CN102321893A - Preparation process of foam metal carrier for post-treatment - Google Patents
Preparation process of foam metal carrier for post-treatment Download PDFInfo
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- CN102321893A CN102321893A CN201110261685A CN201110261685A CN102321893A CN 102321893 A CN102321893 A CN 102321893A CN 201110261685 A CN201110261685 A CN 201110261685A CN 201110261685 A CN201110261685 A CN 201110261685A CN 102321893 A CN102321893 A CN 102321893A
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- foam metal
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Abstract
The invention relates to a preparation process of a foam metal carrier for post-treatment, which is characterized in that: blending thermosetting phenolic resin, alcohol, and nanometer graphite to form conductive slurry, soaking and coating foamed plastics, extruding redundant slurry, drying, electroplating the plastics with iron and nickel, after electroplating, performing deficiency sintering with a preserved temperature in a high temperature furnace so as to prepare the foam metal with a certain porosity. Starting with the optimization of the pre-treatment process flow of foamed plastics, the invention shortens the flow, eliminates pollution procedures, has obvious energy saving and environmental protection effect, is stable and controllable, and has very high practical value.
Description
Technical field
The present invention relates to a kind of aftertreatment and use foam metal carrier preparation technology, can be applied to the aftertreatment industry of vehicle exhaust.
Background technology
Current, the whole world faces the comprehensive challenge of the energy and environment.Aspect the technique means selection of the emission compliance of orthodox car, people still face many difficult problems, for example, how to select the aspect such as carrier and catalyzer of aftertreatment.
The aftertreatment carrier is the key factor that constitutes automobile-used aftertreatment platform, by the end of so far, is the ceramic monolith of import in the overwhelming majority aspect the aftertreatment carrier, and the physical strength of this ceramic monolith is poor slightly, not too is adapted to actual situation of China; Equally, sophisticated metallic carrier becomes the key factor of the Chinese aftertreatment industry development of restriction also by external technology and patent monopolization, and therefore, how obtaining low cost and high performance aftertreatment carrier is to advance this art progressive core content.
Foamed metal is a kind of physical function and the incorporate new engineering material of structural performance.Begin the metal foaming material development beginning of the eighties in the world, metal foaming material possesses light weight, sound insulation, filtration and flame-retarding characteristic, and very strong shock-absorbing and electromagnetic shielding action are arranged again, therefore, is widely used in national defense industry.Rise the nineties, and foamed metal is applied to civilian industry, and for example, high-caliber nickel foam is applied to the preparation of electric capacity and super capacitor.At present, development of China's foamed metal and production technology level occupy prostatitis, the world.
Analyze and actual test shows from structure, foamed metal is optimal post-treating metal carrier, for example; Structural strength is higher than ceramic monolith, and gas channel is disorderly, obtains the catalytic effect of anticipation the most easily; In addition, the coating of catalyzer and construction technology are comparatively simple, therefore; Select metal foam as carrier, possess theoretic advance; But the disadvantage of foamed metal is that price is high, average 250 ~ 350 yuan/liter; Even higher, for the diesel vehicle of 10 liters of engine displacement, need the volume of aftertreatment carrier to be about 15～20 liters; Therefore, if adopt 100% foamed metal as carrier, only carrier part is just up to 5000 ~ 7000 yuan/car; After considering the cost of catalyzer and encapsulation, just cause the cost of car load to raise and to accept, become the obstacle that foamed metal is used.
