CN109890932A - The aluminium composite material with ceramic substrate of lightweight and high tenacity - Google Patents
The aluminium composite material with ceramic substrate of lightweight and high tenacity Download PDFInfo
- Publication number
- CN109890932A CN109890932A CN201780063431.4A CN201780063431A CN109890932A CN 109890932 A CN109890932 A CN 109890932A CN 201780063431 A CN201780063431 A CN 201780063431A CN 109890932 A CN109890932 A CN 109890932A
- Authority
- CN
- China
- Prior art keywords
- aluminum slice
- prefabricated component
- pcm
- complex
- aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like particles
-
- 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
- B22F3/1143—Making porous workpieces or articles involving an oxidation, reduction or reaction step
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/16—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
-
- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Metallurgy (AREA)
- Nanotechnology (AREA)
- Combustion & Propulsion (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
A method of phase-change material aluminium composite material being prepared, this method includes providing aluminum slice and saturated fat acid composition；Composite material is put into and is pressed into mold；The repressed complex of arbitrary shape is provided, repressed complex is heated；Keep complex cooling, it is composite porous to obtain；Phase-change material is provided；And phase-change material provided by making penetrates into composite porous hole.
Description
Cross reference to related applications
This application claims the U.S. Provisional Patent Application Serial No.62/496,256 submitted on October 12nd, 2016 and in
The U.S. Provisional Patent Application Serial No.62/604 that on July 3rd, 2017 submits, 304 equity, in the above-mentioned disclosure respectively applied
Hold and is incorporated herein by quoting entirety (including all figures, table or attached drawing).
Background technique
In auto industry and railway industry using the economic benefit of the lighter but sufficiently rigid foamed aluminium (AF) of structure and
Ecological benefits just become readily apparent from.It is improved the structural intergrity of vehicle and prevented by AF hollow aluminum (Al) alloy framework coated
Hitting property.However, even the specific energy of the aperture made of high-intensitive Al alloy (A306, A356, A206 etc.) and closed pore AF are inhaled
It receives (ω) and is also limited in about 5kJ/kg.Therefore, current vehicle is still largely dependent upon the quality and machinery of frame
Performance.
The prior art includes having the shortcomings that this composite foam of relatively low ratio toughness (specific toughness)
Plastics, and the manufacture of syntactic foam and key difference are illustrated below.Embodiment of the present invention includes having
The improved porous Al composite material than toughness.
Rohatgi (United States Patent (USP) US5899256) describes such a method, wherein by by liquid A l alloy from coal
The adjacent microballoon shell of born of the same parents' flyash injects (melt infiltration), to prepare composite foam Al.It is said that this method can be by cenosphere base
Material is evacuated to the pressure lower than 40kPa.As an example, partial size is about 150 μm, and time of penetration is 5 minutes and infiltration temperature
It is 800 DEG C.What the technology and its various improvement were economically advantageous, but often will lead to the micro-structure in Al composite material and lack
It falls into.For example, the uneven distribution of microballoon (such as < 100 μm) in Al matrix can weaken overall mechanical properties.This method ensure that
The development of powder metallurgy process, wherein Al alloy powder and hollow microsphere is compressed together and be sintered, with obtain it is reliable
Even structure.
Sherman and Doud (United States Patent (USP) No.US9096034) proposes a kind of conventional PM technique, including
The mixture of alumina silicate microballoon (150 μm of ≈) and Al alloy powder (10 μm of ≈, A6061) is suppressed, and in a vacuum
It is sintered in 500 DEG C.Main claim are as follows: before pressing stage, using chemical vapor deposition (CVD) method aluminium to porous
Microballoon is additionally coated.In addition, mixture of powders repeatedly can be suppressed (as in forging), before sintering stage
Obtain thinner hole.Meanwhile the density of disclosed sample is ≈ 2,000kg/m3, toughness is about 30kJ/kg, compares absorptive capacity
It is about 138kJ/kg.
A kind of method of aluminium powder metallurgy is to carry out nitridation in situ to repressed Al particle by the rigidity bonding of AlN
Or strengthen.As described in Liu et al. people, composite foam Al (United States Patent (USP) can be prepared by using nitridation in situ
No.US20100183471).For this purpose, Al6061 alloy bulky grain is suppressed together with other metals and ceramic powders and bonding agent
At prefabricated component, and slowly (0.5 DEG C/min to 0.8 DEG C/min) heating up to 620 DEG C of the temperature in nitrogen atmosphere, with shape
At enhanced AlN skeleton.This method assumes that melting Al alloy penetrates further into prefabricated composite material by the hole that AlN enhances.
Later, author described a kind of similar material, wherein the aluminium in the powder through partial nitridation is made to melt (540 DEG C 12 hours) simultaneously
The hole of all via nitrides is vacuumized into (700 DEG C, 5Pa, 2 hours).It is shown that this compound Al6061 foamed material contains
There is the AlN shell for small (5 μm to 20 μm) being dispersed in aluminium alloy matrix.This give the improved morphotropism of composite material
The ratio toughness of about 17kJ/kg.However, material processing is relative complex and consumes energy.
Schaffer et al. (United States Patent (USP) No.US5902943) is in pure nitrogen gas to by stearic acid (0.1 weight % to 2.0
Weight %) and other known oxygen absorbent (Mg, Zn, Cu and stearic acid) protection thin (> 44 μm) aluminium powder carry out nitrogen treatment.
