CN100548927C - Molded three-dimensional insulator - Google Patents
Molded three-dimensional insulator Download PDFInfo
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- CN100548927C CN100548927C CNB2004800025817A CN200480002581A CN100548927C CN 100548927 C CN100548927 C CN 100548927C CN B2004800025817 A CNB2004800025817 A CN B2004800025817A CN 200480002581 A CN200480002581 A CN 200480002581A CN 100548927 C CN100548927 C CN 100548927C
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- Thermal Insulation (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention provides a kind of molded three-dimensional insulator that is applicable in the terminal cone zone of polluting control device.The present invention also provides a kind of method of making this thermally-insulated body.Comprise in this thermally-insulated body that volumetric shrinkage produces the ceramic fiber that surpasses 10 weight %.Containing aluminum oxide and silicon oxide in these ceramic fibers, is crystallite, crystal or its mixed form.
Description
Cross-reference to related applications
The application requires U.S.'s patent application formerly 60/441664 of submitting on January 22nd, 2003 and the right of priority of U.S.'s patent application formerly 60/456736 of submitting on March 21st, 2003.
Invention field
Molded three-dimensional insulator and the method for making this thermally-insulated body is provided.More particularly, provide a kind of molded three-dimensional insulator that is applicable in the terminal cone zone of polluting control device.
Background of invention
Polluting control device is used in the motor vehicle to reduce topsoil.At present widely used is two kinds of pollution control devices: catalytic converter and diesel particulate filter or trap.Contain one or more catalyzer in the catalytic converter, these catalyzer are coated on the substrate of monoblock type lumphy structure form usually.These monoblock type lumphy structures are pottery normally, but also uses metal monolith.Catalyzer energy oxidizing carbon monoxide, the various hydrocarbons of oxidation, nitrogen oxides reduction, the perhaps mixing of these materials in the waste gas.Diesel particulate filter or trap normally have the wall-flow filter of honeycomb monoblock type lumphy structure, are made by the perviousness crystalline ceramic material.The staggered hole of honeycomb monoblock type lumphy structure is blocked, makes tail gas can enter a hole, flows through the perviousness hole wall and enters another hole, leaves this structure then.
In the prior art structure of these polluted air devices, this monoblock type lumphy structure is closed in the terminal conoidal Shell.Because the diameter of monoblock type lumphy structure is usually greater than automobile tail gas pipe, so should generally include a zone of transition in the end conoidal Shell.This zone of transition is meant from the zone that the diameter that is suitable for the monoblock type lumphy structure narrows down to the diameter that is suitable for connecting waste pipe gradually and is referred to as terminal cone zone.Terminal cone is normally conical, is positioned at the import and the outlet side that pollute control device.
Pollute control device and under comparatively high temps, work usually, such as above about 500 ℃.Therefore, need usually to provide heat insulation in the conoidal Shell endways.Can between monoblock type lumphy structure and metal shell, use the lagging material of assembling pulvilliform formula.Provide heat insulation in the terminal cone zone of conoidal Shell endways.Terminal cone zone has double-walled construction usually, comprises outer ends conoidal Shell and inside end conoidal Shell.Can between inboard and outer ends conoidal Shell, use lagging material.
Summary of the invention
The invention provides a kind of molded three-dimensional insulator.More particularly, this thermally-insulated body is applicable in the terminal cone zone of polluting control device.The present invention also provides the method for making this thermally-insulated body.
The product that one aspect of the present invention provides comprises that its size is applicable to the molded three-dimensional insulator in the terminal cone zone of polluting control device.Comprise in this thermally-insulated body that volumetric shrinkage is no more than 10% ceramic fiber, use thermomechanical analyzer to test and (that is, under the load of about 50 pounds/square inch (345,000 Ns/square metre), the ceramic fiber sample is heated to 1000 ℃, then cooling; Diameter under 750 ℃ of sample in diameter under 750 ℃ of sample in the heating steps and the cooling step is compared).Thermally-insulated body is a self-supporting and seamless, and the compressibility value when packaging density is about 0.4 grams per milliliter is no more than 750,000 Ns/square metre.Can also comprise and the thermally-insulated body internal surface the terminal conoidal Shell of the pollution control device of thermally-insulated body outside surface or its built up section in this product.
The product that second aspect present invention provides comprises that its three-dimensional dimension is applicable to the molded three-dimensional insulator in the terminal cone zone of polluting control device.This thermally-insulated body comprises and contains the ceramic fiber that accounts for its gross weight at least 20 weight % aluminum oxide and at least 30 weight % silicon oxide.These ceramic fibers can be crystallites, crystal or its mixed form.This thermally-insulated body is a self-supporting and seamless, has the compressibility value that is no more than 750,000 Ns/square metre when packaging density is about 0.4 grams per milliliter.This product can also comprise and the thermally-insulated body internal surface, the terminal conoidal Shell of the pollution control device of thermally-insulated body outside surface or its built up section.
Third aspect present invention provides and has comprised the product manufacture method that is applicable to the thermally-insulated body in the terminal cone zone of polluting control device.This method comprises the preparation water slurry, forms molded three-dimensional preformed body and the precast body drying is formed molded three-dimensional insulator with the water slurry vacuum is in full bloom on the perviousness moulding stamper.The water slurry that is used for preparing precast body comprises that volumetric shrinkage is no more than 10% ceramic fiber, and shrinking percentage is obtained by the thermomechanical analyzer test.This thermally-insulated body is a self-supporting, has the compressibility value that is no more than 750,000 Ns/square metre when packaging density is about 0.4 grams per milliliter.
Fourth aspect present invention provides and has comprised the product manufacture method that is applicable to the thermally-insulated body in the terminal cone zone of polluting control device.This method comprises the preparation water slurry, forms molded three-dimensional preformed body with the water slurry vacuum and dry precast body forms molded three-dimensional insulator on the perviousness moulding stamper.The water slurry that is used for preparing precast body comprises the ceramic fiber that contains at least 20 weight % aluminum oxide and at least 30 weight % silicon oxide.These ceramic fibers can be crystallites, crystal or its mixed form.This thermally-insulated body is a self-supporting, has the compressibility value that is no more than 750,000 Ns/square metre when packaging density is about 0.4 grams per milliliter.
Above general introduction of the present invention is not to attempt to illustrate each embodiment of the present invention or embodiment.The following drawings and specify and more specifically to describe these embodiment.
Brief Description Of Drawings
Accompanying drawing 1 is depicted as the pollution control device sectional view that has molded three-dimensional insulator endways between the conoidal Shell inboard and the outside.
Accompanying drawing 2 is a kind of synoptic diagram that are applicable to the molded three-dimensional insulator in the terminal cone zone of polluting control device.
Accompanying drawing 3 is synoptic diagram that another kind is applicable to the molded three-dimensional insulator in the terminal cone zone of polluting control device.
Though can carry out various improvement and variation to the present invention, its feature below will specify as shown in drawings.Be to be understood that the present invention is not limited to described specific embodiment.On the contrary, the present invention covers all improvement in its principle and the scope, is equal to and replaces.
Invention specifies
The invention provides have the molded three-dimensional that is applicable in the terminal cone zone of polluting control device every The method of the product of hot body and this product of manufacturing. Here used phrase " molded three-dimensional insulator " refers to also The non-insulator that is formed by heat insulation plane material. But with the mould with 3D shape or pressing mold form every Hot body. Be different from the insulator that is formed by sheet material, this molded three-dimensional insulator does not have to be opened and provides flat One or more seam of flat insulator.
Accompanying drawing 1 is depicted as the typical case who has endways insulator between the conoidal Shell inboard and the outside and pollutes control Device. Comprise in this pollution control device 10 outside the terminal cone with conical import 14 and outlet 16 Shell 12. This shell is also referred to as tank or cover, is usually made by metals such as stainless steels. Be positioned at shell 12 Section be the monoblock type block structure 18 of being made by pottery or metal material. Can in this monoblock type block structure Contain catalyst. Heat-barrier material 22 surrounds monoblock type block structure 18.
Comprise terminal conoidal Shell inboard 28 and terminal cone in the import 14 of metal shell and outlet 16 zones The external shell outside 26. Molded three-dimensional insulator of the present invention can be used as heat-barrier material 30.
Known from the terminal cone insulator of sheet material or bedding and padding preparation. Can with the sheet material of heat-barrier material or Bedding and padding cut into suitable size and shape, and itself and terminal cone intra-zone are mated. Such as, can Be formed with the taper of seam with the cutting sheet material. The size and dimension that sheet material or bedding and padding is cut into requirement can cause wave Take heat-barrier material. Molded three-dimensional heat insulation physical efficiency produces less waste. And, be difficult to or can't cutting blade Material is to adapt to the terminal cone with complicated shape.
The molded three-dimensional insulator that contains ceramic fibre is known. But some insulator is too hard, is difficult to Be located between the inboard and the outside of the terminal conoidal Shell that pollutes control device. Some insulator has not Uniform thickness. Heat-barrier material with uneven gauge also is difficult to be located in the end that pollutes control device In the cone zone.
One aspect of the present invention provides and has comprised that its size is applicable in the terminal cone zone of polluting control device The product of molded three-dimensional insulator. Comprise in this insulator that cubical contraction is no more than 10% ceramic fibre, Shrinkage factor is obtained by the thermomechanical analyzer test. This insulator is self-supporting and seamless, when packaging density is 0.4 have the compressibility value that is no more than 750,000 Ns/square metre during grams per milliliter. Can also wrap in this product Draw together and the insulator inner surface insulator outer surface, or the terminal cone of the pollution control device of its combination combination Shell.
