EP1958717B1 - Composant pour la production de pièces coulées et son procédé de fabrication - Google Patents

Composant pour la production de pièces coulées et son procédé de fabrication Download PDF

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Publication number
EP1958717B1
EP1958717B1 EP06833601.5A EP06833601A EP1958717B1 EP 1958717 B1 EP1958717 B1 EP 1958717B1 EP 06833601 A EP06833601 A EP 06833601A EP 1958717 B1 EP1958717 B1 EP 1958717B1
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Prior art keywords
casting
fibers
inorganic
mass
mass content
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EP06833601.5A
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German (de)
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EP1958717A4 (fr
EP1958717A1 (fr
Inventor
Yoshimasa Takagi
Akira Yoshida
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Kao Corp
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Kao Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
    • B22C1/08—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for decreasing shrinkage of the mould, e.g. for investment casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C21/00—Flasks; Accessories therefor
    • B22C21/12—Accessories
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/08—Features with respect to supply of molten metal, e.g. ingates, circular gates, skim gates

Definitions

  • the present invention relates to a part for producing castings (hereinafter “part for casting” or simply “part”) that can be use as a runner, etc. in the production of castings and a process of making the part.
  • JP 2004-174605A a technique relating to a part for casting that can be used as a runner, etc. in the production of castings.
  • the technique provides a tube formed of base paper containing organic fiber, inorganic fiber, and a binder, in which the tube is light, easy to handle, and easy to dispose of after use for casting as compared with historically used refractory materials.
  • Such a part for casting containing organic fiber, inorganic fiber, and a binder has a minimized content of the organic fiber in order to reduce the generation of combustion gas (hereinafter sometimes referred simply to as "gas") accompanying thermal decomposition of the organic fiber during casting. If the organic fiber content is reduced, however, the components will have poor dispersibility, tending to result in poor formation to yield a high proportion of defective castings. In the case of making base paper by papermaking, in particular, reduction in organic fiber content is liable to produce wavy paper.
  • the present invention relates to a satisfactory part for casting and a process of producing the part, in which a specific dispersant is used to allow for reducing an organic fiber content.
  • the invention also relates to a satisfactory part for casting having a reduced organic fiber content and a process of producing the part.
  • the present inventors have found that a satisfactory part for casting can be obtained by using a specific dispersant even when an organic fiber content is reduced and completed the invention.
  • the present invention provides a process of producing a part for casting including the step of preparing a raw material slurry containing inorganic fibers, organic fibers, a thermosetting resin, a papermaking binder, and a sulfonate-based and/or a cellulose-based dispersant.
  • the present invention also provides a part for casting containing inorganic fibers, organic fibers, a thermosetting resin, a papermaking binder, and a sulfonate-based and/or a cellulose-based dispersant.
  • the part for casting according to the invention is first described based on its preferred embodiment.
  • the part 10 of the embodiment shown in Fig. 1 contains inorganic powder, inorganic fibers, organic fibers, a thermosetting resin, a papermaking binder, and a water repellant and, in addition, 0.001% to 10% by mass, preferably 0.01% to 10% by mass, of a sulfonate-based and/or a cellulose-based dispersant based on 100% by mass of the total of the inorganic powder, inorganic fibers, organic fibers, thermosetting resin, papermaking binder, and water repellant.
  • Use of such amount of a dispersant enables production of a good part while minimizing the content of the organic fibers.
  • the sulfonate-based dispersant examples include a sodium ⁇ -naphthalenesulfonate-formalin condensate, sodium ligninsulfonate, a sodium melaminesulfonate-formalin condensate, an aromatic aminosulfonic acid sodium salt polymer, sodium polystyrenesulfonate, a styrenesulfonic acid-sodium maleinsulfonate copolymer, sodium polycyclopentadienesulfonate, and an aliphatic dienesulfonic acid sodium salt polymer.
  • Preferred of them is a sodium ⁇ -naphthalenesulfonate-formalin condensate having a degree of polycondensation of 3 to 6 for consideration of the formation of wet base paper (a wet mat of fiber).
  • the cellulose-based dispersant preferably has high water solubility and preferably dissolves completely in a 1% by mass aqueous solution.
  • a cellulose-based dispersant is exemplified by cellulose propylene oxide adduct derivatives, e.g., hydroxypropyl cellulose and hydroxypropylmethyl cellulose. Hydroxypropyl cellulose is preferred for consideration of the formation of wet base paper (a wet fiber mat).
  • the dispersants can be used either individually or as a combination of two or more thereof.
  • the ratio of the inorganic powder/inorganic fibers/organic fibers/thermosetting resin (solid content)/papermaking binder (solid content)/water repellant in the part for casting of the invention is 0-70%/1-60%/1-40%/1-40%/1-10%/0-5% by mass, preferably 40-70%/1-10%/1-25%/1-25%/1-10%/0-5% by mass, more preferably 50-70%/1-8%/1-20%/10-25%/3-7%/0-1% by mass, taking the total of these components as 100% by mass.
  • the content of the inorganic powder being within the range recited, the part has good shape retention during pouring, and a fiber molded article has good surface conditions and good release from a mold.
  • the content of the inorganic fibers being within the range recited, good papermaking properties and good shape retention during pouring are obtained.
  • the organic fiber content being in the range recited, good papermaking properties are obtained, and combustion gas generation during pouring can be held down so as to prevent a blowback (a back-flow of molten metal).
  • the thermosetting resin content falling in that range the casting mold has good molding properties, and a fiber molded article has good shape retention after pouring and good surface smoothness.
