EP0004560A1 - Use of ammonium polyphosphate - Google Patents

Use of ammonium polyphosphate Download PDF

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Publication number
EP0004560A1
EP0004560A1 EP79100638A EP79100638A EP0004560A1 EP 0004560 A1 EP0004560 A1 EP 0004560A1 EP 79100638 A EP79100638 A EP 79100638A EP 79100638 A EP79100638 A EP 79100638A EP 0004560 A1 EP0004560 A1 EP 0004560A1
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Prior art keywords
baths
ammonium
nitric acid
bath
development
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EP79100638A
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German (de)
French (fr)
Inventor
Michael Ahlgrim
Gerhard Dr. Mietens
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Hoechst AG
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Hoechst AG
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    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00—Brightening metals by chemical means
    • C23F3/02—Light metals
    • C23F3/03—Light metals with acidic solutions

Definitions

  • the present invention relates to the use of ammonium polyphosphate - hereinafter abbreviated as APP - to prevent the development of nitrous gases in baths, which consist essentially of acids, contain free nitric acid, and for the surface treatment of metals, in particular aluminum.
  • APP ammonium polyphosphate
  • the present invention also relates to baths suitable for the surface treatment of metals.
  • Baths made of organic and / or inorganic acids are primarily used for the surface treatment of metals (chemical or electrolytic processes).
  • nitric acid is used in a mixture with phosphoric acid, other acids such as sulfuric acid, hydrochloric acid, hydrofluoric acid or acetic acid.
  • sulfuric acid hydrochloric acid
  • hydrofluoric acid hydrofluoric acid
  • acetic acid While in nitric acid-free baths the removal ent standing acid mist is sufficient, when using baths containing nitric acid, the elimination of nitrous gases that form is also necessary. The highly toxic nitrous gases are visibly brown above the treatment solution.
  • nitrates can be reduced with the aid of amidosulfonic acid or urea and other organic amines. It is also known that heavy metal salts catalytically prevent the formation of nitrous gases. For example, there are mixtures of urea, melamine plus copper, nickel and manganese salts or copper, nickel, cobalt and iron salts which have been used to prevent the development of nitrous gas.
  • Another way to prevent the formation of nitrous gases is to add inorganic ammonium compounds.
  • a reduction in the P 2 0 5 content associated therewith is disadvantageous for the glossing process, in particular for gloss solutions containing high P 2 0 5 .
  • NH 4 ions in the form of ammonium nitrate or ammonium sulfate are added to a glossy bath, the consumption of ammonium to prevent the formation of nitrous gas creates an uncontrollable ratio between the ammonium ions present and the increase in the concentration of anions with an adverse effect on the gloss formation, such as nitrate and sulfate .
  • the handling of ammonium nitrate is also not unproblematic because of its easy fragility.
  • Ammonium sulfate is sparingly soluble in highly phosphoric acid solutions, inevitably leads to a higher sulfate content in the solution and thus reduces the gloss effect.
  • the ammonium sulfate is therefore metered in during the technical implementation of the luster in the form of a pre-assembled sulfuric acid solution.
  • ammonium polyphosphates are used to prevent the development of nitrous gases in baths which consist essentially of acids, contain nitric acid and are used for the surface treatment of metals.
  • ammonium polyphosphates are those of the general formula ' in which n is an integer average value of over 400 to about 1000, preferably between 600 to 800, and the ratio of m to n is about 1.
  • ammonium polyphosphates it is advisable to use in amounts of 0.01 to 10.0% by weight, based on the ready-to-use bath.
  • the present invention thus furthermore relates to baths for the surface treatment of metals which consist essentially of acids, free nitric acid and an agent for preventing the development of nitrous gases, which, as an agent for preventing the development of nitrous gases, contain ammonium polyphosphate, preferably in amounts of 0 , 01 to 10.0% by weight, based on the ready-to-use bath.
  • APP Compared to known products, APP has the advantage that it can be incorporated into the bottom of the gloss bath when it is being produced, in order to prevent the formation of nitrous gas in the shipping container. A pressure increase then does not occur.
  • the APP can also be worked into the gloss bath at working temperature (at least 90 ° C) as required. It dissolves quickly with stirring and increases the P 2 O 5 content in the gloss solution, which has a positive effect on the gloss formation. The dosage of the APP can therefore be carried out immediately when the nitrous gases occur without any undesirable side effects.
  • ammonium polyphosphate does not have the aforementioned disadvantages. It is readily soluble and shows no spontaneous reaction when added to the hot bath. In addition, the least amount is required compared to other ammonium phosphates.

