NO322024B1 - Anti-corrosion pigment and its use - Google Patents
Anti-corrosion pigment and its use Download PDFInfo
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- NO322024B1 NO322024B1 NO20004284A NO20004284A NO322024B1 NO 322024 B1 NO322024 B1 NO 322024B1 NO 20004284 A NO20004284 A NO 20004284A NO 20004284 A NO20004284 A NO 20004284A NO 322024 B1 NO322024 B1 NO 322024B1
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- Prior art keywords
- corrosion
- phosphate
- corrosion pigment
- calculated
- pigment according
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- 238000005260 corrosion Methods 0.000 title claims description 43
- 239000000049 pigment Substances 0.000 title claims description 41
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 19
- 229910019142 PO4 Inorganic materials 0.000 claims description 18
- 239000010452 phosphate Substances 0.000 claims description 18
- 230000007797 corrosion Effects 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 6
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 6
- 229910000400 magnesium phosphate tribasic Inorganic materials 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 239000004137 magnesium phosphate Substances 0.000 claims description 3
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 3
- 229960002261 magnesium phosphate Drugs 0.000 claims description 3
- -1 magnesium phosphate compound Chemical class 0.000 claims description 3
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 8
- 230000002401 inhibitory effect Effects 0.000 description 8
- 235000019832 sodium triphosphate Nutrition 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 3
- 239000007900 aqueous suspension Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 239000002987 primer (paints) Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 150000003752 zinc compounds Chemical class 0.000 description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- RBLGLDWTCZMLRW-UHFFFAOYSA-K dicalcium;phosphate;dihydrate Chemical compound O.O.[Ca+2].[Ca+2].[O-]P([O-])([O-])=O RBLGLDWTCZMLRW-UHFFFAOYSA-K 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000012031 short term test Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- ZMPZURBYCNDNBN-UHFFFAOYSA-K aluminum;calcium;phosphate Chemical compound [Al+3].[Ca+2].[O-]P([O-])([O-])=O ZMPZURBYCNDNBN-UHFFFAOYSA-K 0.000 description 1
- DOEVMNBDNQNWEJ-UHFFFAOYSA-K aluminum;magnesium;phosphate Chemical compound [Mg+2].[Al+3].[O-]P([O-])([O-])=O DOEVMNBDNQNWEJ-UHFFFAOYSA-K 0.000 description 1
- MHLMPARDYWGGLE-UHFFFAOYSA-K aluminum;zinc;phosphate Chemical compound [Al+3].[Zn+2].[O-]P([O-])([O-])=O MHLMPARDYWGGLE-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- VLCINIKIVYNLPT-UHFFFAOYSA-J dicalcium;hydrogen phosphate Chemical compound [Ca+2].[Ca+2].OP(O)([O-])=O.[O-]P([O-])([O-])=O VLCINIKIVYNLPT-UHFFFAOYSA-J 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- AYGUCHAPOTYFRT-UHFFFAOYSA-H zinc molybdenum(4+) diphosphate Chemical compound [Zn+2].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O AYGUCHAPOTYFRT-UHFFFAOYSA-H 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
Den foreliggende oppfinnelse vedrører et antikorrosjonspigment for overflatebeskyttelse av metaller eller metallegeringer, særlig for korrosjonsbeskyttelse for malte eller lakkerte metaller eller metallegeringskomponenter, og anvendelse derav. The present invention relates to an anti-corrosion pigment for surface protection of metals or metal alloys, in particular for corrosion protection for painted or lacquered metals or metal alloy components, and use thereof.