  • the papermaking binder content being in that range, the binder makes the powder component in the slurry cling to the fibers while causing the fibers to moderately intermingle with one another to form flocks optimum for sheet formation and thereby securing good yield.
  • the base paper formed by papermaking can be converted into a part for casting with a minimum amount of an adhesive because the adhesive applied is prevented from penetrating into the base paper. Furthermore, after the part for casting is buried in molding sand, the water content of the molding sand is prevented from penetrating into the part.
  • the inorganic powder examples include obsidian, mullite, and graphite including flaky graphite and earthy graphite.
  • One or more than one kind of the inorganic powders can be selected for use.
  • carburizing penetration of carbon into a casting to make the casting brittle
  • inorganic powder having a silica content should be used to prevent carburizing from a casting carbide. It is preferred to use obsidian, mullite, etc. as an inorganic powder.
  • the carbon content of the casting is 4.2% by mass or more, the part does not need to contain inorganic powder.
  • the inorganic fiber serves mainly to constitute the skeleton of the part. For example, it does not burn even with the heat of molten metal and continues serving to retain the shape of the part during casting.
  • the inorganic fiber include artificial mineral fibers, such as carbon fiber and rock wool, ceramic fibers, and natural mineral fibers. They can be used either alone or in combination of two or more thereof.
  • Carbon fiber that maintains high strength even in high temperatures such as pitch-based carbon fiber or polyacrylonitrile (PAN)-based carbon fiber, is preferred for effectively reducing thermal shrinkage accompanying carbonization of the thermosetting resin.
  • PAN-based carbon fiber is especially preferred.
  • the inorganic fiber preferably has an average length of 0.1 to 10 mm, more preferably 0.5 to 8 mm, in view of the quality of a fiber molded product obtained by papermaking technique. Continuous fibers of 10 mm or longer may be used as cut in a slurry in a refiner, etc. to have an average fiber length controlled to 0.1 to 10 mm.
  • organic fibers examples include pulp fibers, fibrillated synthetic fibers, and regenerated fibers (e.g., rayon fiber). These fibers are used either individually or as a mixture of two or more thereof. Preferred of them is pulp fiber from the viewpoint of sheet forming properties, strength after drying, and cost.
  • pulp fibers include not only wood pulp but non-wood pulp, such as cotton pulp, linter pulp, bamboo, and straw. These kinds of pulp, whether virgin or recycled, can be used either alone or in combination thereof. From the standpoint of availability, environmental conservation, and reduction of production cost, used paper pulp is preferred.
  • the organic fibers prefferably have an average length of 0.1 to 20 mm, more preferably 0.5 to 10 mm, from the viewpoint of surface smoothness and impact strength of the resulting base sheet.
  • thermosetting resin is a component necessary to retain the low- and high-temperature strength of the part 10 and to provide a paper tube with good surface properties which contribute to improve the surface smoothness of a casting.
  • the thermosetting resins include phenol resins, epoxy resins, and furan resins. Phenol resins are preferred in view of reduced generation of combustible gas, resistance to burning, and a high carbon residue content after thermal decomposition (carbonization) as high as 25% or more to form a carbonized film to provide a casting with an improved casting surface.
  • carbon residue content refers to a value obtained by heating a thermosetting resin sample in a nitrogen atmosphere from room temperature up to 1200°C at a rate of temperature rise of 50°C/min, measuring the mass of the residue, and dividing the mass of the residue with the mass before heating. The mass after heating is lighter than that before heating because combustion gas is released from the resin during heating.
  • Usable phenol resins include novolak phenol resins requiring a curing agent and resol type phenol resins requiring no curing agent.
  • a low-release phenol resin such as high-molecular-weight resol phenol resins synthesized using a basic catalyst or an acidic catalyst.
  • a curing agent is needed. Since the curing agent easily dissolves in water, it is preferably applied to the surface of a dewatered fiber mat. Preferred examples of the curing agent include hexamethylenetetramine.
  • the thermosetting resins can be used either individually or as a combination of two or more thereof.
  • combustion gas examples include carbon monoxide, carbon dioxide, and hydrocarbons such as methane and ethylene.
  • papermaking binder examples include natural polymers such as starch, gelatin, guar gum, and carboxymethyl cellulose (CMC); water soluble synthetic polymers such as KAIMEN (polyamideamine-epichlorohydrin resin), polyvinyl alcohol (PVA), polyacrylamide (PAM), and polyethylene oxide (PEO); styrene-butadiene latices, acrylonitrile-butadiene latices, acrylic latices, and vinyl acetate latices; and inorganic binders such as colloidal silica and alumina-based binders. Preferred of them are KAIMEN, CMC, and acrylic latices for their powder-fixing properties.
  • KAIMEN polyamideamine-epichlorohydrin resin
  • PVA polyvinyl alcohol
  • PAM polyacrylamide
  • PEO polyethylene oxide
  • styrene-butadiene latices acrylonitrile-butadiene latices
  • the papermaking binder is preferably used in an amount of 0.01% to 5%, more preferably 0.02% to 1%, on a solid basis based on the mass of the organic fibers.
  • These papermaking binders can be used either individually or as a combination of two or more thereof.
  • the part 10 can contain a water repellant to prevent penetration of the adhesive described supra into base paper and to prevent loss of strength due to moisture absorption.
  • Silicone surface active agents, fluorine-containing surface active agents, fat and oil type surface active agents, hydrophobic surface active agents, and hydrophobic polymers can be used as a water repellant.
  • the water repellant is preferably applied to both the inner and outer sides of the part 10 and dried to prevent deterioration of strength due to moisture absorption.
  • the water repellant is advisably used in the form of an aqueous solution or emulsion that is convenient to handle upon use.
