CN101830694B - High-purity stannic oxide electrode ceramic material and preparation method thereof - Google Patents

High-purity stannic oxide electrode ceramic material and preparation method thereof Download PDF

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CN101830694B
CN101830694B CN2010101715450A CN201010171545A CN101830694B CN 101830694 B CN101830694 B CN 101830694B CN 2010101715450 A CN2010101715450 A CN 2010101715450A CN 201010171545 A CN201010171545 A CN 201010171545A CN 101830694 B CN101830694 B CN 101830694B
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涂淑进
张世俭
钟恒飞
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Guangzhou City Baiyun District Shijing Refractory Material Factory
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Abstract

The invention discloses a stannic oxide electrode ceramic material and a preparation method thereof. The stannic oxide electrode ceramic material is prepared from high-purity SnO2 powder, high-purity auxiliary materials of Sb2O3, ZnO and Pr6O11 and a water solution of sodium silicate as an active agent according to specified ratio by using a specified processing technique. The service temperature of the stannic oxide electrode ceramic material is 1,500-1,550DEG C. In addition, the copper content of the stannic oxide electrode ceramic material, which is determined by using an atom absorbing method, is less than 20ppm. The invention is applicable for producing phosphate laser glass.

Description

High-purity stannic oxide electrode ceramic material and preparation method thereof
Technical field
The present invention relates to high-purity stannic oxide electrode ceramic material and preparation method thereof.This material, for the phosphoric acid salt laser glass, also can be used for the various artistic glass that plumbous oxide content is less than 66%.
Background technology
The open CN85100034A of Chinese patent relates to the electrode of electromagnetic flowmeter material consisted of tin dioxide conductive ceramics, belongs to pottery; The formula of this electrode materials is: SnO 2be 100%; CuO is 0～5%; Sb 2o 3be 0.1～10%; ZnO is 0.4～2%; PbO is 0.007%; Fe 2o 3be 0.05%.This pottery adopts ordinary ceramic process, under oxidizing atmosphere, under 1300～1360 ℃, burns till, and its characteristic is the erosion of the various concentration strong acid of ability, and normal temperature conducts electricity very well.
Chinese patent application 200710048050.7 (CN101182096A) relates to the preparation method of the stannic oxide electrode that a kind of glass electric furnace uses, and comprise the following steps: (1) is with tin tetrachloride SnCl 4with metal chloride be raw material, adopt chemical coprecipitation to make precursor, calcining 1-2 hour under 550 ℃-650 ℃, obtain the tindioxide superfine powder of Uniform Doped 1%～3% metal oxide; (2), by waiting static pressure 200MPa moulding, 1250～1400 ℃ of lower sintering 3～8 hours, obtain density>6.5g/cm 3the high compactness stannic oxide electrode.
Chinese patent application 200810237418.9 (CN101439966A) discloses the preparation method of stannic oxide electrode ceramic material, comprises the steps: 1) batching: the quality by sintering aid is SnO 2the 0.5-1.0% of powder quality, choose sintering aid and SnO 2powder, wherein, sintering aid is MnO 2powder and CuO powder, MnO 2powder, CuO powder shared mass percent in sintering aid is: MnO 2powder 5-95%, CuO powder 5-95%; Press Sb 2o 3the quality of powder is SnO 2the 0.1-1.0% of powder quality, choose Sb 2o 3powder, standby; 2) granulation: by SnO 2powder, CuO powder, MnO 2powder, Sb 2o 3powder, organic solvent and batch mixing ball are put into ball grinder, in planetary ball mill, are mixed; The slurry mixed is poured in container, put into that baking oven carries out low-temperature bake until the organic solvent volatilization is complete, then grind, cross opening sieve, obtain mixed powder; 3) cold isostatic compaction: mixed powder is put into to mould, by the cold isostatic press moulding, obtain base substrate; 4) pressureless sintering: base substrate is put into to the sintering oven sintering, obtain stannic oxide electrode ceramic material.
