JP2002339082A - Chromium nitrate solution for surface treatment and production method therefor - Google Patents
Chromium nitrate solution for surface treatment and production method thereforInfo
- Publication number
- JP2002339082A JP2002339082A JP2001149133A JP2001149133A JP2002339082A JP 2002339082 A JP2002339082 A JP 2002339082A JP 2001149133 A JP2001149133 A JP 2001149133A JP 2001149133 A JP2001149133 A JP 2001149133A JP 2002339082 A JP2002339082 A JP 2002339082A
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- Japan
- Prior art keywords
- chromium
- solution
- nitrate
- chromium nitrate
- surface treatment
- 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.)
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- Inorganic Compounds Of Heavy Metals (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は硝酸クロム溶液、特
に金属などの表面処理に使用される硝酸クロム溶液及び
その製造方法に関する。The present invention relates to a chromium nitrate solution, particularly to a chromium nitrate solution used for surface treatment of metals and the like, and a method for producing the same.
【０００２】[0002]
【従来の技術】金属の表面処理には永らくクロム（VI）
あるいはその塩が利用されてきた。しかし、クロム（V
I）は人体に有害であるため、製品にはクロム（VI）は
ごく僅かでも残留することが嫌われている。そのため、
例えばクロムを使用しない表面処理鋼板などの提案が数
多く行われている。しかしながらクロムは、優れた表面
処理被膜を形成するのに有利に作用するものであり、ク
ロム(III)を含有する溶液は人体に無害の表面処理被膜
形成用処理液として利用されている。そのようなクロム
(III)を含有する表面処理溶液として硝酸クロム溶液が
ある。2. Description of the Related Art Chrome (VI) has long been used for metal surface treatment.
Alternatively, their salts have been used. But chrome (V
Since I) is harmful to the human body, it is hated that chromium (VI) remains in the product even if it is very small. for that reason,
For example, there have been many proposals for surface-treated steel sheets that do not use chromium. However, chromium advantageously acts to form an excellent surface treatment film, and a solution containing chromium (III) is used as a treatment solution for forming a surface treatment film harmless to the human body. Such chrome
There is a chromium nitrate solution as a surface treatment solution containing (III).
【０００３】このような硝酸クロム溶液の製造方法とし
ては、無機化学中巻（千谷利三著）等の文献に記載され
ている方法がある。この方法では、まず、塩化クロム
（III）もしくは硫酸クロム（III）等の三価クロム塩類
の水溶液を、アルカリで中和して水酸化クロムの沈殿物
を作り、これを濾別及び洗浄した後、硝酸に溶解して硝
酸クロム溶液を得る。この方法は、製造工程が長く、か
つ複雑であるためコスト高となり工業的に適さない。ま
た、水酸化クロムの沈殿物中にClやSO4等の表面処理に
とって悪影響を及ぼす不純物が混入しやすいため、表面
処理用溶液として適さない。このような不純物の混入を
避けるためには、市販の硝酸クロム一級試薬（例えば和
光純薬製）を純水に溶解して硝酸クロム溶液とすること
もできる。しかしこの方法はコスト的に極めて不利であ
り工業的に採用できない。As a method for producing such a chromium nitrate solution, there is a method described in literatures such as Nakamaki Nakamaki (Toshizo Senya). In this method, first, an aqueous solution of a trivalent chromium salt such as chromium (III) chloride or chromium (III) sulfate is neutralized with an alkali to form a chromium hydroxide precipitate, which is filtered and washed. Dissolved in nitric acid to obtain a chromium nitrate solution. This method is costly due to the long and complicated manufacturing process and is not industrially suitable. In addition, impurities that adversely affect the surface treatment, such as Cl and SO 4, are likely to be mixed into the precipitate of chromium hydroxide, so that it is not suitable as a surface treatment solution. In order to avoid such contamination, a commercially available chromium nitrate primary reagent (for example, manufactured by Wako Pure Chemical Industries, Ltd.) may be dissolved in pure water to form a chromium nitrate solution. However, this method is extremely disadvantageous in cost and cannot be industrially adopted.
【０００４】[0004]
【発明が解決しようとする課題】本発明はこのような従
来技術の問題点を解決することを目的とし、ClやSO4等
の不純物が少なく、表面処理用として好適に利用できる
硝酸クロム溶液を経済的に提供し得る手段を提案するも
のである。SUMMARY OF THE INVENTION An object of the present invention is to solve such a problem of the prior art, and to provide a chromium nitrate solution which contains few impurities such as Cl and SO 4 and can be suitably used for surface treatment. It proposes means that can be provided economically.