  • the water repellants may be used either individually or as a combination of two or more thereof. Silicone, fluorine-containing or fat and oil type emulsions are preferably used.
  • the water repellant When the water repellant is added to a slurry, particularly preferred is an alkyl ketene dimer (AKD), which exhibits excellent water repellency in a neutral region at a small amount and is superior in acid resistance and alkali resistance to rosin, etc.
  • the water repellant may be added in an adequate amount to a raw material slurry or applied to the part. Coating techniques include spraying, brush coating, dipping, and pouring. Spraying, dipping or pouring is preferred for productivity. Coating by "pouring” as used here is achieved by hosing a pumped liquid over the part to be coated. In cases where the part for casting is used in a dry working environment or when the thermosetting resin serves for water repellency depending on its kind or amount used, the water repellant may be dispensed with.
  • the part 10 may contain other components such as a flocculant and a colorant in appropriate amounts in addition to the above described components.
  • the part 10 preferably has a surface roughness Ra of 20 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the surface roughness Ra is measured, e.g., with Surtronic 10 from Rank Taylor Hobson.
  • the part 10 is preferably formed of base paper containing the aforementioned components.
  • the base paper preferably has a tensile strength of 40 N/15 mm or more, more preferably 80 N/15 mm or more.
  • the tensile strength is measured in a tensile test of a 15 mm wide specimen cut out of 0.7 mm thick base paper on a Tensilon universal tester RTA500 from A & D Co., Ltd. When the thickness of a sample is not 0.7 mm, the tensile strength as measured is converted to strength per unit cross-sectional area for comparison.
  • Base paper having a tensile strength within the above range does not tear or break when spirally wound to make paper tubing as a part for casting as in the present embodiment.
  • the part 10 preferably has a compressive strength of 20 N or higher, more preferably 40 N or higher, before use in casting.
  • compressive strength is a compressive strength of the wall of tubing measured as follows. A 60 mm wide specimen cut out of a part for casting is set on a compressive strength testing instrument (e.g., a Tensilon universal tester RTA 500 from A & D) with its cut area horizontal and compressed at a rate of 10 mm/min.
  • the thickness of the part 10 is subject to variation according to where it is applied, it is preferably 0.5 to 6 mm, more preferably 1 to 3 mm, for securing strength required of a part for casting and air permeability and reducing the production cost.
  • the part 10 before use in casting prefferably has a water content of not more than 20% by mass, more preferably 10% by mass or less, to minimize water vapor generation on contact with molten metal.
  • Water vapor generation causes blowback (back flow) of molten metal from the pour spout.
  • the part 10 is composed of two tubular paper plies 11 and 12 each formed of spirally wound base paper.
  • the production of the part 10 starts with preparation of base paper for making the tubular paper plies 11 and 12.
  • Respective raw material slurries for the base paper for making the tubular paper plies 11 and 12 are prepared from the above-described inorganic powder, inorganic fibers, organic fibers, thermosetting resin, papermaking binder, and dispersant. Each of the slurries is converted to a sheet form (wet fiber mat), dewatered, and dried in accordance with a wet papermaking technique to obtain base paper.
  • Examples of the dispersing medium of the slurry include water, white water, and solvents such as ethanol and methanol. Water is preferred in view of stability in wet fiber mat formation and dewatering, stability of quality of the resulting base paper, cost, and ease of handling.
  • the slurry can contain additives including a flocculant and an antiseptic.
  • the slurry thus prepared is then converted into base paper for making paper tubing by a papermaking process.
  • Papermaking can be carried out by any technique selected from, for example, continuous papermaking methods using a cylinder paper machine, a Fourdrinier paper machine, a short-wire paper machine or a twin-wire paper machine, and batchwise papermaking methods including manual papermaking.
  • the wet fiber mat is dewatered to reduce its water content preferably to 30% or smaller, more preferably to 10% or smaller.
  • Dewatering of the fiber layer can be conducted by, for example, suction, blowing pressurized air or pressing with a pressure roll or a pressure plate.
  • the dewatered fiber mat is forwarded to a drying step. Any means for drying that has conventionally been used to dry paper can be used in the drying step.
  • the base paper after dewatering and drying preferably has a tensile strength of 40 N/15 mm or more, more preferably 80 N/15 mm, to be wound into tubing.
  • the tensile strength is measured in a tensile test of a 15 mm wide specimen cut out of 0.7 mm thick base paper on the above mentioned Tensilon universal tester. When the thickness of samples to be measured is not 0.7 mm, the tensile strength as measured is converted to strength per unit cross-sectional area for comparison.
  • the base paper after dewatering and drying preferably has a buckling strength of 3 N or higher, more preferably 4 N or higher, in view of the strength of the resulting part for casting.
  • the buckling strength is measured by a 3-point bending test as follows. A specimen of base sheet measuring 60 mm in width and 100 mm in length is set on a tester with a 40 mm span length, and compressed from above by an indenter having a width of 60 mm and a diameter of 6 mm at the tip. From the same viewpoint, the base paper after dewatering and drying preferably has a buckling displacement of 3 mm or more, more preferably 5 mm or more.
  • the term "buckling displacement" means the amount of displacement of base paper at the maximum stress point in the above described 3-point bending test.
  • the base paper after dewatering and drying generates not more than 250 cc/g, more preferably not more than 200 cc/g, of combustion gas per unit mass of the part at 1000°C.
  • the amount of combustion gas generated is measured using equipment for measuring the amount of generated combustion gas (No. 682 Gas Pressure Tester from Harry W. Dietert Co.).
