CN107841768A - A kind of Al-matrixcomposites and its preparation method and application - Google Patents
A kind of Al-matrixcomposites and its preparation method and application Download PDFInfo
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- CN107841768A CN107841768A CN201711247551.8A CN201711247551A CN107841768A CN 107841768 A CN107841768 A CN 107841768A CN 201711247551 A CN201711247551 A CN 201711247551A CN 107841768 A CN107841768 A CN 107841768A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 78
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims description 57
- 238000007731 hot pressing Methods 0.000 claims description 40
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 30
- 238000000498 ball milling Methods 0.000 claims description 27
- 238000000227 grinding Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 abstract description 16
- 239000001301 oxygen Substances 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000011133 lead Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 22
- 239000000463 material Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 229910052582 BN Inorganic materials 0.000 description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910000464 lead oxide Inorganic materials 0.000 description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000003701 mechanical milling Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910017980 Ag—Sn Inorganic materials 0.000 description 1
- 229910014474 Ca-Sn Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229910020220 Pb—Sn Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F2003/145—Both compacting and sintering simultaneously by warm compacting, below debindering temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a kind of Al-matrixcomposites and its preparation method and application, the Al-matrixcomposites include the shell structure being made up of lead component, and the nuclear structure being made up of manganese dioxide component of shell structure parcel.Embodiment result shows, the surface microhardness scope of Al-matrixcomposites provided by the invention is 59.3~70.7Hv, section microhardness scope is 65.5~78.3Hv, and addition of the manganese dioxide in lead improves the surface microhardness of lead and section microhardness reaches more than one times；Al-matrixcomposites provided by the invention current density in the test of Zinc electrolysis simulated system is 0.05A/cm2When oxygen evolution potential scope be 1.70~1.85V, service life scope is 48000~65600h, and catalytic activity is good, service life length.
Description
Technical field
The present invention relates to metal-base composites technical field, more particularly to a kind of Al-matrixcomposites and preparation method thereof
And application.
Background technology
At present in hydrometallurgy Zinc electrolysis technique, can mainly there are lead and metal, titanium, graphite as anode material
Deng.Wherein, lead and metal have the advantages that cheap, repair ability is strong and is widely applied.In actual production,
The metal used mainly has Pb- (0.8~1.0wt%) Ag and Pb- (0.2~0.3wt%) Ag- (0.06~0.1wt%) Ca,
Although both materials have good stability in an acidic solution, still suffer from that oxygen evolution reaction current potential is higher, service life
Short, the deficiencies of non-deformability is poor.
For problem above, comprehensive research and service condition both at home and abroad, mainly there are following two functionalization optimization routes：
(1) improved binary or multicomponent lead alloy, mainly include：Pb-Ag、Pb-Sn、Pb-Ca、Pb-Sb、Pb-Ba、Pb-
Cd, Pb-Ag-Ca, Pb-Ag-Ti, Pb-Ag-Sn, Pb-Ag-Ca-Sn etc..The main purpose of this method is to give full play to various gold
Synergy between category, improve analysis oxygen electro catalytic activity, corrosion resistance and the mechanical performance of material to a certain extent.So
And this method still has the shortcomings of oxygen evolution reaction current potential is higher, and service life is shorter.
(2) metal based coating anode, matrix mainly have：Titanium-based, aluminium base, stainless base steel, lead base；Coating mainly has：Platinum family
Oxide coating, manganese bioxide coated, brown lead oxide coating etc..The main purpose of this method is to give full play to the machine of metallic matrix
Tool performance and electric conductivity, and the decay resistance and electrocatalysis characteristic of coating.However, this method still has cost of manufacture
The shortcomings of higher, corrosion resistance is not strong, service life is shorter.
It follows that although the improvement of the anode material used in the prior art Zinc electrolysis process can be to a certain degree
The problem of upper to improve the performances such as the oxygen evolution reaction current potential of material, mechanical strength, corrosion resistance, but these materials'use life-spans are shorter
Still do not solve.