Det er kjent å tilføre antikorrosjonspigmenter til malingsmaterialer og lakk, slik som primerbelegg for malte metallkomponenter, hvilke benyttes for å beskytte metallene mot atmosfærisk korrosjon. Tidligere ble det særlig benyttet giftige pigmenter basert på bly eller tungmetallforbindelser eller kromater, som korrosjonshemmende pigmenter. Anvendelsen av slike giftige pigmenter er blitt kraftig begrenset på grunn av den økende oppmerksomhet vedrørende miljøspørsmål. For eksempel i Journal of Coatings Technology" 58, 1986, sider 59-65 blir det bemerket at giftig sinkkromat kan erstattes med sinkfosfat. I nevnte rapport fremholdes også at gode resultater er blitt oppnådd med henholdsvis basisk sinkmolybdenfosfat og sinkaluminiumfosfat It is known to add anti-corrosion pigments to paint materials and varnishes, such as primer coatings for painted metal components, which are used to protect the metals against atmospheric corrosion. In the past, toxic pigments based on lead or heavy metal compounds or chromates were particularly used as corrosion-inhibiting pigments. The use of such toxic pigments has been greatly restricted due to the increasing attention regarding environmental issues. For example, in the Journal of Coatings Technology" 58, 1986, pages 59-65, it is noted that toxic zinc chromate can be replaced with zinc phosphate. In said report, it is also stated that good results have been obtained with basic zinc molybdenum phosphate and zinc aluminum phosphate, respectively
Anvendelsen av tungmetallholdige antikorrosjonspigmenter i belegg-materialer blir imidlertid hele tiden underkastet strengere restriksjoner. Den tyske "MAK-Wert-Komission" (maksimal arbeidsplasskonsentrasjons-grense (MWCL)-kommisjonen) foreslo å kontrollere MWCL med hensyn til sinkfosfat i året 1998.1 USA er, i henhold til EPA-direktivet EPCRA (Emergency Planning and Community Right-To-Know, Section 313), sinkforbindelser i støvform klassifisert som giftige. Med hensyn til avfallsavhending av tungmetallholdige substanser eller belegg (sprøytematerialavfall), er grenseverdier foreskrevet med hensyn til tungmetaller, og de skal ikke overskrides. Tungmetallinnholdet i avfallsvann fra produksjonsanlegg for maling og lakk, elter avfallsvannet som forekommer ved arbeid slik som i sprøyteavlukker, er også begrenset, hvilket leder til et søk for tungmetallfrie antikorrosjonspigmenter som erstatning for sinkforbindelser. However, the use of heavy metal-containing anti-corrosion pigments in coating materials is constantly subject to stricter restrictions. The German "MAK-Wert-Komission" (Maximum Workplace Concentration Limit (MWCL) Commission) proposed to control the MWCL with regard to zinc phosphate in the year 1998.1 The USA is, according to the EPA directive EPCRA (Emergency Planning and Community Right-To- Know, Section 313), zinc compounds in dust form classified as toxic. With regard to waste disposal of heavy metal-containing substances or coatings (spraying material waste), limit values are prescribed with regard to heavy metals, and they must not be exceeded. The heavy metal content in waste water from paint and varnish production facilities, kneading waste water occurring during work such as in spray booths, is also limited, leading to a search for heavy metal-free anti-corrosion pigments as a replacement for zinc compounds.
For eksempel fra patentpublikasjon EP-A-0718377 er det kjent antikorrosjonspigmenter som omfatter en blanding av P-trikalsiumfosfat og fireverdig magnesiumfosfat eller med dikalsiumfosfatdrihydrat. Andre tungmetallfrie fosfatpigmenter er beskrevet i patentpublikasjon DE-C-4021086 og omfatter magnesiumaluminiumortofosfat eller kalsiumaluminiumortofosfat i form av et blandet krystall av aluminiumfosfat og jordalkalifosfat. For example, from patent publication EP-A-0718377 anti-corrosion pigments are known which comprise a mixture of P-tricalcium phosphate and tetravalent magnesium phosphate or with dicalcium phosphate dihydrate. Other heavy metal-free phosphate pigments are described in patent publication DE-C-4021086 and comprise magnesium aluminum orthophosphate or calcium aluminum orthophosphate in the form of a mixed crystal of aluminum phosphate and alkaline earth phosphate.
En god korrosjonshemmende virkning ble funnet med flere tungmetallfrie fosfatpigmenter som er blitt foreslått som erstatninger for sinkforbindelser, men samtidig medførte de en uønsket tendens til bobledannelse og tap av vedheft for belegget, særlig i korttidstester i fuktig miljø, hvilket vanligvis benyttes med hensyn til antikorrosjonstestprosedyrer i malingsindustrien. A good corrosion-inhibiting effect was found with several heavy-metal-free phosphate pigments that have been proposed as substitutes for zinc compounds, but at the same time they entailed an undesirable tendency to bubble formation and loss of coating adhesion, especially in short-term tests in a humid environment, which is usually used with regard to anti-corrosion test procedures in the paint industry.
