JPS5945941A - Formed article of crystallized glass and its manufacture - Google Patents

Abstract

PURPOSE:To enable the manufacture of a formed article of crystallized glass within the frame of the oridinally manufacture process of glass article, by mixing a vitreous substance with a taniolite composition, melting and forming the mixture, and cooling the product. CONSTITUTION:The vitreous substance is an oridinary glass, and the taniolite composition is a fluoromica represented by the formula X0.5-1.0Y2.0-3.0(Z4O10) F2 wherein Y is (3-8)-hedron Mg2Li; X is K<+> (univalent cation) and Z is Si4 (tetrasilicon-type). The amount of the taniolite composition is preferably about 30-70pts.wt. per 100pts.wt. of the whole composition. The composition is molten at 1,200-1,300 deg.C to a viscosity of about 10<1.5>-10<2.0> poise, and formed at the inital temperature and viscosity of about 950-850 deg.C and about 10<3.0>-10<5.0> poise and the final temperature and viscosity of about 950-850 deg.C and about 10<5.5>- 10<7.0> poise, respectively. The formed article is maintained at about 700-850 deg.C for about 40-60min to produce crystals in the formed article.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a crystallized glass molded product and a method for manufacturing the same.

Crystallized glass molded product with fine crystals formed inside the glass molded product 11. It is useful as a molded product with a beautiful appearance that can be compared with natural marble, granite, etc. due to the incidence and reflection of light rays.

12 product names and manufacturing methods for crystallized glass 111'
The major issues are the composition of the raw material mixture that can produce crystals exhibiting the desired adhesiveness of 5ff5A, the appropriate viscosity of the melt to enable molding, and the thermometry of the crystallization heat treatment to produce crystals.

Currently, there are two methods for manufacturing crystallized glass molded products: a melting method and a sintering method. In the sintering method, glass powder with a composition capable of producing a specified crystal is heated at an intermediate temperature range below the melting point, which is below the softening point, and the glass powder is integrated by fusion-like crystal formation. This is a method of obtaining a product by performing a crystallization heat treatment in which crystals are precipitated inside the molded product at a predetermined temperature and time.Furthermore, the melting method completely removes the glass composition that can form a predetermined crystal. This is a method in which the material is melted, molded, and then reheated to complete the crystallization process.

#The wire method is further divided into processing molding method and casting method. Processing and molding methods are suitable for continuously reducing the amount of products, and include roll processing, such as sheet glass, and stamping, such as containers. By manufacturing crystallized glass molded products using this processing and molding method, one can expect stability in quality and economical effects through mass production, so it is especially suitable for plate-like materials used for construction, etc., which are used in large ftK. Manufacturing is
It would be extremely desirable if it were possible under the above-mentioned normal plate glass manufacturing conditions. However, in order to produce a crystallized glass molded product using a normal plate glass production method, there are essential conditions regarding viscosity and temperature. For example, as a standard condition, the viscosity of the raw material mixture is gradually and continuously lowered at the feeder position (13), and the viscosity is gradually and continuously lowered at the feeder position.
200 °C) and 107 bores (750 °C) at the end of molding.
It is a viscosity-temperature condition that has a certain degree of viscosity (around ℃), and the time it takes for 2 hours varies depending on the dimensions of the product, but it is formed after taking it out of the oven.
! It will take about 25 to 50 minutes until the end of 2. Next, it is charged into a lehr, but it is possible to change the temperature of the lehr for a little over an hour. 0°C), and operations such as holding at a constant temperature and for a certain time are possible.

The essential difference between crystallized glass molded products and ordinary glass molded products is that the former undergoes crystallization treatment under strictly controlled conditions of temperature and time. In addition, if the melt is slowly cooled at a constant temperature at which crystals begin to precipitate, the viscosity will rapidly increase and it will become semi-solid (more than 107 Boas). When applied, it is important that the 4J1 structure is such that this phenomenon does not occur until II < construction time of the molding effect. Therefore, it is necessary to obtain a molded product by matching the temperature conditions that prevent crystals from precipitating due to supercooling with the temperature conditions of normal glass manufacturing methods. I have no choice but to do it. In this case, the common operation of the conventional method is the primary crystallization heat treatment, which can be called the crystal nucleation stage or ultrafine crystallization stage, in which the molded product is heated from a low temperature and carried out at a constant temperature. Manufacturing is carried out by adding a second crystallization heat treatment step, which can also be called a crystal growth step, in which the temperature is raised and the temperature is maintained at a constant temperature.