The cost of foamed metal is determined by technological process cost and material cost two aspects, should carry out optimizing process technology cost and material cost simultaneously; Retrieval finds that number of patent application is that ' titanium-based quaternary catalytic foam metal carrier and method of manufacture thereof ' patent of CN201010100422.8 is to adopt with titanium or titanium alloy to smelt the titanium foam metallic substance that obtains three-dimensional fibrous structure; Number of patent application is that CN200810068869.4's ' method of plastic based foam metalizing ' patent is that the plastic based foam is dipped in low-temperature heat curing polymkeric substance silver slurry or low-temperature heat curing polymkeric substance silver slurry is sprayed on the plastic based foam; Make plastic based foamy fiber adhere to conductive layer, and then electroplate and prepare; Number of patent application is CN200610117833.1's ' being applied to the bubble iron chromium aluminum and the manufacture craft thereof of tail gas filtering and support of the catalyst ' patent; Described bubble iron chromium aluminum is to be base material with the foam shape metal, carries out flame plating siderochrome aluminium at the porous surface of base material; Number of patent application is that CN200510032174.7's ' three-dimensional through hole or part hole are connected with each other porous metal foam and preparation method thereof ' patent is one or more particle diameters to be dispersed in the solution that contains caking agent at the metal or alloy powder of 1 ~ 100 μ m process slip; Again these slurries are poured in the through hole polyurethane sponge foam, obtain three-dimensional through-hole foamed metal material through oven dry, sintering; Number of patent application is that CN03208577.X's ' composition metal porous aluminum ' patent is the tridimensional network that adopts the foamed metal skeleton to form, and adopts the hot aluminizing method on this skeleton, to carry out composition metal aluminium; Number of patent application is that CN00133631.2's ' a kind of composite foam metal and preparation method thereof ' patent is earlier foam materials to be prepared conductive layer; Adopt the method for galvanic deposit; Metal refining on foam materials (A); At metal (A) another metal of surface deposition (B), after bakingout process, form composite foam metal again; Number of patent application is that CN02129612.X's ' a kind of porous body of composite metal and preparation method thereof ' patent at first is the core film with the foam materials, on this core film deposition a kind of or more than two kinds or two kinds metal prepare porous metal or porous alloy; Be skeleton with porous metal or porous alloy more afterwards, on this skeleton, adopt the hot dipping method to carry out the hot dipping metal or alloy, can prepare porous body of composite metal.
Above-mentioned patent, all relating to carried out galvanizedly to porous plastics, all can't avoid pre-treatment problem and electroplating technique problem.The characteristics of conventional plastic are non-conductive, and before electroplating, the surface must conduction just can be electroplated.The method of surface metalation comprises the dry method and the wet method of vacuum sputtering.
Dry process and equipment are too expensive, and therefore, wet applications is more; Wet method comprises and is coated with conductive resin method and chemical pretreatment process.There is the shortcoming that film is inhomogeneous, wetting ability is bad and sedimentation velocity is slow in traditional conductive resin method.Thereby majority all is to carry out with chemical pretreatment process.
And traditional preprocessing comprises and degreasing and hydrophilicity-imparting treatment; Hydrophilicity-imparting treatment makes the surface of plastic substrate become hydrophilic by hydrophobic; Method of hydrophilizing comprises mechanical process and chemical method again; Chemical method is to adopt a kind of strong oxidizing property solution that contains chromic anhydride and sulfuric acid mixture to handle, and there is the potential problem of environmental pollution in this operation; Next be to need to adopt the precious metals such as gold and silver, platinum or palladium that possess katalysis to carry out the activation treatment operation; After accomplishing activation treatment; Begin to carry out the electroless plating of porous plastics; Make metals ion reduce deposition in the plating bath on the porous plastics matrix; Will adhere to the layer of metal conducting film through Foam Plastic Surface after the electroless plating, thicknesses of layers generally very thin (0.05 ~ 0.8 μ m), often can not satisfy product mechanical property and intensity aspect request for utilization.Therefore, through after the electroless plating, carry out porous plastics again and electroplate; Can adopt common electroplating technology; Deposited iron and nickel metal increase metal layer thickness, accomplish the foamed metal preparation; This shows that the production process of traditional foamed metal is long, efficient is low, technological process cost height and potential problem of environmental pollution are the disadvantages of present chemical pretreatment process.
Summary of the invention
The object of the present invention is to provide a kind of aftertreatment to use foam metal carrier preparation technology, it is optimized existing preparation technology, has reduced cost, has reduced environmental pollution, and improves the thermal treatment process to finished product.
Technical scheme of the present invention is achieved in that a kind of aftertreatment uses foam metal carrier preparation technology; Its characteristic is: reconcile into electrocondution slurry by heat cured resol, alcohol, nano-graphite, the dip-coating porous plastics squeezes out redundant sizing agent then; After the oven dry; Carry out the plating of iron and nickel, electroplate end back insulation burning in High Temperature Furnaces Heating Apparatus and lack, process the foamed metal of certain porosity.