Under sintering condition (increasing temperature to 600 DEG C to 630 DEG C with 10 DEG C/min) about after ten minutes, appearance of free radicals nitridation.The hair
Bright preferred embodiment suggests that rate of heat addition range is 20 DEG C/min to 40 DEG C/min.As a result, quickly Al nitridation is accumulated
Gather a large amount of thermal energy and controls the quick densifying of Al matrix.However, relatively great amount of resulting AlN significantly improve it is compound
The intensity of material but the ductility for reducing composite material.Here it is such brittleness Al-AlN composite materials not to be suitable for resistance to punching
The reason of hitting property is applied.It should be noted that the getter of conflagration is under the autonomous growth and moderate temperature for triggering AlN phase
The key factor of the densification of composite structure.
Summary of the invention
Embodiment of the present invention is described to be carried out by the way that aluminum slice to be pressed into prefabricated component and extend in nitrogen atmosphere
The preparation method of the time of heat treatment.This method may include additional processing, infiltration, abrasive material such as metal and polymer
Surface, coloring and other known householder method.
Embodiment of the present invention provides material preparation method, and this method includes the rapid thermal treatment of aluminum slice and leads to
It crosses and is permeated using the hole that phase-change material appropriate carries out.Processing that can be additional with further progress, such as polishing, coloring and other
Known method.
Detailed description of the invention
Fig. 1 shows the diagram that aluminum slice is converted into composite material.Three kinds of different states are shown in figure: (1) aluminium is thin
The repressed aluminum slice powder in piece, (2) and (3) have the via nitride of improved mechanical performance and the composite material of sintering.
Fig. 2 shows the figures on the boundary for the annealing conditions for being used to prepare the Al composite material with improved mechanical performance.
Fig. 3 shows (a) compressive stress strain curve of the sample of embodiment 1 and the curve of (b) energy absorption characteristics
Figure.
Fig. 4 shows (a) compressive stress strain curve of the sample of embodiment 2 and the curve of (b) energy absorption characteristics
Figure.
Fig. 5 shows (a) compressive stress strain curve of the sample of embodiment 3 and the curve of (b) energy absorption characteristics
Figure.
Fig. 6 shows the diagram for the material that aluminum slice is converted into for thermal heat storage applications.Three kinds of differences are shown in figure
State: (1) composite wood that repressed aluminum slice powder, the aluminum slice briquetting of (2) through short annealing and (3) are penetrated into through PCM
Material.
Fig. 7 shows center (a) in the composite material through short annealing and the micrograph of (b) proximal edge region shooting
Picture.Sample porosity is about 22%.
Fig. 8 shows (a) accumulation of the composite material through short annealing in (2) hole penetrated into empty (1) hole and CtO
The curve graph of density and (b) specific heat capacity.
Fig. 9 is shown in the composite material through short annealing, porosity or PCM volume fraction to (a) thermal diffusivity and
(b) curve graph of the influence of thermal conductivity.
Figure 10 shows the outer surface of the Al composite material (embodiment 10, referring to table 1) before and after fire resisting test.
Specific embodiment
As used herein, term " Al thin slice " refers to flat Al or Al alloy structure body, thickness range be greater than
40nm and be less than 500nm.
As used herein, term " getter " or " oxygen absorbent " are intended to indicate that can effectively make nitrogen deoxidation at high temperature
Organic or inorganic compound.
As used herein, the diffusion for nitrogenizing driving shows high exothermic heat nitridation and the oxidation of getter due to Al and makes aluminium
Diffuse out Al thin slice.
As used herein, partial nitridation is intended to indicate that by the conflagration for the getter being dispersed on Al thin slice and triggers
Al and N2Between chemical reaction.
Embodiment of the present invention provides the preparation method of the lightweight aluminium composite material with unique texture, the structure energy
Enough improve formability, intensity, morphotropism, than toughness and specific energy absorption capacity.These performances are attributable to by by part nitrogen
Change and combine aluminum slice assemble accumulation orientation (pile-oriented) structure and nitridation driving aluminium diffusion.
Certain embodiments are 3m using specific surface area2/ g to 15m2The aluminum slice of/g.Al thin slice may include less than 5 weights
Measure the oxygen absorbent of %.The pressure that can be used within the scope of about 60MPa to about 500MPa suppresses aluminum slice, to obtain density
Respectively about 2,200kg/m3To about 1,300kg/m3Al thin slice briquetting.It, can be within the temperature range of about 20 DEG C to about 80 DEG C
The compacting of thin slice is carried out by hydrostatic pressing, forging, extrusion or other forming techniques.Al briquetting is indicated for being further processed
The relatively brittle but durable material in stage.It is then possible to (the N in nitrogen atmosphere2> 90%) briquetting is heated to 500 DEG C extremely
600 DEG C of temperature.Heat treatment stages can be since the quick heating (for example, 20 DEG C/min to 50 DEG C/min) of powder compact extremely
Annealing temperature, heat treatment stages can keep 1 minute to 720 minutes time.
The getter of conflagration can trigger Al nitridation spontaneous between the thin slice of connection, and formed and increased in Al briquetting
Strong type duct.Meanwhile the heat of nitridation and getter burning can promote aluminium to expand from the thin slice throughout the established duct AlN
It sheds and.By optimization Al nitridation and diffusion, can obtain there is improved mechanical performance (as than toughness and than absorptive capacity)
Lightweight Al composite material.As herein institute partially described in, preparation method does not limit claimed content.For example, annealed
Some embodiments of composite material have aperture, the polymer, metal alloy or phase-change material of melting can be made to seep by aperture
Enter annealed composite material, to improve mechanical performance and functional character.By using standard precipitation-hardening method, (it can be mentioned
The yield strength of high aluminum slice or annealed flake composite material) it can also be improved the performance of prepared Al composite material.
The density range of annealed flake composite material can be about 1,400kg/m3To 2,600kg/m3, and it is compound
The ratio toughness of material and than absorptive capacity respectively in the range of 5kJ/kg to 60kJ/kg and 10kJ/kg to 95kJ/kg.By several
A possibility that a example shows energy absorption characteristics, these examples are to show content claimed, rather than to its into
Row limitation.
