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INVENTION
Russian Federation Patent RU2081718
Glue and cover the heat resistance COMPOSITION, COATING FOR mold FABRIC, PROCESS FOR COATING AND METHOD FOR PRODUCING heat resistance of coatings in the form of a sheet from the composition
Name of applicant: Sugitanikinzokukogio Co., Ltd.. (JP)
Name of the inventor: Nob uhiro Sugitani [JP]
The name of the patentee: Sugitanikinzokukogio Co., Ltd.. (JP)
Address for correspondence:
Starting date of the patent: 1990.02.21
The invention relates to adhesive and coating compositions having good heat resistance and excellent wear resistance and long service life and after curing.
The inventive composition is made up of two components: a powder mixture consisting of zirconium oxide, 20 - 70 wt. h, sodium aluminate, 1 -. 10 wt. h, yttrium oxide 0.4 -. 10.5 wt. h silica 9.5 -. 78.6 wt. h, and a binder -. sodium silicate, 12.36 - 84.55 wt. hours, supplemented with 5 -. 50.7 wt. h. Water. For use as a coating composition in the mold to a fibrous heat resistant material is added in an amount of 2 - 17 wt. h. Using a composition can be obtained by coating a heat resistant fabric.
DESCRIPTION OF THE INVENTION
The invention relates to the Adhesive and coating compositions providing good resistance to thermal shocks, durability and wear resistance after drying, but also to the covering materials for molds comprising an aqueous dispersion which has a heat-resistant fiber material, and to a web made from an coating composition and heat-resistant fibers.
In recent years, he became interested in adhesive substances containing inorganic components. For example, Japanese Patent N 50-33491 vysokoteplostoykoy is a process for preparing an adhesive composition comprising calcining a mixture composed of particles of high-purity oxide and colloidal silicic acid, and a sodium aluminate in an amount of 2-10% by weight of the total amount of zirconium oxide and silicic acid , wherein calcination is carried out at a temperature of 1,000 o C or higher, and then sputtering is performed thin calcined material. It was stated that an adhesive obtained by this method has a low curing temperature in the range 250-350 o C.
And known method of increasing the service life of molds by mounting or blending heat resistant fibrous material such as potassium titanate (K 2 Ti 6 O 13) polititanokarboksilsilan carbon fiber and the inner surface of the mold or form, using such inorganic adhesive. and a heat resistant sheet was manufactured by using said adhesive composition.
However, the above-mentioned adhesive composition has the disadvantage of its stability after curing. After hardening observed peeling of the coating film. Consequently, as a result of research aimed at improving stability, it has been found that the addition of yttria provides a adhesive film (or coating film) which has an increased stability in comparison with the adhesive composition described in Japanese Patent No. 5,033,491 has a much higher resistance to wear resistance to flaking and drying after thermal shock.
The above disadvantages can be overcome by using adhesives and coating compositions dispersed in water and heat-containing powder mixture consisting of zirconium oxide, sodium aluminate, yttrium oxide, balance silica; and sodium silicate containing a small amount of water.
Heat resistant composition of the present invention is produced by adding sodium silicate containing a small amount of water to the powder mixture of the following components in parts by weight: 20 to 70 zirconia, preferably 25-70, sodium aluminate, 1-10, preferably 2 - 5 , 0,4-10,5 sodium oxide, preferably about 4 to 10% based on the amount of zirconium oxide, silica in an amount of rest 12,36 84,55. If the amount of yttria is less than 0.4 parts by weight it is sufficient stabilizing effect is observed. If the content of yttrium oxide is more than 10.5 wt. h. and then an additional effect is not observed, and hence, the use of an increased amount of yttrium oxide is uneconomical because yttria is expensive If the content of zirconium oxide less than 20 parts by weight the result will occur an insufficient adhesive force and allowing the gradient and inadequate locking function between the ceramic layer and the substrate (e.g., metal substrate). Optionally, the composition may contain a heat resistant pigment, for example, inorganic pigments such as iron oxides, titanium dioxide, which should not affect the harmful effects during and after curing. The composition must withstand a temperature of 1300 o C after curing.
