JPH02175653A - Pottery-like sintered product - Google Patents
Pottery-like sintered productInfo
- Publication number
- JPH02175653A JPH02175653A JP63331485A JP33148588A JPH02175653A JP H02175653 A JPH02175653 A JP H02175653A JP 63331485 A JP63331485 A JP 63331485A JP 33148588 A JP33148588 A JP 33148588A JP H02175653 A JPH02175653 A JP H02175653A
- Authority
- JP
- Japan
- Prior art keywords
- ceramic sintered
- sintered body
- waste sand
- sintered product
- feldspar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000004576 sand Substances 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 239000004927 clay Substances 0.000 claims abstract description 9
- 239000010433 feldspar Substances 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- 239000000919 ceramic Substances 0.000 claims description 26
- 239000002699 waste material Substances 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 11
- 239000005357 flat glass Substances 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000004575 stone Substances 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- -1 Cerben Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、内装タイル、外装タイル、歩道用平板等とし
て利用できる陶磁器質焼結体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a ceramic sintered body that can be used as interior tiles, exterior tiles, sidewalk flat plates, and the like.
［従来の技術及び発明が解決しようとする課題］従来知
られている陶磁器質焼結体は、二酸化珪素の主要な供給
源として、珪石、蝋石、陶石等を使用している。しかし
ながら、この珪石等は高価なため、これらを用いた従来
の陶磁器質焼結体は、製造コストが高くなり、その利用
分野も自ずと限定されている。[Prior Art and Problems to be Solved by the Invention] Conventionally known ceramic sintered bodies use silica stone, Rouseki, pottery stone, etc. as the main source of silicon dioxide. However, since silica stones and the like are expensive, conventional ceramic sintered bodies using them have high manufacturing costs and are naturally limited in their fields of use.
例えば、歩道用平板としてこのような従来の陶磁器質焼
結体が用いられることは少なく、より安価なコンクリー
ト平板が歩道用平板の主流を占めている。しかしながら
、このコンクリート平板は、強度において陶磁器質焼結
体より劣るので、歩道用平板として要求される強度を得
るためには肉厚としなければならなかった。このような
肉厚のコンクリート平板は嵩高で重く、運搬性および施
行性に劣るものであった。For example, such conventional ceramic sintered bodies are rarely used as flat plates for sidewalks, and cheaper concrete plates are the predominant type of flat plates for sidewalks. However, this concrete plate is inferior in strength to ceramic sintered bodies, so it had to be made thicker in order to obtain the strength required for a sidewalk plate. Such thick concrete slabs are bulky and heavy, and have poor transportability and workability.
一方、平板ガラスの研磨には従来より珪砂が用いられて
おり、研磨の後には大量の廃珪砂（いわゆる廃砂）が生
じる。この廃砂は、硬化材で固めて産業廃棄物として廃
棄されており、その再利用は図られていなかった。On the other hand, silica sand has conventionally been used for polishing flat glass, and a large amount of waste silica sand (so-called waste sand) is produced after polishing. This waste sand was hardened with a hardening material and disposed of as industrial waste, and no attempt was made to reuse it.
本発明の目、的は、この廃砂を用いて、従来の陶磁器質
焼結体と同等もしくはそれ以上の特性を有する陶磁器質
焼結体を提供する処にある。An object of the present invention is to use this waste sand to provide a ceramic sintered body having characteristics equal to or better than conventional ceramic sintered bodies.
［課題を解決するための手段］
本発明の陶磁器質焼結体は、二酸化珪素の主供給源とし
て廃砂を用いたものである。[Means for Solving the Problems] The ceramic sintered body of the present invention uses waste sand as the main source of silicon dioxide.
また、廃砂、長石および粘土を主要原料として用いるこ
とが好ましい。It is also preferable to use waste sand, feldspar and clay as the main raw materials.
本発明に用いる廃砂は、平板ガラスの研磨に用いた珪砂
の廃棄物であり、代表的な組成（％）は次のようなもの
である。The waste sand used in the present invention is a waste of silica sand used for polishing flat glass, and its typical composition (%) is as follows.