The content of the invention
It is an object of the invention to provide a kind of Al-matrixcomposites and its preparation method and application, the preparation method energy
Access long service life, and relatively low oxygen evolution potential, the material of preferable non-deformability.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of preparation method of Al-matrixcomposites, comprise the following steps：
Sequentially ball milling and grinding are carried out after manganese dioxide powder raw material is mixed with lead powder raw material, obtains compound；
Vacuum hotpressing is carried out to the compound, obtains Al-matrixcomposites.
Preferably, grain diameter≤20 μm of the manganese dioxide powder raw material.
Preferably, grain diameter≤80 μm of the lead powder raw material.
Preferably, the mol ratio of the manganese dioxide powder raw material and lead powder raw material is 0.1~0.4:1.
Preferably, the speed of the ball milling is 1200~1600r/min, and the time of the ball milling is 1~5min.
Preferably, particle diameter≤20 μm of the compound.
Preferably, the vacuum of the vacuum hotpressing is 7 × 10-3~9 × 10-3Pa；
The pressure of the vacuum hotpressing is 70~90MPa；
The temperature of the vacuum hotpressing is 360~420 DEG C；
The soaking time of the vacuum hotpressing is 10~30min.
Present invention also offers the Al-matrixcomposites that preparation method described in above-mentioned technical proposal obtains, comprising by lead component
The shell structure of composition, and the nuclear structure being made up of manganese dioxide component of shell structure parcel.
Present invention also offers Al-matrixcomposites described in a kind of above-mentioned technical proposal as anode during Zinc electrolysis
Application.
The invention provides a kind of preparation method of Al-matrixcomposites, manganese dioxide powder raw material and lead powder raw material are mixed
Ball milling and grinding are carried out after conjunction, obtains compound；Vacuum hotpressing is carried out to the compound, obtains Al-matrixcomposites.This hair
The bright mixture to manganese dioxide powder raw material and lead powder raw material composition carries out ball milling and grinding, mixes powder body material abundant
Uniformly, the segregation of composition when effectively prevent material shaping；Prepared using vacuum hot pressing technique, on the one hand effectively prevent
Metallic lead is oxidized to the lead oxide of lower valency；On the other hand, during vacuum hotpressing, vacuum-sintering and load pressure are made simultaneously
With, can promote compound accelerate flowing, reset, densification, so as to extend its service life.Meanwhile preparation provided by the invention
Method is simple, short preparation period, and equipment investment is few.
Present invention also offers a kind of Al-matrixcomposites, include the shell structure being made up of lead component, and the shell knot
The nuclear structure being made up of manganese dioxide component of structure parcel.In the present invention, the manganese dioxide powder is a kind of to oxygen evolution reaction
Oxide with high catalytic activity, it adds the oxygen evolution reaction current potential and non-deformability that can effectively reduce lead.Meanwhile two
Addition of the manganese oxide in lead serves dispersion-strengtherning effect, improve material surface and section microhardness one again with
On, and then improve the non-deformability of lead.Oxygen evolution reaction current potential is the important performance parameter of anode material, and its numerical value is lower,
Illustrate that the electro catalytic activity of material is stronger, electrodeposition energy consumption is lower.Embodiment result shows that Al-matrixcomposites of the present invention exist
Current density is 0.05A/cm in the test of Zinc electrolysis simulated system2When oxygen evolution reaction potential range be 1.70~1.85V, use
Life span is 48000~65600h；Surface microhardness scope is 59.3~70.7Hv, and section microhardness scope is 65.5
~78.3Hv.
Embodiment
The invention provides a kind of preparation method of Al-matrixcomposites, comprise the following steps：
Ball milling and grinding are carried out after manganese dioxide powder raw material is mixed with lead powder raw material, obtains compound；
Vacuum hotpressing is carried out to the compound, obtains lead-containing alloy.
The present invention carries out ball milling and grinding after manganese dioxide powder raw material is mixed with lead powder raw material, obtains compound.This
Invention does not have particular/special requirement to the source of the lead powder raw material, and 99.9% commercially available prod is more than using purity.In this hair
In bright, the grain diameter of the lead powder raw material is preferable≤and 80 μm, it is preferred≤60 μm, it is most preferably≤40 μm.
