CN107326208B - A kind of foam magnesium or foam aluminum alloy and preparation method thereof - Google Patents
A kind of foam magnesium or foam aluminum alloy and preparation method thereof Download PDFInfo
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- CN107326208B CN107326208B CN201710466597.2A CN201710466597A CN107326208B CN 107326208 B CN107326208 B CN 107326208B CN 201710466597 A CN201710466597 A CN 201710466597A CN 107326208 B CN107326208 B CN 107326208B
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000006260 foam Substances 0.000 title claims abstract description 88
- 239000011777 magnesium Substances 0.000 title claims abstract description 88
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 25
- 229910000861 Mg alloy Inorganic materials 0.000 claims abstract description 56
- 239000000843 powder Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 37
- 239000008187 granular material Substances 0.000 claims abstract description 26
- ZGBSOTLWHZQNLH-UHFFFAOYSA-N [Mg].S(O)(O)(=O)=O Chemical compound [Mg].S(O)(O)(=O)=O ZGBSOTLWHZQNLH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 46
- 239000011812 mixed powder Substances 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 24
- 229910052786 argon Inorganic materials 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001192 hot extrusion Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 230000002000 scavenging effect Effects 0.000 claims description 2
- 235000001055 magnesium Nutrition 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 31
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 abstract description 27
- 239000011148 porous material Substances 0.000 abstract description 20
- 238000007731 hot pressing Methods 0.000 abstract description 14
- 229910052943 magnesium sulfate Inorganic materials 0.000 abstract description 14
- 235000019341 magnesium sulphate Nutrition 0.000 abstract description 13
- 239000000945 filler Substances 0.000 abstract description 9
- 239000000956 alloy Substances 0.000 abstract description 8
- 238000005476 soldering Methods 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000005266 casting Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000013016 damping Methods 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 230000003139 buffering effect Effects 0.000 description 5
- 239000010440 gypsum Substances 0.000 description 5
- 229910052602 gypsum Inorganic materials 0.000 description 5
- 239000007769 metal material Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011505 plaster Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 238000005495 investment casting Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 and therefore Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009439 industrial construction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005058 metal casting Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910021652 non-ferrous alloy Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 229910000568 zirconium hydride Inorganic materials 0.000 description 1
Classifications
-
- 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
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
- B22F3/1134—Inorganic fillers
-
- 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
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/114—Making porous workpieces or articles the porous products being formed by impregnation
-
- 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
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a kind of foam magnesium or foam aluminum alloys, using sulfuric acid magnesium granules as filler, to be prepared using magnesium powder or magnesium alloy powder as raw material using powder metallurgic method.The invention also discloses the preparation methods of above-mentioned foam magnesium or foam aluminum alloy.The present invention prepares sandwich structure foam magnesium or magnesium alloy using magnesium sulfate as pore creating material, using powder metallurgic method, and magnesium sulfate is not decomposed during the sintering process, thermally expands small, volume stability, so that preparation process is safer reliable.In addition, sulfuric acid magnesium granules are soluble easily in water, SO in magnesium/magnesium sulfate complex course of dissolution4 2‑It is slight to magnesium metal matrix corrosion degree, and the removal of magnesium sulfate is more convenient, the foam magnesium or magnesium alloy materials of preparation are purer.First hot pressing, re-segmenting sintering are conducive to effective soldering between magnesium or magnesium alloy powder particles.Uniformly and hole queueing discipline in three-dimensional space, porosity is 30~65% for its aperture size of foam magnesium or magnesium alloy produced by the present invention.
Description
Technical field
The invention belongs to metal material metallurgy and metal material processing technical field, it is related to a kind of foam magnesium or foam magnesium closes
Gold, the invention further relates to the preparation methods of above-mentioned foam magnesium or foam aluminum alloy.
Background technique
With the fast development of economy and society, defence and military, industrial construction, automotive safety, the protection of the child, sports goods
And daily life utensil proposes new demand to protective materials such as energy-saving and emission-reduction, high-performance impact resisting, damping energy-absorbings.Therefore,
Develop a kind of hot spot that can satisfy the new material that these properties require and have become futurity industry development.
