JPH02184585A - Ceramic product with suppressed reaction of base with silica - Google Patents
Ceramic product with suppressed reaction of base with silicaInfo
- Publication number
- JPH02184585A JPH02184585A JP407389A JP407389A JPH02184585A JP H02184585 A JPH02184585 A JP H02184585A JP 407389 A JP407389 A JP 407389A JP 407389 A JP407389 A JP 407389A JP H02184585 A JPH02184585 A JP H02184585A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- component
- reactive
- base
- ceramic product
- 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 title claims abstract description 69
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 45
- 239000000919 ceramic Substances 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 32
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 230000002401 inhibitory effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 239000002585 base Substances 0.000 abstract description 13
- 239000003513 alkali Substances 0.000 abstract description 6
- 230000009257 reactivity Effects 0.000 abstract description 6
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011022 opal Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000005335 volcanic glass Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
利用分野
本発明は、塩基性成分と反応性であるシリカ成分を含有
するセラミック製品における、塩基・シリカ反応を抑制
したセラミック製品；ならびに塩基・シリカ反応が若干
進行した該セラミック製品における該反応の進行抑制方
法に関する。本発明は、塩基・シリカ反応によってクラ
ック、破損および表面汚染を発生し得る該セラミック製
品の品質改善に極めて有用である。[Detailed Description of the Invention] Field of Application The present invention relates to ceramic products that suppress the base-silica reaction in ceramic products containing a silica component that is reactive with basic components; The present invention relates to a method for inhibiting the progress of this reaction in ceramic products. The present invention is extremely useful for improving the quality of ceramic products that may suffer from cracks, breakage, and surface contamination due to base-silica reactions.
従来の技術および問題点
陶磁器質製品によって代表される塩基・シリカ反応性セ
ラミック製品は、その焼結焼成時にアルカリ・シリカ反
応性のシリカ成分を形成する。該反応性セラミックはア
ルカリと反応して、例えばセラミック製品を貼着する下
地に含まれるアルカリ成分と反応して、アルカリ・シリ
カ反応生成物を形成する。該アルカリ・シリカ反応生成
物の膨張によってクラックおよび破損を形成しそしてそ
の表面析出によって表面汚染を形成する大きな問題があ
った。従来この問題を軽減するためには、（イ）原料中
の反応性シリカ成分の量を低減すること、および（ロ）
高温度焼成によってセラミッり製品を非吸水性にするこ
と等が必要であった。Prior Art and Problems Base-silica-reactive ceramic products, typified by ceramic products, form alkali-silica-reactive silica components during sintering and firing. The reactive ceramic reacts with an alkali, such as an alkali component contained in the substrate to which the ceramic product is attached, to form an alkali-silica reaction product. There has been a major problem in the formation of cracks and fractures due to the expansion of the alkali-silica reaction product and the formation of surface contamination due to its surface precipitation. Traditionally, this problem has been alleviated by (a) reducing the amount of reactive silica components in the raw materials; and (b)
It was necessary to make ceramic products non-water absorbent by high temperature firing.
しかし、上記の（イ）の方法では原料が若干高価となり
そして供給原料の品質が不定のため困難な現状にある。However, the method (a) described above is currently difficult because the raw materials are somewhat expensive and the quality of the raw materials to be supplied is uncertain.
上記の（ロ）の方法では、熱経済および炉の観点から不
利でありそして原料も限定される傾向がある。The above method (b) is disadvantageous from the viewpoint of thermal economy and furnace, and tends to limit the raw materials.
従来、このような塩基・シリカ反応性セラミック製品の
品質を改善する簡易な手段は、未解決の状態にある。本
発明の主目的は、上記の問題を容易に解決する手段を提
供することである。Hitherto, a simple means to improve the quality of such base-silica reactive ceramic products has remained unresolved. The main purpose of the present invention is to provide a means to easily solve the above problems.
