JPH0350190A - Method for synthesizing diamond by combustion flame method - Google Patents
Method for synthesizing diamond by combustion flame methodInfo
- Publication number
- JPH0350190A JPH0350190A JP18708189A JP18708189A JPH0350190A JP H0350190 A JPH0350190 A JP H0350190A JP 18708189 A JP18708189 A JP 18708189A JP 18708189 A JP18708189 A JP 18708189A JP H0350190 A JPH0350190 A JP H0350190A
- Authority
- JP
- Japan
- Prior art keywords
- diamond
- combustion flame
- base material
- substrate
- molten bath
- 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
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 41
- 239000010432 diamond Substances 0.000 title claims abstract description 41
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 24
- 230000002194 synthesizing effect Effects 0.000 title claims description 6
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims description 27
- 150000002484 inorganic compounds Chemical class 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000001308 synthesis method Methods 0.000 claims description 5
- 238000000576 coating method Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 4
- 229910017770 Cu—Ag Inorganic materials 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 229910052745 lead Inorganic materials 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000011780 sodium chloride Substances 0.000 abstract description 2
- 229910009043 WC-Co Inorganic materials 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000007790 scraping Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- LNSPFAOULBTYBI-UHFFFAOYSA-N [O].C#C Chemical group [O].C#C LNSPFAOULBTYBI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- FDTGUDJKAXJXLL-UHFFFAOYSA-N acetylene Chemical group C#C.C#C FDTGUDJKAXJXLL-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は気相法ダイヤモンドの合成法の１種である燃焼
炎法ダイヤモンドの合成法に関し、より詳しくは耐摩耗
性、耐蝕性、高熱伝導性、広域光字的透明性、高電気抵
抗性等の優れた特性を有し、研磨材、研削材、超硬工具
材、光学用部材、電子材料等（ご有用な膜状及び粒状の
ダイヤモンドの合成法に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for synthesizing diamond using a combustion flame method, which is a type of method for synthesizing diamond using a vapor phase method. It has excellent properties such as hardness, wide-area optical transparency, and high electrical resistance. Concerning the synthesis method of
［従来の技術１
本件出願人らは燃焼炎中での非酸化性領域でのダイヤモ
ンドの合成法を開発し、第３５回応用物理学関係連合講
演会において講演予稿集第２分冊４３４頁２９ａ−Ｔ−
１として発表し、且つ特願昭６３−７１７５８号として
出願した０本件発明は前記の発明を実施する方法の改良
に関する。[Prior art 1] The present applicants developed a method for synthesizing diamond in the non-oxidizing region in a combustion flame, and presented the lecture proceedings at the 35th Applied Physics Association Lectures, Vol. 2, p. 434, p. 29a- T-
The present invention, which was announced as No. 1 and filed as Japanese Patent Application No. 63-71758, relates to an improvement in the method of carrying out the above-mentioned invention.
従来、燃焼炎法ダイヤモンドの合成法では基板温度の制
御は水冷又は空冷等の手法で行っていたが基材によって
は十分な制御が行い得なかった。Conventionally, in the combustion flame diamond synthesis method, the substrate temperature has been controlled by methods such as water cooling or air cooling, but depending on the substrate material, sufficient control could not be achieved.
［発明が解決しようとする課題］
燃焼炎法ダイヤモンドの合成に於ても一般の低圧気相法
ダイヤモンド合成と同様に、広い面積に効率的に均質な
ダイヤモンド析出を得ることが重要的な課題となってい
る。[Problem to be solved by the invention] In the combustion flame method diamond synthesis, as in general low-pressure vapor phase diamond synthesis, an important problem is to efficiently obtain homogeneous diamond precipitation over a wide area. It has become.
