CN103038006B - For the method manufacturing aluminium alloy moulded products - Google Patents
For the method manufacturing aluminium alloy moulded products Download PDFInfo
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- CN103038006B CN103038006B CN201180025680.7A CN201180025680A CN103038006B CN 103038006 B CN103038006 B CN 103038006B CN 201180025680 A CN201180025680 A CN 201180025680A CN 103038006 B CN103038006 B CN 103038006B
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- binding agent
- method described
- thermal debinding
- metal
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- 238000000034 method Methods 0.000 title claims abstract description 56
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 238000005238 degreasing Methods 0.000 claims abstract description 25
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 18
- 239000000956 alloy Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000001746 injection moulding Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000002347 injection Methods 0.000 claims abstract description 9
- 239000007924 injection Substances 0.000 claims abstract description 9
- 239000000428 dust Substances 0.000 claims abstract description 5
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 3
- 238000005245 sintering Methods 0.000 claims description 32
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 229920006324 polyoxymethylene Polymers 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 230000018199 S phase Effects 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 230000008602 contraction Effects 0.000 description 10
- 230000004580 weight loss Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004435 Oxo alcohol Substances 0.000 description 6
- 238000007046 ethoxylation reaction Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 210000002615 epidermis Anatomy 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002913 oxalic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000634 wood's metal Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
The present invention relates to by the metal injection molded method for manufacturing moulded products based on aluminium alloy, described method comprise the steps: a) by by metal dust and/or one or more metal alloy powders forms, the metal that is contained in expected alloy mixes with binding agent and prepares raw material；B) green compact are manufactured by raw material described in injection moulding；C) at least in part described binding agent is removed from described green compact by catalysis degreasing and/or solvent degreasing and/or thermal debinding and manufacture brown body；D) sinter to the brown body of small part defat and obtain expected moulded products；It is characterized in that, described binding agent is completely removed by step c), after carrying out one or more aforementioned defatting step, wherein optionally carry out thermal debinding to remove described (residual) binding agent, described thermal debinding is carried out in the oxygen atmosphere comprising at least 0.5 volume %, sinters thereafter the brown body of thus obtained complete defat (de-binding agent).
Description
Metal injection molded technology is the most flourishing, and becomes for manufacturing the small-sized of complexity
A kind of mature technology of parts, produces the global annual turnover of about 1,000,000,000 Euros.It is applied to plastic injection
The forming technique of molding and the combination of the various materials used in powder technology are for many materials
Open interesting new markets.
This manufacture method includes following processing step substantially.First, injectable particle form is manufactured
Raw material, it is made up of metal dust and plastic component, and it is intimately mixed that plastic component comprises at least two
Polymers compositions.Then, by plastic-injection moulding machine, this raw material molding is obtained moulded products.
These so-called " green compact (green body) " generally comprise the plastic binder of about 40 volume %, its
The most so-called defat (debinding) (or " de-binding agent ") step is removed by major part.Gluing of residual
Knot agent component the most so-called " skeleton (backbone) " keeps and guarantees the residual strength of goods after defat.De-
Fat can the most such as be passed through heat, use solvent, be realized by catalysis etc., selected method
The plastic binder used in granule should be adapted to carefully.After degreasing, to described goods i.e. institute
" brown body (the brown body) " of meaning is sintered, in its first step, and " skeleton " of residual
Binding agent is generally by adding heat extraction, and the most described goods are formed close to closely knit through oversintering and contraction
Metal assembly.This technology the most both can be applicable to high-alloy steel, low-alloy steel, noble metal, hard
Matter metal, and can be applicable to again pottery.
Despite the presence of relating to the patent of this technology, but for the metal powder injection molding of aluminum
The most not yet being successfully established, this is the sintering mechanism due to actually aluminium alloy and above-mentioned material
Those sintering mechanisms are entirely different.It is in the unreducible oxide on aluminium powder surface for sintering
Speech constitutes significantly obstruction.For this reason, disclosed publication only describes oxygen-free atmosphere.
