CN103482693A

CN103482693A - Method for preparing TiCN powder by using tetrabutyl titanate and pitch as titanium source and carbon source respectively

Info

Publication number: CN103482693A
Application number: CN201310449161.4A
Authority: CN
Inventors: 吴一
Original assignee: Guilin University of Technology
Current assignee: Guilin University of Technology
Priority date: 2013-09-27
Filing date: 2013-09-27
Publication date: 2014-01-01
Anticipated expiration: 2033-09-27
Also published as: CN103482693B

Abstract

The invention discloses a method for preparing TiCN powder by using tetrabutyl titanate and pitch as a titanium source and a carbon source respectively. The method comprises the following steps: weighing out the tetrabutyl titanate and the pitch according to the mass ratio of 1 to (5-8), dissolving the pitch in anhydrous ethanol, adding the tetrabutyl titanate, and stirring for mixing, so as to prepare a mixed solution with uniformly-mixed liquid phases; drying the mixed solution for 36-48 hours at the temperature of 80-150 DEG C to prepare a precursor; heating the precursor under the protection of a nitrogen atmosphere or an ammonia decomposition atmosphere until the temperature of the precursor reach 1300-2000 DEG C, performing thermal insulation for 1-2 hours, and carrying out carbon thermal reduction and nitridation to prepare the TiCN powder. The purities of the chemical reagents and the raw materials are all industrial-grade purities or above; the compositions of the prepared TiCN powder are controlled by the ratio of the added raw materials; the purity and the particle size are determined by a feeding sequence and a preparation process. The method has the characteristics of uniformity for mixing the raw materials, simple process, low synthetic temperature, short synthetic time, energy conservation, environmental protection and the like.

Description

Be respectively with tetrabutyl titanate and pitch the method that titanium source and carbon source prepare the TiCN powder

Technical field

The invention belongs to TiCN Preparation Technique of Powders field, particularly a kind ofly with tetrabutyl titanate and pitch, be respectively the method that titanium source and carbon source prepare the TiCN powder.

Background technology

TiCN has high-melting-point, high rigidity, high-wearing feature and the special characteristics such as functional, not only be widely used in the reinforcement of grinding tool, cutting tool and matrix material etc., also as energy and material, be used widely, and have a wide range of applications in new function material.

Superfine Ti CN powder is badly in need of in the modern energy industrial development.Tradition TiO ₂with the synthetic TiCN powder of high temperature reduction after the carbon solid phase mixing, with low cost but powder preparation is thicker; At present mainly to take pure titanium, titanium organism or gaseous titanium compound be raw material to superfine Ti CN powder, and with the preparation of the techniques such as vapour deposition, plasma heating, raw material and process costs are high, make superfine Ti CN powder expensive.Research and the low-cost preparation of application superfine Ti CN new technology are highly significant.

The TiCN powder that large-scale industrialization is produced at present is mostly 2 ~ 5 μ m, along with the development of modernization industry, and the especially development of energy industry, increasing to the demand of ultrafine powder TiCN, superfine Ti CN has higher using value, has a extensive future.But the superfine Ti CN powder of existing market supply is because raw materials cost and preparation technology's cost are high and expensive.Therefore the research of carrying out low-cost preparation ultrafine powder TiCN has very large realistic meaning.

The preparation of superfine Ti CN powder is the focus of material supply section scholar research, existing raw material aspect, the aspect of research, process aspect is also arranged.But diverse ways has its relative merits for suitability for industrialized production.

Direct carborization is with simple substance carbon, metallic titanium powder (or TiH ₂) be raw material, at high temperature, in nitrogen-based atmosphere, the direct contact reacts of reactant generates TiCN, and product purity is high, the carbon metering is than large, and technological process is simple.But titanium valve is expensive, the preparation of purification ultrafine titanium powder is more difficult; Reaction process is difficult to be controlled, and the TiCN synthesized needs further grinding fragmentation, causes the purity drop of product, also will further purify, and makes the standby superfine Ti CN powder of this legal system obtain large-scale promotion.