【０００５】[0005]
【課題を解決する手段】本発明者は、三酸化クロムに対
して化学量論的に硝酸クロムを生ずるに必要な量以上の
硝酸を加えた溶液にでんぷん、ブドウ等などの有機還元
剤を過剰に加えて三酸化クロムのすべてを還元して得た
硝酸クロム溶液が表面処理用としての硝酸クロム溶液と
して好ましい特性を有していることを見出し、本発明に
至った。Means for Solving the Problems The present inventor excessively adds an organic reducing agent such as starch, grape or the like to a solution in which nitric acid is added stoichiometrically to chromium trioxide in an amount required to produce chromium nitrate. In addition, the present inventors have found that a chromium nitrate solution obtained by reducing all of chromium trioxide has preferable characteristics as a chromium nitrate solution for surface treatment, and have reached the present invention.
【０００６】本発明の表面処理用硝酸クロム溶液は、Cr
と結合しないフリー硝酸イオンを質量比で全硝酸イオン
量の6%以下、全有機炭素を質量比で硝酸クロムのクロム
に対して0.3〜3%含有している。The chromium nitrate solution for surface treatment according to the present invention comprises Cr
It contains 6% or less of free nitrate ions that do not bind with the total amount of nitrate ions by mass ratio, and 0.3 to 3% of total organic carbon with respect to chromium of chromium nitrate by mass ratio.
【０００７】上記表面処理用硝酸クロム溶液を製造する
に当たっては、三酸化クロムに硝酸を硝酸クロムの生成
当量を超えて過剰に配合して三酸化クロム−硝酸混合溶
液を準備する段階と、前記段階によって得られた三酸化
クロム−硝酸混合溶液に単糖類、二糖類あるいはでんぷ
ん類から選ばれる炭水化物又は該炭水化物から誘導され
るアルコール、アルデヒド、カルボン酸又はこれらの混
合物からなる有機還元剤を過剰に混じて三酸化クロムを
還元して硝酸クロムを生成させる段階と、を順次行うの
がよい。その際、硝酸を硝酸クロムの生成当量に対して
当量比で1〜6%過剰に配合し、かつ還元剤を、三酸化ク
ロムを還元するに必要な量に対して当量比で2〜10%過剰
に添加するのがよい。なお、この硝酸は反応中に揮散す
る量を見こんで添加すべきである。また、有機還元剤の
使用量は、反応速度によって変え、例えばブドウ糖のよ
うに反応の速いものでは3%程度の過剰とし、でんぷんの
ように反応速度の遅いものでは8%程度の過剰とするのが
より好ましい。In producing the chromium nitrate solution for surface treatment, a step of preparing a mixed solution of chromium trioxide and nitric acid by mixing nitric acid in chromium trioxide in excess of the equivalent of chromium nitrate, An excess of an organic reducing agent comprising a carbohydrate selected from monosaccharides, disaccharides or starches or an alcohol, aldehyde, carboxylic acid or a mixture thereof derived from the carbohydrates in the chromium trioxide-nitric acid mixed solution obtained by the above method. And reducing chromium trioxide to form chromium nitrate. At that time, nitric acid is added in an equivalent ratio of 1 to 6% in excess with respect to the production equivalent of chromium nitrate, and the reducing agent is used in an equivalent ratio of 2 to 10% with respect to the amount required to reduce chromium trioxide. It is better to add in excess. In addition, this nitric acid should be added in consideration of the amount which evaporates during the reaction. The amount of the organic reducing agent used is varied depending on the reaction rate.For example, an excess of about 3% is used for a fast-reacting substance such as glucose, and about 8% is used for a low-reaction rate such as starch. Is more preferred.
【０００８】以下、本発明を質量比で約40%の硝酸クロ
ム溶液を製造する場合を例にとって具体的に説明する。
本発明により硝酸クロム溶液を得る典型的な基礎反応式
を、還元剤をでんぷんとした場合、及びブドウ糖とした
場合について示すと次のとおりである。 (a)でんぷんを還元剤とする場合 CrO3 + 3HNO3 + 1/8C6H10O5 → Cr(NO3)3 + 3/4CO2 + 1
7/8H2O (b)ブドウ糖を還元剤とする場合 CrO3 + 3HNO3 + 1/8C6H12O6・H2O → Cr(NO3)3 + 3/4CO
2 + 19/8H2OHereinafter, the present invention will be described in detail by taking as an example the case of producing a chromium nitrate solution having a mass ratio of about 40%.