Foam metal is a kind of special metal material containing foam stomata, is a kind of novel-section of mankind's development in science and technology
Material.Due to its unique porous structure feature, it is made to have both the feature of structural material and functional material, can be used for aviation boat
It, many industrial circles such as petrochemical industry.
Magnesium or magnesium alloy are structural metallic materials most light in current engineer application, compared with aluminium, magnesium small, matter with density
Amount is light, and electromagnetic shielding capability is strong, and biodegrade and bio-absorbable ability are good, and specific strength and specific stiffness are above aluminium.In addition, hcp
Patterns for Close-Packed Hexagonal Crystal structure is more advantageous to the damping characteristics for improving foam magnesium, and therefore, foam magnesium or foam aluminum alloy are more suitable
Together in the material for preparing damping, buffering, heat isolating damping, sound-absorbing and sound insulation, electromagnetic protection.It can be seen that foam magnesium or magnesium alloy are gathered around
Have that density is lower, heat-proof quality, sound insulation value are more excellent, and S. E. A. is higher, and specific surface area is bigger, and can absorb electromagnetism
The series of advantages such as wave and electromagnetic radiation.If foamed material, unique structure and ultralight property is made in magnesium or magnesium alloy
Can there will be better application prospect.
The foam magnesium or magnesium alloy of function admirable are developed, the foam magnesium or magnesium with lightweight, high-strength, high damping energy-absorbing are prepared
Alloy is applied to automobile manufacture industry, the especially component in vehicle impact area, such as metal beam, bumper.When hitting
When, it is mainly consumed in due to impact energy in the deformation process of foam metal, it is thus possible to improve buffering effect, drop to greatest extent
The low damaged condition by collision object.In addition, can also reduce vehicle itself can since foam magnesium or quality of magnesium alloy are lighter
Consumption, this is of great significance to energy-saving and emission-reduction.
However, related foamed aluminium preparation is ground with performance since the activity of magnesium and the oxide structure of magnesium be not fine and close
It is more to study carefully report, and the research of foam magnesium or magnesium alloy is relatively fewer.
Currently, the preparation method of common foam aluminum alloy is mainly the following method:
(1) infiltration casting
Infiltration casting is that the water soluble salt particle that will be handled well is directly accumulated or is made porous preform and is placed in casting mold
It is interior, then the magnesium molten metal of melting is poured into casting mold, thus filling pore.Casting forms spray after cooled and solidified,
Then necessary machining is carried out, foam metal or alloy with three-dimensional connection structure can be obtained in removal filler.The party
The foam metal or alloy hole that method is prepared are evenly distributed, and pore size is easy to control, and preparation process is simple, can produce compared with
Large-sized product.However, since the common filler grain of infiltration casting is NaCl particle, the equilibrium potential of magnesium is-
Cl in 2.37V, Mg/NaCl complex course of dissolution-Heavy corrosion magnesium matrix, therefore hardly result in ideal foam magnesium or magnesium conjunction
Gold.Mao Guobing " preparing foam magnesium and foamed aluminium material with new packing " [Special Processes of Metal Castings and non-ferrous alloy, the 6th phase in 2003,
The 8-10 pages] use vacuum seepage casting with MgSO in a text4With NaCl as filler particles, it is prepared for foam magnesium material,
Mg/MgSO4SO in complex course of dissolution4 2-Magnesium matrix is corroded lighter.However, it is easy to appear seepage flow in this way
Insufficient and seepage flow over-header problem, it is necessary to strict control casting mold waste heat supply temperature, the pouring temperature of Mg liquid, sufficiently large negative pressure and enough
Mg liquid measure could prepare qualified foamed material.Simultaneously as being easy the moisture in sucking air, this method in flow event
There is the risk of explosion in preparation process, and higher cost, operation acquire a certain degree of difficulty.
