JPS621475B2 - - Google Patents
Info
- Publication number
- JPS621475B2 JPS621475B2 JP57007356A JP735682A JPS621475B2 JP S621475 B2 JPS621475 B2 JP S621475B2 JP 57007356 A JP57007356 A JP 57007356A JP 735682 A JP735682 A JP 735682A JP S621475 B2 JPS621475 B2 JP S621475B2
- Authority
- JP
- Japan
- Prior art keywords
- treatment
- manganese phosphate
- manganese
- phosphate
- steel material
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Description
本発明は耐焼付性の高い皮膜が得られるリン酸
マンガン皮膜化成処理方法に関するものである。
従来よりリン酸マンガン皮膜は高トルク、高回
転数を伝達する歯車などの歯面に形成され、摩
擦、摺動部の初期なじみに寄与し、耐焼付性を向
上させる役割をしている。しかしながら、従来、
摩擦面、摺動面の耐焼付性付与を目的に使用され
るリン酸マンガン化成処理液は、水素イオン
（H+）濃度が遊離酸度で５〜８ポイント程度であ
る。しかも処理温度が95〜98℃であるため、鉄鋼
材を従来のリン酸マンガン化成処理液で処理する
と、処理時に被処理材表面が著しくエツチングさ
れ、その粗となつた素地の上に比較的結晶粒の大
きなリン酸マンガン被膜が析出する。このような
素地が粗く、その上に結晶粒の大きなリン酸マン
ガン皮膜が形成された場合、摩擦、摺動の初期に
リン酸マンガン皮膜および素地の凹凸部分が取り
除かれてしまうため、取り除かれた厚みの分だけ
歯車の組付精度が狂うことになる。この様な状態
の歯車はその後高回転、高トルクでの使用におい
て、早い時期に焼付をおこし、騒音発生の原因と
なる。
従つて、摩擦、摺動面に形成されるリン酸マン
ガン処理層は素地粗さが小さく、リン酸マンガン
皮膜結晶の細かいものが望ましい。
本発明は上記した素地粗さが小さく、リン酸マ
ンガン結晶の細かい皮膜を形成する成処理方法を
提供すること、特に摩擦、摺動面に使用される耐
焼付性のすぐれた皮膜を形成する化成処理方法を
提供することを目的とする。
発明者等は従来のリン酸マンガン皮膜化成処理
方法において、リン酸マンガン処理液および処理
温度が得られる皮膜に大きく影響することを見い
出し、多くの研究の結果、本発明を完成したもの
である。
本発明はリン酸マンガン処理液に含まれるマン
ガンイオン（Mn2+）、リン酸イオン（PO３− ４）、硝
酸イオン（NO− ３）の各濃度を0.12〜0.32モル／
、0.08〜0.14モル／、0.18〜0.56モル／と
し、硝酸イオン／リン酸イオンのモル比を1.5〜
8.0とするとともに、処理温度を従来より低く50
〜90℃、より好ましくは75〜85℃とすることを特
徴とするものである。
本発明の方法で処理温度を90℃以下とすること
により主として鉄鋼材素地過度のエツチングを防
止し、素地を滑らかに保つている。
またリン酸マンガン処理液に含まれるマンガン
イオン、リン酸イオン、硝酸イオンの各濃度を上
記の範囲に規定し硝酸イオン／リン酸イオンのモ
ル比を1.5〜8.0としたのは、酸化剤である硝酸イ
オン濃度を高め処理反応をすみやかに進行させ素
地のエツチングを防止しつつ微細なリン酸マンガ
ン結晶の被膜を形成するためである。なお、この
処理液の水素イオン濃度は遊離酸度で1.5〜3.5ポ
イントと低くなつている。
処理時に処理液中に超音波振動を印加すると微
細なリン酸マンガン結晶の生成がより容易にな
る。超音波振動の印加により処理温度が50℃〜70
℃といつた低い温度でも、また水素イオン濃度が
遊離酸度で0.5ポイント程度といつた低い濃度で
も処理が可能になる。
処理液には上記したイオン以外に必要によりニ
ツケルイオン（Ni2+）、カルシウムイオン
（Ca2+）、バナジウムイオン（V3+）などの微量成
分を添加することができる。
また被処理材である鉄鋼材料、リン酸マンガン
処理前の前処理、後処理等は従来の方法と同一で
よい。
本発明の方法により耐焼付性がすぐれたリン酸
マンガン被膜が得られる。なお、本発明の方法で
処理された鉄鋼材の素地粗さはエツチング量が極
めて少く処理前とほとんど差がみられない程度で
ある。また得られるリン酸マンガンの結晶粒も細
かい。このため、高い組付精度を要求される歯車
などには本発明方法が極めて有効に活用できる。
以下、実施例を示す。
第１表に示す５種類の処理液を各成分が所定の
濃度となるようにリン酸（H3PO4）、硝酸
（HNO3）、酸化マンガン（MnO）および酸化ニツ
ケル（NiO）を液に溶解して調製した。なお、組
成に示す各イオンの単位はモル／である。ま
た、いずれの処理液も鉄分を0.1〜0.3ポイント含
む。なお、処理液の遊離酸度（水素イオン濃度）
は次式の処理反応の解離定数で決まる。そのため
遊離酸度はマンガンイオン、リン酸イオンおよび
液温度に依存する。
5Mn2+＋4H2PO4 -→
Mn5H2（PO4）4↓＋6H+
The present invention relates to a manganese phosphate film chemical conversion treatment method that provides a film with high seizure resistance. Traditionally, manganese phosphate films have been formed on the tooth surfaces of gears that transmit high torque and high rotational speeds, contributing to friction and initial conformation of sliding parts, and playing a role in improving seizure resistance. However, conventionally,
