CA2030126C - Process for the chemical conversion of metallic substrates, conversion bath adapted to be used in the same process and concentrate adapted for the preparation of the bath - Google Patents
Process for the chemical conversion of metallic substrates, conversion bath adapted to be used in the same process and concentrate adapted for the preparation of the bathInfo
- Publication number
- CA2030126C CA2030126C CA002030126A CA2030126A CA2030126C CA 2030126 C CA2030126 C CA 2030126C CA 002030126 A CA002030126 A CA 002030126A CA 2030126 A CA2030126 A CA 2030126A CA 2030126 C CA2030126 C CA 2030126C
- Authority
- CA
- Canada
- Prior art keywords
- bath
- ions
- acid
- conversion
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/17—Orthophosphates containing zinc cations containing also organic acids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/46—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates
- C23C22/47—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates containing also phosphates
Abstract
Process for the chemical conversion of metallic substrates comprising the use, at the moment of the phosphatization step proper, of a zinc conversion bath comprising phosphate ions and nitrate ions as well as ferrous or ferric ions and from about 21 to about 100 g/l of at least one organic chelating agent.
Description
2~301~6 , PROCESS FOR THE CHEMICAL COI.v~-nSION OF METALLIC
SUBSTRATES, ~ONV~ION BATH ADAPTED TO BE USED
IN THE SAME PROCESS AND COh~k~ ~ATE ADAPTED
FOR THE PREPARATION OF THE BATH
The invention relates to a process for the chemical conversion of metallic substrates, especially based on iron or galvanized steel, in order to increase their resistance against corrosion, their capacity against deformation or simultaneously both properties.
The invention also relates to a chemical conversion bath adapted to be used in the said process as well as a concentrate adapted for the preparation of the bath.
It is already known to carry out chemical conver-sion of metallic substrates by way of classic crystalline phosphatization treatments due to which a coating of insoluble phosphates is obtained on the surface of the metal.
The crystalline phosphatization treatments which are already known, generally use acid baths which contain at least the following components :
- orthophosphoric acid H3PO4 - a primary phosphate ion H2PO4-- one or several metals selected among zinc, iron, manganese, nickel, copper, cobalt, calcium, - at least one accelerating agent consisting of an oxidizing agent such as chlorate ions, nitrate ions, nitrite or metanitrobenzene sodium sulphonate.
It is possible to carry out these treatments, on the substrates to be treated, by spraying or by immersion.
The said treatments are part of a sequence of operational steps which may comprise:
- one or several degreasing steps, - one or several rinsing steps, - possibly one or several pickling steps, then rinsing steps, - possibly one surface conditioning step, - the phosphatization step proper, - one or several rinsing steps, - possibly a passivation step, generally in chromic medium and a rinsing step.
The thus treated substrates are adapted to be used as such or to receive subsequently an application of lubricant, of protection oil or of paint.
The nature and the composition of the coating of insoluble phosphates obtained essentially depend;
- upon the nature of the substrate, - upon the composition of the phosphatization bath - upon the kind of application of the product (spraying or immersion), - upon the nature of the pretreatment steps.
The prior art discloses various improvements to chemical conversion baths in order to improve the performances of the said baths.
In that connection, according to the French patent FR-A-l 362 202 (filed June 28, 1963) the corrosion resistance of phosphatization coatings is improved by the addition of a small quantity (lower than 2~ and preferably comprised between 0.5 and 1.5~) of organic complexing agents;
in the said patent, resistances against the so-called "neutral salt spray" (standard ASTM-B-117) lower or equal to 25 hours have been recorded.
According to the French patent FR-A-l 585 660 (filed August 28, 1968) the so-called coating weight can be increased by addition of an organic polyacid into a phosphatization bath accelerated with chlorate and almost free of ferrous ions. That patent relates in fact to phosphatization treatments intended for metals which are to be cold worked; now, the phosphatization treatments in question provide coatings whose coating weights are comprised between 16.1 and 32.2 g/m2 3 7 ~ ?~ ~
., ~
and about which it is known that they provide only a low resistance against neutral salt spray when they are tested as such.
Finally, according to the French Patent FR-A-2 531 457 (filed August 3, 1982) the association of chelating agent and of a soluble polyphosphate makes it possible to obtain coatings whose resistance against corrosion is substantially improved, as resistances against neutral salt spray which in some cases are equal to 310 hours are mentioned in connection with metal parts which are only phosphated.
The last mentioned French patent discloses that an excess of polyphosphates might prevent the formation of the crystalline coating and proposes to "ripenN the baths as claimed by variation of the pH
before use.
The contemplated ripening being not instantaneous, the steps of regeneration of the bath must be discontinuous, which constitutes a drawback as most of industrial baths are regenerated continuously.
The object of the invention is above all to overcome said drawback and to provide a chemical conversion bath which, while providing performances equivalent to those of the process disclosed in the French patent FR-A-2 531 457, can be continuously regenerated.
And Applicants had the merit of discovering that in order to achieve the said object, it is necessary to introduce in a zinc conversion bath containing phosphate ions, nitrates ions as well as ferrous or ferric ions at least 20 g/l of an organic chelating agent.