Derfor er målet med den foreliggende oppfinnelse å tilveiebringe nye tungmetallfrie antikorrosjonspigmenter som har korrosjonshemmende egenskaper som er så gode som mulige, og samtidig medfører ingen eller minimal mulig grad av bobledannelse og tap av vedheft for belegget som inneholder dem. Therefore, the aim of the present invention is to provide new heavy metal-free anti-corrosion pigments that have corrosion-inhibiting properties that are as good as possible, and at the same time result in no or minimal possible degree of bubble formation and loss of adhesion for the coating that contains them.
Med den foreliggende oppfinnelse tilveiebringes det et antikorrosjonspigment for overflatebeskyttelse av metaller eller metallegeringer, bestående av en blanding og/eller et reaksjonsprodukt av en magnesiumfosfatforbindelse, særpreget ved at det er en blanding og/eller et reaksjonsprodukt av hydroksyapatitt med trimagnesiumfosfat. The present invention provides an anti-corrosion pigment for surface protection of metals or metal alloys, consisting of a mixture and/or a reaction product of a magnesium phosphate compound, characterized by the fact that it is a mixture and/or a reaction product of hydroxyapatite with trimagnesium phosphate.
Generelt vil antikorrosjonspigmentet tilføres til et beleggingsmateriale. In general, the anti-corrosion pigment will be added to a coating material.
Antikorrosjonspigmentet i henhold til den foreliggende oppfinnelse oppnår målet med oppfinnelsen ved en kombinasjon av høyest mulig grad av korrosjonshemming kombinert med minimalt mulig nivå av bobledannelse og lavest mulig nivå av adhesjonstap for belegget som inneholder pigmentet. Korrosjonshemning i tilfellet med fosfatholdige belegg er avhengig av det vannløselige fosfatinnhold i pigmentet. Fosfationer er uunnværlige for dannelse av beskyttende lag ved grenseflaten mellom metall og belegg ved adkomst av vann og oksygen. De beskyttende lag som dannes omfatter jern-II-fosfat/jern-III-oksid. Nærværet av oksygen forhindrer at jernet går i løsning som hydroksid. Fosfatet bevirker at jernionet forblir på stedet som er angrepet, med dannelse av passiverende lag av jern-III-oksid/jern-II-fosfat. The anti-corrosion pigment according to the present invention achieves the goal of the invention by a combination of the highest possible degree of corrosion inhibition combined with the minimum possible level of bubble formation and the lowest possible level of adhesion loss for the coating containing the pigment. Corrosion inhibition in the case of phosphate-containing coatings is dependent on the water-soluble phosphate content of the pigment. Phosphate ions are indispensable for the formation of a protective layer at the interface between metal and coating when water and oxygen are exposed. The protective layers that form include iron II phosphate/iron III oxide. The presence of oxygen prevents the iron from going into solution as hydroxide. The phosphate causes the iron ion to remain at the site that is attacked, with the formation of a passivating layer of iron-III-oxide/iron-II-phosphate.
Maksimal fosfatløselighet og derav følgende hemmingsegenskaper gir imidlertid samtidig økning av den hydrofile natur for belegget og derved tendens til bobledannelse og tap av adhesjon. Det er derfor gjort forsøk på å finne et kompromiss med et relativt høyt nivå av fosfatløselighet og derved korrosjonshemming, koblet til minimal mulig grad av bobledannelse og minimalt tap av adhesjon for belegget. Dette er oppnådd med antikorrosjonspigmentet i henhold til den foreliggende oppfinnelse, nærmere bestemt dem med vannløselig fosfatinnhold på høyst 1000 mg/l, fortrinnsvis høyst 900 mg/l, særlig foretrukket høyst 800 mg/l. However, maximum phosphate solubility and the resulting inhibition properties simultaneously increase the hydrophilic nature of the coating and thereby tend to bubble formation and loss of adhesion. Attempts have therefore been made to find a compromise with a relatively high level of phosphate solubility and thereby corrosion inhibition, coupled with the minimum possible degree of bubble formation and minimal loss of adhesion for the coating. This has been achieved with the anti-corrosion pigment according to the present invention, more specifically those with a water-soluble phosphate content of no more than 1000 mg/l, preferably no more than 900 mg/l, particularly preferably no more than 800 mg/l.
