JPH01159207A - Molding tool for ultraplastic processing - Google Patents

Abstract

PURPOSE:To obtain a molding tool which possesses sufficient heat resistance and strength to various processing conditions and is superior in surface transfer properties and easy in molding, by specifying the compounding quantity of ultrafine powder, dispersant and water to cement matter substance. CONSTITUTION:A kind or more of 5-1,000pts.vol. ultrafine powder and a 1-5wt.% dispersant and 30wt.% water are added respectively to 100pts.vol. cement matter substance and the total quantity of the cement matter substance and ultrafine powder for kneading and molded into a desired form. Various substance which is not easily water-soluble such as silica dust or silica matter dust titanium oxide or aluminum oxide or zirconium oxide or blast furnace slag can be used as an ingredient constituting the ultrafine powder. When the quantity of the ultrafine powder consumed is less than 5pts.vol., if a water quantity is small, it is hard to obtain favorable flowability in a kneaded matter. When the quantity of the ultrafine powder consumed exceeds 1,000pts.vol., it is hard to obtain flowability, and wear resistance of strength characteristics of the surface also becomes insufficient.

Description

[Detailed description of the invention] The present invention relates to a mold applied to superplastic working.

(Prior Art) A mold for superplastic processing must maintain heat resistance and mechanical strength to withstand processing conditions, and must also have faithful transferability even for complex shapes.

Traditionally, molds include metal molds, ceramic molds, and plaster molds, but metal molds are not durable due to oxidation and creep phenomena under high-temperature conditions, and the disadvantage is that the manufacturing cost of complex-shaped molds increases. Although ceramic molds have excellent strength under high temperatures, they are generally expensive and have the disadvantage that it is extremely difficult to obtain large-sized objects with high dimensional accuracy.

Furthermore, although plaster molds are easy to mold, they lack durability at high temperatures.

(Objective) The present invention provides a mold for superplastic processing that has sufficient heat resistance and strength under various processing conditions, has excellent surface transferability, is easy to mold, and is inexpensive.

(Structure) The mold of the present invention has the following properties for 100 parts by volume of cementitious material:
5-t, ooo volume parts of one or more types of ultrafine powder, 1-5% by weight of a dispersant and 301i weight% or less of water based on the total amount of the cementitious material and ultrafine powder are added and kneaded, and the mixture is kneaded into the required shape. Depending on the desired performance, a part of the cementitious material is molded into a particle size of 1 to 100, which does not participate in the hydration reaction.
Substitute with inert inorganic powder of 100 μm and further increase the particle size of 100 μm.
It is made by mixing aggregate exceeding μm and/or various short fibers.

As the cementitious material used in the present invention, various Portland cements such as normal, early strength, super early strength, and white are commonly used.

In addition, medium-heat, low-heat cements such as blast furnace cement and Flyara 4-Shi-5 cement, sulfate-resistant cement, and alumina cement can be used, and even calcium hydroxide and calcium oxide can be used if appropriate curing methods are used. Can be done.

Also, cements containing blast furnace slag or fly ash in a higher amount than ordinary mixed cements can be used, such as high sulfate cements and improved blast furnace cements.

In addition, in consideration of heat resistance, alumina cement-based materials or cement-based materials with high slag content are preferable.

The particle size of these cementitious substances is usually 10 to 30 μm, but of course particles smaller or larger than this can also be used as long as they have hydraulic properties.

In addition, for these cementitious substances, a quick hardening agent, an expanding agent, a high-strength admixture, and various chemical admixtures, which are usually used in cement concrete, may be used in combination.

The term "ultrafine powder" as used in the present invention means a powder having an average particle size of less than 1 .mu.m and consisting of particles one order of magnitude smaller, preferably two orders of magnitude smaller, than the cementitious material.

There are no particular restrictions on the components that make up the ultrafine powder; for example, silica dust, siliceous dust, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, silica gel, opal silica, various glasses, clay minerals such as bentonite, and their temporary Various materials that are not easily soluble in water can be used, such as porcelain, amorphous aluminosilicate, activated carbon, blast furnace slag, and fly ash.

The amount of ultrafine powder used is 5 to 1.000 parts by volume, more preferably 1 part by volume, per 100 parts by volume of the cementitious material in order to increase the fluidity, moldability, heat resistance, and high strength properties of the mixed material.
0 to 500 parts by volume.

This results in a compressive strength of 600 to 1.0 after curing the product.
00 kgf/- or more.

If the amount of water is less than 5 parts by volume, it is difficult to obtain good fluidity of the mixed material, and if it exceeds 1.000 parts by volume, it is difficult to obtain good fluidity, and the abrasion resistance and strength properties of the surface are also insufficient. becomes.

