CN100569972C - The preparation method of a kind of porous magnesium-expansion perlite or porous AZ91 magnesium alloy-expansion perlite composition material - Google Patents

The preparation method of a kind of porous magnesium-expansion perlite or porous AZ91 magnesium alloy-expansion perlite composition material Download PDF

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CN100569972C
CN100569972C CNB2007100561754A CN200710056175A CN100569972C CN 100569972 C CN100569972 C CN 100569972C CN B2007100561754 A CNB2007100561754 A CN B2007100561754A CN 200710056175 A CN200710056175 A CN 200710056175A CN 100569972 C CN100569972 C CN 100569972C
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magnesium
porous
perlite
magnesium alloy
pearlstone
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CN101240383A (en
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吴耀明
王立民
董龙祥
廖文娟
杨洁
王立东
张洪杰
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The present invention relates to the preparation method of a kind of porous magnesium-expansion perlite or porous AZ91 magnesium alloy-expansion perlite composition material, particularly relate to a kind of be the isolated vias agent with paraffin, be supporter, use the vacuum seepage means to make MAGNESIUM METAL or magnesium alloy seepage flow prepare the method for metal-inorganic non-metallic matrix material in the supporter gap with the perforate perlite.With solid paraffin, whiteruss and sherwood oil be raw material to the perlite surface treatment, the reducing atmosphere that utilizes cracking, charing to produce has been isolated the perlite and Mg generation Mg of the title that natural foam glass is arranged 2The reaction of Si.This organism has solved in compound preparation porous magnesium of metal M g or AZ91 magnesium alloy and natural sintered glass or the foam magnesium base composite material process, has used inorganic separant to bury problems such as corrosion hidden danger as separant.The matrix material absolute density scope that is obtained is 0.79g/cm 3~1.01g/cm 3, the relative density scope is 0.45~0.56.

Description

The preparation method of a kind of porous magnesium-expansion perlite or porous AZ91 magnesium alloy-expansion perlite composition material
Technical field:
The present invention relates to the preparation method of a kind of porous magnesium-expansion perlite or porous AZ91 magnesium alloy-expansion perlite composition material, particularly relating to a kind of is the isolated vias agent with paraffin, with the perforate perlite is supporter, uses the vacuum seepage means to make MAGNESIUM METAL or its alloy seepage flow in the supporter gap and prepare the method for metal-inorganic non-metallic matrix material.
Background technology:
Porous metal and sintered glass have the complementary advantage.Sintered glass, such as multicellular glass, at high salt fog ocean environment and high humidity underground environment, excellent anti corrodibility, stability and long life are arranged, but shortcoming is still to have the fragility of glass.Porous metal such as foamed aluminium, have the ductility of metal, certain intensity and lightweight characteristics, far can not compare with multicellular glass but shortcoming is erosion resistance, stability etc.Porous metal and sintered glass have all been used the long duration, and
Figure C20071005617500031
In long duration, how multicellular glass and foamed metal can be combined with each other,, not be studied the person always and pay close attention to be applied in required occasion.But so far, compound between multicellular glass and the foamed metal also is in the primary research stage, has more technology barriers not obtain breaking through.
Chinese patent CN200510119107.9 number the patent that is entitled as " preparation method of composite material of high magnesium aluminium alloy-expanding ore " is disclosed.The advantage of this patent is to realize compound between porous metal aluminium alloy and the multicellular glass, this multicellular glass is expanded vermiculite or the fine perlite that is referred to as " natural sintered glass ", this matrix material has great permissible stress index, is beneficial to be applied in fixed motorway and to wake up and to show that isolated body, vertiplane rise and fall on energy-absorbing, damping means or other structure-function integration materials such as support, portable liquid-fueled missile transport trolley.But relatively shortcoming is: this compound compound between porous metal magnesium and the multicellular glass of can't expanding to, because be difficult to solve two kinds of chemical reactions between the matrix material.The mentality of designing of similar this patent also has similar announcement No. 03100180.7, No. 03200299.8, No. 200320115557.7 and No. 03100180.7 at the other Chinese patent as Chinese patent.