The present invention does not have any particular/special requirement to the source of the manganese dioxide powder raw material, using people in the art
Commercially available prod known to member；Specifically, the manganese dioxide powder raw material is preferably the pure top grades of GR, purity is more than
90.0%；In the present invention, the grain diameter of the manganese dioxide powder raw material it is preferable≤20 μm, it is preferred≤15 μm,
Most preferably≤10 μm.
In the present invention, the mol ratio of the manganese dioxide powder raw material and lead powder raw material is preferably 0.1~0.4:1, more
Preferably 0.2~0.3:1.
The present invention does not have any particular/special requirement, energy to the hybrid mode of the lead powder raw material and manganese dioxide powder raw material
It is enough to mix the two.
After the manganese dioxide powder raw material is mixed with lead powder raw material, the present invention to the compound that is obtained after mixing sequentially
Carry out ball milling and grinding.In the present invention, the ball milling preferably enters in high energy ball mill well-known to those skilled in the art
OK；The model of the ball mill is specially ZDM-50ML, and the grind box material of the ball mill is preferably high chrome；The ball milling
Speed is preferably 1200~1600r/min, more preferably 1300~1500r/min, most preferably 1350~1450r/min；Institute
The time for stating ball milling is preferably 1~5min, more preferably 2~3min.
The present invention preferably adds ball-milling additive in the mechanical milling process, to play a part of grinding aid and lubrication.In this hair
In bright specific embodiment, the ball-milling additive is stearic acid, and the addition of the ball-milling additive is the 2wt% of ball milling raw material.
In the present invention, if adding ball-milling additive in mechanical milling process, the present invention is preferably removed to ball-milling additive after grinding, in order to avoid
Influence the performance of Al-matrixcomposites.
In the present invention, the main purpose of the ball milling is in order to which manganese dioxide powder raw material is mixed with lead powder raw material
It is even, while certain levigate effect can also be played.
After the ball milling, the present invention is ground to the material after ball milling, obtains compound.In the present invention, it is described to grind
Mill is carried out preferably in agate mortar.The present invention does not have any spy to the embodiment being ground in the agate mortar
It is different to require, it is ground using conventional application method.In the present invention, the main purpose of the grinding is refinement raw material grain
Footpath, the discharging particle diameter of the grinding is preferable≤and 20 μm, it is preferred≤15 μm, most preferably≤10 μm.
After obtaining compound, the present invention carries out vacuum hotpressing to the compound, obtains Al-matrixcomposites.In the present invention
In, the vacuum hotpressing is carried out preferably in vacuum hotpressing stove, after the compound specifically is placed in into graphite jig, then by its
It is placed in progress vacuum hotpressing in vacuum hotpressing stove.In the specific embodiment of the invention, the graphite mold surface scribbles one
Layer boron nitride is as releasing agent.In the specific embodiment of the invention, the model ZT-30-16Y of the vacuum hotpressing stove.
In the present invention, the vacuum of the vacuum hotpressing is preferably 7 × 10-3~9 × 10-3Pa, more preferably 7.5 ×
10-3~8.5 × 10-3Pa, most preferably 8 × 10-3Pa；The pressure of the vacuum hotpressing is preferably 70~90MPa, more preferably
80MPa；The temperature of the vacuum hotpressing is preferably 360~420 DEG C, more preferably 370~390 DEG C, most preferably 380 DEG C；Institute
The time for stating vacuum hotpressing is preferably 10~30min, more preferably 15~25min, most preferably 20min.
In the specific embodiment of the invention, the present invention specifically by mould place it is appropriate after, open vacuum hotpressing stove successively
Cooling circulating water, mechanical pump and diffusion pump, preheat 30min；Then valve is converted, treats that vacuum reaches 7.5 × 10-3~8.5
×10-3Begun to warm up during Pa, while 70~90Mpa of load pressure；Setting heating rate is 10 DEG C/min, rises to 360~420 DEG C
Start 10~30min of insulation；Insulation is heated after terminating to be stopped, and diffusion pump is closed when temperature is cooled to 150 DEG C, is changed after 5min
Valve；Mechanical pump is closed when temperature is down to 80 DEG C；It is finally cooled to room temperature taking-up mould to be stripped, obtains the lead base and answer
Condensation material.