In the crystallization heat treatment process, if the temperature conditions of the first crystallization heat treatment and the second crystallization heat treatment are performed at a temperature higher than the softening temperature at which the molded product deforms, or if they require a long time, .

A special heating furnace process must be added to the post-molding process of normal glass manufacturing methods.

The type of crystals produced in crystallized glass molded products by conventional processing and molding is β-wadistonite.

β-spodumene, β-eucryptite, etc., but the problem with this conventional method is that, as described above, a crystallization heat treatment step by reheating after molding is essential.

This addition process differs slightly depending on the 4'1 group of the crystal.

The temperature of iLII is raised in steps of approximately 700°C or higher, and the final crystallization heat treatment is performed in the temperature range of 1.000 to 1.200°C. Since the temperature is above the softening deformation temperature rrr (s o ~ 850°C), the molded product must be placed on a specific baking table and subjected to crystallization heat treatment to prevent deformation. 4. Melting method Another method, the casting method, has a small difference between the melt eddy current in the state of crystal formation and the crystal precipitation temperature, so that crystal formation can be easily started even at a high cooling rate. This is a 42-manufacturing method for crystallized glass molded products with a composition of
There is a method for producing mica glass ceramics that produces tetrasilicon mica crystals. 1. For producing mica glass ceramics. +1 formation is a crystal of phlogobite or tetrasilicon mica, respectively! 49 products have a composition that produces at least 90% or more during heavy stitching.゛Also, phlogobite (K Mg 3 (A I
Sl 3'Io ) p2. Melting point (m, p) 1375
℃, crystal precipitation temperature (C, I) ) 1375℃] or tetrasilicon mica (KMg2,5 (8i 40..) P2
rn, p 1176°C.

To explain the crystallization state of only 173°C], these om melts (1300-1450°C)
Even at a cooling rate of ~120°C, crystal precipitation begins, and at a cooling rate slower than this, crystal formation is significantly promoted and the degree of dryness rises rapidly, resulting in a drop of 100°C from the respective crystal precipitation temperature.
Since the viscosity becomes a semi-solid viscosity range (107°0 poise) between It is. That is, the viscosity is too high, leading to problems such as fractures and cracks occurring during molding, and insufficient heat resistance of processing equipment. Therefore, the current Mylar glass ceramics are
After obtaining a molded product by pouring the molten material into a mold under supercooled conditions,
Crystallization heat treatment by reheating at 750-850℃ for 1-6
Crystal cough generation stage with time holding and 1000~1150℃
The two-stage operation is an essential step: the crystallization stage, which is held for 1 to 6 hours.

The present invention is based on the conventional β-[7lastonite, β-subodumene-based crystallized glass formation, g-products, or mica-glass-ceramics in a high-temperature, high-viscosity state (Note 2 in 1f4).
It is possible to perform molding and crystallization within the normal glass product manufacturing process (1) without performing 4V molding or crystallization treatment due to long time or temperature. Crystallization process (to increase the crystallization rate by 7d as necessary to title the pattern of one item, or to make the crystallization thicker) 1
Even if the molded product is soft (V), it must be done at a temperature below the temperature at which it will not deform.

The present invention blends glass or glass, the t11 component (hereinafter referred to as gold glass material i + t) with a specific fluorine mica or its derivative, whose crystal precipitation is caused by the mechanism of the bath melting method. By doing so, it has become possible to manufacture crystallized glass molded products using two conventional glass product molding methods and temperature treatment conditions.

Fluorine Mino J has the chemical formula X0.5-1. OY2.0~a
, o (Z4010) 7J\ at F'2. In this formula, X is a cation with coordination d12, which is an interlayer ion of mica crystal, which is a one-layered crystal, and Z is a cation with coordination number 4, which is usually 8iU1 1! ! , is based on 1-silicon Si, and Y is a positive ion with a carbon number of 6 (+') forming an octahedron 1-.