  • the amount of combustion gas generated is preferably as small as possible.
  • the practically reachable lower limit is 0.1 to 1 cc/g.
  • the base paper after dewatering and drying preferably has a surface roughness Ra of 20 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the surface roughness Ra is measured, e.g., with Surtronic 10 from Rank Taylor Hobson.
  • the base paper after dewatering and drying preferably has water repellency of 15% or less, more preferably 10% or less.
  • the water repellency of base paper is measured, e.g., in accordance with the method specified in JIS P8140, paper and board - determination of water absorptiveness - Cobb method. The contact time between a test piece and water was set at 60 seconds.
  • the base sheet after dewatering and drying preferably has a density of 0.62 to 0.9 g/m 3 , more preferably 0.64 to 0.75 g/m 3 . With this density, break of base paper during winding into tubing due to insufficient strength and difficulty in winding due to excessive bending stiffness of base paper are avoided.
  • the resulting webs of base paper was each slit into a strip of predetermined width, and the strips are successively lap-wound helically with an overlap between adjacent turns either in the same direction or different directions to be shaped into a tubular form.
  • the outer strip When wound in the same direction, the outer strip is preferably wound in a manner to cover the exposed edge of the preceding turns of the inner strip. In lap winding, an adhesive is applied as appropriate to form tubing.
  • the width of the strips, the width of overlap, the inner diameter of paper tubing, and the like are decided according to the mass of a casting (i.e., the amount of molten metal passing the paper tube) and required sand-pressure strength of the paper tube (i.e., the strength withstanding the pressure in making a sand mold).
  • the tubing After completion of lap-winding all the plies, the tubing is dried by heating at a prescribed temperature and cut to length to complete the production of a part for casting.
  • the part for casting of the present embodiment is excellent in that the amount of combustion gas it generates during casting is reduced because of its reduced organic fiber content, and yet it retains good formation.
  • the part 10 for casting of the present embodiment generates not more than 250 l/m 2 , preferably not more than 150 l/m 2 , of combustion gas at 1000°C, wherein "m 2 " is the unit of the surface area of the part 10 at an average diameter.
  • the term "average diameter” as used herein denotes a diameter calculated by (inner diameter + outer diameter)/2.
  • the amount of combustion gas generated is preferably as small as possible.
  • the practically reachable lower limit is 1 to 10 l/m 2 .
  • the amount of combustion gas generated at 1000°C is measured using equipment for measuring the amount of generated combustion gas (No. 682 Gas Pressure Tester from Harry W. Dietert Co.).
  • the amount of combustion gas generated from base paper is given in cubic centimeter per gram, while that from a part for casting is in liter per square meter. This is because a part having a smaller inner diameter is more liable to cause blowback (back-flow of molten metal) than a part having a larger inner diameter with the base paper making them being equal, i.e., with the amount of gas generation given in cc/g being equal. That is, the amount given in cc/g is not enough to evaluate proneness to blowback. The reason a part with a smaller inner diameter is more prone to cause a blowback is that the volume of molten metal present in a tubular part is relatively smaller and therefore relatively lighter to be blown up than in a larger-diameter tubular part.
  • the part for casting according to the present invention enjoys the same advantage of ease of handling as of this type of conventional parts.
  • the part for casting is composed of two tubular paper plies, it may be composed of three or more tubular paper plies.
  • the ply structure is selected as appropriate to required sand-pressure strength, required high-temperature strength, the thickness of base paper, and so forth.
  • high-temperature strength refers to mechanical strength of a part on contact with molten metal.
  • the part for casting is formed of base paper previously prepared by a papermaking technique, it is possible to make the part by a conventionally known pulp molding technique using the same raw material slurry as described.
  • a sample sheet for evaluation was prepared using the following raw materials of base paper for tubular paper plies.
  • the resulting sheet of base paper was evaluated for formation (waviness and disperse state of inorganic powder, etc.), surface roughness, and generation of combustion gas in accordance with the methods described below. The results obtained are shown in Table 1.
  • composition of base paper for tubular paper plies Composition of base paper for tubular paper plies (sample for evaluation)
  • Inorganic powder obsidian powder (average particle size: 30 ⁇ m) 65.5% by mass
  • Inorganic fiber carbon fiber (length: 3 mm; Torayca chopped fiber, available from Toray Industries, Inc.) 4% by mass
  • Organic fiber used paper 12% by mass
  • Thermosetting resin resol phenol resin (Bellpearl S-890 from Air Water Bellpearl Inc.) 18% bymass
  • Papermaking binder CMC 0.25% by mass (7)
  • Dispersant sodium ⁇ -naphthalenesulfonate-formalin condensate (Demol N from Kao Corp.) 0.5% by mass
  • the dispersant (8) was added in an amount of 0.5% by mass based on the total (100% by mass) of the components (1) to (7).
  • the waviness on the top side (opposite to the wire side) of the sample paper was evaluated by scoring from 1 to 5 based on the number of projections of 1 mm or more in height counted on that side.
  • the disperse state of inorganic fibers was evaluated by scoring from 1 to 5 based on the number of flocks of inorganic fibers appearing on the back side (wire side) of sample paper.
  • the area ratio of flocks of the inorganic powder and the thermosetting resin was measured on the back side (wire side) of the sample paper and scored for evaluation. When these components are poorly dispersed, they gather on the wire side of paper.
  • Flocks of the inorganic powder are recognizable with the naked eye as flocks of whitish powder.
  • Flocks of the thermosetting resin are recognizable with the naked eye as flocks of yellow powder.
  • the formation was evaluated by the sum of the scores obtained in the evaluations (a) to (c). A higher score means better formation, and a lower score means poor formation.