Accompanying drawing 2 is depicted as a kind of molded three-dimensional insulator 50 with internal surface 52 and outside surface 54.The internal surface 52 of thermally-insulated body 50 can with the terminal conoidal Shell inner abutment of the pollution control device of the inside.The outside surface 54 of thermally-insulated body 50 can with the terminal conoidal Shell adjacency of the pollution control device of outside.Can adopt other shapes, conical substantially thermally-insulated body in the terminal cone zone of polluting control device is provided.A kind of shape is as shown in accompanying drawing 3.
The ceramic fiber that is suitable for has that thermomechanical analyzer (TMA) test obtains is no more than 10% volumetric shrinkage.In the TMA test, load (such as 50 pounds/square inch or 345 Ns/square metre) sample is heated to 1000 ℃ of coolings then.Sample slide calliper rule diameter when measuring 750 ℃ in the heating and cooling cycle calculates the percentage shrinking percentage.The percentage shrinking percentage equals in the heating and cooling step, and the difference of 750 ℃ of slide calliper rule diameters multiply by 100 and divided by 750 ℃ of slide calliper rule diameters in the heating steps.Can test the thermally-insulated body that characterizes ceramic fiber or prepare with TMA by ceramic fiber.When the temperature of thermomechanical analyzer reached 750 ℃, the most of or whole organic substances that contain in the thermally-insulated body all were removed.
In certain embodiments, the volumetric shrinkage of ceramic fiber is no more than 10%, is no more than 8%, is no more than 6%, is no more than 4%, is no more than 3%, is no more than 2%, perhaps is no more than 1%.The shrinking percentage of ceramic fiber is at least 0.5% usually.In certain embodiments, TMA tests the ceramic fiber volumetric shrinkage of acquisition 0.5 to 2%, 0.5 to 3%, 0.5 to 5%, or in 0.5 to 6% the scope.
Volumetric shrinkage during supply is no more than that 10% commercially available ceramic fiber example (when supplying without thermal treatment with regard to the available fiber) includes, but are not limited to crystalline form and contains Al
2O
3(being aluminum oxide) and SiO
2The fiber of (silicon oxide).Al
2O
3To SiO
2Weight ratio (Al
2O
3: SiO
2) more than or equal to 60: 40,65: 35,70: 30,72: 28,75: 25,80: 20,90: 10,95: 5,96: 4,97: 3 or 98: 2.In some specific embodiment, contain in the ceramic fiber and account for the Al that this total weight of fiber is 60 to 98 weight %
2O
3SiO with 2 to 40 weight %
2In some specific embodiment, contain in the ceramic fiber and account for the Al that this total weight of fiber is 70 to 98 weight %
2O
3SiO with 2 to 30 weight %
2Other oxide compounds that can contain trace.Here used term " trace " is meant that content is no more than 2 weight %, is no more than 1 weight %, perhaps is no more than 0.5 weight %.
The ceramic fiber that is suitable for not heat-treating and uses includes, but are not limited to following material, from Mitsubishi Chemical (Tokyl, Japan) product of buying with trade(brand)name " MAFTEC " (such as MLS1, MLS2 and MLS3) contains and accounts for the SiO that total weight of fiber is 28 weight %
2Al with 72 weight %
2O
3(Widness Cheshire, the U.K.) product of buying with trade(brand)name " SAFFIL " (such as SF, LA Bulk, HA Bulk, HX Bulk) contain and account for the SiO that total weight of fiber is 3 to 5 weight % from Saffil Limited
2With 95 to the Al of about 97 weight %
2O
3With (Tonawonda, the NY) product of buying with trade(brand)name " UNIFRAXFIBERFRAX FIBERMAX " contain and account for the SiO that total weight of fiber is 27 weight % from Unifrax
2Al with 72 weight %
2O
3
In certain embodiments, can heat-treat to provide volumetric shrinkage commercially available ceramic fiber less than 10% ceramic fiber.Generally include Al in these fibers
2O
3And SiO
2Al
2O
3To SiO
2Weight ratio (Al
2O
3: SiO
2) more than or equal to 20: 80,30: 70,35: 65,40: 60,45: 55,50: 50,55: 45,60: 40 or 70: 30.Usually the SiO that contains at least 30 weight % in the ceramic fiber
2The Al of at least 20 weight %
2O
3Such as, can contain in the ceramic fiber that is suitable for and account for silicon oxide that total weight of fiber is 30 to 80 weight % and the aluminum oxide of 20 to 70 weight %.In some specific embodiment, can contain in the ceramic fiber and account for silicon oxide that total weight of fiber is 40 to 60 weight % and the aluminum oxide of 40 to 60 weight %.In other specific embodiments, contain in the ceramic fiber and account for silicon oxide that total weight of fiber is 45 to 55 weight % and the aluminum oxide of 45 to 55 weight %.Other oxide compounds that can contain trace.
The ceramic fiber example that is suitable for using after thermal treatment includes, but are not limited to following material, from Thermal Ceramic (Augusta, GA) ceramic fiber of buying with trade(brand)name " KAOWOOL HA BULK " contains and accounts for the SiO that total weight of fiber is 50 weight %
2Al with 50 weight %
2O
3From the ceramic fiber that ThermalCeramics buys with trade(brand)name " CERAFIBER ", contain and account for the SiO that total weight of fiber is 54 weight %
2Al with 46 weight %
2O
3From the ceramic fiber that Thermal Ceramics buys with trade(brand)name " KAOWOOL D73F ", contain and account for the SiO that total weight of fiber is 54 weight %
2Al with 46 weight %
2O
3(Wilmington, the DE) ceramic fiber of buying with trade(brand)name " RATH 2300RT " contain and account for the SiO that total weight of fiber is 52 weight % from Rath
2, the Al of 47 weight %
2O
3And be no more than the Fe of 1 weight %
2O
3, TiO
2With other materials; From the ceramic fiber that Rath buys with trade(brand)name " RATH ALUMINO-SILICATE CHOPPED FIBER ", contain and account for the SiO that total weight of fiber is 54 weight %
2, the Al of 46 weight %
2O
3Other materials with trace; (Buffalo, the NY) ceramic fiber of buying with trade(brand)name " CER-WOOL RT " contain and account for the SiO that total weight of fiber is 49 to 53 weight % from Vesuvius
2, the Al of 43 to 47 weight %
2O
3, the Fe of 0.7 to 1.2 weight %
2O
3, the TiO of 1.5 to 1.9 weight %
2With other materials that are no more than 1 weight %; From the ceramic fiber that Vesuvius buys with trade(brand)name " CER-WOOL LT ", contain and account for the SiO that total weight of fiber is 49 to 57 weight %
2, the Al of 38 to 47 weight %
2O
3, the Fe of 0.7 to 1.5 weight %
2O
3, the TiO of 1.6 to 1.9 weight %
2Other materials with 0 to 0.5 weight %; With the ceramic fiber of buying with trade(brand)name " CER-WOOL HP " from Vesuvius, contain and account for the SiO that total weight of fiber is 50 to 54 weight %
2, the Al of 44 to 49 weight %
2O
3, the Fe of 0 to 0.2 weight %
2O
3, the TiO of 0 to 0.1 weight %
2With other materials that are no more than 0.5 weight %.
Contain SiO among other embodiment of ceramic fiber that are suitable for after thermal treatment, using
2, Al
2O
3And ZrO
2Al
2O
3To SiO
2Weight ratio (Al
2O
3: SiO
2) more than or equal to 20: 80,30: 70,35: 65,40: 60,45: 55,50: 50,55: 45,60: 40 or 70: 30.Contain in the fiber and account for the ZrO of its gross weight at least 3 weight %
2, the SiO of at least 30 weight %
2The Al of at least 20 weight %
2O
3In certain embodiments, contain in the fiber and account for its gross weight and be no more than 5 weight %, be no more than 7 weight %, be no more than 10 weight %, be no more than 12 weight %, be no more than 15 weight %, be no more than 16 weight %, be no more than 20 weight %, or be no more than the ZrO of 25 weight %
2Can contain in the ceramic fiber that to account for total weight of fiber be 30 to 70 weight %, 40 to 65 weight %, 45 to 60 weight %, 45 to 55 weight %, the SiO of 50 to 60 weight %
2Can contain in the ceramic fiber that to account for total weight of fiber be 20 to 60 weight %, 25 to 50 weight %, 25 to 45 weight %, 25 to 40 weight %, 25 to 35 weight %, the Al of 30 to 50 weight % or 30 to 40 weight %
2O
3In certain embodiments, contain in the ceramic fiber and account for the Al that total weight of fiber is 25 to 50 weight %
2O
3, the SiO of 40 to 60 weight %
2ZrO with 3 to 20 weight %
2In other specific embodiments, contain in the ceramic fiber and account for the Al that total weight of fiber is 30 to 40 weight %
2O
3, the SiO of 45 to 60 weight %
2ZrO with 5 to 20 weight %
2Other oxide compounds that can contain trace.