Described electrocondution slurry is the heat cured resol by 3 ~ 6 mass parts, the industrial spirit of alcohol 4 ~ 10 mass parts, and nano-graphite particle diameter 10 ~ 13 μ m of 3 ~ 8 mass parts mix to stir reconciling into electrocondution slurry.
The dip-coating that described porous plastics carries out in electrocondution slurry is the secondary dip-coating, wherein; Whole for the first time the immersion taken out and squeezed out redundant sizing agent, air purge; Oven dry 40 ~ 60min in 80 ~ 120 ℃ the loft drier repeats operation for the first time more then, has prepared the porous plastics that conductive film is arranged.
The described porous plastics that has conductive film carries out traditional plating in plating tank, 4 ~ 8h, galvanized composition can be 1 kinds or 2 kinds in iron and the nickel, and plating iron must be carried out before nickel plating.
After described porous plastics is accomplished iron and nickel plating, after tap water washing 2 times, move in the High Temperature Furnaces Heating Apparatus, heat up with stove, open argon shield, the flow 1 ~ 10L/min of PM is incubated in 500 ~ 650 ℃ High Temperature Furnaces Heating Apparatus, 60 ~ 120min, and thermal treatment is burnt and is lacked.
Described thermosetting resin is not limited to the combination of resol and nano-graphite, also can adopt urea-formaldehyde resin and epoxy resin as sticker.
Positively effect of the present invention is to start with from optimizing porous plastics pre-treating technology flow process, shortens flow process, and operation is polluted in cancellation, raises the efficiency, and energy-conservation obvious with environment protecting, stable and controllable has very high practical value.
Embodiment
Through embodiment the present invention is further described below, embodiment is not equal to restriction the present invention for further illustrating characteristics of the present invention,, all should be included within protection scope of the present invention according to the change that the present invention carries out for those skilled in the art.
Embodiment 1
At first select commercially available urethane foam matrix for use, percentage of open area is 25ppi, cuts into diameter 320mm; Thickness is the discoid blank of 25mm, no matter whether remaining greasy dirt is arranged, all adopts grease-removing agent to clean and degreases; With tap water flushing 2 times, deionized water rinsing 2 times dries moisture then; Indoor drying, the W1=61.8g that weighs, for use; Take by weighing the heat-reactive phenolic resin of 3 parts industry, take by weighing 4 parts industrial spirit, the Nano graphite powder of 5 parts median size 10 μ m specifications (be corresponding to the standard mesh number 1340 technical grade) mixes to stir reconciling into electrocondution slurry; Above-mentioned porous plastics blank is immersed wherein, and at first dip-coating is taken out and is squeezed out redundant sizing agent for the first time; Air purge, insulation 40min in 80 ℃ the loft drier repeats operation for the first time then; Carry out secondary dip-coating and oven dry, prepared the porous plastics that successive has conductive film; W2=392.4g weighs; W2-W1=330.6g.
The porous plastics of above-mentioned conductive film is placed on carries out traditional plating in the plating tank, according to thickness requirement, electroplating time is controlled at 4h, and at first galvanized composition is an iron, dries, and W3=1176.8g weighs; Be moved into behind 2 h in the coating bath that contains nickel salt, electroplate, finish behind 2 h, accomplish metal deposition, dry, W4=1439.8g weighs; W4-W3=263g.Accomplish the foamed metal after iron and nickel are electroplated, with tap water washing 2 times, dry moisture earlier, move in the High Temperature Furnaces Heating Apparatus then; Heat up with stove, open argon shield, the flow 1L/min of PM; In 650 ℃ High Temperature Furnaces Heating Apparatus, be incubated, 60min, the porous plastics that lacks is wherein burnt in thermal treatment; Process the foamed metal finished product, the floating ash of air purge, W5=1106.2g weighs; W4-W5=333.6g.