As the dispersant used in the present invention, a so-called high performance water reducing agent is effective for Portland cement systems.

This surfactant is used to ensure wettability and fluidity in systems with various materials and water, and has high dispersion power without causing excessive air entrainment even when added in large amounts. The main ingredients are salts of melamine sulfonic acid formaldehyde condensates, salts of alkylnaphthalene sulfonic acid formaldehyde condensates, salts of naphthalene sulfonic acid formaldehyde condensates, high molecular weight lignin sulfonates, polycarboxylate salts, etc. An example of this can be given.

In terms of economy and effectiveness, salts of formaldehyde condensates of naphthalene sulfonic acid and alkylnaphthalene sulfonic acids are preferred.

The amount of water reducing agent used is usually 0.3~ for cement.
Although it is used in an amount of 1% by weight, in the present invention, it is preferable to use a larger amount than that, and 1 to 5% by weight is preferable based on the total of cementitious material and ultrafine powder (hereinafter referred to as powder), and Preferably it is 1.5 to 3% by weight.

In the alumina cement system, when using a high performance water reducing agent, various known hardening modifiers alone or in combination are added in an amount of 0.005 to 1% by weight based on the cementitious material.

Hardening modifiers include sulfates, nitrates, Na2Co3°LL salts, CaCl2, Ca(OH)2°, organic acids such as citric acid, tartaric acid, gluconic acid and their salts, borax, boric acid, and the like. .

Note that some tripolyphosphoric acid, pyrophosphoric acid and their salts, and organic acids and their salts also have a dispersing effect, such as the combination of Na citrate and Li citrate, so in that case, other high-performance water reducing agents may be used. It is not necessary to use it together with.

In the present invention, the amount of water mixed is important in order to develop product strength, and the amount is 30 times or less, more preferably 25% by weight or less based on the powder.

In the present invention, it is effective to replace a portion of the cementitious material with inert inorganic powder in order to improve heat resistance, and the higher the temperature, the more remarkable the replacement effect becomes.

The inert inorganic powder (hereinafter referred to as inert powder) used in the present invention means a powder consisting of particles of an inorganic powder material that is inert to water phase reactions.

The particle size of inert powder is such that the smaller the particle size, the larger its specific surface area, making it impossible to maintain fluidity unless a large amount of water is used during cross-talk, and the larger the particle size, the more difficult it is to transfer the surface. Taking into account the possibility that the sex will deteriorate, etc., 1.
~100 μm, preferably 5-88 μm, more preferably 5-44 μm.

Use of this inert powder improves heat resistance and curing shrinkage while maintaining high strength properties.

There are no particular restrictions on the ingredients that make up the inert powder, including oxides,
In addition to non-oxide ceramics, various types of ceramics, refractories, and refractory aggregates are used.

Examples include silica, alumina, mullite, magnesia, spinel, and silicon carbide.

It is not appropriate for the inert powder to be easily soluble in water, and it is preferable to use one that does not have a very high water absorption rate.

Furthermore, the inert powder used depending on the degree of heat resistance required is
It is necessary that it can withstand at least a high temperature higher than the required temperature.

The amount of the inert powder used can be changed arbitrarily with respect to the cementitious material, but 20 to 95 parts by volume based on a total of 100 parts by volume of both powders is effective from the point of view of improving heat resistance.

If it exceeds 95 parts by volume, high strength cannot be obtained.

In the present invention, aggregates having a larger powder diameter can be added to the various materials described above.

Therefore, in the present invention, aggregate refers to those with a particle size exceeding 100 μm, and can be used even with general sand and gravel, and has a Mohs hardness of 6 or more, or a Knoop indenter hardness of 700 kgf.
/-In addition to the hard aggregate selected based on the above criteria, other materials such as metal and glass can also be used.

In addition, if heat resistance is particularly required, chamotte,
Oxide-based refractory plate aggregates such as bauxite, chromite, zirconia, synthetic mullite, alumina, and spinel are preferred.

The amount of these aggregates used is 1.0 parts per 100 parts by weight of powder.
000 parts by weight is preferred (however, this does not apply to special construction methods such as pre-packed construction methods and post-packed construction methods).Furthermore, in the present invention, the above-mentioned cross-wire material may be combined with steel frames, reinforcing bars, fibers, etc. It can be used as tensile and bending reinforcement.

Examples of fibers include cast iron - chatter cutting method fibers;
Metal fibers such as steel fibers and stainless steel fibers, various natural or synthetic mineral fibers such as asbestos, ceramic fibers, and alumina fibers, carbon fibers, glass fibers, and natural or synthetic organic fibers such as polypropylene, vinylon, acrylonitrile, and cellulose. Can be mentioned.