A typical basic reaction formula for obtaining a chromium nitrate solution according to the present invention is as follows when a reducing agent is starch and glucose is used. (a) When starch is used as a reducing agent CrO 3 + 3HNO 3 + 1 / 8C 6 H 10 O 5 → Cr (NO 3 ) 3 + 3 / 4CO 2 + 1
7 / 8H 2 O (b) When glucose is used as a reducing agent CrO 3 + 3HNO 3 + 1 / 8C 6 H 12 O 6・ H 2 O → Cr (NO 3 ) 3 + 3 / 4CO
2 + 19 / 8H 2 O
【０００９】本発明の硝酸クロム溶液はCrと結合しない
フリー硝酸イオンを質量比で全硝酸イオン量の6%以下の
範囲で含有する。すなわち、硝酸イオンを化学量論的に
硝酸クロムを生成するのに十分な量に対して過剰に含有
している。しかし、その量が多いときは、図１に示すよ
うに硝酸クロムの溶解度が低下し、たとえば冬期におい
て溶液の温度が5℃以下となったとき硝酸クロム結晶が
析出する場合があり、したがってその濃度を下げる必要
があり、好ましくない。したがって、フリー硝酸イオン
の量は質量比で全硝酸イオン量の6%以下、好ましくは1
〜5％の範囲とする。The chromium nitrate solution of the present invention contains free nitrate ions which do not bind to Cr within a range of 6% or less by mass of the total amount of nitrate ions. That is, nitrate ions are contained in excess in an amount sufficient to produce chromium nitrate stoichiometrically. However, when the amount is large, the solubility of chromium nitrate decreases as shown in FIG. 1, and for example, when the temperature of the solution becomes 5 ° C. or less in winter, chromium nitrate crystals may precipitate, Needs to be lowered, which is not preferable. Therefore, the amount of free nitrate ions is not more than 6%, preferably 1% of the total amount of nitrate ions by mass ratio.
Within the range of ~ 5%.
【００１０】本発明の硝酸クロム溶液は、全有機炭素を
質量比で硝酸クロムのクロムに対して0.3〜3％含有して
いる。全有機炭素（TOC）とは有機物として溶液中に残
留しているCの総量であって、例えば、島津製作所製TOC
5000型全有機炭素計によって定量される。市場で通常販
売される硝酸クロム溶液にはこのような有機炭素の存在
は認められないが、本発明の場合は、クロム(VI)を確実
に消滅させる効果をもたらしている。しかし、その存在
量が多いときには、硝酸クロム溶液の粘性が上昇し取り
扱いが困難になり、また表面処理剤が焼き付けられたと
き金属板上に炭素系の異物を発生する危険があるので、
その最大値は硝酸クロムのクロムに対して質量比で3%と
する。なお、好ましくは、硝酸クロムのクロムに対して
0.3〜2%とするのがよい。The chromium nitrate solution of the present invention contains 0.3 to 3% by weight of total organic carbon with respect to chromium of chromium nitrate. Total organic carbon (TOC) is the total amount of C remaining in solution as organic matter. For example, TOC manufactured by Shimadzu Corporation
It is determined by a 5000 total organic carbon meter. The presence of such organic carbon is not recognized in the chromium nitrate solution which is usually sold on the market, but in the case of the present invention, the effect of surely eliminating chromium (VI) is brought about. However, when the abundance is large, the viscosity of the chromium nitrate solution increases and handling becomes difficult, and there is a risk of generating carbon-based foreign matter on the metal plate when the surface treatment agent is baked.
The maximum value is 3% by mass relative to chromium of chromium nitrate. Preferably, the chromium of chromium nitrate is
It is good to be 0.3-2%.
【００１１】本発明にかかる硝酸クロム溶液を製造する
には、まず三酸化クロムに硝酸を硝酸クロムの生成当量
以上に配合して三酸化クロム−硝酸混合溶液を準備す
る。硝酸を過剰に添加するのは、クロムイオンに対して
化学量論的に硝酸イオンが不足することがないようにす
るためである。しかし先にも述べたように、硝酸イオン
の存在量があまりに多いときには、冬期における溶液の
取り扱い性が低下するので硝酸の過剰量は硝酸クロムの
生成当量に対して当量比で1〜6%とするのがよい。To produce the chromium nitrate solution according to the present invention, a mixed solution of chromium trioxide and nitric acid is first prepared by mixing chromium trioxide with nitric acid in an amount equal to or more than the equivalent of chromium nitrate. The reason for adding nitric acid in excess is to prevent stoichiometric shortage of nitric acid ions with respect to chromium ions. However, as described above, when the amount of nitrate ions is too large, the handleability of the solution in winter decreases, so the excess amount of nitric acid is 1 to 6% in equivalent ratio to the equivalent amount of chromium nitrate. Good to do.