Consequently, the chemical conversion process according to the invention is characterized by the fact that it comprises the use, at the moment of the phosphatization step proper, of a zinc conversion bath containing phosphate and nitrate ions as well as ferrous or ferric ions and from about 21 to about 100 g/l of at least one organic chelating agent.
The zinc conversion bath according to the invention ~. , ~
203012~
" .
which is characterized by the fact that it comprises phos-phate and nltrate ions as well as ferrous and/or ferric ions as well as from about 21 to about 100 g/l of at least one organic chelating agent, the said chelating agent being selected from the group comprising - polycarboxylic acids, among which citric acid, oxalic acid, malic acid, glutamic acid, tartric acid, aspartic acid, malonic acid and their salts, citric acid being preferred, and - polyhydroxycarboxylic acids among which gluconic acid, glucoheptonic acid, mucic acid and their salts, gluconic acid being preferred.
The salts of the above-mentioned polycarboxylic and polyhydroxycarboxylic acids are selected from the salts of alkaline and earth-alkaline metals, ammonium, iron, zinc, manganese, molybdene, cobalt and nickel.
The zinc ion of which a proportion of 0.5 to 25 g/l is used, can be introduced by any convenient way and especially in the form of one of its salts with nitric, phosphoric, carbonic, gluconic, citric acid or in the form of its oxide. It can be used in association with any metal currently used in phosphatization bath such as for example manganese, nickel, cobalt, calcium, magnesium.
The iron ions, which are used at the proportion of 0.1 to 15 g/l, can be introduced either by dissolution of iron in solid state as for example iron chips, iron powder, iron parts or iron strappings: they can also be introduced by way of salts of iron with sulfuric acid, fluorohydric acid, phosphoric acid or nitric acid; the iron ion can be 3o the ferrous ion or the ferric ion or a mixture of both.
The phosphate ions on the one hand and the nitrate ions on the other hand are used in the said bath in a proportion up to 40 g/l.
The bath according to the invention can also contain fluorhydric acid, fluosilicic acid or fluoboric acid or several of the said acids in order to regulate the 203Q12~
equilibrium between the pickling of the substrate by the acid solution and the growing of the crystalline coating.
The bath according to the invention is prepared by way of dilution starting from a concentrate which is chraracterized by the fact that it comprises - up to 500 g/liter of organic chelating agent, espe-cially the citrate or the gluconate ion, - up to 200 g/l of phosphate ions, - up to 125 g/l of zinc ions, - up to 200 g/l of nitrate ions.
The coatings obtained when carrying out the process according to the invention provide within the meaning of the test according to the standard ASTM B-117, a resistance against neutral salt spray which is comparable to that obtained according to patent FR-A-2 531 457 while permit-ting a continuous regeneration.
The substrates sub;ected to the process according to the invention can be stocked or used without further protection but it is also possible to paint the said substrates in order to further increase their resistance against corrosion; they may be cold worked after a possible application of a lubricant.
A preferred conversion bath comprises :
- from 5 to 40 g/l of phosphate ions ~ from 21 to 100 g/l of citric ions and/or gluconic ions - from 2 to 40 g/l of nitrate ions - from 0.5 to 25 g/l of zinc ions - from 0.1 to 15 g/l of iron.
According to a modification, the said bath com-3o prises from 0.02 to 3 g/l of nickel, cobalt or copper.
A particularly preferred bath comprises :
- from 5 to 20 g/l of phosphate ions - from 21 to 60 g/l of citric ions - from 2 to 40 g/l of nitrate ions - from 2 to 10 g/l of zinc ions - from 0.1 to 15 g/l of iron.
'~ 2030126 , ~ ,, Another particularly preferred bath comprises : -- from 5 to 20 g/l of phosphate ions - from 30 to 80 g/l of gluconic ion - from 2 to 40 g/l of nitrate ion - from 2 to 10 g/l of zinc ion - from 0.1 to 15 g/l of iron.
The chemical conversion bath according to the invention is used by way of spraying on the metallic substrate to be treated or by way of immersion of the substrate within the bath, the immersion being preferred.
The chemical conversion process according to the invention comprises a set of treatment steps, i.e.:
- one or several degreasing steps, - one or several rinsing steps, - possibly, one or several activation or pickling steps, - one rinsing step, - the chemical conversion step proper using the conversion bath according to the invention, - a rinsing step, - a drying step.
Due to the exceptional resistance against dry corrosion of the phosphatization coating obtAine~ when using the bath according to the invention, the process is simplified by suppression of the chromic passivation and protection steps, which follow the chemical phosphatization conversion and which are necessary in connection with the prior art processes.
Preferably, the temperature of the bath according 3o to the invention is comprised between about 40 and about 100~C and more particularly between 70 and 99~C.
The invention will be well understood thanks to the non-limiting examples hereafter indicated and in which are disclosed advantageous embodiments of the bath according to the invention.
,..
. ....