問題点を解決するための手段
本発明者は予想外にも、上記の塩基・シリカ反応性セラ
ミック製品中の反応性シリカ成分に、過酸化水素液（以
下にＨ２０，液ということがある）を接触させることに
よって、該シリカ成分の表面構造が改質されて長期的に
安定化しそしてその反応性が抑制されることを見出した
。Means for Solving the Problems The present inventor unexpectedly added a hydrogen peroxide solution (hereinafter sometimes referred to as H20, liquid) to the reactive silica component in the above-mentioned base-silica reactive ceramic product. It has been found that by contacting the silica component, the surface structure of the silica component is modified and stabilized over a long period of time, and its reactivity is suppressed.
従って本発明によって、塩基性成分と反応性である珪酸
成分および／または珪酸塩成分を含有する吸水性セラミ
ック製品に、過酸化水素水を浸透せしめて反応性シリカ
成分の反応部位を改質してなる、塩基・シリカ反応を抑
制した該セラミック製品が提供される。Therefore, according to the present invention, a water-absorbing ceramic product containing a silicic acid component and/or a silicate component that is reactive with a basic component is impregnated with a hydrogen peroxide solution to modify the reactive site of the reactive silica component. The present invention provides a ceramic product in which the base-silica reaction is suppressed.
本発明は、塩基・シリカ反応が若干進行したセラミック
製品について、該反応の進行抑制にも有利に適用できる
。従って本発明によって、塩基性成分と反応性である珪
酸成分および／または珪酸塩成分を含有するセラミック
製品の表面に出現した塩基・シリカ反応生成物を除去し
、該セラミック製品の該反応生成物が出現した部分に過
酸化水素水を浸透せしめることを特徴とする、該セラミ
ック製品の塩基・シリカ反応の進行抑制方法が提供され
る。The present invention can be advantageously applied to ceramic products in which the base-silica reaction has progressed to a certain extent, and to suppress the progress of the reaction. Therefore, according to the present invention, a base-silica reaction product appearing on the surface of a ceramic product containing a silicic acid component and/or a silicate component that is reactive with a basic component is removed, and the reaction product of the ceramic product is removed. Provided is a method for inhibiting the progress of a base-silica reaction in a ceramic product, which is characterized by infiltrating a hydrogen peroxide solution into the exposed portion.
発明の詳しい記述
（１）塩基・シリカ反応性セラミックスの例示本発明が
有利に適用されるセラミック製品は、代表的には陶器質
、せり恭賀および大部分の磁器質製品である。該吸水性
セラミック製品の場合の２４時間浸漬吸水率は、約０．
２１以上、通常は約０．５％以上そして代表的には約１
ｚ以上である。該セラミック製品の塩基性成分としては
、アルカリ成分が特に塩基・シリカ反応に関与する。反
応性シリカ成分としては、オパール、クリストバライト
、トリジマイト、火山性ガラス、五個等のシリカ鉱物、
およびこれに該当する合成材料がある。一般的には、火
成岩系材料、ガラス粉等も例示される。なお、焼成によ
ってアルカリ・シリカ反応性となる珪酸塩またはその他
の無機質原料も含まれる。Detailed Description of the Invention (1) Examples of Base-Silica Reactive Ceramics Ceramic products to which the present invention is advantageously applied are typically ceramic products, ceramic products, and most porcelain products. The 24-hour immersion water absorption rate of the water-absorbing ceramic product is about 0.
21 or more, usually about 0.5% or more and typically about 1
z or more. As the basic component of the ceramic product, an alkali component is particularly involved in the base-silica reaction. Reactive silica components include opal, cristobalite, tridymite, volcanic glass, and other silica minerals,
There are also synthetic materials that fall under this category. Generally, igneous rock materials, glass powder, etc. are also exemplified. Note that silicates or other inorganic raw materials that become reactive with alkali and silica upon firing are also included.