【００１２】次いでこのようにして準備された三酸化ク
ロム−硝酸混合溶液に還元剤を加わえて、三酸化クロム
を還元させるとともに還元された生成物を硝酸と反応さ
せて硝酸クロムに転換させる。この際、還元剤の使用量
は化学量論的に三酸化クロムを還元するに足る量よりい
くらか過剰にする。これにより三酸化クロムの還元が完
全に行われ、溶液中にクロム（VI）が残留することがな
い。その結果、溶液中には未分解の還元剤が残留する。
しかし、先にも述べたように還元剤の分解生成物である
全有機炭素（TOC）が高すぎると焼き付けられて形成さ
れた被膜上異物が残留することもあるので、還元剤の過
剰添加量は三酸化クロムを還元するのに必要な量に対し
て当量比で2〜10%とするのがよい。Next, a reducing agent is added to the chromium trioxide-nitric acid mixed solution prepared in this way to reduce chromium trioxide, and the reduced product is reacted with nitric acid to be converted to chromium nitrate. At this time, the amount of the reducing agent used is set to be a little more than stoichiometrically enough to reduce chromium trioxide. As a result, chromium trioxide is completely reduced, and chromium (VI) does not remain in the solution. As a result, unresolved reducing agent remains in the solution.
However, as mentioned above, if the total organic carbon (TOC), which is the decomposition product of the reducing agent, is too high, foreign matter may remain on the film formed by baking, so the excess amount of the reducing agent Is preferably 2 to 10% in equivalent ratio to the amount required to reduce chromium trioxide.
【００１３】還元剤として使用できる物質としては、ま
ずブドウ糖などの単糖類、蔗糖などの二糖類あるいはで
んぷん類等の炭水化物がある。これらのうちブドウ糖
は、反応性がよく上記三酸化クロムに対する過剰添加量
を比較的低く押さえることができる利点がある。また、
でんぷんを利用した場合にはその原料に由来するにおい
が製品中に残る場合があるが、ブドウ糖を使用する場合
はこのような問題が生じない。上記のほか、これら炭化
水素を酸化して生成されるアルコール類、アルデヒド
類、エチレングリコールあるいはカルボン酸も利用でき
る。[0013] Substances that can be used as reducing agents include monosaccharides such as glucose, disaccharides such as sucrose, and carbohydrates such as starch. Among them, glucose is advantageous in that it has good reactivity and the amount of excessive addition to chromium trioxide can be kept relatively low. Also,
When starch is used, the odor derived from the raw material may remain in the product, but when glucose is used, such a problem does not occur. In addition to the above, alcohols, aldehydes, ethylene glycol or carboxylic acids generated by oxidizing these hydrocarbons can also be used.
【００１４】[0014]
【実施例】以下実施例により本発明の硝酸クロム溶液の
製造工程を一層具体的に示す。三酸化クロムを2lフラス
コ中で水に溶解して60質量%溶液にした。この三酸化ク
ロム溶液に表１に示す比率で濃硝酸を添加し、撹拌しな
がら70℃まで加温して三酸化クロム−硝酸混合溶液とし
た。EXAMPLES The production process of the chromium nitrate solution of the present invention will be described more specifically by way of the following examples. Chromium trioxide was dissolved in water in a 2 l flask to form a 60% by mass solution. Concentrated nitric acid was added to the chromium trioxide solution at the ratio shown in Table 1 and heated to 70 ° C. with stirring to obtain a chromium trioxide-nitric acid mixed solution.