Be suitable for after thermal treatment, using and containing SiO
2, Al
2O
3And ZrO
2The ceramic fiber example comprise following material, (Augusta, the GA) ceramic fiber of buying with trade(brand)name " KAOWOOL ZR " and " CERACHEM " contain and account for the SiO that total weight of fiber is 50 weight % from Thermal Ceramic
2, the Al of 35 weight %
2O
3ZrO with 15 weight %
2(Tonawonda, the NY) ceramic fiber of buying with trade(brand)name " UNIFRAXFIBERFRAX FIBERMAT " contain and account for the SiO that total weight of fiber is 52 to 57 weight % from Unifrax
2, the Al of 29 to 47 weight %
2O
3With the ZrO that is no more than 18 weight %
2From the ceramic fiber that Unifrax buys with trade(brand)name " UNIFRAX FIBERFRAX DURABACK ", contain and account for the SiO that total weight of fiber is 50 to 54 weight %
2, the Al of 31 to 35 weight %
2O
3, the ZrO of 5 weight %
2, the Fe of 1.3 weight %
2O
3, the TiO of 1.7 weight %
2, the MgO of 0.5 weight % and the CaO that is no more than 7 weight %; (Wilmington, the DE) ceramic fiber of buying with trade(brand)name " RATH 2600HTZ " contain and account for the SiO that total weight of fiber is 48 weight % from Rath
2, the Al of 37 weight %
2O
3, the ZrO of 15 weight %
2With other materials that are no more than 1 weight %; With (Buffalo, the NY) ceramic fiber of buying with trade(brand)name " CER-WOOL HTZ " contain and account for the SiO that total weight of fiber is 44 to 51 weight % from Vesuvius
2, the Al of 33 to 37 weight %
2O
3, the ZrO of 13 to 19 weight %
2, the Fe of 0.1 to 0.6 weight %
2O
3, the TiO of 0.1 to 0.6 weight %
2With other materials that are no more than 1 weight %.
Devitrification (promptly becoming crystallite or crystal state from metamict at least on the part degree) can take place in ceramic fiber in heat treatment process.Usually has only the independent ceramic fiber generation devitrification of part.Be after the thermal treatment, contain amorphous substance and crystalline substance in some independent ceramic fibers, crystallite material, or the mixing of crystal and crystallite material.
Can adopt the amorphous of transmission electron microscope and X-ray diffraction characterized by techniques ceramic fiber, crystal or crystallite character.Here used term " amorphous " is meant the ceramic fiber that does not have crystal or crystallite zone.If ceramic fiber is unbodied, then adopt transmission electron microscope or X-ray diffraction technology can not detect diffraction peak (promptly not having diffraction image).If contain small size crystal block section (being crystallite) in the ceramic fiber, then adopt transmission electron microscopy can detect diffraction peak (being diffraction image), and adopt X-ray diffraction can not detect diffraction peak.Here used term " crystallite " is meant the part that has the part crystalline nature in the ceramic fiber at least, and its crystalline size can be detected by transmission electron microscope, but can not be detected by X-ray diffraction.If contain larger sized crystal block section (being crystal) in the ceramic fiber, then can adopt the X-ray diffraction technology to obtain diffraction image.Here used term " crystal " is meant that the subregion at least in the ceramic fiber has crystalline nature, and its crystalline size can be arrived by the X-ray diffraction technology for detection.Adopt the X-ray diffraction technology can detected minimum crystal dimension can produce usually and clearly do not define the diffraction image at peak than broad.Bigger crystalline size is represented at narrower peak.Can determine crystalline size with the width of diffraction peak.
In some applications, under at least 700 ℃ temperature, ceramic fiber is heat-treated.Such as, can be at least 800 ℃, at least 900 ℃, under the temperature of at least 1000 ℃ or at least 1100 ℃ ceramic fiber is heat-treated.The proper heat treatment temperature keeps the time of thermal treatment temp along with the composition of ceramic fiber and ceramic fiber and changes.International Patent Application WO 99/46028 and United States Patent (USP) 5250269 have further described proper heat treatment method and the heat treated ceramic fiber of process in the reference.
Crystal that forms in heat treatment process or crystallite dimension are relevant with time-temperature relation.Such as, can heat-treat ceramic fiber with the long period at a lower temperature, perhaps under comparatively high temps, ceramic fiber is heat-treated with the short period, form similar crystal or microcrystalline state.Keep the time of thermal treatment temp to be no more than 1 hour, be no more than 40 minutes, be no more than 30 minutes, be no more than 20 minutes, be no more than 20 minutes, be no more than 5 minutes, be no more than 3 minutes or be no more than 2 minutes.Such as, select the proper heat treatment temperature, be no more than 10 minutes short period thermal treatment.
Thermal treatment temp is higher at least 20 ℃ than devitrification temperature (be ceramic fiber when amorphous material becomes crystallite or crystalline material temperature), and at least 30 ℃, at least 40 ℃, at least 50 ℃, at least 60 ℃, at least 70 ℃, at least 80 ℃, at least 90 ℃ or at least 100 ℃.Can determine suitable ceramic fiber heat treatment time and temperature by differential thermal analysis (DTA) technology.For aluminium oxide-silicon oxide fibre, temperature is usually at 700 to 1200 ℃, and 800 to 1200 ℃, in the scope of 900 to 1200 ℃ or 950 to 1200 ℃.
With contain crystallite, the ceramic fiber of crystal or its mixing region is compared, complete unbodied ceramic fiber can produce usually greatly and to shrink.When amorphous fiber was made molded said three-dimensional body, remarkable contraction can take place when polluting the high temperature that can reach in the control device being heated in this product.Use when containing the lagging material of amorphous fiber in the terminal cone zone of polluting control device, the lagging material that shrinks because of heating can move between the terminal conoidal Shell inboard and the outside.This mobile meeting is broken lagging material, the forfeiture heat-blocking action.
At least the made molded three-dimensional insulator of ceramic fiber that contains part crystal or crystallite can be repeated to be heated to the Applicable temperature that pollutes control device, cooling then.Crystallite or crystalline ceramic fiber have ability to bear for the further contraction that meeting influences the thermally-insulated body performance.
For through heat treated ceramic fiber, there is poising action between the fragility of fiber and the low-shrinkage.Crystal or micro crystal material ceramic fiber are more crisp than amorphous ceramic fiber.The lagging material of being made by crystal or micro-crystalline ceramic fiber compares easier fracture of thermally-insulated body of being made by amorphous fiber.On the other hand, crystal or micro-crystalline ceramic fiber can have lower shrinking percentage than amorphous ceramic fiber.
When packaging density is 0.4 grams per milliliter, thermally-insulated body of the present invention has and is no more than 750,000 Ns/square metre, is no more than 700,000 Ns/square metre, is no more than 650,000 Ns/square metre, be no more than 600,000 Ns/square metre, be no more than 550,000 Ns/square metre, be no more than 500,000 Ns/square metre, be no more than 450,000 Ns/square metre, be no more than 400,000 Ns/square, be no more than 300,000 Ns/square metre, be no more than 200,000 Ns/square metre, or be no more than 100,000 Ns/square metre compressibility value.When packaging density was 0.4 grams per milliliter, the compressibility value was 50,000 Ns/square metre usually at least; But, if packaging density, then can use the thermally-insulated body with low compressibility value greater than 0.4 grams per milliliter.Here used term " packaging density " is meant thermally-insulated body density in the fixed interval (FI) (such as thermally-insulated body usually under pressure).In certain embodiments, when packaging density was 0.4 grams per milliliter, the compressibility value was 75,000 Ns/square metre or at least 100 thousand Ns/square metre at least.Such as, compressibility value at 50 to 750,000 Ns/square metre, 50 to 500,000 Ns/square metre, 50 to 300,000 Ns/square metre, 75 to 400,000 Ns/square metre, 75 to 300,000 Ns/square metre, in the scope of 100 to 400,000 Ns/square metre or 100 to 300,000 Ns/square metre.Fracture or cracked phenomenon can not take place during the compression thermally-insulated body.
Thermally-insulated body is normally flexible.Here used term " pliable and tough " is meant that the 3D shape of thermally-insulated body can deform or bending, and pollutes the shell inboard, China and foreign countries, terminal cone zone of control device and the form fit between the outside, and does not break fracture or cracked.Flexible thermally-insulated body can be compressed on thickness direction usually.
Second aspect present invention also provides a kind of its size to be applicable to pollute the molded three-dimensional insulator in the terminal cone zone of control device.Comprise in the thermally-insulated body containing and account for the ceramic fiber of total weight of fiber for the silicon oxide of the aluminum oxide of at least 20 weight % and at least 30 weight %.Ceramic fiber is a crystallite, crystal or its mixed form.Thermally-insulated body is a self-supporting and seamless, when packaging density is about 0.4 grams per milliliter, has the compressibility value that is no more than 750,000 Ns/square metre.The ceramic fiber that is suitable for as mentioned above.Can also comprise and the thermally-insulated body internal surface the terminal conoidal Shell of the pollution control device of thermally-insulated body outside surface or its built up section in the product.
The method that forms molded three-dimensional insulator is: preparation earlier contains the water slurry of ceramic fiber.Except ceramic fiber, can contain organic binder bond in the water slurry composition.Organic binder bond can improve globality, suppleness and the processibility of molded three-dimensional insulator.More flexible lagging material can be located between the terminal conoidal Shell inboard and the outside of polluting control device more simply.
The consumption of organic binder bond accounts for thermally-insulated body weight and is no more than 20 weight %.In certain embodiments, the content of organic binder bond accounts for thermally-insulated body weight and is no more than 10 weight %, is no more than 5 weight %, perhaps is no more than 3 weight %.When in polluting control device, using thermally-insulated body under the common high temperature, can from thermally-insulated body, burn usually and remove organic binder bond.
