CN106567128B

CN106567128B - A kind of preparation method of conductive potassium titanate whisker

Info

Publication number: CN106567128B
Application number: CN201610404418.8A
Authority: CN
Inventors: 邓昭平; 周茜洋; 杨倩
Original assignee: Chengdu Univeristy of Technology
Current assignee: Chengdu Univeristy of Technology
Priority date: 2016-06-12
Filing date: 2016-06-12
Publication date: 2019-05-17
Anticipated expiration: 2036-06-12
Also published as: CN106567128A

Abstract

A kind of method preparing conductive potassium titanate crystal whisker is provided, potassium titanate crystal whisker is taken it is characterized in that sequentially including the following steps:, appropriate amount of deionized water is added, it is proportionally added into Conductive Titanium Oxide Powder Material, it is proportionally added into pink salt under stiring, antimonic salt and niobium pentaoxide, it is eventually adding appropriate reducing agent (zinc, magnesium, iron or their mixture), it is reacted 60-180 minutes after adding reducing agent, pH value is adjusted to 2-4 range with ammonium hydroxide, with the potassium titanate crystal whisker of the isolated adherency conductive titanium dioxide powder of centrifuge or pumping and filtering device, washing 2 times, it is dried 6-13 hours in 130 DEG C of -180 DEG C of ranges, in the conductive potassium titanate crystal whisker of 220 DEG C of -350 DEG C of roastings acquisition in 2.0-5.0 hours.

Description

A kind of preparation method of conduction potassium titanate crystal whisker

Technical field

The invention belongs to the preparation field of functional material, in particular to a kind of preparation method of conductive potassium titanate crystal whisker.

Background technique

There are four types of crystal forms for potassium titanate crystal whisker, usually use K₂O.nTiO₂To indicate its composition, wherein n=1,2,4,6,8, it In structure and performance significant difference, wherein potassium titanate crystal whisker has high resistance to the potassium titanate crystal whisker of six titaniums using more It is hot, high-wearing feature, corrosion resistance, the characteristics such as low heat conductivity, in composite reinforcement, friction material, porous ceramics, enhancing There is good application prospect in the fields such as alloy, heat insulation heat proof material, due to its good stability and with the good phase of resin Capacitive also obtains extensive concern in paint field.Composite material and high-end coating (such as high-end car paint) are in material property The performance of anti-radiation, antistatic and anti-shielding etc. needs more and more prominent, therefore it is conductive to have increasing need for crystal whisker materials.

There are many ways to preparing conductive potassium titanate crystal whisker, may be summarized to be two major classes: one kind is the method with chemical plating One layer of conductive metal layer is plated on potassium titanate crystal whisker；Second class is to coat one layer on potassium titanate crystal whisker by the methods of salt hydrolysis Antimony-doped stannic oxide (ATO) conductive layer.The shortcomings that first method is to pollute generation environment in plating process；Second class The shortcomings that method is that conductivity is good not as good as former.Currently, the conductive potassium titanate crystal whisker used both at home and abroad is usually to use second Method preparation, there is presently no the conductive potassium titanate crystal whisker manufacturing enterprises of a scale in China.Conductive potassium titanate crystal whisker exists It requires to be usually resistivity 90-190 Ω m, whiteness (L value) 68-89 using technical parameter on car paint.

Under study for action, it has been found that one kind is simple and easy, production cost is low, is easy to the conductive potassium titanate crystal whisker of upper scale.

Summary of the invention

The purpose of the present invention is to provide a kind of methods for preparing conductive potassium titanate crystal whisker, and principle is: will prepare Out, stannic oxide that resistivity is 1-5 Ω m mix antimony and mix niobium Conductive Titanium Oxide Powder Material and adhere on potassium titanate crystal whisker, glue Attached dose is tin, the oxide or hydroxide of antimony and niobium element composition finally obtain adhesive type and lead by the heat treatment compared with low temperature Electric potassium titanate crystal whisker.The present invention has the advantages that resistivity almost can achieve the level of Conductive Titanium Oxide Powder Material；Because increasing The amount for having added titanium elements, makes in system that titanium elements ratio improves, the ratio of potassium obtains relative reduction；Material cost and operation at This is low, and process stabilizing is easy to upper scale.The disadvantage is that: because conductive powder body is to be connected on whisker by the mode adhered to, make whisker Become unsmooth, adhesion layer may also be uneven, as long as but technology controlling and process is good, can match with downstream product, specific resistance rate Big conductive whiskers more have extensive market prospects.