Carbothermic method is the traditional method of TiCN powder suitability for industrialized production.This technique is with TiO ₂for the titanium source, take graphite, carbon black, activated carbon etc. is the C source, under high temperature, nitrogen group protecting atmosphere, and TiO ₂generated the TiCN powder by the C reduction.Advantage is: raw materials cost is low; Technique is simple, and production efficiency is higher; The granularity of TiCN is micron order.But raw material is poor by the mechanically mixing homogeneity; TiCN is also easily oxidized.With regard to current production technology, the powder synthesized can not meet the requirement of fine ceramics fully on granularity and purity.

Also have some other method to prepare superfine Ti CN, but generally have the high organic compound as high pure metal titanium valve, titanium of ingredient requirement etc.; The synthesis technique complexity, as need heating plasma, microwave heating, vapour deposition etc., appointed condition requires the problems such as high, and preparation method or complex process or output are limited, cause cost high.Exploitation high-level efficiency, TiCN ultrafine powder technology cheaply, remain the emphasis of countries nowadays scientist and business circles research.

Summary of the invention

The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of and be respectively with tetrabutyl titanate and pitch the method that titanium source and carbon source prepare the TiCN powder.

Concrete steps are:

(1) take tetrabutyl titanate and pitch according to mass ratio 1:5 ~ 8, first pitch is dissolved in dehydrated alcohol, and then add tetrabutyl titanate to be uniformly mixed, make the mixed uniformly mixed solution of liquid phase.

(2) mixed solution step (1) made under 80 ~ 150 ℃ dry 36 ~ 48 hours, make presoma.

(3) presoma step (2) made is heated to 1300 ~ 2000 ℃ under nitrogen atmosphere or ammonia dissolving atmosphere protection, is incubated 1 ~ 2 hour and carries out carbothermic reduction and nitrogenize, makes the TiCN powder.

The purity of described chemical reagent and raw material is technical grade and above purity.

The composition of the prepared TiCN powder of the present invention is controlled by the proportioning that adds raw material, and the purity of powder and granularity are determined jointly by order of addition(of ingredients) and preparation technology.

The advantage of the inventive method:

(1) take pitch as carbon source, take tetrabutyl titanate as the titanium source, through carbothermic reduction and nitrogenize, high-purity, the superfine Ti CN of low-cost preparation.

(2) method for preparing TiCN with tradition is compared, and has that raw material mixes, technique is simple, synthesis temperature is low, generated time is short and the characteristics such as energy-conserving and environment-protective.

embodiment

embodiment:

(1) take 1 gram tetrabutyl titanate and 7 gram pitches, first pitch is dissolved in dehydrated alcohol, and then adds tetrabutyl titanate to be uniformly mixed, make the mixed uniformly mixed solution of liquid phase.

(2) step (1) is made to mixed solution under 115 ℃ dry 42 hours, make presoma.

(3) presoma step (2) made is heated to 1450 ℃ under the ammonia dissolving atmosphere protection; be incubated and within 1 hour 45 minutes, carry out carbothermic reduction and nitrogenize; make the TiCN powder, gained TiCN powder is the superfine Ti CN powder that particle diameter is 150 ~ 300 nanometers through the testing graininess analysis.

The purity of described chemical reagent and raw material is technical grade.

Claims

1. a method for preparing the TiCN powder is characterized in that concrete steps are:

(1) take tetrabutyl titanate and pitch according to mass ratio 1:5 ~ 8, first pitch is dissolved in dehydrated alcohol, and then add tetrabutyl titanate to be uniformly mixed, make the mixed uniformly mixed solution of liquid phase;

(2) mixed solution step (1) made under 80 ~ 150 ℃ dry 36 ~ 48 hours, make presoma;

(3) presoma step (2) made is heated to 1300 ~ 2000 ℃ under nitrogen atmosphere or ammonia dissolving atmosphere protection, is incubated 1 ~ 2 hour and carries out carbothermic reduction and nitrogenize, makes the TiCN powder;

2. the method for preparing the TiCN powder according to claim 1 is characterized in that: the composition of prepared TiCN powder is controlled by the proportioning that adds raw material, and the purity of powder and granularity are determined jointly by order of addition(of ingredients) and preparation technology.