The organic binder bond material that is suitable for comprises polymer water emulsion, solvent based polyalcohol and not solvent-laden polymkeric substance.The organic binder bond polymkeric substance and the elastomerics (such as the natural rubber breast, styrene-butadiene latex, the latex of butadiene-acrylonitrile latex and acrylate and methacrylate polymers or multipolymer) that comprise the latex form in the polymer water emulsion.Solvent base polymeric adhesive agent material comprises vinylformic acid, urethane, vinyl-acetic ester, polymkeric substance such as Mierocrystalline cellulose or rubber-based organic polymer.Not solvent-laden polymkeric substance comprises natural rubber, styrene butadiene rubbers and other elastomericss.
In certain embodiments, the organic binder bond material comprises the vinylformic acid aqueous emulsion.The advantage of ACRYLIC EMULSION is to have good ageing property, and can form does not have corrosive products of combustion.The ACRYLIC EMULSION that is suitable for includes, but are not limited to (Philadelphia, PA) product of buying with trade(brand)name " RHOPLEXTR-934 " (a kind of solids content is the vinylformic acid aqueous emulsion of 44.5 weight %) and " RHOPLEX HA-8 " (a kind of solids content is the acrylic copolymer aqueous emulsion of 45.5 weight %) from Rohm and Hass; From ICIResins US (Wilmington, MA) product of buying with trade(brand)name " NEOCRYL XA-2022 " (a kind of solids content is 60.5% acrylic resin water dispersion); With from Air Products and Chemical, Inc. (Philadelphia, PA) product of buying with trade(brand)name " AIRFLEX 600BP DEV " (a kind of solids content is the ethylene vinyl acetate terpolymer aqueous emulsion of 55 weight %).
Organic binder bond also comprises softening agent, tackifier or its mixing.Softening agent can soften polymeric matrix, improves the snappiness and the moldability of thermally-insulated body.Such as, can comprise softening agent in the organic binder bond, such as from Monsanto (St.Louis, MO) the bisphosphate isodecyl diphenyl ester of buying with trade(brand)name " SANTICIZER 148 ".Tackifier or tackifying resin help lagging material is combined.A kind of suitable tackifier are from Eka Nobel, Inc. (Toronto, Canada) product of buying with trade(brand)name " SNOWTACK 810A ".
Can comprise the mineral colloid material in the water slurry.This mineral colloid material plays the effect of inorganic adhesive, helps to remove ceramic fiber from water slurry as condensing agent, forms molded three-dimensional preformed body, also plays the effect of filler, perhaps plays this two effects simultaneously.Mineral colloid is clay or metal hydroxides normally.
In some applications, the mineral colloid material forms under the ceramic fiber existence condition.The method that forms the mineral colloid material is: add one or more water-soluble precursors in water slurry.Preceding physical efficiency is reacted in water slurry and is formed metal hydroxides.In water slurry, form the mineral colloid material cohesion of mineral colloid is minimized, improve the whole slurry and the homogeneity that mineral colloid distributes in the precast body that forms.The pH of slurry should be high enough to form metal hydroxides.By change pH, reaction times and temperature, precursor concentration and precursor relative proportion can change the size of colloidal solid.The pH of slurry is at least about 3 usually.The mineral colloid material that is suitable for comprises metal hydroxides, such as aluminium hydroxide, and silicon hydroxide, titanium hydroxide, yttrium hydroxide or its mixing.
An example of mineral colloid metal hydroxides is alkali metal aluminate and aluminium reactant salt and the aluminium hydroxide that forms.More particularly, can be by sodium aluminate and Tai-Ace S 150, aluminum phosphate, aluminum chloride, aluminum nitrate or the reaction of its blended form aluminium hydroxide.Another kind of colloidal aluminium hydroxide is to be at least about 3 and formed by Tai-Ace S 150 by the pH regulator with slurry.
The mineral colloid material accounts for the ceramic fiber gross weight usually and is no more than 50 weight %.In certain embodiments, the content of mineral colloid material accounts for the ceramic fiber gross weight and is no more than 40 weight %, is no more than 30 weight %, is no more than 20 weight %.Such as, can be that the sodium aluminate of 1 to 20 weight % mixes with the Tai-Ace S 150 of 1 to 20 weight % with accounting for the ceramic fiber gross weight, form alumine hydroxide colloid.In example more specifically, the sodium aluminate of 3 to 15 weight % can be mixed with the Tai-Ace S 150 of 3 to 15 weight %, perhaps the sodium aluminate with 5 to 12 weight % mixes with the Tai-Ace S 150 of 5 to 12 weight %, forms alumine hydroxide colloid.In other embodiments, can prepare alumine hydroxide colloid from Tai-Ace S 150.Such as, prepare alumine hydroxide colloid from accounting for Tai-Ace S 150 that the ceramic fiber gross dry weight is 10 to 40 weight % or the Tai-Ace S 150 of 15 to 30 weight %.The per-cent of every kind of precursor (such as Tai-Ace S 150 or sodium aluminate) heavily is benchmark with presoma all.
The mineral colloid material plays the effect of tackiness agent, and ceramic fiber is combined.In some applications, inorganic adhesive can improve the temperature buffer of thermally-insulated body.Organic binder bond can issue estranged separating at the high temperature in polluting control device usually.The thermally-insulated body that does not contain inorganic adhesive can rupture in some cases, and the forfeiture heat insulating function.
The mineral colloid material can be dispersed in the molded three-dimensional insulator.At this moment, thermally-insulated body can keep globality when making and use the product that contains thermally-insulated bodys such as pollution control device.
In certain embodiments, product comprises one or two terminal conoidal Shell of molded three-dimensional insulator and pollution control device.Terminal conoidal Shell can with the internal surface of thermally-insulated body, outside surface is adjacent, perhaps adjacent with its surfaces externally and internally simultaneously (that is, thermally-insulated body can between two terminal conoidal Shells).Terminal conoidal Shell during some is used links to each other with thermally-insulated body.Terminal conoidal Shell links to each other by frictional force.
Third aspect present invention provides the manufacture method that comprises the product that is applicable to the molded three-dimensional insulator in the terminal cone zone of polluting control device.This method comprises the preparation water slurry, forms molded three-dimensional preformed body with the water slurry vacuum forming and dry precast body forms molded three-dimensional insulator on the perviousness moulding stamper.The water slurry that is used for preparing precast body comprises that volumetric shrinkage is no more than 10% ceramic fiber, and shrinking percentage is tested acquisition on thermomechanical analyzer.Thermally-insulated body is a self-supporting, when packaging density is 0.4 grams per milliliter, has the compressibility value that is no more than 750,000 Ns/square metre.
Usually contain in the water slurry that to account for the slurry gross weight be the solid that is no more than 30 weight %.Such as, contain in the slurry and account for the solid that the slurry gross weight is no more than 20 weight % or is no more than 10 weight %.Usually contain the solid that accounts for slurry gross weight at least 1% in the slurry.Such as, contain the solid of at least 2 weight % or at least 3 weight % in the slurry.In certain embodiments, contain 1 to 10 weight % in the slurry, the solid of 2 to 8 weight % or 3 to 6 weight %.Solids content is higher to be favourable, because at this moment only need remove less water just can prepare precast body.But solids content can more difficult mixing than higher slurry.
Used water can be well water in the slurry, surface water, or desalt and the water of impurity such as organic compound through handle removing.When using well water or surface water in water slurry, the salt in the water (such as calcium salt and magnesium salts) plays the effect of inorganic adhesive.In certain embodiments, used water is deionized water, distilled water or its mixing.
Can also contain other additives in the water slurry composition.These additives comprise defoamer, the agent of wadding a quilt with cotton with fixed attention, tensio-active agent and analogue.Can also contain toughener, such as organic fibre and glass fibre.The organic fibre that is suitable for comprises artificial silk and cellulosic fibre.
In some applications, do not contain expanding material in the slurry.Expanding material tends to separate from molded three-dimensional insulator.When one reason dissociated out from thermally-insulated body, expanding material can move and impact thermally-insulated body or monoblock type lumphy structure.Such as, when being used for polluting the terminal cone zone of control device, have the vehicle that pollutes control device if start, then expanding material can bump thermally-insulated body or one-piece construction.The disruptive possibility takes place and increases in thermally-insulated body under this condition.Situation is very serious if break, and then this product can't continue to play the effect of lagging material.If big chip enters in the import, then the monoblock type lumphy structure also can begin to stop up.
During the preparation water slurry, at first in water, add ceramic fiber and fully stirring.In certain embodiments, use the low mixer of shearing.Can use and anyly can excessively not cut off the blending means of ceramic fiber.With compare without heat treated fiber, rupture through heat treated fiber is easier.Compare with having more the thermal treatment ceramic fiber of macrocrystal, the micro-crystalline ceramic fiber is more difficult to rupture.
Ceramic fiber in the water slurry composition has usually and is no more than 40 millimeters mean length.In certain embodiments, mean length is no more than 30 millimeters, is no more than 25 millimeters, is no more than 20 millimeters, is no more than 15 millimeters, or is no more than 10 millimeters.Mean length is usually greater than 0.5 millimeter.In certain embodiments, mean length is greater than 1 millimeter or greater than 2 millimeters.Such as, not 0.5 to 40 millimeter of average fiber length, 0.5 to 25 millimeter or 1 to 40 millimeter.
The mean diameter of suitable ceramic fiber is no more than 20 microns usually.In certain embodiments, mean diameter is no more than 10 microns or be no more than 8 microns.Mean diameter is usually greater than 0.5 micron, 1 micron or 2 microns.
Though can after forming the ceramic fiber water slurry, add organic binder bond more usually according to the component of any sequential addition of water slurry.Can after in water slurry, adding organic binder bond, add the precursor of mineral colloid material or mineral colloid material again.In reaction process, to continue to stir, form the mineral colloid material, guarantee that colloidal materials is blended in the slurry equably.