The compositions of the present invention, the coating film strength may be impaired due to abrupt vaporization of water, and therefore to eliminate this possibility composition should be dried in air or at a temperature of about 90 o C for from 20 minutes to 3 hours. Typically, curing is carried out at a temperature of 200-350 o C for 20 min. up to 3 hours. At higher temperatures, there may be adverse effects due to the presence of residual water on the surface of the covering plate. At lower temperatures, a satisfactory curing is impossible.
Therefore, the present invention and relates to a method of using a heat resistant composition of the type described above, including the imposition of the composition to the substrate, but also the extraction of water at a temperature ranging from room temperature to 90 o C after applying the substrate on the counter member when the composition is used as an adhesive, and then reacting curing at 200-350 o C.
The coating material for the mold is formed by dispersing the short heat-resistant fibers, for example, selected from the group consisting of potassium titanate fiber (K 2 Ti 6 O 13) polititanokarboksilsilana fibers, carbon fibers (whiskers) dispersed in water by adding it, the water being added in the number of parts 5-50,73 composed by dispersing superimposed on the inner surface of the mold and cured as described above, providing a very good wear resistance and heat resistance and, by exfoliation resistance, high durability, and in addition, good separation of the molded products using the mold.
From the viewpoint of dispersibility convenient to heat resistant fiber used was short and capable of dispersing in water, such as a short fiber length of from 5 to 200 microns and a diameter of 0.05 to 5 microns.
The coating after being applied to the inner surface of the mold, is freed from water at a temperature ranging from room temperature to 90 o C, and it then hardens by reaction at a temperature of 200-350 o C.
Base metal (substrate) for the mold of the present invention may be any, for example, copper, copper alloys, steel, aluminum, aluminum alloys, magnesium, magnesium alloys. Surprisingly, it was found that the composition of the present invention allows the use of metals with a low melting point that is easily processed, or alloys containing no iron, for example, copper alloys, aluminum, aluminum alloys, magnesium, magnesium alloys.
Potassium titanate, which can be used as a heat resistant short fiber of the present invention is disclosed in "Study of the synthesis of potassium titanate fibers," Scientific and Technical Report N 34, 1982, with the. 1 37, the Institute for Research of Inorganic Materials Agency for Research and Technology. The purpose of this fiber is to improve the heat and wear resistance, and also in improving the mold release. This fiber can be thin, having a length of 5200 microns, preferably 10 to 50 microns, and a diameter of 0.05 5 mm. The amount of potassium titanate added with an aqueous dispersion of a heat resistant composition of the present invention is generally 2, 17 wt. parts.
The present invention and relates to the sheet material in the form of a heat-resistant fabric, the dried coating which has a thickness of 50 400 microns, preferably 200 250 microns, formed by dispersing heat-resistant short fibers from materials such as at least one selected from the group consisting of potassium titanate (K 2 Ti 6 O 13) in the form of fibers, polititanokarboksilsilanovoe fiber, carbon fiber, ceramic fiber and other whiskers, dispersed in water, which is added in an amount of up to 50.73 wt. parts in the coating composition of the present invention; and the invention relates to a coating material for the mold in which the sheet is attached to the inner surface of the mold by means of the adhesive composition of the present invention.
Heat-resistant woven fabric that can be used in the present invention may be anyone which can be satisfactorily on the overlay coating composition is an aqueous dispersion. Such webs may be made of twisted or untwisted filaments may be knitted from carbon, titanium, alumina or silicon carbide fibers. Although the thickness of the fabric is not particularly limited, it is preferred that it be relatively thin: 10-1000 microns in cases when it is required to provide increased accuracy.