（２）過酸化水素液
本発明にて使用するＨ２０．液としては、工業用に安価
に市販されている＋１ 、Ｏ、が３０〜３５重量％のＨ
２０゜水溶液の希釈液が有利に使用できる。使用するＨ
２０、水の濃度（重ｆｆｉ％）は、一般的に０．１〜３
５％の範囲であり、通常は０．３〜ｉｏｓ程度であり、
そして代表的には１〜５％程度である。処理時間は、Ｈ
３０，液の濃度および製品の吸水率に依存するが、一般
的に数分間〜数時間で効果的である。(2) Hydrogen peroxide solution H20. used in the present invention. As a liquid, +1, O, which is commercially available at low cost for industrial use, contains 30 to 35% by weight of H.
A dilute solution of 20° aqueous solution can advantageously be used. H to use
20. The concentration of water (weight ffi%) is generally 0.1 to 3
It is in the range of 5%, usually about 0.3 to ios,
And typically it is about 1 to 5%. Processing time is H
30. Depending on the concentration of the liquid and the water absorption rate of the product, it is generally effective within several minutes to several hours.
該反応性セラミックスをＨ２０，液にて浸透処理するに
は、Ｈ３０，水に浸漬（例えば１ 、５％！度にて数時
間以上）するか、またはＨ８０，水をスプレーすること
ができる。一般的に、浸透処理した後に、処理済セラミ
ックスを水洗するのが好ましい場合もあるが、水洗しな
くともよい。To infiltrate the reactive ceramic with H20, water, it can be immersed in H30, water (for example, at 1.5%! degree for several hours or more), or it can be sprayed with H80, water. Generally, after the infiltration treatment, it may be preferable to wash the treated ceramics with water, but washing with water may not be necessary.
（３）具体例１〜２
本発明を適用するセラミック製品の代表例として、吸水
率５％のせり器タイル素地を下記のようにして調製した
。すなわち、生滑石および陶石の混合物６３ｉｆｌｔ％
と長石およびペタライトの混合物３０重量％を混合し、
長石の粒子径が約２ミクロン以上になる程度までボール
ミルで細磨し泥漿とする。(3) Specific Examples 1 to 2 As a representative example of a ceramic product to which the present invention is applied, a tile base with a water absorption rate of 5% was prepared as follows. That is, a mixture of raw talc and pottery stone 63iflt%
and 30% by weight of a mixture of feldspar and petalite,
The feldspar is ground into slurry using a ball mill until the particle size is about 2 microns or more.
これに泥漿粘土７５を混合した後、脱水製粉し坏土を作
る。この坏土をプレス圧３００ｋｇ／平方ｃｒｎで加圧
し、充填率０．７の成形体（１００Ｘ １００Ｘ ５ｎ
ｍ）に成形する。この成形体を最高温度１１５０℃にて
３６時間焼成し、せっ恭賀のタイル素地を得た。該タイ
ル素地の２４時間浸漬吸水率は５％であった。After mixing slurry clay 75 with this, it is dehydrated and milled to make clay. This clay was pressed at a press pressure of 300 kg/sq. crn to form a molded body (100X 100X 5n
m). This molded body was fired at a maximum temperature of 1150° C. for 36 hours to obtain a Sekyoga tile base. The 24-hour immersion water absorption rate of the tile base was 5%.
例！（実施例）では、このタイル素地を２％のＨｌｏ。example! (Example), this tile substrate was treated with 2% Hlo.
水に２４時間浸漬しそして流水にて水洗したものを用い
た。例２（比較例）では、Ｈ２０，水にて処理しないタ
イル素地をそのまま用いた。The sample was immersed in water for 24 hours and washed with running water. In Example 2 (comparative example), a tile base that was not treated with H20 and water was used as it was.