Fluorine mica crystal (44 structure is 8404) Tetrahedrons are in the form of a hexagonal mesh plate, with two sheets above and below, between which ions with octahedral coordination are bonded. This structure is called a tablet, and this tablet is a layered structure. The two tablets are stacked together, and alkali 1 or alkaline earth metal ions are bonded between the tablets, which is called an interlayer ion.The basic form of this fluorocarbon mica crystal is determined by the composition of the crystal. The melting method involves melting the blended raw materials and precipitating the crystals by treating the melt under constant temperature conditions, and the melting method in which the blended raw materials are heated in the form of a mixed powder or molded product.

Reactions such as dehydration and decomposition of adsorbed water occur one after another.

A solid-state reaction in which atoms at crystal lattice points on the surface of two particles enter the radius of action of atoms on the surface of another particle due to thermal vibration of the solid particles even before the melting temperature is reached, and bonds are broken to form a crystal. There are crystals produced by this solid phase reaction, even though the melting method can be applied. Whether or not crystals can be formed by the melting method or the in-phase reaction method is determined by experimenting with various compositions.

The fluorine mica crystals produced in the crystallized glass molded product in the present invention belong to a mechanism in which crystals are produced by a melting method, and contain taeniolite crystals as a main component. Duolite has the general formula of the 77-element mica: Xo, s-t, o Y2. O-3,o (Z401G
) i'2, Y is Mg2Li (3-octahedral type) and can be classified as follows depending on the composition of X and Z.

(1) X is ll1IIi positive - (off (DK + Tel) F
), Z Ka Si.

(Tetrasilicon!σ) 2 representative examples: 1(M[2Li (Si, 0.o)F”2.
iil, ylH point (nl, l) )1
210°C9 crystal precipitation point (C, +3) 1185”C
)(2) Lla2 where X is 21111 l”is ion
"t, Sr2+, 1) b2+- or Cd"+
2 representative cases where Z is 81: CI3a 85 Mg2Li (Si, 01o)
t”□, m, p 1070°qc, p 10
50℃] (5ro5+v1g21ii (5i40.o) F□
, In, pl 050°c, p 10503 (PI) 04 1~1gz Li (si 401
o) F2, ■1.1) 1. 1 2
(Lc, pH 201 These (11, (2) Taeniolite 1fii
Assuming that crystals are formed by lθmi, the force in (3) below (0 (3) Y is Mg 2Li and
)” ” l i * is Cd2 → ゛teariT Z KaA
I S + 3 or 138 i, 9 typical examples of taeniolite crystals: (laO, 6MN<2Li (Al5i301°) l
i', , m-pl 225℃, C, I) 1225℃
] (f3ao4 Mg2I, + (1-3S+3o,o
) 1. '2, rn, p968℃, C, r)96
8° C.] To precipitate the Duolite crystals and Duolite M conductor crystals (hereinafter referred to as Duolite crystals) of (1), (2), and (3) above on glass.

As the raw material, a taeniolite crystal may be used, or its raw material composition (hereinafter referred to as a duolite composition) may be used.

The present invention relates to the above-mentioned taeniolite composition.

The purpose is achieved by a composition that combines a glassy substance.

The glassy substance used in the present invention may be a raw material badge capable of forming glass, or a frit-like glass obtained by vitrifying a raw material badge in advance and then pulverizing it. Examples of glass components include:

8102 Al20B-B2O3Ca0
1g20 - Na2O is this lc P2O
5,11aO, 84gO, ZnO, PbO.

'rib2. It is made by adding ZrO2, etc. as appropriate.2 In terms of the usual classification of glass products, it is temporary glass, bottle glass, pressed glass, lighting glass, and sealing glass.

Glass materials such as crystal glass can be used. When selecting the composition of the glass material, care must be taken to maintain a viscosity-temperature condition that does not inhibit the formation of taeniolite crystals and allows molding by other processing methods to be completed without any problems.

That is, the composition formula X of taeniolite. 5~to Mg2L
1(5i40..) In F2, for example I(
- Taeniolite (KMg2Li (5r4C1,o)
For the purpose of producing Ii"2 crystals, other ions Ba 2+ that compete with the coordination 1 to position 14 of X in the chemical formula,
Regarding Pb 2+ , Zn 2 + etc.←1
．． It is necessary to limit the crystal formation rate by these ions to within a certain value, preferably about 20% in the entire composition, and also to limit the crystal formation rate by these ions to about 20%.
The same as above is also applied when the purpose is to obtain the raw 1.7 of Lt (S+40to) F2). Furthermore, in the case of a taeniolite a conductor, A13+ coordinates to the phase t of Z and becomes 7
Regarding 133+, it is also necessary to limit the crystal formation rate due to these ions to within about 20% in the entire composition.