Chinese patent discloses the patent that is entitled as " inorganic phase magnesium-base porous compound material and preparation method " for No. 200410012166.1.The advantage of this invention is: excel at leveraging natural mineral matter for human used, though can not prevent (Mg, Fe, Al) 3[(Si, Al) 4O 10] (OH) 24H 2The vigorous reaction that O vermiculite class particle and Mg are taken place; But can make the best use of the situation, utilize vermiculite to be the response type pore-forming material, the position that self occupies after the vermiculite loss for reaction also just stays hole, obtains composite porous thus.Obviously, its relative defective is: this preparation method still fundamentally realizes " natural sintered glass "---expanded vermiculite of porous and MAGNESIUM METAL compound.
Chinese patent discloses the patent that is entitled as " preparation method of foam composite material of magnesium alloy-pearlite " for No. 200510119108.3.The advantage of this invention is to realize compound between porous magnesium alloy and the natural sintered glass, and the method that is adopted has stoped the reaction between perlite or vermiculite class particle and the Mg substantially for to use carbonated rare earth, lime carbonate and aluminium powder to be separant; But shortcoming is relatively: the carbonated rare earth that forms 2~3 crystal water as the carbonated rare earth of separant, easy suction, this brings new problem for the production quality control in producing in the future, if the local carbonated rare earth that decomposition occurs not having then can increase the corrosion of matrix material because of its suction.Lime carbonate is inferior to carbonated rare earth as the performance of separant, one of product after it decomposes is CaO, and CaO is that highly basic, Mg are the amphoteric element material, although it is can Al powder and Mg form the erosion resistance that magnalium increases the Mg matrix in Al powder, the flow event by being mixed in lime carbonate, limited to improving erosion resistance after all.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method of porous magnesium-expansion perlite composition material.Particularly to provide a kind of be the isolated vias agent with paraffin, be supporter, use the vacuum seepage means to make MAGNESIUM METAL or its alloy seepage flow prepare the method for metal-inorganic non-metallic matrix material in the supporter gap with the perforate perlite.Replace inorganic separant with organism paraffin as separant, can solve in magnesium alloy and the natural sintered glass recombination process, use inorganic separant to bury problems such as corrosion hidden danger.
The present invention based on cardinal principle be: paraffin is alkane, applies the thin paraffin of one deck in advance on the perlite particle surface, 680 ℃~750 ℃ seepage flow temperature, paraffin generation cracking and carbonization reaction, cracking goes out-CH n-and the C that goes out of charing all be reducing substances.This cracking and carbonization reaction product can be isolated the chemical reaction between magnesium matrix and the natural sintered glass on the one hand; The gaseous product of cracking and charing also can play certain through hole effect on the other hand; Simultaneously, this reduction atmosphere is beneficial to the oxidation of avoiding magnesium or magnesium alloy skeleton, thus the fragility of the little magnesium alloy skeleton of alkali and raising toughness.But, although agent has many benefits such as isolation, through hole and creation reduction atmosphere as isolated vias with organism paraffin, yet also simultaneously and depositing blast, burning equivalent risk.How the present invention evades the risk of using paraffin and bring into play organism paraffin to greatest extent: adopt solid paraffin-whiteruss-sherwood oil ternary system to be filming agent, its corresponding principle of design is as follows:
1., this system can make the wide modelization of carbon number distribution: belong to the paraffin of alkane, its composition meets C nH 2n+2The chemical general formula of alkane.N value in the paraffin that sell in market is 16~35, and often carries a certain amount of isoparaffin and naphthenic hydrocarbon secretly.Whiteruss is pure structure alkane and the numerical value of n wherein, and promptly carbonatoms is less than solid paraffin.Select a part of pure structure alkane whiteruss to sneak in the solid paraffin, can court of a feudal ruler feldspar wax in the distribution of low carbon number direction.Sherwood oil also is an alkane, and its n value is also littler than whiteruss, adds sherwood oil in the mixed wax system that solid paraffin and whiteruss are formed, and can be that the n value in 16 the mixed wax system extends to 8 with n value minimum.Obviously, the thin paraffin of perlite particle surface-coated runs into 680 ℃~750 ℃ the high temperature magnesium liquid generation cracking and the product of carbonization reaction, with alkane chemical general formula C nH 2n+2In the numerical value difference of n and product difference; The result of the wide modelization of alkane carbon number distribution cause cracking and carbonizing production variation, overcome because the paraffin reaction product brought of reaction preference is single that single reaction violent and blast or react negative effect such as incomplete.