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

Abstract

Ammonium polyphosphates are used for preventing the evolution of nitrous gases in baths which consist essentially of acids and contain free nitric acid and also baths which are used for the surface treatment of metals.

Description

Die vorliegende Erfindung betrifft die Verwendung von Ammoniumpolyphosphat - nachfolgend abgekürzt als APP bezeichnet - zur Verhinderung der Entwicklung nitroser Gase in Bädern, welche im wesentlichen aus Säuren bestehen, freie Salpetersäure enthalten, und zur Oberflächenbehandlung von Metallen, insbesondere Aluminium, dienen. Außerdem betrifft die vorliegende Erfindung für die Oberflächenbehandlung von Metallen geeignete Bäder.The present invention relates to the use of ammonium polyphosphate - hereinafter abbreviated as APP - to prevent the development of nitrous gases in baths, which consist essentially of acids, contain free nitric acid, and for the surface treatment of metals, in particular aluminum. The present invention also relates to baths suitable for the surface treatment of metals.

Zur Oberflächenbehandlung von Metallen (chemische oder elektrolytische Verfahren) werden in erster Linie Bäder aus organischen und/oder anorganischen Säuren verwendet. Je nach Art der zu behandelnden Metalle wird hierbei Salpetersäure im Gemisch mit Phosphorsäure, anderen Säuren, wie Schwefelsäure, Salzsäure, Flußsäure oder Essigsäure, eingesetzt. Während bei salpetersäurefreien Bädern die Beseitigung entstehender Säurenebel ausreichend ist, wird bei Verwendung von Bädern, die Salpetersäure enthalten, auch die Beseitigung von sich bildenden nitrosen Gasen erforderlich. Die stark giftigen nitrosen Gase entstehen sichtbar braun über der Behandlungslösung.Baths made of organic and / or inorganic acids are primarily used for the surface treatment of metals (chemical or electrolytic processes). Depending on the type of metals to be treated, nitric acid is used in a mixture with phosphoric acid, other acids such as sulfuric acid, hydrochloric acid, hydrofluoric acid or acetic acid. While in nitric acid-free baths the removal ent standing acid mist is sufficient, when using baths containing nitric acid, the elimination of nitrous gases that form is also necessary. The highly toxic nitrous gases are visibly brown above the treatment solution.

Sowohl schon bei der Herstellung der salpetersauren Bäder als auch bei deren späteren Gebrauch sind gesundheitsschädliche Belästigungen des Betriebspersonals gegeben.Both in the manufacture of the nitric acid baths and in their later use there are harmful nuisances to the operating personnel.

Es ist bereits bekannt, daß Nitrate mit Hilfe von Amidosulfonsäure bzw. Harnstoff und anderen organischen Aminen reduziert werden können. Außerdem ist bekannt, daß Schweraetallsalze die Bildung von nitrosen Gasen katalytisch verhindern. So befinden sich im Handel Mischungen aus Harnstoff, Melamin zuzüglich Kupfer-, Nickel- und Mangansalzen bzw. Kupfer-, Nickel-, Kobalt- und Eisensalzen, die man zur Verhinderung der Nitrosegasentwicklung'eingesetzt hat.It is already known that nitrates can be reduced with the aid of amidosulfonic acid or urea and other organic amines. It is also known that heavy metal salts catalytically prevent the formation of nitrous gases. For example, there are mixtures of urea, melamine plus copper, nickel and manganese salts or copper, nickel, cobalt and iron salts which have been used to prevent the development of nitrous gas.

