. And (3) polarizing the wafer in silicone oil under the direct-current voltage of 6kV after silver burning, wherein the polarizing temperature is 100 ℃, and the polarizing time is 35min, so as to obtain the piezoelectric composite material.
Reference is made to example 3:
taking 100g of the product of the present invention as an example, the raw material components used to mass ratio are shown in Table 4.
TABLE 4 raw material composition to mass ratio
TiO in the melted titanium slag 2 The content is 50.0 percent, fe 2 O 3 The content is 31.5%, siO 2 6.4% MgO, 5.7% Al 2 O 3 The content was 3.3%.
The CaO content in the fly ash is less than 5.0%, wherein SiO 2 The content is 49.1 percent, al 2 O 3 The content was 40.8%.
The sodium salt is sodium hydroxide.
(1) Crushing and ball milling molten titanium slag, sieving with a 100-mesh sieve to obtain molten titanium slag powder, weighing molten titanium slag, barium carbonate and bismuth oxide according to the proportion in the table, fully mixing, weighing sodium hydroxide, adding the mixture, fully mixing again, pressing the mixture into a block sample under the pressure of 5MPa, and keeping the pressure for 10min.
(2) Heating the block sample to 900 ℃ in an air atmosphere, preserving heat for 1 hour, then continuously heating to 1100 ℃, preserving heat for 0.5 hour, and cooling the sample to room temperature along with a furnace after the heat preservation is finished.
(3) Polishing the block sample after high-temperature sintering until two surfaces are smooth, coating conductive silver paste on two sides of the wafer through screen printing templates, then placing the wafer into a muffle furnace for silver burning, wherein the silver burning temperature is 600 ℃, the heat preservation time is 30min, and polarizing the wafer in silicone oil under 6kV direct current voltage after silver burning is finished, wherein the polarizing temperature is 120 ℃, and the polarizing time is 25min, thus obtaining the piezoelectric composite material.
Reference is made to example 4:
taking 100g of the product of the present invention as an example, the raw material components used to mass ratio are shown in Table 5.
TABLE 5 raw material composition to mass ratio
TiO in the melted titanium slag 2 The content is 55.0%, fe 2 O 3 The content is 26.2%, siO 2 6.4% MgO, 5.9% Al 2 O 3 The content was 3.3%.
The CaO content in the fly ash is less than 5.0%, wherein SiO 2 The content is 49.1 percent, al 2 O 3 The content was 40.8%.
The sodium salt is sodium hydroxide.
(1) Crushing and ball milling molten titanium slag, sieving with a 200-mesh sieve to obtain molten titanium slag powder, weighing molten titanium slag, barium carbonate and bismuth oxide according to the proportion in the table, fully mixing, weighing sodium hydroxide, adding the mixture, fully mixing again, and pressing the mixture into a block sample under the pressure of 6MPa, wherein the pressure maintaining time is 5min.
(2) Heating the block sample to 950 ℃ in air atmosphere, preserving heat for 0.5 hour, then continuously heating to 1150 ℃, preserving heat for 0.5 hour, and cooling the sample to room temperature along with a furnace after the heat preservation is finished.
(3) Polishing the block sample after high-temperature sintering until two surfaces are smooth, coating conductive silver paste on two sides of the wafer through screen printing templates, then placing the wafer into a muffle furnace for silver burning, wherein the silver burning temperature is 600 ℃, the heat preservation time is 30min, and polarizing the wafer in silicone oil under 6kV direct current voltage after silver burning is finished, wherein the polarizing temperature is 120 ℃, and the polarizing time is 20min, so that the piezoelectric composite material is obtained.
Reference is made to example 5:
taking 100g of the product of the invention as an example, the raw material components used are used in the mass ratios shown in Table 6.
TABLE 6 raw material composition to mass ratio
TiO in the melted titanium slag 2 The content is 60.0 percent, fe 2 O 3 The content is 20.8 percent, siO 2 The content of the aluminum alloy is 6.5%, the content of MgO is 6.1%, and the content of the aluminum alloy is Al 2 O 3 The content was 3.2%.