ＳｉＯ８１，３〜９２．８
ＡＮ２０３ １．４〜３，４
Ｆｅ２０３ １．４− ３．４
ＣａＯ２，９〜 ４．９
Ｍｇ０ Ｏ〜 １．５
Ｎａ２０ １．０〜３．０
に２０ ０．５〜２，５
この廃砂は、二酸化珪素の重要な供給源であり、焼成す
ることにより、強力な焼結力を生じ、他の陶磁器原料と
強固に結合する。従って、この廃砂を用いた本発明の陶
磁器質焼結体は、従来の珪石等を用いた陶磁器質焼結体
と同等もしくはそれ以上の強度を有するので、歩道用平
板として利用する場合には、薄くて軽量の歩道用平板が
得られる。また、内装タイル、外装タイルとして用いた
場合でも、従来の陶磁器質焼結体からなるタイルと比べ
て遜色がない。SiO81,3~92.8 AN203 1.4~3,4 Fe203 1.4- 3.4 CaO2,9~ 4.9 Mg0 O~ 1.5 Na20 1.0~3.0 to 20 0.5~ 2,5 This waste sand is an important source of silicon dioxide, and when fired, it produces a strong sintering force and strongly bonds with other ceramic raw materials. Therefore, the ceramic sintered body of the present invention using this waste sand has a strength equal to or higher than that of the conventional ceramic sintered body using silica stone, etc., and therefore, when used as a sidewalk flat plate, , a thin and lightweight sidewalk plate can be obtained. Moreover, even when used as an interior tile or an exterior tile, it is comparable to tiles made of conventional ceramic sintered bodies.
他の陶磁器原料としては、市販されている長石、粘土、
セルベン、珪灰石、カオリン、陶石、蝋石等を用いるこ
とができる。その中でも、長石および粘土を主要原料と
して加えると、より一層強度の優れた陶磁器質焼結体を
得ることができる。Other ceramic raw materials include commercially available feldspar, clay,
Cerben, wollastonite, kaolin, potter's stone, Rouseki, etc. can be used. Among them, if feldspar and clay are added as main raw materials, a ceramic sintered body with even greater strength can be obtained.
なお、廃砂、長石および粘土を主要原料とする場合には
、これらの配合割合（重量比）を、３０〜８０ ： ６
０〜１０：１０とすることが好ましい。In addition, when using waste sand, feldspar, and clay as the main raw materials, the mixing ratio (weight ratio) of these is 30 to 80:6.
It is preferable to set it as 0-10:10.
上記の陶磁器原料の外に、
■乾燥強度を高めるためにシリカゾル溶液やアルミナの
コロイド溶液を、
■配合粒子を均一に混合させるための解膠剤としてピロ
リン酸ソーダ水溶液、苛性ソーダ水溶液、水ガラス等を
、
■焼結体の吸水率を低下させるとともに曲げ強度を向上
させるためにソーダ灰、炭酸カルシウム、硼酸等を、
それぞれ添加してもよい。In addition to the above ceramic raw materials, ■ silica sol solution and alumina colloidal solution to increase dry strength, ■ sodium pyrophosphate aqueous solution, caustic soda aqueous solution, water glass, etc. as deflocculants to uniformly mix the blended particles. (2) Soda ash, calcium carbonate, boric acid, etc. may be added to reduce the water absorption rate of the sintered body and improve the bending strength.
陶磁器原料として、廃砂、長石および粘土を用いる場合
には、解膠剤としてピロリン酸ソーダ水溶液を用いるこ
とが好ましい。When waste sand, feldspar, and clay are used as ceramic raw materials, it is preferable to use an aqueous solution of sodium pyrophosphate as the deflocculant.
［実施例コ
次に、本発明を実施例および比較例により具体的に説明
する。[Examples] Next, the present invention will be specifically explained using Examples and Comparative Examples.
実施例１〜６、比較例１〜２ 以下の工程に従って、陶磁器質焼結体を製造した。Examples 1-6, Comparative Examples 1-2 A ceramic sintered body was manufactured according to the following steps.
（１）前処理
ガラス研磨で生じた廃砂は、含水率が高いため、遠赤外
線ヒータで乾燥させて調整した後、フレットミルで粉砕
した。６０メツシユパスのものを用いた。(1) Pretreatment Since the waste sand generated during glass polishing has a high moisture content, it was dried with a far-infrared heater to adjust it, and then pulverized with a fret mill. A 60 mesh pass was used.
（２）調合・撹拌
表１に示す割合（重量部）の各原料を撹拌混合した。当
初は水または水溶液を添加せずに２０分間撹拌し、その
のち水または解膠剤水溶液を加えて更に１０分間撹拌し
た。(2) Preparation/Stirring Each raw material in the proportions (parts by weight) shown in Table 1 was stirred and mixed. Initially, the mixture was stirred for 20 minutes without adding water or an aqueous solution, and then water or an aqueous deflocculant solution was added and stirred for an additional 10 minutes.
（３）解砕 混合物を解砕機により直径３ ｍｍ以下の団粒とした。(3) Crushing The mixture was made into aggregates with a diameter of 3 mm or less using a crusher.
