EP2328835A1 - Procédé de préparation de phosphate de titane iv - Google Patents

Procédé de préparation de phosphate de titane iv

Info

Publication number
EP2328835A1
EP2328835A1 EP09783060A EP09783060A EP2328835A1 EP 2328835 A1 EP2328835 A1 EP 2328835A1 EP 09783060 A EP09783060 A EP 09783060A EP 09783060 A EP09783060 A EP 09783060A EP 2328835 A1 EP2328835 A1 EP 2328835A1
Authority
EP
European Patent Office
Prior art keywords
titanium
phosphate
oxygen compound
phosphoric acid
solution
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.)
Withdrawn
Application number
EP09783060A
Other languages
German (de)
English (en)
Inventor
Bernd Proft
Martin Dehnen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Venator Germany GmbH
Original Assignee
Sachtleben Chemie GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sachtleben Chemie GmbH filed Critical Sachtleben Chemie GmbH
Publication of EP2328835A1 publication Critical patent/EP2328835A1/fr
Withdrawn legal-status Critical Current

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
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum

Definitions

  • the invention relates to a process for the preparation of titanium-IV-phosphate in the form of a phosphate acid solution and in particulate form and its use for the treatment of surfaces.
  • a phosphatizing process also includes various pre- and post-treatment stages.
  • the cleaning of the metal surface which is generally carried out with alkaline or acidic cleaners and the metal surface of oils, fats, oxides and adhering solid particles freed. If the cleaning is carried out with mild alkaline cleaners, it is in principle possible to combine the cleaning with the activation of the metal surface. In general, however, the activation joins as a separate process step to the cleaning.
  • the activation of the metal surface has the task at the shortest possible Phosphatier stipulate the formation of a to ensure the most finely crystalline zinc phosphate layer.
  • a criterion for the effect of a Aktiv istsmitteis is therefore the Mmdestphosphatierzeit.
  • the suitability for the formation also of fine crystalline zinc phosphate layers can be determined on the basis of the layer weights or by scanning electron micrographs.
  • Titanium IV phosphates are formed in the reaction of aqueous titanium IV salt solutions with soluble phosphates or phosphoric acid.
  • products with activating properties are only obtained under particular manufacturing conditions such as those described in US Pat. Nos. 2 310 239 and 2 456 947, which give details of the nature and concentration of the raw materials, temperature and pH range of manufacture.
  • variations in the performance effect are obtained from batch to batch.
  • activators based on titanium-IV-phosphate A disadvantage of the use of activators based on titanium-IV-phosphate is that the activation bath must be prepared with demineralized water. The reason for this is that the alkaline earth metal ions present in the tap water as destabilizing agents destabilize titanium IV phosphate in activation baths. These alkaline earth metal ions can also be introduced by rinsing water into the activation bath.
  • EP 454211 relates to an activating agent based on titanium-IV-phosphate for the activation of metal surfaces prior to Zmkphosphatmaschine and its use for the approach of Aktivierungsbadern.
  • the task is solved by the treatment of titanium dioxide with phosphoric acid.
  • surface-rich titanium dioxide types and titania precursors react with phosphoric acid to form poorly soluble solids.
  • the inventors have succeeded in making a sol of formal in Phosphoric acid having a formal TIa (PCU) 4 content of 100-120 g / l phosphoric acid by reaction of titanium dioxide with concentrated phosphoric acid with a concentration of 85 wt .-%, preferably more than 89 wt .-% to produce.
  • PCU formal TIa
  • the invention is directed to a process for producing titanium phosphate, comprising the steps of: introducing a titanium-oxygen compound in aqueous phosphoric acid having a concentration of more than 85% by weight; Treating the suspension thus obtained in a temperature range of more than 50 ° C to 150 ° C until complete dissolution of the titanium-oxygen compound, wherein the titanium-oxygen compound is used in step a) in a dried form.
  • the titanium-oxygen compound in step a) is preferably used in a form which is dried to constant mass at temperatures of less than 110 ° C.
  • the titanium-oxygen compound is used in step a) in a purified form, especially as titanium dioxide and and in particular in the anatase modification.
  • step a) use of the titanium-oxygen compound in step a) in particulate form in a crystallite size of 7 to 300 nm is preferable.
  • titanium-oxygen compound examples include titanium oxides or hydroxides, which are suitable as Ninmate ⁇ alien and can be optionally used to call, under the designation S 150, S 140 and S 240 of Kemira, under the Designation P 25 of Degussa, as VKR 611, Hombikat UV100 and Hombifme N of Sachtleben, XT 25376 of Norton, DT 51 of Thann et Mulhouse and Bayoxide TA-DW-I, Bayoxide T AK-1 of Bayer, are commercially available , Most suitably proved the titanium dioxide Hombifme N.