2. solid paraffin-whiteruss-sherwood oil ternary system also can make the coating thin-walled property.The fusing point of solid paraffin is many more than 45 ℃, if directly must melt paraffin by outer heating with the solid paraffin coatedparticles, and crosses outer heating temperature and generally will can reduce above the fusing point of solid paraffin more than 40 ℃, paraffin viscosity.Because the coating thickness of paraffin coatedparticles is directly proportional with the paraffin viscosity, paraffin is wanted thin-walled property at the perlite top coat, and the paraffin viscosity can not be crossed greatly prerequisite; What is more important, stronger because the perlitic specific surface of perforate is very big to paraffin viscosity adhesive capacity, cause coating thin-walled property difficulty more.So the paraffin viscosity is minimised as the sufficient and necessary condition of coating thin-walled property.Sneak into whiteruss in the solid paraffin, when reducing fusing point, also reduce viscosity; Sneak into sherwood oil again, more significantly reduce viscosity, for the coating thin-walled property lays the foundation.
3. accompanying drawing 1 of the present invention provides the photo in kind of selected perforate pearlstone, has very big specific surface from the visible this natural sintered glass of this photo, thereby stronger to the paraffin adhesive capacity, causes coating thin-walled property difficulty more.The result of accompanying drawing 2 and accompanying drawing 3 discloses: the wide modelization of the carbon number distribution of solid paraffin-whiteruss-sherwood oil ternary system and coating thin-walled property, can directly influence the variation of matrix material relative density.
The present invention takes following technical scheme to realize:
With commercially available purity is that 99.5% metal magnesium ingot, AZ91 magnesium alloy ingot and pearlstone are raw material, with chemical pure solid paraffin, whiteruss and sherwood oil is coating material, the particle of pearlstone does not wherein sieve and directly uses, and its particulate size-grade distribution interval is 8~60 orders; With solid paraffin and whiteruss according to the mixed of the whiteruss of the corresponding 55g of solid paraffin of 45g evenly, constitute the mixed wax system that consists of 45wt% solid paraffin-55wt% whiteruss; Getting 50g in this mixed wax system mixes wax and dilutes with the sherwood oil of 200ml~1000ml, the diluent that will mix wax again is poured into the top of pearlstone, and the below of pearlstone is a filter screen so that unnecessary diluent flows through, and the unnecessary diluent that flows through screen cloth is put into rapidly to be preserved in the encloses container to avoid volatilization and in order to using next time; And the pearlstone of filter screen top has dipped in to hang up and has mixed the wax diluent, will dip in rapidly hang up mix the wax diluent the pearlstone bulk storage to the well-ventilated place, at room temperature placed at least 20 minutes so that mix the wax diluent and form solid film on the perlite surface; The thousand seed weight scope that the surface coats the expanded perlite granule of going up solid film is 0.36g~0.64g; This particle with overlay film is put in the suction pouring mould again, vacuum meter on connecting the vacuum tank of inhaling casting mould shows when vacuum tightness reaches 0.04Pa, 680 ℃~850 ℃ liquid metal magnesiums or liquid AZ91 magnesium alloy are poured over the top of pearlstone in the mold, and open vacuum hand valve simultaneously and begin to inhale casting; Inhale casting and finish the postcooling demoulding, obtain porous magnesium-expansion perlite composition material of the present invention; This matrix material
Figure C20071005617500051
Density range is 0.79g/cm 3~1.01g/cm 3, relative density scope relative and magnesium or AZ91 magnesium alloy is 0.45~0.56, and pairing stress range is 7.5MPa~12.5MPa during strain 2%, and pairing stress range is 7.8MPa~27.5MPa during strain 20%.