EXEMPLE 1 (comparative) A conversion bath according to the prior art is prepared, the said bath comprising besides water the following ions :
Zn++ : 6 g/l total PO4 : 16.7 g/l NO ~ : 10 g/l total Fe : 1 g/l Ni++ : 0.2 g/l.
The temperature of the said bath is brought to 95~C; the free acidity is brought within the requested range corresponding to 8.0 points using concentrated sodium hydroxide (the free acidity is determined by titration of 10 ml of cold solution with a N/10 sodium hydroxide solution sufficient to bring the pH to 3.6).
Cold rolled plates of steel containing O . 02~ of carbon and corresponding to the quality ZES normally used in the motorcar industry, the lengths and the widths of the said plates being 150 mm x 140 mm, are subjected to the following set of treatments :
Step 1: Alkaline degreasing within an aquous solution based on the degreasing agents commercialized by the Applicants under the trademarks RIDOLINE 1550 CF/2 (1.5% v/v) and RIDOSOL 550 CF (1.5% v/v).
Temperature: 60~C
Duration of the treatment: 3 minutes.
Step 2: Cold rinsing with tap water during 2 minutes.
Step 3: Nitric pickling Pickling agent: 60% nitric acid in aqueous solution (10% v/v) Temperature: 20~C
Duration of the treatment: 10 seconds.
Step 4: Cold rinsing with tap water during 1 minute.
Step 5: The conversion proper at a temperature of 95~C
during 30 minutes.
Step 6: Cold tap water rinsing during 10 seconds.
Step 7: Drying within a drying box at a temperature of about 95~C during 10 minutes.
",,, The thus treated plates are sub~ected to the neutral salt spray at a concentration of 5~ (according to the standard ASTM B-117).
After 1 hour exposition to the salt spray, a very homogeneous 50% rust forming is obtained.
EXAMPLE 2 (comparative) A conversion bath according to the prior art is prepared by addition to the bath according to example 1 of a quantity of 10 g/l of citric acid. The free acidity of the bath is brought to 15.0 points. The same treatment as above-mentioned is carried out on the same cold rolled steel plates. After 8 hours of exposition a homogeneous rust formation of 50% is obtained.
A conversion bath according to the invention is prepared by addition to the bath according to example 1 of a quantity of 30 g/l of citric acid. The free acidity of the new bath is brought to 18Jl9 points. In the same way as in example 1 cold rolled steel plates are treated and there is obtained locally after 150 hours of exposition a rust formation of 10%.
TABLE I
Amount of citric Salt spray test Example acid in the bath -------------------------------25 No. (g/l)Beginning of 50% rust the rust 1 0 immediate less than l h 2 10 5 h 8 h 3 30 haze after several rust 3o 100 h spots after 150 h This example is intended to show the possibility of using the process on various industrial parts.
The treatment of the parts which consist of cemented steel HRC 55 (containing 0.55% of carbon in the , .~..
mass) and of cold rolled steel XC lO (containing 0.1% of carbon).
The three following compositions are prepared:
Composition A
56.7 g Of water are mixed with 20 g of citric acid and 22.3 g of phosphoric acid Of a concentration of 75%.
In the said mixture is dissolved an amount of 1 g of metallic iron.
Composition B
46.7 g of water are mixed with 30 g of citric acid and 22.3 g of phosphoric acid of a concentration of 75%.
An amount of 1 g of metallic iron is dissolved in this mixture.
Composition C
An amount of 7. 5 g of zinc oxide and an amount of 1 g of nickel nitrate containing 20% of nickel are dis-solved in a mixture cont~ ni ng 74.8 g of water and 16.7 g of nitric acid of a concentration of 60%.
The set of treatments is the same as the set disclosed in example 1, except step 3, the nitric pickling being replaced by an aqueous phosphoric pickling carried out within an aqueous solution containing 7.75% v/v of phosphoric acid of a concentration Of 75% during 2 minutes at a temperature of 60 ~ C .
The baths used at the moment of the conversion step proper are constituted as follows :
. Bath 1: - 800 ml of water - 100 ml of composition A
- 100 ml of composition C
3o . Bath 2: - 800 ml of water - 100 ml of composition B
- 100 ml of composition C.
Two series of steel parts corresponding respecti-vely to the quality XC 10 and HRC 55, which had been previously subjected to the set Of treatments according to example 1 within which bath 1 is used with the parts 20301~
,, consisting of XC 10 steel and bath 2 with the parts of HRC
55 steel, are then subjected to the neutral salt spray test according to the standard ASTM B-117; the duration at the end of which the red rust appears is recorded.
The results are recorded in table II.
TABLE II
Parts Treatment according to example 1 with consisting ---------------------------------------------of steel bath 1 bath 2 10 of the type (20 g/l of citric (30 g/l of citric acid) acid) XC 10 beginning of the rust no rust after 400 h after 700 h _____________ _____________________________________________ HRC 55 beginning of the rust beginning of the rust after 10 h after 40 h It is noticed that, when using in the bath accord-ing to the invention a concentration of citrate ion higher than 20 g/l, a significant implo~e.nent of the resistance against corrosion is obtained, even than using a steel difficult to be treated as a cemented steel of the type HRC
55.