Vacuum hotpressing parameter set by the present invention has following advantage：Higher vacuum prevents metallic lead in high temperature
Under be oxidized to the lead oxide of lower valency；Preference temperature of the vacuum hotpressing temperature control more than the fusing point (327.502 DEG C) of lead,
And in the range of suitable soaking time, it ensure that lead powder raw material all melts, the lead of molten state recrystallizes in temperature-fall period
Recrystallization lead is formed afterwards, manganese dioxide powder is wrapped up entirely, avoids the presence of part lead powder raw material in material after being molded.Together
When, higher vacuum hotpressing temperature also shortens the vacuum hotpressing time；The vacuum-sintering of vacuum hotpressing process and load pressure
Act on simultaneously, compound can be promoted to accelerate flowing, reset, densification.
After the vacuum hotpressing terminates, present invention demoulding after vacuum hotpressing stove cooling can obtain the lead-containing alloy.
Present invention also offers the Al-matrixcomposites that preparation method described in a kind of above-mentioned technical proposal obtains, comprising by lead
The shell structure that component is formed, and the nuclear structure being made up of manganese dioxide component of shell structure parcel.Lead of the present invention
In based composites, addition of the manganese dioxide in lead serves dispersion-strengtherning effect, improves the surface of lead and showing for section
More than one times of microhardness, improve the non-deformability of material to the greatest extent.
Present invention also offers Al-matrixcomposites described in a kind of above-mentioned technical proposal as anode in Zinc electrolysis process
In application.The present invention to the Al-matrixcomposites as anode when, the application process during Zinc electrolysis is not any
Particular/special requirement, using routine application method carry out use.In the specific embodiment of the invention, the Zinc electrolysis process
Simulated solution system be：Zn2+50g/L, H2SO4150g/L, 35 DEG C.In the present invention, the Al-matrixcomposites are in zinc electricity
Current density is 0.05A/cm in product simulated system test2When oxygen evolution potential scope be 1.70~1.85V, service life scope
For 48000~65600h；Surface microhardness scope is 59.3~70.7Hv, section microhardness scope is 65.5~
78.3Hv。
Al-matrixcomposites provided by the invention and its preparation method and application are carried out in detail with reference to embodiment
Illustrate, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
Take manganese dioxide powder raw material 0.005mol, lead powder raw material 0.05mol, mole of manganese dioxide powder and lead powder raw material
Than controlling 0.1:1.Lead powder raw material is well mixed with manganese dioxide powder raw material and is put into ball mill, with 1350r/min's
Speed ball milling 3min.Compound is taken out, agate mortar fine grinding 30min is placed, compound is uniformly dispersed and is refined, discharge particle diameter
Less than 20 μm.The abundant compound for mixing refinement is put in graphite jig, mould need to smear boron nitride as releasing agent, then
It is placed in vacuum hotpressing stove, 7.5 × 10-3Under Pa vacuums, 360 DEG C, load pressure 75Mpa are heated to, is incubated 30min.
The vacuum hot pressing technique technique is：Mould is placed to appropriate, opening cooling circulating water, mechanical pump and diffusion successively
Pump, preheat 30min；Then valve is converted, treats that vacuum reaches 7.5 × 10-3Begun to warm up during Pa while load pressure 75Mpa；
Setting heating rate is 10 DEG C/min, rises to 360 DEG C and starts to be incubated 30min；Insulation is heated after terminating to be stopped, and treats that temperature is cooled to
Close diffusion pump at 150 DEG C, conversion valve after 5min；Mechanical pump is closed when temperature is down to 80 DEG C；Room temperature is finally cooled to take
Go out mould to be stripped, obtain the Al-matrixcomposites.
The surface microhardness of the Al-matrixcomposites brings up to 59.3Hv from 28Hv of pure lead or so, and section is micro- hard
Degree brings up to 65.5Hv.In Zn2+50g/L, H2SO4150g/L, in 35 DEG C of solution systems, the Al-matrixcomposites are close in electric current
Spend 0.05A/cm2When oxygen evolution potential be 1.83V, service life 52800h.
