CN103922741A - CeO2 system PTCR thermal sensitive ceramic material and preparation method thereof - Google Patents

CeO2 system PTCR thermal sensitive ceramic material and preparation method thereof Download PDF

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Publication number
CN103922741A
CN103922741A CN201410110313.2A CN201410110313A CN103922741A CN 103922741 A CN103922741 A CN 103922741A CN 201410110313 A CN201410110313 A CN 201410110313A CN 103922741 A CN103922741 A CN 103922741A
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content
ceo
ceramic material
ptcr
thermal sensitive
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Inventor
朱兴文
刘怡茵
张甜甜
王生伟
朱欣然
沈思月
姜文中
周晓
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Abstract

The invention relates to a CeO2 system PTCR thermal sensitive ceramic material and a preparation method thereof. A formula of the system material is CeO2+aNa2CO3+bK2CO3+cD+dM+eBi2O3, wherein a, b=0.01-0.30; D is an adding element, is at least one element in Nb, Sb or La, the content c is between 0.0003 and 0.01; M is at least one of Al2O3 and SiO2, the content d is between 0 and 0.03; and the content Bi2O3 e is between 0.10-0.80. The material is prepared by taking a traditional ceramic technology, and is prepared by sintering for 10-120 minutes at the temperature of 950-1200 DEG C in flowing nitrogen. The PTC effect of the novel ceramic material is obvious, the lift drag ratio can reach 104, the resistor nonlinear coefficient can reach more than 20%/DEG C, and the performance of the ceramic material is close to that of a traditional BaTiO3 system PTCR thermal sensitive ceramic material.