As shown in Figure 1, certain embodiments of the present invention are described by the way that aluminum slice is pressed into prefabricated component and is extended
The preparation method for the time being heat-treated in nitrogen atmosphere.This method may include additional processing, such as metal and polymer
Infiltration, abrasive material surface, coloring and other householder methods.
Preparation method according to some embodiment may include following four step: step 1, wherein it is thin to can provide aluminium
Piece, the aluminum slice show as the aluminum or aluminum alloy for the precipitation-hardening state for being partially coated with aliphatic acid composition；Step 2,
In can provide the prefabricated component of arbitrary shape, which is made of aluminum slice and additive powder or the prefabricated component includes aluminium
Thin slice and additive powder, additive powder such as metal (Al, Ti, Mg, Ni, Cu, Sn, Zr, Zn, Sc, Fe, Si, Pb or V) and it
Carbide, nitride or boride；Step 3, wherein can prefabricated component be heated and be annealed；And step 4, wherein can
Keep annealed prefabricated component cooling, to obtain porous Al composite material.
In step 1, aluminum slice can be relatively pure (99.5%min) compound or the conjunction containing following additive
Gold: Cu, Fe, Si, Zn, Ni, Mn, Mg, Ge, Ti, Pb, Zr or V.The average thickness range of Al thin slice can be about 40nm to about
500nm.In certain embodiments, the average thickness of aluminum-based powder is about 80nm to 10000nm.The other sizes of thin slice can be with
For the arbitrary dimension of 40nm to 1mm.Powder size distribution in particular range will not distort the desired embodiment party of the present invention
Case.Fatty acid getter can change in 0.3 weight % between 5 weight % in the accounting in Al flake composition, and should
Accounting can be the importance of nitridation and the combination of triggering Al thin slice during heating treatment.
In step 2, aluminum slice can be mixed with one or more following additives: metal (Al, Ti, Mg, Ni, Cu,
Sn, Zr, Zn, Sc, Fe, Si, Pb or V) and their carbide, nitride or boride, to obtain powder composition.Add
Add agent approximately round, size range is 50nm to 1mm.
Powder composition can be stirred by stirring blade, to obtain runny powder.Then the powder can be filled
Progressive die has in (or extruder), and is suppressed in the pressure limit of about 60MPa to about 500MPa.It can be to powder composition
It is suppressed repeatedly, to obtain 1,200kg/m3The above 2,200kg/m3Density below.It, can be with other than hydrostatic pressing
Powder composition is squeezed out to be configured to have the long span object of constant cross-section profile.In some embodiments, aluminum slice
It can be with 3D printing at the briquetting with specific dimensions.
In step 3, powder can be moved in the heating furnace of the nitrogen atmosphere with flowing.Nitrogen gas purity
It can be 90% to 99.9999%.Heating furnace can be closed, or can be the semi-open-type with material conveyer.
Heating furnace, which can ensure that, quickly heats up to powder up to 600 DEG C of temperature.The rate of heat addition may range from 5 DEG C/min extremely
100℃/min.Gas flow rate can change in 10ml/min between 10000ml/min.It, can be in the case where semi-open-type furnace
Heating appropriate is controlled by conveyor belt speed.Once prefabricated component reaches set temperature, then anneal duration continues not surpass
Spend 720 minutes.Deviation heating condition can damage the structurally and mechanically performance of material.In many cases, due to intragranular AlN
Skeleton undue growth can be such that toughness reduces.
In step 4, annealed prefabricated component can be cooled to the specific temperature lower than 50 DEG C.Furthermore, it is possible to pass through
Toughening is carried out to annealed composite material using standard precipitation-hardening method.
Compared with AF, aluminium alloy matrix is around closelypacked ceramic sacculus (100 μm to 500 μm of Al2O3Or 15 μm extremely
175 μm of Al2O3-SiO2) typical compound foamed aluminum (SAF) in terms of absorbing impact energy more effective (ω ≈ 20kJ/
Kg to 50kJ/kg).Although typical SAF can have bigger compression strength, (40MPa to 350MPa), they are half crisp
Property and can lower than 5% strain under rupture.Ratio toughness (ω as these SAFt) as a result, until material breaks
Energy absorption is 3kJ/kg to 5kJ/kg.The ceramic sacculus (for example, 100 μm of < <) of smaller size can be improved breaking strain and
Toughness.However, the ceramic microsphere of smaller size can technically limit conventional SAF production, such as pass through adjacent ceramics
Sacculus injects liquid Al alloy (~730 DEG C).Until 880 DEG C, liquid aluminium will not make aluminium oxide surface wettability, and liquid aluminium
Al can be hindered to be adhered to the microballoon with unfolded surface area.As a result, Al and Al2O3Between peak shear strength be about
40MPa.However, in having an X-rayed biradical matter SAF, 6061 alloy of liquid A soaked strongly at about 700 DEG C 5 μm to 20 μm it is hollow
Porous Al N skeleton.The SAF ruptures under the stress of about 200MPa and 17% strain, and it is 14kJ/kg that this, which is equivalent to than toughness,.
If stephanoporate framework keeps brittleness, especially with the stephanoporate framework of large volume of AlN without alloy substrate.In addition, only
Composite foam with aluminum matrix is vulnerable to influence of fire.One kind possible solution can be for using with steel matrix or ceramics
The heavier composite material of matrix.
In certain embodiments, it can use the hollow ceramic (Al that diameter dimension range is 50 μm to 1000 μm2O3、
SiO2, SiC and their combination) sacculus or sphere.For example, sacculus can be coated with thin aluminium layer, to assign powder combinations
Aluminum slice in object is with better adhesion.Thin slice and sacculus can uniformly be mixed and are pressed into the porous of specific pore rate
Briquetting.It is then possible to be heat-treated under conditions of being provided in manufacturing step 3 to repressed mixture.