Potassium titanate is that it contains the potassium ion of alkali metal with titanium dioxide difference, from semiconductor theory it is found that monovalence Potassium ion will play the role of charge recombination center or charge trap herein, it is very big to the Conductivity of semiconductor, Therefore product its resistivity for directly coat antimony-doped stannic oxide acquisition with potassium titanate crystal whisker can be insulated Body, experiments have shown that true, also the way it goes, this is also the country so far without the original of the low conductive potassium titanate crystal whisker product of resistivity Cause.

The present invention sequentially includes the following steps:

(1) adherency of the conductive powder body on potassium titanate crystal whisker

10 parts of potassium titanate crystal whiskers are taken by mass parts (following dosage is mass parts)；50 parts of deionized water (deionizations are added Water consumption influences product quality little)；2-15 parts of Conductive Titanium Oxide Powder Material, is added pink salt under stiring, if pink salt With SnCl₄.5H₂O counts additional amount 2.6-4.2 parts；Then antimonic salt is added, if antimonic salt is with SbCl₃Additional amount 0.13-0.39 parts of meter； It is added niobium pentaoxide 0.1-0.5 parts；Be eventually adding reducing agent (zinc, magnesium, iron or their mixture, under same dosage, The selection of reducing agent does not influence end product quality), if reducing agent additional amount 0.5-1.5 parts 0.5-1.5 parts in terms of zinc, And start recording reaction time when adding reducing agent, reaction 60-180 minute after, with ammonium hydroxide adjustment pH value 2-4 range, with from The potassium titanate crystal whisker that scheming or pumping and filtering device obtain adherency conductive titanium dioxide powder (selects centrifuge or pumping and filtering device not Influence product quality), remove filtrate after with the deionized water of 3-5 times of volume wash 2 times for use, the adherency conduction titanium dioxides of acquisition The potassium titanate crystal whisker wet feed of titanium valve body is brown or light grey.The equipment replacements blenders such as Ball-stirring mill, ball mill can also be used Medium bead equipment is added to realize aforesaid operations.

The invention contribution is: the stannic oxide that prepared, resistivity is 1-5 Ω m is mixed antimony by 1. It mixes niobium Conductive Titanium Oxide Powder Material to adhere on potassium titanate crystal whisker, adhesive is the oxide or hydrogen of tin, antimony and niobium element composition Oxide, these adhesives itself are also belonging to conductive material after subsequent step process, so to the electric conductivity of system It influences little；It is that it has same doping effect with antimony and is conducive to face first 2. addition niobium element has reached two purposes Discoloration is shallow, so its addition can reduce the dosage of antimony, shoal favorably to product colour, secondly, general semiconductor material Conductivity has drift, and addition niobium plays stabilization to conductivity readings；3. add reducing agent (zinc, magnesium, iron or they Mixture) to achieve the goal be to by valence control principle, make finally be burnt into powder system and oxygen vacancy occur, reduction is at high price Consumption of the compound state to n-type doping.

(2) drying of conductive titanium dioxide powder titanium potassium titanate crystal whisker is adhered to

The potassium titanate crystal whisker wet feed of adherency conductive titanium dioxide powder must be dried, drying will be in 130 DEG C of -180 DEG C of models Progress is enclosed, general drying time 6-13 hours, the too low drying time of temperature was too long, the too high electric conductivity that will affect product of temperature.

(2) roasting and crushing of predecessor wet feed

Product after drying is put into cabinet-type electric furnace, is obtained within 2.0-5.0 hours from room temperature to 220 DEG C of -350 DEG C of roastings The conductive potassium titanate crystal whisker of loose bulk crushes to obtain conductive potassium titanate crystal whisker by airslide disintegrating mill, and what this method obtained leads Electric potassium titanate crystal whisker appearance color is the canescence with blue phase, test display 10 Ω cm-80 Ω cm of resistivity；Whiteness (L value) 83- 88, the properties such as draw ratio of whisker depend on the property of setting each other off of selected potassium titanate crystal whisker.