(2) investment casting
Investment casting is that the slurries with fire resistance are filled in through-hole foam sponge, and roasting after air-dried, hardening makes
Foam sponge is decomposed and is removed, and three-dimensional netted precast body is formed.Then molten metal bath is cast in the precast body, is coagulated
Gu refractory material is removed after again, obtaining has three-dimensional netted foam metal material.A kind of Chinese patent " production foam aluminum alloy
Method " (application number: 200810054490, publication number: 101220424, publication date: 2008.07.16) disclose a kind of production
First foam-like plaster cast is made in gypsum slurry by the method for foam aluminum alloy, this method, pours liquid magnesium alloy after its hardening
It infuses in model hole, forms the complex of magnesium alloy and gypsum, remove gypsum after cooling and solidifying, foam magnesium conjunction can be obtained
Gold.The advantages of this method is that pore structure copies the pattern of precast body sponge completely, regular and controllable.But this method
There is also many problems, are mainly reflected in: (a) preparation of plaster cast needs could complete for more than ten hour, long preparation period,
And the defects of prepared plaster cast may be cracked, be collapsed；(b) pouring metal melt process is needed plaster cast
Links, complex technical process, the higher cost such as preheated, vacuumized.Casting process is also easy to occur to collapse to cause office
Portion's metal or alloy liquid wraps up gypsum, and subsequent gypsum is removed difficult.(c) due to surface tension problem, model hole must be enough
Greatly, otherwise molten metal is difficult to fill with whole network, therefore, is controlled using this investment casting foam pores ratio (density of material)
It is more difficult to make.
(3) powder metallurgic method
Powder metallurgic method is uniformly to be mixed magnesium or magnesium alloy powder with pore creating material, and the powder mixed is pressed into cause
Then precast body is put into heat-agglomerating in furnace by close precast body, make pore creating material heat resolve or subsequent dissolution and had
There is the foam magnesium material of certain pore size structure.Metal hydride such as TiH2Or ZrH2Etc. being more satisfactory common pore-creating at present
Agent, but its price is costly.Chinese patent " magnesium-based foamed composite and preparation " (application number: CN200410012162.3,
Publication number: CN1560291, publication date: 2005.01.05) it discloses using cheap MgCO3As pore creating material, powder smelting is utilized
Golden method prepares foam aluminum alloy.However, MgCO3It is possible to that foam magnesium conjunction can be remained in the oxide that sintering is thermally decomposed to generate
Jin Zhong generates corrosion, while the CO generated to magnesium matrix2Also chemical reaction can occur with magnesium-based body opening inner wall and generates MgO, this is not
Product flexibility is only reduced, is also easy to cause the hole of foam magnesium to occlude.A kind of Chinese patent " foam magnesium for buffering energy-absorbing material
Preparation method " (application number: CN201410145164.3, publication number: CN103862051A, publication date: 2014.06.18) disclosure
Foam magnesium is prepared by ingredient mixing, compression moulding and sintering processes using urea and magnesium powder.But in sintering process, due to
Urea can decompose in different temperatures range and generate different products, and thermal decomposition product is complex, the porous foam magnesium or magnesium of preparation
Alloy is not pure enough, and control is got up extremely difficult.
It can be seen that there are variety of problems for the preparation of foam magnesium or magnesium alloy, there is an urgent need to develop a kind of novel pore creating materials
And corresponding preparation method, deficiency present in current foam magnesium preparation process is solved, to obtain even pore distribution, pore size
Controllably, density of material is controllable, and foam magnesium or magnesium alloy with good comprehensive performance.
Summary of the invention
The object of the present invention is to provide a kind of foam magnesium or foam aluminum alloys, have even pore distribution, pore size can
The controllable feature of control, density of material.
It is a further object of the present invention to provide the preparation methods of above-mentioned foam magnesium or foam aluminum alloy.
The technical scheme adopted by the invention is that a kind of foam magnesium or foam aluminum alloy, are original with magnesium powder or magnesium alloy powder
Material, using sulfuric acid magnesium granules as filler, is prepared using powder metallurgic method.
Foam magnesium or foam aluminum alloy are sandwich structure, and foam magnesium or magnesium alloy two sides are magnesium alloy plate.
Foam magnesium or foam aluminum alloy porosity are 30~65%.
