CN103011801A

CN103011801A - Method for preparing ATO-based PTC (positive temperature coefficient) material

Info

Publication number: CN103011801A
Application number: CN2011102888894A
Authority: CN
Inventors: 李志祥; 许高杰; 李勇; 蒋俊; 段雷
Original assignee: Ningbo Institute of Material Technology and Engineering of CAS
Current assignee: Ningbo Institute of Material Technology and Engineering of CAS
Priority date: 2011-09-21
Filing date: 2011-09-21
Publication date: 2013-04-03
Anticipated expiration: 2031-09-21
Also published as: CN103011801B

Abstract

The invention relates to a method for preparing an ATO-based PTC (positive temperature coefficient) material, comprising the following steps: preparing PS glass powder by using diammonium phosphate and stannous oxide or by using diammonium hydrogen phosphate and stannous oxide; mixing 5-40% by mass of PS glass powder, 40-90% by mass of tin source matter, 1-30% by mass of antimony source material and 0-25% by mass of doping agent; pressing and forming the mixed powder, and treating at the temperature of 300-1,200 DEG C for 0.5-48 hours to obtain the ATO-based PTC material. The raw materials adopted by the method do not comprise lead or other raw materials which can cause severe pollution to environment, thereby causing less pollution to environment. The heat treatment temperature of the prepared ATO-based PTC material is reduced significantly, and the energy consumption is reduced. The prepared ATO-based PTC material has the advantage of good chemical stability of the SnO2-based material. The method has the advantages that raw materials are easily available, procedures are short, the process is simple, requirements on equipment are low, cost is low, industrialization is easy to realize. The ATO-based PTC material can be used in the acidic, neutral and alkaline conditions and has a wide range of application.

Description

A kind of preparation method of ATO matrix PTC material

Technical field

The present invention relates to a kind of preparation method of ATO matrix PTC material, the ATO material of the method preparation can be applied to automatic control heating field.This materials chemistry character is stable, can use under the abominable chemical environment such as strong acid, highly basic.

Background technology

Tindioxide (SnO ₂) be that a kind of energy gap is the N-shaped semiconductor material of 3.6eV.Because its high electron mobility (109.56cm ²/ Vs), high carrier concentration (1.23 * 1O ¹⁹Cm ³), high light transmittance, the physicochemical property such as high refractive index (1.9-2) and stability at elevated temperature are mixed and unadulterated SnO ₂Based transparent film is used widely, as being used for anti-electrostatic filler, transparent conducting coating, ultraviolet shielded film, gas sensor, photo-electric display, solar cell, lithium ion cell electrode, the aspects such as voltage dependent resistor.

Material has PTC (Positive Temperature Coefficient) effect, and namely the resistance value of material increases along with the rising of temperature.General most metals has positive temperature coefficient, and pottery has NTC (Negative TemperatureCoefficient) effect mostly, for the pottery with PTC effect, is called the PTC pottery.Because pottery has good resistance to elevated temperatures and antioxidant property, so the PTC pottery is generally all for the preparation of the automatic control heating material.According to the peculiar resistance-temperature of this material, current-voltage and electric current-timing relationship characteristic, all be widely used at aspects such as computer, communication equipment, conditioning unit, refrigerator, beauty appliance, electric prospection, electronic toys.Traditional PTC pottery is mainly with BaTiO ₃And PbTiO ₃The base ceramic main, because lead-containing materials easily causes environmental pollution in use and production process, at present, the use of lead-containing materials has strictly been limited in a lot of countries and regions.BaTiO ₃Base pottery is because Curie temperature lower (Tc～120 ℃) generally can only be applied in the low temperature field, and BaTiO ₃The sintering temperature very high (＞1300 ℃) of pottery, energy consumption is larger.The SnO that Sb mixes ₂Electro-conductive material has the advantages such as power density is high, chemical stability good, low pollution, the fields such as foot basin heating tube, small-sized bottled water station heating tube have been widely used at present, but because the ATO pottery has the NTC effect, give and used of seat belts certain hidden danger, therefore, be necessary to develop the ATO matrix PTC material.

Summary of the invention

Technical problem to be solved by this invention provides a kind of preparation method of ATO matrix PTC material, the method raw material is easy to get, technique is simple, not high to equipment requirements, cost is low, be easy to industrialization, and the ATO materials chemistry character of preparation is stable, can use under the abominable chemical environment such as strong acid, highly basic.

The present invention solves the problems of the technologies described above the technical scheme that adopts: a kind of preparation method of ATO matrix PTC material is characterized in that may further comprise the steps:

1) preparation PS glass powder: with Secondary ammonium phosphate, tin protoxide, perhaps take Secondary ammonium phosphate, tin protochloride as raw material, the P in the raw material ₂O ₅With the mol ratio of Sn be 0.2～0.9,400～1000 ℃ of thermal treatments 10～100 minutes, glass melt is quenched after raw material is mixed, grind and obtain PS glass powder;

2) with tin source material, antimony source material, doping agent, and the binding agent of employing PS glass powder, according to massfraction 40～90%, 1%～30%, 0%～25% and 5%～40% mixes;

3) with after the above-mentioned mixed pressed by powder moulding, obtained the ATO matrix PTC material in 0.5～48 hour 300～1200 ℃ of thermal treatments.