又、特に析出ダイヤモンドの機械的な特性の応用、すな
わちダイヤモンド析出時の基板温度および析出終了後の
冷却過程における基板温度制御により析出ダイヤモンド
と基板の付着強度を増大させることが必要である。In addition, it is necessary to increase the adhesion strength between the precipitated diamond and the substrate by applying the mechanical properties of the precipitated diamond, that is, by controlling the substrate temperature during diamond precipitation and during the cooling process after the completion of the precipitation.
［課題を解決するための手段］
本件発明者らはより安定し且つより均一な基板温度を制
御する手法に付き鋭意研究した結果、析出基板を低融点
金属又は無機化合物の溶融浴に接触させることにより前
記の課題を大幅に改善できることを見出し本件発明を完
成するに至った。[Means for Solving the Problems] As a result of intensive research by the present inventors on a method for controlling a more stable and more uniform substrate temperature, the inventors of the present invention discovered that a method for controlling a substrate temperature more stably and uniformly resulted in a method of bringing a deposition substrate into contact with a molten bath of a low melting point metal or an inorganic compound. The inventors have found that the above-mentioned problems can be significantly improved and have completed the present invention.
すなわち、本件発明の要旨は燃焼炎法ダイヤモンドの合
成法において、ダイヤモンド析出基材の燃焼炎の吹付け
の反対側の面を融点１２００℃以下の金属、合金、又は
無機化合物の溶融浴に接触させて基材温度を制御するこ
とを特徴とする燃焼炎法ダイヤモンドの合成法にある。That is, the gist of the present invention is that, in the combustion flame method diamond synthesis method, the surface of the diamond precipitation base material on the opposite side from which the combustion flame is blown is brought into contact with a molten bath of a metal, alloy, or inorganic compound having a melting point of 1200°C or less. The present invention relates to a method for synthesizing diamond using a combustion flame method, which is characterized by controlling the temperature of the base material.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
ダイヤが生成する基材温度は５００−１３００℃の範囲
であると言われ、このためには融点が１２００℃以下の
金属、合金、又は無機化合物に析出基材を部分的に浸漬
させるのがよい。融点が１２００℃以下の金属、合金、
無機化合物としてはＰｂ、 Ｚｎ、Ｓｎ、 ＡＩ。The temperature of the base material at which diamond is formed is said to be in the range of 500-1300°C, and for this purpose it is best to partially immerse the precipitated base material in a metal, alloy, or inorganic compound with a melting point of 1200°C or lower. . Metals and alloys with a melting point of 1200°C or less,
Inorganic compounds include Pb, Zn, Sn, and AI.
Ｃｕ、 Ｃｕ−Ａｇ合金、半田合金、ＮａＣ１その他ソ
ルトバス等に用いられるものが好ましい。Preferred are Cu, Cu-Ag alloy, solder alloy, NaCl, and other materials used in salt baths.
これらのものはガスバーナーの燃焼炎自身の熱によって
融解せしめてもよいが、多くの場合、電熱ヒーター、シ
ースヒーター等によってスタート時、予熱を行って融液
化してダイヤモンド合成を行うのがよい。These materials may be melted by the heat of the combustion flame of a gas burner, but in many cases, it is preferable to preheat the material using an electric heater, sheath heater, etc. at the time of start, and then molten it to synthesize diamond.