I denne sammenheng blir det vannløselige fosfatinnhold i fosfatpigmentene bestemt ved en prosedyre hvorved 20 g av en prøve av fosfatpigmentene kokes i 180 ml avionisert vann i 5 minutter og fylles opp til 200 ml etter avkjøling til omgivelsestemperatur. Suspensjonen filtreres med et foldet filter (602 H 1/2). Ortofosfatinnholdet i det klare filtrat bestemmes ved kalorimetri. In this context, the water-soluble phosphate content of the phosphate pigments is determined by a procedure whereby 20 g of a sample of the phosphate pigments is boiled in 180 ml of deionized water for 5 minutes and filled up to 200 ml after cooling to ambient temperature. The suspension is filtered with a pleated filter (602 H 1/2). The orthophosphate content in the clear filtrate is determined by calorimetry.
I henhold til oppfinnelsen kan hydroksyapattiten med formelen Ca5(P04)3OH benyttes i form av en blanding og/eller som et reaksjonsprodukt omfattende hydroksyapatitt og trimagnesiumfosfat. Når det i denne sammenheng henvises til reaksjonsproduktene av hydroksyapatitt med trimagnesiumfosfat, menes alle produkter som kan fremstilles ved felles presipitering ved reaksjon av kalsiumhydroksid, magnesiumhydroksid og ortofosforsyre. Slike produkter kan være blandkrystaller, definerte forbindelser og/eller rene blandinger. Antikorrosjonspigmentet blir oppnådd ved reaksjon i vandig suspensjon med agitasjon ved forhøyet temperatur. According to the invention, the hydroxyapatite with the formula Ca5(PO4)3OH can be used in the form of a mixture and/or as a reaction product comprising hydroxyapatite and trimagnesium phosphate. When reference is made in this context to the reaction products of hydroxyapatite with trimagnesium phosphate, all products which can be produced by joint precipitation by reaction of calcium hydroxide, magnesium hydroxide and orthophosphoric acid are meant. Such products can be mixed crystals, defined compounds and/or pure mixtures. The anti-corrosion pigment is obtained by reaction in an aqueous suspension with agitation at an elevated temperature.
Antikorrosjonspigmentet i henhold til oppfinnelsen inneholder hensikts-messig i henhold til analyse opp til 10 vekt%, fortrinnsvis opp til 9 vekt%, især opp til 7 vekt%, magnesiumoksid, beregnet på basis av glødetapsfri sammensetning. The anti-corrosion pigment according to the invention appropriately contains, according to analysis, up to 10% by weight, preferably up to 9% by weight, especially up to 7% by weight, of magnesium oxide, calculated on the basis of a composition without loss of glow.
Antikorrosjonspigmentene i henhold til oppfinnelsen benyttes fortrinnsvis for korrosjonsbeskyttelse av metalldeler eller metallegeringsdeler. Partikkel-størrelsen av antikorrosjonspigmentene er fordelaktig mindre enn 5 (im. Et eksempel på en sammensetning som er vanlig i praktisk bruk, for et primerbelegg eller underbelegg, er som følger: The anti-corrosion pigments according to the invention are preferably used for corrosion protection of metal parts or metal alloy parts. The particle size of the anti-corrosion pigments is advantageously less than 5 (im. An example of a composition common in practical use, for a primer coating or undercoating, is as follows:
I sammenligningstestene i det etterfølgende ble hemningseffekten In the comparison tests that followed, the inhibition effect was
bestemt ved en korttidstest i henhold til Ruf ("farbe + lack", 101 [1995], s. 922-927), på den ene side ved fuktning med destillert vann og på den annen side ved fuktning med en 0,3 % NaCl-løsning. Ved testen i henhold til Ruf ble det frem-stilt vandig pasta fra like volumforhold av pigmentet som skulle bestemmes, og determined by a short-term test according to Ruf ("farbe + lack", 101 [1995], pp. 922-927), on the one hand by wetting with distilled water and on the other hand by wetting with a 0.3% NaCl -solution. In the test according to Ruf, an aqueous paste was prepared from equal volume ratios of the pigment to be determined, and
destillert vann og pastaene ble påført et filterpapir med mål 3 x 34 cm ved hjelp av en duk med åpninger, i en tykkelse på 100 um. Hull av ca. 60 mm størrelse ble symmetrisk anordnet i folien. Filterpapiret utstyrt med pigment ble ført direkte på substratet som skulle undersøkes og fuktning ble bevirket med destillert vann og 0,3 % NaCl-løsning, henholdsvis, for å tilveiebringe de fuktige forhold. Varigheten av testen er fra 10 til 12 timer. Testforløpet kan registreres fotografisk. Sluttbedømning utføres direkte eller fjerning av filterpapiret og substansrestene. Kjernerust (C) bestemmes som prosentandel rust som er blitt dannet under substanskjernen (mellom C 0 og C 100), og overflaterust (S) bestemmes som prosentandel overflaterust (mellom S 0 og S 100). Så langt som mulig skal det med en substans med god korrosjonshemmende virkning ikke forekomme rust. distilled water and the pastes were applied to a filter paper measuring 3 x 34 cm using a cloth with openings, to a thickness of 100 µm. Hole of approx. 60 mm size was symmetrically arranged in the foil. The filter paper equipped with pigment was placed directly on the substrate to be examined and wetting was effected with distilled water and 0.3% NaCl solution, respectively, to provide the moist conditions. The duration of the test is from 10 to 12 hours. The test process can be recorded photographically. Final assessment is carried out directly or removal of the filter paper and substance residues. Core rust (C) is determined as the percentage of rust that has formed under the substance core (between C 0 and C 100), and surface rust (S) is determined as the percentage of surface rust (between S 0 and S 100). As far as possible, rust should not occur with a substance with a good corrosion-inhibiting effect.
