CN100378870C - Process for preparing nano-oxide conducting powder - Google Patents
Process for preparing nano-oxide conducting powder Download PDFInfo
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- CN100378870C CN100378870C CNB200510010676XA CN200510010676A CN100378870C CN 100378870 C CN100378870 C CN 100378870C CN B200510010676X A CNB200510010676X A CN B200510010676XA CN 200510010676 A CN200510010676 A CN 200510010676A CN 100378870 C CN100378870 C CN 100378870C
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Abstract
The present invention relates to a method for preparing nanometer oxide conductive powder, which belongs to the technical field of a conductive material. The conductive powder is nanometer oxide conductive powder of which the surface is wrapped by stannum oxide mixing antimony. A prepared acidic solution containing stannum and the antimony and a precipitating agent of alkaline liquor are simultaneously dropped in stirred oxide slurry by a liquid distributor, the flow capacity of the acidic solution and the alkaline liquor is regulated to control the pH value of a system between 1.5 and 5 and carry out a smooth reaction, and the hydrolysate of the stannum and the antimony is co-deposited on the particle surface of oxide powder; after the standing operation of the coating product of the deposition is carried out, light-colored oxide conductive powder is obtained by washing, filtration, drying, calcination and pulverization. The present invention has the advantages of large yield, high automation degree, stable quality, low cost, etc., and the obtained product has the advantages of low antimony content, light-colored powder, low resistance, easy dispersion, heat resistance, corrosion resistance, high stability and good wave penetrating property; permanent conductive additive agents with various colours, which are close to white, etc. The present invention has wide application prospect.
Description
Technical field
The present invention relates to a kind of nano-oxide conducting powder and preparation method thereof, belong to the electric conducting material technical field.
Background technology
Conducting powder is widely used in each industrial department and people's daily life fields such as oil, chemical industry, electronics, communication, automobile, papermaking, weaving, pottery, Aero-Space, in the time of in making an addition to coating, printing ink, plastics, rubber, fiber, can be made into antistatic product.
It is powder, organic powder and metal oxide powder that tradition conducting powder commonly used has metal powder, charcoal.Organic conductive filler non-refractory, not corrosion-resistant, resistance to water, oil resistance, poor durability and antistatic behaviour instability only can be applicable to relative humidity greater than 60% environment, surface resistivity is generally greater than 100 megaohms; Black conductive graphite, the carbon black bad dispersibility, the goods darker in color is difficult for toning, and operational environment is easily stained in production and use; Silver, aluminium, copper, the easy oxidation of metal dusts such as nickel, corrosion-resistant is disturbed the defective of radio wave, cost an arm and a leg and color darker.
Research about light-colour electrically conductive powder mainly concentrates on Japan and Europe, and China also has some at present.Its right of the clear 63-233016 of Japan Patent and feature request are needle-like titanium dioxide, and length is 1-10um, and draw ratio is greater than three, and its requirement is too loaded down with trivial details to the pre-soda acid processing of titanium dioxide, and cost is higher, and, Sb
2O
3/ SnO
2Mass ratio is up to 21.87%, and the content of antimony has determined the depth of powder color.British patent NO.2252551 discloses the preparation method of a kind of silicon dioxide and the conducting powder of the tin oxide that contains antimony, this method is used earlier coated with silica titanium dioxide, form the intermediate layer, controlled condition is deposited on its particle surface washing with the hydrolysate of tin antimony again, drying and calcining forms, the powder resistance that this method obtains higher (300-400 Ω .cm), and step is too much.Domestic patent 03115830.7 its claim and feature are that the nitrate solution of tin, antimony and ammoniacal liquor and stream are added in the distilled water, and sediment gets conductive powder body through Overheating Treatment, though conductivity is good, tin antimony consumption is big, and color is dark excessively, and cost is higher.Its claim of Chinese patent 0111881.X and feature are in producing the solution of antimonic salt, pink salt to be added in the slurries of titanium dioxide respectively or antimonic salt mixes with pink salt afterwards in the adding titanium dioxide slurries, the middle online constant control of not making pH value, the pH value of its terminal point is 7～13, the strong basicity environment must cause the non-coprecipitated of antimony tin, the doping effect of antimony is affected, the too high (Sb in the embodiment of antimony content
2O
3/ SnO
2Mass ratio is up to 25%).