Another technical solution of the present invention is, the preparation method of a kind of foam magnesium or foam aluminum alloy specifically press with
Lower step is implemented:
Step 1, required magnesium powder or magnesium alloy powder and sulfuric acid magnesium granules are weighed according to expected porosity, dried, and mixed equal
It is even；
Step 2, mixed-powder step 1 obtained is packed into mold, and after vibration dispersion is smooth, it is prefabricated for carrying out hot extrusion
Body；
Step 3, the precast body that step 2 obtains is sintered, cleaned to get finished product is arrived.
Feature of the present invention also resides in,
Drying temperature is 120~140 DEG C in step 1,2~3h of drying time.
Be added in mixed process in step 1 mixed-powders of dehydrated alcohol, magnesium powder or magnesium alloy powder and sulfuric acid magnesium granules with
The ratio of dehydrated alcohol is 10~15g/ml, and in closed container, argon gas protection is lower to be carried out mixed process.
Mixed-powder is packed into mold with sandwich structure in step 2, i.e., by two pieces of magnesium alloy plates with a thickness of 1~2mm point
It is not placed in mixed powder particles two sides up and down.
Hot pressing temperature is 300~400 DEG C in step 2, and hot pressing pressure is 150~200MPa, 0.5~1.5h of heat-insulation pressure keeping.
Sintering is specially and precast body is placed in vacuum argon gas furnace in step 3, is sintered using segmented: being first warming up to
150~200 DEG C, 10~15 DEG C/min of heating rate, keep the temperature 0.5~1h；Then raise temperature to 300~350 DEG C, heating rate 5~
10 DEG C/min, keep the temperature 0.5~1h；580~600 DEG C, 3~5 DEG C/min of heating rate are finally warming up to, and keeps the temperature 2~3h, with furnace
It is cooled to room temperature.
Cleaning specifically: sintered precast body is subjected to ultrasonic cleaning in alkalescent NaOH aqueous solution, when cleaning
Between 4~6h.
The invention has the advantages that
(1) present invention prepares sandwich structure foam magnesium or magnesium alloy using powder metallurgic method, and sulfuric acid magnesium granules is selected to make
For pore creating material, magnesium sulfate is not decomposed during sintering process, thermally expands small, volume stability, and preparation process is safer
Reliably.In addition, sulfuric acid magnesium granules are soluble easily in water, SO in magnesium/magnesium sulfate complex course of dissolution4 2-To relatively active gold
Category magnesium matrix extent of corrosion is slight, and the removal of pore creating material magnesium sulfate is more convenient, and the foam magnesium or magnesium alloy materials of preparation are purer
Only.
(2) using first heat pressing process, it is help to obtain fine and close precast body, and be conducive between magnesium or magnesium alloy powder particles
Effective soldering.
(3) divide different temperature zones control heating rate and sintering time, can crack to avoid thermal expansion, be conducive to magnesium or
Effective soldering between magnesium alloy powder particles.
(4) magnesium alloy plate of 1~2mm is placed in two sides above and below mixed powder when prepared by precast body, and it is good to help to obtain soldering
Good sandwich type foam magnesium or magnesium alloy.
(5) a kind of foam magnesium of controlled porosity or the new method of magnesium alloy preparation are proposed, aperture size is uniformly simultaneously
And hole queueing discipline in three-dimensional space.
Detailed description of the invention
Fig. 1 is the process flow chart of the preparation method of foam magnesium or foam aluminum alloy of the present invention；
Fig. 2 is that foam magnesium or foam aluminum alloy of the present invention prepare hot pressing schematic diagram.
In figure, 1. pressure rams, 2. extrusion cylinders, 3. mixing powder particles, 4. backing plates, 5. heating coils, 6. lower magnesium alloy plates, 7.
Upper magnesium alloy plate.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
The present invention provides a kind of foam magnesium or foam aluminum alloys, and with partial size be 25~150 μm, purity is greater than 99.9%
Magnesium powder or magnesium alloy powder are raw material, and the sulfuric acid magnesium granules for being 25~250 μm using partial size are prepared into as filler using powder metallurgic method
It arrives.With sandwich structure, porosity is 30~65%.