Videre ble det vannløselige fosfatinnhold og bobledannelse bestemt i en kortids-væreksponeringsprosedyre i henhold til DIN 53 209.1 dette tilfelle ble konvensjonelle korrosjonstester som vanligvis benyttes i malingsindustrien utøvet i form av en saltsprøytingstest i henhold til DIN 50 021, og konden-sasjons vanntest i henhold til DIN 50 017.1 dette henseende ble en alkydharpiks-primer i henhold til forannevnte sammensetning påført på industrielt avfettede stålplater St 1405, i hvert tilfelle med et innhold på 25 volum% antikorrosjonspigment, og med en tørrfilmtykkelse på mellom 40 og 50 um. Resultatene er opplistet i tabellen som følger. I tillegg til antikorrosjonspigmentene i henhold til oppfinnelsen inkluderer tabellen også antikorrosjonspigmenter i henhold til kjent teknikk, hvilke følgelig ligger utenfor oppfinnelsens omfang. Furthermore, the water-soluble phosphate content and bubble formation were determined in a short-term weather exposure procedure according to DIN 53 209.1 In this case, conventional corrosion tests that are usually used in the paint industry were carried out in the form of a salt spray test according to DIN 50 021, and condensation water test according to DIN 50 017.1 in this regard, an alkyd resin primer according to the aforementioned composition was applied to industrially degreased steel plates St 1405, in each case with a content of 25% by volume of anti-corrosion pigment, and with a dry film thickness of between 40 and 50 µm. The results are listed in the table that follows. In addition to the anti-corrosion pigments according to the invention, the table also includes anti-corrosion pigments according to known technology, which are consequently outside the scope of the invention.
Verdiene i den foregående tabell viser at dikalsiumhydrogenfosfatet som er kjent som et antikorrosjonspigment har en god hemmende virkning men gir tendens til alvorlig bobledannelse. The values in the preceding table show that the dicalcium hydrogen phosphate, which is known as an anti-corrosion pigment, has a good inhibitory effect but tends to cause serious bubble formation.
Sinkfosfat medfører ikke bobledannelse men har relativt dårlig hemmende virkning i den initielle fase ved væreksponering og bør erstattes på grunn av sitt tungmetallinnhold. Zinc phosphate does not cause bubbles but has a relatively poor inhibitory effect in the initial phase of weather exposure and should be replaced due to its heavy metal content.
Kalsium/magnesiumaluminiumtripolyfosfatene har en god kombinasjon av hemmende virkning og bestandighet mot bobledannelse, mens en sammen-ligning med kalsiumaluminiumtripolyfosfat og magnesiumaluminiumtripoly-fosfat viser en synergistisk virkning av kalsium/magnesiumaluminiumtripoly-fosfatene. The calcium/magnesium aluminum tripolyphosphates have a good combination of inhibitory effect and resistance to bubble formation, while a comparison with calcium aluminum tripolyphosphate and magnesium aluminum tripolyphosphate shows a synergistic effect of the calcium/magnesium aluminum tripolyphosphates.
Hydroksyapatitt har også en god kombinasjon av hemmende virkning og bestandighet mot bobledannelse, særlig reaksjonsproduktet med trimagnesiumfosfat. Hydroxyapatite also has a good combination of inhibitory effect and resistance to bubble formation, especially the reaction product with trimagnesium phosphate.