  • the surface roughness Ra was measured with Surtronic 10 from Rank Taylor Hobson in accordance with the operation manual.
  • the amount of combustion gas generated was measured using an instrument for measuring the amount of generated combustion gas (No. 682 Gas Pressure Tester from Harry W. Dietert Co.) as follows.
  • the furnace inner temperature was set at 1000°C.
  • One-tenth gram (nominal mass) of the sample was weighed out with precision of milligram and placed on the mount of the instrument, and the amount of combustion gas generated was measured in accordance with the instruction manual.
  • the amount of combustion gas generated was calculated as programmed based on the integration of the rate of combustion gas generation. Calculation was made based on the amount of combustion gas after an elapse of 30 seconds.
  • the rate of combustion gas generation and the amount of combustion gas generated were analyzed on Chromato Pack C-R4A from Shimadz Corp.
  • Example 1 A sample sheet of base paper was prepared in the same manner as in Example 1, except for replacing the dispersant of Example 1 with the one described below. The resulting paper was evaluated in the same manner as in Example 1. The results obtained are shown in Table 1.
  • Dispersant hydroxypropyl cellulose (Klucel H from Hercules). This dispersant, being sparingly soluble, was preliminarily diluted with water to a 1% concentration and then added to a 0.5% by mass on a solid basis.
  • a sample sheet of base paper was prepared in the same manner as in Example 1, except for using no dispersant.
  • a sample sheet of base paper was prepared in the same manner as in Example 1, except for using the following raw materials of base paper for tubular paper plies.
  • the amount of the organic fiber was doubled, and any dispersant was not added.
  • Composition of base paper for tubular paper plies (sample for evaluation) (1) Inorganic powder: obsidian powder (average particle size: 30 ⁇ m) 48% by mass (2) Inorganic fiber: carbon fiber (length: 3 mm; Torayca chopped fiber, available from Toray Industries, Inc.) 9.5% by mass (3) Organic fiber: used paper 24% by mass (4)
  • Thermosetting resin resol phenol resin (Bellpearl S-890 from Air Water Bellpearl Inc.) 18% by mass (5) Papermaking binder: KAIMEN 0.25% by mass (6) Papermaking binder: CMC 0.25% by mass (7) Water repellant not added (8) Dispersant not added Total of (1) to (8): 100% by mass Table 1 Formation Surface Roughness Ra ( ⁇ m) Combustion Gas from Paper (c
  • a two-ply tubular part for casting (paper tube) as illustrated in Fig. 1 was formed of base paper having the following composition.
  • the resulting part was evaluated for combustion gas generation and blowback in accordance with the method described below. The results obtained are shown in Table 2.
  • Inorganic powder obsidian (Nice Catch Flower # 330 from Kinsei Matec Co., Ltd.) 57.3% by mass
  • Inorganic fiber carbon fiber (Pyrofil TR03CM from Mitsubishi Chemical Industries, Co., Ltd.) 7.2% by mass
  • Organic fiber recycled paper 11.5% by mass
  • Thermosetting resin resol phenol resin (Bellpearl S-890 from Air Water Bellpearl Inc.) 17.5% by mass
  • Papermaking binder KAIMEN 3.0% by mass
  • Papermaking binder CMC 3.0% by mass
  • Water repellant alkyl ketene dimer 0.5% by mass Total of (1) to (7): 100% by mass
  • Dispersant sodium ⁇ -naphthalenesulfonate-formalin condensate (DemolN from Kao Corp.) 0.5% by mass
  • the dispersant (8) was added in an amount of 0.5% by mass based on the total (100% by mass) of the components (1) to (7).
  • Form of part for casting The base paper for tubing (thickness; 0.7 mm) was slit into strips having widths of 80 mm and 82 mm.
  • the 80 mm wide strip was spirally lap-wound onto a mandrel having an outer diameter of 50 mm as a first ply.
  • the 82 mm wide strip was spirally lap-wound on the first ply while applying an adhesive to the 82 mm wide strip in a manner as to cover the exposed edge of the 80 mm strip to make a paper tube as a part for casting shown in Fig. 1 .
  • the amount of combustion gas generated was measured using an instrument for measuring the amount of generated combustion gas (No. 682 Gas Pressure Tester from Harry W. Dietert Co.) as follows.
  • the furnace inner temperature was set at 1000°C.
  • One-tenth (0.1) gram (nominal mass) of the sample was weighed out with precision of milligram and placed on the mount of the instrument, and the amount of combustion gas generated was measured in accordance with the instruction manual.
  • the amount of combustion gas generated was calculated as programmed based on the integration of the rate of combustion gas generation. Calculation was made based on the amount of combustion gas after an elapse of 30 seconds.
  • the rate of combustion gas generation and the amount of combustion gas generated were analyzed on Chromato Pack C-R4A from Shimadz Corp.
  • a casting mold 1 illustrated in Fig. 2 was made by burying paper tubes 2 to 4 measuring 50 cm, 30 cm, and 5 cm in length, respectively, all having an inner diameter of 50 mm, connected with pottery elbows, in the cured sand (molding sand) containing a furan resin. Two hundred fifty kilograms of molten metal at 1400°C was poured in the mold through the pour spout 5, and a blowback from the pour spout was observed with the naked eye and rated as follows.
  • a two-ply tubular part for casting was made in the same manner as in Example 3, except that base paper was prepared using the following composition (the amount of the organic fibers was doubled, and any dispersant was not used).
  • the resulting part for casting was evaluated in the same manner as in Example 3. The results are shown in Table 2.