内枠寸法が１ｍ強Ｘ１ｍ強の箱状の容器を水平に配置し
、重量比にてポルトランドセメントｌおよび海砂５から
なる下地用モルタルを５ｃｍの厚さに入れて水和硬化さ
せた。その上にポルトランドセメントおよび水からなる
貼着用モルタルを５ｍｍの厚さに入れて、更にその上に
上記のタイル素地試料１０ｘｌＯ枚を目地間隔をおいて
貼着した。アルカリ・シリカ反応促進のために、該試料
を温度４０℃、相対湿度９５％の環境試験室中に３か月
保持した。本発明による例１では、タイル素地表面およ
び目地表面のクラックおよび汚染は目視にて検出されな
かった。比較例である例２では、素地表面および目地部
分に径０．５〜２ｃｍの円形状のアルカリシリカ反応生
成物（水ガラス）がｌｍＸ１ｍあたり６〜ｌＯ個程度検
出された。なお、上記の円形状反応生成物は、モルタル
（特に下地モルタル）中のアルカリ成分がタイル素地中
に侵入して、アルカリシリカ反応をおこしそしてその反
応生成物がタイル素地表面および側面に出現したもので
ある。A box-shaped container with an inner frame size of a little over 1 m x a little over 1 m was placed horizontally, and a foundation mortar consisting of 1 liter of Portland cement and 5 parts of sea sand in a weight ratio of 5 cm was poured into the container and allowed to harden by hydration. A mortar for adhesion consisting of Portland cement and water was placed thereon to a thickness of 5 mm, and 10 x 10 of the above tile base samples were adhered thereon at joint intervals. In order to accelerate the alkali-silica reaction, the sample was kept in an environmental test chamber at a temperature of 40° C. and a relative humidity of 95% for 3 months. In Example 1 according to the invention, no cracks or contamination on the tile substrate surface or joint surface were visually detected. In Example 2, which is a comparative example, approximately 6 to 10 circular alkali-silica reaction products (water glass) with a diameter of 0.5 to 2 cm were detected per 1 m x 1 m on the surface of the substrate and in the joints. The above-mentioned circular reaction products are caused by the alkali components in the mortar (especially the base mortar) penetrating into the tile base, causing an alkali-silica reaction, and the reaction products appearing on the surface and sides of the tile base. It is.
（４）参考例３〜４
上記のせっ４質タイル素地のアルカリ・シリカ反応性を
、ＪＩＳ＾５３０８付属四８に従っ付属上８タルバー法
によって試験した。該タイル素地を該ＪＩＳに規定する
粒度に粉砕しそして混合した。例３では、該粉砕物を１
．５％のＨ２０，水に２４時間浸漬しそして水洗したも
のを用いた。例４では、未処理の該粉砕物を使用した。(4) Reference Examples 3 to 4 The alkali-silica reactivity of the above-mentioned stone tile bases was tested by the Talver method according to JIS^5308 Attachment 48. The tile base was ground to a particle size specified in the JIS and mixed. In Example 3, the pulverized material was
．． It was immersed in 5% H20 and water for 24 hours and then washed with water. In Example 4, the untreated pulverized product was used.
その他は、ＪＩＳ Ａ３３０ｇの付属書８の規定に従っ
て実施した。その結果を下表に示す。Other procedures were carried out in accordance with the provisions of Appendix 8 of JIS A330g. The results are shown in the table below.
すなわち、例４は非常に有害であり、そして例３ではア
ルカリ・シリカ反応が充分に抑制されていることが実証
された。That is, Example 4 was very harmful, and Example 3 demonstrated that the alkali-silica reaction was sufficiently suppressed.
作用および効果
塩基成分およびこれと反応性のシリカ成分が共存するセ
ラミックス中の塩基・シリカ反応（特にアルカリシリカ
反応）は、該セラミックスの耐久性および汚染に極めて
有害であるが、本質的に未解決の状態にあった。本発明
の作用は、充分には解明されていないが、該反応性セラ
ミックスにＨ８０，液を浸漬等によって浸透させること
によって該シリカ成分の反応性部位であるゲル状物質が
改質されて、その反応性が効果的に抑制される効果を達
成するものと思考される。例えば、反応性シリカ成分は
代表的に１＝ｓｉ−０の反応部位を有するが、この場合
にはＨ２０，水が作用して長期的に安定なミ５ｉ−ＯＨ
構造に改質されそしてその反応性も充分に抑制されるも
のと思考される。しかしながら、本発明はこのような代
表的な理論に拘束されるものではない。Actions and Effects Base-silica reactions (especially alkali-silica reactions) in ceramics where a base component and a silica component reactive with this coexist are extremely harmful to the durability and contamination of the ceramics, but are essentially unsolved. was in a state of Although the action of the present invention is not fully elucidated, by infiltrating the reactive ceramics with H80 liquid by immersion or the like, the gel-like substance that is the reactive site of the silica component is modified. It is thought that this achieves the effect of effectively suppressing reactivity. For example, reactive silica components typically have 1=si-0 reaction sites, but in this case, H20 and water act to create long-term stable mi5i-OH.