An aqueous bath is prepared containing (weight/
volume):
- 25 g/l of citric acid - 10 g/l of N03 ion - 16.7 g/l of P04 ion - 1 g/l of Fe++ ion - 6 g/l of Zn++ ion - 1 g/l of Mn++ ion.
The bath is heated to 95~C and the free acidity is brought to a value equal to 20 points using sodium hydro-xide.
Cold rolled galvanized steel sheets of the type ZES
are subjected to a sequence of treatments identical to that disclosed in example 1 (the conversion step using the 20:~126 ""
above-mentioned bath), except steps 3 and 4 which are abandoned. After that treatment, the steel sheets are subjected to the neutral salt spray test (standard ASTM
B-117) and, after an exposition during 400 h, no rust is observed.
Cold rolled galvanized steel parts of the type ZES, parts made of steel having a low carbon content of the type XC 10 and parts consisting of steel having a high carbon content of the type XC 55 (0.55~ of carbon) are subjected to the conversion process comprising the following steps:
Step 1: Alkaline degreasing with an aqueous solution based on degreasing agents commercialized by the Appli-cants under the tr~ rkS RIDOLINE 1550 CF (2 to 1.5% v/v) and RIDOSOL 550 CF (0.15~ v/v).
Temperature: 60~C.
Duration of treatment: 4 minutes.
Step 2: Cold rinsing with tap water during 2 minutes.
Step 3: Phosphoric pickling within an aqueous solution.
Pickling agent: phosphoric acid having a concen-tration of 75% (7.75% v/v).
Temperature: 55~C.
Duration of treatment: 4 minutes.
Step 4: Cold rinsing with tap water during 1 minute.
Step 5: Nitric pickling in an aqueous solution.
Pickling agent: nitric acid having a concentration of 60% (10% v/v).
Temperature: 20~C.
Duration of treatment: 20 seconds.
Step 6: Cold rinsing with tap water during 1 minute.
Step 7: Conversion proper at 95~C during 15 minutes.
Step 8: Rinsing with cold tap water during 10 seconds.
Step 9: Drying in the drying box at a temperature of about 95~C during 10 minutes.
In that example, the conversion bath mentioned at step 7 has the following composition:
~ 203()1~6 .,.~ , - 51 g/l of gluconate ion - 3.6 g/l of zinc ion - 8.2 g/l of phosphate ions - 16.g g/l of nitrate ion - 0.5 g/l of iron ions.
Its pH is equal to 2.7.
The parts and the sheets treated under these condi-tions are sub~ected to the neutral salt spray according to standard ASTM B-117, the duration after which rust appears being recorded.
The results are indicated in Table III.
TABLE III
Steel of which Duration at the end of which 1the tested parts red rust appears are consisting of Strips of the ZES type higher than 480 h ___________________________________________________________ XC 10 about 400 h ___________________________________________________________ XC 55 about 400 h
SUBSTRATES, ~ONV~ION BATH ADAPTED TO BE USED
IN THE SAME PROCESS AND COh~k~ ~ATE ADAPTED
FOR THE PREPARATION OF THE BATH
The invention relates to a process for the chemical conversion of metallic substrates, especially based on iron or galvanized steel, in order to increase their resistance against corrosion, their capacity against deformation or simultaneously both properties.
The invention also relates to a chemical conversion bath adapted to be used in the said process as well as a concentrate adapted for the preparation of the bath.
It is already known to carry out chemical conver-sion of metallic substrates by way of classic crystalline phosphatization treatments due to which a coating of insoluble phosphates is obtained on the surface of the metal.
The crystalline phosphatization treatments which are already known, generally use acid baths which contain at least the following components :
- orthophosphoric acid H3PO4 - a primary phosphate ion H2PO4-- one or several metals selected among zinc, iron, manganese, nickel, copper, cobalt, calcium, - at least one accelerating agent consisting of an oxidizing agent such as chlorate ions, nitrate ions, nitrite or metanitrobenzene sodium sulphonate.
It is possible to carry out these treatments, on the substrates to be treated, by spraying or by immersion.
The said treatments are part of a sequence of operational steps which may comprise:
- one or several degreasing steps, - one or several rinsing steps, - possibly one or several pickling steps, then rinsing steps, - possibly one surface conditioning step, - the phosphatization step proper, - one or several rinsing steps, - possibly a passivation step, generally in chromic medium and a rinsing step.
The thus treated substrates are adapted to be used as such or to receive subsequently an application of lubricant, of protection oil or of paint.
The nature and the composition of the coating of insoluble phosphates obtained essentially depend;
- upon the nature of the substrate, - upon the composition of the phosphatization bath - upon the kind of application of the product (spraying or immersion), - upon the nature of the pretreatment steps.
The prior art discloses various improvements to chemical conversion baths in order to improve the performances of the said baths.
In that connection, according to the French patent FR-A-l 362 202 (filed June 28, 1963) the corrosion resistance of phosphatization coatings is improved by the addition of a small quantity (lower than 2~ and preferably comprised between 0.5 and 1.5~) of organic complexing agents;
in the said patent, resistances against the so-called "neutral salt spray" (standard ASTM-B-117) lower or equal to 25 hours have been recorded.