Embodiment 2
At first select commercially available urethane foam matrix for use, percentage of open area is 25ppi, cuts into diameter 320mm; Thickness is the discoid blank of 25mm, no matter whether remaining greasy dirt is arranged, all adopts grease-removing agent to clean and degreases; With tap water flushing 2 times, deionized water rinsing 2 times dries moisture then; Indoor drying, the W1=61.8g that weighs, for use; Take by weighing the heat-reactive phenolic resin of 6 parts industry, take by weighing 10 parts industrial spirit, 8 parts median size 13 μ m (be corresponding to the standard mesh number 1000 technical grade) Nano graphite powder mixes to stir reconciling into electrocondution slurry; The porous plastics blank is immersed wherein, and at first dip-coating is taken out and is squeezed out redundant sizing agent for the first time; Air purge, insulation 60min in 120 ℃ the loft drier repeats operation for the first time then; Carry out secondary dip-coating and oven dry, prepared the porous plastics that successive has conductive film; W2=386.5 weighs; W2-W1=324.4g.
The foamed plastics of above-mentioned conductive film is carried out traditional plating in electroplating bath, according to thickness requirement, electroplating time is controlled at 4h, and at first the composition of Dian Duing is an iron, dries, and W3=1169.6g weighs; Be moved into behind 4 h in the coating bath that contains chromic salts, electroplate, finish behind 4 h, accomplish the metal deposition, dry, W4=1668.7g weighs; W4-W3=499.1g.Foamed metal after the plating of completion embodiment 7 with tap water washing 2 times, dries moisture earlier, moves in the High Temperature Furnaces Heating Apparatus then; Heat up with stove, open argon shield, the flow 10L/min of PM; In 500 ℃ High Temperature Furnaces Heating Apparatus, be incubated, 120min, the porous plastics that lacks is wherein burnt in thermal treatment; Process the foamed metal finished product, the floating ash of air purge, W5=1337.9g weighs; W4-W5=330.9g.
Embodiment 3
With the heat cured resol of 4 mass parts, the industrial spirit of 6 mass parts, the nano-graphite of 5 mass parts mixes to stir reconciling into electrocondution slurry,
Described nano-graphite is selected particle diameter 11 μ m (being the nano-graphite of 1200 technical grade corresponding to the standard mesh number) for use; Described thermosetting resin has been selected resol for use; But other heat cured resin all can adopt, and the film that forms after the thermosetting resin drying is very good to the affinity of water; The nano-graphite that adds is selected the specification of particle diameter 11 μ m for use; Mainly be after considering the thermosetting resin drying formed film thickness below 11 μ m; Nano-graphite particulate to form individual layer is arranged; Resol can adopt alcohol to dissolve, and the adding of alcohol is to guarantee that Nano graphite powder also can be wetting by thermosetting resin institute, and the film of formation is more continuous and fine and close; In electrocondution slurry, carry out dip-coating to porous plastics, at first dip-coating is taken out and is squeezed out redundant sizing agent for the first time; Air purge, insulation 40 ~ 60min in 80 ~ 120 ℃ the loft drier repeats operation for the first time then; Carry out secondary dip-coating and oven dry, prepared the porous plastics that successive has conductive film; In plating tank, carry out traditional plating to the porous plastics of accomplishing conductive film, according to thickness requirement, electroplating time is controlled at nickel, and galvanized composition can be a kind or 2 kinds in iron and the nickel, for example, iron, or iron/nickel combination, plating iron must be carried out before nickel plating; Accomplish the foamed metal after iron and nickel are electroplated, adopt tap water flushing 2 times, move into then in the High Temperature Furnaces Heating Apparatus, heat up with stove; Open argon shield, the flow 1 ~ 10L/min of PM, insulation in 500 ~ 650 ℃ High Temperature Furnaces Heating Apparatus, 60 ~ 120min; Thermal treatment burn to lack porous plastics wherein, the reason that feeds argon gas be early stage the coating of sedimentary iron, may not 100% be override, if thermal treatment in air by nickel; Iron is caused partial intensity to reduce significantly by oxidation rapidly, produces waste product.
Claims (6)
1. foam metal carrier preparation technology is used in an aftertreatment; Its characteristic is: reconcile into electrocondution slurry by heat cured resol, alcohol, nano-graphite, the dip-coating porous plastics squeezes out redundant sizing agent then; After the oven dry; Carry out the plating of iron and nickel, electroplate end back insulation burning in High Temperature Furnaces Heating Apparatus and lack, process the foamed metal of certain porosity.
