High temperature negative temperature coefficient thermistor material and preparation method thereof

Abstract

A composite thermistor material, a preparation method and an application thereof. The perovskite structure oxide and the pyrochlorite structure oxide are composite by solid state reaction method, which comprise process of ball milling, drying, and calcining. Then the thermistor ceramics with high temperature resistance and controllable B value are sintered at high temperature after mould forming, then the thermistor disks are coated by platinum paste, and then the platinum wire is welded as the lead wire to form thermistor element. The thermistor of the invention can realize temperature measurement from room temperature to 1000 C. and has good negative temperature coefficient thermistor characteristics. The thermistor coefficient B can be adjusted by changing the two-phase ratio to meet the requirements of different systems.

Claims

1. A composite for a negative temperature coefficient (NTC) thermistor material, which is characterized by comprising a perovskite oxide and a pyrochlorite oxide, wherein the molar ratio of the perovskite oxides and the pyrochlorite oxide is (70:30) to (90:10); the perovskite oxides contains yttrium, manganese and chromium, the pyrochlorite oxide contains calcium, titanium, tungsten and cerium.

2. The composite according to claim 1, wherein the perovskite oxide and the pyrochlorite oxide are YCr.sub.0.5Mn.sub.0.5O.sub.3 and CaWO.sub.4CeTi.sub.2O.sub.6, respectively.

3. The composite according to claim 1, wherein the molar mass ratio of yttrium, manganese, chromium in the perovskite oxide is (2-2.5):(0.8-1.2):(0.8-1.2), and the molar mass ratio of calcium, titanium, tungsten, cerium in the pyrochlorite oxide is (0.8-10.2):(0.8-10.2):(0.8-1.2):(2-2.5).

4. The composite according to claim 3, wherein the molar mass ratio of yttrium, manganese, chromium in the perovskite oxide is 2:1:1, and the molar mass ratio of the calcium, titanium, tungsten, cerium in the pyrochlorite oxide is 1:1:1:2.

5. A method for preparing a composite thermistor material, comprising the steps of: (1) mixing and grinding pure Y.sub.2O.sub.3, Mn.sub.2O.sub.3 and Cr.sub.2O.sub.3 as a ground mixture, wherein the molar mass ratio of Y.sub.2O.sub.3:Mn.sub.2O.sub.3:Cr.sub.2O.sub.3, is 2:1:1; and then sintering the ground mixture at the temperature of 1100-1300 C. for 1-2 hours to obtain a YCr.sub.0.5Mn.sub.0.5O.sub.3 oxide powder; (2) mixing and grinding pure CaCO.sub.3, CeO.sub.2, TiO.sub.2 and WO.sub.3 as a ground powder, wherein the molar mass ratio of CaCO.sub.3:CeO.sub.2:TiO.sub.2:WO.sub.3 is 2:2:2:1; then grinding and drying the ground powder at the temperature of 950 C.1050 C. for 3 h to obtain a CaWO.sub.4CeTi.sub.2O.sub.6 oxide powder; (3) adding a PVA adhesive to make the YCr.sub.0.5Mn.sub.0.5O.sub.3 powder in the step (1) form a granular uniform dispersion, sintering the granular uniform dispersion at temperature of 1400-1600 C. for 1-2 h to obtain a perovskite oxide YCr.sub.0.5Mn.sub.0.5O.sub.3 powder; (4) mixing and grinding the perovskite oxide YCr.sub.0.5Mn.sub.0.5O.sub.3 powder and the CaWO.sub.4CeTi.sub.2O.sub.6 oxide powder for 4-8 h to obtain an uniformly mixed powder, wherein the molar ratio of the perovskite oxide YCr.sub.0.5Mn.sub.0.5O.sub.3 powder: the CaWO.sub.4CeTi.sub.2O.sub.6 oxide powder is (70:30) to (90:10); (5) adding the uniformly mixed powder into the PVA adhesive as to form a granular uniformly dispersed powders, then molding the granular uniformly dispersed powders into a disk; (6) sintering the disk at temperature of 1400 C. to form a tunable B value thermistor material; (7) coating a platinum paste on surface of the tunable B value thermistor material, and keeping the temperature at 1200 C. for 2 h to obtain a thermistor material; (8) cutting the thermistor material into a thermistor chip, and welding a platinum wire lead to the thermistor chip.

6. The method for preparing the composite according to claim 5, wherein in the step (3), adding the PVA adhesive to the perovskite oxide YCr.sub.0.5Mn.sub.0.5O.sub.3 powder and sintering at temperature of 1400-1500 C.