本発明の基本的例を第１図に図示する。第１図において
、１は酸素−アセチレンバーナー ２は燃焼炎不完全燃
焼領域、３は超硬基板、４はＳＵＳ製低融点金属浴槽、
５は鉛の融液、６は基板位置調整支持台、７は低融点金
属の飛沫防止カバーである。第１図のように鉛の溶融浴
の中に超硬焼結板１ＩＣ−Ｇｏをダイヤモンドコーティ
ングする面を鉛溶融面より数ｌｌｌ１１の位置に保持し
て燃焼炎をダイヤモンド析出状態に調整しつつ基板に垂
直に吹きつけるようにしてダイヤモンドを基板表面に析
出させる。又、燃焼炎バーナーを基板上方に移動可能な
ようにセットすれば基板全面にわたってダイヤモンドを
析出させることができる。A basic example of the invention is illustrated in FIG. In Fig. 1, 1 is an oxygen-acetylene burner, 2 is a combustion flame incomplete combustion region, 3 is a carbide substrate, 4 is a low melting point metal bath made of SUS,
5 is a lead melt, 6 is a substrate position adjustment support, and 7 is a splash prevention cover made of a low melting point metal. As shown in Fig. 1, a cemented carbide sintered plate 1IC-Go is placed in a lead molten bath with the surface to be diamond coated several lll11 away from the lead molten surface, and while the combustion flame is adjusted to a state where diamond is precipitated, the substrate is heated. Diamond is deposited on the surface of the substrate by blowing the diamond perpendicularly to the surface of the substrate. Furthermore, if the combustion flame burner is set so as to be movable above the substrate, diamond can be deposited over the entire surface of the substrate.
本発明の特徴は低融点融液に基材の大半が浸されている
ため融点上の所定の温度に基材の温度が設定されるとと
もに、融液の比熱が大きいため安定性が高い。すなわち
、ダイヤモンドコーティング部位に近い部分がダイヤモ
ンド合成に好ましい基材温度（８００〜１１００℃）に
近い温度に設定される。従って燃焼炎に近い部分の熱が
金属浴に速やかに流されて定温度勾配が形成され、しか
も従来の水冷等の冷却法に比べて緩やかになり、これが
ためダイヤモンドコートがより均一性が高く、熱的急冷
の度合が小さいので付着力が高（なる。The feature of the present invention is that most of the base material is immersed in a low melting point melt, so the temperature of the base material is set to a predetermined temperature above the melting point, and the melt has a large specific heat, so stability is high. That is, the temperature of the portion near the diamond coating area is set to be close to the base material temperature (800 to 1100° C.) preferable for diamond synthesis. Therefore, the heat near the combustion flame is quickly flowed into the metal bath, forming a constant temperature gradient, which is more gradual than with conventional cooling methods such as water cooling, which makes the diamond coating more uniform. Because the degree of thermal quenching is small, the adhesion is high.
付着力はスクレーピング試験（ばくり強度試験）で水冷
方式が３〜４ ｋｇｆ ／ ｍｍ程度であるのに対して
鉛浴法では４〜５．２ ｋｇｆ ／ｍｍのものが容易に
得られる。The adhesion strength in the scraping test (scraping strength test) is about 3 to 4 kgf/mm in the water cooling method, whereas it is easily 4 to 5.2 kgf/mm in the lead bath method.
次に前記した予熱、温度維持の方法を第２図に図示する
。第２図において符号３．４．５．７は第１図と同じで
あるから説明を省略し、８は熱電対、９はシースヒータ
ー ＩＯはヒーターコントローラー １１は電源である
。第２図のような装置を用いることによって金属又は無
機化合物の溶融浴を適度な温度に保つことが可能である
。Next, the method of preheating and temperature maintenance described above is illustrated in FIG. In FIG. 2, reference numerals 3, 4, 5, and 7 are the same as in FIG. 1, so the explanation will be omitted. 8 is a thermocouple, 9 is a sheath heater, IO is a heater controller, and 11 is a power source. By using an apparatus as shown in FIG. 2, it is possible to maintain a molten bath of metal or inorganic compound at an appropriate temperature.