Preparation method's of the present invention advantage is: the paraffin with cheapness coats cheap pearlstone in room temperature, utilize the chemical reaction between alkane generation cracking and carbonization reaction isolation magnesium matrix and the natural sintered glass, create the elasticity of the reduction atmosphere raising magnesium alloy skeleton in the flow event, this preparation method's technical process is short, coat that energy consumption is little, raw materials cost is low, workable, do not stay corrosion hidden danger, be beneficial to and produce high-quality porous magnesium or magnesium alloy-expansion perlite composition material, reach goal of the invention.
Description of drawings:
Fig. 1 is the photo in kind of the particle randomly drawed out of the used perforate fine perlite of the present invention.
From this photo as seen: this " natural cellular glass " all show at random at aspects such as skeleton structure, hole distributions and The feature of nature is opposite with the nonrandom rule feature that the pure cellular glass that manually synthesizes shows.
Fig. 2 is the graph of a relation of benzinum addition of the present invention and porous magnesium-expansion perlite composition material relative density.
The actual conditions of synthetic this composite is: adopt 45wt% solid paraffin-55wt% atoleine-benzinum three Unit's system is that expanded perlite covering, this covering compound method are at the 45wt% of 5g solid paraffin-55wt% liquid Add the benzinum of varying number in the mixed wax of paraffin, the seepage flow body is metal M g, and the seepage flow temperature is 750 ℃. From scheming as seen: Rely on the benzinum addition to change wide model and the thin wall coated degree of the carbon number distribution of control coating film, it is multiple to reach control The purpose of condensation material relative density.
Fig. 3 is the pass of benzinum addition of the present invention and porous AZ91 magnesium alloy-expansion perlite composition material relative density The figure of system.
The actual conditions of composite diagram 3 composites and the condition of Fig. 2 are basic identical; Difference a bit is to use AZ91 magnesium Alloy replaces simple metal magnesium as seepage flow body and skeleton. As seen the result of Fig. 3 and Fig. 2 contrasts: the curve performance of Fig. 3 and Fig. 2 Go out bigger otherness, its reason is: increased the elements such as Al, Zn, seepage flow mistake in the AZ91 magnesium alloy than simple metal magnesium Paraffin generation cracking and carbonization reaction in the journey since newly-increased element so that catalytic condition changes, it is poor to cause crackate etc. to occur The opposite sex also has influence on the composite relative density and the otherness of benzinum addition relation thus.
Fig. 4 is the stress-strain curve of porous magnesium-expansion perlite composition material of the present invention.
The wherein preparation of organic coating agent or consist of: 45wt% solid paraffin-55wt% atoleine mixed
Figure C20071005617500061
Wax 5g with The 20ml benzinum mixes, and the seepage flow body is metal M g, and the seepage flow temperature is 750 ℃. From scheming as seen: the strain 10%~25% In the scope, its load-deformation curve be characterized as level and smooth rising.
Fig. 5 is the stress-strain curve of porous AZ91 magnesium alloy-expansion perlite composition material of the present invention.
The sample of Fig. 5 and the unique difference of Fig. 4 sample are that replacing pure metal magnesium with the AZ91 magnesium alloy is seepage flow body and skeleton.Other synthesis conditions etc. are all identical.By curve contrast among Fig. 5 and Fig. 4 as seen: stress-strain curve is in 10%~25% range of strain among Fig. 5, the shape of curve is not level and smooth relatively but contains tangible crest and trough, its reason still can be summed up as: increased Al than pure metal magnesium in the AZ91 magnesium alloy, elements such as Zn, paraffin generation cracking and carbonization reaction in the flow event are because newly-increased element makes catalytic condition change, cause crackate etc. otherness to occur and have influence on the matrix material porosity thus and communicating aperture quantity increases, the discontinuous support frame of communicating aperture finally causes curve crest and trough to occur in compression process.
Fig. 6 is the cross-sectional picture of porous magnesium-expansion perlite composition material sample of the present invention.
By this figure as seen: contacting between MAGNESIUM METAL skeleton and the natural sintered glass pearlstone very is closely, and can not find the vestige that the Mg-Si reaction takes place substantially, and macrobead and short grained pearlstone all have distribution at this cross section; The randomness that expanded perlite granule distributes causes belonging to the magnesium frame configuration, and random character also appears in distribution such as wall thickness, and this random character can avoid matrix material to occur anisotropy, the elastic range that the increase framework deformation provides during force compresses outside being subjected to.