Can use any suitable molding technique as known in the art or mould to make precast body.In some applications, can adopt vacuum forming technology to prepare molded three-dimensional preformed body.The perviousness moulding stamper is placed slurry.When vacuumizing, the solid in the slurry can be deposited on the surface of moulding stamper.In some applications, can remove moulding stamper from slurry, the shape identical with moulding stamper with shape keeps the device pairing.Sedimentary ceramic fiber keeps between the device at moulding stamper and formation.This shape keeps device and moulding stamper to be pressed together, and further gets rid of moisture, forms the precast body that has smoother surface and compare uniform thickness.Shape keeps device or moulding stamper to can be used as male mold part (that is, if moulding stamper is a male mold part, then shape maintenance device is a female die member, if perhaps moulding stamper is a female die member, then forming the maintenance device is male mold part).
Can comprise screen cloth in the perviousness moulding stamper.Can select suitable mesh size, make liquid ingredient rather than ceramic fiber pass through screen cloth.Such as, mesh size scope can be 20 (about 850 microns) to 80 orders (about 180 microns), or 30 (about 600 microns) are to 80 orders.If mesh size is too little, then screen cloth is easy to blocked.If mesh size is too big, then screen cloth can't keep ceramic fiber (promptly can't form precast body).Under the routine operation condition, have the part solid when drawing back vacuum and from slurry, be deposited on the screen cloth.
Can be with the molded three-dimensional insulator of the dry formation of precast body.If precast body is quite firm, then can not use upholder to carry out drying.That is, on moulding stamper, after the moulding, can from pressing mold, remove precast body, further dry.In certain embodiments, use moulding stamper, shape keeps device or its combination to support dry precast body simultaneously.This additional upholder helps to prevent that precast body was damaged before exsiccation and hardening.Can use any method as known in the art that precast body is carried out drying.Such as, can in baking oven or at room temperature, carry out drying to precast body.When carrying out drying in baking oven, temperature can be up to about 200 ℃.In some applications, drying temperature can be up to about 150 ℃ or 125 ℃.
In some applications, can in the contact moudling pressing mold, carry out drying to precast body.In the drying process, use one air or nitrogen gas stream to purge moulding stamper.Purging the air of moulding stamper or nitrogen gas stream and can be room temperature or high temperature can.Can purge or impact precast body and moulding stamper surface in contact opposed outer surface with other air or nitrogen gas stream.
In some applications, United States Patent (USP) 5078822 is similar with the described content of 6596120B2 in molding process and the reference.Can use and comprise that multi-part pressing mold and shape keep the die module of device to make the three-dimensional preformed body.The multi-part pressing mold is the perviousness moulding stamper, generally includes inner frame and shell.Have vacuum system in the whole inside of inner frame, can in pressing mold, provide vacuum take-off and vacuum to distribute.The shell of moulding stamper has screen cloth.Such as, the mesh size of screen cloth is 20 to 80 orders.The multi-part moulding stamper is a perviousness.Die module can be placed slurry, can keep separating the device multi-part moulding stamper from shape like this.
Vacuum unit can be linked to each other with the multi-part moulding stamper, deposition contains the layer of ceramic fiber on moulding stamper.The outside dimension of settled layer (being the outside dimension of precast body) equals at least, if not slightly greater than, the interior dimensions that lay the overseas shell of the terminal pyramidal area of pollution control device of the thermally-insulated body that makes.Under wet condition, in the precast body inserted-shape maintenance device that pressing mold can be supported (such as, shape keeps device to can be used as the external end conoidal Shell that pollutes control device).When keeping device or precast body to keep device to take place to contact fully precast body part inserted-shape, can remove moulding stamper with shape.In some applications, the precast body contact shape keeps device still to obtain the support of moulding stamper simultaneously.
Perhaps, the size and dimension of multi-part moulding stamper can prepare with shape keep device matching precast body (such as, shape keeps device to can be used as the interior extremity conoidal Shell that pollutes control device).Under wet condition, the precast body inserted-shape that moulding stamper can be supported keeps in the device.Precast body is kept in the device by the part inserted-shape or precast body when keeping the device generation to contact fully with shape, can remove pressing mold.In some applications, the precast body contact shape keeps device still to obtain the support of moulding stamper simultaneously.
Can on precast body, exert pressure, increase the exposure level between precast body and the shape maintenance device.That is, precast body can be pressed into shape keeps in the device.Can be by removing the vacuum that puts on moulding stamper, by to perviousness moulding stamper application of air or nitrogen,, precast body is transferred to shape keep in the device perhaps by additive method as known in the art and take out moulding stamper.Remove after the moulding stamper, keep the molectron of device to place baking oven, transpiring moisture from precast body precast body and shape.
When the precast body between moulding stamper and shape maintenance device was exerted pressure, prefabricated physical efficiency was pressed into shape and keeps in the device.In some applications, precast body can keep dry in the device in shape, forms by friction and shape to keep device bonded thermally-insulated body.Such as, can make and the inside or the external end conoidal Shell bonded thermally-insulated body that pollute control device.
Precast body and shape keep the pressure fitted of device can form the thermally-insulated body with smoother surface.That is, compare with the thermally-insulated body that only uses moulding stamper preparation, often more level and smooth by precast body being pressed into the thermally-insulated body that shape keeps device to make.And the pressure fitted by precast body and shape maintenance device can improve precast body and the thickness evenness that makes thermally-insulated body.
Precast body is pressed into shape to be kept can also forming the thermally-insulated body with clean edge in the device.That is, exert pressure and to cut off the ceramic fiber of precast body edge, reduce extending beyond the ceramic fiber quantity that shape keeps device edge.
In some applications, other inorganic adhesive can be applied to the surface of molded three-dimensional insulator, thermally-insulated body further hardens.Such as, can be before or after drying, the solution of other inorganic adhesive is coated on the internal surface or outside surface of 3D shape.The other inorganic adhesive that is suitable for comprises, such as alumina sol, titanium oxide sol, zirconia sol, colloid silica suspensoid, clay, fire-resistant coating be such as the silicon carbide suspensoid, perhaps aluminium or phosphatic solution.Use suitable other inorganic adhesive can provide pliable and tough with consistent thermally-insulated body usually.If used too much inorganic adhesive, then thermally-insulated body may become too hard (promptly not pliable and tough) and can't compress (that is the force value when, packaging density is about 0.4 grams per milliliter is greater than 750,000 Ns/square metre).The other inorganic adhesive that adds on the precast body surface is no more than the 1 weight % that accounts for precast body or thermally-insulated body dry weight usually.Such as, the consumption that is added to lip-deep other inorganic adhesive is no more than 5 weight % of precast body or thermally-insulated body dry weight, is no more than 3 weight % or is no more than 1 weight %.
During other were used at some, other organic binder bond or material can be used as the internal surface that coating is coated on thermally-insulated body, the outside surface of thermally-insulated body, or its combination.Use the slickness that this coating can improve thermally-insulated body, reduce the friction of thermally-insulated body, simplify being positioned to pollute between the inside and outside shell in control device terminal cone zone thermally-insulated body or the operation of its combination.Can comprise in the organic coating, such as polyolefine material or acryhic material.
The variation in thickness of thermally-insulated body depends on application.The variable that influences thickness is such as being time length and vacuum tightness.Time length, long more (being moulding pressing mold time span in slurry under vacuum condition) can cause forming thicker precast body and thermally-insulated body usually.Similarly, the vacuum tightness of identical time length Nei Genggao can cause forming thicker precast body and thermally-insulated body usually.In polluting the terminal cone zone of control device during as heat insulation device, the thickness of thermally-insulated body usually in 1 to 25 millimeter scope, in certain embodiments, thickness whole be uniform in shape.Thickness evenness is subjected to the influence (being that smaller ceramic fiber tends to form the more uniform precast body of thickness) of ceramic fiber size.Easier being located between the outside and inner shell of polluting the terminal cone of control device zone of thermally-insulated body with suitable uniform thickness.
The bulk density of molded three-dimensional insulator (density when promptly not having pressure) changes along with the process of preparation thermally-insulated body.Bulk density is usually in the scope of 0.1 to 0.4 grams per milliliter.In certain embodiments, thermally-insulated body has 0.15 to 0.3,0.2 to 0.4, or the bulk density of 0.2 to 0.3 grams per milliliter.
Fourth aspect present invention provides and has comprised the manufacture method that is applicable to the product that pollutes the molded three-dimensional insulator in the terminal cone of the control device zone.This method comprises the preparation water slurry, forms molded three-dimensional preformed body with the water slurry vacuum is in full bloom on the perviousness moulding stamper, and with the molded three-dimensional insulator of the dry formation of precast body.The water slurry that is used for preparing precast body comprises the ceramic fiber that contains at least 20 weight % aluminum oxide and at least 30 weight % silicon oxide.Ceramic fiber can be a crystallite, crystal or its mixed form.Thermally-insulated body is a self-supporting, when packaging density is 0.4 grams per milliliter, has the compressibility value that is no more than 750,000 Ns/square metre.
The method for preparing molded three-dimensional insulator can be used to prepare seamless or make part.In certain embodiments, this product is seamless.Here used term " seamless " is meant does not have thermally-insulated body to form material separation or non-continuous event in the molded three-dimensional insulator, such as cut channel in the lagging material or notch.That is to say do not have notch in the seamless thermally-insulated body, cut channel, other separation phenomenons of the release stress that perhaps in the thermally-insulated body subregion, forms.Accompanying drawing 2 and 3 is synoptic diagram of seamless molded three-dimensional insulator.Any lines of representing on the product surface are all represented shade, are used to show 3D shape.