In addition, steel rods and FR, which have traditionally been used as reinforcing materials,
It is also possible to use a P-rod or even a molded body made of alumina fiber, and these reinforcing materials are often necessary, especially for large-sized ones.

From the viewpoint of not impairing fluidity, short metal fibers with a length of about 3 mm or even shorter whiskers are preferable.

When considering heat resistance and expecting a composite effect up to high temperatures, metal fibers such as stainless steel fibers, whiskers, inorganic fibers, and molded products thereof are useful.

In the present invention, the above-mentioned method of cross-conducting the cross-conducting materials does not require any special means, but it is effective to perform vacuum defoaming at the time of cross-contamination.

As the manufacturing method of the present invention, a conventional method can be used.

For example, manufacturing by only pouring is possible.

The molded product obtained by molding the kneaded material is cured, and there are no particular restrictions on the curing conditions.

However, if the cementitious material/inert powder ratio of the powder is small, or if calcium hydroxide, calcium oxide, or a product that produces them is used as the cementitious material,
Temperatures higher than 0.degree. C. are desirable, and wet curing at 40 to 50.degree. C. or higher, or in some cases even higher temperatures and high-temperature and high-pressure curing are also required.

Note that pre-firing at the superplastic working temperature is also important from the viewpoint of the lifespan of the mold.

In order to improve the yield strength of the surface of the present invention, it is also possible to perform plating, thermal spraying, etc. on the surface.

Plating is a method of electroless plating and electroplating, and the metal layer is plated with various metals such as copper, nickel, chromium, zinc, gold, silver, and tin, iron, etc.

A42203, SiC, diamond and P T F E (Polytetr
Various types of plating can be performed, such as composite plating and porous plating, in which afluoroethylene) or the like is co-deposited.

Thermal spraying includes metal spraying such as aluminum, nickel, chromium, copper, stainless steel, zinc, tin, lead, iron, and alloys thereof, and ceramic spraying such as alumina and tungsten carbide.

The thickness of the surface layer by these plating and thermal spraying is 0.001
A range of 0.2 mm is preferred.

If the thickness of the surface layer is less than 0.001 mm, there is no effect of improving the yield strength of the surface of the present invention by forming the surface layer, and even if the thickness of the surface layer is greater than 0.2 mm, no further improvement in yield strength can be expected. .

Considering the purpose of the present invention, which takes advantage of good transferability, the smaller the thickness of the surface layer, the more preferable it is, and the upper limit of the thickness is 9.2 mm.

Using the mold of the present invention produced by the above method, it is possible to superplastically process fine grained superplastic metal materials, thermoplastic carbon fiber composite materials, and the like.

The mold of the present invention can be used as a mold for superplastic processing methods such as vacuum forming, blow molding, pneumatic basil forming, deep drawing, and forging.
It is used at low strain rates of 10-'/sec.

(Effects) According to the present invention, it has become possible to easily form a mold with high mechanical strength at high temperatures and to provide a mold for superplastic working with excellent surface transferability.

(Example 1) Using the composition shown in Table 1, the outer diameter 1 shown in FIG.
A female mold with a diameter of 0.00 mm and a depth of 100 mm was manufactured.

After molding, it was cured in humid air at 50°C for 1 day, dried at 1'00°C for 1 day, and then heated to 1,000°C and held for 10 hours. The compressive strength and bending strength are shown in the table.

Next, the mold of the present invention obtained was subjected to superplastic working by blow molding as shown in FIG.

Processing material is δ/γ two-phase stainless steel plate thickness 2ml1
1. Press pressure 30kgf/ad, 1.000℃, air pressure 1゜atm (gauge pressure), strain rate 10-'/
100 shot moldings were carried out, but there was no breakage of the mold or tearing of the cylindrical product, and all desired products were obtained.

Table-1 Cement materials used: "Denka Alumina Cement No. 1" [manufactured by Denki Kagaku Kogyo ■] Ultrafine powder 1: Alumina ultrafine powder (average particle size by TEM: 0.2 μm) Ultrafine powder 2: Silica fume (average particle size by TEM) Diameter: 0.2 μm) Water reducing agent: Cellflow 110PJ [Daiichi Kogyo Seiyaku special product] Aggregate: double scorched earth shale (China Great Wall Ware, particle size: 0.3-1.0 ma+, Mohs hardness: 8) Fiber: Alumina Fiber "Denka Arsen" [manufactured by Denki Kagaku Kogyo ■] Curing regulator: Na25o4 (reagent grade) (Example 2) A female mold similar to that in Example 1 was produced using the composition shown in Table 2. Na.

