JPH04198862A - Capillary column for gas chromatograph - Google Patents
Capillary column for gas chromatographInfo
- Publication number
- JPH04198862A JPH04198862A JP33169290A JP33169290A JPH04198862A JP H04198862 A JPH04198862 A JP H04198862A JP 33169290 A JP33169290 A JP 33169290A JP 33169290 A JP33169290 A JP 33169290A JP H04198862 A JPH04198862 A JP H04198862A
- Authority
- JP
- Japan
- Prior art keywords
- coated
- column
- mum
- ceramic
- capillary column
- 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.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 238000004817 gas chromatography Methods 0.000 claims description 4
- 230000003064 anti-oxidating effect Effects 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 16
- 238000000576 coating method Methods 0.000 abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 6
- 150000004706 metal oxides Chemical class 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010453 quartz Substances 0.000 abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 4
- 150000001340 alkali metals Chemical class 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract 2
- 238000007254 oxidation reaction Methods 0.000 abstract 2
- 238000005524 ceramic coating Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- -1 alkoxy metals Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 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
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/60—Construction of the column
- G01N30/6052—Construction of the column body
Landscapes
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の背景〕
〈産業上の利用分野〉
本発明は耐熱性の改良されたガスクロマトグラフ用キャ
ピラリーカラムに関する。DETAILED DESCRIPTION OF THE INVENTION [Background of the Invention] <Industrial Application Field> The present invention relates to a capillary column for gas chromatography with improved heat resistance.
〈従来の技術〉
最近、石英製キャピラリーをガスクロマトグラフィーの
カラムに用いると分離能が良いことから多用されるよう
になっている。しかし、石英製キャピラリーは機械的強
度か低いためキャピラリーの表面を耐熱性樹脂又はアル
ミニウムで被覆している。<Prior Art> Recently, quartz capillaries have been widely used in gas chromatography columns because of their good separation performance. However, since the quartz capillary has low mechanical strength, the surface of the capillary is coated with heat-resistant resin or aluminum.
しかしなから、従来のカラムでは耐熱性樹脂コーティン
グしたカラムで３２０℃〜３８０℃程度の温度でしか使
用できず、アルミニウムコーティングしたカラムでも４
００℃以上の高温では短時間しか使用できない。４００
℃以上の温度では機械的強度かまだ十分でなくその改善
が強く望まれている。一方、非イオン界面活性剤、ワッ
クス、原油、オリゴマー等に対し、更に高温で長時間安
定したカラムか望まれている。However, conventional columns coated with heat-resistant resin can only be used at temperatures of about 320°C to 380°C, and even columns coated with aluminum can only be used at temperatures of about 320°C to 380°C.
It can only be used for a short time at high temperatures of 00°C or higher. 400
Mechanical strength is still insufficient at temperatures above °C, and improvement thereof is strongly desired. On the other hand, for nonionic surfactants, waxes, crude oil, oligomers, etc., there is a need for columns that are stable at higher temperatures for longer periods of time.
本発明は上記従来技術の欠点を克服し、ガラスキャピラ
リーカラムの高温での機械的強度の改善を目的とするも
のであり、アルミコートキャピラリーカラムの表面を耐
熱性を有する特定の保護膜で被覆することにより目的を
達成するものである。The present invention aims to overcome the above-mentioned drawbacks of the prior art and improve the mechanical strength of glass capillary columns at high temperatures by coating the surface of an aluminum-coated capillary column with a specific heat-resistant protective film. It accomplishes its purpose.
即ち、本発明の耐熱性が改善されたガスクロマトグラフ
用キャピラリーカラムは、表面をセラミックス系酸化防
止保護膜で被覆したアルミニウムコートキャピラリーカ
ラムからなることを特徴とするものである。That is, the capillary column for gas chromatography with improved heat resistance of the present invention is characterized by comprising an aluminum-coated capillary column whose surface is coated with a ceramic anti-oxidation protective film.
本発明によれば、５ｏｏ！ｃ以上といった高温での使用
においても、熱酸化劣化によるカラムの破損等が有効に
防止される。According to the invention, 5oo! Even when used at high temperatures such as c or higher, damage to the column due to thermal oxidative deterioration is effectively prevented.
本発明においてアルミニウムコートキャピラリー上に被
覆されるセラミックス系酸化防止保護膜は、金属酸化物
系ポリマーを含有する塗布液を塗布した後、常温乾燥ま
たは低温加熱することにより耐熱性に優れたセラミック
スの膜として形成することができる。In the present invention, the ceramic anti-oxidation protective film coated on the aluminum-coated capillary is made of a ceramic film with excellent heat resistance by drying at room temperature or heating at low temperature after applying a coating solution containing a metal oxide polymer. It can be formed as
金属酸化物系ポリマーとしては、下記の構造を有するア
ルカリ金属、オルガノポリ金属、オルガノアルコキシ金
属、アルコキシ金属、変成アセチルアセトネート金属を
用いることができる。As the metal oxide polymer, alkali metals, organopolymetals, organoalkoxy metals, alkoxy metals, and modified acetylacetonate metals having the following structures can be used.