Diese Chemikalienmischungen verhindern zwar die Nitrosegasentwicklung in einem gebrauchsfertigen Bad, sie reagieren jedoch mit der salpetersäurehaltigen Lösung permanent weiter, was zum erhöhten Salpetersäure-Verbrauch und zu einer unkontrollierbaren Überkonzentration von Fremdmetallen in den Bädern führt. Dabei wird die Glänzwirkung der Bäder auf die Metalloberflächen negativ beeinflußt. Eine zu hohe, Konzentration an Katalysatormetallen führt zwangsläufig zum Neuansatz der Behandlungslösung. Der hohe Anteil an organischen Aminen in den bekannten Inhibitoren gestattet nicht deren Zugabe zu den Bädern bei höheren Temperaturen, wie es z.B. beim chemischen-Glänzen von Aluminium erforderlich ist. Die Behandlungslösung muß dann um ca. 30°C abgekühlt werden, weil die Zudosierung der Inhibitoren mit einer heftigen exothermen Reaktion verbunden ist. Nach der Zugabe muß dann das Bad wieder auf Behandlungstemperatur gebracht werden. Die bereits erwähnte Reaktion zwischen Salpetersäure und den zur Verhinderung der Nitrosegasentwicklung eingesetzten Verbindungen macht deren Einarbeiten bei der Konfektionierung der Bäder unmöglich. Es wurde dann in den geschlossenen Versandgebinden ein nicht zulässiger Überdruck entstehen, hervorgerufen durch die bei der Reaktion der Amine mit Salpetersäure sich bildenden Gase.Although these chemical mixtures prevent the development of nitrous gas in a ready-to-use bath, they continue to react with the nitric acid-containing solution, which leads to increased nitric acid consumption and an uncontrollable over-concentration of foreign metals in the baths. The gloss effect of the baths on the metal surfaces is negatively affected. Too high a concentration of catalyst metals inevitably leads to a new preparation of the treatment solution. The high proportion of organic amines in the known inhibitors does not allow them to be added to the baths at higher temperatures, as is required, for example, when aluminum is chemically shiny. The treatment solution must then be cooled by approx. 30 ° C because the metering in of the inhibitors is associated with a violent exothermic reaction. After the encore the bath must then be brought back to the treatment temperature. The already mentioned reaction between nitric acid and the compounds used to prevent the development of nitrous gas makes it impossible to incorporate them in the assembly of the baths. An inadmissible overpressure was then created in the closed shipping containers, caused by the gases formed during the reaction of the amines with nitric acid.

Eine andere Möglichkeit, die Bildung nitroser Gase zu verhindern, besteht in der Zugabe von anorganischen Ammoniumverbindungen. Insbesondere für hoch P205-haltige Glänzlösungen ist eine damit verbundene Reduzierung des P205-Gehaltes für den Glänzprozeß von Nachteil. Werden einem Glänzbad NH4-Ionen in Form von Ammoniumnitrat bzw. Ammoniumsulfat zugesetzt, so entsteht durch den Verbrauch von Ammonium für die Verhinderung der Nitrosegasbildung ein unkontrollierbares Verhältnis zwischen vorhandenen Ammoniumionen und der Konzentrationserhöhung von Anionen mit nachteiliger Wirkung auf die Glanzbildung, wie Nitrat und Sulfat. Die Handhabung von Ammoniumnitrat ist wegen seiner leichten Zersetzlichkeit zudem nicht unproblematisch. Ammoniumsulfat ist in hoch phosphorsauren Lösungen schwer löslich, führt zwangsweise zu höherem Sulfatgehalt in der Lösung und mindert dadurch die Glänzwirkung. Die Zudosierung des Ammoniumsulfates erfolgt deshalb bei der technischen Durchführung des Glänzens in Form einer vorkonfektionierten schwefelsauren Lösung.Another way to prevent the formation of nitrous gases is to add inorganic ammonium compounds. A reduction in the P 2 0 5 content associated therewith is disadvantageous for the glossing process, in particular for gloss solutions containing high P 2 0 5 . If NH 4 ions in the form of ammonium nitrate or ammonium sulfate are added to a glossy bath, the consumption of ammonium to prevent the formation of nitrous gas creates an uncontrollable ratio between the ammonium ions present and the increase in the concentration of anions with an adverse effect on the gloss formation, such as nitrate and sulfate . The handling of ammonium nitrate is also not unproblematic because of its easy fragility. Ammonium sulfate is sparingly soluble in highly phosphoric acid solutions, inevitably leads to a higher sulfate content in the solution and thus reduces the gloss effect. The ammonium sulfate is therefore metered in during the technical implementation of the luster in the form of a pre-assembled sulfuric acid solution.