【００１５】得られた三酸化クロム−硝酸溶液に同じく
表１に示すような還元剤比率で、でんぷんあるいはブド
ウ糖を撹拌しながら添加し、液温をほぼ95℃に維持しな
がら還元反応を進行させた。還元剤を添加し終えてから
ジフェニールカルバジドを試薬として反応液中のクロム
(VI)の有無を確認し、クロム（VI）が検出されなくなる
まで撹拌を継続した。試験No.4の場合を除き0.5〜1.5時
間で還元反応が完了した。しかし、試験No.4の場合は、
上記時間内に還元反応が完了しなかった。でんぷんの反
応速度が遅く、その当量過剰添加比率が5%では実用的な
反応速度に達しなかったためであろうと考えられる。反
応終了後、常温まで冷却し、水を加えて所定の濃度（硝
酸クロム濃度40質量%）に調整した。得られた製品の分
析値を表2に示す。Starch or glucose is added to the obtained chromium trioxide-nitric acid solution in the same reducing agent ratio as shown in Table 1 while stirring, and the reduction reaction is allowed to proceed while maintaining the liquid temperature at about 95 ° C. Was. After the addition of the reducing agent, the chromium in the reaction mixture is treated with diphenylcarbazide as a reagent.
The presence or absence of (VI) was confirmed, and stirring was continued until no chromium (VI) was detected. Except for Test No. 4, the reduction reaction was completed in 0.5 to 1.5 hours. However, in the case of test No. 4,
The reduction reaction was not completed within the above time. This is probably because the reaction rate of starch was low, and the reaction rate did not reach a practical rate when the equivalent addition ratio was 5%. After the completion of the reaction, the reaction mixture was cooled to room temperature and adjusted to a predetermined concentration (chromium nitrate concentration: 40% by mass) by adding water. Table 2 shows the analysis values of the obtained products.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【表２】 [Table 2]
【００１８】表2に示すようにこのようにして得られた
硝酸クロム溶液を常法でクロメート処理を行ったとこ
ろ、クロム（VI）の溶出がなく、かつSO4やClが少な
く、浴安定性が高く、耐食性が優れた被膜が生成した。
なお。No.4の場合はクロム(VI)が残存していたので、ク
ロメート処理には使用しなかった。As shown in Table 2, the chromium nitrate solution thus obtained was subjected to a chromate treatment by a conventional method. As a result, there was no elution of chromium (VI), the amount of SO 4 and Cl was small, and the bath stability was low. With high corrosion resistance.
In addition. No. 4 was not used for chromate treatment because chromium (VI) remained.
【００１９】[0019]
【発明の効果】本発明は上記のように構成したので表面
処理用に適した硝酸クロム溶液を経済的に製造すること
ができ、またそれを用いて優れた表面処理をすることが
できる。また、本発明の硝酸クロム溶液はクロム（VI）
を含有しないので、それによる健康障害などを引き起こ
すことがない。As described above, according to the present invention, a chromium nitrate solution suitable for surface treatment can be economically produced, and excellent surface treatment can be performed using the same. In addition, the chromium nitrate solution of the present invention comprises chromium (VI)
Because it does not contain, it does not cause health problems.
【図１】 硝酸クロムの溶解度に及ぼす硝酸濃度の影響
を示すグラフである。FIG. 1 is a graph showing the effect of nitric acid concentration on the solubility of chromium nitrate.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G048 AA10 AB02 AC08 AE05 AE07 AE08 4K026 BA06 BB08 CA19 CA32 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G048 AA10 AB02 AC08 AE05 AE07 AE08 4K026 BA06 BB08 CA19 CA32
Claims (3)
比で全硝酸イオン量の6%以下、全有機炭素を質量比で硝
酸クロムのクロムに対して0.3〜3%含有することを特徴
とする表面処理用硝酸クロム溶液。The present invention is characterized in that free nitrate ions that do not bind to Cr are contained in a mass ratio of 6% or less of the total amount of nitrate ions, and that all organic carbons are contained in a mass ratio of 0.3 to 3% with respect to chromium of chromium nitrate. Chromium nitrate solution for surface treatment.
当量以上に配合して三酸化クロム−硝酸混合溶液を準備
する段階と、 前記段階によって得られた三酸化クロム−硝酸混合溶液
に単糖類、二糖類あるいはでんぷん類から選ばれる炭水
化物又は該炭水化物から誘導されるアルコール、アルデ
ヒド、カルボン酸又はこれらの混合物からなる有機還元
剤を過剰に混じて三酸化クロムを還元して硝酸クロムを
生成させる段階と、を順次行うことを特徴とする表面処
理用硝酸クロム溶液の製造方法。2. A step of preparing a mixed solution of chromium trioxide and nitric acid by mixing nitric acid with chromium trioxide in an amount equal to or greater than the production equivalent of chromium nitrate, and adding a monosaccharide to the mixed solution of chromium trioxide and nitric acid obtained in the step. A step of reducing chromium trioxide by excessively mixing an organic reducing agent comprising a carbohydrate selected from disaccharides or starches or an alcohol, aldehyde, carboxylic acid or a mixture thereof derived from the carbohydrate to form chromium nitrate And (c) are sequentially performed.