又、コーティング終了後の徐冷方法は第３図のような方
法をとってもよい。即ち第３図に於て１２は水槽、１３
は水導入管、１４は水排出管である。水槽１２中にＳＵ
Ｓ！！！低融点金属浴槽４に浸しておき鉛の融液な所定
の温度に維持しつつダイヤモンド合成を行う。コーティ
ング終了は酸素−アセチレンの燃焼を止めるとほぼ同時
にＳＵＳ製浴槽４を引き上げ徐冷する。本件発明者の実
験によると基板、すなわち鉛面側に当る裏面直下の温度
はコーティング終了時には９００℃であったが、約１５
分間程度で２５０℃まで冷却した。この効果によりダイ
ヤモンド膜と基板との付着力（スクレーピング試験機に
よる）はサンプル数１８の平均で５．０ｋｇｆ ／ｍｍ
と従来に比べ２０％以上も向上していることが判明した
。Further, the slow cooling method after coating may be as shown in FIG. 3. That is, in Fig. 3, 12 is a water tank, 13
14 is a water inlet pipe, and 14 is a water discharge pipe. SU in tank 12
S! ! ! It is immersed in a low melting point metal bathtub 4 and diamond synthesis is performed while maintaining the lead melt at a predetermined temperature. To complete the coating, almost at the same time as the combustion of oxygen-acetylene is stopped, the SUS bathtub 4 is pulled up and slowly cooled. According to experiments conducted by the inventor of the present invention, the temperature directly below the back surface of the substrate, which corresponds to the vertical side, was 900°C at the end of coating, but was approximately 15°C.
It was cooled to 250°C in about a minute. Due to this effect, the adhesion force between the diamond film and the substrate (using a scraping tester) was 5.0 kgf/mm on average for 18 samples.
It was found that this was an improvement of more than 20% compared to the conventional method.
［実施例］
第３図に示す装置に於て、低融点金属浴槽ＳＵＳ製５０
Ｘ １００深さ４０ｍｍに８合目程度鉛を入れ、基板Ｗ
Ｃ−Ｃｏ焼結板１０（幅）ＸＳＤ（長さ）×５（板厚）
（ｍｍ）を基板上面から２ｍｍ浸漬させるようにセ
ットし、又基板に外接するように表面をＮｉ無電解メツ
キした加工銅板を鉛の飛沫防止用カバーとして設置した
。[Example] In the apparatus shown in FIG. 3, a low melting point metal bathtub made of SUS 50
Pour lead into the 8th station to a depth of 40 mm and place the board W.
C-Co sintered plate 10 (width) x SD (length) x 5 (thickness)
(mm) was set so as to be immersed 2 mm from the top surface of the substrate, and a processed copper plate whose surface was electrolessly plated with Ni was installed as a cover to prevent lead splash so as to circumscribe the substrate.
アセチレン−酸素炎バーナーにアセチレン１ｌｆｆ／ｍ
ｉｎ、酸素ガス１Ｏｆｆ／ｍｉｎ （アセチレン／酸
素比１．１）を供給し、燃焼炎を形成し、火口〜基板表
面距離７ｍｍで基板に垂直にセットし、基板端より ３
．３ｍｍ／分の移動速度でバーナーを基板表面に平行に
移動してダイヤモンド膜のコーティングを行った。この
とき基板温度は９００℃に維持されていた。Acetylene - Acetylene 1lff/m in oxygen flame burner
In, supply oxygen gas 1Off/min (acetylene/oxygen ratio 1.1) to form a combustion flame, set perpendicularly to the substrate with a distance of 7 mm from the crater to the substrate surface, and 3.
．． The diamond film was coated by moving the burner parallel to the substrate surface at a moving speed of 3 mm/min. At this time, the substrate temperature was maintained at 900°C.
コーティング処理後基板表面を光学顕微鏡で観察したと
ころ、ダイヤモンド自形を含んだ結晶が緻密に堆積した
膜状析出物が基板全面及び側面の１ｆｆＩｆｆｉ以上に
均一に析出していた。又、この膜の付着力をスクレーピ
ング試験で測定したところ４．７ｋｇｆ／ｎｕ＋＋であ
った。さらにこの析出膜のラマン分析測定の結果、ｉ−
カーボンをわずかに含む良質なダイヤモンドであること
を確認した。After the coating process, the surface of the substrate was observed with an optical microscope, and it was found that a film-like precipitate in which crystals containing diamond euhedral shapes were densely deposited was uniformly deposited on the entire surface and side surfaces of the substrate over 1ffIffi. Further, the adhesion force of this film was measured by a scraping test and was found to be 4.7 kgf/nu++. Furthermore, as a result of Raman analysis of this deposited film, i-
It was confirmed that it was a high-quality diamond that contained a small amount of carbon.