The CaO content in the fly ash is less than 5.0%, wherein SiO 2 The content is 49.1 percent, al 2 O 3 The content was 40.8%.
The sodium salt is sodium carbonate.
(1) Crushing and ball milling molten titanium slag, sieving with a 200-mesh sieve to obtain molten titanium slag powder, weighing molten titanium slag, barium carbonate and bismuth oxide according to the proportion in the table, fully mixing, weighing sodium carbonate, adding into the mixture, fully mixing again, pressing the mixture into a block sample under the pressure of 3MPa, and keeping the pressure for 20min.
(2) The above block was heated to 950 ℃ in an air atmosphere and kept for 1 hour, then the temperature was further raised to 1050 ℃ and kept for 1 hour. And cooling the sample to room temperature along with the furnace after the heat preservation is finished.
(3) Polishing the block sample after high-temperature sintering until two surfaces are smooth, coating conductive silver paste on two sides of the wafer through screen printing templates, then placing the wafer into a muffle furnace for silver burning, wherein the silver burning temperature is 600 ℃, the heat preservation time is 30min, and polarizing the wafer in silicone oil under 6kV direct current voltage after silver burning is finished, wherein the polarizing temperature is 120 ℃, and the polarizing time is 20min, so that the piezoelectric composite material is obtained.
Reference is made to comparative example 1:
taking 100g of the product of the present invention as an example, the raw material components used to mass ratio are shown in Table 7.
TABLE 7 raw material composition to mass ratio
TiO in the melted titanium slag 2 The content is 42.4 percent, fe 2 O 3 The content is 39.6%, siO 2 6.4% MgO, 5.4% Al 2 O 3 The content was 3.4%.
The CaO content in the fly ash is less than 5.0%, wherein SiO 2 The content is 49.1 percent, al 2 O 3 The content was 40.8%.
(1) Crushing and ball milling molten titanium slag, sieving with a 200-mesh sieve to obtain molten titanium slag powder, weighing molten titanium slag, barium carbonate and bismuth oxide according to the proportion in the table, fully mixing, weighing sodium hydroxide, adding the mixture, fully mixing again, pressing the mixture into a block sample under the pressure of 3MPa, and keeping the pressure for 20min.
(2) Heating the block sample to 850 ℃ in an air atmosphere, preserving heat for 2 hours, then continuously heating to 1050 ℃, preserving heat for 2 hours, and cooling the sample to room temperature along with a furnace after the heat preservation is finished.
(3) Polishing the block sample after high-temperature sintering until two surfaces are smooth, coating conductive silver paste on two sides of the wafer through screen printing templates, then placing the wafer into a muffle furnace for silver burning, wherein the silver burning temperature is 600 ℃, the heat preservation time is 30min, and polarizing the wafer in silicone oil under 6kV direct current voltage after silver burning is finished, wherein the polarizing temperature is 90 ℃, and the polarizing time is 40min, so that the piezoelectric composite material is obtained.
Reference is made to comparative example 2:
taking 100g of the product of the present invention as an example, the raw material components used to mass ratio are shown in Table 8.
TABLE 8 raw material composition to mass ratio
TiO in the melted titanium slag 2 The content is 45.0 percent, fe 2 O 3 The content is 36.8 percent, siO 2 6.4% MgO, 5.5% Al 2 O 3 The content was 3.4%.
The sodium salt is sodium hydroxide.
(1) Crushing and ball milling molten titanium slag, sieving with a 150-mesh sieve to obtain molten titanium slag powder, weighing molten titanium slag, barium carbonate and bismuth oxide according to the proportion in the table, fully mixing, weighing sodium hydroxide, adding the mixture, fully mixing again, pressing the mixture into a block sample under the pressure of 4MPa, and keeping the pressure for 15min.