The concrete difficult problem being associated with above-mentioned aluminum processing is the relatively low fusing point of aluminum
(660 DEG C), when being added to the alloying element of such as stannum, its fusing point reduces further.This causes moulding
The difficult problem that the defat of property component must complete in very low temperatures, and make the suitable process time
Window is generally for too short for ensureing the completely removing of plastic component.Without completely removing plasticity
Component, then can occur the reaction of less desirable organic residue component and metal component, and interference is sintered by this
Technique, thus reduce by the engineering properties of product obtained by the method.
Liu et al. describes a kind of method in Powder Metallurgy 51,78-83 (2008), wherein
Adding the stannum as alloying metal and MAG block, magnesium is as " sacrificial metal ", i.e. as oxygen and moisture
Trapping agent.
Contrary with this background technology, it is an object of the invention to develop a kind of metal injection molding technology,
It has the aluminum moulded products of good mechanical properties in simple and reproducible mode for manufacturing.
Summary of the invention
The present inventor has realized this purpose, and it is by providing one for being made by metal injection molded
The method making moulded products based on aluminium alloy, described method comprises the steps:
A) by by metal dust and/or one or more metal alloy powders forms, be contained in institute's phase
Treat that the metal in alloy mixes with binding agent and prepares raw material；
B) green compact are manufactured by raw material described in injection moulding；
C) catalysis degreasing and/or solvent degreasing and/or thermal debinding are passed through at least in part by described binding agent
Remove from described green compact and manufacture brown body；
D) sinter to the brown body of small part defat and obtain expected moulded products；
The method is characterized in that, in step c), described binding agent is completely removed, wherein optionally exist
Thermal debinding is carried out to remove (residual) binding agent, institute after having carried out one or more aforementioned defatting step
State thermal debinding to carry out in the atmosphere comprising at least 0.5 volume % oxygen, sinter thereafter thus obtained complete
The brown body of full defat (de-binding agent).
The method can obtain highly purified aluminium alloy moulded products, and its reason is due in step c)
Middle binding agent is completely removed, without there is the reaction do not expected of alloy properties metal and plastic material.
Even if at relatively low temperature, realizing owing to there is oxygen in atmosphere completely removing binding agent.
Contrary with existing teaching, need to definitely prevent oxygen from existing according to existing teaching, and the inventor have discovered that
A small amount of oxygen of at least 0.5 volume % will not dramatically increase the oxidation of aluminum, and contribute to quickly and
Defat completely.Composition according to mixture of powders and temperature conditions, be suitable for use with such as at 20-100 body
Oxygen content between long-pending %, it means that it is even possible that use pure O2Gas.
Aluminium alloy contains one or more other metals being not subject to any specific restrictions in addition to aluminum.
Alloy collocation component (alloy partner) is preferably selected from magnesium, copper, silicon and manganese, and particularly preferably contains
The ratio of 0.5-25 weight %, with obtain having the moulded products of expectation character.According to the present invention, no
Need the metal of such as bismuth, stannum, lead, indium or zinc, or the alloy of such as Woods metal, above-mentioned metal
Or alloy has significantly lower fusing point, and can be used as in some cases reducing when fusing starts
The sintering aid of temperature, but the most still can add as alloy collocation component, with
Sintered body to respective alloy.It is particularly advantageous to use the alloy form of other metal and aluminum, i.e. makees
For so-called master alloy powder.
According to the present invention it is preferred to use known at a lower temperature with regard to removable binding agent, the most excellent
Select binding agent based on polyacetals, such as polyformaldehyde (POM), its e.g. by BASF at EP
413,231, WO94/25205, especially at EP 446, disclosed in 708, and can be with trade markIt is commercially available.For described binding agent, wish that there is higher polyacetals ratio,
Preferably by 50-95%, the polyacetals of even more preferably 80-90% is constituted, with at low temperatures and at oxygen
Can quickly and completely remove in the presence of gas.Or, it is possible to use binding agent body based on wax and polymer
System, wax is removed by aforesaid solvent degreasing as main component, i.e. exists at oxygen according to the present invention
Under carry out removing before thermal debinding.