Have conductive powder body resistivity problem of higher in the more than existing invention, the doped chemical antimony addition of use is many, and cost is higher and cause the color of conductive powder body darker easily, the whiteness deficiency.In addition, said method is applicable to the conductive powder body preparation of titanium oxide powder granularity greater than micron, and nano-powder then need make powder fully disperse before coating.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, provide a kind of whiteness and conductivity all good nano-oxide light-colored conductive powder and industrial processes thereof.
Technical scheme of the present invention is: this nano-oxide conducting powder is the nano-oxide conducting powder that is coated with antimony doped tin oxide, nano-oxide is a kind of nano-metal-oxide of stable performance or the mixture of multiple nano-metal-oxide, and the nano-metal-oxide of stable performance can be a nano-TiO
2, SiO
2, Al
2O
3Powder etc.The volume resistance of conducting powder is 10～400 Ω .cm, and the whiteness index is L=70-86, Sb
2O
3With SnO
2Mass ratio be 0.03～0.15, SnO
2With the mass ratio of oxide carrier be 0.1～0.3.
The preparation method of this nano-oxide conducting powder may further comprise the steps successively:
1.1 with particle mean size less than 200nm's and the mixture carrier of stable performance a kind of metal oxide or multiple metal oxide, as TiO
2Or SiO
2, Al
2O
3In, or both above mixtures wherein, in the reactor that can heat, stir with deionized water or distilled water by the amount of 50～200g/L, and add polyphosphoric acid or polyphosphate is made dispersant, oxide powder is uniformly dispersed.Polyphosphoric acid or polyphosphate are the polyphosphoric acid acid and the various salt thereof of n 〉=3, and as lithium, sodium, potassium, ammonia salt etc., the molar concentration of its adding is 0.001～0.02mol/L.Dispersant can be eliminated the reunion of nano oxide powder, makes the tin oxide coating layer more even, is coated on the surface of oxide primary particle densely.
1.2 the acidic mixed solution that preparation is made up of the hydrochloric acid of tin, antimony or nitrate or sulfate, the concentration of tin is 0.1～2mol/L in this acidic mixed solution, Sb
2O
3With SnO
2Mass ratio be 0.03～0.15.The preparation of acidic mixed solution is under 30～90 ℃ of temperature, nitric acid or sulfuric acid or hydrochloric acid are added dropwise in the mixture of glass putty and antimony powder, the equivalent of nitric acid or sulfuric acid or hydrochloric acid is 2～10N, or pink salt and antimonic salt are dissolved in the nitric acid or sulfuric acid or hydrochloric acid of 2～8N.Pink salt is one or more in STANNOUS SULPHATE CRYSTALLINE, stannic chloride, stannous chloride, nitric acid tin or the pink salt of being with the crystallization water, and antimonic salt is one or more in antimony sulfate, nitric acid antimony or the antimony chloride.In acidic mixed solution, also can add the chelating agent tartaric acid or the tartrate that promote antimony, tin codeposition, the tartrate anion of the chelating agent that adds and the mol ratio of antimony are 1～6, antimony can more effectively be entrained on the lattice of tin when chelating agent can make co-precipitation, reduce the consumption of antimony significantly, and the nano-oxide conducting powder color that obtains is shoaled.
1.3 with acidic mixed solution and alkali lye precipitation reagent, splash in the reactor that fills homodisperse oxidate powder carrier and keep stirring simultaneously with tiny drop by liquid distribution trough, by regulating the flow of acid, alkali lye, the hierarchy of control under 30～90 ℃ of temperature, keep pH value smooth reaction in 1.5～5 scopes, make the hydrolysis of tin antimony and produce codeposition, be coated on the oxide powder particle surface equably.Liquid distribution trough is the filter of band micropore, and its micro-pore diameter is 1～5mm, be spaced apart 1～5cm (selecting according to actual needs); The alkali lye precipitation reagent is one or more the mixed liquor in ammoniacal liquor, carbonic acid ammonia, ammonium hydrogencarbonate, sodium acid carbonate, sodium carbonate, the NaOH, and its equivalent is 2～10N; The Flow-rate adjustment of acid, alkali lye can adopt online pH value control system, mix acid liquor and alkali lye are added liquid distribution trough by quantitative by-pass cock or electromagnetically operated valve, in reactor, insert PH probe acquired signal, by PH meter with set pH value and compare, and quantitative by-pass cock of FEEDBACK CONTROL or electromagnetically operated valve, the addition of control mix acid liquor and alkali lye; Online pH value controlling reaction time is 0.5～4 hour.