Überraschenderweise wurde nun gefunden, daß sich diese Schwierigkeiten leicht überwinden lassen, wenn man zur Verhinderung der Entwicklung nitroser Gase in Bädern, welche im wesentlichen aus Säuren bestehen, freje Salpetersäure enthalten und zur Oberflächenbehandlung von Metallen dienen, Ammoniumpolyphosphate verwendet.Surprisingly, it has now been found that these difficulties can be easily overcome if ammonium polyphosphates are used to prevent the development of nitrous gases in baths which consist essentially of acids, contain nitric acid and are used for the surface treatment of metals.

Als Ammoniumpolyphosphate eignen sich insbesondere solche der allgemeinen Formel'

Figure imgb0001
in welcher n einen ganzzahligen Durchschnittswert von über 400 bis etwa 1000, vorzugsweise zwischen 600 auf 800, bedeutet und das Verhältnis von m zu n etwa 1 beträgt.Particularly suitable ammonium polyphosphates are those of the general formula '
Figure imgb0001
 in which n is an integer average value of over 400 to about 1000, preferably between 600 to 800, and the ratio of m to n is about 1.

Es empfiehlt sich, die Ammoniumpolyphosphate in Mengen von 0,01 bis 10,0 Gewichts%, bezogen auf das gebrauchsfertige Bad, einzusetzen.It is advisable to use the ammonium polyphosphates in amounts of 0.01 to 10.0% by weight, based on the ready-to-use bath.

Ein weiterer Gegenstand der vorliegenden Erfindung sind somit Bäder zur Oberflächenbehandlung von Metallen, die im wesentlichen aus Säuren bestehen, freie Salpetersäure und ein Mittel zur Verhinderung der Entwicklung nitroser Gase enthalten, welche als Mittel zur Verhinderung der Entwicklung nitroser Gase Ammoniumpolyphosphat, vorzugsweise in Mengen von 0,01 bis 10,0 Gewichts%, bezogen auf das gebrauchsfertige Bad, enthalten.The present invention thus furthermore relates to baths for the surface treatment of metals which consist essentially of acids, free nitric acid and an agent for preventing the development of nitrous gases, which, as an agent for preventing the development of nitrous gases, contain ammonium polyphosphate, preferably in amounts of 0 , 01 to 10.0% by weight, based on the ready-to-use bath.

Gegenüber bekannten Produkten hat APP den Vorteil, daß es sich schon bei der Herstellung des Glänzbades in dieses im Unterschuß einarbeiten läßt, um die Nitrosegasbildung bereits im Versandgebinde zu verhindern. Eine Druckerhöhung tritt dann nicht auf. Das APP kann außerdem bei Arbeitstemperatur (mindestens 90°C) in das Glänzbad je nach Bedarf eingearbeitet werden. Es löst sich schnell unter Rühren und erhöht in'der Glänzlösung den P2O5-Gehalt, was sich auf die Glanzbildung positiv auswirkt. Die Dosierung des APP kann also ohne störende Nebenwirkungen sofort beim Auftreten der nitrosen Gase erfolgen.Compared to known products, APP has the advantage that it can be incorporated into the bottom of the gloss bath when it is being produced, in order to prevent the formation of nitrous gas in the shipping container. A pressure increase then does not occur. The APP can also be worked into the gloss bath at working temperature (at least 90 ° C) as required. It dissolves quickly with stirring and increases the P 2 O 5 content in the gloss solution, which has a positive effect on the gloss formation. The dosage of the APP can therefore be carried out immediately when the nitrous gases occur without any undesirable side effects.

Die Verwendung anderer Ammoniumphosphate zeigt dagegen folgende Nachteile:

  • Um mit Ammoniumdihydrogenphosphat die gleiche Wirkung wie mit APP zu erreichen, ist eine größere Menge (ca. die doppelte Menge, bezogen auf#den Stickstoffgehalt) erforderlich.
In contrast, the use of other ammonium phosphates has the following disadvantages:
  • In order to achieve the same effect with ammonium dihydrogen phosphate as with APP, a larger amount (approx. Twice the amount, based on the nitrogen content) is required.