The blending ratio of the Duolite composition and the glass material is preferably 30 to 70 f4) + q parts when the entire composition is expressed as 100 parts by weight.

In the combination of the Duolite composition and the glassy substance according to the present invention, (after the 1L melt is discharged from the furnace and the molding is completed, the temperature - viscous temperature at iM time of 30 to 50 minutes) 'F is furnace exit, fluid movement (12 (10 to 13
00°C, viscosity 101.5 to 1020 poise) to the time of molding with a feeder etc.
At the start of molding (950-1100℃ l (ILO~
1050 poise), at the end of molding (50-850℃,
10"5 to 1 (1"' poise), which corresponds to the range of normal plate glass, and during this period, the current 11' increase in viscosity due to crystal formation etc. does not occur, and molded products without damage can be produced. I can do it. Crystallization heat is applied to generate crystals within the molded product.
This can be achieved by holding the temperature at 0 to 850°C for 40 to 60 minutes, and it can be carried out continuously within the temperature range of the slow cooling process after the completion of molding, so crystallized glass molding can be performed almost within the framework of the normal glass product manufacturing process. can complete the product.

Furthermore, among the duolite compositions, those in which X is Ba2+ [for example, Ba05Mg, Li(5i401
o) F2. BaMg2Li (A18i30to
) F.

BaMg2Lx (BS:B 016) F2)
Since this has the effect of lowering the viscosity of the molten material, it not only prevents the viscosity from rapidly changing from the time of the molten material until the end of molding, but also has the effect of prolonging the time required in the housing at the end of molding.

In the present invention, the fluorine mica to be mixed with the glassy substance has a teniolite composition as its main component, but other fluorine mica can be added thereto. For example, as mentioned above, Ba-teniolite has a viscosity-lowering effect, so it can be used as phlogobite (KMg3 (A18i30so)).
li', ) ten to some silicon mica [KMgLi (
When coexisting with fluorine mica having good crystallinity such as 8j4010) Fz), crystal formation of these fluorine mica in the high temperature range (1400 to 1200°C) is suppressed.

The amount of fluorine mica added is 80 parts by weight or less per 100 parts by weight of 13a-teniolite. When this crystal suppression phenomenon is observed using electron micrographs when cooling at a rate of at least about 100°C or more per minute, it is found that very fine crystals (
Precipitation of I+-j (10 to 30 μm in diameter) is observed, but 11tt+ and (7) are insignificant.

In this way, by mixing a taeniolite composition with phlogovite, etc., the increase in viscosity of the mixed melt with a glassy substance is suppressed, and the conditions that allow molding (Standard Example 1) are suppressed.
04°0 poise-1000℃~107°0 poise-75
0°C).

Furthermore, when a combination of phlogopite, I(-tetrasilicon mica, and Ba-teniolite composition) is heat-treated for crystallization, Ba-teniolite-based mica is formed when kept at 700 to 850°C for about 1 hour at the end of molding. Crystals are generated and smoked using microcrystals of phlogobite or silicon mica that have previously been generated in the molded product as crystal nuclei, and the amount of crystallization can be increased.This combination Naturally, not only individual crystals of Ha-teniolite and partially phrogonite or partially silicon mica but also solid solution crystals between the two are formed.

For example, LSa(1,6rνIg 2 L I(b i
40B. ) F2 and K-Mga (Al5i301
o) “In addition to 2, K Ba Mg, Lt (AI 2
St 601g) Solid solution crystals such as F4 are also formed in some parts. When the product that has undergone crystallization heat treatment in this way is further heated at 1000 to 100 T for 1 to 2 hours, the growth of f(-70 gobite, 1" or some silicate mica crystals is remarkable. , crystals with a diameter of 1 to 3 are precipitated, and a beautiful mottled pattern can be imparted to the grown product.