1.4 the coating product that will precipitate left standstill more than 0.5 hour, washed then, filter, and drying, calcining is pulverized, and obtains light oxide conductive powder, and calcining heat is that 350～650 ℃, time are 1～3 hour; Can filter 2～5 times, drying can be carried out under 80～120 ℃.
The nano-metal-oxide powder (carrier) of stable performance can also be leucocratic mineral powders such as mica, barite, calcium carbonate, can be with wherein one or more mixture as the carrier of antimony doped tin oxide deposition.
The present invention is by the electric conductivity of further investigation stibium doping stannic oxide and the Zeta potential figure of Zeta potential figure and oxide carrier powder thereof, utilize polyphosphoric acid or polyphosphate to make the oxide nonmetallic powder before coating be dispersed into individual particle as the dispersant of oxide, thereby make conductive layer can be coated on the individual particle surface, obtain the low powder of resistivity; Utilize tartaric acid and its esters as the chelating agent control antimony of antimony and the coprecipitation process of tin, antimony can more effectively be entrained on the lattice of tin, reduce the consumption of antimony; Utilize accurate On-Line Control Method that technological parameter is controlled in the best narrow scope simultaneously, make stibium doping stannic oxide more firm, be coated on equably on the surface of oxide of the titanium dioxide of high degree of dispersion or other stable performance, form a skim, and the controllable thickness of film, conductivity are also adjustable.Therefore, it is big that this method has output, the automaticity height, and quality is highly stable, the advantage that cost is low; The product that this method obtains has the low (Sb of antimony content
2O
3/ SnO
2Mass ratio is less than 15%), powder is of light color, resistance is lower advantage, wide industrial prospect is arranged.
The present invention also has easy dispersion, and is heat-resisting, and stability is high, and corrosion-resistant, wave is good, and characteristics such as good conductivity easily are modulated into versicolor permanent conductive additives such as near-white.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples.
Fig. 1 is a process chart of the present invention:
Fig. 2 is the titanium dioxide conductive powder body XRD figure spectrum of the embodiment of the invention 3;
Fig. 3 is the titanium dioxide conductive powder body XRD figure spectrum of the embodiment of the invention 5;
Fig. 4 is the titanium dioxide conductive powder body TEM figure of the embodiment of the invention 5.
Embodiment
Embodiment 1: this nano-oxide conducting powder is the nano-TiO that is coated with antimony doped tin oxide
2Conducting powder, its volume resistance are 400 Ω .cm, and the whiteness index is L=84.2, Sb
2O
3With SnO
2Mass ratio be 0.03, SnO
2With TiO
2Mass ratio be 0.2.
The preparation method of this nano-oxide conducting powder may further comprise the steps successively:
1.1 TiO with 10g particle mean size 130nm
2, add in the 200mL distilled water in the reactor, to add molar concentration again be the polyphosphoric acid of 0.001mol/L and stir, and makes TiO
2Be uniformly dispersed.
1.2 under 60 ℃ of temperature, with 4.653g SnCl
45H2O and 0.094g SbCl
3Be dissolved in the hydrochloric acid of 60ml 8N, (concentration of tin is 0.22mol/L, Sb to obtain acidic mixed solution
2O
3With SnO
2Mass ratio be 0.03);
1.3 with acidic mixed solution and equivalent is the ammonia precipitation process agent of 2N, by micro-pore diameter be 1mm, the liquid distribution trough that is spaced apart 1cm splashes into simultaneously with tiny drop and fills homodisperse TiO
2And in the reactor that keep to stir,, regulate the flow of acid, alkali lye by online pH value control system, the hierarchy of control under 60 ℃ of temperature, to keep pH value be 1.5 smooth reactions 1 hour, make the hydrolysis of tin antimony and produce codeposition, be coated on TiO equably
2On the surface.Online pH value control system is that mix acid liquor and alkali lye are added liquid distribution trough by quantitative by-pass cock or electromagnetically operated valve, in reactor, insert PH probe acquired signal, by PH meter with set pH value and compare, and quantitative by-pass cock of FEEDBACK CONTROL or electromagnetically operated valve, the addition of control mix acid liquor and alkali lye.