Chinese patent application 200810237419.3 (CN101439967A) discloses a kind of preparation method of high compactness stannic oxide ceramic, and it comprises the steps: 1) batching: the quality by sintering aid is SnO 20.5～5.0% of powder quality, choose sintering aid and SnO 2powder, wherein, sintering aid is MnO 2powder and CuO powder, MnO 2powder, CuO powder shared mass percent in sintering aid is: MnO 2powder 5～95%, CuO powder 5～95%; 2) ball mill mixing: by SnO 2powder, CuO powder, MnO 2powder, organic solvent and batch mixing ball are put into ball grinder, in planetary ball mill, are mixed, and obtain slurry; 3) dry: slurry is poured in Glass Containers, put into baking oven and carry out low-temperature bake until solvent evaporates is complete, after grinding, cross opening sieve, obtain mixed powder; 4) calm molded: as mixed powder is carried out to die forming, vacuumize after putting into plastic jacket, then the vacuum state plastic jacket that mixed powder will be housed to put into the cold isostatic press moulding, obtain base substrate; 5) pressureless sintering: the base substrate of acquisition is put into the sintering oven sintering, obtains high compactness stannic oxide ceramic.
Tin oxide electrode in published technology generally adds copper or manganese.And neither adding copper, the present invention do not add manganese yet.The advantage of prior art is that price is relatively cheap, but has following shortcoming: 1, use temperature is lower; 2, normal temperature resistance is larger; 3, easily make glass coloring; 4, be not suitable for laser glass.
Purpose of the present invention
The invention provides a kind of preparation method of novel stannic oxide electrode ceramic material, overcome the shortcoming of prior art, the method comprises the following steps:
1) powder mixes: according to the ratio weighing of formula, first water glass is dissolved in a certain amount of pure water, then for example, (diameter is 8-12mm, preferably 9-11mm, more preferably 10mm) zirconium oxide balls adds in ball milling, then adds respectively powder and additive mixing and ball milling; Ball mill can be with inorganic corundum ball grinder.Ball milling mixing time 2～30 hours.
2) drying: by mixed slurry in Electric heat oven more than 120 ℃ temperature dry more than 14 hours, detect moisture by national standard and be less than 0.3%.
3) pulverize: the powder of mixing was ground to the opening sieve below 30 orders, obtain uniform mixed powder.
4) cold isostatic compaction: by the punching block of powder dress if any gum cover, the pressure pressurize of 200～250MPa 3～10 minutes, press to obtain base substrate.
5) base substrate finishing: repair billet surface smooth.
6) with no pressure neutral atmosphere sintering: base substrate is packed into and made high-purity stannic oxide electrode ceramic material of the present invention through 1450～1550 ℃ of insulations calcining in 3～20 hours in sintering oven.
Technical solution of the present invention
The raw material that used in the present invention has: SnO 2; Sb 2o 3; ZnO; Pr 6o 11; And sodium silicate aqueous solution.SnO 2, Sb 2o 3, ZnO and Pr 6o 11four kinds of raw materials are all preferably powder (fine particle) or coarse particles form.For pulverous raw material, its mean particle size is<600 μ m, preferably<300 μ m, more preferably<100 μ m, more more preferably<50 μ m, most preferably 0.5-5 μ m; For the raw material of coarse particles shape, its mean particle size is between 600 μ m to 5000 μ m, preferably between 600 μ m to 2000 μ m, more preferably between 300 μ m to 1000 μ m, more more preferably between 100 μ m to 500 μ m.
" mean particle size " refers to expect equal granularity in the present invention, unless otherwise mentioned.
Sb in the present invention 2o 3, ZnO and Pr 6o 11as additive; Water glass is made promoting agent, is generally to use with the form of the aqueous solution.
Preferably, the raw material used is: SnO 2, purity>=99.5%; Sb 2o 3, purity>=99.5%; ZnO, purity>=99.5%; Pr 6o 11, purity>=99%; With the degree Beaume sodium silicate aqueous solution that is 52%.In the present invention, the special raw material used in an embodiment all is required to meet above requirement.
The relative weight ratio of raw material is in the present invention: 100 parts of SnO 2, 0.5～1.5 part of (preferably 0.7～1.3, more preferably 0.8～1.1) Sb 2o 3, 0.1～1.5 part of (preferably 0.3～1.3, more preferably 0.5～1.1) ZnO, 0.1～1.5 part of (preferably 0.2～1.1, more preferably 0.3～0.8) Pr 6o 11, the sodium silicate aqueous solution of 0.05～0.5 part (preferably 0.1～0.3, more preferably 0.15～0.25).Preferably, SnO wherein 2purity>=99.5%; Sb 2o 3purity>=99.5%; ZnO purity>=99.5%; Pr 6o 11purity>=99%; With sodium silicate aqueous solution be the sodium silicate aqueous solution of degree Beaume (preferably 50～52%) (being recorded by Beaumé scale) that be 46～55%.
