CN102021606A - High performance room temperature cured titanium boride cathode coating for aluminium reduction cell - Google Patents
High performance room temperature cured titanium boride cathode coating for aluminium reduction cell Download PDFInfo
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- CN102021606A CN102021606A CN 201010604205 CN201010604205A CN102021606A CN 102021606 A CN102021606 A CN 102021606A CN 201010604205 CN201010604205 CN 201010604205 CN 201010604205 A CN201010604205 A CN 201010604205A CN 102021606 A CN102021606 A CN 102021606A
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- titanium boride
- room temperature
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Abstract
The invention discloses a high performance room temperature cured titanium boride cathode coating for an aluminium reduction cell. The coating is characterized by taking titanium boride powder as a base material, adding phenolic resins, acrylic resins and a curing agent on the basis of the conventional auxiliary material composition, firstly mixing the materials to prepare paste, then applying the paste on the carbon cathode of the aluminium reduction cell, carrying out curing for at least 24 hours at room temperature and then carrying out carbonization according to the optimum carbonization temperature rising system worked out based on variation of mass and energy of the coating paste in the process of high temperature carbonization variation, wherein the phenolic resins and the acrylic resins have the advantages of excellent heat resistance, higher carbon yield and the like. The invention can realize room temperature curing of the TiB2 cathode coating, improve the impact damage resistance capability and toughness of the coating and reduce the resistivity, obtain the TiB2 cathode coating with less deformation and optimum performance and more advantageously promote the popularization and application of the TiB2 cathode coating.
Description
Technical field
The invention belongs to the technical field of cathode of aluminium electrolytic bath coating, be specifically related to the aluminum electrolyzing cell used ambient cure titanium boride cathode coating of a kind of high-performance.
Background technology
Titanium boride (TiB
2) fusing point height, electric conductivity height, compactness is good, hardness is big, soaking of anti-molten aluminum liquid and cryolite melts can now have been become the preferred material of making the wettable inert cathode coating of used for aluminium electrolysis by superperformances such as aluminium liquid complete wetting.But in order to make TiB
2Can be bonded in the carbon anode/cathode surface of used for aluminium electrolysis, be everlasting with TiB
2Be added with thermosetting resin, solidifying agent and solvent etc. in the thickener as the cathode of base-material, so that TiB
2Powdex along with the rising of temperature, makes resin crosslinks, polymerization become insoluble, infusible solid, thereby plays TiB under the effect of solidifying agent
2Be bonded in the effect on carbon cathode surface.The solidified top temperature is 220～240 ℃, behind the hot setting, and TiB
2Cathode also needs from the high temperature cooling to the room temperature, and then coating is carried out again high temperature carbonization, could make that coated cathode is that aluminium cell is used, plays its corresponding effect.Because in whole curing, carbonization process, coating will experience by room temperature and rise to high temperature, drops to room temperature then, rises to pyritous thermal cycling process again, thereby coating will be subjected to comparatively intensive thermal shock, causes after the coating charing cracking, layering easily or comes off.Hot setting TiB in addition
2Cathode needs to increase in addition the thermal source solidified coating, solidifies the cost height, difficulty of construction is big, the time is long, and solidification process bothers, and has seriously hindered TiB
2Applying of cathode.
For fear of the hot setting process, solve a series of problems that hot setting brought, CN1245537 patent disclosure " a kind of ambient cure used for aluminium electrolysis titanium boride cathode coating ", after though the titanium boride cathode coating paste formula that this technology provides can at room temperature solidify, the heat that utilizes electrolysis of aluminum sinter process process to produce, disposable intensification charing TiB
2Cathode, but because its TiB
2What the thermosetting resin in the cathode paste formula mainly adopted is Resins, epoxy, and there are shortcomings such as shock-resistant damage ability, poor toughness, resistivity height, charring rate are low in the Resins, epoxy after solidifying, has also hindered TiB to a certain extent
2Applying of cathode.
Summary of the invention
The objective of the invention is defective, provide a kind of new high-performance aluminum electrolyzing cell used ambient cure titanium boride cathode coating at above-mentioned aluminum electrolyzing cell used titanium boride cathode coating.