According to the French patent FR-A-l 585 660 (filed August 28, 1968) the so-called coating weight can be increased by addition of an organic polyacid into a phosphatization bath accelerated with chlorate and almost free of ferrous ions. That patent relates in fact to phosphatization treatments intended for metals which are to be cold worked; now, the phosphatization treatments in question provide coatings whose coating weights are comprised between 16.1 and 32.2 g/m2 3 7 ~ ?~ ~
., ~
and about which it is known that they provide only a low resistance against neutral salt spray when they are tested as such.
Finally, according to the French Patent FR-A-2 531 457 (filed August 3, 1982) the association of chelating agent and of a soluble polyphosphate makes it possible to obtain coatings whose resistance against corrosion is substantially improved, as resistances against neutral salt spray which in some cases are equal to 310 hours are mentioned in connection with metal parts which are only phosphated.
The last mentioned French patent discloses that an excess of polyphosphates might prevent the formation of the crystalline coating and proposes to "ripenN the baths as claimed by variation of the pH
before use.
The contemplated ripening being not instantaneous, the steps of regeneration of the bath must be discontinuous, which constitutes a drawback as most of industrial baths are regenerated continuously.
The object of the invention is above all to overcome said drawback and to provide a chemical conversion bath which, while providing performances equivalent to those of the process disclosed in the French patent FR-A-2 531 457, can be continuously regenerated.
And Applicants had the merit of discovering that in order to achieve the said object, it is necessary to introduce in a zinc conversion bath containing phosphate ions, nitrates ions as well as ferrous or ferric ions at least 20 g/l of an organic chelating agent.
Consequently, the chemical conversion process according to the invention is characterized by the fact that it comprises the use, at the moment of the phosphatization step proper, of a zinc conversion bath containing phosphate and nitrate ions as well as ferrous or ferric ions and from about 21 to about 100 g/l of at least one organic chelating agent.
The zinc conversion bath according to the invention ~. , ~
203012~
" .
which is characterized by the fact that it comprises phos-phate and nltrate ions as well as ferrous and/or ferric ions as well as from about 21 to about 100 g/l of at least one organic chelating agent, the said chelating agent being selected from the group comprising - polycarboxylic acids, among which citric acid, oxalic acid, malic acid, glutamic acid, tartric acid, aspartic acid, malonic acid and their salts, citric acid being preferred, and - polyhydroxycarboxylic acids among which gluconic acid, glucoheptonic acid, mucic acid and their salts, gluconic acid being preferred.
The salts of the above-mentioned polycarboxylic and polyhydroxycarboxylic acids are selected from the salts of alkaline and earth-alkaline metals, ammonium, iron, zinc, manganese, molybdene, cobalt and nickel.
The zinc ion of which a proportion of 0.5 to 25 g/l is used, can be introduced by any convenient way and especially in the form of one of its salts with nitric, phosphoric, carbonic, gluconic, citric acid or in the form of its oxide. It can be used in association with any metal currently used in phosphatization bath such as for example manganese, nickel, cobalt, calcium, magnesium.
The iron ions, which are used at the proportion of 0.1 to 15 g/l, can be introduced either by dissolution of iron in solid state as for example iron chips, iron powder, iron parts or iron strappings: they can also be introduced by way of salts of iron with sulfuric acid, fluorohydric acid, phosphoric acid or nitric acid; the iron ion can be 3o the ferrous ion or the ferric ion or a mixture of both.
The phosphate ions on the one hand and the nitrate ions on the other hand are used in the said bath in a proportion up to 40 g/l.
The bath according to the invention can also contain fluorhydric acid, fluosilicic acid or fluoboric acid or several of the said acids in order to regulate the 203Q12~
equilibrium between the pickling of the substrate by the acid solution and the growing of the crystalline coating.
The bath according to the invention is prepared by way of dilution starting from a concentrate which is chraracterized by the fact that it comprises - up to 500 g/liter of organic chelating agent, espe-cially the citrate or the gluconate ion, - up to 200 g/l of phosphate ions, - up to 125 g/l of zinc ions, - up to 200 g/l of nitrate ions.
The coatings obtained when carrying out the process according to the invention provide within the meaning of the test according to the standard ASTM B-117, a resistance against neutral salt spray which is comparable to that obtained according to patent FR-A-2 531 457 while permit-ting a continuous regeneration.
The substrates sub;ected to the process according to the invention can be stocked or used without further protection but it is also possible to paint the said substrates in order to further increase their resistance against corrosion; they may be cold worked after a possible application of a lubricant.
A preferred conversion bath comprises :
- from 5 to 40 g/l of phosphate ions ~ from 21 to 100 g/l of citric ions and/or gluconic ions - from 2 to 40 g/l of nitrate ions - from 0.5 to 25 g/l of zinc ions - from 0.1 to 15 g/l of iron.
According to a modification, the said bath com-3o prises from 0.02 to 3 g/l of nickel, cobalt or copper.