It is thought that the structure is modified and the reactivity is sufficiently suppressed. However, the present invention is not limited to such representative theory.
本発明による製品および抑制方法は、塩基成分（特にア
ルカリ成分）と接触する反応性シリカ成分含有セラミッ
クスの長期的安定化に極めて有用である。The products and suppression methods according to the invention are extremely useful for the long-term stabilization of reactive silica component-containing ceramics that come into contact with base components, especially alkaline components.
Claims (2)
は珪酸塩成分を含有する吸水性セラミック製品に、過酸
化水素水を浸透せしめて反応性シリカ成分の反応部位を
改質してなる、塩基・シリカ反応を抑制した該セラミッ
ク製品。(1) A water-absorbing ceramic product containing a silicic acid component and/or a silicate component that is reactive with a basic component is impregnated with a hydrogen peroxide solution to modify the reaction site of the reactive silica component. This ceramic product suppresses the base-silica reaction.
は珪酸塩成分を含有するセラミック製品の表面に出現し
た塩基・シリカ反応生成物を除去し、該セラミック製品
の該反応生成物出現部分に過酸化水素水を浸透せしめる
ことを特徴とする、該セラミック製品の塩基・シリカ反
応の進行抑制方法。(2) Remove the base-silica reaction product appearing on the surface of the ceramic product containing the silicic acid component and/or silicate component that is reactive with the basic component, and remove the base-silica reaction product appearing on the surface of the ceramic product, and A method for inhibiting the progress of a base-silica reaction in a ceramic product, the method comprising impregnating the ceramic product with a hydrogen peroxide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1004073A JPH0633201B2 (en) | 1989-01-11 | 1989-01-11 | Ceramic products with suppressed base-silica reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1004073A JPH0633201B2 (en) | 1989-01-11 | 1989-01-11 | Ceramic products with suppressed base-silica reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02184585A true JPH02184585A (en) | 1990-07-19 |
| JPH0633201B2 JPH0633201B2 (en) | 1994-05-02 |
Family
ID=11574632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1004073A Expired - Lifetime JPH0633201B2 (en) | 1989-01-11 | 1989-01-11 | Ceramic products with suppressed base-silica reaction |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0633201B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5913626A (en) * | 1982-07-13 | 1984-01-24 | Nissha Printing Co Ltd | Manufacture of substrate having metallic oxide film |
| JPS5935078A (en) * | 1982-08-23 | 1984-02-25 | 日立化成工業株式会社 | Manufacture of expansive graphite formed body |
| JPS62116781A (en) * | 1985-11-15 | 1987-05-28 | Agency Of Ind Science & Technol | Formation of calcium phosphate film |
-
1989
- 1989-01-11 JP JP1004073A patent/JPH0633201B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5913626A (en) * | 1982-07-13 | 1984-01-24 | Nissha Printing Co Ltd | Manufacture of substrate having metallic oxide film |
| JPS5935078A (en) * | 1982-08-23 | 1984-02-25 | 日立化成工業株式会社 | Manufacture of expansive graphite formed body |
| JPS62116781A (en) * | 1985-11-15 | 1987-05-28 | Agency Of Ind Science & Technol | Formation of calcium phosphate film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0633201B2 (en) | 1994-05-02 |
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