Generally, in mechanical milling process, various additives (are Sb 2o 3, ZnO and Pr 6o 11) and SnO 2the part by weight of powder and abrading-ball is 1: 0.9～2.0, preferably 1: 1.0～1.5, more preferably 1: 1.1～1.3, and additional 25～40% pure water mixing and ball milling 2～30 hours (preferably 3～20 hours, more preferably 4～15 hours).
Water glass is dissolved in pure water and makes degree Beaume be 46～55% sodium silicate aqueous solution of (preferably 50～52%), standby.
Most preferably, the tindioxide powder as raw material meets following technical indicator:
SnO 2>=99.5%; Cu≤3PPM; Fe≤150PPM; Pb≤140PPM; Burn and lose≤0.025%; Whiteness>=84.5; Account for whole SnO 2the SnO of the ratio that the 98wt% of powder total amount is above 2powder has<granularity of 5 microns.
In first embodiment of the present invention, the preparation method of stannic oxide electrode ceramic material is provided, it comprises the steps:
1) ball milling processing:
According to following material rate weighing: the SnO of 100 weight parts 2powder, the Sb of 0.5～1.5 weight part (preferably 0.6～1.3, more preferably 0.7～1.1) 2o 3, the ZnO of 0.1～1.5 weight part (preferably 0.6～1.3, more preferably 0.7～1.1), the Pr of 0.1～1.5 weight part (preferably 0.2～1.1, more preferably 0.3～0.8) 6o 11, Sb wherein 2o 3, ZnO and Pr 6o 11the weight summation be 1.0-3.0 weight part (preferably 1.5-2.5 weight part, more preferably 2.2 weight parts), the sodium silicate aqueous solution of 0.05～0.5 weight part (preferably 0.1～0.3, more preferably 0.15～0.25);
Mechanical milling process: above 0.1～1.0 weight part sodium silicate aqueous solution of having got ready is dissolved in or be blended in the water of 10-35 weight part (preferably 15-30 weight part) after join in ball mill, then add SnO 2powder and additive Sb 2o 3, ZnO and Pr 6o 11, then add the water of 35～10 weight parts, sealing mixing and ball milling 2～30 hours (preferably 3～20 hours, more preferably 4～15 hours);
2) drying;
3) pulverize;
4) cold isostatic compaction;
5) optional base substrate finishing: repair billet surface smooth;
6) sintering.
In second embodiment based on first embodiment of the present invention, the preparation method of stannic oxide electrode ceramic material is provided, it comprises the steps:
1) ball milling processing:
According to following material rate weighing: the SnO of 100 weight parts 2powder (mean particle size 5～0.5 μ m), the Sb of 0.5～1.5 weight part (preferably 0.6～1.3, more preferably 0.7～1.1) 2o 3(mean particle size 5～0.5 μ m), the ZnO (mean particle size 5～0.5 μ m) of 0.1～1.5 weight part (preferably 0.6～1.3, more preferably 0.7～1.1), the Pr of 0.1～1.5 weight part (preferably 0.2～1.1, more preferably 0.3～0.8) 6o 11(mean particle size 5～0.5 μ m), wherein Sb 2o 3, ZnO and Pr 6o 11the weight summation be 1.0-3.0 weight part (preferably 1.5-2.5 weight part, more preferably 2.2 weight parts), the sodium silicate aqueous solution of 0.05～1.0 weight part (preferably 0.1～0.5, more preferably 0.15～0.25);
Mechanical milling process: above 0.05～1.0 weight part sodium silicate aqueous solution of having got ready is dissolved in or for example be blended into, in the water of 10-35 weight part (15 or 25 weight parts) after join in ball mill, then 40～60 weight parts (for example 50 weight parts) (for example diameter is 8-12mm, preferred 10mm) zirconium oxide balls adds that in ball mill, (preferably, requiring various additives (is Sb 2o 3, ZnO and Pr 6o 11) and SnO 2the part by weight of powder and abrading-ball is 1: 0.9～2.0 (preferably 1: 1.2～1.6)), then add respectively and account for SnO 2the SnO of 35～65wt% of the total consumption of powder (i.e. 100 weight parts) (preferably 40～60%, more preferably 50wt%) 2powder, whole consumption are the additive (Sb of 1.0-3.0 weight part (preferably 1.5-2.5 weight part, more preferably 2.2 weight parts) 2o 3, ZnO and Pr 6o 11), account for SnO 2the SnO of the residue 65～35wt% of the total consumption of powder (preferably 60～40%, more preferably 50wt%) 2powder, and then add 60～40 weight parts (for example 50 weight parts) (for example diameter is 8-12mm, preferred 10mm) water of zirconium oxide balls and 35～10 weight parts (for example 20 or 10 weight parts), sealing mixing and ball milling 2～30 hours (preferably 3～20 hours, more preferably 4～15 hours);
2) drying;
3) pulverize;
4) cold isostatic compaction;
5) optional base substrate finishing: repair billet surface smooth;
6) sintering.