In order to reach purpose of the present invention, the inventor has carried out deep research, find that the coating charing is physics, the chemical process of a complexity, small molecules phase transformations such as solvent, water had wherein both been comprised, the further polycondensation of resin, the reaction between the different sorts resin also comprises the reaction of resin and pitch, asphalt coking, a plurality of quality and energy variation processes such as resin charing.And in the carbonization process, thickeners such as resin will become infusible solid by viscous liquid, and with TiB
2Be bonded in the cathode carbon pieces surface, form cathode, the structure of its molecule is that to become the plane netted by linear earlier, becomes solid netted at last.On the basis of further investigation, through a large amount of experiment screenings, determined the aluminum electrolyzing cell used ambient cure titanium boride cathode coating of new high-performance provided by the invention at last, this coating is to be mixed into thickener earlier by following each component materials by mass percentage, be applied in then on the carbon cathode of aluminium cell, in ambient cure after at least 24 hours high temperature carbonization form:
TiB
2Powder diameter is 3-5 μ m 30-70%
The single diameter of short carbon fiber is 6-7 μ m, and length is 2-4mm 0.5-2%
Resol 2130 5-10%
Acrylic resin MA-619 5-10%
Coal tar 0.5-1.5%
Ethanol 2-5%
Acetone 2-5%
The Graphite Powder 99 particle diameter is less than 150 μ m 2.7-7%
The petroleum coke powder particle diameter is less than 250 μ m 4-10%
Negative electrode particle footpath is less than 150 μ m 2-5%
The carbon fiber powder particle diameter is less than 0.074 μ m 0.5-1.5%
Oxidized bitumen powder footpath is less than 150 μ m 4-7%
Dodecyl dicarboxylic acid 0.5-2%
Tetraisopropoxy titanium 0.5-2%
Tosyl chloride 0.4-1%
Sulfovinic acid 0.4-1%.
The present invention is also at the curing characteristics of the resol 2130 that adopts in the above method, acrylic resin MA-619 and solidifying agent etc., analyze by the coating thickener being carried out comprehensive heat, fully understand in the high temperature carbonization process, the variation that the quality of coating thickener and energy take place, make best charing temperature increasing schedule, not only realize TiB
2The ambient cure of cathode, but also obtained the TiB of deformation minimum, performance the best
2Cathode.
Determining of coating charing temperature increasing schedule:
According to the DTG-DDTA curve (as shown in Figure 1) of coating thickener, the coating thickener is in the reaction difference that each temperature section took place as can be known, and temperature rise rate also should be different at each temperature section.Therefore can determine the charing temperature increasing schedule according to following 3 principles.
(1) at the fast temperature section of pace of change, must slow down temperature rise rate;
(2) at the slow temperature section of pace of change, can accelerate temperature rise rate;
(3), heat-up rate must be reduced to minimum at all violent temperature section of the pace of change of quality and energy.
Do a large amount of careful researchs just because of the present invention, thereby made the present invention compared with prior art, had following beneficial effect:
1,, thereby can either realize TiB because the resol selected for use of the present invention and acrylic resin have excellent heat resisting, higher advantages such as charring rate
2The ambient cure of cathode, thus the hot setting heating installation removed from, simplify construction, reduce TiB
2Cathode cracking, the possibility that comes off reduce TiB
2The cathode application cost can improve shock-resistant damage ability, toughness and the resistivity of coating again, promotes TiB
2Applying of cathode.
2, because the ambient cure TiB that is used for aluminium cell that the present invention is providing
2On the basis of the method for cathode, also analyze by the coating thickener being carried out comprehensive heat, according to the quality of high temperature carbonization change procedure floating coat thickener and the variation of energy generation, make best charing temperature increasing schedule, thereby can obtain the TiB of deformation minimum, performance the best
2Cathode.
Description of drawings
Fig. 1 is the DTG-DDTA curve of coating thickener of the present invention;
Fig. 2 is the electron scanning micrograph of the prepared cathode cross-section morphology of the embodiment of the invention 1;
Fig. 3 is the electron scanning micrograph of the prepared cathode cross-section morphology of the embodiment of the invention 2;
Fig. 4 is the electron scanning micrograph of the prepared cathode cross-section morphology of the embodiment of the invention 3;
Fig. 5 is the electron scanning micrograph of the prepared cathode cross-section morphology of the embodiment of the invention 4.
Embodiment
Provide embodiment below so that the present invention is carried out concrete description; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, content still belongs to protection scope of the present invention to some nonessential improvement and the adjustment that the present invention makes to the person skilled in the art in this field according to the present invention.
The titanium boride cathode coating paste formula of present embodiment sees Table 1.