Defat in the method step c) of the present invention may be included in the single thermal debinding step in the presence of oxygen
Suddenly, wherein binding agent is completely removed.It is alternatively possible to carry out one or more aforementioned defatting step
To remove major part binding agent, then carry out the thermal debinding step of the present invention to remove in the presence of oxygen
The binding agent of residual.Aforesaid defatting step can also is that the thermal debinding under the absence or presence of oxygen
Step.This means to be also possible to carry out using different degreasing process parameters, such as in different temperatures
Lower or in different atmosphere, such as, with or without oxygen or have air or pure oxygen
Multi-step thermal debinding process is carried out under Deng.
In a preferred embodiment of the invention, in step c), it is used for removing residual in the presence of oxygen
Catalysis degreasing and/or solvent degreasing is carried out before staying the thermal debinding of binding agent.Walk in these aforesaid defats
In Zhou, the major part of binding agent removes from compositions, thus only has " skeleton " component still
Need to be removed by thermal debinding subsequently.
Preferably carry out in the presence of at least one acid in nitric acid, oxalic acid, formic acid and acetic acid
Catalysis degreasing, because these acid accelerate completely removing of preferred polyacetals binding agent by acidolysis, and
It is not result in that do not expect with alloy compositions side reaction.In the case of solvent degreasing, pass through use-case
As the suitable solvent of acetone, normal heptane, water etc. or the extraction of mixed solvent remove the main of binding agent
Part.According to the present invention, particularly preferably use the catalysis degreasing using the oxalic acid through distillation.
As it has been described above, for removing the thermal debinding process of remaining binder relatively low in step c)
At a temperature of carry out, to avoid oxidation reaction, the aluminum especially avoiding being contained in mixture of powders
Oxidation reaction.The most relatively low temperature refers to the temperature of substantially less than aluminum fusing point, preferably shorter than
The temperature of 500 DEG C, the more preferably temperature between 100 DEG C-420 DEG C.Particularly preferably for optimizing phase
Answering mixture of powders and design temperature distribution (profile), it provides less than 5K/min, the most not
The rate of heat addition more than 1-2K/min.By this way, treat that this mixture of defat is by gentle and equal
Even heating.
The sintering step d) of the inventive method concrete is not limited by any, except must be the most complete
Remove outside binding agent.But it is preferred for being sintered step when forming liquid phase, below will further
Describe in detail.
The known technology of aluminium alloy moulded products is manufactured based on following by powder metallurgy compressing and forming process
Theory hypothesis: the surface of the alumina particles that aluminium oxide in substrate covers is caused mechanicalness to damage by compression method,
Described infringement can produce metallurgical reaction.But, by the brown body of (completely) defat that injection moulding obtains
Be actually the packed bed of metal dust, the oxide epidermis of metal not by any mechanical load, from
And do not affected by this known mechanism.This means between powder particle, there is no direct metal--Au
Belong to contact.But, by properly selecting sintering condition, the inventive method is successfully achieved required
Contraction, wherein the compacting of this sintered body becomes obvious, thus is successfully obtained and is compacted to maximum
The profiled part of possible degree.
Therefore, according to the present invention, following embodiment is preferred, wherein in step d), in shape
The brown body of complete defat is sintered when becoming liquid phase.It is not intended to be bound by any theory, the present inventor
Believe partly in intermediate state, but main in stable state, i.e. it is in thermal dynamic equilibrium with solid Al phase
The liquid phase of state is by micro-crack, micropore or similar " the opening in the oxide epidermis of metal powder granulates
Hole " and pass through the subepidermal creep of oxide, needed for being formed between metal in mixture of powders
Contact, thus promote to form the most closely knit sintered body from the brown body of complete defat.Particularly preferably exist
In step d), between corresponding aluminium alloy solidus temperature and liquidus temperature at a temperature of be sintered,
Therefore the time point of each in sintering process, by selecting proper temperature to be distributed, controlled alloyage
A part for metal is in a liquid state, and this can be effectively prevented and lose dimensional stability.