Embodiment 2
Take manganese dioxide powder raw material 0.01mol, lead powder raw material 0.05mol, mole of manganese dioxide powder and lead powder raw material
Than controlling 0.2:1.Lead powder raw material is well mixed with manganese dioxide powder raw material and is put into ball mill, with 1400r/min's
Speed ball milling 3min.Compound is taken out, agate mortar fine grinding 30min is placed, compound is uniformly dispersed and is refined, discharge particle diameter
Less than 20 μm.The abundant compound for mixing refinement is put in graphite jig, mould need to smear boron nitride as releasing agent, then
It is placed in vacuum hotpressing stove, 8.0 × 10-3Under Pa vacuums, 380 DEG C, load pressure 80Mpa are heated to, is incubated 20min.
The vacuum hot pressing technique technique is：Mould is placed to appropriate, opening cooling circulating water, mechanical pump and diffusion successively
Pump, preheat 30min；Then valve is converted, treats that vacuum reaches 8.0 × 10-3Begun to warm up during Pa while load pressure 80Mpa；
Setting heating rate is 10 DEG C/min, rises to 380 DEG C and starts to be incubated 30min；Insulation is heated after terminating to be stopped, and treats that temperature is cooled to
Close diffusion pump at 150 DEG C, conversion valve after 5min；Mechanical pump is closed when temperature is down to 80 DEG C；Room temperature is finally cooled to take
Go out mould to be stripped, obtain the Al-matrixcomposites.
The surface microhardness of the Al-matrixcomposites brings up to 70.7Hv from 28Hv of pure lead or so, and section is micro- hard
Degree brings up to 78.3Hv.In Zn2+50g/L, H2SO4150g/L, in 35 DEG C of solution systems, the Al-matrixcomposites are close in electric current
Spend 0.05A/cm2When oxygen evolution potential be 1.70V, service life 65600h.
Embodiment 3
Take manganese dioxide powder raw material 0.015mol, lead powder raw material 0.05mol, mole of manganese dioxide powder and lead powder raw material
Than controlling 0.3:1.Lead powder raw material is well mixed with manganese dioxide powder raw material and is put into high energy ball mill, with 1450r/
Min speed ball milling 2min.Compound is taken out, agate mortar fine grinding 30min is placed, compound is uniformly dispersed and is refined, go out
Expect that particle diameter is less than 20 μm.The abundant compound for mixing refinement is put in graphite jig, mould need to smear boron nitride as the demoulding
Agent, then it is placed in vacuum hotpressing stove, 8.5 × 10-3Under Pa vacuums, 400 DEG C, load pressure 85Mpa are heated to, insulation
15min。
The vacuum hot pressing technique technique is：Mould is placed to appropriate, opening cooling circulating water, mechanical pump and diffusion successively
Pump, preheat 30min；Then valve is converted, treats that vacuum reaches 8.5 × 10-3Begun to warm up during Pa while load pressure 85Mpa；
Setting heating rate is 10 DEG C/min, rises to 400 DEG C and starts to be incubated 15min；Insulation is heated after terminating to be stopped, and treats that temperature is cooled to
Close diffusion pump at 150 DEG C, conversion valve after 5min；Mechanical pump is closed when temperature is down to 80 DEG C；Room temperature is finally cooled to take
Go out mould to be stripped, obtain the Al-matrixcomposites.
The surface microhardness of the Al-matrixcomposites brings up to 68.8Hv from 28Hv of pure lead or so, and section is micro- hard
Degree brings up to 75.4Hv.In Zn2+50g/L, H2SO4150g/L, in 35 DEG C of solution systems, the Al-matrixcomposites are close in electric current
Spend 0.05A/cm2When oxygen evolution potential be 1.76V, service life 56000h.
Embodiment 4
Take manganese dioxide powder raw material 0.02mol, lead powder raw material 0.05mol, mole of manganese dioxide powder and lead powder raw material
Than controlling 0.4:1.Lead powder raw material is well mixed with manganese dioxide powder raw material and is put into ball mill, with 1600r/min's
Speed ball milling 5min.Compound is taken out, agate mortar fine grinding 30min is placed, compound is uniformly dispersed and is refined, discharge particle diameter
Less than 20 μm.The abundant compound for mixing refinement is put in graphite jig, mould need to smear boron nitride as releasing agent, then
It is placed in vacuum hotpressing stove, 9 × 10-3Under Pa vacuums, 420 DEG C, load pressure 90Mpa are heated to, is incubated 10min.