(2) Heating the block sample to 800 ℃ in an air atmosphere, preserving heat for 1 hour, then continuously heating to 1000 ℃, preserving heat for 1 hour, and cooling the sample to room temperature along with a furnace after the heat preservation is finished.
(3) Polishing the block sample after high-temperature sintering until two surfaces are smooth, coating conductive silver paste on two sides of the wafer through screen printing templates, then placing the wafer into a muffle furnace for silver burning, wherein the silver burning temperature is 600 ℃, the heat preservation time is 30min, and polarizing the wafer in silicone oil under 6kV direct current voltage after silver burning is finished, wherein the polarizing temperature is 100 ℃, and the polarizing time is 35min, so as to obtain the piezoelectric composite material.
Reference is made to comparative example 3:
taking 100g of the product of the present invention as an example, the raw material components used to mass ratio are shown in Table 9.
TABLE 9 raw material composition and mass ratio
TiO in the melted titanium slag 2 The content is 50.0 percent, fe 2 O 3 The content is 31.5%, siO 2 6.4% MgO, 5.7% Al 2 O 3 The content was 3.3%.
The CaO content in the fly ash is less than 5.0%, wherein SiO 2 The content is 49.1 percent, al 2 O 3 The content was 40.8%.
The sodium salt is sodium hydroxide.
(1) And crushing and ball milling the molten titanium slag, and sieving the crushed and ball milled titanium slag with a 100-mesh sieve to obtain molten titanium slag powder. The melted titanium slag, the barium carbonate and the bismuth oxide are respectively weighed according to the proportion in the table and are fully and uniformly mixed. Then, sodium hydroxide is weighed and added to the mixture, and the mixture is thoroughly mixed again. The mixture was pressed into a block under a pressure of 5MPa for a dwell time of 10min.
(2) The above block was heated to 600℃under an air atmosphere and incubated for 1 hour.
(3) Polishing the block sample after high-temperature sintering until two surfaces are smooth, and coating conductive silver paste on two sides of the wafer through a screen printing template. And then placing the wafer into a muffle furnace to burn silver, wherein the silver burning temperature is 600 ℃, and the heat preservation time is 30min. And (3) polarizing the wafer in silicone oil under the direct-current voltage of 6kV after silver burning, wherein the polarizing temperature is 120 ℃, and the polarizing time is 25min, so as to obtain the piezoelectric composite material.
Reference is made to comparative example 4:
taking 100g of the product of the present invention as an example, the raw material components used to mass ratio are shown in Table 10.
TABLE 10 raw material composition to mass ratio
TiO in the melted titanium slag 2 The content is 55.0%, fe 2 O 3 The content is 26.2%, siO 2 6.4% MgO, 5.9% Al 2 O 3 The content was 3.3%.
The CaO content in the fly ash is 17.6%, siO 2 The content is 51.3%, al 2 O 3 The content was 20.4%.
The sodium salt is sodium hydroxide.
(1) Crushing and ball milling molten titanium slag, sieving with a 200-mesh sieve to obtain molten titanium slag powder, weighing molten titanium slag, barium carbonate and bismuth oxide according to the proportion in the table, fully mixing, weighing sodium hydroxide, adding the mixture, fully mixing again, and pressing the mixture into a block sample under the pressure of 6MPa, wherein the pressure maintaining time is 5min.
(2) The above block sample was heated to 950 ℃ under air atmosphere and kept for 0.5 hours, then continued to be heated to 1150 ℃ and kept for 0.5 hours. And cooling the sample to room temperature along with the furnace after the heat preservation is finished.
(3) Polishing the block sample after high-temperature sintering until two surfaces are smooth, coating conductive silver paste on two sides of the wafer through screen printing templates, then placing the wafer into a muffle furnace for silver burning, wherein the silver burning temperature is 600 ℃, the heat preservation time is 30min, and polarizing the wafer in silicone oil under 6kV direct current voltage after silver burning is finished, wherein the polarizing temperature is 120 ℃, and the polarizing time is 20min, so that the piezoelectric composite material is obtained.