Table 1
Each material in the table 1 is mixed into earlier thickener, be applied in then on the carbon cathode of aluminium cell, self-vulcanizing 24 hours.Get coating thickener sample simultaneously and do comprehensive heat analysis, the result as shown in Figure 1.According to the comprehensive hot analytical results of Fig. 1, according to the method for determining the charing temperature increasing schedule in the summary of the invention, determine the concrete charing speed change temperature increasing schedule of coating thickener, as shown in table 2.In actual applications, the heat that both can utilize electrolysis of aluminum sinter process process to produce by the charing speed change temperature increasing schedule that table 2 provides carries out high temperature carbonization, also can adopt special high temperature carbonization equipment to carry out high temperature carbonization, but the heat that preferably utilizes electrolysis of aluminum sinter process process to produce carries out high temperature carbonization, to reach the effect of energy-saving consumption-reducing.Gained TiB behind the high temperature carbonization
2Cathode, flawless does not come off, bonding strength greater than the tensile strength of used for aluminium electrolysis semi-graphite cathode carbon block (＞3.0MPa); 25 ℃ resistivity is: 27.3 μ Ω m; Functional with aluminum-liquid wetting, possess the primary condition of the Aluminium Electrolysis of being applied to.
In addition, the cross-section morphology of the titanium boride cathode coating of present embodiment preparation is seen Fig. 2.White portion is TiB among the figure
2, bar-like portion is a carbon fiber.As seen from the figure, TiB
2Be dispersed in the coating uniformly, and carbon fiber is embedded between the blapharoplast, flawless and crafters in the coating, bonding fine between each phase, the weave construction densification, gas molecule that carbonization reaction discharged and heat are left a trace in coating.Because TiB
2Be dispersed in the coating uniformly, thereby helped to improve the electric property of material.And carbon fiber is embedded between the blapharoplast, thereby can play the fiber reinforcement effect, helps to improve the mechanical property of material.
Table 2
The titanium boride cathode coating paste formula of present embodiment sees Table 3.
Table 3
The constructional method of present embodiment and definite cathode charing speed change temperature increasing schedule are with embodiment 1, slightly.Gained TiB behind the high temperature carbonization
2Cathode, flawless does not come off, bonding strength greater than the tensile strength of used for aluminium electrolysis semi-graphite cathode carbon block (＞3.0MPa); 25 ℃ resistivity is: 26.6 μ Ω m; Functional with aluminum-liquid wetting, possess the primary condition of the Aluminium Electrolysis of being applied to.
In addition, the cross-section morphology of the titanium boride cathode coating of present embodiment preparation is seen Fig. 3.As seen from the figure, TiB
2Be dispersed in the coating uniformly, and carbon fiber is embedded between the blapharoplast, flawless and crafters in the coating, bonding fine between each phase, the weave construction densification, gas molecule that carbonization reaction discharged and heat are left a trace in coating.Because TiB
2Be dispersed in the coating uniformly, thereby helped to improve the electric property of material.And carbon fiber is embedded between the blapharoplast, thereby can play the fiber reinforcement effect, helps to improve the mechanical property of material.
Embodiment 3
The titanium boride cathode coating paste formula of present embodiment sees Table 4.
Table 4
The constructional method of present embodiment and definite cathode charing speed change temperature increasing schedule are with embodiment 1, slightly.Gained TiB behind the high temperature carbonization
2Cathode, flawless does not come off, bonding strength greater than the tensile strength of used for aluminium electrolysis semi-graphite cathode carbon block (＞3.0MPa); Open porosity＜13%; 25 ℃ resistivity is: 31.4 μ Ω m; Functional with aluminum-liquid wetting, possess the primary condition of the Aluminium Electrolysis of being applied to.
In addition, the cross-section morphology of the titanium boride cathode coating of present embodiment preparation is seen Fig. 4.As seen from the figure, TiB
2Be dispersed in the coating uniformly, and carbon fiber is embedded between the blapharoplast, flawless and crafters in the coating, bonding fine between each phase, the weave construction densification, gas molecule that carbonization reaction discharged and heat are left a trace in coating.Because TiB
2Be dispersed in the coating uniformly, thereby helped to improve the electric property of material.And carbon fiber is embedded between the blapharoplast, thereby can play the fiber reinforcement effect, helps to improve the mechanical property of material.
Embodiment 4
Present embodiment titanium boride cathode coating paste formula sees Table 5.
Table 5
The constructional method of present embodiment and definite cathode charing speed change temperature increasing schedule are with embodiment 1, slightly.Gained TiB behind the high temperature carbonization
2Cathode, flawless does not come off, bonding strength greater than the tensile strength of used for aluminium electrolysis semi-graphite cathode carbon block (＞3.0MPa); Open porosity＜14%; 25 ℃ resistivity is: 24.2 μ Ω m; Functional with aluminum-liquid wetting, possess the primary condition of the Aluminium Electrolysis of being applied to.