In other embodiments, can prepare the thermally-insulated body that seam is arranged.Here used term " seam " is meant the material separation phenomenon, such as cut channel in the lagging material or notch.Can discharge stress with seam, perhaps improve the consistence (that is, in some applications, seam can strengthen the ability of the outside of polluting control device and interior extremity conoidal Shell between location thermally-insulated body) of thermally-insulated body in encapsulation process.Seam can extend on the thermally-insulated body thickness direction, and perhaps the whole thickness by thermally-insulated body extends.
Invention has been described by predictive embodiment for foregoing, and described content is feasible, but present unforeseen unsubstantiality improvement is equal to it.
Embodiment
Testing method
Volumetric shrinkage
Use has the volumetric shrinkage of the MFE-715 type Theta Dilatronic II thermal analyzer (from Theta Industries, Inc., Port Washington, NY acquisition) of chart recorder according to thermo-mechanical analysis (TMA) method mensuration ceramic fiber.With diameter is 11 millimeters round cutting fibre sample, and places on the pressing plate of process furnace.The 7 mm dia quartz pushrods (about 35.6 cm long) that support 1350 gram counterweights are placed on the sample, and close process furnace.This is equivalent to apply the load of about 50 pounds/square inch (345,000 Ns/square metre) on sample.Sample and counterweight were stablized about 5 minutes, be warming up to 1000 ℃ with 15 ℃/minute speed then.Baking oven reaches after 1000 ℃, closes process furnace and is cooled to room temperature.Sample cools off in process furnace.The slit that records between rod end and pressing plate equals thickness of sample, on chart recorder the thickness of sample in the heating and cooling cycle is mapped.Calculate contraction percentage with the 750 ℃ of thickness (T1) that write down in heating period and 750 ℃ of thickness (T2) of writing down in the cooling period.According to following equation volume calculated shrinking percentage:
The % volumetric shrinkage=[(T1-T2)/T1] * 100.
Can be to containing or not having the sample of organic binder bond material to carry out the TMA test.Organic materials usually can burnedly fall at about 500 ℃.In heating period, be fiber and inorganic adhesive and the particulate thickness that may exist basically at 750 ℃ of thickness of sample that record.Further during heated sample, if 750 ℃ of thickness that at this moment record less than the thickness of sample in heating period, are clearly in the cooling period in the filament contraction that takes place below 1000 ℃ then.
Compressibility
Compressibility be fixedly the lagging material in the hole under room temperature (such as about 20 to 25 ℃) to the tolerance of compression ability to bear, with the power of unit surface, thousand Ns of/square metre expressions.(Research Triangle Park, NC) the compression verification machine of Zhi Zaoing is taken advantage of on 3.8 centimetres the square lagging material sample at about 3.8 centimetres and is tested with MTS SystemsCorp.Test machine has immobilized press table and the top board that links to each other with load cell.Sample is placed on the press table, and the speed reduction top board with 30.48 centimeters/minute reaches the solid gap of being determined by the packaging density that requires.Compression sample when top board reaches the gap of packaging density setting first, lagging material shows peak action power.Stop pressing plate then, kept 15 seconds in this position, the relaxation of lagging material generation at this moment, the reactive force of generation reduces.Here used term " rate of compression value " is meant the rate of compression that maintenance recorded afterwards in 15 seconds.The rate of compression value depends on packaging density.
Packaging density be limit the space inner thermal insulator density (promptly, lagging material is under the pressure), be usually located in the terminal cone of the double-walled that pollutes control device between two nested concentric conoidal Shells (that is, terminal cone zone generally includes the thermally-insulated body between inboard and outer ends cone two shells).Terminal conoidal Shell is meant the shell that pollutes in the terminal cone of the control device zone.The packaging density of thermally-insulated body is normally uniform in whole thermally-insulated body between two terminal conoidal Shells, but also is not that such was the case with.With the basic weight (gram/square centimeter) of lagging material divided by the space (centimetre) can be in the hope of packaging density (grams per milliliter).The thermally-insulated body of cutting known area is also weighed and can be determined basic weight.
In pollution control device assembly with the terminal cone of double-walled, the abutment of thermally-insulated body and outer ends conoidal Shell, the outside surface of inside end conoidal Shell and thermally-insulated body adjacency.Perhaps thermally-insulated body is placed on the outside surface of inside end conoidal Shell, make the abutment of thermally-insulated body and outer ends conoidal Shell.These two terminal conoidal Shells are pressed together the thermally-insulated body between compression inboard and the outer ends conoidal Shell.Inboard and outer ends conoidal Shell is welded together in the less end of cone usually.Further the thermally-insulated body in two terminal conoidal Shell gaps is compressed, when terminal conoidal Shell is welded together first, in abutting connection with the unit surface reactive force maximum that thermally-insulated body produced of two shells.At short notice, relaxation can take place in thermally-insulated body usually between inboard and outside shell, and shell is produced less pressure.The pressure that reduces is enough to make thermally-insulated body to be retained in original position in use.
RCFT (full-scale condition device to test)
RCFT has simulated in the conventional use condition in the terminal cone of the double-walled gap on the metallic pollution control device, measures lagging material and is installed in the pressure that is produced under the situation between the device inboard and outer ends conoidal Shell under the simulated conditions being similar to.Lagging material is placed in two 50.8 millimeters and takes advantage of between 50.8 millimeters the stainless steel platen, makes pressing plate close, and the packaging density that makes lagging material is 0.4 grams per milliliter.Pressing plate is independently control, is heated to differing temps, simulates the inside end conoidal Shell temperature in the hot exhaust gas that is exposed to the outer ends conoidal Shell temperature in the low air at room temperature and is exposed to the pollution device in use.Pressing plate is heated to design temperature shown in the following table 4.According to from inboard and outer ends conoidal Shell in its value of trying to achieve of thermal expansivity under temperature separately, reduce and increase distance between pressing plate.Temperature on first pressing plate (being pressing plate 1) is elevated to about 450 ℃, and during higher slightly expansion situation that simulation inside end conoidal Shell takes place near hot exhaust gas the time, this gap slightly reduces.Along with temperature continues to increase, the expansion of metal on second pressing plate (being pressing plate 2), this gap slightly increases.Pressing plate 1 simulation inside end conoidal Shell, pressing plate 2 simulation outer ends conoidal Shells, platen temperature is as shown in following table 4.Use the computer-controlled load bracket of Sintech ID and from MTS Systems Corp., Research Triangle Park, the tension gage that NC obtains is measured the pressure that the fixed material is produced.Suitable thermally-insulated body can produce pressure usually in the gap in the whole heating and cooling cycle, particularly in pressing plate kept 900 ℃ and 530 ℃ 15 seconds, pressure at this moment was minimum.
Embodiment 1
Preparation contains 95.5 weight % water in 5 gallons of plastic lining drums, 2.95 weight % ceramic fibers, the slurry of 0.95 weight % sodium aluminate and 0.6 weight % activared carbon sulfur aluminium (the aluminum sulfate aqueous solution form with 50% is added).Use the low mixer of shearing of technical grade to carry out stirring at low speed, slowly add ceramic fiber in the 15.4 gug water in drum, increase the stirring velocity of mixer simultaneously, disperse ceramic fiber that the megalump of fiber is smashed.All ceramic fibers interpolations add sodium aluminate, stir about 3 minutes after finishing.Slowly add alum liquor then, restir slurry 5 minutes becomes evenly up to slurry.
It is from Thermal Ceramics that present embodiment prepares used ceramic fiber, Augusta, the aluminum silicate fiber that GA buys with trade(brand)name " KAOWOOL HA-BULK ".The composition of this ceramic fiber is about 50% aluminum oxide and 50% silicon oxide.Fiber is heat-treated, and the volumetric shrinkage that the TMA test is determined is 4.5%, heats bulk fibres about 3 minutes at 1060 ℃, carries out sufficient thermal treatment.After Overheating Treatment, the mean diameter of fiber is about 3 microns, and mean length is less than about 10 millimeters.When using X-ray diffraction analysis, be source of radiation with copper K α line, 2 θ angles are about 22.5 broad peak when spending.Contain crystalline region in the fiber, but crystalline size is big inadequately, can't forms the narrow peak of diffraction.The heat treated identical fibre of process does not have about 47% volumetric shrinkage, and is unbodied.
The moulding stamper screen cloth side that will link to each other with vacuum system immerses in the slurry that mixes, and forms precast body.Pressing mold has the elliptic cone tee section that is formed by 50 eye mesh screens, and precast body is shaped as the open truncation elliptic cone in top and bottom.The cone open top is that diameter is about 10.5 centimetres of ellipses of taking advantage of 3.8 centimetres, and the cone base opening is that diameter is about 12.1 centimetres of ellipses of taking advantage of 4.3 centimetres.High about 7 centimetres of cone.The precast body wall thickness is about the 1.5-15 millimeter, and this depends on the processing conditions of selection.Can change dipping time and vacuum tightness, make thickness of sample and basic weight be suitable for final application.
Meet the requirements of after the wall thickness, from slurry, shift out pressing mold and the precast body that links to each other, cover precast body with plastics bag.Plastics bag is simulated the former of two part mold, keeps the precast body material to stay original position.Make vacuum continue several seconds again, up to the precast body hardening and discharged most of moisture.Close vacuum, in pressing mold, blast pressurized air, make the precast body demoulding, from pressing mold, shift out precast body carefully.