  • the present invention provides a part for casting which has a reduced content of organic fibers while retaining excellent formation so as to reduce generation of combustion gas during casting.
  • the invention also provides a process for advantageously making a part for casting having the above effects.
  • the present invention is applicable to various casting mold parts constituting a casting mold, such as a pouring cup, a runner, a gate, a gas vent, a feeder, and a mold cavity, and production of such parts.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
  • Paper (AREA)

Claims (13)

  1. Procédé de fabrication d'une pièce pour coulage comprenant l'étape de préparation d'une suspension de matières premières comprenant des fibres inorganiques, des fibres organiques, une résine thermodurcissable, un liant pour la fabrication de papier et un agent dispersant à base de sulfonate et/ou à base de cellulose.
  2. Procédé de fabrication d'une pièce pour coulage selon la revendication 1, dans lequel la suspension de matières premières comprend en outre une poudre inorganique et/ou un agent hydrofuge.
  3. Procédé de fabrication d'une pièce pour coulage selon la revendication 2, dans lequel la teneur en masse de la poudre inorganique est de 0 % à 70 %, la teneur en masse des fibres inorganiques est de 1 % à 60 %, la teneur en masse des fibres organiques est de 1 % à 40 %, la teneur en masse de la résine thermodurcissable est de 1 % à 40 %, la teneur en masse du liant pour la fabrication de papier est de 1 % à 10 % et la teneur en masse de l'agent hydrofuge est de 0 % à 5 %, le total de la poudre inorganique, des fibres inorganiques, des fibres organiques, de la résine thermodurcissable, du liant pour la fabrication de papier et de l'agent hydrofuge étant de 100 %.
  4. Procédé de fabrication d'une pièce pour coulage selon l'une quelconque des revendications 1 à 3, dans lequel l'agent dispersant à base de sulfonate est un condensat de β-naphtalènesulfonate-formaline de sodium ayant un degré de polycondensation de 3 à 6.
  5. Procédé de fabrication d'une pièce pour coulage selon l'une quelconque des revendications 1 à 3, dans lequel l'agent dispersant à base de cellulose est un produit d'addition d'oxyde de propylène dérivé de cellulose.
  6. Procédé de fabrication d'une pièce pour coulage selon l'une quelconque des revendications 2 à 4, dans lequel la suspension de matières premières contient au moins l'un d'une obsidienne, d'une mullite et d'un graphite en tant que poudre inorganique, au moins l'une d'une fibre de carbone, d'une laine de roche et d'une fibre de céramique en tant que fibres inorganiques, et au moins l'une d'une résine phénolique, d'une résine époxy et d'une résine furannique en tant que résine thermodurcissable.
  7. Pièce pour coulage comprenant des fibres inorganiques, des fibres organiques, une résine thermodurcissable, un liant pour la fabrication de papier et un agent dispersant à base de sulfonate et/ou à base de cellulose.
  8. Pièce pour coulage selon la revendication 7, qui génère au plus 250 l/m2 de gaz de combustion à 1 000 °C.
  9. Pièce pour coulage selon la revendication 7 ou 8, qui comprend en outre une poudre inorganique et/ou un agent hydrofuge.
  10. Pièce pour coulage selon la revendication 9, dans laquelle la teneur en masse de la poudre inorganique est de 0 % à 70 %, la teneur en masse des fibres inorganiques est de 1 % à 60 %, la teneur en masse des fibres organiques est de 1 % à 40 %, la teneur en masse de la résine thermodurcissable est de 1 % à 40 %, la teneur en masse du liant pour la fabrication de papier est de 1 % à 10 % et la teneur en masse de l'agent hydrofuge est de 0 % à 5 %, le total de la poudre inorganique, des fibres inorganiques, des fibres organiques, de la résine thermodurcissable, du liant pour la fabrication de papier et de l'agent hydrofuge étant de 100 %.
  11. Pièce pour coulage selon l'une quelconque des revendications 7 à 10, dans lequel l'agent dispersant à base de sulfonate est un condensat de β-naphtalènesulfonate-formaline de sodium ayant un degré de polycondensation de 3 à 6.
  12. Pièce pour coulage selon l'une quelconque des revendications 7 à 10, dans lequel l'agent dispersant à base de cellulose est un produit d'addition d'oxyde de propylène dérivé de cellulose.
  13. Pièce pour coulage selon l'une quelconque des revendications 9 à 12, dans lequel la suspension de matières premières contient au moins l'un d'une obsidienne, d'une mullite et d'un graphite en tant que poudre inorganique, au moins l'une d'une fibre de carbone, d'une laine de roche et d'une fibre de céramique en tant que fibres inorganiques, et au moins l'une d'une résine phénolique, d'une résine époxy et d'une résine furannique en tant que résine thermodurcissable.