In addition, the present invention relates to a method of coating the mold, comprising the steps of: impregnating a heat resistant fabric of the type described above, a coating composition, if necessary by adding water in an amount of up to 50.73 wt. parts overlay or securing the resulting web on the inner surface of the mold by using a heat resistant adhesive of the present invention, the removal of water at a temperature ranging from room temperature to 90 o C, the implementation of the curing reaction at a temperature of 200 - 300 o C, and the invention relates to a coating material, obtained by this method.
The following will describe an example of the present invention, which uses a composition for use in the mold.
First, the composition is administered in an amount of water of the present invention to 50.73 wt. parts, and then dispersed short fibers of potassium titanate in an amount of 2.17 wt. parts. The resulting dispersion was applied onto the mold surface to be coated, then drying the produce at a temperature from ambient to 90 o C for one hour or more, and then curing is carried out at a temperature of 200 350 o C. Coat the gate, vent, feeder, and the housing and forms .
Form having coating made by the method, which includes the potassium titanate fiber has a satisfactory heat resistance required for casting, and a superior wear resistance, and the molded product can be easily removed from the mold after filling metal. In addition, even after 10,000 casting performed without re overlay coating material to the shape, there was no deviation of the surface shape of molded articles, ie mold were sufficiently reliable to use.
In addition, the present invention relates to a heat resistant fabric made overlay coating compositions of the present invention on a heat resistant fabric of the type described high, and the dry film thickness was 50-400 m. Was added a small amount of water, if necessary.
and, the present invention relates to a method for producing a heat-resistant coating, which is a web formed casting an aqueous dispersion containing a composition of the type described above, together with at least one of the described heat resistant short fibers onto a peelable permeable substrate, for example, wire mesh etc. Then water is removed at a temperature from ambient to 90 o C, and then raise the resulting material layer. This sheet can then be dried during use.
The thickness of the fabric is not important, it depends on the application. For example, if the web is applied to the inner surface of the mold, it is usually this thickness is about 50-1000 microns. However, if the dimensional accuracy is not required, the web thickness may be even larger.
Next, description will be given of two preferred embodiments of the invention in which the composition of the present invention is used for production of paintings.
First, the composition of the present invention containing water added to the water in an amount of 50.73 wt. parts, dispersed therein 2.17 wt. parts of a short potassium titanate fiber, and a 2.17 wt. parts of another ceramic fiber, e.g., alumina. The obtained dispersion composition is poured in a predetermined amount onto a filter paper, a filter mounted in the suction in which the suction is removed by the action of the water main. The resulting material was dried for 1-3 hours. at a temperature from ambient to 90 o C.
The thickness of the dry web, one obtained by casting, up to about 600 microns. In addition, to obtain a thicker fabric, and casting operations can be repeated removal of water, after which the curing reaction can be carried out.
The second embodiment involves dispersing a short potassium titanate fibers and ceramic fibers such as alumina in water. Then, the resulting dispersion is poured in a certain amount on the filter paper, mounted in the suction filter in which the main quantity of water extracted by suction to give the material in web form. A certain amount of the aqueous dispersion composition of the present invention for atomizing the sheet material. The resulting material is slightly dried at room temperature, after which produce atomization and re-drying for 1-3 hours. at a temperature from ambient to 90 o C. These webs are cured for 1.3 hr. at a temperature of 200-350 o C. These can then be used, for example, for fixing or overlay.
The resulting web can be suitably attached to the predetermined element, withstanding temperatures up to about 1300 o C.
The present invention will be described in more detail by examples.