（４）成形
解砕物を金型に入れ、３００ｋｇ／ａｔの成形圧で、１
５０＋＋＋ｍＸ １５０＋＋＋ｍＸ ９ｍ＋ｎの大きさ
に成形した。(4) Put the molded crushed material into a mold and press 1 at a molding pressure of 300 kg/at.
It was molded to a size of 50+++m x 150+++m x 9m+n.
（５）乾燥
成形品を、遠赤外線ヒータを用いて、２００℃で約２時
間乾燥させた。(5) The dried molded product was dried at 200° C. for about 2 hours using a far-infrared heater.
（６）焼成
乾燥品を、ローラーハースキルンを用いて、ローラース
ピード３．３ｍ／Ｈｒ、焼成温度１１５０〜１２００℃
で、２．５〜３．０時間、焼成した。(6) Baking and drying the product using a roller hearth kiln at a roller speed of 3.3 m/Hr and a firing temperature of 1150 to 1200°C.
It was baked for 2.5 to 3.0 hours.
乾燥工程および焼成工程における収縮率並びにでき上が
った陶磁器質焼結体の物性（比重、吸水率、摩耗減量、
曲げ強度、外観）を以下に示す方法で測定して表１に併
記した。Shrinkage rate in the drying process and firing process and physical properties of the finished ceramic sintered body (specific gravity, water absorption rate, abrasion loss,
The bending strength and appearance) were measured by the methods shown below and are also listed in Table 1.
■ 収縮率
ＪＩＳ Ａ ５２０９ ７．２項の測定器具を用い
て、成形品および焼結体の寸法を測定し、成形品を基準
として算出した。■ Shrinkage rate The dimensions of the molded product and sintered body were measured using a measuring instrument specified in JIS A 5209 Section 7.2, and the shrinkage rate was calculated based on the molded product.
■ 比重
ＪＩＳ Ａ ５２０９ ７．２項の測定器具を用い
て、寸法を測定し、別途求めた重量から算出した。■ Specific gravity The dimensions were measured using a measuring instrument specified in JIS A 5209 Section 7.2, and calculated from the separately determined weight.
■ 吸水率
ＪＩＳ Ａ ５２０９ ７．５項の方法で測定した
。■Water absorption rate Measured according to the method specified in JIS A 5209 Section 7.5.
■ 摩耗減量
ＪＩＳ Ａ ５２０９ ７．７項の方法で測定した
。■ Abrasion loss Measured by the method specified in JIS A 5209 Section 7.7.
■ 曲げ強度
ＪＩＳ Ａ ５２０９ ７．８項の方法で測定した
。■ Bending strength Measured according to the method specified in JIS A 5209 Section 7.8.
■ 外観
ひび割れ、割れ、ばち、または、そりが少しでも認めら
れたものを×とし、いずれも認められなかったものを○
とした。■ Items with any visible cracks, splits, burrs, or warping are marked as ×, and items with none of the above are marked as ○.
And so.
（以下余白）
表から明らかなように、実施例１〜６の陶磁器質焼結体
は、曲げ強度が大きいだけでなく、他の物性も優れてい
る。また、廃砂、長石および粘土を主要原料とする場合
には、焼成に適する組成範囲が広いので、種々の用途に
応じて適宜に配合割合を選択することができ、利用分野
が広い。(The following is a blank space) As is clear from the table, the ceramic sintered bodies of Examples 1 to 6 not only have high bending strength but also have excellent other physical properties. Furthermore, when waste sand, feldspar, and clay are used as main raw materials, the range of composition suitable for firing is wide, so the blending ratio can be appropriately selected according to various uses, and the field of use is wide.
これに対し、比較例１の陶磁器質焼結体は、一般的な内
装タイルの組成により構成されたものであり、内装タイ
ルの標準的な物性を示している。しかしながら、主要原
料である珪石は高価であり、経済的には不利である。ま
た、比較例２の陶磁器質焼結体は、廃砂のみで構成した
ものであり、外観に難があった。On the other hand, the ceramic sintered body of Comparative Example 1 was composed of a common interior tile composition and exhibited standard physical properties for interior tiles. However, silica stone, which is the main raw material, is expensive and economically disadvantageous. Furthermore, the ceramic sintered body of Comparative Example 2 was composed only of waste sand and had a poor appearance.
比較例３
市販の歩道用コンクリート平板（３００ｍｍ Ｘ３００
＋ｎｍｎｍＸ６Ｏについて、比重および曲げ強度を測定
した。比重は２．５、曲げ強度は４２ｋｇｆ／ｃ♂であ
った。Comparative Example 3 Commercially available concrete slab for sidewalk (300mm x 300
+nmnmX6O was measured for specific gravity and bending strength. The specific gravity was 2.5 and the bending strength was 42 kgf/c♂.