Eksempel 1 (sammenlignende) Example 1 (comparative)
Produksjon av antikorrosjonspigment omfattende surt aluminiumtripolyfosfat og kalsium- og magnesiumoksid. Production of anti-corrosion pigment comprising acidic aluminum tripolyphosphate and calcium and magnesium oxide.
0,5 mol magnesiumoksid og 0,5 mol kalsiumoksid ble agitert i vandig løsning med et faststoffinnhold på 30 %, med surt aluminiumtripolyfosfat (AIH2P3O10), ved 60 °C i 3 timer. Molforholdet kalsium/magnesium/aluminium var derved 0,5:0,5:1. Det oppnådde produkt ble filtrert av, tørket og knust. 0.5 mol of magnesium oxide and 0.5 mol of calcium oxide were agitated in aqueous solution with a solid content of 30%, with acidic aluminum tripolyphosphate (AIH2P3O10), at 60 °C for 3 hours. The molar ratio calcium/magnesium/aluminium was therefore 0.5:0.5:1. The product obtained was filtered off, dried and crushed.
Eksempel 2 Example 2
Fremstilling av antikorrosjonspigment omfattende kalsiumhydroksid, magnesiumhydroksid og fosforsyre. Production of anti-corrosion pigment comprising calcium hydroxide, magnesium hydroxide and phosphoric acid.
2,6 mol kalsiumhydroksid og 0,5 mol magnesiumhydroksid, så vel som 2 mol 75 % ortofosforsyre, ble agitert i vandig suspensjon med et faststoffinnhold på 30 % i 1,5 time ved 60 °C. Det oppnådd produkt ble filtrert av, tørket og knust. 2.6 moles of calcium hydroxide and 0.5 moles of magnesium hydroxide, as well as 2 moles of 75% orthophosphoric acid, were agitated in aqueous suspension with a solids content of 30% for 1.5 hours at 60°C. The product obtained was filtered off, dried and crushed.
Eksempel 3 (sammenlignende) Example 3 (comparative)
Fremstilling av antikorrosjonspigment omfattende surt aluminiumtripolyfosfat og hydroksyapatitt, kalsiumoksid og magnesiumoksid. Production of anti-corrosion pigment comprising acidic aluminum tripolyphosphate and hydroxyapatite, calcium oxide and magnesium oxide.
0,2 mol kalsiumoksid, 0,2 mol magnesiumoksid og 0,2 mol hydroksyapatitt ble agitert i vandig suspensjon med et faststoffinnhold på 30 %, med 0,4 mol surt aluminiumtripolyfosfat ved temperatur på 80 °C. Molforholdet kalsium/magnesium/aluminium var 3:0,5:1. Det oppnådde produkt ble filtrert ut, tørket og knust. 0.2 mol of calcium oxide, 0.2 mol of magnesium oxide and 0.2 mol of hydroxyapatite were agitated in aqueous suspension with a solids content of 30%, with 0.4 mol of acidic aluminum tripolyphosphate at a temperature of 80°C. The molar ratio calcium/magnesium/aluminium was 3:0.5:1. The product obtained was filtered out, dried and crushed.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19807808A DE19807808A1 (en) | 1998-02-26 | 1998-02-26 | Anti-corrosive pigment and its use |
| PCT/DE1999/000466 WO1999043757A1 (en) | 1998-02-26 | 1999-02-20 | Corrosion-protective pigment and use thereof |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO20004284L NO20004284L (en) | 2000-08-25 |
| NO20004284D0 NO20004284D0 (en) | 2000-08-25 |
| NO322024B1 true NO322024B1 (en) | 2006-08-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO20004284A NO322024B1 (en) | 1998-02-26 | 2000-08-25 | Anti-corrosion pigment and its use |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1056812B1 (en) |
| JP (1) | JP4367883B2 (en) |
| KR (1) | KR20010041229A (en) |
| AU (1) | AU3023699A (en) |
| DE (2) | DE19807808A1 (en) |
| NO (1) | NO322024B1 (en) |
| WO (1) | WO1999043757A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL143551A0 (en) * | 2001-06-04 | 2002-04-21 | Pigmentan Ltd | Paints and coatings composition useful for corrosion inhibition and a method for production therefor |
| JP5290542B2 (en) * | 2007-06-28 | 2013-09-18 | テイカ株式会社 | Antirust pigment composition |