Since aluminum slice is conducting medium, thus rapid thermal treatment can be carried out by using induction heating method.For
Continuous briquetting (bar, web, profile etc.) can be put into pipe (carbon, quartz, the oxygen for accommodating gas atmosphere by such case
Change aluminium, glass or other ceramic materials) in.Furthermore, it is possible to make pipe continuously across induction coil, thus in the briquetting of encapsulation
Generate Joule heat.
Nitrogen atmosphere can be replaced with other common gas or vacuum.For example, heat treatment stages can be carried out as described below:
The nitrogen atmosphere for the flowing for being used to anneal is changed into argon gas, hydrogen, ammonia or vacuum.Annealing in other gases or vacuum
Sustainable 1 minute to 720 minutes.The purity for substituting gas can be 90% to 99.9999%.
It can be by making liquid metal alloy or polymer (UHMW polyethylene, poly-methyl methacrylate based on Mg or Al
Ester, epoxy resin and other similar enhanced polymer partially or even wholly penetrate into annealed in certain embodiments
Composite porous structure, so that it be made to be improved.
In certain embodiments, material preparation includes slight sintered preforms, is then carried out with phase-change material appropriate
Aperture is penetrated into.There is no limit to composite material for the extra process of such as polishing, coloring and other methods etc.
In certain embodiments, the preparation method of the embodiment of composite material may comprise steps of: step 1,
It wherein can provide the aluminum or aluminum alloy for being coated with the wafer state of saturated fat acid composition；Step 2, wherein can provide arbitrary shape
The repressed complex of shape, wherein the complex includes aluminum slice；Step 3, wherein can be carried out to repressed complex
Short annealing；Step 4, composite porous to obtain wherein can make to partially sinter body cooling；Step 5, wherein can provide main
PCM based on fatty acid material；Step 6, wherein PCM provided by can making penetrates into composite material duct.
In step 1, aluminium powder can be relatively pure (99.5%min) compound or the conjunction containing following additive
Gold: Cu, Fe, Si, Zn, Ni, Mn, Mg, Ge, Ti, Pb or Zr.Aluminium powder can have any particle of average about 100nm to about 1mm
Distribution of lengths.Powder size distribution in the prescribed limit will not distort desirable embodiments of the invention.Aluminum slice is put down
Equal thickness can be about 40nm to 500nm.The ratio that FA is saturated in Al flake composition can be in 0.3 weight % to 5 weight %
Between change, to avoid the unnecessary oxidation of repressed Al thin slice during heating treatment.
In certain embodiments, step 1 may include providing the aluminium (99.5%min) of pulverulence or being classified as 2xxx extremely
The aluminium alloy of 9xxx series.The length distribution range of aluminum slice can be about 100nm to about 1mm.Aluminium powder can contain at least 0.3
Weight % and less than or equal to 5 weight % saturated fatty acid as getter.
In step 2, powder composition can be stirred by stirring blade, to obtain runny powder.Then may be used
The powder is put into mold (or extruder), and is suppressed in the pressure limit of about 70MPa to about 310MPa.It can be right
Powder is suppressed repeatedly, to obtain 1,300kg/m3The above 2,200kg/m3Density below.Other than hydrostatic pressing,
Aluminum slice can be squeezed out to be configured to have the long span object of constant cross-section profile.
In step 3, by repressed powder moving into the heating chamber with the nitrogen flowed, the purity is high of nitrogen
In 90%.Heating furnace can be closed, or can be the semi-open-type with material conveyer.Heating furnace is it is ensured that powder
Briquetting quickly heats up to about 500 DEG C to 600 DEG C of temperature.The rate of heat addition range for being heated to annealing temperature can be for 5 DEG C/min extremely
100℃/min.In the case where semi-open-type furnace, heating appropriate can be controlled by conveyor belt speed.Once material reaches
To set temperature, then anneal duration is persistently no more than 720 minutes.
It in certain embodiments, include at least 95% nitrogen and the arbitrary proportion of residue 5% containing nitrogen atmosphere
H2O、NH3And O2。
In step 4, the alumina particles partially sintered is made quickly (> 40 DEG C/min) to be cooled to the specific temperature lower than 50 DEG C.
It is quickly cooled down the undesirable oxidation that can prevent aluminium surface.
In steps of 5, can provide main (being greater than or equal to 70%) is had by what the saturated fatty acid of different proportion was constituted
Machine PCM.PCM fusing point needed for the ratio depends on the actual conditions of TES application.In certain embodiments, PCM includes conventional
Coconut oil.
In step 6, selected PCM can directly penetrate into porous aluminium composite material.It is possible, firstly, to by selected PCM
PCM fusing point 3 is heated to again to 4 times of temperature.Secondly, can by composite porous immersion PCM and cultivate it is 1 hour to 12 small
When a period of time.Alternative infiltration method can be vacuum infiltration, and conditional is to evacuate porous body and seep the PCM of heat
Enter duct.PCM can fill up porous material in a few minutes.In certain embodiments, by by means of 10Pa to 100Pa's
Pressure evacuates duct, to enable the hole of PCM filling aluminum ontology.In other embodiments, made by means of ultrasonic wave
The hole of PCM filling aluminum ontology.
In certain embodiments, composite material can be cut, polished, be laminated and coloured.
The present invention includes but is not limited to following exemplary embodiment.
Embodiment 1. is a kind of to prepare phase-change material-aluminium composite material method, this method comprises:
The aluminum slice for being coated with saturated fat acid composition is provided；
Aluminum slice is put into and is pressed into mold；
The repressed complex of arbitrary shape is provided；
Heat repressed complex；
Keep complex cooling, it is composite porous to obtain；
Phase-change material (PCM) comprising saturated fatty acid is provided；And
PCM provided by making penetrates into composite porous hole.