7. A process for preparing a composite thermistor with the composite for the NTC thermistor material of claim 1, wherein a platinum wire is bonded on two ends of a thermistor chip after cutting treatment, and a high-temperature thermistor with lead is formed after treatment at the temperature of 1200 C.

8. A process for preparing a high-temperature dense ceramic thermistor temperature sensor, wherein the high-temperature dense ceramic thermistor temperature sensor is made with the composite for the NTC thermistor material of claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic diagram of the resistance and temperature characteristic curve in embodiment 1;

(2) FIG. 2 is a schematic diagram of the resistance and temperature characteristic curve in embodiment 1;

(3) FIG. 3 is a schematic diagram of the resistance and temperature characteristic curve in embodiment 1;

(4) FIG. 4 is a schematic diagram of the resistance and temperature characteristic curve in embodiment 1;

DETAILED DESCRIPTION OF THE EMBODIMENTS

(5) For clear understanding of the objectives, features and advantages of the present invention, detailed description of the present invention will be given below in conjunction with accompanying drawings and specific embodiments. It should be noted that the embodiments described herein are only meant to explain the present invention, and not to limit the scope of the present invention.

(6) The composite NTC thermistor material in the present invention is formed by perovskite structure oxide and pyrochlorite structure oxide. The molar ratio of the two materials is (70:30)(90:10), and the perovskite structure oxide contains yttrium, manganese and chromium. The pyrochlorite oxide containing calcium, titanium, tungsten and cerium. Among them, perovskite oxide and pyrochlorite oxide are YCr.sub.0.5Mn.sub.0.5O.sub.3 and CaWO.sub.4CeTi.sub.2O.sub.6, respectively. The molar ratio of yttrium, manganese and chromium in perovskite oxide is 2:1:1, and the molar ratio of calcium, titanium, tungsten and cerium in calcined chlorite oxide is 1:1:1:2. The composite NTC thermistor material can be prepared according the following steps:

(7) (1) The analytical pure Y.sub.2O.sub.3, Mn.sub.2O.sub.3 and Cr.sub.2O.sub.3 are mixed grinding, and the molar ratio of the three is 2:1:1, then calcined the mixture at 1200 C. for 1-2 hours to obtain the YCr.sub.0.5Mn.sub.0.5O.sub.3 oxide powder;

(8) (2) The analytical pure CaCO.sub.3, CeO.sub.2, TiO.sub.2 and WO.sub.3 were mixed to grind, and the molar ratio of the four was 2:2:2:1, and then calcined the dried powder at 1000 C. for 3 h to obtain the CaWO.sub.4CeTi.sub.2O.sub.6 oxide powder;

(9) (3) The perovskite oxide YCr.sub.0.5Mn.sub.0.5O.sub.3 powder was prepared and the PVA binder was added to the perovskite oxide powder to disperse the perovskite oxide powder evenly, and the uniformly dispersed particles were sintered directly at 1400-1600 C. for 1-2 h.

(10) (4) Taking step (3) perovskite oxide YCr.sub.0.5Mn.sub.0.5O.sub.3 powder after sintering, and preparing calcined chlorite oxide CaWO.sub.4CeTi.sub.2O.sub.6 powder in step (2), grinding them uniformly for 4-8 h. The molar ratio of perovskite oxide YCr.sub.0.5Mn.sub.0.5O.sub.3 powder to calcined chlorite oxide CaWO.sub.4CeTi.sub.2O.sub.6 powder is (70:30)(90:10);
(5) Mixing and grinding the uniform powder in step (4) and adding the PVA binder to form the uniformly dispersed granular particles again, and then forming the uniformly dispersed particles into a wafer after the mold molding;
(6) The formed wafer is sintered at 1400 C. to form a B value adjustable thermistor material;
(7) The platinum paste is coated on the surface of the sintered thermistor material in step (6) and then kept at 1200 C. for 2 h;
(8) The thermistor material obtained in step (7) is cut according to the requirement, and the platinum lead is welded to the cut thermistor chip.

(11) The composite thermistor material is used to prepare a composite thermistor. The platinum wire was bonded to the two ends of the thermistor chip after cutting, and the high temperature thermistor with lead was formed after high temperature treatment at 1200 C.

(12) The composite thermistor material can also be used to fabricate high temperature dense ceramic thermistor temperature sensor.