A particularly preferred bath comprises :
- from 5 to 20 g/l of phosphate ions - from 21 to 60 g/l of citric ions - from 2 to 40 g/l of nitrate ions - from 2 to 10 g/l of zinc ions - from 0.1 to 15 g/l of iron.
'~ 2030126 , ~ ,, Another particularly preferred bath comprises : -- from 5 to 20 g/l of phosphate ions - from 30 to 80 g/l of gluconic ion - from 2 to 40 g/l of nitrate ion - from 2 to 10 g/l of zinc ion - from 0.1 to 15 g/l of iron.
The chemical conversion bath according to the invention is used by way of spraying on the metallic substrate to be treated or by way of immersion of the substrate within the bath, the immersion being preferred.
The chemical conversion process according to the invention comprises a set of treatment steps, i.e.:
- one or several degreasing steps, - one or several rinsing steps, - possibly, one or several activation or pickling steps, - one rinsing step, - the chemical conversion step proper using the conversion bath according to the invention, - a rinsing step, - a drying step.
Due to the exceptional resistance against dry corrosion of the phosphatization coating obtAine~ when using the bath according to the invention, the process is simplified by suppression of the chromic passivation and protection steps, which follow the chemical phosphatization conversion and which are necessary in connection with the prior art processes.
Preferably, the temperature of the bath according 3o to the invention is comprised between about 40 and about 100~C and more particularly between 70 and 99~C.
The invention will be well understood thanks to the non-limiting examples hereafter indicated and in which are disclosed advantageous embodiments of the bath according to the invention.
,..
. ....
EXEMPLE 1 (comparative) A conversion bath according to the prior art is prepared, the said bath comprising besides water the following ions :
Zn++ : 6 g/l total PO4 : 16.7 g/l NO ~ : 10 g/l total Fe : 1 g/l Ni++ : 0.2 g/l.
The temperature of the said bath is brought to 95~C; the free acidity is brought within the requested range corresponding to 8.0 points using concentrated sodium hydroxide (the free acidity is determined by titration of 10 ml of cold solution with a N/10 sodium hydroxide solution sufficient to bring the pH to 3.6).
Cold rolled plates of steel containing O . 02~ of carbon and corresponding to the quality ZES normally used in the motorcar industry, the lengths and the widths of the said plates being 150 mm x 140 mm, are subjected to the following set of treatments :
Step 1: Alkaline degreasing within an aquous solution based on the degreasing agents commercialized by the Applicants under the trademarks RIDOLINE 1550 CF/2 (1.5% v/v) and RIDOSOL 550 CF (1.5% v/v).
Temperature: 60~C
Duration of the treatment: 3 minutes.
Step 2: Cold rinsing with tap water during 2 minutes.
Step 3: Nitric pickling Pickling agent: 60% nitric acid in aqueous solution (10% v/v) Temperature: 20~C
Duration of the treatment: 10 seconds.
Step 4: Cold rinsing with tap water during 1 minute.
Step 5: The conversion proper at a temperature of 95~C
during 30 minutes.
Step 6: Cold tap water rinsing during 10 seconds.
Step 7: Drying within a drying box at a temperature of about 95~C during 10 minutes.
",,, The thus treated plates are sub~ected to the neutral salt spray at a concentration of 5~ (according to the standard ASTM B-117).
After 1 hour exposition to the salt spray, a very homogeneous 50% rust forming is obtained.
EXAMPLE 2 (comparative) A conversion bath according to the prior art is prepared by addition to the bath according to example 1 of a quantity of 10 g/l of citric acid. The free acidity of the bath is brought to 15.0 points. The same treatment as above-mentioned is carried out on the same cold rolled steel plates. After 8 hours of exposition a homogeneous rust formation of 50% is obtained.
A conversion bath according to the invention is prepared by addition to the bath according to example 1 of a quantity of 30 g/l of citric acid. The free acidity of the new bath is brought to 18Jl9 points. In the same way as in example 1 cold rolled steel plates are treated and there is obtained locally after 150 hours of exposition a rust formation of 10%.
TABLE I
Amount of citric Salt spray test Example acid in the bath -------------------------------25 No. (g/l)Beginning of 50% rust the rust 1 0 immediate less than l h 2 10 5 h 8 h 3 30 haze after several rust 3o 100 h spots after 150 h This example is intended to show the possibility of using the process on various industrial parts.
The treatment of the parts which consist of cemented steel HRC 55 (containing 0.55% of carbon in the , .~..
mass) and of cold rolled steel XC lO (containing 0.1% of carbon).
The three following compositions are prepared:
Composition A
56.7 g Of water are mixed with 20 g of citric acid and 22.3 g of phosphoric acid Of a concentration of 75%.
In the said mixture is dissolved an amount of 1 g of metallic iron.
Composition B
46.7 g of water are mixed with 30 g of citric acid and 22.3 g of phosphoric acid of a concentration of 75%.
An amount of 1 g of metallic iron is dissolved in this mixture.
Composition C
An amount of 7. 5 g of zinc oxide and an amount of 1 g of nickel nitrate containing 20% of nickel are dis-solved in a mixture cont~ ni ng 74.8 g of water and 16.7 g of nitric acid of a concentration of 60%.
