BE402237A - PROCESS AND RAW MATERIAL FOR THE PRODUCTION OF PHOSPHATE COATINGS - Google Patents

PROCESS AND RAW MATERIAL FOR THE PRODUCTION OF PHOSPHATE COATINGS

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Publication number
BE402237A
BE402237A BE402237DA BE402237A BE 402237 A BE402237 A BE 402237A BE 402237D A BE402237D A BE 402237DA BE 402237 A BE402237 A BE 402237A
Authority
BE
Belgium
Prior art keywords
phosphate
manganese
nitrate
nitrates
bath
Prior art date
Application number
Other languages
French (fr)
Original Assignee
Metal Finishing Research Corp.
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 Metal Finishing Research Corp. filed Critical Metal Finishing Research Corp.
Publication of BE402237A publication Critical patent/BE402237A/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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
    • C23C22/08Orthophosphates
    • C23C22/18Orthophosphates containing manganese cations
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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
    • C23C22/08Orthophosphates
    • C23C22/18Orthophosphates containing manganese cations
    • C23C22/186Orthophosphates containing manganese cations containing also copper cations

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  • 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

       

   <Desc/Clms Page number 1> 
 



  " Procédé et matière premiéres pour la production de revê- tements en phosphate." 
L'invention se rapporte à un procédé perfectionné de production de revêtements en phosphate et, en partioulier, à la production sur du fer ou de l'acier d'un revêtement qui   ocnvient   en tami que support   assurant 1 adhérence   de oouleurs ou analogues devant être appliquées sur le métal. 



   Il est connu depuis longtemps de produire des revête- .. ments en phosphate sur du fer ou de l'aoier à l'aide d'un bain de phosphate dilué, mais ce n'est que relativement récemment que l'on découvrit que la formation de revête- ments de cette espèce peut être considérablement   accélérée,   si l'on additionne à la solution traitée du nitrate de sou- de ou un autre agent équivalent. Dans les cas ou l'on tra- vaille en plongeait les objets devant reoevoir le revête- ment, dans un bain, l'addition continuelle du nitrate de soude-rend, cependant, parfois, le bain trop :biche en soude de sorte que la teneur en phosphate de fer ou de manganése 

 <Desc/Clms Page number 2> 

 du bain diminue dans une telle mesure que le bain perd toute son efficacité.

   Pour cette raison, la présente invention préconise, pour compléter le bain, l'addition de nitrate d'un élément qui passe dans le revêtement ou bien forme une combinaison insoluble aveo les oonstituamts de la solu- tion et peut, dès lors, être précipité , ou bien encore se volatilise et peut être expulsé de cette manière; en d'autres termes, l'addition d'un nitrate qui n'introduit dans le bain aucun élément , susoeptible d'augmenter d'une manière préjudiciable la concentration de ce bain. En rap- port aveo oela, on obtient dans une autre forme de   réali-   sation de l'invention, une teneur en manganèse élevée du bain, ce qui est très désirable, car le phosphate de mangà- nèse donne sur le métal un revêtement de très bonne quali- té. 



   Un exemple de la   fonnation   d'un bain et de la manière de compléter ce dernier conformément au principe exposé se- ra décrit ci-après, de même que certains des principes sur lesquels reposent les différentes formes de réalisation possibles de l'invention. 



   Le nitrate de soude est facile à obtenir et oonvient pour être employé simultanément aveo des,phosphates en vue de formation du bain initial. Le rapport entre le nitrate de soude et les phosphates mélangés à ce dernier et dissous dans l'eau peut varier. Par exemple, un mélange de 50 kgs. de xxxxxx nitrate de soude avec environ 52 kgs. de phosphate de manganèse   prjmaire   ( phosphate bibasique de manganèse), s'est avéré , comme approprié, bien que le rapport entre le nitrate de soude et le phosphate peut varier dans de larges limites. Si on le désire, ce mélange peut recevoir une addi- tion d'environ 19 grammes de carbonate de ouivre.

   Une   quan-   titi d'environ 16 à 23 Kgs. de ce mélange dissoute dans en-   viral   400 litres d'eau, donne un bain qui produit rapidement un revêtement uniforme sur les pièces à traiter qui y sont 

 <Desc/Clms Page number 3> 

 plongées. Bien que par lui-même le ouivre ne soit pas   néoes-   saire, l'addition d'une petite quantité de cuivre accélère , cependant, la formation du revêtement. Cet effet se remar que surtout sur des surfaces qui, pour une saison queloon- que, sont plus difficilement attaquables. 