1.4 the coating product that will precipitate left standstill 0.5 hour, washed then, filters 5 times (silver chlorate solution is detected less than chloride ion), after 80 ℃ of following dryings, 650 ℃ of calcinings 1 hour, through pulverizing, obtained light TiO again
2Conducting powder.
Embodiment 2: this nano-oxide conducting powder is the nanometer SiO that is coated with antimony doped tin oxide
2Conducting powder, its volume resistance are 180 Ω .cm, and the whiteness index is L=71.3, Sb
2O
3With SnO
2Mass ratio be 0.15, SnO
2With SiO
2Mass ratio be 0.3.
The preparation method of this nano-oxide conducting powder may further comprise the steps successively:
1.1 SiO with 40g particle mean size 200nm
2, add in the 200mL distilled water in the reactor, to add molar concentration again be the sodium polyphosphate of 0.01mol/L and stir, just SiO
2Be uniformly dispersed.
1.2 under 30 ℃ of temperature, with 27.92g SnCl
4H2O and 2.82g SbCl
3Be dissolved in the hydrochloric acid of 70ml 2N, (concentration of tin is 1.138mol/L, Sb to obtain acidic mixed solution
2O
3With SnO
2Mass ratio be 0.15);
1.3 with acidic mixed solution and equivalent is the ammonia precipitation process agent of 10N, by micro-pore diameter be 5mm, the liquid distribution trough that is spaced apart 5cm splashes into simultaneously with tiny drop and fills the SiO that all disperses
2And in the reactor that keep to stir,, regulate the flow of acid, alkali lye by online pH value control system, the hierarchy of control under 30 ℃ of temperature, to keep pH value be 5 smooth reactions 4 hours, make the hydrolysis of tin antimony and produce codeposition, be coated on SiO equably
2On the surface.Online pH value control system is that mix acid liquor and alkali lye are added liquid distribution trough by quantitative by-pass cock or electromagnetically operated valve, in reactor, insert PH probe acquired signal, by PH meter with set pH value and compare, and quantitative by-pass cock of FEEDBACK CONTROL or electromagnetically operated valve, the addition of control mix acid liquor and alkali lye.
1.4 the coating product that will precipitate left standstill 3 hours, washed then, filters 2 times (silver chlorate solution is detected less than chloride ion), after 120 ℃ of following dryings, 350 ℃ of calcinings 3 hours, through pulverizing, obtained light SiO again
2Conducting powder.
Embodiment 3: this nano-oxide conducting powder is the nano-TiO that is coated with antimony doped tin oxide
2Conducting powder, its volume resistance are 28 Ω .cm, and the whiteness index is L=84.5, Sb
2O
3With SnO
2Mass ratio be 0.1, SnO
2With TiO
2Mass ratio be 0.25.
The preparation method of this nano-oxide conducting powder may further comprise the steps successively:
1.1 TiO with 1165g particle mean size 50nm
2, add in the 11.65L distilled water in the reactor, to add molar concentration again be the potassium polyphposphate of 0.002mol/L and stir, and makes TiO
2Be uniformly dispersed.