Die Löslichkeit von Diammoniumhydrogenphosphat gegenüber APP ist schlechter und um die gleiche Wirkung wie mit APP zu erreichen, ist ebenfalls etwa die doppelte Menge Diammoniumhydrogenphosphat notwendig.The solubility of diammonium hydrogenphosphate compared to APP is worse and in order to achieve the same effect as with APP, about twice the amount of diammonium hydrogenphosphate is also necessary.

Neben einer schlechteren Löslichkeit als bei APP tritt bei Zugabe von Triammoniumphosphat in die Glänzlösung eine heftige Reaktion auf, die vor der Zudosierung ein Abkühlen der Glänzlösung erforderlich machen würde. Außerdem wird, bezogen auf den Stickstoffgehalt, auch etwa die doppelte Menge als bei APP benötigt.In addition to poorer solubility than with APP, a violent reaction occurs when triammonium phosphate is added to the glossy solution, which would require the glossy solution to cool down before metering in. In addition, based on the nitrogen content, about twice as much as with APP is required.

Das Ammoniumpolyphosphat besitzt die vorgenannten Nachteile nicht. Es ist gut löslich und zeigt keine spontane Reaktion bei Zugabe in das heiße Bad. Außerdem wird die geringste Menge gegenüber anderen Ammoniumphosphaten benötigt.The ammonium polyphosphate does not have the aforementioned disadvantages. It is readily soluble and shows no spontaneous reaction when added to the hot bath. In addition, the least amount is required compared to other ammonium phosphates.

Beispiel 1example 1

Zum Glänzen von Aluminium wird eine Lösung folgender Zusammensetzung eingesetzt:

  • 90 Gew% Phosphorsäure (85 %)
  • 4 Gew% Schwefelsäure (96 %)
  • 6 Gew% Salpetersäure (63 %)
A solution of the following composition is used to shine aluminum:
  • 90% by weight phosphoric acid (85%)
  • 4% by weight sulfuric acid (96%)
  • 6% by weight nitric acid (63%)

Die Bildung nitroser Gase soll bei der Herstellung des Glänzbades und beim Versand vermieden werden. Hierzu wurden insgesamt drei Lösungen hergestellt:

  • Lösung A = Al-Glänzbad ohne Zusätze
  • Lösung B = Al-Glänzbad mit einer handelsüblichen Mischung, bestehend aus Melamin, Harnstoff und Kupfer-, Nickel- sowie Mangansalzen,in einer Menge von 3 Gew%, bezogen auf das fertige Bad
  • Lösung C = Al-Glänzbad mit 3 Gew% Ammoniumpolyphosphat, bezogen auf das fertige Bad
    Figure imgb0002
The formation of nitrous gases should be avoided during the manufacture of the gloss bath and during shipping. A total of three solutions were created for this:
  • Solution A = Al gloss bath without additives
  • Solution B = Al gloss bath with a commercially available mixture consisting of melamine, urea and copper, nickel and manganese salts in an amount of 3% by weight, based on the finished bath
  • Solution C = Al gloss bath with 3% by weight ammonium polyphosphate, based on the finished bath
    Figure imgb0002

Beispiel 2Example 2

Wirkunsweise des.Ammoniumpolyphosphates während der Behandlung von Aluminium in der Glänzlösung. Formulierung wie Beispiel 1.

Figure imgb0003
Mode of action of the ammonium polyphosphate during the treatment of aluminum in the gloss solution. Formulation as example 1 .
Figure imgb0003

Claims (6)