A manganese phosphate chemical conversion treatment liquid used for the purpose of imparting seizure resistance to friction surfaces and sliding surfaces has a hydrogen ion (H + ) concentration of about 5 to 8 points in terms of free acidity. Moreover, since the treatment temperature is 95 to 98℃, when steel materials are treated with conventional manganese phosphate chemical conversion treatment liquid, the surface of the treated material is markedly etched during the treatment, and relatively crystals are formed on the rough substrate. A manganese phosphate film with large grains is deposited. If such a substrate is rough and a manganese phosphate film with large crystal grains is formed on it, the manganese phosphate film and the uneven parts of the substrate will be removed at the initial stage of friction and sliding, so it will not be removed. The accuracy of gear assembly will be affected by the thickness. When gears in such a state are subsequently used at high rotations and high torques, they will seize at an early stage, causing noise generation. Therefore, it is desirable that the manganese phosphate treated layer formed on the friction and sliding surface has low surface roughness and fine crystals of the manganese phosphate coating. The present invention provides a chemical treatment method for forming a fine film of manganese phosphate crystals with low surface roughness as described above, and in particular, a chemical treatment method for forming a film with excellent seizure resistance for use on friction and sliding surfaces. The purpose is to provide a processing method. The inventors discovered that in the conventional manganese phosphate film chemical conversion treatment method, the manganese phosphate treatment solution and treatment temperature greatly affect the film obtained, and as a result of much research, they completed the present invention. In the present invention, each concentration of manganese ion (Mn 2+ ), phosphate ion ( PO 3-4 ), and nitrate ion (NO - 3 ) contained in the manganese phosphate treatment solution is set to 0.12 to 0.32 mol/
, 0.08 to 0.14 mol/, 0.18 to 0.56 mol/, and the molar ratio of nitrate ion/phosphate ion to 1.5 to 0.56 mol/.
8.0 and the processing temperature is lower than before.
It is characterized by a temperature of ~90°C, more preferably 75-85°C. By controlling the treatment temperature to 90° C. or lower in the method of the present invention, excessive etching of the steel material is mainly prevented and the material is kept smooth. In addition, the concentration of manganese ions, phosphate ions, and nitrate ions contained in the manganese phosphate treatment solution was specified within the above range, and the molar ratio of nitrate ions/phosphate ions was set to 1.5 to 8.0 because of the oxidizing agent. This is to increase the concentration of nitrate ions so that the treatment reaction proceeds quickly, thereby preventing etching of the substrate and forming a film of fine manganese phosphate crystals. Note that the hydrogen ion concentration of this treatment liquid is low at 1.5 to 3.5 points in terms of free acidity. When ultrasonic vibrations are applied to the processing solution during processing, formation of fine manganese phosphate crystals becomes easier. The processing temperature can be increased from 50℃ to 70℃ by applying ultrasonic vibration.