In addition, the cross-section morphology of the titanium boride cathode coating of present embodiment preparation is seen Fig. 5.As seen from the figure, TiB
2Be dispersed in the coating uniformly, and carbon fiber is embedded between the blapharoplast, flawless and crafters in the coating, bonding fine between each phase, the weave construction densification, gas molecule that carbonization reaction discharged and heat are left a trace in coating.Because TiB
2Be dispersed in the coating uniformly, thereby helped to improve the electric property of material.And carbon fiber is embedded between the blapharoplast, thereby can play the fiber reinforcement effect, helps to improve the mechanical property of material.
Claims (1)
1. aluminum electrolyzing cell used ambient cure titanium boride cathode coating of high-performance, this coating is to be mixed into thickener earlier by following each component materials by mass percentage, be applied in then on the carbon cathode of aluminium cell, in ambient cure after at least 24 hours high temperature carbonization form:
TiB
2Powder diameter is 3-5 μ m 30-70%
The single diameter of short carbon fiber is 6-7 μ m, and length is 2-4mm 0.5-2%
Resol 2130 5-10%
Acrylic resin MA-619 5-10%
Coal tar 0.5-1.5%
Ethanol 2-5%
Acetone 2-5%
The Graphite Powder 99 particle diameter is less than 150 μ m 2.7-7%
The petroleum coke powder particle diameter is less than 250 μ m 4-10%
Negative electrode particle footpath is less than 150 μ m 2-5%
The carbon fiber powder particle diameter is less than 0.074 μ m 0.5-1.5%
Oxidized bitumen powder footpath is less than 150 μ m 4-7%
Dodecyl dicarboxylic acid 0.5-2%
Tetraisopropoxy titanium 0.5-2%
Tosyl chloride 0.4-1%
Sulfovinic acid 0.4-1%.
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| CN 201010604205 CN102021606B (en) | 2010-12-24 | 2010-12-24 | High performance room temperature cured titanium boride cathode coating for aluminium reduction cell |
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|---|---|---|---|
| CN 201010604205 CN102021606B (en) | 2010-12-24 | 2010-12-24 | High performance room temperature cured titanium boride cathode coating for aluminium reduction cell |
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| CN102021606B CN102021606B (en) | 2012-04-18 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212845A (en) * | 2011-05-24 | 2011-10-12 | 昆明冶金研究院 | Method for preparing TiB2 cathode coating for aluminium electrolysis |
| WO2013177846A1 (en) * | 2012-05-30 | 2013-12-05 | 深圳市新星轻合金材料股份有限公司 | Process for preparing transition metal boride and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4308115A (en) * | 1980-08-15 | 1981-12-29 | Aluminum Company Of America | Method of producing aluminum using graphite cathode coated with refractory hard metal |
| CN1443875A (en) * | 2002-03-08 | 2003-09-24 | 中南大学 | Titanium boride coating formula for cathode of aluminium electrolytic bath |
| CN1537974A (en) * | 2003-04-15 | 2004-10-20 | 中南大学 | Normal temperature solidified titanium boride cathode coating for aluminium electrolysis |
-
2010
- 2010-12-24 CN CN 201010604205 patent/CN102021606B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4308115A (en) * | 1980-08-15 | 1981-12-29 | Aluminum Company Of America | Method of producing aluminum using graphite cathode coated with refractory hard metal |
| CN1443875A (en) * | 2002-03-08 | 2003-09-24 | 中南大学 | Titanium boride coating formula for cathode of aluminium electrolytic bath |
| CN1537974A (en) * | 2003-04-15 | 2004-10-20 | 中南大学 | Normal temperature solidified titanium boride cathode coating for aluminium electrolysis |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212845A (en) * | 2011-05-24 | 2011-10-12 | 昆明冶金研究院 | Method for preparing TiB2 cathode coating for aluminium electrolysis |
| CN102212845B (en) * | 2011-05-24 | 2012-10-31 | 昆明冶金研究院 | Method for preparing TiB2 cathode coating for aluminium electrolysis |
| WO2013177846A1 (en) * | 2012-05-30 | 2013-12-05 | 深圳市新星轻合金材料股份有限公司 | Process for preparing transition metal boride and application thereof |
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| CN102021606B (en) | 2012-04-18 |
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Granted publication date: 20120418 Termination date: 20121224 |