In the single step of the inventive method, the composition of corresponding atmosphere is the most specifically restricted, removes
Outside oxygen is existed for the thermal debinding in step c)；Those skilled in the art can select for often
Individual step is most suitable for the atmosphere of corresponding mixture of powders, it is possible to select vacuum.But, sintering step d)
Preferably in atmosphere that be extremely dried, containing nitrogen, i.e. in pure nitrogen gas, (" divide at normal pressure or decompression
Pressure sintering ") under carry out, or preferably having less than the nitrogen of dew point and the pure inert gas (helium of-40 DEG C
Gas, argon) gaseous mixture in carry out, this is because the existence of nitrogen can remarkably promote powder particle and product
The moistening of raw metal bath.
Can optionally carry out suitably other process after described sintering step, process by this other, will
Finished product profiled part is maintained under expected shape.For example, it is possible to the known high temperature insostatic pressing (HIP) (HIP) of application
Technique and reach the final densities needed for profiled part.In the process, still suffer from after a sintering step
Residual Pore sealed under the influence of the external gas pressure and high temperature.
Accompanying drawing explanation
Fig. 1 is the green compact (top) and the photo of sintered body (lower section) obtained from embodiment 9；
Fig. 2 is the green compact (left side) and the photo of sintered body (right side) obtained from embodiment 10.
The present invention is carried out the most detailed by the specific illustrative embodiment below with reference to indefiniteness
Thin description.
Embodiment
By all raw materials of preparing in following example at 190 DEG C, in the laboratory mixed connection machine of heating
Homogenize.Use the inventive method as described below, according to ISO 2740, by injection moulding from these
Raw material forms the bar for tension test or hollow cylinder respectively.Use hydraulic injection molding machine
(Battenfeld HM 600/130) and PIM equipment are used for manufacturing green compact.
In the first step, first raw material is filled with in the hopper of injection (mo(u)lding) machine.For manufacturing green compact
Injection molding technique comprise the following steps: use the internal hot injection machine barrel with rotary screw,
Make pretreatment adds pan feeding plasticizing, and according to default parameter (such as include rotating speed, the volume that feeds intake,
Back pressure etc.) carry out estimate (predose).Then the amount of estimate is injected in the equipment of fully tempering.
Depend on raw material and the binding agent wherein used, the plasticization temperature in injection cylinder 120 DEG C-
Between 220 DEG C, and in tempering equipment, temperature is between 25 DEG C-140 DEG C.Through the sufficiently long cooling cycle
Afterwards, open injection forming equipment, and green compact are unloaded from described equipment with operating apparatus and takes out.
Embodiment 1-extension test bar: solvent degreasing/thermal debinding
By the metal powder mixture that is available commercially (from Ecka's
) and by wax/heat
Moulding material constitute solvent bonding agent be thoroughly mixed and obtain raw material, described metal powder mixture by aluminum,
The magnesium composition of the silicon of 14 weight %, the copper of 2.5 weight % and 0.6% weight.
*Being available commercially of the magnesium of aluminum, the silicon of 14 weight %, the copper of 2.5 weight % and 0.6 weight %
Metal powder mixture (from Ecka).
The defat of extension test bar and sintering
In the baking oven of 60 liters, at 45 DEG C, by using the solvent extraction of acetone, first by this raw material
Defat 12 hours.
Thus obtained brown body contains the remaining binder of about 14.5 weight %, subsequently containing pure oxygen
In the atmosphere of gas, by the thermal debinding according to the present invention, use 1 hour from 150 DEG C-320 DEG C, so
The Temperature Distribution of 1.5 hours of rear employing 320 DEG C-420 DEG C removes remaining binder.Then will thus obtain
The brown body of the complete defat arrived under 560 ° of C in the pure nitrogen gas (dew point :-50 ° of C) sintering 1 hour with
In.
Result
Length Contraction rate: 11.6%
Bar diameter shrinkage factor: 12.25%
Sintered density: 2.36g/cm3
Embodiment 2-extension test bar: thermal debinding in a single step
*Foundry alloy is made up of aluminum and the magnesium of 50/50
**Poly-(the methyl methacrylate) (PMMA being available commercially；From BASF)
The defat of extension test bar and sintering
According to following degreasing process, in the presence of 200 ls/h of pure oxygens, enter in 40 liters of baking ovens
Row thermal debinding thoroughly:
-with the heating rate to 130 DEG C of 2K/min；
-temperature is maintained at 130 DEG C 4 hours；
-with the heating rate to 200 DEG C of 2K/min；
-temperature is maintained at 200 DEG C 5 hours；
-with the heating rate to 420 DEG C of 2K/min；
-temperature is maintained at 420 DEG C 4 hours；
Weight loss total 24.2% during thermal debinding.