   Après qu'un   bain la   été forma de la manière décrite ci- dessus, il peut être   oomplété   par l'addition de phosphate de manganèse, pouvant, si on le désire, oontenir du cuivre, et par celle de nitrate de manganèse. Une addition de 100 grammes de carbonate de cuivre par 45 Kgs. de phosphate de manganèse est employée avantageusement pour compléter un bain ayant la   oanposition   décrite. Le ouivre peut aussi être ajouté en quantités moindres ou plus   grande, ,   mais il y a lieu , cependant, de noter qu'une teneur en ouivre trop élevée nuit aux qualités du revêtement.

   Il oonvient de ne pas mélangent de   ocnserver   en cet état le nitrate de man- ganèse et le phosphate de manganèse primaire ( phosphate bibasique de manganèse) avant de les introduire dans le   bain,car   autrement il se produirait une réaction entre le nitrate et le phosphate primaire, ce qui affablirait très fortement   l'efficacité   de lamatiérs. 



   Le nitrate de manganèse absorbe facilement l'humidité de l'air oe qui rend difficile sa manipulation. En ajoutant du phosphate de manganèse no mal ou bien du phosphate de manganèse   secondaire-,,.au   nitrate de manganèse, on réduit considérablement les difficultés qui se présentent sous ce rapport, et l'on augmente en même temps la teneur en manganèse du bain, sans y introduire des éléments ind0sirable Il ne se produit aucune réaction nuisible entre le phospha- te de manganèse normal ou secondaire et le nitrate de manganèse. le phosphate de manganèse normal ou secondaire (phos- phates mono-basiques de manganèse) peut être ajouté au ni- trate dans des proportions pouvant varier très fortement; 

 <Desc/Clms Page number 4> 

 toutefois, le rapport de 2 parties de phosphate pour 3 parties de nitrate s'est avéré come approprié.

   Si le phos- phate et le nitrate sont mélanges dans cette proportion¯, ce mélange en poudre est stable et peut être aisément   @   transporté et traité. Si la solution est complétée en par- ties égales de ce mélange et du phosphate de manganèse primaire, le bain obtenu est d'une efficacité très satis- 
 EMI4.1 
 faisante. D'habidl.ude , on introduitaveo le phosphate un peu de ouivre. 



   Si le bain est préparé avec du phosphate de manganèse   primaiee   ( phosphate bibasique de manganèse) et du nitrate de manganèse, sans employer du nitrate de soude, et s'il est complété par les   mâmes   substances, il fonctionne, au début, d'une manière   satisfaisante,   mais son% effet s'affaiblit rapidement au point de devenir finalement insuf- fisant, bien que cet inconvénient puisse être quelque peu réduit par la présence du ouivre.

   Si, parcontre, le bain est préparé en Employant un mélange de nitrate de soude et de phosphate de manganèse primaire, et s'il est complété par le même mélange, bien que son fonctionnement soit satis-   faisaA   au début et donne satisfaction pendant longtemps, il se produit, cependant, peu à peu un accroissement progres- sif de   la\teneur   en sodium et une diminution de la quantité de phosphates de manganèse et de fer présents , jusqu'au moment ou finalement le bain devient inefficace. En prépa- rait le bain à. l'aide du mélange de phosphate de manganèse primaire et de nitrate de soude, ayant le complétant par l'addition de phosphates de manganèse et de nitrate de man- ganèse de la manière décrite ci-dessus, on maintient l'effi-   oaoité   du bain aussi constante que possible.

   Dans tous ces cas, la présence du ouivre augmente   l'efficacité.   



   Si l'on procède de la manière décrite, il ne se produit   aucune   substitution préjudiciable dée phosphates de fer et 

 <Desc/Clms Page number 5> 

 de manganèse par le phosphate de soude, et sa proportion par rapport aux autres constituants du bain n'augmente pas non plus autre mesure; un équilibre parfait continue à subsister dans la solution, qui produit ainsi très rapi- dement un revêtement   excellent   pour faire adhérer la cou- leur, et très riche en phosphate de manganèse. 