Embodiment:
Embodiment 1:
With commercially available purity is that 99.5% metal magnesium ingot and pearlstone are raw material, with chemical pure solid paraffin, whiteruss and sherwood oil is coating material, the big and small particle of pearlstone does not wherein sieve and directly uses, and its particulate size-grade distribution interval is 8~60 orders; With solid paraffin and whiteruss according to the mixed of the whiteruss of the corresponding 55g of solid paraffin of 45g evenly, constitute the mixed wax system that consists of 45wt% solid paraffin-55wt% whiteruss; Getting 50g in this mixed wax system mixes wax and dilutes with the sherwood oil of 200ml, the diluent that will mix wax again is poured into the top of pearlstone, and the below of pearlstone be filter screen so that unnecessary diluent flows through, the unnecessary diluent that flows through screen cloth is put into rapidly to be preserved in the encloses container to avoid volatilization and in order to using next time; And the pearlstone of filter screen top has dipped in to hang up and has mixed the wax diluent, will dip in rapidly hang up mix the wax diluent the pearlstone bulk storage to the well-ventilated place, at room temperature placed 50 minutes so that mix the wax diluent at perlite surface formation solid film; The thousand seed weight that the surface coats the expanded perlite granule of going up solid film is 0.64g; This particle with overlay film is put in the suction pouring mould again, vacuum meter on connecting the vacuum tank of inhaling casting mould shows when vacuum tightness reaches 0.04Pa, 850 ℃ liquid metal magnesiums are poured over the top of pearlstone in the mold, and open vacuum valve simultaneously and begin to inhale casting; Inhale casting and finish the postcooling demoulding, obtain porous magnesium-expansion perlite composition material of the present invention; The absolute density of this matrix material is 0.79g/cm 3, relative density relative and magnesium is 0.45, and pairing stress is 6.1MPa during strain 2%, and pairing stress is 7.8MPa during strain 20%.
Embodiment 2:
All the other are with embodiment 1.Different is: 1. 50g mixes the sherwood oil dilution of wax with 1000ml; 2. the thousand seed weight of overlay film expanded perlite granule is 0.36g; 3. to transfer the time of putting be 20 minutes to the film forming room temperature; 4. the seepage flow temperature is 680 ℃; 5. the absolute density of matrix material is 0.945g/cm 36. the relative density of matrix material is 0.54; 7. pairing stress is 12.5MPa during strain 2%; 8. pairing stress is 22.1MPa during strain 20%.
Embodiment 3:
All the other are with embodiment 1.Different is: 1. 50g mixes the sherwood oil dilution of wax with 600ml; 2. the thousand seed weight of overlay film expanded perlite granule is 0.51g; 3. to transfer the time of putting be 30 minutes to the film forming room temperature; 4. the seepage flow temperature is 750 ℃; 5. the absolute density of matrix material is 0.88g/cm 36. the relative density of matrix material is 0.50; 7. pairing stress is 11MPa during strain 2%; 8. pairing stress is 21MPa during strain 20%.
Embodiment 4:
All the other are with embodiment 1.Different is: 1. seepage flow liquid pure metal magnesium is replaced with the AZ91 magnesium alloy; 2. the absolute density of matrix material is 0.91g/cm 33. the relative density of matrix material is 0.51; 4. pairing stress is 12MPa during strain 2%; 5. pairing stress is 26MPa during strain 20%.
Embodiment 5:
All the other are with embodiment 2.Different is: 1. seepage flow liquid pure metal magnesium is replaced with the AZ91 magnesium alloy; 2. the absolute density of matrix material is 0.91g/cm 33. the relative density of matrix material is 0.51; 4. pairing stress is 10.1MPa during strain 2%; 5. pairing stress is 27.5MPa during strain 20%.