1.2 under 40 ℃ of temperature, with 677.5g SnCl
45H2O and 45.58g SbCl
3Be dissolved in the hydrochloric acid of 6.991 liters of 6N, (concentration of tin is 0.276mol/L, Sb to obtain acidic mixed solution
2O
3With SnO
2Mass ratio be 0.1), add a certain amount of chelating agent tartaric acid again in sour mixed solution, the mol ratio that makes tartrate anion and antimony is 2;
1.3 with acidic mixed solution and equivalent is the ammonia precipitation process agent of 6N, by micro-pore diameter be 2mm, the liquid distribution trough that is spaced apart 2cm splashes into simultaneously with tiny drop and fills homodisperse TiO
2And in the reactor that keep to stir,, regulate the flow of acid, alkali lye by online pH value control system, the hierarchy of control under 40 ℃ of temperature, to keep pH value be 2.2 smooth reactions 1.5 hours, make the hydrolysis of tin antimony and produce codeposition, be coated on TiO equably
2On the surface.Online pH value control system is that mix acid liquor and alkali lye are added liquid distribution trough by quantitative by-pass cock or electromagnetically operated valve, in reactor, insert PH probe acquired signal, by PH meter with set pH value and compare, and quantitative by-pass cock of FEEDBACK CONTROL or electromagnetically operated valve, the addition of control mix acid liquor and alkali lye.
1.4 the coating product that will precipitate left standstill 3 hours, washed then, filter 23 time (silver chlorate solution is detected less than chloride ion), after 100 ℃ of following dryings, 500 ℃ of calcinings 1.5 hours, through pulverizing, obtained light TiO again
2Conducting powder.
Embodiment 4: this nano-oxide conducting powder is the nano-TiO that is coated with antimony doped tin oxide
2And SiO
2Conducting powder, its volume resistance are 25 Ω .cm, and the whiteness index is L=81.2, Sb
2O
3With SnO
2Mass ratio be 0.05, SnO
2With TiO
2And SiO
2The mass ratio of mixed oxide is 0.2.
The preparation method of this nano-oxide conducting powder may further comprise the steps successively:
1.1 TiO with 665g particle mean size 130nm
2With the SiO of 500g particle mean size less than 200nm
2, add in the 11.65L distilled water in the reactor, to add molar concentration again be the sodium polyphosphate of 0.002mol/L and stir, and mixed oxide is uniformly dispersed.
1.2 under 45 ℃ of temperature, with 542.03g SnCl
4H2O and 18.23g SbCl
3Be dissolved in the hydrochloric acid of 3 liters of 6N, (concentration of tin is 0.52mol/L, Sb to obtain acidic mixed solution
2O
3With SnO
2Mass ratio be 0.05), add a certain amount of chelating agent tartaric acid again in sour mixed solution, the mol ratio that makes tartrate anion and antimony is 4;
1.3 with acidic mixed solution and equivalent is the ammonia precipitation process agent of 7N, by micro-pore diameter be 3mm, the liquid distribution trough that is spaced apart 3cm splashes into simultaneously with tiny drop and fills homodisperse TiO
2And SiO
2And in the reactor that keeps stirring, by online pH value control system, regulate the flow of acid, alkali lye, the hierarchy of control under 50 ℃ of temperature, to keep pH value be 3.5 smooth reactions 1.2 hours, make the hydrolysis of tin antimony and produce codeposition, be coated on the mixed oxide surface equably.Online pH value control system is that mix acid liquor and alkali lye are added liquid distribution trough by quantitative by-pass cock or electromagnetically operated valve, in reactor, insert PH probe acquired signal, by PH meter with set pH value and compare, and quantitative by-pass cock of FEEDBACK CONTROL or electromagnetically operated valve, the addition of control mix acid liquor and alkali lye.
1.4 the coating product that will precipitate left standstill 2 hours, washed then, filters 4 times (silver chlorate solution is detected less than chloride ion), after 80 ℃ of following dryings, 600 ℃ of calcinings 1.2 hours, through pulverizing, obtained light oxide conductive powder again.
Embodiment 5: this nano-oxide conducting powder is to be coated with SnO
2And Sb
2O
3The nano-TiO of codeposit
2Conducting powder, its volume resistance are 250 Ω .cm, and the whiteness index is L=86, Sb
2O
3With SnO
2Mass ratio be 0.05, SnO
2With TiO
2Mass ratio be 0.25.
The preparation method of this nano-oxide conducting powder may further comprise the steps successively:
1.1 TiO with 20g particle mean size 50nm
2, add in the 200mL distilled water in the reactor, to add molar concentration again be the sodium polyphosphate of 0.001mol/L and stir, and makes TiO
2Be uniformly dispersed.