1. Verwendung von Ammoniumpolyphosphaten zur Verhinderung der Entwicklung nitroser Gase in Bädern, welche im wesentlichen aus Säuren bestehen, freie Salpetersäure enthalten und zur Oberflächenbehandlung von Metallen dienen.1. Use of ammonium polyphosphates to prevent the development of nitrous gases in baths, which consist essentially of acids, contain free nitric acid and are used for the surface treatment of metals. 2. Verwendung von Ammoniumpolyphosphaten der allgemeinen Formel
Figure imgb0004
in welcher n einen ganzzahligen Durchschnittswert von über 400 bis etwa 1000 bedeutet und das Verhältnis von m zu n etwa 1 beträgt, nach Anspruch 1.2. Use of ammonium polyphosphates of the general formula
Figure imgb0004
 in which n is an integer average value of over 400 to about 1000 and the ratio of m to n is about 1, according to claim 1. 3. Verwendung von Ammoniumpolyphosphaten, in denen n eine ganze Zahl zwischen 600 und 800 bedeutet , nach Anspruch 2.3. Use of ammonium polyphosphates, in which n is an integer between 600 and 800, according to claim 2. 4. Verwendung von Ammoniumpolyphosphaten in Mengen von 0,01 bis 10,0 Gewichts%, bezogen auf das gebrauchsfertige Bad nach einem der Ansprüche 1 bis 3.4. Use of ammonium polyphosphates in amounts of 0.01 to 10.0% by weight, based on the ready-to-use bath according to one of claims 1 to 3. 5. Bäder zur Oberflächenbehandlung von Metallen, die im wesentlichen aus Säuren bestehen, freie Salpetersäure und ein Mittel zur Verhinderung der Entwicklung nitroser Gase enthalten, dadurch gekennzeichnet, daß sie als Mittel zur Verhinderung der Entwicklung nitroser Gase Ammoniumpolyphosphat enthalten.5. baths for the surface treatment of metals, which consist essentially of acids, contain free nitric acid and an agent for preventing the development of nitrous gases, characterized in that they contain ammonium polyphosphate as a means for preventing the development of nitrous gases. 6. Bäder nach Anspruch 5, dadurch gekennzeichnet, daß sie O,C1 bis 10,0 Gewichts% Ammoniumpolyphosphat, bezogen auf das gebrauchsfertige Bad, enthalten.6. Baths according to claim 5, characterized in that they contain O, C1 to 10.0% by weight ammonium polyphosphate, based on the ready-to-use bath.
EP79100638A 1978-03-31 1979-03-05 Use of ammonium polyphosphate Withdrawn EP0004560A1 (en)

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DE2813870 1978-03-31
DE19782813870 DE2813870A1 (en) 1978-03-31 1978-03-31 USE OF AMMONIUM POLYPHOSPHATE

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017067906A1 (en) 2015-10-20 2017-04-27 Clariant International Ltd Mixtures of ammonium polyphosphate and at least one soluble ionic compound containing sulfate and/or is capable of releasing sulfate ions
WO2022171489A1 (en) 2021-02-15 2022-08-18 Clariant International Ltd Compositions comprising ammonium polyphosphates

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3202612A (en) * 1960-12-05 1965-08-24 Monsanto Co Composition for bright polishing aluminum
DE2234494A1 (en) * 1971-07-14 1973-02-08 Hitachi Ltd Dissolving core wire of wire spray - using nitric acid contg inhibitor for development of gaseous nitrogen oxides
FR2248236A1 (en) * 1973-10-18 1975-05-16 Veba Chemie Ag
SU514912A1 (en) * 1973-01-26 1976-05-25 Уральский научно-исследовательский институт трубной промышленности Chemical polishing solution

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3202612A (en) * 1960-12-05 1965-08-24 Monsanto Co Composition for bright polishing aluminum
DE2234494A1 (en) * 1971-07-14 1973-02-08 Hitachi Ltd Dissolving core wire of wire spray - using nitric acid contg inhibitor for development of gaseous nitrogen oxides
SU514912A1 (en) * 1973-01-26 1976-05-25 Уральский научно-исследовательский институт трубной промышленности Chemical polishing solution
FR2248236A1 (en) * 1973-10-18 1975-05-16 Veba Chemie Ag

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017067906A1 (en) 2015-10-20 2017-04-27 Clariant International Ltd Mixtures of ammonium polyphosphate and at least one soluble ionic compound containing sulfate and/or is capable of releasing sulfate ions
US11628589B2 (en) 2015-10-20 2023-04-18 Clariant International Ltd Mixtures of ammonium polyphosphate and at least one soluble ionic compound containing sulfate and/or is capable of releasing sulfate ions
WO2022171489A1 (en) 2021-02-15 2022-08-18 Clariant International Ltd Compositions comprising ammonium polyphosphates

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DE2813870A1 (en) 1979-10-18
AT359800B (en) 1980-11-25
ATA234979A (en) 1980-04-15

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