［発明の効果〕
以上のように、本発明の陶磁器質焼結体は、従来の珪石
等を用いた陶磁器質焼結体と同等もしくはそれ以上の物
性を有し、しかも、従来廃棄されていた廃砂を有効に利
用するので極めて安価に製造できる。[Effects of the Invention] As described above, the ceramic sintered body of the present invention has physical properties equivalent to or better than conventional ceramic sintered bodies using silica stone, etc. Since waste sand is effectively used, it can be manufactured at an extremely low cost.
従って、内装タイル、外装タイル、歩道用平板等として
、広い分野に利用できる。特に、歩道用平板として用い
る場合には、従来のコンクリート平板の約１／３の厚さ
とすることができ、しかも比重も小さいので、大幅な軽
量化が図れる。Therefore, it can be used in a wide range of fields, such as interior tiles, exterior tiles, sidewalk plates, etc. In particular, when used as a sidewalk flat plate, the thickness can be approximately 1/3 of that of a conventional concrete flat plate, and the specific gravity is also small, resulting in a significant weight reduction.
Claims (3)
焼結体。1. Ceramic sintered body using waste sand as the main source of silicon dioxide.
結体。2. Ceramic sintered body made from waste sand, feldspar, and clay as main raw materials.
６０〜１０：１０である請求項２記載の陶磁器質焼結体
。3. The weight ratio of waste sand, feldspar and clay is 30 to 80:
The ceramic sintered body according to claim 2, wherein the ratio is 60 to 10:10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63331485A JPH0674169B2 (en) | 1988-12-27 | 1988-12-27 | Ceramic sinter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63331485A JPH0674169B2 (en) | 1988-12-27 | 1988-12-27 | Ceramic sinter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02175653A true JPH02175653A (en) | 1990-07-06 |
| JPH0674169B2 JPH0674169B2 (en) | 1994-09-21 |
Family
ID=18244173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63331485A Expired - Lifetime JPH0674169B2 (en) | 1988-12-27 | 1988-12-27 | Ceramic sinter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0674169B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09125186A (en) * | 1995-10-30 | 1997-05-13 | Toto Ltd | Functionally gradient material, sealing member for electric discharge lamp using functionally gradient material, and production of functionally gradient material |
| KR100480794B1 (en) * | 2002-05-09 | 2005-04-06 | 주식회사공간세라믹 | A Clay Brick Using Fine Powder Of Waste Silica Stone And Manufacturing Method Thereof |
| JP2008156181A (en) * | 2006-12-26 | 2008-07-10 | Nippon Sheet Glass Co Ltd | Method for producing silica ceramic |
| KR100976705B1 (en) * | 2008-01-04 | 2010-08-18 | 경기대학교 산학협력단 | A method for producing of ceramic support for recycling of spent foundry sand |
| CN109053174A (en) * | 2018-10-24 | 2018-12-21 | 宿松汉邦新型建材有限公司 | A kind of snowflake white sand ceramic tile and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS511506A (en) * | 1974-06-26 | 1976-01-08 | Hitachi Ltd | |
| JPS5116310A (en) * | 1974-07-31 | 1976-02-09 | Okuma Chuzo Kk | Tairukijino seizoho |
-
1988
- 1988-12-27 JP JP63331485A patent/JPH0674169B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS511506A (en) * | 1974-06-26 | 1976-01-08 | Hitachi Ltd | |
| JPS5116310A (en) * | 1974-07-31 | 1976-02-09 | Okuma Chuzo Kk | Tairukijino seizoho |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09125186A (en) * | 1995-10-30 | 1997-05-13 | Toto Ltd | Functionally gradient material, sealing member for electric discharge lamp using functionally gradient material, and production of functionally gradient material |
| KR100480794B1 (en) * | 2002-05-09 | 2005-04-06 | 주식회사공간세라믹 | A Clay Brick Using Fine Powder Of Waste Silica Stone And Manufacturing Method Thereof |
| JP2008156181A (en) * | 2006-12-26 | 2008-07-10 | Nippon Sheet Glass Co Ltd | Method for producing silica ceramic |
| KR100976705B1 (en) * | 2008-01-04 | 2010-08-18 | 경기대학교 산학협력단 | A method for producing of ceramic support for recycling of spent foundry sand |
| CN109053174A (en) * | 2018-10-24 | 2018-12-21 | 宿松汉邦新型建材有限公司 | A kind of snowflake white sand ceramic tile and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0674169B2 (en) | 1994-09-21 |
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