Description

CeO 2it is PTCR thermal sensitive ceramic material and preparation method thereof
Technical field
The present invention relates to a kind of novel semi-conductor stupalith and preparation method thereof, there is positive temperature coefficient of resistance (PTCR) effect through the material of semiconductor, be a kind of novel lead-free PTCR sensitive ceramic resistor material, belong to piezoelectric ceramics material preparation process technical field.
Background technology
PTCR pottery generally refers to have positive temperature coefficient of resistance thermistor material or the components and parts of (Positive Temperature Coefficient of Resistance).Typical PTCR material is the semiconductor ceramic material taking barium titanate as base, is characterized in the time that envrionment temperature rises to certain some temperature (Curie temperature or switch temperature point) its resistance value several orders of magnitude that will surge.Change along with the variation of impressed voltage hardly as its heating power of heating element with this material, thereby have the function of automatic constant-temperature.Simultaneously because it has that component structure is simple, with low cost, save energy, the flames of anger and the series of advantages such as safe and reliable be widely used in industry and Military Electronic Equipment, and the field such as household electrical appliance.
Modal PTCR thermal sensitive ceramics element is ABO 3the BaTiO of type 3sill.For improving the working temperature of ceramic component, currently all move agent to add plumbous oxide or leaded compound as the temperature that improves Curie temperature, or move agent taking strontium titanate as Curie temperature and reduce Curie point, or plumbous, strontium acting in conjunction is moved agent as Curie point, this type of thermal sensitive ceramics is that lead tolerance is higher or content of strontium is high, be easy to volatilization, make ceramic stability decreases.For example, to disclose a kind of equation for No. ZL96106337.8 be (Sr to Chinese invention patent 1-xpb x) Ti yo 3pTC stupalith system, wherein x=0.1 ~ 0.9, y=0.8 ~ 1.2; Semiconductor constituent content is 0.012 ~ 2mol%, and this invention has obtained the good PTC sensitive ceramic resistor of over-all properties device.
As everyone knows, heavy metal element Pb is to the toxic effect of human body, on the impact of environment more so.According to estimates, 1 gram of lead can cause the soil pollution of 1 square metre, and this pollution is chronicity, will face compared with hang-up from now on to the disposal of discarded leaded PTC element.Therefore, a lot of countries of the world have all recognized this problem, formulate one after another relevant policies and limit the use of even forbidding lead-containing materials.European Union started to carry out ROHS standard from 2006.Although ROHS standard as PTC pottery, piezoelectric ceramics etc. are made as special case, allows leaded electronic ceramics to continue to use.This real genus caving-in bash, because technically there is no the substitute of this class component at present.Therefore, researching and developing non-lead is that ptc material is to national economy and social development important in inhibiting.
Find out thus, although environmentally friendly PTCR thermal sensitive ceramic material has far-reaching social effect and economic benefit, but from documents and materials and the patent delivered, functional, to have positive temperature coefficient, thermal sensitive ceramics thermal control material that liftdrag is high achievement report is quite few.Therefore, develop PTCR thermal sensitive ceramic material unleaded, stable performance and become a very important problem, there is important social effect and will produce great economic benefit.
Summary of the invention
The object of this invention is to provide a kind of manufacturing property good, there is positive temperature coefficient, PTCR sensitive ceramic resistor material that liftdrag is high.
The present invention prepared functional, there is positive temperature coefficient, PTCR sensitive ceramic resistor material that liftdrag is high, it is characterized in that following material mixture ratio composition and preparation technology:
A. the main component of this material is to contain the metallic elements such as Na, K, Ce, Bi, and concrete material prescription is: CeO 2+ ana 2cO 3+ bk 2cO 3+ cd+ dm+ ebi 2o 3, wherein, a, b=0.01 ~ 0.30; D is trace additives, is at least one element in Nb, Sb, La etc., its content c=0.0003 ~ 0.01; M is additive, can be Al 2o 3, SiO 2, its content d=0 ~ 0.03; Bi 2o 3for sintering aid, content e=0.10 ~ 0.80.
B. the initial raw materials of the invention process process is selected from the Bi of analytical pure or SILVER REAGENT 2o 3, K 2cO 3, Na 2cO 3, CeO 2, Sb 2o 3, Nb 2o 5, SiO 2, Al 2o 3or other inorganic salt micron-sized powder that contains these metallic elements.Weigh according to above-mentioned materials formula, taking zirconia balls and alcohol as medium, by above-mentioned raw materials in planetary mills with the rotating speed ball milling of 100 ~ 500 revs/min 0.5 ~ 24 hour, after oven dry, obtain the above-mentioned oxide compound or other inorganic salt powder that mix.
C. the powder after drying is added to PVA(concentration 5 ~ 15wt% of 2 ~ 15wt%) granulation, with the disk of pressure compacting Φ 10 × 2.0mm of 5 ~ 20MPa.
D. the disk suppressed is thermal treatment 0.5 ~ 5 hour (building-up reactions) in air atmosphere at 800 ~ 950 DEG C, then in flowing nitrogen atmosphere, at 950 ~ 1200 DEG C, be incubated 10 ~ 120 minutes sintering.The surface of sintered sample applies with the ag paste electrode of ohmic contact after grinding, and by electrode at 450 ~ 550 DEG C of sintered heat insulating 5 ~ 120min, electrode is solidified, so just obtain a kind of CeO 2it is PTCR ceramic material sample.