In the 3rd embodiment based on second embodiment of the present invention, the preparation method of stannic oxide electrode ceramic material is provided, it comprises the steps:
1) ball milling processing:
According to following material rate weighing: the SnO of 100 weight parts 2powder (mean particle size 5～0.5 μ m), the Sb of 0.5～1.5 weight part (preferably 0.6～1.3, more preferably 0.7～1.1) 2o 3(mean particle size 5～0.5 μ m), the ZnO (mean particle size 5～0.5 μ m) of 0.1～1.5 weight part (preferably 0.6～1.3, more preferably 0.7～1.1), the Pr of 0.1～1.5 weight part (preferably 0.2～1.1, more preferably 0.3～0.8) 6o 11(mean particle size 5～0.5 μ m), wherein Sb 2o 3, ZnO and Pr 6o 11the weight summation be 1.0-3.0 weight part (preferred 1.5-2.5 weight part, more preferably 2.2 weight parts), 0.05 the sodium silicate aqueous solution (preferably its degree Beaume is in 49～55% scopes) of～0.5 weight part (preferably 0.1～0.4, more preferably 0.15～0.3);
Mechanical milling process: above 0.1～1.0 weight part sodium silicate aqueous solution of having got ready is dissolved in or for example be blended into, in the water of 20-40 weight part (25 or 35 weight parts) after join in ball mill, then (for example diameter is 8-12mm, preferably 10mm) zirconium oxide balls of 40～60 weight parts (for example 50 weight parts) is added in ball milling; Preferably, requiring various additives (is Sb 2o 3, ZnO and Pr 6o 11) and SnO 2the part by weight of powder and abrading-ball is 1: 0.9～2.0 (preferably 1: 1.2～1.6)), then add respectively and account for SnO 2the SnO of 35～65wt% of the total consumption of powder (i.e. 100 weight parts) (preferably 40～60%, more preferably 50wt%) 2additive (the Sb of powder, whole consumption (1.0-3 weight part, preferably 1.5-2.5 weight part, more preferably 2.2 weight parts) 2o 3, ZnO and Pr 6o 11), account for SnO 2the SnO of the residue 65～35wt% of the total consumption of powder (preferably 60～40%, more preferably 50wt%) 2powder, and then add 60～40 weight parts (for example 50 weight parts) (for example diameter is 8-12mm, preferred 10mm) water of zirconium oxide balls and 40～20 weight parts (for example 35 or 25 weight parts), sealing mixing and ball milling 2～30 hours (preferably 3～20 hours, more preferably 4～15 hours);
2) drying;
3) dried mixed powder pulverizing: by step 2) obtained grinds, and crosses the opening sieve of 25-35 order (preferably 30 orders (600 μ m)), obtains uniform mixed powder; Preferably, now detect (by GB/T 3007-2006) powder moisture and be less than 0.5wt%);
4) cold isostatic compaction: powder is incorporated with in the punching block of gum cover, the pressure pressurize of 200～250MPa 3～10 minutes, press to obtain base substrate;
5) optional base substrate finishing: repair billet surface smooth;
6) with no pressure neutral atmosphere sintering: base substrate is packed in sintering oven and calcined in 3～20 hours through 1450～1550 ℃ of insulations, make high-purity stannic oxide electrode ceramic material of the present invention.
In step 1) in general, ball milling can be with inorganic corundum ball grinder.
Preferably, in first or second embodiment, wherein in step 2) in drying be following operation: by mixed slurry in Electric heat oven more than 120 ℃ temperature dry more than 14 hours, after pulverizing, sampling Detection (by GB/T 3007-2006) moisture preferably is less than 0.5%.
Preferably, in the present invention and special meet following technical indicator as the tindioxide powder of raw material in an embodiment:
SnO 2>=99.5%; Cu≤3PPM; Fe≤150PPM; Pb≤140PPM; Burn and lose≤0.025%; Whiteness>=84.5; The SnO that ratio 98wt% is above 2the mean particle size of powder<5 μ m).