Detailed description of the invention

Fig. 1 is the scanning electron microscope (SEM) photograph of conductive potassium titanate crystal whisker prepared by embodiment 1.

Specific embodiment

Embodiment 1: 10 grams of potassium titanate crystal whiskers are taken；50 ml deionized waters are added；2 grams of Conductive Titanium Oxide Powder Material, It is added with stirring SnCl₄.5H₂O2.6 grams；Then SbCl is added₃0.13 gram；It is added 0.1 gram of niobium pentaoxide；It is eventually adding zinc 0.5 gram, and start recording reaction time when adding zinc adjusts pH value 2.4 with ammonium hydroxide, uses pumping and filtering device after reaction 180 minutes The potassium titanate crystal whisker of adherency conductive titanium dioxide powder is obtained, washs 2 with the deionized water of 5 times of filter cake volumes again after removing filtrate It is secondary stand-by, the potassium titanate crystal whisker wet feed of adherency conductive titanium dioxide powder must be dried, drying will be carried out at 130 DEG C, drying Time 13 hours.The material of drying is roasted from room temperature to 220 DEG C and obtains within 5.0 hours the conductive potassium titanate crystalline substance of loose bulk Must, it crushes to obtain conductive potassium titanate crystal whisker by airslide disintegrating mill, the conductive potassium titanate crystal whisker appearance color that this method obtains is Canescence with blue phase, test display 21 Ω cm of resistivity；Whiteness (L value) 87.

Embodiment 2: 10 grams of potassium titanate crystal whiskers are taken；50 ml deionized waters are added；5 grams of Conductive Titanium Oxide Powder Material, It is added with stirring SnCl₄.5H₂3 grams of O；Then SbCl is added₃0.2 gram；It is added 0.3 gram of niobium pentaoxide；It is eventually adding zinc 1 Gram, and start recording reaction time when adding zinc adjusts pH value 3 with ammonium hydroxide, is obtained with pumping and filtering device after reaction 100 minutes Adhere to conductive titanium dioxide powder potassium titanate crystal whisker, remove filtrate after again with the deionized water of 4 times of filter cake volumes wash 2 times to With, to adherency conductive titanium dioxide powder potassium titanate crystal whisker wet feed must dry, drying will 150 DEG C carry out, drying time 7 Hour.The material of drying is roasted from room temperature to 300 DEG C and obtains within 4.0 hours the conductive potassium titanate crystal whisker of loose bulk, warp It crosses airslide disintegrating mill to crush to obtain conductive potassium titanate crystal whisker, the conductive potassium titanate crystal whisker appearance color that this method obtains is band blue phase Canescence, test display 18 Ω cm of resistivity；Whiteness (L value) 84.

Embodiment 3: 10 grams of potassium titanate crystal whiskers are taken；50 ml deionized waters are added；10 grams of Conductive Titanium Oxide Powder Material, It is added with stirring SnCl₄.5H₂4 grams of O；Then SbCl is added₃0.34 gram；It is added 0.35 gram of niobium pentaoxide；It is eventually adding zinc 1.8 grams, and start recording reaction time when adding zinc adjusts pH value 3.2 with ammonium hydroxide, uses pumping and filtering device after reaction 160 minutes The potassium titanate crystal whisker of adherency conductive titanium dioxide powder is obtained, washs 2 with the deionized water of 4 times of filter cake volumes again after removing filtrate It is secondary stand-by, the potassium titanate crystal whisker wet feed of adherency conductive titanium dioxide powder must be dried, drying will be carried out at 140 DEG C, drying Time 7.5 hours.The material of drying is roasted from room temperature to 340 DEG C and obtains within 4.5 hours the conductive potassium titanate of loose bulk Whisker crushes to obtain conductive potassium titanate crystal whisker, the conductive potassium titanate crystal whisker appearance color that this method obtains by airslide disintegrating mill For the canescence with blue phase, test display 16 Ω cm Ω cm of resistivity；Whiteness (L value) 83.