EP06833601.5A 2005-11-30 2006-11-29 Composant pour la production de pièces coulées et son procédé de fabrication Expired - Fee Related EP1958717B1 (fr)

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PCT/JP2006/323797 WO2007063888A1 (fr) 2005-11-30 2006-11-29 Composant pour la production de pièces coulées et son procédé de fabrication

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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4002200B2 (ja) * 2002-03-13 2007-10-31 花王株式会社 鋳物製造用抄造部品
JP5680490B2 (ja) * 2010-06-25 2015-03-04 花王株式会社 鋳物製造用構造体
CN104884186B (zh) * 2012-12-28 2017-09-26 花王株式会社 铸件制造用结构体的制造方法以及铸型等结构体
CN104338892A (zh) * 2013-07-31 2015-02-11 见得行股份有限公司 用于添加湿砂模的安定剂
CN104943243A (zh) * 2015-06-19 2015-09-30 姚伟 纸质浇注陶管的制备工艺
CN104985109A (zh) * 2015-07-06 2015-10-21 安徽三联泵业股份有限公司 一种泵体铸造用呋喃树脂负载纳米碳纤维改性型砂
CN105834367A (zh) * 2016-05-13 2016-08-10 湖州炜炎环保科技有限公司 一种铸造用纸质浇道管制备工艺
TWI630041B (zh) * 2017-05-09 2018-07-21 皇廣鑄造發展股份有限公司 鑄造用澆道保護管及其製造方法
CN108296424B (zh) * 2017-09-27 2020-04-10 柳州市柳晶科技股份有限公司 一种以纤维素为胶粘剂制备的3d打印覆膜砂
CN110170611A (zh) * 2019-04-03 2019-08-27 张储 一种铸造用纤维型壳成型工艺

Family Cites Families (70)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1941277A (en) * 1930-08-14 1933-12-26 Burgess Lab Inc C F Manufacture of ether derivatives of carbohydrates like cellulose
US1925584A (en) * 1932-06-25 1933-09-05 Richardson Co Production of pulps containing thermoplastic substances
US2006392A (en) * 1933-04-10 1935-07-02 Carey Philip Mfg Co Material and article containing fiber and method of making the same
US2269455A (en) * 1940-02-17 1942-01-13 Castings Patent Corp Mold and sprue sleeve therefor
US2523377A (en) * 1946-12-24 1950-09-26 Hercules Powder Co Ltd Preparation of cellulose ethers
US2626213A (en) * 1948-12-21 1953-01-20 Raybestos Manhattan Inc Asbestos dispersions and method of forming same
BE501107A (fr) * 1950-02-09
US2772603A (en) * 1950-09-12 1956-12-04 Owens Corning Fiberglass Corp Fibrous structures and methods for manufacturing same
US2807543A (en) * 1954-01-18 1957-09-24 Raymond C Mcquiston Method of preparing fiber dispersions containing an elastomeric binder
US2962415A (en) * 1956-03-05 1960-11-29 Hurlbut Paper Company Specialty papers containing a resin dispersant and retention aid and process for producing the same
US2962414A (en) * 1956-03-05 1960-11-29 Hurlbut Paper Company High strength specialty papers and processes for producing the same
US2906660A (en) * 1956-04-17 1959-09-29 American Mach & Foundry Glass fiber dispersions, sheets, plastic impregnated sheets and methods of forming
US2971844A (en) * 1959-06-29 1961-02-14 Bosanac Beatrice Method for preparing linden blossom tea concentrate
US3116199A (en) * 1961-07-19 1963-12-31 Fmc Corp Water-laid web
US3236719A (en) * 1961-08-14 1966-02-22 Owens Corning Fiberglass Corp Fibrous structures containing glass fibers and other fibers
US3418203A (en) * 1965-09-07 1968-12-24 Owens Illinois Inc Process of forming water-laid products of cellulosic fibers and glass fiber containing ligno-sulfonic acid and sodium silicate and products thereof
US3773513A (en) * 1969-09-12 1973-11-20 Xerox Corp Dimensionally stable photographic paper containing glass fibers
US3844337A (en) * 1972-12-18 1974-10-29 Packaging Corp America Pouring sprue
US4081168A (en) * 1974-09-12 1978-03-28 Foseco Trading, A.G. Hot top lining slabs and sleeves
US4069859A (en) * 1975-03-03 1978-01-24 Sato Technical Research Laboratory Ltd. Direct pouring method using self-fluxing heat-resistant sheets
SE401918B (sv) * 1976-01-19 1978-06-05 Rockwool Ab Sett att framstella en mineralfiberprodukt
DE2941644C2 (de) * 1978-10-17 1982-11-11 Matsushita Electric Industrial Co., Ltd., Kadoma, Osaka Lautsprechermembran und Verfahren zu ihrer Herstellung
AU526880B2 (en) * 1978-12-27 1983-02-03 Dyson Refractories Ltd. Runners etc for bottom pouring
FR2553121B1 (fr) * 1983-10-06 1986-02-21 Arjomari Prioux Feuille papetiere, son procede de preparation et ses applications notamment comme produit de substitution des voiles de verre impregnes
CN86100068B (zh) * 1986-01-07 1988-12-28 孙孟全 球形保温冒口套
DE3725248A1 (de) * 1987-07-30 1989-02-09 Henkel Kgaa Antimikrobiell wirksame, aromatisierte zubereitungen
US4981166A (en) * 1989-06-27 1991-01-01 Brown Foundry Systems, Inc. Foundry paper riser and system therefor
US5205340A (en) * 1989-06-27 1993-04-27 Brown Foundry System, Inc. Insulated paper sleeve for casting metal articles in sand molds
CN1017030B (zh) * 1990-07-24 1992-06-17 鸡西市柳毛石墨矿 配制钢锭模涂料用固体粉料
US5830548A (en) * 1992-08-11 1998-11-03 E. Khashoggi Industries, Llc Articles of manufacture and methods for manufacturing laminate structures including inorganically filled sheets