1.2 under 75 ℃ of temperature, with 11.63g SnCl
4H2O and 0.39g SbCl
3Be dissolved in the hydrochloric acid of 30ml 8N, (concentration of tin is 1.1mol/L, Sb to obtain acidic mixed solution
2O
3With SnO
2Mass ratio be 0.05);
1.3 with acidic mixed solution and equivalent is the ammonia precipitation process agent of 8N, by micro-pore diameter be 3mm, the liquid distribution trough that is spaced apart 2.5cm splashes into simultaneously with tiny drop and fills homodisperse TiO
2And in the reactor that keep to stir,, regulate the flow of acid, alkali lye by online pH value control system, the hierarchy of control under 75 ℃ of temperature, to keep pH value be 1.9 smooth reactions 1 hour, make the hydrolysis of tin antimony and produce codeposition, be coated on TiO equably
2On the surface.Online pH value control system is that mix acid liquor and alkali lye are added liquid distribution trough by quantitative by-pass cock or electromagnetically operated valve, in reactor, insert PH probe acquired signal, by PH meter with set pH value and compare, and quantitative by-pass cock of FEEDBACK CONTROL or electromagnetically operated valve, the addition of control mix acid liquor and alkali lye.
1.4 the coating product that will precipitate left standstill 2.5 hours, washed then, filters 4 times (silver chlorate solution is detected less than chloride ion), after 60 ℃ of following dryings, 400 ℃ of calcinings 2 hours, through pulverizing, obtained light TiO again
2Conducting powder.
Embodiment 6: this nano-oxide conducting powder is to be coated with SnO
2And Sb
2O
3The nanometer Al of codeposit
2O
3Conducting powder, its volume resistance are 200 Ω .cm, and the whiteness index is L=85, Sb
2O
3With SnO
2Mass ratio be 0.1, SnO
2With Al
2O
3Mass ratio be 0.1.
The preparation method of this nano-oxide conducting powder may further comprise the steps successively:
1.1 Al with 100g particle mean size 100nm
2O
3, add in the 1L distilled water in the reactor, to add molar concentration again be the sodium polyphosphate of 0.015mol/L and stir, and makes Al
2O
3Be uniformly dispersed.
1.2 under 90 ℃ of temperature, the sulfuric acid of 10N is added dropwise in the mixture of 7.88g glass putty and 0.835g antimony powder, (concentration of tin is 2mol/L, Sb to obtain acidic mixed solution
2O
3With SnO
2Mass ratio be 0.04), add a certain amount of chelating agent tartaric acid again in sour mixed solution, the mol ratio that makes tartrate anion and antimony is 6;
1.3 with acidic mixed solution and equivalent is ammoniacal liquor, the carbonic acid ammonia mixed precipitant of 10N, by micro-pore diameter be 1.5mm, the liquid distribution trough that is spaced apart 1cm splashes into simultaneously with tiny drop and fills homodisperse Al
2O
3And in the reactor that keep to stir,, regulate the flow of acid, alkali lye by online pH value control system, the hierarchy of control under 90 ℃ of temperature, to keep pH value be 5 smooth reactions 1 hour, make the hydrolysis of tin antimony and produce codeposition, be coated on Al equably
2O
3On the surface.Online pH value control system is that mix acid liquor and alkali lye are added liquid distribution trough by quantitative by-pass cock or electromagnetically operated valve, in reactor, insert PH probe acquired signal, by PH meter with set pH value and compare, and quantitative by-pass cock of FEEDBACK CONTROL or electromagnetically operated valve, the addition of control mix acid liquor and alkali lye.
1.4 the coating product that will precipitate left standstill 2 hours, washed then, filters 5 times (make in the cleaning solution inspection and do not detect sulfate ion), after 90 ℃ of following dryings, 500 ℃ of calcinings 1.5 hours, through pulverizing, obtained light oxide conductive powder again.
Embodiment 7: this nano-oxide conducting powder is to be coated with SnO
2And Sb
2O
3The nano-TiO of codeposit
2Conducting powder, its volume resistance are 10 Ω .cm, and the whiteness index is L=83.5, Sb
2O
3With SnO
2Mass ratio be 0.06, SnO
2With TiO
2Mass ratio be 0.3.