The preparation method of above-mentioned foam magnesium or foam aluminum alloy, process flow is as shown in Figure 1, specific real according to the following steps
It applies:
Step 1, the calculating and weighing of raw material:
According to expected porosity, the quality of required magnesium powder and sulfuric acid magnesium granules is calculated according to formula (1-1) and (1-2).
Corresponding raw material are weighed according to calculated value:
m1=V × ρ1×(1-P) (1-1)
m2=V × ρ2×P (1-2)
In formula, P is expected porosity, m1And m2The respectively quality of magnesium powder and sulfuric acid magnesium granules, ρ1And ρ2Respectively magnesium powder
With the density of sulfuric acid magnesium granules, wherein pure magnesium powder density is 1.74g/cm3, magnesium alloy powder density is (1.8~2.1) g/cm3Sulphur
Sour magnesium granules density is 2.66g/cm3；
Step 2, it dries:
Weighed magnesium powder or magnesium alloy powder and sulfuric acid magnesium granules are dried respectively, inhaled with removing powder granule surface
Attached gas and moisture, improves its mobility.Wherein, drying temperature is 120~140 DEG C, 2~3h of drying time；
Step 3, powder is mixed:
By after drying magnesium powder and sulfuric acid magnesium granules carry out mixed powder, for promote magnesium powder or magnesium alloy powder and sulfuric acid magnesium granules it
Between it is well-bonded, prevent from being layered, dehydrated alcohol be added during mixed powder, the ratio for mixing powder particles and dehydrated alcohol is 10~
15g/ml.Meanwhile being contacted and surface oxidation in order to avoid mixing magnesium powder during powder with oxygen, powder is mixed in closed rustless steel container
It carries out, mixed powder process is filled with argon gas；
Step 4, it charges:
Uniformly mixed mixed powder is fitted into mold with sandwich structure, i.e., by two pieces of same materials with a thickness of 1~2mm
Or the magnesium alloy plate of unlike material is respectively placed in mixed powder particles two sides, then swing die ontology up and down, time of vibration is at least
30s eliminates " arch bridge " effect that powder generates, and improves powder density uniformity, and it is whole to pave mixed powder particles under vibration；
Step 5, hot pressing:
Hot pressing is carried out to mixed powder particles using hydraulic press, with promote preliminary soldering between magnesium powder or magnesium alloy powder particles or
Mechanical adhesion, and then it is more advantageous to subsequent sintering.Hot pressing is as shown in Fig. 2, be placed in 2 bottom of extrusion cylinder for lower magnesium alloy plate 6
On portion's backing plate 4, it is packed into mixed powder particles 3 in extrusion cylinder 2, and places upper magnesium alloy plate on mixed powder particles 3, pressure ram 1 is downward
Movement, when it touches upper magnesium alloy plate 7, continues slowly to pressurize, so that pressing pressure is 150~200MPa.It then gives and adds
Heat coil 5, which is powered, heats compacting sample, wherein hot pressing temperature is 300~400 DEG C, 0.5~1.5h of heat-insulation pressure keeping.To
Mold temperature is down to i.e. openable mold at 100 DEG C or less, obtains precast body；
Step 6, it is sintered:
Precast body is placed in vacuum argon gas furnace and is sintered, is evacuated to before sintering less than 200Pa, then passes to argon gas
It to 1atm, takes out three times repeatedly, then is passed through argon gas to 1atm.It begins to warm up at this time, is warming up to 150~200 DEG C, heating rate 10~
15 DEG C/min, keep the temperature 0.5~1h；300~350 DEG C, 5~10 DEG C/min of heating rate are then raised temperature to, 0.5~1h is kept the temperature；Most
After be warming up to 580~600 DEG C, 3~5 DEG C/min of heating rate, and keep the temperature 2~3h, cool to room temperature with the furnace；
Step 7, it cleans:
By sintered sample, (0.001mol/L) carries out ultrasonic cleaning in alkalescent NaOH aqueous solution, is filled out with removal
Expect particle, 4~6h of scavenging period.