This precast body is self-supporting (that is, when placing the surface to go up, precast body can keep its shape basically, can not break or be out of shape).Dry precast body is 40 minutes in 150 ℃ baking oven, forms to be suitable for carrying out heat insulation tapered three-dimensional thermally-insulated body in the terminal cone zone of polluting device.The thermally-insulated body that makes is independently (that is can support when, thermally-insulated body is placed on the plane himself weight and can not break).When the thickness direction compress slightly discharged then, thermally-insulated body is rebound resilience (that is, the thickness of thermally-insulated body can recover, but not necessarily returns to original thickness, as long as pressure is no more than the rupture strength of fiber) slightly with hand.
Embodiment 2
In the stainless steel mixing tank for coating colors that is equipped with the online propeller type blender of high speed, add about 178 gug water, the preparation slurry.Slowly add 5.7 kilograms of heat treated ceramic fibers of process (as described in example 1 above), improve blender speed simultaneously, keep dispersion and smash the fiber megalump to maximum value.Add 1.1 kilograms of latex (solids content is the ethylene vinyl acetate terpolymer aqueous emulsion of 55 weight %, and from Air Products, Philadelphia, PA buys with trade(brand)name " AIRFLEX 600BP ") then, stir about 5 minutes.Add 1.9 kilograms of activared carbon sulfur aluminium then, the aqueous solution form adding with 50% solids content adds 178 gug water again, adds 90.7 gram defoamers (from Henkel, Germany buys with trade(brand)name " FOAMASTER III ") then.Stirred slurry about 10 minutes, up to becoming evenly.Pump into then in plastic-lined 55 gallons (208 liters) drums.With the dry weight is base (promptly not moisture), contains 78 weight % thermal treatment ceramic fibers in the said composition, 8 weight % latex, 13 weight % Tai-Ace S 150 and 1 weight % defoamer.
Stir slurry once more with blender, and blast air formation homogeneous dispersion.The multi-part moulding stamper is immersed in the slurry, on pressing mold from slurry deposition solid, up to meeting the requirements of thickness, weight and density, preparation taper precast body.On pressing mold from slurry deposition capacity solid, form thermally-insulated body after making the precast body drying, its target thickness is about the 8.0-9.0 millimeter, target weight is about 30 grams, target density is about 0.20 grams per milliliter.
Comprise inner frame and shell in the multi-part moulding stamper structure.Have vacuum system in the whole inside of inner frame, can in moulding stamper, realize the distribution of vacuum take-off and vacuum.The shell of moulding stamper has the screen cloth in per 6.45 square centimeters of 900 holes.The outside surface of the terminal cone interior extremity of shell shape and size and pollution control device double-walled conoidal Shell be complementary (that is, the shape of shell is corresponding to the inside end conoidal Shell that pollutes the terminal cone of control device zone).
The still moist precast body of the demoulding from the moulding stamper, at room temperature dried overnight forms thermally-insulated body.Perhaps can or use the dry precast body of other drying processs in baking oven.
The thermally-insulated body that makes has the shape of frustoconical sheets, and the top circular opening diameter is about 5.5 centimetres, and the oval opening diameter in bottom is about 15 centimetres and takes advantage of 10 centimetres.Isolate about 4.5 centimetres of height, thick about 8.2 millimeters.Independent thermally-insulated body has snappiness, and (that is, heat insulation physical efficiency can not be ruptured or break by slight bending; The snappiness thermally-insulated body is flexible) and elastic.The volumetric shrinkage of thermally-insulated body is about 4.5%.Compressibility to the thermally-insulated body material is tested, and data are as shown in table 1.These values are the average of 3 tests of each sample.
Embodiment 3
Use the pulp preparation precast body of die module from embodiment 2, this precast body is arranged in the outer ends conoidal Shell (that is, polluting the outer ends conoidal Shell of control device) that pollutes the terminal cone of double-walled on the control device.The die module that is used for this precast body comprises that multi-part moulding stamper and shape keep device.This multi-part moulding stamper has inner frame and shell.It is the outer ends conoidal Shell that is used to pollute control device that shape keeps device.The pressing mold of this multi-part pressing mold and the foregoing description 2 is similar, and difference is that the shell of multi-part moulding stamper is slightly smaller than polluting inside end conoidal Shell described in the terminal cone of the control device zone.This less moulding stamper can form outside dimension and keep device identical with shape, but its wall thickness is greater than the precast body of big moulding stamper manufacturing wall thickness.Shape keeps device with respect to the position of multi-part moulding stamper slurry to be flowed between shape maintenance device and the moulding stamper easily when this assembly is immersed in the slurry and vacuumize in moulding stamper.Meet the requirements of after precast body thickness and the density, stop to vacuumize, from slurry, take out whole assembly.Precast body is inserted into to form and keeps being subjected to the support of moulding stamper simultaneously in the device.Then air is blown out from moulding stamper, make precast body demoulding from pressing mold, precast body is pressed into shape keeps in the device.Can make precast body and shape keep the device stress coupling.The thermally-insulated body that can have clean edge by the preparation of pressure coupling.When moulding stamper and shape keep pushing precast body between the device, ceramic fiber that can the trim edge place.That is, there is not too much fiber around the edge of terminal cone thermally-insulated body.
Can keep keeping taking out the device dry precast body afterwards in the device or from shape in shape.Precast body can form the thermally-insulated body that size and outer appearnce are similar to embodiment 2 in dried overnight under the room temperature (about 20 to 25 ℃), and difference is that the wall of present embodiment thermally-insulated body is thicker.Terminal cone thermally-insulated body is independent, pliable and tough and elastic.The wall thickness increase allows compression thermally-insulated body when control device is polluted in assembling, and heat insulation physical efficiency maintenance compression to a certain degree is to be retained in original position in use.
Embodiment 4
Prepare slurry according to process described in the embodiment 2, difference is that slurry consists of 356 premium on currency, 5.7 kilograms of thermal treatment ceramic fibers, 1.07 kilograms of latex (AIRFLEX 600BP), 1.2 the activared carbon sulfur aluminum water solution of kilogram 50% solids content and 90.7 gram defoamers (FOAMASTER III).With the dry weight is base (promptly not moisture), and said composition is 82 weight % heat treatment of fibre, 8 weight % latex, 9 weight % Tai-Ace S 150 and 1 weight % defoamer.Prepare precast body according to process described in the embodiment 3, difference is that the size of multi-part moulding stamper is identical with the outside surface of inside end conoidal Shell in the terminal cone of the pollution control device zone basically.Use shape as described in example 3 above to keep device.The dry air precast body spends the night, and forms thermally-insulated body.
The outward appearance of this thermally-insulated body and size are similar to the thermally-insulated body of embodiment 3, and difference is that the wall thickness of taper thermally-insulated body is about 8.2 millimeters, and the interior dimensions of thermally-insulated body is roughly identical with the outside dimension of inside end conoidal Shell in the terminal cone of the pollution control device zone.Independently thermally-insulated body is pliable and tough and elastic.Volumetric shrinkage is about 4.5%, and the compressibility test result is as shown in table 3.
Embodiment 5
Prepare in the stainless steel mixing tank for coating colors with online propeller type mixer and to contain 96.2 weight % water, 2.97 weight % thermal treatment ceramic fiber (as described in example 1 above), 0.24 weight % sodium aluminate, 0.3 the slurry of the activared carbon sulfur aluminum water solution of weight % latex (AIRFLEX 600BP latex) and 0.3 weight %50% solids content.Contain about 183.6 liters (48.5 gallons) well water in the slurry.Mixer stirs with high speed when adding sodium aluminate.Slowly add ceramic fiber, improve mixer speed to maximum value, loosen collagen fibre is also smashed the fiber megalump.After the fiber dispersion, added latex and stir about 5 minutes.Slowly add alum liquor then, stirred slurry about 10 minutes, up to becoming evenly.Make thermally-insulated body according to process described in the embodiment 2.This independent thermally-insulated body is pliable and tough, and elastic, volumetric shrinkage is about 4.5%.The compressibility of test lagging material under different packaging densities and basic weight.The result is as shown in table 3.
Further use the full-scale condition device to test to estimate the terminal cone of embodiment 5, the result is as shown in table 4.In three heating and cooling cycles, between two pressing plates, keep-up pressure.
Embodiment 6
Prepare thermally-insulated body according to process described in the embodiment 3, difference is that used fiber is from Vesuvius, Buffalo, and the Cer-Wool HP fiber that NY obtains was 1060 ℃ of thermal treatments 3 minutes.It is fibrous that supplier provides is the Al of 44 to 49 weight %
2O
3, the SiO of 50 to 54 weight %
2, the Fe of 0 to 0.2 weight %
2O
3, the TiO of 0 to 0.1 weight %
2With less than other materials of 0.5 weight %.The volumetric shrinkage of this fiber is 3.2%.
Embodiment 7
Prepare thermally-insulated body according to process described in the embodiment 3, difference is that used fiber is that (Tokyo, Japan) the SNSC fiber of Huo Deing is through Overheating Treatment from ShinnikaTC.Fibrous is about 54 weight % silicon oxide and about 46 weight % aluminum oxide.This fiber 1060 ℃ through Overheating Treatment, volumetric shrinkage is 2.6%.