Embodiment 2. is according to the method for embodiment 1, and wherein the distribution of lengths of aluminum slice is 100nm to 1, and 000,
000nm。
Embodiment 3. according to the method for any one of embodiment 1 to 2, wherein aluminum slice with a thickness of about 80nm extremely
300nm。
Embodiment 4. is according to the method for any one of embodiment 1 to 3, and wherein aluminum slice contains at least 0.3 weight %
And it is less than or equal to the saturated fatty acid of 5 weight %.
Embodiment 5. is according to the method for any one of embodiment 1 to 4, wherein suppressing aluminum slice, to obtain
1,200kg/m3The above 2,200kg/m3Density below.
Embodiment 6. is according to the method for any one of embodiment 1 to 5, wherein utilizing the nitrogen of flowing in heating chamber
Gas heats repressed complex,
That in its middle chamber includes the H of at least 95% nitrogen and remaining 5% arbitrary proportion containing nitrogen atmosphere2O、NH3
And O2。
Embodiment 7. is according to the method for any one of embodiment 1 to 6, wherein making repressed complex to be greater than 40
DEG C/rate of min is cooled to the temperature lower than 50 DEG C.
Embodiment 8. is according to the method for any one of embodiment 1 to 7, wherein by means of the pressure of 10Pa to 100Pa
Hole is evacuated, so that the PCM be made to penetrate into the hole.
Embodiment 9. is according to the method for any one of embodiment 1 to 8, wherein passing through the fusing point that PCM is heated to PCM
3 times to 4 times of temperature, and complex is immersed in PCM 1 hour to 12 hours, to make the hole of PCM infiltration complex.
Embodiment 10. is according to the method for any one of embodiment 1 to 9, and wherein PCM includes at least 70% saturated fat
Fat acid.
A kind of method for preparing the aluminum-base composite body with ceramic substrate of embodiment 11., this method comprises:
The aluminum slice for being partly coated with aliphatic acid composition is provided；
It is put into aluminum slice in a mold and is suppressed；
The prefabricated component of arbitrary shape is provided, which is made of aluminum slice；
Prefabricated component is heated and annealed；And
Keep annealed prefabricated component cooling, to obtain porous aluminium composite material.
Embodiment 12. further comprises according to the method for embodiment 11:
Prefabricated component is heated using the nitrogen of flowing in heating chamber；And
Keep annealed prefabricated component cooling, to obtain that there is the aluminium composite material of aluminium nitride (AlN) matrix.
Embodiment 13. is according to the method for any one of embodiment 11 to 12, and wherein aluminum slice includes following substance:
Cu, Fe, Si, Zn, Ni, Mn, Mg, Ge, Ti, Pb, Zr, V or their carbide, nitride or boride.
Embodiment 14. is according to the method for any one of embodiment 11 to 13, the wherein ratio model of aliphatic acid composition
Enclosing can be 0.3 weight % to 5 weight %.
Embodiment 15. is according to the method for any one of embodiment 11 to 14, wherein to aluminum slice and fatty acid composition
Object is suppressed, to obtain 1,200kg/m3The above 2,200kg/m3Density below.
Embodiment 16. is according to the method for any one of embodiment 11 to 15, wherein prefabricated component is heated in heating furnace,
Temperature range in heating furnace is 500 DEG C to 600 DEG C.
Embodiment 17. further comprises according to the method for any one of embodiment 11 to 16
Hollow ceramic spheres are provided；
Hollow ceramic spheres and aluminum slice are mixed and suppressed；
The prefabricated component of arbitrary shape is provided, which includes aluminum slice and hollow ceramic spheres；And
Keep annealed prefabricated component cooling, it is composite porous to obtain.
Embodiment 18. is according to the method for embodiment 17, and wherein hollow ceramic spheres include Al2O3、SiO2, SiC or it
Combination.
Embodiment 19. is according to the method for any one of embodiment 17 to 18, the wherein diameter ruler of hollow ceramic spheres
Very little range is 50 μm to 1000 μm.
Embodiment 20. further comprises according to the method for any one of embodiment 17 to 19:
Use Mg, Al, ultra-high molecular weight polyethylene, polymethyl methacrylate, epoxy resin or other enhanced polymerizations
Object penetrates into composite porous.
All patents, patent application, provisional application and the publication for being mentioned above or quoting are with them and this specification
The reconcilable degree of clearly teaching be incorporated herein by quoting whole (including all attached drawings and table).
The following are the examples for illustrating to implement method of the invention.These examples are not necessarily to be construed as limiting.Unless otherwise saying
Bright, otherwise all percentage are by weight, and all solvent mixture proportions are by volume.
Embodiment 1
As shown in Fig. 2, the boundary in claimed annealing conditions manufactures one group of sample.The preparation method of embodiment 1
The following steps are included: step 1, provide that average thickness is about 70nm and specific surface area is about 10m2The aluminum slice powder of/g.Al is thin
Piece contains the stearic acid of about 1.5 weight %；Step 2, aluminum slice is stirred, it is then cold under the pressure of about 70MPa to 380MPa
Hydrostatic pressing is prefabricated component, and the porosity of the prefabricated component is 25% to 50%；Step 3, with the rate of 20 DEG C/min by powder
Prefabricated component is heated to 520 DEG C, wherein the nitrogen that purity is 99.95% is used as flowing atmosphere.After reaching annealing temperature, by material
It shelves at an annealing temperature 30 minutes；Step 4, annealed prefabricated component is made to be cooled to about 25 DEG C with the rate of 20 DEG C/min.