   Tandis que pour compléter le bain on emploie de préfé-   renoe,   pour les raisons exposées, du nitrate de manganèse, il est cependant, possible aussi, dans une certaine mesu- re d'y introduire des nitrates d'autres métaux , tels que , par exemple, ceux du magnésium, calcium, baryum , strontium, zinc, cadmium ou fer, qui passent à l'état de phosphates dans le revêtement. Il est en outre également possible d'em- ployer le nitrate d'un élément te que le chrome,   l'aluni-   nium, le thorium ou le aérium qui forment dans la solution de phosphate un précipité insoluble ou bien encore, le nitrate d'un corps tel que le bore, qui se volatilise. Dans tous ces cas , il ne se produit aucun enrichissement du bain en éléments à action nuisible . 



   Il va de soi, que le procédé décrit ci-dessus peut subir divers changements ou modofioations sans sortir du cadre de l'invention. 



   REVENDICATIONS. 



   1. Procédé pour la production de revêtements sur du fer ou de l'acier, caractérisé en ce que la solution, dans la- quelle on immerge les objets devant reoevoir un revêtement, est préparée à l'aide des phosphates acides et du nitrate d'un métal alcalin, et sa force est ensuite maintenue par l'addition de phosphates acides et de nitrates dont les radi- oaux ne restent pas dans la solution, ou bien qui n'intro- duisent dans le bain aucun élément susceptible d'amener une conoentration préjudiciable de ce dernier.



   <Desc / Clms Page number 1>
 



  "Process and raw materials for the production of phosphate coatings."
The invention relates to an improved process for the production of phosphate coatings and, in particular, to the production on iron or steel of a coating which acts as a backing ensuring the adhesion of colors or the like to be. applied to metal.



   It has long been known to produce phosphate coatings on iron or wood using a dilute phosphate bath, but it is only relatively recently that it has been discovered that The formation of such coatings can be considerably accelerated by adding sodium nitrate or the like to the treated solution. In cases where one works by dipping the objects to receive the coating, in a bath, the continual addition of the nitrate of soda, however, sometimes makes the bath too much: doe in soda so that the iron or manganese phosphate content

 <Desc / Clms Page number 2>

 of the bath decreases to such an extent that the bath loses all its effectiveness.

   For this reason, the present invention recommends, to complete the bath, the addition of nitrate of an element which passes through the coating or else forms an insoluble combination with the constituents of the solution and can therefore be precipitated. , or else volatilizes and can be expelled in this way; in other words, the addition of a nitrate which does not introduce any element into the bath, which can adversely increase the concentration of this bath. In relation to this, in another embodiment of the invention, a high manganese content in the bath is obtained, which is very desirable, since the manganese phosphate gives the metal a coating of. very good quality.



   An example of the formation of a bath and of the manner of completing the latter in accordance with the principle set forth will be described below, as well as some of the principles on which the various possible embodiments of the invention are based.



   Nitrate of soda is easy to obtain and is suitable for being used simultaneously with phosphates for the formation of the initial bath. The ratio of sodium nitrate to the phosphates mixed with the latter and dissolved in water can vary. For example, a mixture of 50 kgs. of xxxxxx sodium nitrate with about 52 kgs. of primary manganese phosphate (bibasic manganese phosphate) has been found to be suitable, although the ratio of sodium nitrate to phosphate may vary within wide limits. If desired, this mixture can receive an addition of about 19 grams of black carbonate.

   A quantity of approximately 16 to 23 Kgs. of this mixture dissolved in en- viral 400 liters of water, gives a bath which rapidly produces a uniform coating on the parts to be treated which are there

 <Desc / Clms Page number 3>

 dives. Although drunk by itself is not necessary, the addition of a small amount of copper, however, accelerates the formation of the coating. This effect is noticed especially on surfaces which, for a given season, are more difficult to attack.



   After a bath has been formed in the manner described above, it can be completed by the addition of manganese phosphate, which may, if desired, contain copper, and by addition of manganese nitrate. An addition of 100 grams of copper carbonate per 45 Kgs. of manganese phosphate is advantageously employed to complete a bath having the oanposition described. Drunk can also be added in smaller or larger amounts, but it should be noted, however, that too high a drunk content adversely affects the qualities of the coating.

   It is important not to mix the manganese nitrate and the primary manganese phosphate (bibasic manganese phosphate) in this state before adding them to the bath, otherwise a reaction would take place between the nitrate and the phosphate. primary, which would very strongly establish the effectiveness of the matings.



   Manganese nitrate readily absorbs moisture from the air which makes it difficult to handle. By adding manganese phosphate no mal or secondary manganese phosphate - ,,. To manganese nitrate, the difficulties which arise in this connection are considerably reduced, and at the same time the manganese content of the bath is increased. without introducing undesirable elements into it. No detrimental reaction occurs between normal or secondary manganese phosphate and manganese nitrate. normal or secondary manganese phosphate (mono-basic manganese phosphates) can be added to the nitrate in proportions which can vary greatly;

 <Desc / Clms Page number 4>

 however, the ratio of 2 parts phosphate to 3 parts nitrate has been found to be suitable.