The set of treatments is the same as the set disclosed in example 1, except step 3, the nitric pickling being replaced by an aqueous phosphoric pickling carried out within an aqueous solution containing 7.75% v/v of phosphoric acid of a concentration Of 75% during 2 minutes at a temperature of 60 ~ C .
The baths used at the moment of the conversion step proper are constituted as follows :
. Bath 1: - 800 ml of water - 100 ml of composition A
- 100 ml of composition C
3o . Bath 2: - 800 ml of water - 100 ml of composition B
- 100 ml of composition C.
Two series of steel parts corresponding respecti-vely to the quality XC 10 and HRC 55, which had been previously subjected to the set Of treatments according to example 1 within which bath 1 is used with the parts 20301~
,, consisting of XC 10 steel and bath 2 with the parts of HRC
55 steel, are then subjected to the neutral salt spray test according to the standard ASTM B-117; the duration at the end of which the red rust appears is recorded.
The results are recorded in table II.
TABLE II
Parts Treatment according to example 1 with consisting ---------------------------------------------of steel bath 1 bath 2 10 of the type (20 g/l of citric (30 g/l of citric acid) acid) XC 10 beginning of the rust no rust after 400 h after 700 h _____________ _____________________________________________ HRC 55 beginning of the rust beginning of the rust after 10 h after 40 h It is noticed that, when using in the bath accord-ing to the invention a concentration of citrate ion higher than 20 g/l, a significant implo~e.nent of the resistance against corrosion is obtained, even than using a steel difficult to be treated as a cemented steel of the type HRC
55.
An aqueous bath is prepared containing (weight/
volume):
- 25 g/l of citric acid - 10 g/l of N03 ion - 16.7 g/l of P04 ion - 1 g/l of Fe++ ion - 6 g/l of Zn++ ion - 1 g/l of Mn++ ion.
The bath is heated to 95~C and the free acidity is brought to a value equal to 20 points using sodium hydro-xide.
Cold rolled galvanized steel sheets of the type ZES
are subjected to a sequence of treatments identical to that disclosed in example 1 (the conversion step using the 20:~126 ""
above-mentioned bath), except steps 3 and 4 which are abandoned. After that treatment, the steel sheets are subjected to the neutral salt spray test (standard ASTM
B-117) and, after an exposition during 400 h, no rust is observed.
Cold rolled galvanized steel parts of the type ZES, parts made of steel having a low carbon content of the type XC 10 and parts consisting of steel having a high carbon content of the type XC 55 (0.55~ of carbon) are subjected to the conversion process comprising the following steps:
Step 1: Alkaline degreasing with an aqueous solution based on degreasing agents commercialized by the Appli-cants under the tr~ rkS RIDOLINE 1550 CF (2 to 1.5% v/v) and RIDOSOL 550 CF (0.15~ v/v).
Temperature: 60~C.
Duration of treatment: 4 minutes.
Step 2: Cold rinsing with tap water during 2 minutes.
Step 3: Phosphoric pickling within an aqueous solution.
Pickling agent: phosphoric acid having a concen-tration of 75% (7.75% v/v).
Temperature: 55~C.
Duration of treatment: 4 minutes.
Step 4: Cold rinsing with tap water during 1 minute.
Step 5: Nitric pickling in an aqueous solution.
Pickling agent: nitric acid having a concentration of 60% (10% v/v).
Temperature: 20~C.
Duration of treatment: 20 seconds.
Step 6: Cold rinsing with tap water during 1 minute.
Step 7: Conversion proper at 95~C during 15 minutes.
Step 8: Rinsing with cold tap water during 10 seconds.
Step 9: Drying in the drying box at a temperature of about 95~C during 10 minutes.
In that example, the conversion bath mentioned at step 7 has the following composition:
~ 203()1~6 .,.~ , - 51 g/l of gluconate ion - 3.6 g/l of zinc ion - 8.2 g/l of phosphate ions - 16.g g/l of nitrate ion - 0.5 g/l of iron ions.
Its pH is equal to 2.7.
The parts and the sheets treated under these condi-tions are sub~ected to the neutral salt spray according to standard ASTM B-117, the duration after which rust appears being recorded.
The results are indicated in Table III.
TABLE III
Steel of which Duration at the end of which 1the tested parts red rust appears are consisting of Strips of the ZES type higher than 480 h ___________________________________________________________ XC 10 about 400 h ___________________________________________________________ XC 55 about 400 h
Claims (2)
1. Process for the chemical conversion comprising the use, at the moment of the phosphatization step proper, of a zinc conversion bath free of chlorate ions and having a temperature of 70 to 99°C, containing from 0.5 to 25g/l of zinc ion, from 5 to 40g/l of phosphate ions, from 2 to 40g/l of nitrate ions as well as from 0.1 to 15 g/l of iron ions and from 21 to 100g/l ofat least an organic chelating agent consisting of a polycarboxylic acid selected from the group comprising oxalic acid, malic acid, glutamic acid, tartric acid, aspartic acid, malonic acid and citric acid, or the salts thereof.