The major advantage of PTCR thermal sensitive ceramic material of the present invention is: 1. can utilize K, Na constituent content to move agent as Curie temperature; 2. jointly realize the semiconductor of element material by micro-donor doping and nitrogen atmosphere sintering, by adding a certain amount of additive can suppress grain growing, improve electric strength and the stability of material; 3. not leaded in formula, realize the unleaded of stable performance, high lift-drag ratio PTCR material.
The electrical property of PTCR sensitive ceramic resistor material of the present invention can be realized following parameter request: minimum resistance: <10 4Ω cm, liftdrag: Rmax/Rmin>10 4, temperature coefficient of resistance α >20%.Specifically see embodiment.
Brief description of the drawings
Fig. 1 a, sample K-1 be the resistance-temperature characteristics curve after sintering under air and nitrogen atmosphere;
Fig. 1 b, sample K-2 be the resistance-temperature characteristics curve after sintering under air and nitrogen atmosphere;
Fig. 1 c, sample K-3 be the resistance-temperature characteristics curve after sintering under air and nitrogen atmosphere;
The resistance-temperature characteristics curve of Fig. 2, sample N-1, N-2 and N-3;
The resistance-temperature characteristics curve of Fig. 3, sample NK-1 and NK-2.
Embodiment
Content of the present invention is done further description by above step and following embodiment.Following examples just meet several examples of the technology of the present invention content, do not illustrate that the present invention only limits to the content described in following enforcement.
embodiment 1
This example is pressed CeO 2+ 0.25k 2cO 3+ 0.003d+ dal 2o 3+ 0.25bi 2o 3prepare burden, wherein D is Nb 2o 5or Sb 2o 3, d=0 ~ 0.004, initial raw materials is selected Bi 2o 3, K 2cO 3, CeO 2, Nb 2o 5, Al 2o 3, Sb 2o 3.After calculating weight by mol ratio in molecular formula, weigh, weigh quality as table 1:
Weigh according to the formula of allocation sheet one, taking zirconia balls and alcohol as medium, in material: ball: alcohol=1:2.5:1.5(weight) ratio by above-mentioned raw materials in planetary mills with the rotating speed ball milling of 280 revs/min 4 hours, after oven dry, obtain the above-mentioned oxide powder mixing.Powder after oven dry adds the PVA(polyvinyl alcohol of 9wt%, concentration 10wt%) granulation, with the disk of pressure compacting Φ 10 × 2.0mm of 10MPa.
The disk of suppressing is thermal treatment 2 hours (making it abundant solid state reaction) in air atmosphere at 900 DEG C, then in nitrogen, at 1030 DEG C, be incubated 30 minutes sintering.The surface of sintered sample applies with the ag paste electrode of ohmic contact after grinding, and by electrode at 490 DEG C of sintered heat insulating 8min, electrode is solidified, obtain PTCR thermistor ceramic component, the row of going forward side by side carries out resistance-temperature characteristics measurement.Prepared material presents fabulous PTC effect, and its performance as shown in Table 2 and Figure 1.
embodiment 2
This example is pressed CeO 2+ 0.25na 2cO 3+ cd+0.25Bi 2o 3prepare burden, wherein D is Nb 2o 5or Sb 2o 3, c=0.002 ~ 0.003, initial raw materials is selected Bi 2o 3, Na 2cO 3, CeO 2, Nb 2o 5, Sb 2o 3.After calculating weight by mol ratio in molecular formula, weigh, weigh quality as table 3:
Weigh according to the formula of allocation sheet one, taking zirconia balls and alcohol as medium, in material: ball: alcohol=1:2.5:1.5(weight) ratio by above-mentioned raw materials in planetary mills with the rotating speed ball milling of 280 revs/min 4 hours, after oven dry, obtain the above-mentioned oxide powder mixing.Powder after oven dry adds the PVA(polyvinyl alcohol of 9wt%, concentration 10wt%) granulation, with the disk of pressure compacting Φ 10 × 2.0mm of 10MPa.
The disk of suppressing is thermal treatment 2 hours (making it abundant solid state reaction) in air atmosphere at 900 DEG C, then in nitrogen, at 1100 DEG C, be incubated 30 minutes sintering.The surface of sintered sample applies with the ag paste electrode of ohmic contact after grinding, and by electrode at 490 DEG C of sintered heat insulating 8min, electrode is solidified, obtain PTCR thermistor ceramic component, the row of going forward side by side carries out resistance-temperature characteristics measurement.The electrical resistance temperature of prepared material presents ascendant trend, and maximum resistance can reach 10 with minimum resistance ratio 2, its performance is as shown in table 4 and Fig. 2.
embodiment 3
This example is pressed CeO 2+ ana 2cO 3+ bk 2cO 3+ 0.003sb 2o 3+ 0.25bi 2o 3prepare burden, a, b=0.10-0.15, initial raw materials is selected Bi 2o 3, K 2cO 3, Na 2cO 3, CeO 2, Sb 2o 3.After calculating weight by mol ratio in molecular formula, weigh, weigh quality as table 5:
Weigh according to the formula of allocation sheet one, taking zirconia balls and alcohol as medium, in material: ball: alcohol=1:2.5:1.5(weight) ratio by above-mentioned raw materials in planetary mills with the rotating speed ball milling of 280 revs/min 4 hours, after oven dry, obtain the above-mentioned oxide powder mixing.Powder after oven dry adds the PVA(polyvinyl alcohol of 9wt%, concentration 10wt%) granulation, with the disk of pressure compacting Φ 10 × 2.0mm of 10MPa.
The disk of suppressing is thermal treatment 2 hours (making it abundant solid state reaction) in air atmosphere at 900 DEG C, then in nitrogen, at 1070 DEG C, be incubated 30 minutes sintering.The surface of sintered sample applies with the ag paste electrode of ohmic contact after grinding, and by electrode at 490 DEG C of sintered heat insulating 8min, electrode is solidified, obtain PTCR thermistor ceramic component, the row of going forward side by side carries out resistance-temperature characteristics measurement.Prepared material all has certain PTC effect, and performance is as shown in table 6 and Fig. 3.