The vacuum hot pressing technique technique is：Mould is placed to appropriate, opening cooling circulating water, mechanical pump and diffusion successively
Pump, preheat 30min；Then valve is converted, treats that vacuum reaches 9 × 10-3Begun to warm up during Pa while load pressure 90Mpa；If
It is 10 DEG C/min to put heating rate, rises to 420 DEG C and starts to be incubated 10min；Insulation is heated after terminating to be stopped, and treats that temperature is cooled to
Close diffusion pump at 150 DEG C, conversion valve after 5min；Mechanical pump is closed when temperature is down to 80 DEG C；Room temperature is finally cooled to take
Go out mould to be stripped, obtain the Al-matrixcomposites.
The surface microhardness of the Al-matrixcomposites brings up to 65.3Hv from 28Hv of pure lead or so, and section is micro- hard
Degree brings up to 70.8Hv.In Zn2+50g/L, H2SO4150g/L, in 35 DEG C of solution systems, the Al-matrixcomposites are close in electric current
Spend 0.05A/cm2When oxygen evolution potential be 1.85V, service life 48000h.
As seen from the above embodiment, the surface microhardness scope of Al-matrixcomposites provided by the invention be 59.3~
70.7Hv, section microhardness scope are 65.5~78.3Hv, and the surface that addition of the manganese dioxide in lead improves lead is micro-
Hardness and section microhardness reach more than one times；Al-matrixcomposites provided by the invention are in the test of Zinc electrolysis simulated system
Current density is 0.05A/cm-2When oxygen evolution potential scope be 1.70~1.85V, service life scope is 48000~65600h,
Catalytic activity is good, service life length.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of Al-matrixcomposites, is comprised the following steps：
Ball milling and grinding are sequentially carried out after manganese dioxide powder raw material is mixed with lead powder raw material, obtains compound；
Vacuum hotpressing is carried out to the compound, obtains Al-matrixcomposites.
2. preparation method according to claim 1, it is characterised in that the grain diameter of the manganese dioxide powder raw material≤
20μm。
3. preparation method according to claim 1, it is characterised in that grain diameter≤80 μm of the lead powder raw material.
4. according to the preparation method described in claims 1 to 3 any one, it is characterised in that the manganese dioxide powder raw material
Mol ratio with lead powder raw material is 0.1~0.4:1.
5. according to the preparation method described in claims 1 to 3 any one, it is characterised in that the speed of the ball milling is 1200
~1600r/min, the time of the ball milling is 1~5min.
6. according to the preparation method described in claims 1 to 3 any one, it is characterised in that the μ of the particle diameter of the compound≤20
m。
7. according to the preparation method described in claims 1 to 3 any one, it is characterised in that the vacuum of the vacuum hotpressing
For 7 × 10-3~9 × 10-3Pa；
The pressure of the vacuum hotpressing is 70~90MPa；
The temperature of the vacuum hotpressing is 360~420 DEG C；
The soaking time of the vacuum hotpressing is 10~30min.
8. the Al-matrixcomposites that preparation method described in claim 1~7 any one obtains, include the shell being made up of lead component
Structure, and the nuclear structure being made up of manganese dioxide component of shell structure parcel.
9. application of the Al-matrixcomposites described in claim 8 as anode during Zinc electrolysis.
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2017
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| GB1369047A (en) * | 1970-09-30 | 1974-10-02 | Mitsui Mining & Smelting Co | Moulding method and packing structure for catalyst for use in purification of waste gas containing carbon monoxide |
| JPH01119688A (en) * | 1987-11-04 | 1989-05-11 | Japan Carlit Co Ltd:The | Resin molded electrode and production thereof |
| CN101705500A (en) * | 2009-11-12 | 2010-05-12 | 北京有色金属研究总院 | Composite anode and preparation method thereof |
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