The preparation method of this nano-oxide conducting powder may further comprise the steps successively:
1.1 TiO with 100g particle mean size 200nm
2, add in the 1L distilled water in the reactor, to add molar concentration again be the polyphosphoric acid lithium of 0.015mol/L and stir, and makes TiO
2Be uniformly dispersed.
1.2 under 30 ℃ of temperature, sulfuric acid and the nitric acid of 2N is added dropwise in the mixture of 23.62g glass putty and 1.5g antimony powder, (concentration of tin is 0.1mol/L, Sb to obtain acidic mixed solution
2O
3With SnO
2Mass ratio be 0.06), add a certain amount of chelating agent tartaric acid again in sour mixed solution, the mol ratio that makes tartrate anion and antimony is 1;
1.3 with acidic mixed solution and equivalent is ammonium hydrogencarbonate, the sodium acid carbonate mixed precipitant of 2N, by micro-pore diameter be 4mm, the liquid distribution trough that is spaced apart 4cm splashes into simultaneously with tiny drop and fills homodisperse TiO
2And in the reactor that keep to stir,, regulate the flow of acid, alkali lye by online pH value control system, the hierarchy of control under 30 ℃ of temperature, to keep pH value be 1.5 smooth reactions 4 hours, make the hydrolysis of tin antimony and produce codeposition, be coated on TiO equably
2On the surface.Online pH value control system is that mix acid liquor and alkali lye are added liquid distribution trough by quantitative by-pass cock or electromagnetically operated valve, in reactor, insert PH probe acquired signal, by PH meter with set pH value and compare, and quantitative by-pass cock of FEEDBACK CONTROL or electromagnetically operated valve, the addition of control mix acid liquor and alkali lye.
1.4 the coating product that will precipitate left standstill 3 hours, washed then, filters 2 times (make in the cleaning solution inspection and do not detect sulfuric acid, nitrate ion), after 80 ℃ of following dryings, 550 ℃ of calcinings 1.8 hours, through pulverizing, obtained light TiO again
2Conducting powder.
The resistance measurement of the light titanium dioxide conducting powder that the present invention produced is that 5 gram conducting powder are packed in the PVC plastic tube, applies the pressure measxurement volume resistance R of 10Mpa at two ends, calculates by formula=R (A/L) again.A is the plastic tube area of section in the formula, and L is the height of compression back conduction powder agglomates.Whiteness is measured according to GB/T5950-1996, carries out on the whiteness instrument.
Claims (8)
1. nano-oxide conducting powder, it is characterized in that this conducting powder is the nano-oxide conducting powder that is coated with antimony doped tin oxide, nano-oxide is a kind of nano-metal-oxide of stable performance or the mixture of multiple nano-metal-oxide, the nano-metal-oxide of stable performance can be nano TiO 2, SiO2, Al2O3 powder, the volume resistance of conducting powder is 10-400 Ω cm, the whiteness index is L=70-86, the mass ratio of Sb2O3 and SnO2 is 0.03-0.15, and the mass ratio of SnO2 and oxide carrier is 0.1-0.3.
2. the preparation method of the described nano-oxide conducting powder of claim 1 is characterized in that may further comprise the steps successively:
1.1 with particle mean size less than a kind of metal oxide of 200nm and stable performance or the mixture carrier of multiple metal oxide, amount by 50-200g/L stirs in the reactor that can heat with deionized water or distilled water, and add polyphosphoric acid or polyphosphate is made dispersant, oxide powder is uniformly dispersed;
1.2 the acidic mixed solution that preparation is made up of the hydrochloric acid of tin, antimony or nitrate or sulfate, the concentration of tin is 0.1-2mol/L in this acidic mixed solution, and the mass ratio of Sb2O3 and SnO2 is 0.03-0.15;
1.3 with acidic mixed solution and alkali lye precipitation reagent, splash in the reactor that fills homodisperse oxide powder and keep stirring simultaneously with tiny drop by liquid distribution trough, by regulating the flow of acid, alkali lye, the hierarchy of control under 30-90 ℃ of temperature, keep pH value smooth reaction in the 1.5-5 scope, make the hydrolysis of tin antimony and produce codeposition, be coated on the oxidate powder surface equably;
1.4 the coating product that will precipitate left standstill more than 0.5 hour, washed then, filter, and drying, calcining is pulverized, and obtains light oxide conductive powder, and calcining heat is that 350-650 ℃, time are 1-3 hour.