Processing is possible even at low temperatures, such as ℃, and at low hydrogen ion concentrations, such as about 0.5 points of free acidity. In addition to the above-mentioned ions, trace components such as nickel ions (Ni 2+ ), calcium ions (Ca 2+ ), vanadium ions (V 3+ ), etc. can be added to the treatment solution as necessary. Further, the steel material to be treated, the pre-treatment before the manganese phosphate treatment, the post-treatment, etc. may be the same as in the conventional method. By the method of the present invention, a manganese phosphate coating with excellent seizure resistance can be obtained. Note that the roughness of the steel material treated by the method of the present invention has an extremely small amount of etching, and there is almost no difference between the roughness and the roughness of the steel material before treatment. The crystal grains of the manganese phosphate obtained are also fine. Therefore, the method of the present invention can be extremely effectively applied to gears that require high assembly accuracy. Examples are shown below. Phosphoric acid (H 3 PO 4 ), nitric acid (HNO 3 ), manganese oxide (MnO), and nickel oxide (NiO) are added to the five types of treatment solutions shown in Table 1 so that each component has the specified concentration. Prepared by dissolving. Note that the unit of each ion shown in the composition is mol/. In addition, each treatment solution contains 0.1 to 0.3 points of iron. In addition, the free acidity (hydrogen ion concentration) of the processing solution
is determined by the dissociation constant of the treatment reaction in the following equation. Therefore, free acidity depends on manganese ions, phosphate ions, and liquid temperature. 5Mn 2+ +4H 2 PO 4 - → Mn 5 H 2 (PO 4 ) 4 ↓＋6H +
【表】
第１表に示す５種類のうち処理液Ｒは本発明の
方法で規定した処理液の組成範囲外のもので比較
のため用いたものである。次に、これら５種類の
処理液を用い第２表に示す処理条件で、８×８×
15mmのSCM鋼の試験片をリン酸マンガン被膜化
成処理を行なつた。なお、前処理として各試験片
の８×８mmの一端面を炭化珪素（SiC）砥粒で表
面粗さ１〜２μにラツピングし、その後トリクロ
ルエチレンで脱脂した。なお、リン酸マンガン被
膜化成処理の処理時間を５分間とした。処理後各
試験片につき素地粗さ、リン酸マンガン結晶の状
態およびリン酸マンガン皮膜化成処理面の焼付レ
ベル（Kg−Km）を調べた。なお、焼付レベルは、
上記試験片を620回転／分で回転する直径60mmの
SCMリング（浸炭処理後表面粗さ１〜２μにラ
ツピング）の外周にデフギヤ用潤滑油（GL―
５）の存在下に押しつけ、段階的に加圧力を増加
し、焼付を生じるまでの加圧力と摺動距離との積
（Kg―Km）を焼付レベルとした。それらの結果を
合せて第２表に示す。なお、結晶状態の結果で◎
は結晶が極めて微細、〇は微細、△は中、×は粗
い（被覆不完全）を示す。また超音波としては、
出力100W、周波数19KHz、液量３の条件で印
加し処理時間５分間全て超音波を印加した。[Table] Of the five types shown in Table 1, treatment liquid R is outside the composition range of treatment liquids specified in the method of the present invention and was used for comparison. Next, using these five types of treatment liquids and the treatment conditions shown in Table 2, 8×8×
A 15 mm SCM steel specimen was treated with manganese phosphate coating. As a pretreatment, one end surface of each test piece measuring 8×8 mm was lapped with silicon carbide (SiC) abrasive grains to a surface roughness of 1 to 2 μm, and then degreased with trichlorethylene. Note that the treatment time for the manganese phosphate film chemical conversion treatment was 5 minutes. After treatment, the roughness of the substrate, the state of the manganese phosphate crystals, and the baking level (Kg-Km) of the chemical conversion treated surface of the manganese phosphate film were examined for each test piece. In addition, the burn-in level is
The above specimen was rotated at 620 revolutions/min with a diameter of 60 mm.
Lubricating oil for differential gear (GL-
5), the pressure was increased stepwise, and the product (Kg-Km) of the pressure and the sliding distance until seizure occurred was defined as the seizure level. The results are shown in Table 2. In addition, as a result of the crystal state, ◎
indicates extremely fine crystals, 〇 indicates fine crystals, △ indicates medium crystals, and × indicates coarse crystals (incomplete coverage). Also, as ultrasound,
Ultrasonic waves were applied under the conditions of an output of 100 W, a frequency of 19 KHz, and a liquid volume of 3 for a total processing time of 5 minutes.
【表】
第２表の形成されたリン酸マンガン皮膜の特性
より明らかなように、本発明の処理方法で試験し
た試験No.１〜９は素地粗さが１〜５μと滑らかで
あり、結晶状態も微細で耐焼付性も300Kg−Km〜
520Kg−Kmとすぐれている。これに対し比較例で
ある試験No.101、102の皮膜は素地粗さが５〜９μ
と粗く、耐焼付性も210Kg−Km〜370Kg−Kmと低
い。
なお超音波振動の印加は、素地の滑らかさ、結
晶状態、耐焼付性のいずれにも良い結果を与える
ことが確認された。[Table] As is clear from the characteristics of the manganese phosphate films formed in Table 2, test Nos. 1 to 9 tested using the treatment method of the present invention had a smooth substrate roughness of 1 to 5μ, and The condition is fine and the seizure resistance is 300Kg-Km~
It is excellent at 520Kg−Km. On the other hand, the coatings of test Nos. 101 and 102, which are comparative examples, have a substrate roughness of 5 to 9 μm.