2. Process according to claim 1, wherein the bath used comprises from 5 to 20g/l of phosphate ions, from 21 to 60g/l of citric ions, from 2 to 40g/l of nitrate ions, from 2 to 10g/l of zinc ions and from 0.1 to 15g/l of iron ions.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8915042 | 1989-11-16 | ||
| FR8915042A FR2654440B1 (en) | 1989-11-16 | 1989-11-16 | PROCESS FOR THE CHEMICAL CONVERSION OF METAL SUBSTRATES, BATH USED IN THIS PROCESS AND CONCENTRATE FOR THE PREPARATION OF THE BATH. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2030126A1 CA2030126A1 (en) | 1991-05-17 |
| CA2030126C true CA2030126C (en) | 1999-05-11 |
Family
ID=9387459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002030126A Expired - Fee Related CA2030126C (en) | 1989-11-16 | 1990-11-16 | Process for the chemical conversion of metallic substrates, conversion bath adapted to be used in the same process and concentrate adapted for the preparation of the bath |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0433118B1 (en) |
| JP (1) | JPH0730454B2 (en) |
| AT (1) | ATE132917T1 (en) |
| CA (1) | CA2030126C (en) |
| DE (1) | DE69024774T2 (en) |
| ES (1) | ES2084680T3 (en) |
| FR (1) | FR2654440B1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2968127B2 (en) * | 1992-04-24 | 1999-10-25 | 日本パーカライジング株式会社 | Acid displacement plating solution for zinc or galvanized steel sheet |
| JP2968147B2 (en) * | 1993-04-07 | 1999-10-25 | 日本パーカライジング株式会社 | Acid displacement plating solution composition for zinc-containing metal plated steel sheet |
| DE19733972A1 (en) * | 1997-08-06 | 1999-02-11 | Henkel Kgaa | Alkaline band passivation |
| WO2006108108A2 (en) * | 2005-04-06 | 2006-10-12 | Rem Technologies, Inc. | Superfinishing of high density carbides |
| JP4845050B2 (en) * | 2007-10-04 | 2011-12-28 | ユケン工業株式会社 | Concentrated liquid composition for hexavalent chromium-free surface conversion treatment with improved stability |
| JP5225466B2 (en) * | 2009-12-07 | 2013-07-03 | 新日鐵住金株式会社 | Chromate-free precoated steel plate with excellent red rust corrosion resistance |
| EP2892850B1 (en) * | 2012-09-05 | 2017-11-15 | Compass Minerals America Inc. | Methods and compositions to prevent caking of sodium chloride and prevent transition metal stains |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE975008C (en) * | 1952-08-06 | 1961-08-03 | American Chem Paint Co | Process for the production of phosphate coatings on zinc and its alloys |
| GB866377A (en) * | 1958-11-28 | 1961-04-26 | Pyrene Co Ltd | Improvements relating to the production of phosphate coatings on metals |
| US3116178A (en) * | 1961-05-29 | 1963-12-31 | Lubrizol Corp | Phosphating solutions |
| BE635970A (en) * | 1962-11-13 | |||
| FR1585660A (en) * | 1967-10-18 | 1970-01-30 | ||
| US3767476A (en) * | 1971-08-31 | 1973-10-23 | Us Army | Method and composition for phosphatizing steel under pressure |
| SU1090761A1 (en) * | 1982-07-19 | 1984-05-07 | Московский Ордена Трудового Красного Знамени Вечерний Металлургический Институт | Solution for catodic application of protective films to titanium alloys |
| DE3927613A1 (en) * | 1989-08-22 | 1991-02-28 | Metallgesellschaft Ag | METHOD FOR PRODUCING PHOSPHATE COATINGS ON METAL SURFACES |
-
1989
- 1989-11-16 FR FR8915042A patent/FR2654440B1/en not_active Expired - Fee Related
-
1990
- 1990-11-15 AT AT90403233T patent/ATE132917T1/en not_active IP Right Cessation
- 1990-11-15 ES ES90403233T patent/ES2084680T3/en not_active Expired - Lifetime
- 1990-11-15 DE DE69024774T patent/DE69024774T2/en not_active Expired - Fee Related
- 1990-11-15 EP EP90403233A patent/EP0433118B1/en not_active Expired - Lifetime
- 1990-11-16 CA CA002030126A patent/CA2030126C/en not_active Expired - Fee Related
- 1990-11-16 JP JP2308953A patent/JPH0730454B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0433118A1 (en) | 1991-06-19 |
| FR2654440A1 (en) | 1991-05-17 |
| DE69024774T2 (en) | 1996-07-04 |
| DE69024774D1 (en) | 1996-02-22 |
| CA2030126A1 (en) | 1991-05-17 |
| FR2654440B1 (en) | 1993-07-30 |
| ES2084680T3 (en) | 1996-05-16 |
| EP0433118B1 (en) | 1996-01-10 |
| JPH03173778A (en) | 1991-07-29 |
| JPH0730454B2 (en) | 1995-04-05 |
| ATE132917T1 (en) | 1996-01-15 |
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