In addition, in the present invention, in the combination of the duolite composition described in 1 and other fluorine mica, not only the fluorine mica h4i product is introduced by the melting method, but also the product is produced by the in-phase reaction of a certain gutter. By adding element 11 to fluorine mica, -C crystals can coexist. Those with a composition based on solid phase reaction have the general formula Y of fluorine mica,
Z digit fffKpe2+, 1. +o3+, co
3+, cr3+, NIZ+, Ni”.

Cu2→, 81n2+, Tia+, +pH4
There are many cases in which ions such as +, l5c4+, and o are coordinated, and each of these is a brilliant Zlj colored fluorine mica crystal. Therefore, the two-colored horn yarn Mino J A
1'i Selecting the composition of the product, a variety of colors for the crystallized glass molded product, llAl, i□J'
fj can be done.

To give an example of this yuzu (1(Iv1g15Col, 5
(A18i.

010) l! '2 t c, t l 1 0
0 ”(:, i:' 14p also i':l: h7
Bright color 1 + [1 (84g2.s Ni o2 (Al
Si 301o) l+'2, c, t
l 0 0 0°C, green yellow] + [i(Mg2.
-2. +10 Coo, as-0,2 (Al8i301
0) F2# C-1L 000'C brown], [K
Fe3(lI'e8i301(,) li"2.c
, t 6500, black-gray].

[1(I~4gto Mn2.0 (AIS+,
0. ,, ) l”2 , c, 1 1
000℃, brown), [KA
lTi" (Al5i30□.) "'z *
c, t 800℃, beige color] etc.

The introduction of fluorine mica through the above-mentioned solid phase reaction mechanism, which is co-formed with the duolite mica that is the main subject of the present invention, depends on the appearance of the crystallized glass molded product, such as the size of the crystals, the pattern and color tone, and the roll. It is determined by considering the suitability of manufacturing conditions such as slow cooling of the molten material during molding. The amount of fluorine mica to be co-formed is 30 parts by weight or less when the sum of the teniolite composition, one phlogovite in the teniolite composition, or one part silicon mica in the teniolite composition is 100 parts by weight. . The fluorine mica to be co-formed may be not only its crystals but also raw material compositions for crystal formation (these are referred to as other fluorine mica compositions). Therefore, in the present invention, other fluorine mica compositions that can be added to the taeniolite composition include the above-mentioned l(-phlogovite) and the colored fluorine mica.

Hereinafter, the crystallized glass molded product of the present invention will be specifically explained with reference to Examples.

Actual example 1 The component composition of the glassy substance is 810272%.

Na2O13.5%, Ca012.2%, Mg01.
0%.

A1203 +, 'l''e 2o3 1.3% 145-tin part and Ba-duolite (13ao
The component composition of 5Mg2T, i (5i40.g)F2) is 5I0254.5%, l1a017.4%
, Li2O3, 4%, Mg09.1%, Mgl
A raw material badge containing 55 parts by weight of 1'215.6% was melted at 1400° C., and a crystallized glass molded product was manufactured in accordance with the manufacturing process of plate glass. The viscosity of the molten material was 300 l at a cooling rate of 35 minutes from 1350°C to 900°C from the time it was taken out of the furnace, through the feeder, and just before it was charged into the molding machine.
'C-10'' Poise.

1200℃-1028 H7, 1100'C-1
0”Ho7s, l 000”C-1045;f! 7
900℃10 Boss 7-? l' with fc. 90
I'& was molded into a plate-like body with a thickness of about 2 Oram by roll molding at 0°C to 80°C, and crystallized at a temperature of 800°C for 50 minutes to obtain a milky white crystallized glass molded product. The physical properties of this molded product include a porosity of 0. Ratio - fj2
．． 79. Hardness (Shore) 85. Transverse rupture strength 920 kg/
cr/l, and according to X-ray diffraction, electron microscopy and other measurements, Bao, I, MgzLj (8!40
30 to 40% by weight of mica crystals, which are mainly (95% or more) F2 crystals, are generated in the molded product.

It was observed that the crystal grain size was distributed between 300 and 700 μm.

Example 2 In the formulation of the above-mentioned molded product, 16.5 parts by weight of 55 parts by weight of Ba-taeniolite was added to phlogono(a) [KMg3
(Al5s30,.)F2] composition of 8i0241°8%
, 2010.9%, Al20311.8%, Mg
A plate-like body was produced by replacing O18.7% with one consisting of MgFz 16.8%. The blend was melted in a melting furnace for 145 minutes.
The molten material melted at 0°C and then taken out from the furnace was
Cool to -0°C.