After molding, it was cured in humid air at 50°C for 3 days, dried at 100°C for 1 day, and then further heated to 1,000°C and held for 10 hours. The compressive strength and bending strength were as shown in the table below. .

Next, using the obtained mold of the present invention, superplastic working was performed using the same processing conditions and processing materials as in Example 1.

Twenty shots were molded, but there was no damage to the mold or tearing of the cylindrical product, and all desired products were obtained.

Table 2 Materials used: Cement: "Denka Alumina Cement No. 1" [manufactured by Denki Kagaku Kogyo ■] Ultrafine powder Nijirica Huyum (average particle size by TEM: 0.2 μm) Dispersant Nitripolyphosphate sodium (reagent) Hardening modifier Niboric acid ( reagent grade).

Aggregate Niotabi Chamotte (particle size, 0.7 arm or less)
Fiber: Alumina fiber "Denka Arsen" [manufactured by Denki Kagaku Kogyo ■] (Example 3) A female mold similar to that in Example 1 was produced using a composition having the formulation shown in Table 3.

After molding, it was cured in water at 50°C for 7 days, dried at 100°C for 1 day, and then further heated to 1.000°C and held for 10 hours. The compressive strength and bending strength are shown in the table.

Next, using the obtained mold of the present invention, superplastic working was performed using the same processing conditions and processing materials as in Example 1.

No. 25 shot molding was performed, but there was no damage to the mold or tearing of the cylindrical product, and all desired products were obtained.

(Leaving space below) Table 3 Materials used: Cement: “Ordinary Portland cement” [manufactured by Andes Cement Joint Venture ■] Slag: Blast furnace slag slag (fineness is 3,500 cal/g in Blaine value), ultra-fine powdered Nijiri Cahyum (according to TEM) Average particle size: 0.2 µm) Gypsum: Anhydrous gypsum (powderness is 4,500 d17g according to Blaine value) Water reducing agent: "Cellflow 110P" [manufactured by Dai-Kogyo Seiyaku Aji] Aggregate Niotabi Chamotte (fine powder, 0.2 μm) 7 mm or less) Fiber: Alumina fiber “Denka Arsen” [Denki Kagaku Kogyo ■
(Example 4) Using the composition shown in Table 4, a female mold for processing a multi-stage rectangular tube made of A7475 with a corner IR one step height of 15 mm shown in FIG. 2 was manufactured.

After molding, it was cured in humid air at 50°C for 1 day, dried at 100°C for 1 day, and then further heated to 600°C and held for 10 hours. The compressive strength and bending strength are shown in the table.

Next, the obtained mold of the present invention was subjected to superplastic working by air pressure vacuum forming as shown in FIG.

The processing material is A 7475, plate thickness 2m+a, press pressure 3kgf/crd, 500℃, vacuum pressure 0.01atm.
(gauge pressure), compressed air pressure of 1 atm (gauge pressure), and strain rate of 10-47 seconds. However, there was no damage to the mold, including wear at 18 corners, or tearing of the multi-stage rectangular tube product. All desired products were obtained.

Table-4 Material used: Cement: "Denka Alumina Cement No. 1" [manufactured by Denki Kagaku Kogyo ■] Inert powder: Heavy burnt earth shale (Great Wall Ware, Mohs hardness 8) 44 μm sieve passed ultrafine powder Nijirikahium - (by TEM) Average particle size: 0.2 μm) Water reducing agent:
"Cellflow 110P" [manufactured by Dai-Kogyo Seiyaku Aji] Aggregate: Reduced iron powder passed through a 100 μm sieve "Metalette" [manufactured by Nippon Magnetic Separation] Fiber: 5US430, φ60 μi x length 3 mm hardened by chatter cutting method [manufactured by Tokyo Steel Ltd.] Conditioner: Na2SO4 (Reagent-grade) (Example 5) A female mold similar to Example 4 was produced using the same formulation as Example 4.

After curing in humid air for 1 day at 50 DEG C., electroless plating was performed on the surface of the mold of the present invention under the conditions shown in Table 5.

After drying the electroless plated mold of the present invention at 100°C for one day, the temperature was further raised to 600°C and held for 10 hours.

The electroless plated mold of the present invention was subjected to superplastic working by pressure-air vacuum forming in the same manner as in Example 4.

Processing material is A7475, plate thickness 2mm, press pressure 3kgf/cut, 500℃, vacuum pressure 0.01at.
m (gauge pressure), compressed air pressure 1 atm (gauge pressure),
Molding was carried out for 1,000 shots at a cutting speed of 10-4/sec, but there was no breakage at any corner of the mold or tearing of the corner product, and all desired products were obtained.