量比で1〜6%過剰に配合し、かつ還元剤を、三酸化クロ
ムを還元するに必要な量に対して当量比で2〜10%過剰に
添加することを特徴とする請求項２記載の表面処理用硝
酸クロム溶液の製造方法。3. An excess of 1 to 6% of nitric acid in an equivalent ratio with respect to the equivalent of chromium nitrate, and a reducing agent in an equivalent ratio of 2 to 2 with respect to the amount required for reducing chromium trioxide. 3. The method for producing a chromium nitrate solution for surface treatment according to claim 2, wherein the chromium nitrate solution is added in an excess of 10%.
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| WO2003071973A1 (en) * | 2002-02-25 | 2003-09-04 | Dentsply International Inc. | Coated dental handpiece |
| WO2005056478A1 (en) * | 2003-12-10 | 2005-06-23 | Nippon Chemical Industrial Co., Ltd. | Aqueous solution of chromium salt and method for producing same |
| JP2007331961A (en) * | 2006-06-13 | 2007-12-27 | Nippon Denko Kk | Method for producing chromium chloride solution and chromium chloride solution for surface treatment |
| JP2008214765A (en) * | 2008-06-18 | 2008-09-18 | Nippon Chem Ind Co Ltd | Method for producing chromium phosphate aqueous solution |
| JP2008248394A (en) * | 2008-06-03 | 2008-10-16 | Nippon Chem Ind Co Ltd | Aqueous solution of chromium phosphate and method for manufacturing the same |
| WO2010026884A1 (en) | 2008-09-05 | 2010-03-11 | 日本化学工業株式会社 | Method for producing aqueous solution containing chromium (iii) source |
| CN102409328A (en) * | 2011-11-02 | 2012-04-11 | 甘肃蓝科石化高新装备股份有限公司 | Surface modification method of alloy fiber |
| RU2639782C1 (en) * | 2016-06-28 | 2017-12-22 | Закрытое акционерное общество "Русский Хром 1915" | Method for producing solution of chromium nitrate (iii) |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003071973A1 (en) * | 2002-02-25 | 2003-09-04 | Dentsply International Inc. | Coated dental handpiece |
| WO2005056478A1 (en) * | 2003-12-10 | 2005-06-23 | Nippon Chemical Industrial Co., Ltd. | Aqueous solution of chromium salt and method for producing same |
| US7641721B2 (en) | 2003-12-10 | 2010-01-05 | Nippon Chemical Industrial Co., Ltd. | Aqueous solution of chromium salt and method for producing same |
| US8083842B2 (en) | 2003-12-10 | 2011-12-27 | Nippon Chemical Industrial Co., Ltd. | Aqueous solution of chromium salt and method for producing same |
| JP2007331961A (en) * | 2006-06-13 | 2007-12-27 | Nippon Denko Kk | Method for producing chromium chloride solution and chromium chloride solution for surface treatment |
| JP2008248394A (en) * | 2008-06-03 | 2008-10-16 | Nippon Chem Ind Co Ltd | Aqueous solution of chromium phosphate and method for manufacturing the same |
| JP4659855B2 (en) * | 2008-06-03 | 2011-03-30 | 日本化学工業株式会社 | Chromium phosphate aqueous solution |
| JP2008214765A (en) * | 2008-06-18 | 2008-09-18 | Nippon Chem Ind Co Ltd | Method for producing chromium phosphate aqueous solution |
| JP4677011B2 (en) * | 2008-06-18 | 2011-04-27 | 日本化学工業株式会社 | Method for producing aqueous chromium phosphate solution |
| WO2010026884A1 (en) | 2008-09-05 | 2010-03-11 | 日本化学工業株式会社 | Method for producing aqueous solution containing chromium (iii) source |
| CN102409328A (en) * | 2011-11-02 | 2012-04-11 | 甘肃蓝科石化高新装备股份有限公司 | Surface modification method of alloy fiber |
| RU2639782C1 (en) * | 2016-06-28 | 2017-12-22 | Закрытое акционерное общество "Русский Хром 1915" | Method for producing solution of chromium nitrate (iii) |
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