It is rough and has a low seizure resistance of 210Kg-Km to 370Kg-Km. It was confirmed that the application of ultrasonic vibration gave good results in terms of the smoothness, crystalline state, and seizure resistance of the substrate.
Claims (1)
浸漬することにより鉄鋼材料の表面にリン酸マン
ガン皮膜を形成する方法において、 リン酸マンガン処理液は、マンガンイオンを
0.12〜0.32モル／、リン酸イオンを0.08〜0.140
モル／および硝酸イオンを0.18〜0.56モル／
含み、該硝酸イオン／リン酸イオンがモル比で
1.5〜8.0の範囲にあり、その処理液の温度が50〜
90℃であることを特徴とするリン酸マンガン皮膜
化成処理方法。 ２ 鉄鋼材料がリン酸マンガン処理液に浸漬され
ているときに処理液に超音波振動を加える特許請
求の範囲第１項記載の方法。 ３ 鉄鋼材料は摩擦、摺動部材である特許請求の
範囲第１項記載の方法。 ４ 処理液の温度は75〜85℃である特許請求の範
囲第１項記載の方法。[Claims] 1. In a method of forming a manganese phosphate film on the surface of a steel material by immersing the steel material in a manganese phosphate treatment solution for a certain period of time, the manganese phosphate treatment solution contains manganese ions.
0.12-0.32 mol/, phosphate ion 0.08-0.140
mol/and nitrate ion from 0.18 to 0.56 mol/
Contains, the nitrate ion/phosphate ion molar ratio
It is in the range of 1.5 to 8.0, and the temperature of the processing liquid is 50 to 8.0.
A manganese phosphate film chemical conversion treatment method characterized by a temperature of 90°C. 2. The method according to claim 1, wherein ultrasonic vibration is applied to the treatment liquid while the steel material is immersed in the manganese phosphate treatment liquid. 3. The method according to claim 1, wherein the steel material is a friction or sliding member. 4. The method according to claim 1, wherein the temperature of the treatment liquid is 75 to 85°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP735682A JPS58123882A (en) | 1982-01-20 | 1982-01-20 | Chemical conversion treatment giving manganese phosphate film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP735682A JPS58123882A (en) | 1982-01-20 | 1982-01-20 | Chemical conversion treatment giving manganese phosphate film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58123882A JPS58123882A (en) | 1983-07-23 |
| JPS621475B2 true JPS621475B2 (en) | 1987-01-13 |
Family
ID=11663675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP735682A Granted JPS58123882A (en) | 1982-01-20 | 1982-01-20 | Chemical conversion treatment giving manganese phosphate film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58123882A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4941930A (en) * | 1986-09-26 | 1990-07-17 | Chemfil Corporation | Phosphate coating composition and method of applying a zinc-nickel phosphate coating |
| JPS6435244U (en) * | 1987-08-26 | 1989-03-03 | ||
| JPH04113024A (en) * | 1990-08-31 | 1992-04-14 | Daido Metal Co Ltd | Sliding member made of al bearing alloy excellent in non-seizure property |
| US5728235A (en) * | 1996-02-14 | 1998-03-17 | Henkel Corporation | Moderate temperature manganese phosphate conversion coating composition and process |
| US5595611A (en) * | 1996-02-14 | 1997-01-21 | Henkel Corporation | Moderate temperature manganese phosphate conversion coating composition and process |
| CA2398771A1 (en) * | 2000-01-31 | 2001-08-02 | Henkel Corporation | Phosphate conversion coating process and composition |
| JP2006077840A (en) * | 2004-09-08 | 2006-03-23 | Tsubakimoto Chain Co | Tensioner |
| CN105645370B (en) * | 2016-01-06 | 2017-09-12 | 昆明理工大学 | A kind of preparation method of sheet hureaulite |
| CN110760827A (en) * | 2019-10-30 | 2020-02-07 | 湖南金裕环保科技有限公司 | High-temperature black manganese phosphating solution, preparation method and application thereof |
| CN112962089B (en) * | 2021-01-29 | 2023-02-24 | 沈阳帕卡濑精有限总公司 | Environment-friendly and efficient nickel-free manganese phosphating agent and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5241735A (en) * | 1975-09-29 | 1977-03-31 | Nissan Motor Co Ltd | Temperature control method of reactor |
-
1982
- 1982-01-20 JP JP735682A patent/JPS58123882A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58123882A (en) | 1983-07-23 |
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