The electroless plating layer had a thickness of about 0.10 (mm) and remained firmly attached to the mold of the present invention without peeling or cracking even after molding.

In addition, after the temperature was raised to 600°C, adhesive "Hardlock C-323J (manufactured by Denki Kagaku Kogyo ■)" was applied to the surface of the electroless plating layer.
After applying to a thickness of 0.1 mm or less, a diameter of 100 m is applied to the surface.
After adhesion of iron adhesive plates of 1.0 m and hardening of the adhesive, a vertical tensile test (ASTM C190-72) was conducted, and the results are shown in Table 6.

(Example 6) Using the composition shown in Table 1, the outer diameter 7 shown in FIG.
In order to process an aluminum-bronze disc shape of 0 mm and thickness of 30 mm, a pair of upper and lower molds each having a hollow cavity of the same shape as the product was manufactured.

After molding, it was cured in a humid air at 50°C for 1 day, dried at 100°C for 1 day, and then further heated to 1.000"C and held for 10 hours. Table 1 shows the compressive strength and bending strength. .

Next, superplastic forging was carried out using the obtained mold of the present invention as shown in FIG.

The processing material used was aluminum bronze with a diameter of 30 mm and a height of 100+*m, and the mold clamping pressure was 200 kgf/ai! , molding pressure 10
0 kgf/ad, 20 at strain rate 10-1/sec
Shot molding was performed, but there was no damage to the mold or cracking of the product, and all desired products were obtained.

Table-5 (Margin below) Table-6

[Brief explanation of the drawing]

FIGS. 1 to 3 are sectional views showing how the mold of the present invention is used in Examples. Patent Applicant Denki Kagaku Kogyo Co., Ltd. Patent Applicant Komatsu Ltd. Agent Patent Attorney Hiroshi Nakamura Figure 1 Air Vacuum Area Figure 3 ↓ Procedural Amendment 1) September 21, 1988 Patent Office Director Yoshi 1) Mr. Bun Yi
1. Indication of the case 1988 Patent Application No. 319825 2. Title of the invention: Molding mold for superplastic processing 3. Relationship with the person making the amendment Patent applicant address: 1-4 Yurakucho, Chiyoda-ku, Tokyo 1 name
Name Denki Kagaku Kogyo Co., Ltd. Representative Shimura Text Part 4, Agent 5, Date of amendment order (voluntary) 6, Subject of amendment 7, Contents of amendment (1) Page 24 of the specification, Table (Table 6) Insert the following sentence between the column ``4. Brief explanation of the drawing''. (Example 7) A mold having an irregular box shape shown in FIG. 4 was manufactured using the blended composition shown in Table 7. After molding, it was cured in humid air at 50°C for 1 day, dried at 100°C for 1 day, and then heated to 300°C and held for 10 hours. The compressive strength and bending strength were as shown in Table 7. Using Zn-22AI with a plate thickness of 2 + u as the processing material,
Press pressure 10kgf/ad, 275℃, vacuum pressure 0.01
atm (gauge pressure), pneumatic pressure 5 atm (gauge pressure), strain rate 5 x 10'/sec, 500 shi
Although molding was carried out, there was no damage to the mold or tearing of the product, and all desired products were obtained. (Leaving space below) Table 7 Materials used: Cement = “Denka Alumina Cement No. 1” [manufactured by Denki Kagaku Kogyo ■] Ultra-fine powdered rainbow cahuum (average particle size by TEM: 0.2 μm) Water reducing agent: “
Cellflow 110P” [manufactured by Daiichi Kogyo Seiyaku ■] Hardening regulator: Na2 So4 (reagent grade) Bone
Material Direduced iron powder passed through a lOOμm sieve "Metalette" [manufactured by Nippon Magnetic Separation ■] Fiber: Cast iron fiber by chatter cutting method, length 2 ■ [manufactured by Kobe Casting Works ■] (2) No. 24, simple drawing In the section “Explanation”, “3rd
(3) On page 6, in line 11, replace rNa2cOsJ with r
Correct as Na2 CO3J. (4) r in page 15, line 9, and page 21, line 5, respectively.
Correct Na2 So4 J to rNa2 SO4J. (5) Add Figure 4 of the drawing. Figure 4 (Mamuro area)

Claims (1)

[Claims] Ultrafine powder 5 to 1,0 per 100 parts by volume of cementitious material
00 parts by volume, 1 to 5% by weight of a dispersant and 30% by weight or less of water based on the total amount of the cementitious material and ultrafine powder, kneaded, and molded into a required mold for superplastic processing. Molding mold.