Then sintering described test strip in pure nitrogen gas 1 hour, oven temperature is set as 665 DEG C, and
630 DEG C are corresponded approximately in oven interior.
Result
Length Contraction rate: 12.27%
Bar diameter shrinkage factor: 14.52%
Sintered density: 2.46g/cm3
Embodiment 3-extension test bar: twice thermal debinding
*There is the C of the ethoxylation of 7 EO-unit13-C15-oxo alcohol.
The defat of extension test bar and sintering
First, in 50 liters of baking ovens, with the air of 500 ls/h, carry out at 180 DEG C for the first time
Thermal debinding 14 hours.Weight loss is 27.0%.
Hereafter, in pure nitrogen gas, at a temperature of at most 420 DEG C, in 1 hour, carry out second time heat
Defat, is being set as in the baking oven at a temperature of 665 DEG C carrying out 1 hour sintering the most again.
Result
Length Contraction rate: 9.5%
The shrinkage factor of bar diameter: 11.4%
Sintered density: 2.13g/cm3
Embodiment 4-extension test bar: catalysis/thermal debinding
*There is the C of the ethoxylation of 7 EO-unit13-C15-oxo alcohol.
The defat of extension test bar and sintering
First, in 50 liters of baking ovens, use the HNO of 2 volume %3, in the nitrogen (industry of 500l/h
Level) in, at 140 DEG C, carry out catalysis degreasing 10 hours.Weight loss is 22.1%.Hereafter, at table
The derivatives (outgrowth) of pearl is observed, it is assumed that it is formed with nitric acid reaction by Mg on face.
Hereafter, as described in embodiment 3, at a temperature of at most 420 DEG C in pure nitrogen gas
Carry out 1 hour interior thermal debinding, the most again carry out 1 being set as in the baking oven at a temperature of 665 DEG C
Hour sintering.
Result
Length Contraction rate: 10.7%
The shrinkage factor of bar diameter: 14.65%
Sintered density: 2.36g/cm3
Catalysis/the thermal debinding of embodiment 5-extension test bar
*There is the C of the ethoxylation of 7 EO-unit13-C15-oxo alcohol.
The defat of tensile bar and sintering
First, at 140 DEG C, carry out catalysis degreasing 24 hours according to embodiment 4, use at distillation dish
On 80 grams of anhydrous oxalic acids replace nitric acid.Weight loss is 23.0%.When using oxalic acid, at table
Derivatives does not occur on face.Hereafter, thermal debinding and sintering are carried out still according to embodiment 4.
Result
Length Contraction rate: 14.28%
Bar diameter shrinkage factor: 15.68%
Sintered density: 2.42g/cm3
Embodiment 6-extension test bar: catalysis/thermal debinding
*The magnesium of aluminum, the silicon of 14 weight %, the copper of 2.5 weight % and 0.6 weight % commercially available
The metal powder mixture (from Ecka) arrived.
*There is the C of the ethoxylation of 7 EO-unit13-C15-oxo alcohol.
The defat of extension test bar and sintering
First, catalysis degreasing is carried out according to embodiment 5.Weight loss is 25.2%.Hereafter, use
It is set as the oven temperature of 560 DEG C, carries out thermal debinding and sintering according to embodiment 4.
Result
Length Contraction rate: 11.2%
The shrinkage factor of bar diameter: 13.2%
Sintered density: 2.45g/cm3
Embodiment 7-extension test bar: catalysis/thermal debinding
*Foundry alloy is made up of aluminum and the magnesium of 50/50；
*There is the C of the ethoxylation of 7 EO-unit13-C15-oxo alcohol.
The defat of extension test bar and sintering
First, catalysis degreasing is carried out according to embodiment 5.Weight loss is 23.2%.Hereafter, according to
Embodiment 4 carries out thermal debinding and sintering.