Prior powder metallurgy method prepares foam magnesium or magnesium alloy generally using urea or carbonate as foaming agent, foaming agent
Thermal decomposition product is complex, volatile matter pollutes atmospheric environment, and can generate corrosion to magnesium matrix；And the present invention is relative to tradition
Method has the following characteristics that
(1) sandwich structure foam magnesium or magnesium alloy are prepared using powder metallurgic method, selects sulfuric acid magnesium granules as pore-creating
Agent.Since magnesium sulfate is not decomposed during sintering process of the present invention, small, volume stability is thermally expanded, preparation process is more
Securely and reliably.Therefore, present invention process process is pollution-free, odorlessness.In addition, sulfuric acid magnesium granules are soluble easily in water, magnesium/magnesium sulfate is multiple
SO in fit course of dissolution4 2-Slight to relatively active magnesium metal matrix corrosion degree, the removal of pore creating material magnesium sulfate is more
Convenient, the foam magnesium or magnesium alloy materials of preparation are purer.
(2) using first heat pressing process, it is help to obtain fine and close precast body, and be conducive between magnesium or magnesium alloy powder particles
Effective soldering.
(3) divide different temperature zones control heating rate and sintering time, can crack to avoid thermal expansion, be conducive to magnesium or
Effective soldering between magnesium alloy powder particles.
(4) magnesium alloy plate of 1~2mm is placed in two sides above and below mixed powder when prepared by precast body, and it is good to help to obtain soldering
Good sandwich type foam magnesium or magnesium alloy.
(5) a kind of foam magnesium of controlled porosity or the new method of magnesium alloy preparation are proposed, aperture size is uniformly simultaneously
And hole queueing discipline in three-dimensional space.
Embodiment 1
(1) quality of required powder particle the calculating and weighing of raw material: is calculated according to formula (1-1) and (1-2).This reality
The expection porosity for applying example is 30%, therefore the mass percent for weighing magnesium powder and sulfuric acid magnesium granules is respectively 60.42% He
39.58%；
(2) it dries: weighed magnesium powder and sulfuric acid magnesium granules is dried respectively, drying temperature is 120 DEG C, drying time
For 2h.Wherein, pore creating material magnesium sulfate partial size is 250 μm, and magnesium powder is 150 μm；
(3) it mixes powder: the two being filled with to argon gas in closed rustless steel container and carries out mixed powder, and nothing is added during mixed powder
Water-ethanol, the ratio for mixing powder particles and dehydrated alcohol is 10g:1ml；
(4) it charges: uniformly mixed sample is fitted into mold with sandwich structure.Will two pieces with a thickness of 1mm's
AZ31 magnesium alloy plate is respectively placed in mixed powder particles two sides up and down, and then swing die ontology 30s, improves powder density uniformity,
And mixed powder particles is made to flow to surfacing under vibration；
(5) hot pressing hot pressing: is carried out for precast body to mixed powder particles using hydraulic press.Wherein, pressing pressure 150MPa,
Temperature is 300 DEG C, heat-insulation pressure keeping 0.5h.Mold is opened when mold temperature is down to 60 DEG C, obtains precast body；
(6) it is sintered: precast body being placed in vacuum argon gas furnace and is sintered, vacuum argon gas furnace is vacuumized before sintering
Logical argon gas, repeatedly for three times, sintering process lead to argon gas protection.150 DEG C, 10 DEG C/min of heating rate are warming up to, 0.5h is kept the temperature；Then
300 DEG C, 5 DEG C/min of heating rate are warming up to, 0.5h is kept the temperature；580 DEG C, 3 DEG C/min of heating rate are then heated to, and 580
DEG C heat preservation 2h, finally cool to room temperature with the furnace；
(7) clean: by sintered sample, (0.001mol/L) carries out ultrasonic cleaning in alkalescent NaOH aqueous solution
4h removes filler particles.
Originally it is uniform to apply the foam magnesium material aperture structure that example obtains, porosity is 30% or so, and is had compared with high impact-resistant
Intensity and good damping energy absorption capacity.