As sodium silicate aqueous solution, use degree Beaume in 49～55% scopes, more preferably in 50～54% scopes, the more preferably sodium silicate aqueous solution in 51～53% scopes.
Advantage of the present invention: the advantage of this high-purity stannic oxide electrode ceramic material is to glass non-coloring, high temperature resistant.Using sintering aid is ZnO, Pr 6o 11deng.
Resistance and resistivity that the temperature-raising method resistance furnace is measured the tin oxide electrode stupalith are all lower than the prior art, and iron level is less than or equal to 150ppm, and lead content is less than or equal to 140ppm, and copper content is less than 20ppm.
The use temperature of stannic oxide electrode ceramic material of the present invention can reach the temperature between 1500～1550 ℃.
Finally, the invention provides a kind of stannic oxide electrode ceramic material, its special type is that it comprises or consists of the following composition: the SnO of 100 weight parts 2sb with 0.5～1.5 weight part as additive 2o 3, the ZnO of 0.1～1.5 weight part and the Pr of 0.1～1.5 weight part 6o 11, Sb wherein 2o 3, ZnO and Pr 6o 11the weight summation be the 1.0-3.0 weight part, and 0.05～0.5 weight part (preferably 0.1～0.4 weight part) water glass; Be that iron level is less than or equal to 150ppm, lead content is less than or equal to 140ppm, copper content is less than 20ppm.Detection method is atomic absorption method.
Embodiment:
Below in conjunction with specific embodiment, the present invention is further elaborated, and these embodiment are just to illustrating the present invention, but do not limit the scope of the invention.Protection scope of the present invention is defined by the following claims.
Embodiment 1
According to following material rate weighing: the SnO of 10kg 2powder (purity 99.6wt%, mean particle size 1 μ m), the Sb of 0.1kg 2o 3(purity 99.6wt%, mean particle size 1.5 μ m), the ZnO of 0.07kg (purity 99.6wt%, mean particle size 1.5 μ m), the Pr of 0.05kg 6o 11(purity 99.1wt%, mean particle size 1.2 μ m), the sodium silicate aqueous solution that the degree Beaume of 0.012kg is 52%; Wherein require the purity of raw material to be: SnO 2, purity>=99.5wt%; Sb 2o 3, purity>=99.5wt%; ZnO, purity>=99.5wt%; Pr 6o 11, purity>=99wt%;
By the diameter of 5kg, be that the 10mm zirconium oxide balls adds in ball mill, the sodium silicate aqueous solution that the degree Beaume of then 0.012kg having been got ready is 52% and 2kg water dissolve each other and join in ball mill, add respectively afterwards the SnO of 5kg 2the additive of powder, the 0.22kg (Sb of 0.1kg 2o 3, the ZnO of 0.07kg and the Pr of 0.05kg 6o 11), add 5kgSnO again 2the diameter of powder and 5kg is 10mm zirconium oxide balls and 2kg water, then seals mixing and ball milling 6 hours;
Dry: by mixed slurry in Electric heat oven more than 120 ℃ temperature dry more than 14 hours, be less than 0.3wt% by national standard (GB/T 3007-2006) detection moisture;
Pulverize: the powder of mixing was ground to the opening sieve of 30 orders (600 μ m), and obtained uniform mixed powder;
Cold isostatic compaction: the powder after granulation is incorporated with in the punching block of gum cover, the pressure pressurize of 220MPa 7 minutes, press to obtain base substrate;
Base substrate finishing: repair billet surface smooth;
With no pressure neutral atmosphere sintering: base substrate is packed in sintering oven through 1450 ℃ of insulations calcining in 5 hours, make high-purity stannic oxide electrode ceramic material of the present invention.
Embodiment 2:
Repeat the operation of embodiment 1, just, through 1500 ℃ of insulations calcining in 5 hours, make high-purity stannic oxide electrode ceramic material of the present invention.
Embodiment 3:
Repeat the operation of embodiment 1, just, through 1550 ℃ of insulations calcining in 5 hours, make high-purity stannic oxide electrode ceramic material of the present invention.
Embodiment 4:
Repeat the operation of embodiment 1, just with the sodium silicate aqueous solution of the degree Beaume 52% of 0.006kg, make promoting agent, and SnO 2, Sb 2o 3, ZnO, Pr 6o 11mass ratio be 1: 0.008: 0.005: 0.004, total consumption of these four kinds of raw materials is 1017g (additive is additional), with 350ml water mixing and ball milling evenly, oven dry, grinding, moulding, make high-purity stannic oxide electrode ceramic material of the present invention through 1500 ℃ of insulations calcining in 5 hours.