   If the phosphate and nitrate are mixed in this proportion, this powder mixture is stable and can be easily transported and processed. If the solution is made up in equal parts of this mixture and of the primary manganese phosphate, the bath obtained is of a very satisfactory efficiency.
 EMI4.1
 doing. Usually, a little drunk is introduced into the phosphate.



   If the bath is prepared with primary manganese phosphate (bibasic manganese phosphate) and manganese nitrate, without using sodium nitrate, and if it is supplemented with the same substances, it initially works in a satisfactorily, but its effect quickly weakens to the point of eventually becoming insufficient, although this disadvantage may be somewhat reduced by the presence of the drunk.

   If, on the other hand, the bath is prepared by employing a mixture of sodium nitrate and primary manganese phosphate, and if it is completed by the same mixture, although its operation is satisfactory at the beginning and gives satisfaction for a long time, there occurs, however, little by little a gradual increase in the sodium content and a decrease in the amount of manganese and iron phosphates present, until finally the bath becomes ineffective. In preparing the bath in. with the aid of the mixture of primary manganese phosphate and sodium nitrate, supplementing it with the addition of manganese phosphates and manganese nitrate in the manner described above, the effectiveness of the product is maintained. bath as constant as possible.

   In all these cases, the presence of the ouivre increases the effectiveness.



   If one proceeds as described, no detrimental substitution of iron phosphates and

 <Desc / Clms Page number 5>

 manganese by sodium phosphate, and its proportion relative to the other constituents of the bath does not increase either; a perfect equilibrium continues to exist in the solution, which thus very quickly produces a coating excellent for color adherence, and very rich in manganese phosphate.



   While to complete the bath, for the reasons explained, manganese nitrate is preferably used, however, it is also possible to a certain extent to introduce therein nitrates of other metals, such as: for example, those of magnesium, calcium, barium, strontium, zinc, cadmium or iron, which pass to the state of phosphates in the coating. It is also also possible to use the nitrate of an element such as chromium, aluminum, thorium or aerium which forms an insoluble precipitate in the phosphate solution, or else the nitrate of 'a substance such as boron, which volatilizes. In all these cases, no enrichment of the detrimental elements occurs.



   It goes without saying that the process described above can undergo various changes or modifications without departing from the scope of the invention.



   CLAIMS.



   1. Process for the production of coatings on iron or steel, characterized in that the solution in which the objects to be coated are immersed is prepared with the aid of acid phosphates and nitrate d. 'an alkali metal, and its strength is then maintained by the addition of acid phosphates and nitrates, the radicals of which do not remain in the solution, or else which do not introduce into the bath any element liable to bring a detrimental concentration of the latter.


    

Claims (1)