US5242006A (en) * 1992-10-14 1993-09-07 Eudelio Ortega Drapery weight and method
DK169925B1 (da) * 1993-02-23 1995-04-03 Dacompa As Fremgangsmåde og anlæg til fremstilling af formet emne og formet emne
CN1037589C (zh) * 1993-06-19 1998-03-04 包钢耐火材料厂 铸锭用轻质绝热板及其制造工艺
JP3139918B2 (ja) * 1993-12-28 2001-03-05 株式会社キャディック・テクノロジ−・サ−ビス 耐火物成形品の製造方法および耐火物成形品用バインダ
US5766686A (en) * 1996-03-01 1998-06-16 North American Refractories Co. Spray insulating coating for refractory articles
JPH09253792A (ja) * 1996-03-25 1997-09-30 Nissan Motor Co Ltd 鋳造用紙中子およびその製造方法
US5806712A (en) * 1996-10-30 1998-09-15 Crane Co. Vending machine for dispensing beverage containers
JP2001517273A (ja) * 1997-03-31 2001-10-02 ファイバーマーク インコーポレイテッド 金属繊維及び金属粉末のシートとその製造方法
AU6763798A (en) * 1997-03-31 1998-10-22 Fibermark, Inc. Method of making a metal fiber sheet
US6264045B1 (en) * 1997-06-02 2001-07-24 Hitco Carbon Composites, Inc. High performance filters comprising an inorganic composite substrate and inorganic fiber whiskers
US6278448B1 (en) * 1998-02-17 2001-08-21 Microsoft Corporation Composite Web page built from any web content
DE69935784T2 (de) * 1998-02-23 2007-08-16 Kao Corporation Verfahren zur herstellung eines geformten faserprodukts
WO1999042661A1 (fr) * 1998-02-23 1999-08-26 Kao Corporation Procede de fabrication de produits formes par moulage de pulpe agglomeree
JP3962146B2 (ja) * 1998-03-03 2007-08-22 Ｎｓｋワーナー株式会社 湿式摩擦材及びその製造方法
US5989390A (en) * 1999-01-06 1999-11-23 Knowlton Specialty Papers, Inc. Friction paper containing activated carbon
WO2000044986A1 (fr) * 1999-01-29 2000-08-03 Kao Corporation Procede de fabrication d'un corps forme par moulage de pate
GB0004681D0 (en) * 2000-02-28 2000-04-19 Saffil Limited Method of making fibre-based products and their use
US7077933B2 (en) * 2000-03-01 2006-07-18 Kao Corporation Pulp molded body
AU2001246855A1 (en) * 2000-04-11 2001-10-23 Kao Corporation Method of producing pulp moldings
CN1177974C (zh) * 2000-04-18 2004-12-01 花王株式会社 纸浆模成形体的制造方法及所用的抄纸模
US20020096278A1 (en) * 2000-05-24 2002-07-25 Armstrong World Industries, Inc. Durable acoustical panel and method of making the same
EP1186704A1 (fr) * 2000-09-08 2002-03-13 Ruey Ling Chen Papier en fibres de carbone de type asphalte, et son procédé de fabrication
JP2002207612A (ja) * 2001-01-12 2002-07-26 Hitachi Ltd ログ解析方法及びその実施装置並びにその処理プログラムを記録した記録媒体
US6533897B2 (en) * 2001-04-13 2003-03-18 Fmj Technologies, Llc Thermally and structurally stable noncombustible paper
US6488811B1 (en) * 2001-04-30 2002-12-03 Owens Corning Fiberglas Technology, Inc. Multicomponent mats of glass fibers and natural fibers and their method of manufacture
JP3415607B2 (ja) * 2001-07-24 2003-06-09 花王株式会社 繊維成形体の製造方法
WO2003016627A1 (fr) * 2001-07-31 2003-02-27 Kao Corporation Procede de production d'un produit forme de fibres creuses, corps forme de fibres creuses et dispositif de production d'un corps forme de fibres creuses
US20040045690A1 (en) * 2001-08-03 2004-03-11 Keiji Eto Molded pulp product, and method and apparatus for production thereof
JP4002200B2 (ja) * 2002-03-13 2007-10-31 花王株式会社 鋳物製造用抄造部品
US6616802B1 (en) * 2002-04-10 2003-09-09 Fibermark, Inc. Process and apparatus for making a sheet of refractory fibers using a foamed medium
JP4471629B2 (ja) * 2002-11-13 2010-06-02 花王株式会社 鋳物製造用部品の製造方法
JP3995649B2 (ja) * 2002-11-29 2007-10-24 花王株式会社 鋳物製造用の鋳型又は構造体
WO2004052572A1 (fr) * 2002-12-09 2004-06-24 Kao Corporation Sable de fonderie spherique
JP4154727B2 (ja) * 2003-04-22 2008-09-24 王子製紙株式会社 湿式法不織布ならびにその製造方法
JP4439315B2 (ja) * 2004-03-31 2010-03-24 花王株式会社 抄造成形体の製造方法
EP1754554B1 (fr) * 2004-06-10 2019-03-06 Kao Corporation Structure destinée à la production de pièces coulées
JP4601531B2 (ja) * 2004-10-12 2010-12-22 花王株式会社 繊維成形体の製造方法及び装置、繊維成形中間体並びに繊維成形体
US9802866B2 (en) * 2005-06-09 2017-10-31 United States Gypsum Company Light weight gypsum board
US20070039703A1 (en) * 2005-08-19 2007-02-22 Lee Jerry H Wet formed mat having improved hot wet tensile strengths
US20080135721A1 (en) * 2006-12-06 2008-06-12 General Electric Company Casting compositions for manufacturing metal casting and methods of manufacturing thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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KR20080072013A (ko) 2008-08-05
CN101316665B (zh) 2011-04-27
EP1958717A4 (fr) 2011-04-13
CN101316665A (zh) 2008-12-03
WO2007063888A1 (fr) 2007-06-07
KR101205749B1 (ko) 2012-11-28
US20090211717A1 (en) 2009-08-27
EP1958717A1 (fr) 2008-08-20

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