Claims (2)

1. a CeO 2be PTCR thermal sensitive ceramic material, the main component that it is characterized in that this material is to contain Na, K, Ce, Bi metallic element, and concrete material prescription is: CeO 2+ ana 2cO 3+ bk 2cO 3+ cd+ dm+ ebi 2o 3, wherein, a, b=0.01 ~ 0.30; D is trace additives, is at least one element in Nb, Sb, La, its content c=0.0003 ~ 0.01; M is additive, is Al 2o 3or SiO 2, its content d=0 ~ 0.03; Bi 2o 3for sintering aid, content e=0.10 ~ 0.80.
2. by CeO claimed in claim 1 2be the preparation method of PTCR thermal sensitive ceramic material, it is characterized in that the method has following step of preparation process:
A. press material prescription batching: CeO 2+ ana 2cO 3+ bk 2cO 3+ cd+ dm+ ebi 2o 3, wherein, a, b=0.01 ~ 0.30; D is trace additives, is at least one element in Nb, Sb, La, its content c=0.0003 ~ 0.01; M is additive, is Al 2o 3or SiO 2, its content d=0 ~ 0.03; Bi 2o 3for sintering aid, content e=0.10 ~ 0.80; Initial raw materials is selected from the Bi of analytical pure or SILVER REAGENT 2o 3, K 2cO 3, Na 2cO 3, CeO 2, Sb 2o 3, Nb 2o 5, SiO 2, Al 2o 3or other inorganic salt micron-sized powder that contains these metallic elements; Weigh according to above-mentioned materials formula, taking zirconia balls and alcohol as medium, by above-mentioned raw materials in planetary mills with the rotating speed ball milling of 100 ~ 500 revs/min 0.5 ~ 24 hour, after oven dry, obtain the above-mentioned oxide compound or other inorganic salt powder that mix;
B. the powder after drying is added to the PVA of 2 ~ 15wt%, concentration 5 ~ 15wt%, granulation, with the disk of pressure compacting Φ 10 × 2.0mm of 5 ~ 20MPa;
C. the disk suppressed is thermal treatment 0.5 ~ 5 hour (building-up reactions) in air atmosphere at 800 ~ 950 DEG C, then in flowing nitrogen atmosphere, at 950 ~ 1200 DEG C, be incubated 10 ~ 120 minutes sintering; The surface of sintered sample applies with the ag paste electrode of ohmic contact after grinding, and by electrode at 450 ~ 550 DEG C of sintered heat insulating 5 ~ 120min, electrode is solidified, so just obtain CeO 2it is PTCR ceramic material sample.
CN201410110313.2A 2014-03-24 2014-03-24 CeO2 system PTCR thermal sensitive ceramic material and preparation method thereof Pending CN103922741A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1731540A (en) * 2005-08-29 2006-02-08 上海维安热电材料股份有限公司 Novel manufacturing method for laminate ceramic positive temperature coefficient thermosensitive resistor
CN101792316A (en) * 2010-01-28 2010-08-04 中南大学 High-Curie-point lead-free PTCR (Positive Temperature Coefficient of Resistance) thermo-sensitive ceramic material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1731540A (en) * 2005-08-29 2006-02-08 上海维安热电材料股份有限公司 Novel manufacturing method for laminate ceramic positive temperature coefficient thermosensitive resistor
CN101792316A (en) * 2010-01-28 2010-08-04 中南大学 High-Curie-point lead-free PTCR (Positive Temperature Coefficient of Resistance) thermo-sensitive ceramic material

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Application publication date: 20140716