EXAMPLES OF COMPOSITIONS
example 1
23 g of sodium silicate containing 5 ml of water was added to 50 g of a powder mixture consisting of 60 parts by weight of zirconium oxide, 40 parts by weight of silica, 5 parts by weight of sodium aluminate and 4,8 parts by weight of yttrium oxide, then kneaded to a viscous paste-like state.
example 2
20 g of sodium silicate containing 5 ml of water was added to 50 g of a powder mixture consisting of 50 parts by weight of zirconium oxide, 55 parts by weight of silica, 5 parts by weight of sodium aluminate and 2 parts by weight of yttrium oxide, and they are then transferred to a viscous a paste.
example 3
24 g of sodium silicate containing 4 ml of water was added to 50 g of a powder mixture consisting of 40 parts by weight of zirconium oxide, 65 parts by weight of silica, 5 parts by weight of sodium aluminate and 2 parts by weight of yttrium oxide, then kneaded to form a viscous a paste.
example 4
22 g of sodium silicate containing 4 ml of water was added to 50 g of a powder mixture consisting of 30 parts by weight of zirconium oxide, 65 parts by weight of silica, 5 parts by weight of sodium aluminate and 1,5 parts by weight of yttrium oxide, then kneaded to a viscous paste-like state.
EXAMPLES OF COMPOSITIONS
example 5
10 g of a potassium titanate fiber having an average length of 20 microns and a mean diameter of 0.9 microns, dispersed in an aqueous dispersion of 50 g of a pasty material described in Example 1, containing 5 ml of water. The resulting dispersion is laid on a woven fabric of carbon fibers having a thickness of 500 microns to give a wet film thickness of 300 microns (dry film thickness of about 215 microns).
The resulting material was dried at a temperature of 90 o C for 1 hour and then was cured at 250 o C for 2 hours.
Then, using 50 g of the composition described in Example 1, the above-described cured carbon fiber woven fabric secured to the inner surface of the sprue and on the surface of a copper alloy mold intended for casting automotive crankcase. The resulting fabric was dried similarly at 90 o C for 1 hour and then was cured at 250 o C for 2 hours.
When using the mold made in this manner, casting crankcases for automobile engines, in the form cooled to 350-400 o C, it was found that after 10,000 casting mold surface shape is not changed, and the surface state of molded product was satisfactory. The product can be easily removed from the mold.
example 6
Using 50 g of the composition described in Example 2, the carbon fiber fabric thickness 500 microns secured on the inner surface on the surface of the gate, and so on. N., A copper alloy mold designed to cast an automotive engine crankcase. The resulting fabric was dried similarly at 90 o C for 1 hour and then was cured at 250 o C for 2 hours.
When using the mold made in this manner it has been found that when casting crankcases of automobile engines, in the form of cooled until the temperature of 350-400 o C, after 10,000 casting mold surface shape is not changed, the state of the surface of the product was satisfactory. The product can be easily removed from the mold.
example 7
6 g of potassium titanate fiber and 4 g of alumina fibers of an average length of 20 microns and a mean diameter of 0.9 microns introduced into an aqueous dispersion of 50 g of the composition described in Example 2, containing 4 mol of water.
The resulting dispersion was imposed on the inner surface of a steel mold and dried at 90 o C for 1 hour, and it was then cured for 2 hours, to obtain a coating film with having a thickness of about 230 microns when dry.
Then thus made was used to form casting crankcases automotive engine. And even after the casting of 10,000 crankcases shape of the surface of the mold has not changed, the state of the surface of products was satisfactory. The product can be easily removed from the mold.
LEAF PRODUCTION
example 8
6 g of potassium titanate fiber and 4 g of alumina fibers of an average length of 20 microns and a mean diameter of 0.9 microns introduced into an aqueous dispersion resulting from addition of 5 ml of water to 50 g of the dispersion of Example 3. The filter paper is laid on Nutsche folder having an internal diameter of 100 mm.
The dispersion of Example 1 was sprayed on the filter paper and the ground water extracted by suction to form a web of approximately 1 mm thick. The web or sheet is removed together with the filter paper, and then put it into the unused filter paper and dried in air at room temperature for 1 hour. The resulting web had a thickness of about 0.6 mm.
example 9
50 g of the dispersion of Example 1 was sprayed onto a woven fabric of fibers polititanokarboksilsilanovogo, having a wet film thickness of 300 .mu.m, drying and then held at 90 o C for 1 hour, obtaining a web having a coating layer from a dry film thickness of 265 microns.