（アルカリ金属） （オルガノポリ金属）（
オルガノアルコキシ金属） （アルコキシ金属アセチ
ルアセトネート金属）
（但し、ＭはＳ ｌ ％ Ａ Ｉ ＳＴ ｉ−、Ｚ ｒ
などの金属、ＭｌはＮａ、Ｌ ｉ、に、Ｒ３Ｎなどのア
ルカリ金属を示す）
上記金属酸化物系ポリマーに酸化ケイ素、酸化チタン、
硫酸バリウム、酸化ジルコニウム、ホウ酸、酸化マグネ
シウム等の無機フィラーを添加して用いることができる
。(alkali metal) (organopolymetal) (
Organoalkoxy metal) (Alkoxy metal acetylacetonate metal) (However, M is S l % A I ST i-, Z r
(Ml represents Na, Li, and alkali metals such as R3N) The above metal oxide-based polymers include silicon oxide, titanium oxide,
Inorganic fillers such as barium sulfate, zirconium oxide, boric acid, and magnesium oxide can be added and used.
被覆される酸化防止膜の膜厚は５μｍ〜２０μｍが好ま
しい。５μｍ未満では所望の耐熱性付与効果が得られず
、２０μｍ超過では柔軟性が悪くなり、膜の剥離等の問
題か生ずる。The thickness of the coated antioxidant film is preferably 5 μm to 20 μm. If the thickness is less than 5 μm, the desired effect of imparting heat resistance cannot be obtained, and if it exceeds 20 μm, flexibility may deteriorate and problems such as peeling of the film may occur.
上記酸化防止膜を被覆した本発明のキャピラリーカラム
は、例えば以下のような方法により製造することができ
る。The capillary column of the present invention coated with the above-mentioned antioxidant film can be manufactured, for example, by the following method.
第１図は、本発明のキャピラリーカラムの一製造例を示
す概略図である。FIG. 1 is a schematic diagram showing an example of manufacturing a capillary column of the present invention.
第１図において、先ず石英管１を溶融炉２にて加熱溶融
し、外径５００μｍ以下の細管となるよう炉の他端から
速度を調節しながら引き出す。引出し直後、ただちにア
ルミニウムコーティングを行い、引き続いてセラミック
スコーティング剤をダイス５にて塗布し、硬化炉６で硬
化させた後巻取機７にて巻取ることにより製品とする。In FIG. 1, first, a quartz tube 1 is heated and melted in a melting furnace 2, and then pulled out from the other end of the furnace while adjusting the speed so as to form a thin tube with an outer diameter of 500 μm or less. Immediately after being drawn out, an aluminum coating is applied, followed by a ceramic coating agent applied with a die 5, hardened in a curing furnace 6, and then wound up with a winder 7 to form a product.
ここで、セラミックスコーティングの膜厚は巻取速度お
よびセラミックスコーティング剤の濃度により調整でき
るが、一般的には巻取速度は細管の外径によりほぼ決っ
ているので、セラミックスコーティング剤の固形分濃度
により膜厚の調整を行うのが通常である。この場合、上
記の所望の膜厚を得るには、セラミックスコーティング
剤の固形分濃度を通常１０〜３０重量％程度に保つ必要
かある。Here, the thickness of the ceramic coating can be adjusted by the winding speed and the concentration of the ceramic coating agent, but generally the winding speed is determined by the outer diameter of the capillary, so it depends on the solid content concentration of the ceramic coating agent. Usually, the film thickness is adjusted. In this case, in order to obtain the above-mentioned desired film thickness, it is usually necessary to maintain the solid content concentration of the ceramic coating agent at about 10 to 30% by weight.
本発明においては、５００℃以上の温度で耐熱性であり
且つ柔軟な塗膜の得られるものであれば、任意のセラミ
ックスコーティング剤を使用することができる。このよ
うなコーティング剤の具体例として、例えばセラミ力Ｃ
ＲＣ−１５００、Ｇ−１３００、Ｇ−１５００等〔（株
）日板研究新製〕かある。このセラミ力は金属酸化物系
ポリマーと無機フィラーとからなっており、加熱硬化さ
せると耐熱性と柔軟性を有するセラミックスの膜を形成
する。In the present invention, any ceramic coating agent can be used as long as it is heat resistant at temperatures of 500° C. or higher and provides a flexible coating. As a specific example of such a coating agent, for example, Ceramic C
There are RC-1500, G-1300, G-1500, etc. [manufactured by Nichiban Kenkyushin Co., Ltd.]. This ceramic material is made of a metal oxide polymer and an inorganic filler, and when heated and cured, it forms a ceramic film that is heat resistant and flexible.