The viscosity at 1200℃ is 10 poise, 1i00
The viscosity at °C was 104.2 poise. A portion of it was poured onto a heat-resistant stainless steel plate and rapidly cooled to obtain a sample piece. When this sample piece was observed, it was found that fine crystals around 10 μm were distributed fairly homogeneously. The molten material at about 1100°C is sent to a feeder, then charged into a roller molding machine via the feeder, and molded into a plate-like material with a thickness of about 20 yn with a viscosity of 1060 poise between 90 (1 and 80 f'10). A molded product with no damage was obtained. Next, a primary crystallization heat treatment was performed by heating at 800°C for about 1 hour, and a secondary crystallization heat treatment was further performed at 1050°C for about 1 hour to obtain a crystallized glass molded product. When this was measured, it was found that 1 to 70 govite crystals were scattered in the molded product in a size of 500 μm to 2000 μm, and the polished surface had a beautiful marble-like appearance.

Example 3 11 pieces (1) 5 inches suitable for light bulb glass as base material glass
267.4%, Al2031.0%, 13203
4.5%, Ca04.6%, K2O12.0%
, Na2O2, 5%, Zn04.0%, Ba0
60 parts by weight of raw material badge adjusted to 4%.

(2) Seven element strength (Ba Mg2L1 (A18i10
1g))-2 composition] for the purpose of crystal formation
434%, Ba0 1 8. 5%,
IJi20 3. 5%.

MgF216.6%, Mg0 9.6%, B20
．． To 8.4%? J@ 35 parts by weight of prepared raw material badges.

(3) Co-synthesized fluorine mica (K Mgts COt
, s(A18i, 01o) F2 composition] 5i0236%, 209.5%,
Co20325%, MgF'219.3%, Al
5 parts by weight of raw material badge adjusted to 20310.2%.

These raw material badges (1), (2), and (3) were homogeneously mixed to prepare a raw material badge.

11 (g) of manufacturing raw material badges were collected in an 8iC crucible and melted in a Matsufuru-type Elema furnace at 1400°C for 30 minutes.

Take out the furnace and heat the melt together with the crucible in the atmosphere at 1400°G.
Cool the crucible at a cooling rate of 30 to 359 C/min at 100°C1, then heat the outer periphery of the crucible from 1100°C to 1000°C for at least 20 minutes to adjust the temperature drop, and remove the melt from the crucible. Then, it was rolled and molded at 850 to 20℃ using an experimental mini roller made of Stellite heat-resistant steel to a width of 10 mm.
α, a pale blue molded body with a length of about 35 crrL was obtained. When the temperature of the molded body reached 750°C, it was put into a '1E air furnace which had been kept at 750°C in advance, held at 750°C to 740°C for 25 minutes, and then completely stopped for two energizations and cooled in the furnace. . After the molded body is taken out of the furnace, its top and bottom surfaces are polished using a conventional method. f!
By cutting the surface, we obtain a crystallized glass molded product. The product had a beautiful pattern of homogeneous clusters of pale blue sesame-like crystals. In addition, the physical properties of the product are soil specific gravity 281
．． Bending strength: 7201, g/crl, Shore hardness: 9
2. Charpy impact strong bloom 2.61Kgm / C11,
The coefficient of thermal expansion (30-500°G) was 75×10”.

Example 4 Formulation (1) Glass x 11 formation (Ichiha %) Table 1 (2) Fluorine mica composition Table 2 Door structure table of crystallized glass molded product It became beautiful.

Product performance Table 4

Claims (1)

[Claims] 0) A crystallized glass molded product comprising a molten and solidified glass substance and taeniolite crystals. (2) A crystallized glass molded product consisting of a molten solidified glass substance, taeniolite crystals, and other fluorine mica composition crystals. (3) A glassy substance and a taeniolite composition are mixed, melted, and processed and molded. A method for producing a crystallized glass molded product, which comprises then cooling. (4) A method for producing a crystallized glass molded product, which comprises mixing a glassy substance with a taeniolite composition and another fluorine mica composition, melting the mixture, processing and molding the mixture, and then cooling it.