Embodiment 2
(1) quality of required powder particle the calculating and weighing of raw material: is calculated according to formula (1-1) and (1-2).This reality
The expection porosity for applying example is 50%, therefore the mass percent for weighing magnesium powder and sulfuric acid magnesium granules is respectively 39.55% He
60.45%；
(2) it dries: weighed magnesium powder and sulfuric acid magnesium granules is dried respectively, drying temperature is 130 DEG C, drying time
For 2.5h.Wherein, pore creating material magnesium sulfate partial size is 150 μm, and magnesium powder is 75 μm；
(3) it mixes powder: the two being filled with to argon gas in closed rustless steel container and carries out mixed powder, and nothing is added during mixed powder
Water-ethanol, the ratio for mixing powder particles and dehydrated alcohol is 12g:1ml；
(4) it charges: uniformly mixed sample is fitted into mold with sandwich structure.I.e. by one piece with a thickness of 1.5mm's
ZK60 magnesium alloy plate and one piece of AZ31 magnesium alloy plate with a thickness of 1.2mm are respectively placed in mixed powder particles or more two sides, then vibrate
Die ontology 30s improves powder density uniformity, and mixed powder particles is made to flow to surfacing under vibration；
(5) hot pressing hot pressing: is carried out for precast body to mixed powder particles using hydraulic press.Wherein, pressing pressure 180MPa,
Temperature is 350 DEG C, heat-insulation pressure keeping 1h.I.e. openable mold when mold temperature is down to 100 DEG C or less obtains precast body；
(6) it is sintered: precast body being placed in vacuum argon gas furnace and is sintered, vacuum argon gas furnace is vacuumized before sintering
Logical argon gas, repeatedly for three times, sintering process lead to argon gas protection.180 DEG C, 12 DEG C/min of heating rate are warming up to, 0.8h is kept the temperature；Then
320 DEG C, 8 DEG C/min of heating rate are warming up to, 0.6h is kept the temperature；590 DEG C, 4 DEG C/min of heating rate are then heated to, and 590
DEG C heat preservation 2.5h, finally cool to room temperature with the furnace；
(7) clean: by sintered sample, (0.001mol/L) carries out ultrasonic cleaning in alkalescent NaOH aqueous solution
5h removes filler particles.
The foam magnesium material that the present embodiment obtains, aperture structure is uniform, porosity up to 50%, and have good toughness,
Higher impact strength and excellent buffering energy-absorbing.
Embodiment 3
(1) quality of required powder particle the calculating and weighing of raw material: is calculated according to formula (1-1) and (1-2).This reality
The expection porosity for applying example is 65%, therefore weighing density is 1.9g/cm3Magnesium aluminum-alloy powder and sulfuric acid magnesium granules quality hundred
Divide than being respectively 27.78% and 72.22%；
(2) it dries: weighed magnesium powder and sulfuric acid magnesium granules is dried respectively, drying temperature is 140 DEG C, drying time
For 3h.Wherein, pore creating material magnesium sulfate partial size is 25 μm, each half that magnesium aluminum-alloy powder is 25 μm and 150 μm；
(3) it mixes powder: the two being filled with to argon gas in closed rustless steel container and carries out mixed powder, and nothing is added during mixed powder
Water-ethanol, the ratio for mixing powder particles and dehydrated alcohol is 15g:1ml；
(4) it charges: uniformly mixed sample is fitted into mold with sandwich structure.Will two pieces with a thickness of 1.8mm's
WE43 magnesium alloy plate is respectively placed in mixed powder particles two sides up and down, and then swing die ontology 30s, improves powder density uniformity,
And mixed powder particles is made to flow to surfacing under vibration；
(5) hot pressing hot pressing: is carried out for precast body to mixed powder particles using hydraulic press.Wherein, pressing pressure 200MPa,
Temperature is 400 DEG C, heat-insulation pressure keeping 1.5h.I.e. openable mold when mold temperature is down to 50 DEG C obtains precast body；
(6) it is sintered: precast body being placed in vacuum argon gas furnace and is sintered, vacuum argon gas furnace is vacuumized before sintering
Logical argon gas, repeatedly for three times, sintering process lead to argon gas protection.200 DEG C, 15 DEG C/min of heating rate are first warming up to, 1h is kept the temperature；Then
350 DEG C, 10 DEG C/min of heating rate are warming up to, 1h is kept the temperature；600 DEG C, 5 DEG C/min of heating rate are then heated to, and at 600 DEG C
3h is kept the temperature, finally cools to room temperature with the furnace；
(7) clean: by sintered sample, (0.001mol/L) carries out ultrasonic cleaning in alkalescent NaOH aqueous solution
6h removes filler particles.