3. the preparation method of nano-oxide conducting powder as claimed in claim 2 is characterized in that polyphosphoric acid or polyphosphate are the polyphosphoric acid acid and the various salt thereof of n 〉=3, and the molar concentration of its adding is 0.001-0.02mol/L.
4. the preparation method of nano-oxide conducting powder as claimed in claim 2, the preparation that it is characterized in that acidic mixed solution is under 30-90 ℃ of temperature, nitric acid or sulfuric acid or hydrochloric acid are added dropwise in the mixture of glass putty and antimony powder, and the equivalent of nitric acid or sulfuric acid or hydrochloric acid is 2-10N; Or pink salt and antimonic salt be dissolved in the nitric acid or sulfuric acid or hydrochloric acid of 2-8N.
5. as the preparation method of claim 2 or 3 described nano-oxide conducting powders, it is characterized in that pink salt is one or more in STANNOUS SULPHATE CRYSTALLINE, stannic chloride, stannous chloride, nitric acid tin or the pink salt of being with the crystallization water, antimonic salt is one or more in antimony sulfate, nitric acid antimony or the antimony chloride.
6. as the preparation method of claim 2 or 3 described nano-oxide conducting powders, it is characterized in that adding chelating agent tartaric acid or the tartrate that promotes antimony, tin codeposition in acidic mixed solution, the tartrate anion of the chelating agent of adding and the mol ratio of antimony are 1-6.
7. the preparation method of nano-oxide conducting powder as claimed in claim 2 is characterized in that the alkali lye precipitation reagent is one or more the mixed liquor in ammoniacal liquor, carbonic acid ammonia, ammonium hydrogencarbonate, sodium acid carbonate, sodium carbonate, the NaOH, and its equivalent is 2-10N.
8. the preparation method of nano-oxide conducting powder as claimed in claim 2, the Flow-rate adjustment that it is characterized in that acid, alkali lye can adopt online pH value control system, mix acid liquor and alkali lye are added liquid distribution trough by quantitative by-pass cock or electromagnetically operated valve, in reactor, insert PH probe acquired signal, by PH meter with set pH value and compare, and quantitative by-pass cock of FEEDBACK CONTROL or electromagnetically operated valve, the addition of control mix acid liquor and alkali lye; The online reaction time is 0.5-4 hour.
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| CN102583524B (en) * | 2012-01-31 | 2014-02-05 | 厦门大学 | Preparation method for conductive titanium dioxide powder |
| JP6071360B2 (en) | 2012-09-14 | 2017-02-01 | 三井金属鉱業株式会社 | Conductive particles |
| CN103985430A (en) * | 2014-05-28 | 2014-08-13 | 天津大学 | Antimony-doped tin oxide cladding titanium dioxide composite conductive material and preparation method |
| CN105238100A (en) * | 2015-10-23 | 2016-01-13 | 渤海大学 | Method for preparing light-colored conductive titanium dioxide |
| CN106115776A (en) * | 2016-06-30 | 2016-11-16 | 渤海大学 | A kind of preparation method of TiO2 baseline shape conductive powder body |
| WO2018110489A1 (en) * | 2016-12-15 | 2018-06-21 | 株式会社堀場製作所 | Method for evaluating alkalinity of urea water |
| CN106601373B (en) * | 2017-01-18 | 2018-04-13 | 福州大学 | A kind of Ag wraps up mesoporous SiO2The preparation method of conductive powder body |
| CN106710722B (en) * | 2017-01-18 | 2018-05-04 | 福州大学 | A kind of Ni wraps up mesoporous SiO2The preparation method of conductive powder body |
| CN115012056B (en) * | 2022-06-30 | 2023-09-26 | 江南大学 | Polyamide 56 antistatic fiber and preparation method thereof |
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