Embodiment 4: 10 grams of potassium titanate crystal whiskers are taken；50 ml deionized waters are added；13 grams of Conductive Titanium Oxide Powder Material, It is added with stirring SnCl₄.5H₂3.8 grams of O；Then SbCl is added₃0.36 gram；It is added 0.33 gram of niobium pentaoxide；It is eventually adding 1.1 grams of zinc, and start recording reaction time when adding zinc adjusts pH value 3.1 with ammonium hydroxide, is set with suction filtration after reaction 110 minutes The standby potassium titanate crystal whisker for obtaining adherency conductive titanium dioxide powder is washed with the deionization of 4 times of filter cake volumes again after removing filtrate It washs 2 times for use, the potassium titanate crystal whisker wet feed of adherency conductive titanium dioxide powder must be dried, drying will be carried out at 160 DEG C, be dried The dry 6.5 hours time.The material of drying is roasted from room temperature to 290 DEG C and obtains within 4 hours the conductive potassium titanate of loose bulk Whisker crushes to obtain conductive potassium titanate crystal whisker, the conductive potassium titanate crystal whisker appearance color that this method obtains by airslide disintegrating mill For the canescence with blue phase, test display 19 Ω cm of resistivity；Whiteness (L value) 85.

Embodiment 5: 10 grams of potassium titanate crystal whiskers are taken；50 ml deionized waters are added；7 grams of Conductive Titanium Oxide Powder Material, It is added with stirring SnCl₄.5H₂4.1 grams of O；Then SbCl is added₃0.33 gram；It is added 0.30 gram of niobium pentaoxide；It is eventually adding 1.0 grams of zinc, and start recording reaction time when adding zinc adjusts pH value 3.0 with ammonium hydroxide, is set with suction filtration after reaction 130 minutes The standby potassium titanate crystal whisker for obtaining adherency conductive titanium dioxide powder is washed with the deionization of 4 times of filter cake volumes again after removing filtrate It washs 2 times for use, the potassium titanate crystal whisker wet feed of adherency conductive titanium dioxide powder must be dried, drying will be carried out at 160 DEG C, be dried The dry 6 hours time.The material of drying is roasted from room temperature to 280 DEG C and obtains within 4.5 hours the conductive potassium titanate of loose bulk Whisker crushes to obtain conductive potassium titanate crystal whisker, the conductive potassium titanate crystal whisker appearance color that this method obtains by airslide disintegrating mill For the canescence with blue phase, test display 125 Ω cm of resistivity；Whiteness (L value) 88.

Claims

1. a method for preparing conductive potassium titanate whiskers is characterized in that carrying out the following steps: get 10 parts of potassium titanate whiskers; add 50 parts of deionized water; 2-15 parts of titanium dioxide conductive powder, in stirring Add tin salt, the amount of tin salt added is 2.6-4.2 parts in SnCl ₄ .5H ₂ O; then antimony salt is added, and the amount of antimony salt added in SbCl ₃ is 0.13-0.39 part; 0.1-0.5 part of niobium pentoxide is added; Finally, add the reducing agent zinc, the amount of the reducing agent is 0.5-1.5 parts in terms of zinc, and start recording the reaction time when the reducing agent is added. After 60-180 minutes of reaction, adjust the pH value range with ammonia water to 2-4, and use a centrifuge to adjust the pH value. Or the potassium titanate whiskers adhering to the conductive titanium dioxide powder are obtained by suction filtration equipment, and after removing the filtrate, wash twice with 3-5 times the volume of deionized water, and the obtained potassium titanate whiskers adhering to the conductive titanium dioxide powder are wetted. The material is brown or light gray; the wet material of potassium titanate whiskers adhering to the conductive titanium dioxide powder is dried, and the drying is carried out in the range of 130°C-180°C, and the drying time is 6-13 hours. The temperature is raised from room temperature to 220℃-350℃ for 2.0-5.0 hours to obtain loose bulk conductive potassium titanate whiskers, which are pulverized by a jet mill to obtain conductive potassium titanate whiskers. The appearance color of the conductive potassium titanate whiskers is It is gray-white with blue phase, and the resistivity of the conductive potassium titanate whiskers is 10Ωcm-80Ωcm; the whiteness is 83-88, and the aspect ratio of the whiskers depends on the corresponding properties of the selected potassium titanate whiskers.