Embodiment 8-12
With preparing thermally-insulated body through heat treated various ceramic fibers.1060 ℃ ceramic fiber carry out table 5 shown in the thermal treatment of time.Give thermal treatment volumetric shrinkage afterwards.Fibrous as follows:
The Al that contains 46 weight %
2O
3SiO with 54 weight %
2KAOWOOL HP (obtaining) from ThermalCeramics;
The Al that contains 51 weight %
2O
3With 48 to 52% SiO
2CERWOOL HTA46 (obtaining) from Vesuvius;
The SiO that contains 50 weight %
2, the Al of 35 weight %
2O
3And the ZrO of 15 weight %
2KAOWOOL ZR (obtaining) from Thermal Ceramics;
The SiO that contains 28 weight %
2Al with 78 weight %
2O
3MAFTEC MLS (obtaining) from MitsubishiChemical; With
SAFILL LDM (obtaining) from Safill.
Claims (23)
1. product that comprises terminal cone thermally-insulated body, described terminal cone thermally-insulated body comprises that volumetric shrinkage that (a) thermomechanical analyzer records is no more than 10% ceramic fiber and (b) accounts for ceramic fiber weight and is the mineral colloid material less than 50 weight %, wherein said terminal cone thermally-insulated body is flexible, self-supporting, seamless, taper, and on thickness direction, can fully be compressed, to be compressed between the inboard of terminal conoidal Shell in polluting the terminal cone zone of control device and the outside, when packaging density was about 0.4 grams per milliliter, described terminal cone thermally-insulated body had the compressibility value that is no more than 750,000 Ns/square metre.
2. product as claimed in claim 1 is characterized in that, described product also comprises with the internal surface of described terminal cone thermally-insulated body and linking to each other, and links to each other with the outside surface of described terminal cone thermally-insulated body, perhaps the terminal conoidal Shell of the pollution control device of combined situation.
3. product as claimed in claim 1 is characterized in that, comprises in the described ceramic fiber accounting for the Al of its weight at least 20 weight %
2O
3The SiO of at least 30 weight %
2
4. product as claimed in claim 3 is characterized in that described ceramic fiber is a crystal, crystallite or its array configuration.
5. product as claimed in claim 1 is characterized in that, when packaging density was about 0.4 grams per milliliter, described terminal cone thermally-insulated body had the compressibility value that is no more than 600,000 Ns/square metre.
6. product as claimed in claim 1 is characterized in that, described terminal cone thermally-insulated body also comprises organic binder bond.
7. product as claimed in claim 1 is characterized in that, described terminal cone thermally-insulated body does not contain expanding material.
8. a pollution control device that comprises as each described product among the claim 1-7 is characterized in that, described terminal cone thermally-insulated body is clipped between the inboard and terminal conoidal Shell of the terminal conoidal Shell outside.
9. pollution control device that comprises terminal cone thermally-insulated body, described terminal cone thermally-insulated body are clipped between the inboard and terminal conoidal Shell of the terminal conoidal Shell outside, and described terminal cone thermally-insulated body comprises:
(a) volumetric shrinkage that records of thermomechanical analyzer be no more than 10% ceramic fiber and
(b) account for ceramic fiber weight and be mineral colloid material less than 50 weight %,
Wherein said terminal cone thermally-insulated body is flexible, and self-supporting is seamless, taper, and be compressed between the described inboard of conoidal Shell and the outside endways on the thickness direction.
10. pollution control device that comprises terminal cone thermally-insulated body, described terminal cone thermally-insulated body are clipped between the inboard and terminal conoidal Shell of the terminal conoidal Shell outside, and described terminal cone thermally-insulated body comprises:
(a) contain and account for ceramic fiber weight and be the Al of at least 20 weight %
2O
3The ceramic fiber of the silicon-dioxide of at least 30 weight %, described ceramic fiber is a crystallite, crystal or its array configuration, and with the volumetric shrinkage that thermomechanical analyzer records be no more than 10% and
(b) account for described ceramic fiber weight and be mineral colloid material less than 50 weight %,
Wherein said terminal cone thermally-insulated body is flexible, and self-supporting is seamless, and taper, and can fully be compressed on thickness direction to be compressed between the described inboard of conoidal Shell endways and the outside.
11., it is characterized in that the described inboard of terminal conoidal Shell is with one of outside or link to each other with the surface of described terminal cone thermally-insulated body separately as claim 9 or 10 described pollution control devices.
12., it is characterized in that described thermally-insulated body also comprises organic binder bond as claim 9 or 10 described pollution control devices.
13. pollution control device as claimed in claim 10 is characterized in that, when packaging density was about 0.4 grams per milliliter, described terminal cone thermally-insulated body had the compressibility value that is no more than 750,000 Ns/square metre.
14., it is characterized in that when packaging density was about 0.4 grams per milliliter, described terminal cone thermally-insulated body had the compressibility value that is no more than 600,000 Ns/square metre as claim 9 or 10 described pollution control devices.
15., it is characterized in that described terminal cone thermally-insulated body does not contain expanding material as claim 9 or 10 described pollution control devices.
16. make the method for polluting control device for one kind, described pollution control device has terminal cone zone, this end cone zone comprises the terminal cone thermally-insulated body between the inboard and terminal conoidal Shell of the terminal conoidal Shell outside, and described method comprises:
Prepare a kind of water slurry, this water slurry contains (a) and records volumetric shrinkage by thermomechanical analyzer and be no more than 10% ceramic fiber and (b) account for ceramic fiber weight and be the mineral colloid material less than 50 weight %;
Precast body with water slurry vacuum forming cone-shaped on the perviousness moulding stamper;
With the precast body drying, make terminal cone thermally-insulated body, described terminal cone thermally-insulated body is flexible, self-supporting, seamless, taper, and on thickness direction, can fully be compressed, to be compressed between the inboard of terminal conoidal Shell in polluting the terminal cone zone of control device and the outside.
17. method as claimed in claim 16 is characterized in that, described ceramic fiber is crystallite or crystalline form.
18. method as claimed in claim 16 is characterized in that, contains in the described ceramic fiber to account for the Al of its weight at least 20 weight %
2O
3The SiO of at least 30 weight %
2
19. make the method for polluting control device for one kind, described pollution control device has terminal cone zone, this end cone zone comprises the terminal cone thermally-insulated body between the inboard and terminal conoidal Shell of the terminal conoidal Shell outside, and described method comprises:
Prepare a kind of water slurry, this water slurry comprises that (a) contains and accounts for ceramic fiber weight and be the Al of at least 20 weight %
2O
3The ceramic fiber of the silicon-dioxide of at least 30 weight %, described ceramic fiber is a crystallite, crystal or its array configuration, and be no more than 10% and (b) account for ceramic fiber weight for less than the mineral colloid material of 50 weight % with the volumetric shrinkage that thermomechanical analyzer records;
Precast body with water slurry vacuum forming cone-shaped on the perviousness moulding stamper; With
With the precast body drying, make terminal cone thermally-insulated body, described terminal cone thermally-insulated body is flexible, self-supporting, seamless, taper, expanding material do not contained, and on thickness direction, can fully be compressed, to be compressed between the inboard that is suitable for terminal conoidal Shell in polluting the terminal cone zone of control device and the outside.
20. as claim 16 or 19 described methods, it is characterized in that, described vacuum forming process comprises that also precast body is inserted a shape to be kept in the device, support precast body with the perviousness moulding stamper simultaneously, make precast body keep between device and the perviousness moulding stamper and by removing the perviousness moulding stamper precast body being transferred to shape maintenance device in shape.
21. method as claimed in claim 20 is characterized in that, it is inside end conoidal Shell or the outer ends conoidal Shell that pollutes control device that this shape keeps device.
22. method as claimed in claim 20 is characterized in that, this end cone thermally-insulated body links to each other with terminal conoidal Shell.
23. as claim 16 or 19 described methods, it is characterized in that, also comprise organic binder bond in the described slurry.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US44166403P | 2003-01-22 | 2003-01-22 | |
| US60/441,664 | 2003-01-22 | ||
| US60/456,736 | 2003-03-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1741976A CN1741976A (en) | 2006-03-01 |
| CN100548927C true CN100548927C (en) | 2009-10-14 |
Family
ID=36093941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800025817A Expired - Lifetime CN100548927C (en) | 2003-01-22 | 2004-01-22 | Molded three-dimensional insulator |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100548927C (en) |
| ZA (1) | ZA200506623B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2487342B1 (en) * | 2007-06-13 | 2018-04-18 | 3M Innovative Properties Company | Erosion resistant mounting material and method of making and using the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0573834B1 (en) * | 1992-05-21 | 1996-04-17 | Minnesota Mining And Manufacturing Company | Catalytic converter having a metallic monolith mounted by a heat-insulating mat of refractory ceramic fibers |
| US5736109A (en) * | 1995-06-30 | 1998-04-07 | Minnesota Mining And Manufacturing Company | Intumescent sheet material and paste with organic binder |
| CN1292721A (en) * | 1998-03-11 | 2001-04-25 | 尤尼弗瑞克斯有限公司 | Support element for fragile structures such as catalytic converters |
-
2004
- 2004-01-22 CN CNB2004800025817A patent/CN100548927C/en not_active Expired - Lifetime
-
2005
- 2005-08-18 ZA ZA200506623A patent/ZA200506623B/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0573834B1 (en) * | 1992-05-21 | 1996-04-17 | Minnesota Mining And Manufacturing Company | Catalytic converter having a metallic monolith mounted by a heat-insulating mat of refractory ceramic fibers |
| US5736109A (en) * | 1995-06-30 | 1998-04-07 | Minnesota Mining And Manufacturing Company | Intumescent sheet material and paste with organic binder |
| CN1292721A (en) * | 1998-03-11 | 2001-04-25 | 尤尼弗瑞克斯有限公司 | Support element for fragile structures such as catalytic converters |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA200506623B (en) | 2006-08-30 |
| CN1741976A (en) | 2006-03-01 |
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Granted publication date: 20091014 |