  • Hombifme N dissolves particularly well in the concentrated phosphoric acid, but should preferably be previously dried under mild conditions (110 0 C max) to constant mass. Too intensive drying, for example at 130 ° C and 150 ° C leads to a poorer solubility, as well, if the product still contains much residual moisture. Accordingly, the titanium dandy is preferably dried to constant mass.
  • the titanium dioxide is preferably used in an amount of 0.1 to 2.0 mol / L of phosphoric acid.
  • solubility in 85% phosphoric acid is sufficient, improved solubility in 89% phosphoric acid was observed, which is preferably used to prepare the solution.
  • the use of high concentrated phosphoric acid makes it possible to achieve even better solubility of titanium dioxide. This is on the one hand by adding phosphorus pentoxide to 85 with phosphoric acid Wt .-%, preferably 89 wt .-% possible, on the other hand, by the use of pure, crystalline phosphoric acid, but only melted (mp. 42 ° C) must be.
  • the phosphate-acid solution of titanium phosphate obtainable according to the invention can already be used for the surface treatment of metals and inorganic particles.
  • titanium phosphate will also be compounds such as titanyl phosphate or mixtures with titanium phosphate. It is crucial that the erfmdungsgetoole method is performed.
  • this phosphate-acid solution is first filtered. This is followed by neutralization of the resulting filtrate with, for example, aqueous ammonia solution, separation and washing of the precipitated particles with water, and drying of the particles, preferably at elevated temperature.
  • the particles thus obtained may be redissolved for use in concentrated phosphoric acid (> 85%).
  • the titanium-IV-phosphate prepared according to the invention can be used, for example, for the activation of metal surfaces prior to Zmkphosphatierung, is easy to prepare and leads in its use in the approach of Aktivierungsbadern to stable Aktivierungsbadern with a long service life, which also guarantee the formation of fine crystalline zinc phosphate coatings in a short time .
  • titanium-IV-phosphate especially in phosphate acid solution, the corrosion of metallic surfaces can be prevented, and it can be achieved phosphating the surface, where by chemical reactions of metallic surfaces with the titanium-IV-phosphate solution, a conversion layer is formed from firmly adhering metal phosphates.
  • This phosphating can be applied to steel but can also be used for galvanized or cadmium steels and aluminum. Inventive main applications are corrosion protection,
  • the layer structure is also formed by titanium cations from the phosphate solution, and in addition metal cations from the base material are involved.
  • the phosphate layer thus obtained according to the invention adheres very well to the substrate and, due to the microporous or microcapillary layer structure, permits a good coating
  • the phosphate layer thus prepared can be used very well as a substrate for further coatings. In addition, it makes it difficult to rust on damaged areas of the coating.
  • the corrosion protection of the phosphating can be improved by oiling or waxing.
  • the phosphate layers have good sliding properties, which can be used for the cold forming of steel.
  • the erfmdungsgeolin prepared titanium IV phosphate can be used in the flame retardancy of plastics by an intumescent layer is generated on the substrate to be protected. Serving as fire protection "swelling" or foaming of materials is referred to in the art as intumescence. Such intumescent building materials increase in volume under the influence of heat and decrease in density and are generally used in preventative structural fire protection.
  • the titanium phosphate according to the invention can generally be used there for the surface treatment of metals, graphite electrodes, inorganic particles and organic materials such as textile materials, where it depends on the application of a passivating protective layer on the surface of the substrate.
  • the gel-form product was filtered through a glass fiber filter MN 85/90 and washed. After washing for four days and twice reslurrying each in about 2 L of hot TE water, a conductivity in the wash filtrate of about 700 pS / cm could be achieved. Then the washing was stopped. The resulting solid was dried at 130 ° C. The solid was characterized by specific surface area, porosimetry, UV / VIS, X-ray diffractometry and SEM.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention concerne un procédé de préparation de phosphate de titane IV sous forme d'une solution acide de phosphate et sous forme particulaire, et son utilisation pour le traitement de surfaces.
EP09783060A 2008-09-16 2009-09-15 Procédé de préparation de phosphate de titane iv Withdrawn EP2328835A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008047533A DE102008047533A1 (de) 2008-09-16 2008-09-16 Verfahren zur Herstellung von Titan-IV-phosphat
PCT/EP2009/061980 WO2010031779A1 (fr) 2008-09-16 2009-09-15 Procédé de préparation de phosphate de titane iv