2. a kind of aftertreatment foam metal carrier preparation technology according to claim 1; It is characterized in that described electrocondution slurry; Be heat cured resol by 3 ~ 6 mass parts; The industrial spirit of alcohol 4 ~ 10 mass parts, nano-graphite particle diameter 10 ~ 13 μ m of 3 ~ 8 mass parts mix to stir reconciling into electrocondution slurry.
3. a kind of aftertreatment foam metal carrier preparation technology according to claim 1 is characterized in that the dip-coating that described porous plastics carries out in electrocondution slurry, be twice dip-coating; Wherein, whole for the first time the immersion taken out and squeezed out redundant sizing agent; Air purge; Oven dry 40 ~ 60min in 80 ~ 120 ℃ the loft drier repeats operation for the first time more then, has prepared the porous plastics that conductive film is arranged.
4. a kind of aftertreatment foam metal carrier preparation technology according to claim 3; It is characterized in that the described porous plastics that has conductive film carries out traditional plating in plating tank; 4 ~ 8h, galvanized composition can be 1 kinds or 2 kinds in iron and the nickel, and plating iron must be carried out before nickel plating.
5. a kind of aftertreatment foam metal carrier preparation technology according to claim 4, it is characterized in that described porous plastics is accomplished iron and electroplated with nickel after, wash 2 times with tap water after; In the immigration High Temperature Furnaces Heating Apparatus, heat up, open argon shield with stove; Flow 1 ~ the 10L/min of PM; Insulation in 500 ~ 650 ℃ High Temperature Furnaces Heating Apparatus, 60 ~ 120min, thermal treatment is burnt and is lacked.
6. a kind of aftertreatment foam metal carrier preparation technology according to claim 1 is characterized in that described thermosetting resin also comprises the thermosetting resin of other type, like the combination of urea-formaldehyde resin, epoxy resin and nano-graphite.
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| CN201110261685A CN102321893A (en) | 2011-09-06 | 2011-09-06 | Preparation process of foam metal carrier for post-treatment |
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| CN201110261685A CN102321893A (en) | 2011-09-06 | 2011-09-06 | Preparation process of foam metal carrier for post-treatment |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61207593A (en) * | 1985-03-09 | 1986-09-13 | Sumitomo Electric Ind Ltd | Production of porous metallic body |
| CN1434528A (en) * | 2002-01-21 | 2003-08-06 | 深圳市格林美环境材料有限公司 | Plate of nickel cell and preparation method thereof |
| CN1542061A (en) * | 2003-04-29 | 2004-11-03 | 比亚迪股份有限公司 | Plastic foam electrically-conducting paint and manufacturing method thereof |
| CN1730697A (en) * | 2005-08-10 | 2006-02-08 | 广州有色金属研究院 | Porous foam nickel base alloy and its preparation method |
| CN101104893A (en) * | 2006-07-14 | 2008-01-16 | 中国科学院金属研究所 | Metal/carbonyl composite foaming material and preparation method thereof |
| CN101298686A (en) * | 2007-04-30 | 2008-11-05 | 比亚迪股份有限公司 | Method for preparing foamed metal |
| CN101342786A (en) * | 2008-08-15 | 2009-01-14 | 陈群星 | Plastic based foam metalizing method |
-
2011
- 2011-09-06 CN CN201110261685A patent/CN102321893A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61207593A (en) * | 1985-03-09 | 1986-09-13 | Sumitomo Electric Ind Ltd | Production of porous metallic body |
| CN1434528A (en) * | 2002-01-21 | 2003-08-06 | 深圳市格林美环境材料有限公司 | Plate of nickel cell and preparation method thereof |
| CN1542061A (en) * | 2003-04-29 | 2004-11-03 | 比亚迪股份有限公司 | Plastic foam electrically-conducting paint and manufacturing method thereof |
| CN1730697A (en) * | 2005-08-10 | 2006-02-08 | 广州有色金属研究院 | Porous foam nickel base alloy and its preparation method |
| CN101104893A (en) * | 2006-07-14 | 2008-01-16 | 中国科学院金属研究所 | Metal/carbonyl composite foaming material and preparation method thereof |
| CN101298686A (en) * | 2007-04-30 | 2008-11-05 | 比亚迪股份有限公司 | Method for preparing foamed metal |
| CN101342786A (en) * | 2008-08-15 | 2009-01-14 | 陈群星 | Plastic based foam metalizing method |
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