Result
Length Contraction rate: 12.6%
The shrinkage factor of bar diameter: 13.25%
Sintered density: 2.56g/cm3
Embodiment 8-hollow cylinder: catalysis/thermal debinding
*Foundry alloy is made up of aluminum and the magnesium of 50/50；
*There is the C of the ethoxylation of 7 EO-unit13-C15-oxo alcohol.
The defat of hollow cylinder and sintering
First, thermal debinding is carried out according to embodiment 5.Weight loss is 23.7%.Hereafter, according to reality
Execute example 4 and carry out thermal debinding and sintering.
Result
High shrinkage rate: 17.24%
Diameter shrinkage factor: 14.48%
Sintered density: 2.59g/cm3
Embodiment 9-extension test bar: catalysis/thermal debinding
*Foundry alloy is made up of aluminum and the magnesium of 50/50；
**Poly-(the methyl methacrylate) (PMMA being available commercially；From BASF).
The defat of extension test bar and sintering
First, catalysis degreasing is carried out according to embodiment 5.Weight loss is 25.7%.Hereafter, according to
Embodiment 4 carries out thermal debinding and sintering.
Result
Length Contraction rate: 13.57%
The shrinkage factor of bar diameter: 19.55%
Sintered density: 2.59g/cm3
Embodiment 10-hollow cylinder: catalysis/thermal debinding
*Foundry alloy is made up of aluminum and the magnesium of 50/50；
**Poly-(the methyl methacrylate) (PMMA being available commercially；From BASF).
The defat of hollow cylinder and sintering
First, catalysis degreasing is carried out according to embodiment 5.Weight loss is 25.6%.Hereafter, according to
Embodiment 4 carries out thermal debinding and sintering.
Result
High shrinkage rate: 16.52%
Diameter shrinkage factor: 14.48%
Sintered density: 2.56g/cm3
Therefore, the method for the present invention can provide aluminium alloy sinters body by injection moulding, and it is applicable to
The actual application of different field, including transport, building, mechanical engineering, packaging industry, steel industry,
The field such as electronic engineering, household electrical appliance, such as be used for dispelling the heat as the radiating piece in electronic equipment or
Assembly as air conditioning system.
Claims (21)
1. for by the metal injection molded method manufacturing moulded products based on aluminium alloy, described
Method comprises the steps:
A) by by metal dust and/or one or more metal alloy powders forms, be contained in institute's phase
Treat that the metal in alloy mixes with binding agent and prepares raw material；
B) green compact are manufactured by raw material described in injection moulding；
C) by catalysis degreasing and/or solvent degreasing and/or thermal debinding, by described binding agent from described green compact
Middle removing, to manufacture brown body；
D) sinter to the brown body of small part defat and obtain expected moulded products；
It is characterized in that being completely removed by described binding agent in step c), wherein optionally carrying out one or many
Carrying out thermal debinding after individual aforementioned defatting step to remove any binding agent, described thermal debinding is comprising
The atmosphere of at least 0.5 volume % oxygen is carried out, sinters thereafter the brown of thus obtained complete defat
Body.
2. the method described in claim 1, it is characterised in that described aluminium alloy contains in addition to aluminum
One or more are selected from magnesium, copper, silicon and the metal of manganese.
3. the method described in claim 1 or 2, it is characterised in that described aluminium alloy contain except aluminum it
Outer percentage ratio is respectively one or more metals of 0.5-25 weight %.
4. the method described in claim 1 or 2, it is characterised in that one or more metals described are used
Make one or more master alloy powders.
5. the method described in claim 1 or 2, it is characterised in that by binding agent based on polyacetals,
As described binding agent.
6. the method described in claim 5, it is characterised in that described binding agent based on polyacetals is poly-
Formaldehyde binders.
7. the method described in claim 5, it is characterised in that described binding agent is by the bunching of 50-95%
Aldehyde is constituted.
8. the method described in claim 5, it is characterised in that described binding agent is by the bunching of 80-90%
Aldehyde is constituted.