Embodiment 1

(13) A, preparing the composite NTC thermistor material, which specifically includes the following steps:

(14) a, the prepared perovskite oxide YCr.sub.0.5Mn.sub.0.5O.sub.3, and PVA binder are added to disperse the raw powder into granular form, then the uniformly dispersed powder is sintered at 1400-1600 C. for 1-2 h;

(15) b, after sintering, perovskite oxide YCr.sub.0.5Mn.sub.0.5O.sub.3 powder was obtained and mixed with the prepared CaWO.sub.4CeTi.sub.2O.sub.6 powder for 4-8 h at the molar ratio of 70:30;

(16) c, the uniform powder was added to the binder to form the granular uniform dispersed powder again, and then formed the disk after the mould forming;

(17) d, the formed disk was sintered at 1400-1500 temperature to form a B value adjustable thermistor material;

(18) e, the platinum paste was coated on the surface of the sintered thermistor material and kept for 2 h at 1200 C.;

(19) f, the platinum coated thermistor material is cut according to the requirement, and the platinum lead is welded to the cut thermistor chip;

(20) g, the resistivity at room temperature (25 C.) is 2540 (k *cm), the resistivity at high temperature (900 C.) 0.0076 (k *cm), B value (25-200) is 4378, B value (200-800) is 4797, the temperature resistance curve is shown in FIG. 1;

Embodiment 2

(21) B, preparing the composite NTC thermistor material, which specifically includes the following steps:

(22) a, the prepared perovskite oxide YCr.sub.0.5Mn.sub.0.5O.sub.3, and PVA binder are added to disperse the raw powder into granular form, then the uniformly dispersed powder is sintered at 1400-1600 C. for 1-2 h;

(23) b, after sintering, perovskite oxide YCr.sub.0.5Mn.sub.0.5O.sub.3 powder was obtained and mixed with the prepared CaWO.sub.4CeTi.sub.2O.sub.6 powder for 4-8 h at the molar ratio of 80:20;

(24) c, the uniform powder was added to the binder to form the granular uniform dispersed powder again, and then formed the disk after the mould forming;

(25) d, the formed disk was sintered at 1400-1500 temperature to form a B value adjustable thermistor material;

(26) e, the platinum paste was coated on the surface of the sintered thermistor material and kept for 2 h at 1200 C.;

(27) f, the platinum coated thermistor material is cut according to the requirement, and the platinum lead is welded to the cut thermistor chip;

(28) g, the resistivity at room temperature (25 C.) is 151.62 (k *cm), the resistivity at high temperature (900 C.) 0.0048 (k *cm), B value (25-200) is 3798, B value (200-800) is 4370, the temperature resistance curve is shown in FIG. 2;

Embodiment 3

(29) C, preparing the composite NTC thermistor material, which specifically includes the following steps:

(30) a, the prepared perovskite oxide YCr.sub.0.5Mn.sub.0.5O.sub.3, and PVA binder are added to disperse the raw powder into granular form, then the uniformly dispersed powder is sintered at 1400-1600 C. for 1-2 h;

(31) b, after sintering, perovskite oxide YCr.sub.0.5Mn.sub.0.5O.sub.3 powder was obtained and mixed with the prepared CaWO.sub.4CeTi.sub.2O.sub.6 powder for 4-8 h at the molar ratio of 90:10;

(32) c, the uniform powder was added to the binder to form the granular uniform dispersed powder again, and then formed the disk after the mould forming;

(33) d, the formed disk was sintered at 1400-1500 temperature to form a B value adjustable thermistor material;

(34) e, the platinum paste was coated on the surface of the sintered thermistor material and kept for 2 h at 1200 C.;

(35) f, the platinum coated thermistor material is cut according to the requirement, and the platinum lead is welded to the cut thermistor chip;

(36) g, the resistivity at room temperature (25 C.) is 30 (k *cm), the resistivity at high temperature (900 C.) 0.0022 (k *cm), B value (25-200) is 3263, B value (200-800) is 4135, the temperature resistance curve is shown in FIG. 3;

Embodiment 4

(37) D, preparing the composite NTC thermistor material, which specifically includes the following steps:

(38) a, the analytical pure Y.sub.2O.sub.3Mn.sub.2O.sub.3Cr.sub.2O.sub.3 was mixed with the molar ratio of 2:1:1 and then calcined at 1200 C. for 1-2 h to obtain the YCr.sub.0.5Mn.sub.0.5O.sub.3 oxide powder.

(39) b, the powder obtained in step a is dried and added with binder to disperse the particles evenly, and the disk is formed by mould forming process.

(40) d, the formed disk was sintered at 1400-1500 temperature to form a thermistor material;

(41) e, the platinum paste was coated on the surface of the sintered thermistor material and kept for 2 h at 1200 C.;

(42) f, the platinum coated thermistor material is cut according to the requirement, and the platinum lead is welded to the cut thermistor chip;

(43) g, the resistivity at room temperature (25 C.) is 21.54 (k *cm), the resistivity at high temperature (800 C.) 0.01864 (k *cm), B value (25-200) is 2881, B value (200-800) is 3083, the temperature resistance curve is shown in FIG. 4.