〈実施例〉
実施例１〜３
「試験片Ｊ
市販のアルミコートキャピラリーカラム０、 ２５ｗｍ
１ＤＸ １０＋＋＋ （東京化成製）を２０ｃｏ＋に
カットした。<Example> Examples 1 to 3 "Test piece J Commercially available aluminum coated capillary column 0, 25wm
1DX 10+++ (manufactured by Tokyo Kasei) was cut to 20co+.
「セラミックコーティングした試験片」上記試験片をア
ルカリ脱脂後、セラミックコーティング剤セラミ力ＣＲ
Ｃ−１５００（（株）日板研究所製）をイソプロパツー
ル、エタノール−２，１て２倍に希釈した液にデツピン
グし、１５０℃、３０分加熱硬化し皮膜を形成させた。"Ceramic coated test piece" After degreasing the above test piece with alkali, the ceramic coating agent Ceramic Strength CR
C-1500 (manufactured by Nichiban Kenkyusho Co., Ltd.) was poured into a solution diluted 2 times with isopropanol and ethanol-2.1, and heated and cured at 150° C. for 30 minutes to form a film.
「耐熱試験と評価方法」
各試験片をＧＣ８７００（パーキンエルマー社製）で昇
温し耐熱試験を行った後、直径１０ｍｎ＋のステンレス
パイプにまきつけ破損の有無を比較した。その結果を表
−１に示す。"Heat Resistance Test and Evaluation Method" After each test piece was heated with GC8700 (manufactured by PerkinElmer) and subjected to a heat resistance test, it was wrapped around a stainless steel pipe with a diameter of 10 mm+ and the presence or absence of damage was compared. The results are shown in Table-1.
表−１
（試験片の破損した割合％）
Ａ、セラミックコーティングした試験片の破損した割合
％
Ｂ セラミックコーティングしない試験片の破損した割
合％
尚、この時用いた試験片を熱処理せずそのまま直径１０
ｍｍのステンレスパイプにまきつけた時の破損割合は２
５％であった。Table-1 (Percentage of damaged test pieces) A. Percentage of damaged test pieces with ceramic coating B. Percentage of broken test pieces with no ceramic coating The test pieces used at this time were not heat-treated and had a diameter of 10 mm.
The breakage rate when wrapped around mm stainless steel pipe is 2.
It was 5%.
表−１から明らかなように、本発明によるセラミックコ
ーティング処理をすることにより約１／３〜１／１０に
破損割合は減少し、高温での耐久性の効果が認められた
。As is clear from Table 1, by applying the ceramic coating treatment according to the present invention, the failure rate was reduced to about 1/3 to 1/10, and the effect of durability at high temperatures was recognized.
第１図は、本発明のキャピラリーカラムの一製造例を示
す概略図である。
１・・・石英管、２・・・溶融炉、３・・・内厚測定器
、４・・・アルミニウムコーティング、５・・・セラミ
ックスコーティングダイス、６・・・硬化炉、７・・・
巻取機。
出願人代理人 佐 藤 −雄
第
英管
融炉
厚測定器
ノミニウムツーティ〉グ
ラミックスコーテイ〉り々イス
ヒ炉
取機
１図FIG. 1 is a schematic diagram showing an example of manufacturing a capillary column of the present invention. DESCRIPTION OF SYMBOLS 1... Quartz tube, 2... Melting furnace, 3... Inner thickness measuring device, 4... Aluminum coating, 5... Ceramics coating die, 6... Hardening furnace, 7...
Winding machine. Applicant's agent Sato -Yuichi Eiichi tube melting furnace thickness measuring device Nominium Twoty〉Gramix Kotei〉Riri Isuhi furnace removal machine 1 diagram
Claims (1)
ニウムコートキャピラリーカラムからなることを特徴と
する、耐熱性が改良されたガスクロマトグラフ用キャピ
ラリーカラム。A capillary column for gas chromatography with improved heat resistance, characterized by consisting of an aluminum-coated capillary column whose surface is coated with a ceramic anti-oxidation protective film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33169290A JPH04198862A (en) | 1990-11-29 | 1990-11-29 | Capillary column for gas chromatograph |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33169290A JPH04198862A (en) | 1990-11-29 | 1990-11-29 | Capillary column for gas chromatograph |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04198862A true JPH04198862A (en) | 1992-07-20 |
Family
ID=18246515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33169290A Pending JPH04198862A (en) | 1990-11-29 | 1990-11-29 | Capillary column for gas chromatograph |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04198862A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5853678A (en) * | 1993-03-17 | 1998-12-29 | Nipon Sanso Corporation | Method for removing hydrides, alkoxides and alkylates out of a gas using cupric hydroxide |
-
1990
- 1990-11-29 JP JP33169290A patent/JPH04198862A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5853678A (en) * | 1993-03-17 | 1998-12-29 | Nipon Sanso Corporation | Method for removing hydrides, alkoxides and alkylates out of a gas using cupric hydroxide |
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