According to ISO13314, almost equal to diameter and thickness (cylindrical sample of 9.2mm to 10.0mm) carries out quasi-static
Compression verification.It is surveyed using 810 material testing systems (MTS Systems Corporation, USA) with gravity flow plate
Examination, with~10-3The initial strain rate of 1/s equably loads.It polishes the top surface and bottom surface of each sample, to obtain
The better depth of parallelism.Capacity for energy absorption (J/m3) it can be the work done during compression of per unit volume, and may be calculated compression and answer
Power-strain σ (ε) area under a curve:
Wherein σ (MPa) and ε (cm cm-1) it is respectively compression stress and strain.In this case, strain stress changes
Until collapse or densification levels, wherein ε=e2。
In the case where toughness, until structure breaking, structure breaking the first maximum value in the ε of domain occurs for energy-absorbing
e1Place.
Specific energy absorption capacity and than toughness be per unit weight value, and calculate it is as follows:
U=Ud-1 (2)
Wherein d is the density of composite material.
Fig. 3 a shows the quasistatic compression load-deformation curve of the sample of embodiment 1.Fig. 3 b shows embodiment 1
The ratio toughness of sample and result than absorptive capacity.
Embodiment 2
One group of sample is manufactured in another boundary of claimed annealing conditions.The preparation method of embodiment 2 can be with
Substantially the same manner as Example 1 and only different in step 3, embodiment 2 was using about 580 DEG C of annealing temperature and about 420 minutes
Annealing time.
Fig. 4 a shows the quasistatic compression load-deformation curve of the sample of embodiment 2.Fig. 4 b shows embodiment 2
The ratio toughness of sample and result than absorptive capacity.
Embodiment 3
One group of sample is manufactured in another boundary of claimed annealing conditions.The preparation method of embodiment 3 can be with
It is substantially the same manner as Example 1 and only different in step 3, annealing temperature and about 240min of the embodiment 3 using about 560 DEG C
Annealing time.
Fig. 5 a shows the quasistatic compression load-deformation curve of the sample of embodiment 3.Figure 5b shows that embodiments 3
The ratio toughness of sample and result than absorptive capacity.
Embodiment 4
Embodiment 4 represents the composite material of thermal conductivity minimum but the highest most lightweight of heat storage capacity.The preparation side of embodiment 4
Method provides average thickness and is about 60nm and contains the aluminum slice powder of following impurity: O the following steps are included: step 12(~1.5
Weight %), Pb (< 0.03 weight %).Getter indicates the stearic acid that content is about 1.5 weight %；Step 2, aluminum slice is stirred,
Then cold isostatic compaction is briquetting under the pressure of about 70MPa, and the porosity of the briquetting is about 47%；Step 3, with 40 DEG C/
Repressed powdered sample is heated to 600 DEG C by the rate of min, wherein by the nitrogen of 99.5% purity, the O of 50ppm2With
The H of 50ppm2O is as flowing atmosphere.After reaching annealing temperature, material is shelved in furnace one minute；Step 4, make agglomerated material
About 25 DEG C are quickly cooled to the rate of 40 DEG C/min；Step 5, the non-RBD coconut of the saturated fatty acid containing about 94% is provided
Oil；And step 6, PCM is penetrated into directly in sample by immersion-storage method, it is 1 hour time-consuming.
The porosity of annealed composite material is about 47%.Fig. 8, Fig. 9 show prepared composite material example
Key performance.
Embodiment 5
Embodiment 5 represents the most fine and close composite material that thermal conductivity is maximum but heat storage capacity is minimum.The preparation side of embodiment 5
Method can be substantially the same manner as Example 4, and only different in step 3, and embodiment 5 uses under the pressure of about 310MPa to thin
Piece carries out cold isostatic compaction, to obtain the briquetting that porosity is about 22%.The porosity of annealed composite material is about
22%.
Fig. 8, Fig. 9 show the key performance of prepared composite material example.
Embodiment 6 to 9
Other than border condition, the intermediate result in Fig. 8, Fig. 9 has been characterized other embodiments (embodiment 6 to 9), described
32% other embodiments are different in step 3, and are compressed to the porosity of following rough estimate respectively: 26%,
38%, 42%.The porosity of annealed composite material is respectively about 26%, 32%, 38% and 42%.
Embodiment 10,11
In order to test fire resistance, composite sample is prepared according to embodiment 14 to 20, sample shape is cylinder, thick
Degree and diameter are respectively about 4mm and about 28mm.Two different samples of porosity are put into electric heating batch-type furnace (Nabertherm
N11/H 1280) in, quick (20 DEG C/min) are heated to 1000 DEG C and are kept for 90 minutes.Table 1 shows test condition to Al oxygen
Change the influence of caused geometry variation and mass change.Visual observations do not have material deformation during being shown in fire resisting test
Sign.According to measurement, material volume increase is unobvious, is lower than 3%.
The influence of the variation to the volume of composite material, quality and density is tested in 1. fire resisting of table
In testing, sample (embodiment 10) surface modification form (for example, with reference to Figure 10).However, slight polishing can
Spot is removed from surface.Therefore, the characteristic that the visual appearance of material can keep it bright after being exposed to fire.
It should be understood that the purpose that embodiment as described herein and embodiment are merely to illustrate, and in view of ability
Field technique personnel, which will associate, to be carry out various modifications or changes to it, therefore these modifications or changeses are included in the application's
In spirit and scope and scope of the appended claims.In addition, any invention disclosed herein or its embodiment is any
Element or limitation can be with disclosed herein any and/or every other element or limitation (shapes individually or in any combination
Formula) or its any other is invented or its embodiment is combined, and expected all these combinations are in the scope of the present invention
It is interior, but not limited to this.