Reference is made to comparative example 5:
taking 100g of the product of the present invention as an example, the raw material components used to mass ratio are shown in Table 11.
TABLE 11 raw material composition and mass ratio
TiO in the melted titanium slag 2 The content is 45.0 percent, fe 2 O 3 The content is 36.8 percent, siO 2 6.4% MgO, 5.5% Al 2 O 3 The content was 3.4%.
The CaO content in the fly ash is less than 5.0%, wherein SiO 2 The content is 49.1 percent, al 2 O 3 The content was 40.8%.
The sodium salt is sodium hydroxide.
(1) Crushing and ball milling molten titanium slag, sieving with a 150-mesh sieve to obtain molten titanium slag powder, weighing molten titanium slag, barium carbonate and bismuth oxide according to the proportion in the table, fully mixing, weighing sodium hydroxide, adding the mixture, fully mixing again, pressing the mixture into a block sample under the pressure of 4MPa, and keeping the pressure for 15min.
(2) Heating the block sample to 850 ℃ under the air atmosphere, preserving heat for 1 hour, then continuously heating to 1050 ℃, preserving heat for 1 hour, and cooling the sample to room temperature along with a furnace after the heat preservation is finished.
(3) Polishing the block sample after high-temperature sintering until two surfaces are smooth, coating conductive silver paste on two sides of the wafer through screen printing templates, then placing the wafer into a muffle furnace for silver burning, wherein the silver burning temperature is 600 ℃, the heat preservation time is 30min, and polarizing the wafer in silicone oil under 6kV direct current voltage after silver burning is finished, wherein the polarizing temperature is 100 ℃, and the polarizing time is 35min, so as to obtain the piezoelectric composite material.
Please refer to the piezoelectric composite materials prepared in examples 1-5 and comparative examples 1-5 for performance verification tests:
packaging the sample obtained in example 2 to obtain a piezoelectric sensor, placing the sensor in cement clinker, aging to form a spandrel girder with the size of 17cm multiplied by 4cm multiplied by 3cm as shown in fig. 4, and embedding the spandrel girder into a simulated pavement with the length of 2.0m, the width of 0.2m and the spandrel girder spacing of 1.0m as shown in fig. 5;
different loads pass through the spandrel girder at a constant speed, an Arduino Uno development board is adopted to collect data, and a Python programming is adopted to import the data into a MySQL database by the upper machine, so that data recording and management are realized;
tests such as dynamic load speed measurement, weighing, overspeed alarm and the like are carried out through simulation scenes, and the results show that for the action of the same load, the peak shapes of the voltages generated by different sensors are similar, the peak voltage generated by the same sensor is increased along with the increase of the load, the peak voltages and the load are well positively correlated, and functions such as traffic flow monitoring, overspeed alarm and dynamic weighing can be realized by combining roadbed sensing with a program, so that the system has high reliability;
the experiment shows that the cement-based piezoelectric composite material prepared by the invention can be applied to the field of intelligent transportation and has wide application prospect.
The properties of the piezoelectric composites prepared in examples 1 to 5 and comparative examples 1 to 5 are shown in Table 12:
table 12 properties of piezoelectric composites prepared in examples and comparative examples
From table 12, it can be derived that:
as can be seen from the results of example 1 and comparative example 1, if sodium salt is not added, the sample strength is low and pulverization is easy, indicating that sodium salt has a significant effect on improving the mechanical properties of the composite material.
As can be seen from the result of comparative example 2, when the content of the fly ash is 0, the mechanical strength of the material is obviously reduced compared with that of example 1, because the silicon-aluminum composite oxide in the fly ash can react with sodium salt to form a low-melting-point substance, and the mechanical property of the material is improved.
As can be seen from the results of example 3 and comparative example 3, when the firing temperature is too low, the material is difficult to mold and the mechanical strength is poor.