| DE102009028667A1 (en) * | 2009-08-19 | 2011-03-03 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Anticorrosive pigment having core-shell structure, useful as component of anticorrosive coating material e.g. powder lacquer, comprises a core comprising metal particles/alloy, and a shell comprising inner-, intermediate- and outer-layers |
| JP5674382B2 (en) * | 2009-08-24 | 2015-02-25 | 菊水化学工業株式会社 | Anti-rust paint |
| JP5469208B2 (en) * | 2012-07-03 | 2014-04-16 | テイカ株式会社 | Antirust pigment composition |
| CN115103883A (en) * | 2019-12-12 | 2022-09-23 | 化学制造布敦海姆两合公司 | Phosphate-containing anticorrosive pigment |
| DE102019134205A1 (en) * | 2019-12-12 | 2021-06-17 | Chemische Fabrik Budenheim Kg | Corrosion protection pigment containing phosphate |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1040410A (en) * | 1973-12-13 | 1978-10-17 | Ralph L. Walker | Coating compositions |
| JPS56129638A (en) * | 1980-03-12 | 1981-10-09 | Toyo Soda Mfg Co Ltd | Manufacture of rust preventive pigment |
| HU198523B (en) * | 1985-06-13 | 1987-08-28 | Magyar Aluminium | Active anticorrosion pigment composition for coating materials and process for its production |
| DE4021086A1 (en) * | 1990-07-03 | 1992-01-09 | Heubach Hans Dr Gmbh Co Kg | CORROSION PROTECTION PIGMENTS BASED ON TERTIANS ERDALKALI ALUMINUM PHOSPHATES AND METHOD FOR THE PRODUCTION THEREOF |
| JPH04310510A (en) * | 1991-04-03 | 1992-11-02 | Teika Corp | Production of dihydrogen aluminum tripolyphosphate (ii) type |
| JP3218401B2 (en) * | 1991-08-02 | 2001-10-15 | 日本化学工業株式会社 | Rust prevention pigment composition |
| JP3004486B2 (en) * | 1992-09-22 | 2000-01-31 | テイカ株式会社 | Rust prevention pigment composition |
| JP3186908B2 (en) * | 1993-07-15 | 2001-07-11 | テイカ株式会社 | Rust prevention pigment composition |
| JPH07138775A (en) * | 1993-09-21 | 1995-05-30 | Teika Corp | Rust-preventive pigment composition |
| JPH07145340A (en) * | 1993-11-22 | 1995-06-06 | Teika Corp | Coating composition |
| NO312911B1 (en) * | 1994-12-22 | 2002-07-15 | Budenheim Rud A Oetker Chemie | Anti-corrosion pigment and its use |
| DE19541895A1 (en) * | 1994-12-22 | 1996-06-27 | Budenheim Rud A Oetker Chemie | Corrosion protection pigment and its application |
| JPH0912931A (en) * | 1995-07-04 | 1997-01-14 | Teika Corp | Coating composition for precoated steel plate |
-
1998
- 1998-02-26 DE DE19807808A patent/DE19807808A1/en not_active Withdrawn
-
1999
- 1999-02-20 AU AU30236/99A patent/AU3023699A/en not_active Abandoned
- 1999-02-20 WO PCT/DE1999/000466 patent/WO1999043757A1/en active IP Right Grant
- 1999-02-20 DE DE59911194T patent/DE59911194D1/en not_active Expired - Lifetime
- 1999-02-20 KR KR1020007009319A patent/KR20010041229A/en not_active Application Discontinuation
- 1999-02-20 JP JP2000533500A patent/JP4367883B2/en not_active Expired - Fee Related
- 1999-02-20 EP EP99911608A patent/EP1056812B1/en not_active Expired - Lifetime
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2000
- 2000-08-25 NO NO20004284A patent/NO322024B1/en not_active IP Right Cessation
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| Publication number | Publication date |
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| AU3023699A (en) | 1999-09-15 |
| NO20004284L (en) | 2000-08-25 |
| JP4367883B2 (en) | 2009-11-18 |
| WO1999043757A1 (en) | 1999-09-02 |
| DE19807808A1 (en) | 1999-09-02 |
| EP1056812B1 (en) | 2004-12-01 |
| JP2002504615A (en) | 2002-02-12 |
| EP1056812A1 (en) | 2000-12-06 |
| DE59911194D1 (en) | 2005-01-05 |
| NO20004284D0 (en) | 2000-08-25 |
| KR20010041229A (en) | 2001-05-15 |
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