9. the method described in claim 1 or 2, it is characterised in that step c) only is included in oxygen and exists
Under thermal debinding, this thermal debinding is carried out in one or more steps, and removes whole binding agent.
10. the method described in claim 1 or 2, it is characterised in that step c) includes solvent degreasing,
To remove the described binding agent of major part, the most described thermal debinding is to remove the binding agent of residual.
Method described in 11. claim 1 or 2, it is characterised in that step c) includes catalysis degreasing,
To remove binding agent described in major part, the most described thermal debinding is to remove the binding agent of residual.
Method described in 12. claim 11, it is characterised in that depositing selected from least one following acid
Carry out catalysis degreasing in case: nitric acid, oxalic acid, formic acid and acetic acid.
Method described in 13. claim 12, it is characterised in that the oxalic acid of distillation is used as described acid.
Method described in 14. claim 1, it is characterised in that carry out institute at a temperature of less than 500 DEG C
State thermal debinding, to remove the binding agent of any residual.
Method described in 15. claim 14, it is characterised in that use between 100 DEG C-420 DEG C
Specified temp distribution carries out described thermal debinding, to remove the binding agent of any residual.
Method described in 16. claims 14 or 15, it is characterised in that for removing the viscous of residual
In the described thermal debinding processing procedure of knot agent, the rate of heat addition is less than 5K/min.
Method described in 17. claim 16, it is characterised in that the described rate of heat addition is less than 2K/min.
Method described in 18. claim 17, it is characterised in that the described rate of heat addition is less than 1
K/min。
Method described in 19. claim 1 or 2, it is characterised in that in step d), is forming liquid
The brown body of complete defat is sintered by phase time.
Method described in 20. claim 19, it is characterised in that in the solidus temperature of corresponding aluminium alloy
And at a temperature of between liquidus temperature, carry out described sintering.
Method described in 21. claim 1 or 2, it is characterised in that reach after described thermal debinding step
The rate of heat addition to the temperature being sintered is 4-20K/min.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ATA534/2010 | 2010-04-01 | ||
| ATA534/2010A AT509613B1 (en) | 2010-04-01 | 2010-04-01 | METHOD FOR PRODUCING MOLDINGS FROM ALUMINUM ALLOYS |
| PCT/AT2011/000157 WO2011120066A1 (en) | 2010-04-01 | 2011-03-31 | Method for producing shaped bodies from aluminium alloys |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103038006A CN103038006A (en) | 2013-04-10 |
| CN103038006B true CN103038006B (en) | 2016-12-14 |
Family
ID=
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0329475A2 (en) * | 1988-02-18 | 1989-08-23 | Sanyo Chemical Industries Ltd. | Mouldable composition |
| EP0413231B1 (en) * | 1989-08-16 | 1993-06-09 | BASF Aktiengesellschaft | Process for the production of an inorganic sintered body |
| EP0446708B1 (en) * | 1990-03-08 | 1995-01-04 | BASF Aktiengesellschaft | Thermoplastic materials for manufacturing metallic articles |
| CN101147972A (en) * | 2006-09-22 | 2008-03-26 | 精工爱普生株式会社 | Method for producing sintered body and sintered body |
| CN101279367A (en) * | 2008-05-28 | 2008-10-08 | 北京科技大学 | Injection forming method for preparing high Niobium containing Ti-Al alloy components |
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0329475A2 (en) * | 1988-02-18 | 1989-08-23 | Sanyo Chemical Industries Ltd. | Mouldable composition |
| EP0413231B1 (en) * | 1989-08-16 | 1993-06-09 | BASF Aktiengesellschaft | Process for the production of an inorganic sintered body |
| EP0446708B1 (en) * | 1990-03-08 | 1995-01-04 | BASF Aktiengesellschaft | Thermoplastic materials for manufacturing metallic articles |
| CN101147972A (en) * | 2006-09-22 | 2008-03-26 | 精工爱普生株式会社 | Method for producing sintered body and sintered body |
| CN101279367A (en) * | 2008-05-28 | 2008-10-08 | 北京科技大学 | Injection forming method for preparing high Niobium containing Ti-Al alloy components |
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