Claims (20)
1. a kind of prepare phase-change material-aluminium composite material method, this method comprises:
The aluminum slice for being coated with saturated fat acid composition is provided；
The aluminum slice is put into and is pressed into mold；
The repressed complex of arbitrary shape is provided；
Heat the repressed complex；
Keep the complex cooling, it is composite porous to obtain；
Phase-change material (PCM) comprising saturated fatty acid is provided；And
PCM provided by making penetrates into the composite porous hole.
2. according to the method described in claim 1, wherein the distribution of lengths of the aluminum slice is 100nm to 1,000,000nm.
3. according to the method described in claim 1, wherein the aluminum slice with a thickness of about 80nm to 300nm.
4. according to the method described in claim 1, wherein the aluminum slice contains at least 0.3 weight % and is less than or equal to 5 weights
Measure the saturated fatty acid of %.
5. according to the method described in claim 1, wherein suppressing the aluminum slice, to obtain 1,200kg/m3Above 2,
200kg/m3Density below.
6. according to the method described in claim 1, wherein being heated in heating chamber using the nitrogen of flowing described repressed
Complex, and
Wherein the nitrogen containing atmosphere in the chamber includes the H of at least 95% nitrogen and remaining 5% arbitrary proportion2O、NH3With
O2。
7. according to the method described in claim 1, wherein making the repressed complex cold with the rate greater than 40 DEG C/min
But to the temperature for being lower than 50 DEG C.
8. according to the method described in claim 1, wherein hole is evacuated by means of the pressure of 10Pa to 100Pa, to make described
PCM penetrates into the hole.
9. according to the method described in claim 1, wherein by the way that the PCM to be heated to 3 times to 4 times of the fusing point of the PCM
Temperature, and the complex is immersed to 1 hour to 12 hours in PCM a period of time, so that the PCM be made to penetrate into institute
It states in the hole of complex.
10. according to the method described in claim 1, wherein the PCM includes at least 70% saturated fatty acid.
11. a kind of method for preparing the aluminum-base composite body with ceramic substrate, this method comprises:
The aluminum slice for being partly coated with aliphatic acid composition is provided；
It is put into the aluminum slice in a mold and is suppressed；
The prefabricated component of arbitrary shape is provided, the prefabricated component includes the aluminum slice；
The prefabricated component is heated and annealed；And
Keep the annealed prefabricated component cooling, to obtain porous aluminium composite material.
12. according to the method for claim 11, further comprising:
The prefabricated component is heated using the nitrogen of flowing in heating chamber；And
Keep the annealed prefabricated component cooling, to obtain that there is the aluminium composite material of aluminium nitride (AlN) matrix.
13. according to the method for claim 11, wherein the aluminum slice include following substance: Cu, Fe, Si, Zn, Ni, Mn,
Mg, Ge, Ti, Pb, Zr, V or their carbide, nitride or boride.
14. according to the method for claim 11, wherein the proportional region of aliphatic acid composition is 0.3 weight % to 5 weights
Measure %.
15. according to the method for claim 11, wherein suppressing the aluminum slice and the aliphatic acid composition, with
Obtain 1,200kg/m3The above 2,200kg/m3Density below.
16. according to the method for claim 11, wherein the prefabricated component is heated in heating furnace, wherein in the heating furnace
Temperature range be 500 DEG C to 600 DEG C.
17. according to the method for claim 11, further comprising
Hollow ceramic spheres are provided；
The hollow ceramic spheres and aluminum slice are mixed and suppressed；
The prefabricated component of arbitrary shape is provided, the prefabricated component includes the aluminum slice and hollow ceramic spheres；And
Keep the annealed prefabricated component cooling, it is composite porous to obtain.
18. according to the method for claim 17, wherein the hollow ceramic spheres include Al2O3、SiO2, SiC or they
Combination.
19. according to the method for claim 17, wherein the diameter dimension range of the hollow ceramic spheres be 50 μm extremely
1000μm。
20. according to the method for claim 17, further comprising:
Use Mg, Al, ultra-high molecular weight polyethylene, poly- (methyl methacrylate), epoxy resin or other enhanced polymers
It penetrates into described composite porous.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201662496256P | 2016-10-12 | 2016-10-12 | |
| US62/496,256 | 2016-10-12 | ||
| US201762604304P | 2017-07-03 | 2017-07-03 | |
| US62/604,304 | 2017-07-03 | ||
| PCT/IB2017/001432 WO2018069772A1 (en) | 2016-10-12 | 2017-10-09 | Lightweight and highly tough aluminum composite with ceramic matrix |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109890932A true CN109890932A (en) | 2019-06-14 |
| CN109890932B CN109890932B (en) | 2021-03-26 |
Family
ID=61905248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780063431.4A Active CN109890932B (en) | 2016-10-12 | 2017-10-09 | Lightweight and high toughness aluminum composite with ceramic matrix |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109890932B (en) |
| WO (1) | WO2018069772A1 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1030445A (en) * | 1987-05-13 | 1989-01-18 | 兰克西敦技术公司 | Metal-matrix composite |
| CN101089209A (en) * | 2007-07-12 | 2007-12-19 | 北京科技大学 | Method for preparing high Nb-Ti-Lu porous material |
| CN102181270A (en) * | 2011-04-28 | 2011-09-14 | 华南理工大学 | Composite phase change material for heat dissipation of lithium battery and device |
| CN103361505A (en) * | 2012-12-27 | 2013-10-23 | 华东理工大学 | Preparation method of FeAl-based porous material |