［比較例］
実施例の鉛の融液による冷却の代りに従来行われている
水冷式のホルダーで行った以外は実施例と同様の条件で
試験を行った。[Comparative Example] A test was conducted under the same conditions as in the example except that a conventional water-cooled holder was used instead of cooling with the lead melt in the example.
基板上にコーティングされたダイヤモンド表面は実施例
の場合に比較して自形のでた結晶はやや少なく、ラマン
分光測定の結果でもｉ−カーボン成分がやや多かった。The surface of the diamond coated on the substrate had slightly fewer euhedral crystals than in the example, and the results of Raman spectroscopy showed that the i-carbon component was slightly larger.
このコーテイング膜の付着力はスクレーピング試験の結
果的３．１ｋｇｆ／ｍｍであった。The adhesion force of this coating film was 3.1 kgf/mm as a result of a scraping test.
本発明の方法により自形の発達したダイヤモンドの膜が
付着力の大きいものとして合成でき、例えばシェアリン
グ切断機の超硬ブレードへのコーティング等に好適に応
用される。By the method of the present invention, a diamond film with developed euhedral shape can be synthesized with a strong adhesion force, and is suitably applied, for example, to coating a carbide blade of a shearing cutting machine.
第１図は本発明の基本的な例を説明する正面図、第２図
は基板の回りの金属浴等の予熱、温度維持の方法を説明
する正面図、第３図は金属浴槽等を水冷させた例を説明
する正面図である。Figure 1 is a front view illustrating a basic example of the present invention, Figure 2 is a front view illustrating a method for preheating and maintaining the temperature of a metal bath, etc. around a substrate, and Figure 3 is a front view explaining a method for water cooling a metal bath, etc. It is a front view explaining the example where it was made.
Claims (2)
モンド析出基材の燃焼炎の吹付けの反対側の面を融点１
２００℃以下の金属、合金、又は無機化合物の溶融浴に
接触させて基材温度を制御することを特徴とする燃焼炎
法ダイヤモンドの合成法。(1) In the combustion flame diamond synthesis method, the surface of the diamond precipitation base material on the opposite side from which the combustion flame is blown is heated to a melting point of 1.
A method for synthesizing diamond using a combustion flame method, which comprises controlling the substrate temperature by bringing it into contact with a molten bath of a metal, alloy, or inorganic compound at a temperature of 200° C. or less.
させることを特徴とする請求項１の燃焼炎法ダイヤモン
ドの合成法。(2) The combustion flame diamond synthesis method according to claim 1, characterized in that a combustion flame burner set above the base material is moved.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18708189A JP2709148B2 (en) | 1989-07-19 | 1989-07-19 | Synthesis method of combustion flame method diamond |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18708189A JP2709148B2 (en) | 1989-07-19 | 1989-07-19 | Synthesis method of combustion flame method diamond |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0350190A true JPH0350190A (en) | 1991-03-04 |
| JP2709148B2 JP2709148B2 (en) | 1998-02-04 |
Family
ID=16199798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18708189A Expired - Fee Related JP2709148B2 (en) | 1989-07-19 | 1989-07-19 | Synthesis method of combustion flame method diamond |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2709148B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011128134A (en) * | 2009-11-17 | 2011-06-30 | Satoru Takamori | Method of investigating inside of concrete structure existing underwater |
-
1989
- 1989-07-19 JP JP18708189A patent/JP2709148B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011128134A (en) * | 2009-11-17 | 2011-06-30 | Satoru Takamori | Method of investigating inside of concrete structure existing underwater |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2709148B2 (en) | 1998-02-04 |
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