As preferably, described tin source material is any one of tindioxide, stannous oxalate, tin protochloride, the perhaps mixture of their arbitrary combination.

As preferably, described antimony source material is the mixture of antimonous oxide, butter of antimony or their arbitrary combination.

As preferably, described doping agent is the mixture of cerium dioxide, cobalt oxide or their arbitrary combination.

As preferably, described step 1) P in the raw material ₂O ₅With the mol ratio of Sn be 0.2～0.4.

At last, described step 3) thermal treatment temp in is 400～800 ℃, time 2 h.

Compared with prior art, the invention has the advantages that: do not contain the plumbous raw material that waits serious environment pollution in the starting material, do not disturb less to environment; With respect to BaTiO ₃Pottery (sintering temperature＞1300 ℃) and traditional ATO pottery (sintering temperature＞1400 ℃), thermal treatment temp significantly reduces, and energy consumption descends; In addition, as a kind of novel ATO material, it has SnO ₂The advantage that the sill chemical stability is good can be applied to the abominable field of chemical environment of strong acid, highly basic etc.The raw material that this preparation method adopts is easy to get, and flow process is few, and technique is simple, and not high to equipment requirements, cost is low, is easy to industrialization.

Description of drawings

Fig. 1 a-1c: the electromicroscopic photograph of product;

Fig. 2 a-2c: the X-ray diffractogram of product;

Fig. 3 a-3c: the resistance-temperature curve of product.

Embodiment

Embodiment is described in further detail the present invention below in conjunction with accompanying drawing.

Embodiment 1

Take Secondary ammonium phosphate and tin protoxide as raw material, P ₂O ₅With the mol ratio of Sn be 0.3,900 ℃ of thermal treatments 15 minutes, then by shrend, the glass dregs that obtains is pulverized acquisition PS glass powder after raw material is mixed.Take by weighing the PS glass powder of 1 gram, the stannous oxalate of 5 grams, the tin protochloride of 0.2 gram, the antimonous oxide of 0.5 gram, 0.1 the cerium dioxide of gram, above-mentioned raw materials is mixed, and compression moulding is then 600 degree thermal treatments 2 hours, obtain product a, the stereoscan photograph of product a is seen Fig. 1 a, and x-ray diffractogram of powder is seen Fig. 2 a, the resistance of product-temperature curve 3a.

Embodiment 2

Take Secondary ammonium phosphate and tin protochloride as raw material, P ₂O ₅With the mol ratio of Sn be 0.4,600 ℃ of thermal treatments 15 minutes, then by shrend, the glass dregs that obtains is pulverized acquisition PS glass powder after raw material is mixed.Take by weighing the PS glass powder of 1.5 grams, the tindioxide of 5 grams, 0.5 the antimonous oxide of gram, the cerium dioxide of 0.3 gram mixes above-mentioned raw materials, compression moulding, then 500 degree thermal treatments 2 hours, obtain product b, the stereoscan photograph of product b is seen Fig. 1 b, x-ray diffractogram of powder is seen Fig. 2 b, the resistance of product-temperature curve 3b.

Embodiment 3

Take Secondary ammonium phosphate and tin protoxide as raw material, P ₂O ₅With the mol ratio of Sn be 0.3,900 ℃ of thermal treatments 15 minutes, then by shrend, the glass dregs that obtains is pulverized acquisition PS glass powder after raw material is mixed.Take by weighing the PS glass powder of 1.0 grams, the stannous oxalate of 5 grams, the antimonous oxide of 0.4 gram, the cerium dioxide of 0.25 gram, 0.2 gram cobalt oxide, above-mentioned raw materials is mixed, and compression moulding is then 500 degree thermal treatments 2 hours, obtain product c, the stereoscan photograph of product c is seen Fig. 1 c, and x-ray diffractogram of powder is seen Fig. 2 c, the resistance of product-temperature curve 3c.

Claims

1. the preparation method of an ATO matrix PTC material is characterized in that may further comprise the steps:

2. preparation method according to claim 1 is characterized in that described tin source material is any one of tindioxide, stannous oxalate, tin protochloride, the perhaps mixture of their arbitrary combination.

3. preparation method according to claim 1 is characterized in that described antimony source material is the mixture of antimonous oxide, butter of antimony or their arbitrary combination.

4. preparation method according to claim 1 is characterized in that described doping agent is the mixture of cerium dioxide, cobalt oxide or their arbitrary combination.

5. preparation method according to claim 1 is characterized in that described step 1) raw material in P ₂O ₅With the mol ratio of Sn be 0.2～0.4.

6. preparation method according to claim 1 is characterized in that described step 3) in thermal treatment temp be 400～800 ℃, time 2 h.