After curing the fabric at a temperature of 300 o C it has been found that the heat resistance it equaled to 1300 o C temperature.
example 10
6 g of potassium titanate fiber and 4 g of alumina fibers of an average length of 20 microns and a mean diameter of 0.9 microns introduced into an aqueous dispersion resulting from addition of 5 ml of water to 50 g of the dispersion of Example 4 and the resulting dispersion mixed. The mixture is poured onto a wire very fine mesh and dried at a temperature of 90 o C for 1 hour.
Thereafter, the resulting film was peeled off from the grid, receiving sheet.
EXAMPLES LEAF
example 11
The web formed in Example 8 was attached or stamped on the inner surface and the similar surface mold of copper alloy casting automotive crankcase via dispersion described in Example 4, the mold had three layers: a nickel layer applied electroplated coating layer from an alloy cobalt, chromium and molybdenum, used as an intermediate, and a coating layer of a porous ceramic Al 2 O 3 / ZrO 3, used as an external, except that said fabric laid or fastened in place of the ceramic layer.
Fixed web was dried at 90 o C for 1 hour and then cured at 250 o C in an oven.
When using the mold made in this manner it has been found that when casting crankcases cooled automotive engine in the form of 350-400 o C until the temperature after 10,000 casting mold surface shape is not changed, the state of the surface of the product was satisfactory. The product can be easily removed from the mold.
Heat resistant composition of the present invention not only has excellent heat and wear resistance and the ability to disengage, in addition, it has a high durability. and after curing, this film is more stable compared with the adhesive composition described in Japanese Patent No. 5033491. Heat resistant composition of the present invention provides significant economic benefits from the introduction into the industry as an adhesive and (or) its coating in those areas which require heat and wear resistance, and a good release ability.
CLAIM
-
The adhesive and heat resistant coating composition dispersed in water containing zirconium dioxide, sodium aluminate and silica-material, characterized in that it further comprises yttrium oxide, silicon dioxide and water as well as the silica-containing material is sodium silicate of the following component ratio, mass parts . :
Zircon oxide 20 70
Aluminate natpiya January 10
Oxide ittpiya 0.4 10.5
Dioxide kpemniya 9.5 78.6
Silicate natpiya 12,36 84,55
Water 50.73 5.00
-
Coating of the adhesive and coating a heat-resistant composition for mold comprising a particulate material, silica-material and water, characterized in that the particulate material it contains zirconium oxide, sodium aluminate, silica, yttrium oxide, waterglass as a silica-containing material, and further comprising at least one kind of heat-resistant fiber having a length of 5-200 mm and a diameter of 0.05-5.0 microns, selected from the group consisting of potassium titanate fiber (K 2 Ti 6 O 15) polititanokarboksilsilanovogo fibers, carbon fibers, ceramic fiber in the following ratio, in parts by weight.
Zirconium oxide 20-70
Sodium aluminate 1-10
Yttrium oxide 0,4-10,5
Silica 9,5-78,6
Sodium silicate 12,36-84,55
fiber 2-17
Water 5,00-50,73
Fabric comprising a heat resistant fabric with a coating applied thereto, characterized in that the coating has a composition of claim 2, wherein the dry film thickness of 50-400 microns.
A process for coating a casting mold, comprising mounting the mold on the inner surface of a heat-resistant fabric web, characterized in that a sheet according to claim 3 and its fixation is accomplished by the adhesive composition of claim 1 having a composition, dried at room temperature to 90 o C and cured at 200-350 o C.
A method for producing a heat-resistant coating in web form comprising a substrate nalivka adhesive composition, separating the web from the substrate, wherein the adhesive composition nalivka performed on permeable substrate, wherein the adhesive composition coating has a composition of claim 2, before separating the web from the substrate is performed drying it at a temperature from ambient to 90 o C.
print version
Publication date 31.10.2006gg
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