Embodiment 5:
Repeat the operation of embodiment 1, just with the sodium silicate aqueous solution of the degree Beaume 52% of 0.006kg, make promoting agent, press SnO 2, Sb 2o 3, ZnO, Pr 6o 11mass ratio be 1: 0.008: 0.007: 0.003 weighing 1000g SnO 2and additive (Sb 2o 3, ZnO, Pr 6o 11) amount and 400ml water mixing and ball milling evenly, oven dry, grinding, moulding, make high-purity stannic oxide electrode ceramic material of the present invention through 1530 ℃ of insulations calcining in 5 hours.
The resistance of measuring the tin oxide electrode stupalith is the sample with 1*1*7cm, uses the conduction silver paste to connect sample and platinum wire lead-in wire.
The resistance of tin oxide electrode stupalith and resistivity
Figure GSA00000119404700101
Figure GSA00000119404700111
Physicals contrast: inspecting standard GB/T 2997-2000 (2004)
Performance The coventional type of prior art Embodiment 1 Embodiment 2 Embodiment 5
Apparent porosity (%) ≤1 5 4.9 4.7
Body close (volume density) (g/cm 3) ≥6.60 6.30 6.35 6.20
1600 ℃ of cracking resistances Poor Excellent Excellent Excellent
Iron (Fe) content ＞200ppm ≤110ppm ≤105ppm ≤110ppm
Lead content ＞200ppm ≤100ppm ≤90ppm ≤105ppm
Copper content ＞50ppm ＜20ppm ＜20ppm ＜20ppm
The stannic oxide electrode ceramic material obtained by method of the present invention has the following advantages:
1) improve use temperature: former use temperature is 1350～1400 ℃; Present use temperature can be 1500～1550 ℃ of scopes;
2) reduce electrode normal temperature and high temperature resistance (temperature-raising method resistance furnace mensuration): referring to the subordinate list of front;
3) minimizing is painted to glasswork: (simultaneous test heats up in the white glass material);
4) reach the service requirements of laser glass: laser glass requires iron level low simultaneously, generally lower than 500ppm, preferably lower than 300ppm, more preferably less than 150ppm, again more preferably less than 50ppm, without copper and manganese, have copper copper content be less than 20ppm.Detection method is atomic absorption method.

Claims (3)

1. the preparation method of stannic oxide electrode ceramic material, it comprises the steps:
1) ball milling processing:
According to following material rate weighing: the SnO of 100 weight parts 2powder, the Sb of 0.5～1.5 weight part 2o 3, the ZnO of 0.1～1.5 weight part, the Pr of 0.1～1.5 weight part 6o 11, Sb wherein 2o 3, ZnO and Pr 6o 11the weight summation be the 1.0-3.0 weight part, the sodium silicate aqueous solution of 0.05～1.0 weight part;
Mechanical milling process: above 0.05～1.0 weight part sodium silicate aqueous solution that oneself gets ready is dissolved in or be blended in the water of 10-35 weight part after join in ball mill, then the zirconium oxide balls of 40～60 weight parts is added in ball mill, then add successively and account for SnO 2the SnO of 35～65wt% of total consumption 100 weight parts of powder 2powder, as the Sb of 0.5～1.5 weight part of additive 2o 3, the Pr of the ZnO of 0.1～1.5 weight part and 0.1～1.5 weight part 6o 11, Sb wherein 2o 3, ZnO and Pr 6o 11the weight summation be the 1.0-3.0 weight part, account for SnO 2the SnO of the residue 65～35wt% of the total consumption of powder 2powder, and then add the zirconium oxide balls of 60～40 weight parts and the water of 35～10 weight parts, sealing mixing and ball milling 2～30 hours;
2) drying;
3) pulverize;
4) cold isostatic compaction;
5) optional base substrate finishing: repair billet surface smooth;
6) sintering.
2. according to the process of claim 1 wherein step 4) cold isostatic compaction carries out as follows:
Powder is incorporated with in the punching block of gum cover, under the pressure of 200～250MPa, pressurize is 3～10 minutes, presses to obtain base substrate.
3. according to the process of claim 1 wherein step 6) sintering carries out as follows:
Base substrate is packed in sintering oven through 1450～1550 ℃ of insulations calcining in 3～20 hours, make stannic oxide electrode ceramic material.
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