The foam magnesium material that the present embodiment obtains, aperture structure is uniform, porosity up to 65%, and have good toughness,
Higher impact strength and excellent buffering energy-absorbing.
Claims (3)
1. the preparation method of a kind of foam magnesium or foam aluminum alloy, which is characterized in that specifically implement according to the following steps:
Step 1, required magnesium powder or magnesium alloy powder and sulfuric acid magnesium granules are weighed according to expected porosity, dried, and be uniformly mixed；
The mixed-powder and dehydrated alcohol of dehydrated alcohol, magnesium powder or magnesium alloy powder and sulfuric acid magnesium granules are added in the mixed process
Ratio be 10~15g/ml, in closed container, argon gas protection is lower to be carried out mixed process；
Step 2, mixed-powder step 1 obtained is packed into mold, and after vibration dispersion is smooth, progress hot extrusion is precast body；
The mixed-powder is packed into mold with sandwich structure, i.e., is respectively placed in two pieces of magnesium alloy plates with a thickness of 1~2mm mixed
Two sides above and below powder particles；
The extrusion temperature is 300~400 DEG C, and hot extrusion pressure pressure is 150~200MPa, 0.5~1.5h of heat-insulation pressure keeping；
Step 3, the precast body that step 2 obtains is sintered, cleaned to get finished product is arrived,
The sintering is specially that precast body is placed in vacuum argon gas furnace, is sintered using segmented: being first warming up to 150~200
DEG C, 10~15 DEG C/min of heating rate keeps the temperature 0.5~1h；300~350 DEG C, 5~10 DEG C/min of heating rate are then raised temperature to,
Keep the temperature 0.5~1h；580~600 DEG C, 3~5 DEG C/min of heating rate are finally warming up to, and keeps the temperature 2~3h, cools to room with the furnace
Temperature.
2. the preparation method of a kind of foam magnesium according to claim 1 or foam aluminum alloy, which is characterized in that the step
Drying temperature is 120~140 DEG C in 1,2~3h of drying time.
3. the preparation method of the preparation method of a kind of -2 described in any item foam magnesiums or foam aluminum alloy according to claim 1,
It is characterized in that, the cleaning specifically: sintered precast body is subjected to ultrasonic cleaning in alkalescent NaOH aqueous solution,
4~6h of scavenging period.
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| US11913092B2 (en) * | 2018-07-06 | 2024-02-27 | Cellmo Materials Innovation, Inc. | Magnesium-based alloy foam |
| CN110804736A (en) * | 2019-09-26 | 2020-02-18 | 安徽自动化仪表有限公司 | Anticorrosion process for cable bridge |
| CN112846184A (en) * | 2020-09-10 | 2021-05-28 | 宿迁市河海大学研究院 | Porous magnesium alloy with through hole structure prepared by reaction sintering powder metallurgy method and preparation method thereof |
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| JP2860427B2 (en) * | 1989-09-05 | 1999-02-24 | 博 木村 | Method for producing sintered body made of amorphous alloy powder |
| CN102774075A (en) * | 2012-07-19 | 2012-11-14 | 西安交通大学 | Composite protection plate for porous metal-packaging ceramic and preparation method thereof |
| CN104046826A (en) * | 2014-05-29 | 2014-09-17 | 河海大学 | Foamed magnesium-based material and preparation method thereof |
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| JP2860427B2 (en) * | 1989-09-05 | 1999-02-24 | 博 木村 | Method for producing sintered body made of amorphous alloy powder |
| CN102774075A (en) * | 2012-07-19 | 2012-11-14 | 西安交通大学 | Composite protection plate for porous metal-packaging ceramic and preparation method thereof |
| CN104046826A (en) * | 2014-05-29 | 2014-09-17 | 河海大学 | Foamed magnesium-based material and preparation method thereof |
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