Publications (1)

Publication Number Publication Date
EP2328835A1 true EP2328835A1 (fr) 2011-06-08

Family

ID=41503654

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09783060A Withdrawn EP2328835A1 (fr) 2008-09-16 2009-09-15 Procédé de préparation de phosphate de titane iv

Country Status (6)

Country Link
US (1) US20110185945A1 (fr)
EP (1) EP2328835A1 (fr)
JP (1) JP2012502871A (fr)
DE (1) DE102008047533A1 (fr)
MX (1) MX2011002810A (fr)
WO (1) WO2010031779A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6015453B2 (ja) * 2013-01-08 2016-10-26 堺化学工業株式会社 多孔質結晶性α型リン酸水素チタン１水和物球状粒子の製造方法
CN105063577A (zh) * 2015-08-25 2015-11-18 山东建筑大学 一种耐高温磷酸钙盐-磷灰石膜层的制备方法
CN108574093B (zh) * 2018-05-08 2020-11-06 浙江农林大学 一种碳/焦磷酸钛复合材料及其制备方法
CN113041965B (zh) * 2021-03-11 2022-04-29 廊坊师范学院 一种磷酸钛溶胶的制备方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB419522A (en) * 1933-02-07 1934-11-07 Howard Spence Improvements in the preparation and use of titanium compounds
IT429345A (fr) 1941-10-25 1900-01-01
US2456947A (en) 1944-12-21 1948-12-21 Westinghouse Electric Corp Corrosion resistant coating for metal surfaces
US3471252A (en) * 1966-01-22 1969-10-07 Mizusawa Industrial Chem Process for the preparation of titanium compounds which are substantially free from metallic impurities
US3914381A (en) * 1969-03-18 1975-10-21 Mizusawa Industrial Chem Process for the preparation of substantially pure phosphorus oxyacid salts of metals of group IV b{41
DE1937035A1 (de) * 1969-07-21 1971-01-28 Dow Chemical Co Titanphosphat-Kristalle
US3955017A (en) * 1971-11-26 1976-05-04 Imperial Chemical Industries Limited Method of coating metal phosphates on organic polymeric substrates
DE3635343A1 (de) 1986-10-17 1988-04-28 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen
DE3814287A1 (de) * 1988-04-28 1989-11-09 Henkel Kgaa Polymere titanphosphate, verfahren zu ihrer herstellung und ihre verwendung zur aktivierung von metalloberflaechen vor einer zinkphosphatierung
DE4012795A1 (de) 1990-04-21 1991-10-24 Metallgesellschaft Ag Aktivierungsmittel fuer die phosphatierung
US5733519A (en) * 1996-02-05 1998-03-31 Monsanto Company Method for producing a dispersible, fine titanium pyrophosphate powder
JP2000063110A (ja) * 1998-08-12 2000-02-29 Tosoh Corp リン酸チタンの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010031779A1 *

Also Published As

Publication number Publication date
MX2011002810A (es) 2011-04-21
JP2012502871A (ja) 2012-02-02
US20110185945A1 (en) 2011-08-04
DE102008047533A1 (de) 2010-04-15
WO2010031779A1 (fr) 2010-03-25

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