As can be seen from the results of example 4 and comparative example 4, when high-calcium fly ash is used as a raw material, the piezoelectric properties and mechanical properties of the material are significantly reduced, because Ca and titanyl octahedra and silicon oxygen tetrahedra have strong binding force, and the formation of barium titanate and sodium aluminosilicate is suppressed.
As can be seen from the results of example 5 and comparative example 5, when low-titanium melt titanium slag is used as a raw material, the piezoelectric properties of the material are lowered because the content of barium titanate significantly affects the piezoelectric properties of the composite material.
While the invention has been described above with reference to the accompanying drawings, it will be apparent that the invention is not limited to the embodiments described above, but is intended to be within the scope of the invention, as long as such insubstantial modifications are made by the method concepts and technical solutions of the invention, or the concepts and technical solutions of the invention are applied directly to other occasions without any modifications.
Claims (8)
1. A0-3 type leadless piezoelectric composite material is characterized by comprising a piezoelectric phase and an aluminosilicate phase, wherein the piezoelectric phase is perovskite type barium titanate and bismuth ferrite, and the chemical formula is BaTiO 3 With BiFeO 3 The aluminosilicate phase is sodium feldspar with a frame-shaped structure, and the chemical formula is Na 2 (Mg,Al)(Al,Si) 2 O 7 The volume fraction of the piezoelectric phase in the composite material is 45.0-77.0%, and the silicate phase accounts for 23.0-55.0%.
2. The 0-3 type leadless piezoelectric composite according to claim 1, wherein the mass fraction of Ba in the piezoelectric phase is 17-32%, the mass fraction of Ti is 6-17%, the mass fraction of Bi is 15-34%, and the mass fraction of Fe is 3-9%.
3. A lead-free piezoelectric composite material of type 0-3 according to claim 1, wherein the piezoelectric composite material has a piezoelectric coefficient d 33 Is 0.1-3.5 pC/N.
4. A method of synthesizing a lead-free piezoelectric composite material of type 0-3 according to any one of claims 1-3, wherein the raw materials used include molten titanium slag and, the method comprising the steps of: crushing and ball milling molten titanium slag, mixing the crushed and ball milled titanium slag with fly ash, barium salt, bismuth oxide and sodium salt, fully mixing, pressing and forming, heating to 800-950 ℃ under an air atmosphere, preserving heat for 0.5-2 h, then heating to 1050-1200 ℃, preserving heat for 0.5-2 h, cooling a sample along with a furnace to room temperature, polishing a sintered block sample to be flat on two sides, coating conductive silver paste on two sides of a wafer through a screen printing template, putting the wafer into a muffle furnace for silver firing, wherein the silver firing temperature is 600 ℃, the preserving heat time is 30min, polarizing the wafer in silicone oil under the direct current voltage of 6kV after the silver firing is finished, and the polarizing temperature is 90-120 ℃ and the polarizing time is 20-40 min to obtain the piezoelectric composite material.
5. The method for synthesizing a type 0-3 lead-free piezoelectric composite material according to claim 4, wherein the sodium salt is NaOH or Na 2 CO 3 The mass of the sodium salt accounts for 1.7 to 4.1 percent of the total weight of the raw materials.
6. The method for synthesizing the 0-3 type leadless piezoelectric composite according to claim 4, wherein the titanium content in the molten titanium slag is 42.4-60.0%, the iron content is 20.8-39.6%, and the mass ratio of the fly ash to the molten titanium slag is 20-40%.
7. The method for synthesizing a type 0-3 lead-free piezoelectric composite material according to claim 4, wherein the barium salt is BaCO 3 The mass ratio of the barium salt to the total amount of the raw materials is 29.2-40.1%.
8. The method for synthesizing a type 0-3 lead-free piezoelectric composite material according to claim 4, wherein the bismuth oxide is Bi 2 O 3 The mass proportion of bismuth oxide is 16.5-32.3% of the total amount of the raw materials.
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