Embodiment 6:
All the other are with embodiment 3.Different is: 1. seepage flow liquid pure metal magnesium is replaced with the AZ91 magnesium alloy; 2. the absolute density of matrix material is 1.01g/cm 33. the relative density of matrix material is 0.56; 4. pairing stress is 7.5MPa during strain 2%; 5. pairing stress is 27.2MPa during strain 20%.

Claims (1)

1, the preparation method of a kind of porous magnesium-expansion perlite or porous AZ91 magnesium alloy-expansion perlite composition material, it is characterized in that: with commercially available purity is that 99.5% metal magnesium ingot, AZ91 magnesium alloy ingot and pearlstone are raw material, with chemical pure solid paraffin, whiteruss and sherwood oil is coating material, wherein the expanded perlite granule that granularity is different does not sieve and directly uses, and the size-grade distribution interval of this expanded perlite granule is 8~60 orders; With solid paraffin and whiteruss according to the mixed of the whiteruss of the corresponding 55g of solid paraffin of 45g evenly, obtain consisting of the mixed wax system of 45wt% solid paraffin-55wt% whiteruss; Getting 50g in this mixed wax system mixes wax and dilutes with the sherwood oil of 200ml~1000ml, the diluent that will mix wax again is poured into the top of pearlstone, and the below of pearlstone is a filter screen so that unnecessary diluent flows through, and the unnecessary diluent that flows through screen cloth is put into rapidly to be preserved in the encloses container to avoid volatilization and in order to using next time; And the pearlstone of filter screen top has dipped in to hang up through this operation and has mixed the wax diluent, will dip in rapidly hang up mix the wax diluent the pearlstone bulk storage to the well-ventilated place, at room temperature placed at least 20 minutes so that mix the wax diluent and form solid film on the pearlstone surface; This particle with overlay film is put in the suction pouring mould again, vacuum meter on connecting the vacuum tank of inhaling casting mould shows when vacuum tightness reaches 0.04Pa, 680 ℃~850 ℃ liquid metal magnesiums or liquid AZ91 magnesium alloy are poured over the top of pearlstone in the mold, and open vacuum valve simultaneously and begin to inhale casting; Inhale casting and finish the postcooling demoulding, obtain porous magnesium-expansion perlite or porous AZ91 magnesium alloy-expansion perlite composition material; The absolute density scope of this matrix material is 0.79g/cm 3~1.01g/cm 3, when being 0.45-0.56, strain 2% with respect to the relative density scope of magnesium: the stress range of porous magnesium-expansion perlite composition material is 11MPa~12.5MPa, and the stress range of porous AZ91 magnesium alloy-expansion perlite composition material is 7.5MPa~12MPa; And during strain 20%: the stress range of porous magnesium-expansion perlite composition material is 7.8MPa~22.1MPa, and the stress range of porous AZ91 magnesium alloy-expansion perlite composition material is 26MPa~27.2MPa.
CNB2007100561754A 2007-10-16 2007-10-16 The preparation method of a kind of porous magnesium-expansion perlite or porous AZ91 magnesium alloy-expansion perlite composition material Expired - Fee Related CN100569972C (en)

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CN107699723B (en) * 2017-09-29 2019-05-14 重庆理工大学 The preparation method of magnesium-base porous compound material containing ceramic hollow ball
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CN1792504A (en) * 2005-12-26 2006-06-28 中国科学院长春应用化学研究所 Process for preparing composite material of high magnesium aluminium alloy-expanding ore
CN1792505A (en) * 2005-12-26 2006-06-28 中国科学院长春应用化学研究所 Process for preparing foam composite material of magnesium alloy-pearlite
CN101037734A (en) * 2006-03-17 2007-09-19 中国科学院合肥物质科学研究院 Porosity aperture controllable magnesium foam material and preparation method thereof

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JP2004156067A (en) * 2002-11-01 2004-06-03 Mitsubishi Pencil Co Ltd Method for making fine crystal grain in cast article of magnesium alloy
CN1792504A (en) * 2005-12-26 2006-06-28 中国科学院长春应用化学研究所 Process for preparing composite material of high magnesium aluminium alloy-expanding ore
CN1792505A (en) * 2005-12-26 2006-06-28 中国科学院长春应用化学研究所 Process for preparing foam composite material of magnesium alloy-pearlite
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