2. Procédé selon la revendication 1,caractérisé en ce <Desc/Clms Page number 6> qu'on emploie , comme nitrates d'addition, des nitrates d'éléments qui passent à l'état de bases de phosphates dans le revêtement à produire, et, de préférence... des classe @ @ éléments de la xxxx à laquelle appartiennent le magnésium, le calcium, le baryum, le manganèse le zino, le cadmium et le fer. 2. Method according to claim 1, characterized in that <Desc / Clms Page number 6> that the nitrates of elements which pass to the form of phosphate bases in the coating to be produced, and, preferably ... class @ @ elements of the xxxx to which belong magnesium, calcium, barium, manganese, zino, cadmium and iron. 3. Prooédé selon la revendication 1, caractérisé en cequ'en emploie, comme nitrates d'addition des nitrates d'éléments qui se volatilisent ultérieurement et s'élimi- nent ainsi de la solution, et, de préférence, du nitrate de bore. 3. Process according to claim 1, characterized in that it employs, as addition nitrates, nitrates of elements which subsequently volatilize and are thus eliminated from the solution, and preferably boron nitrate. 4. Procédé selon la revendication 1, caractérisé en ce qu'on emploie oonme nitrates d'addition, des nitrates des éléments qui forment des combinaisons insolubles avec les constituants de la solution, et, de préférenoe, des nitrates des éléments de la classe à laquelle appar- tiennent le chrome, l'aluminium, le thorium, et le oérium. 4. Method according to claim 1, characterized in that one uses oonme addition nitrates, nitrates of the elements which form insoluble combinations with the constituents of the solution, and, preferably, nitrates of the elements of the class to which belong chromium, aluminum, thorium, and oerium. 5. Procédé selon les revendioations 1 à 4,oaraoté- risé en ce qu'on introduite dans la solution un oonstituant soluble oontenant du ouivre . 5. Process according to Claims 1 to 4, characterized in that a soluble oonstituant oontaining ouivre is introduced into the solution. 6. Procédé selon les revendications 1 à 5, caractéri- sé en ce qu'on utilise comme nitrate de complément, du nitrate de manganèse. 6. Process according to claims 1 to 5, characterized in that manganese nitrate is used as complement nitrate. 7. Prooédé selon la revendication 6,oaraotérisé en ce que le métal alcalin employé pour préparer le bain,est le sodium . 7. The method of claim 6, oaraotérisé in that the alkali metal used to prepare the bath is sodium. 8. Procédé selon la revendication 6,oaraotérisé en ce qu'on emploie comme phosphate acide, du phosphate de manganèse primaire ( phosphate bibasique de manganèse). 8. The method of claim 6, oaraotérisé in that used as acid phosphate, primary manganese phosphate (bibasic manganese phosphate). 9. Prooédé selon la revendication 8,caractérisé en oe que le phosphate de manganése primaire est ajouté séparément à l'état pulvérulent et le nitrate de manganèse est ajouté, mélangé avec un phosphatede manganèse moins acide que le phosphate de manganèse primaire. <Desc/Clms Page number 7> 9. Process according to claim 8, characterized in that the primary manganese phosphate is added separately in the pulverulent state and the manganese nitrate is added, mixed with a manganese phosphate less acidic than the primary manganese phosphate. <Desc / Clms Page number 7> 10. Procédé selon la revendication 9, caractérisé en ce que les deux constituants pulvérulents employés pour compléter le bain, sont utilisés en quantités à. peu près égales. 10. The method of claim 9, characterized in that the two pulverulent constituents used to complete the bath are used in amounts to. roughly equal. Il'. Procédé et matière premières pour production de revêtements en phosphate , tels que décrits oiudes- sus. He'. Process and raw materials for the production of phosphate coatings, as described above.
BE402237D 1933-03-27 1934-03-27 PROCESS AND RAW MATERIAL FOR THE PRODUCTION OF PHOSPHATE COATINGS BE402237A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US427921XA 1933-03-27 1933-03-27
US770798XA 1933-03-27 1933-03-27
US662998A US2001754A (en) 1933-03-27 1933-03-27 Method and material for producing phosphate coating

Publications (1)

Publication Number Publication Date
BE402237A true BE402237A (en) 1934-04-30

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Family Applications (1)

Application Number Title Priority Date Filing Date
BE402237D BE402237A (en) 1933-03-27 1934-03-27 PROCESS AND RAW MATERIAL FOR THE PRODUCTION OF PHOSPHATE COATINGS

Country Status (4)

Country Link
US (1) US2001754A (en)
BE (1) BE402237A (en)
FR (1) FR770798A (en)
GB (1) GB427921A (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE746470C (en) * 1935-02-18 1944-07-21 Metallgesellschaft Ag Process for refreshing zinc phosphate rust protection baths
DE966914C (en) * 1936-05-01 1957-09-19 Metallgesellschaft Ag Process for the formation of phosphate coatings
DE974004C (en) * 1937-06-02 1960-08-18 Metallgesellschaft Ag Process to improve the non-cutting deformation of workpieces made of iron and zinc
US2927873A (en) * 1952-03-26 1960-03-08 Bofors Ab Method of increasing the resistance of metals to corrosion
US3178319A (en) * 1958-06-05 1965-04-13 Geraldine D Henricks Phosphate coating compositions and methods of making and using the same
US3261723A (en) * 1962-11-30 1966-07-19 Lubrizol Corp Method for reducing combustion chamber deposits in internal combustion engines
US3467589A (en) * 1966-10-19 1969-09-16 Hooker Chemical Corp Method of forming a copper containing protective coating prior to electrodeposition of paint
DE2632626A1 (en) * 1975-07-25 1977-02-10 Ici Ltd BASE MATERIAL COATED WITH A METAL PHOSPHATE COATING

Also Published As

Publication number Publication date
GB427921A (en) 1935-05-02
FR770798A (en) 1934-09-20
US2001754A (en) 1935-05-21

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