| CN104131194A (en) * | 2014-07-21 | 2014-11-05 | 昆明理工大学 | Preparation method of porous aluminum or aluminum alloy |
| CN106191505A (en) * | 2016-07-08 | 2016-12-07 | 湘潭大学 | A kind of preparation method of new type high temperature antioxidation porous material |
| CN106497519A (en) * | 2016-09-30 | 2017-03-15 | 中国科学院深圳先进技术研究院 | A kind of heat conduction with phase change piece and preparation method, the producing device of Woelm Alumina skeleton |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100056816A1 (en) * | 2006-11-01 | 2010-03-04 | Wallin Sten A | Shaped porous bodies of alpha-alumina and methods for the preparation thereof |
| EP2293872A1 (en) * | 2008-04-30 | 2011-03-16 | Dow Technology Investments LLC | Porous body precursors, shaped porous bodies, processes for making them, and end-use products based upon the same |
| CN103055947B (en) * | 2011-10-21 | 2015-04-15 | 中国石油化工股份有限公司 | Preparation method of alumina support |
| CN103100426B (en) * | 2011-11-09 | 2015-02-18 | 中国石油化工股份有限公司 | Preparation method of alumina carrier |
| CN103787389B (en) * | 2012-11-01 | 2016-06-22 | 中国石油化工股份有限公司 | A kind of production method of alumina support |
| CN104449589B (en) * | 2014-12-03 | 2017-12-08 | 北京科技大学 | A kind of porous base composite phase-change material preparation method for wide temperature range waste heat recovery |
-
2017
- 2017-10-09 WO PCT/IB2017/001432 patent/WO2018069772A1/en active Application Filing
- 2017-10-09 CN CN201780063431.4A patent/CN109890932B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1030445A (en) * | 1987-05-13 | 1989-01-18 | 兰克西敦技术公司 | Metal-matrix composite |
| CN101089209A (en) * | 2007-07-12 | 2007-12-19 | 北京科技大学 | Method for preparing high Nb-Ti-Lu porous material |
| CN102181270A (en) * | 2011-04-28 | 2011-09-14 | 华南理工大学 | Composite phase change material for heat dissipation of lithium battery and device |
| CN103361505A (en) * | 2012-12-27 | 2013-10-23 | 华东理工大学 | Preparation method of FeAl-based porous material |
| CN104131194A (en) * | 2014-07-21 | 2014-11-05 | 昆明理工大学 | Preparation method of porous aluminum or aluminum alloy |
| CN106191505A (en) * | 2016-07-08 | 2016-12-07 | 湘潭大学 | A kind of preparation method of new type high temperature antioxidation porous material |
| CN106497519A (en) * | 2016-09-30 | 2017-03-15 | 中国科学院深圳先进技术研究院 | A kind of heat conduction with phase change piece and preparation method, the producing device of Woelm Alumina skeleton |
Non-Patent Citations (3)
| Title |
|---|
| JINGHUA JIANG, YINGYING ZHU, ET. AL.: "Preparation and performances of bulk porous Al foams impregnated with phase-change-materials for thermal storage", 《PROGRESS IN NATURAL SCIENCE: MATERIALS INTERNATIONAL》 * |
| KRZYSZTOF KARCZEWSKI *, WOJCIECH JERZY STĘPNIOWSKI, ET. AL.: "Fabrication of Fe-Al Intermetallic Foams via Organic Compounds Assisted Sintering", 《MATERIALS》 * |
| 杜景红，曹建春编著: "《无机非金属材料学》", 31 August 2016, 冶金工业出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109890932B (en) | 2021-03-26 |
| WO2018069772A1 (en) | 2018-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11969797B2 (en) | Syntactic metal matrix materials and methods | |
| Nishimura et al. | Reactive sintering of Ni3Al under compression | |
| JP2022517021A (en) | Method of preparing metal material or metal composite material | |
| Konopka et al. | Fabrication of Al2O3–Al composites by infiltration method and their characteristic | |
| CN105624451B (en) | A kind of high-strength and high ductility closed-cell aluminum foam and preparation method thereof | |
| Luo et al. | Recent advances in the design and fabrication of strong and ductile (tensile) titanium metal matrix composites | |
| Rabiei et al. | Processing and characterization of a new composite metal foam | |
| US5269830A (en) | Process for synthesizing compounds from elemental powders and product | |
| KR100638479B1 (en) | Fabrication method of bulk amorphous alloy and bulk amorphous composite by spark plasma sintering | |
| Amosov et al. | Producing TiC-Al cermet by combustion synthesis of TiC porous skeleton with spontaneous infiltration by aluminum melt | |
| CN109890932A (en) | The aluminium composite material with ceramic substrate of lightweight and high tenacity | |
| Ujah et al. | Investigating the nanomechanical and thermal characteristics of Ti20-Al20-V20-Fe20-Ni20 HEA developed via SPS for high energy applications | |
| JP2004346368A (en) | Method for manufacturing composite material, and composite material | |
| Hsu et al. | Fabrication of 17‐4PH Stainless Steel Foam by a Pressureless Powder Space Holder Technique | |
| CN105648247B (en) | A kind of titanium alloy particle reinforced aluminum matrix composites and preparation method thereof | |
| EP0830329A1 (en) | Method for manufacturing a composite material | |
| Haught et al. | Mullite whisker felt and its application in composites | |
| JP6942434B2 (en) | Manufacturing method of high-density iron-based sintered material | |
| KR102444652B1 (en) | high volume reinforced aluminum composite and method of manufacturing the same | |
| Shinoda et al. | Development of creep-resistant tungsten carbide copper cemented carbide | |
| Mamedov | Properties of highly-dense iron‐base powder metallurgy materials pressed without zinc stearate | |
| Smorygo et al. | Ti6Al4V foams prepared by PM/space-holder method: effect of sintering temperature on mechanical properties | |
| JP4758246B2 (en) | Functional composite material having ceramic-enclosed metal with closed cell structure and method for producing the same | |
| Zhang et al. | Investigation into manufacturing Fe–Cu–C alloy parts through indirect selective laser sintering | |
| Pan et al. | Enhancement of energy absorption in Mg–3Al–1Zn foam with 316L hollow spheres |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |