US 2002O174915A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2002/0174915 A1
Futsuhara et al. (43) Pub. Date: Nov. 28, 2002
(54) CHEMICAL CONVERSION REAGENT FOR (22) Filed: Mar. 27, 2002
MAGNESIUM ALLOY, SURFACE-TREATING
METHOD, AND MAGNESIUM ALLOY (30) Foreign Application Priority Data
SUBSTRATE
Mar. 28, 2001 (JP)...................................... 2001-0941.95
(75) Inventors: Masanobu Futsuhara, Yokohama-shi Publication Classification
(JP); Satoshi Miyamoto, Toyonaka-shi
(JP); Katsuyoshi Yamasoe, Sakura-shi
(JP); Kiyotada Yasuhara, Kashiwa-shi (51) Int. Cl." ..................................................... C23C 22/78
(JP) (52) U.S. Cl. .............................................................. 148,254
Correspondence Address: (57) ABSTRACT
SUGHRUE MION, PLLC The objective of the present invention is to impart coating
2100 Pennsylvania Avenue, NW film adhesion, corrosion resistance and rust prevention to
Washington, DC 20037-3213 (US) magnesium alloys.
(73) Assignee: NIPPON PAINT CO.,LTD. A chemical conversion reagent for a magnesium alloy which
comprises a phosphate ion and a permanganate ion and has
(21) Appl. No.: 10/106,098 pH of 1.5 to 7.
US 2002/0174915 A1
CHEMICAL CONVERSION REAGENT FOR
MAGNESIUM ALLOY, SURFACE-TREATING
METHOD, AND MAGNESIUM ALLOY
SUBSTRATE
FIELD OF THE INVENTION
0001. The present invention relates to a chemical con
version reagent for magnesium alloys which imparts high
corrosion resistance, rust prevention, and coating film adhe
Sion, a Surface-treating method which comprises using Said
chemical conversion reagent, and a magnesium alloy Sub
strate obtained by the method. The surface-treating method
of the invention is Suitable for the Surface treatment of
magnesium alloys which are used in applications requiring
corrosion resistance, rust prevention, coating film adhesion,
and electrical conductivity, for example electronic compo
nents Such as portable telephones and personal computer
housings, and household electrical appliances Such as tele
Vision receivers. In accordance with the Surface-treating
method of the invention, the high oxidizing power of a
permanganate ion is utilized to encourage formation of a
magnesium oxide coat and, at the same time, the reaction of
permanganate and magnesium ions with a phosphate ion is
utilized to form a coat comprising a phosphorus-manganese
compound and a phosphorus-magnesium compound,
whereby a chemical conversion film having excellent cor
rosion resistance, rust prevention, and coating film adhesion
can be produced on the magnesium alloy.
BACKGROUND OF THE INVENTION
0002 The common method of chemical conversion treat
ment for a magnesium alloy comprises dipping the magne
sium alloy in a chemical conversion reagent containing a
hexavalent chromium as described in JIS-H8651 and MIL
M-3171, for instance. However, hexavalent chromium
exerts harmful effects on the environment and human physi
ology. Therefore, the working environment for the Surface
treatment is unfavorable and a Sophisticated effluent disposal
System is required for preventing discharge of the hexava
lent chromium into the environment. The use of hexavalent
chromium has the disadvantage that, in addition to Said
harmful effects on the environment and human physiology,
an additional capital expenditure is required for the Surface
treating equipment. Furthermore, it is likely that its use will
be controlled or prohibited by law in many countries of the
world in near future. Therefore, development of a chemical
conversion treatment technology for magnesium Supplant
ing chromating treatment, the So-called nonchromate chemi
cal conversion treatment technology, is awaited.
0003) Regarding such nonchromate chemical conversion
treatment methods, Some of them are described in Japanese
Kokai Publication Hei-07-126858. Thus, a treatment
method using a magnesium phosphate treatment as a base
and a phosphate treatment method involving additional use
of a metal other than chromium, Such as Zirconium, titanium
or Zinc, are mentioned as the prior art. However, as pointed
out in Japanese Kokai Publication Hei-07-126858, these
Surface-treating methods are disadvantageous in that they
are not practical because of a time-consuming treatment
Step, involve a long time for the treatment and/or cannot
impart Sufficient corrosion resistance, rust prevention or
coating film adhesion, etc.
0004. As a technology overcoming the above disadvan
tages, Japanese Kokai Publication Hei-07-126858 discloses
Nov. 28, 2002
a manganese phosphate treatment. This manganese phos
phate treatment method is characterized in that not only a
bivalent manganese ion (Mn) and a phosphate ion but also
an aliphatic amine, an aromatic amine, or a heterocyclic
amine compound is formulated in a chemical conversion
bath. Furthermore, this Solution is optionally Supplemented
with one member Selected from a nitrate ion, a Sulfate ion
and a fluorine-containing compound. It is described that by
this treatment method, a coat having excellent corrosion
resistance, rust prevention and coating film adhesion can be
formed on a magnesium alloy. However, addition of an
amine compound is not an eco-friendly practice and, more
over, the composition of this treating Solution is So much
complicated that bath control is rendered difficult.
0005) Japanese Kokai Publication Hei-08-35073 dis
closes a chemical conversion treatment method employing a
permanganate ion. It is Stated that by adding a promoter Such
as a mineral acid or a fluoride to an aqueous permanganate
Solution, a chemical conversion coat having Satisfactory
corrosion resistance can be formed. However, the coat So
formed is not a manganese phosphate coat but a coat
composed of manganese oxide and manganese hydroxide,
not containing a phosphate bond, and, therefore, is not fully
Satisfactory in coating film adhesion.
SUMMARY OF THE INVENTION
0006 The prior art mentioned above has several draw
backs, namely (1) hexavalent chromium exerting harmful
effects on human physiology and the environment is con
tained, (2) a treatment step is time-consuming and compli
cated, (3) a high temperature is required for the treatment,
(4) corrosion resistance, rust prevention and coating film
adhesion cannot be imparted as Satisfactory as for the
chromated coat, and/or (5) bath composition is complicated.
The object of the present invention is to overcome these
disadvantages.
0007. The present invention relates to a chemical con
version reagent for a magnesium alloy
0008 which comprises a phosphate ion and a per
manganate ion and
0009) has pH of 1.5 to 7.
0010. The concentration of a compound serving as a
Source of said phosphate ion is preferably 20 to 50 g/L and
the concentration of a compound Serving as a Source of Said
permanganate ion is preferably 1 to 10 g/L.
0011. The present invention further relates to a surface
treating method
0012 which comprises a step of bringing said
chemical conversion reagent into contact with a
magnesium alloy Substrate.
0013 Said magnesium alloy substrate is preferably Sub
jected to degreasing, pickling, and desmutting treatments in
advance and, more preferably, Said pickling treatment is
carried out with a reagent containing at least one member
Selected from the group consisting of Sulfuric acid, nitric
acid, phosphoric acid, and a fluorine-containing compound.
0014. The present invention is further directed to a mag
nesium alloy Substrate obtainable by Said Surface-treating
method.
US 2002/0174915 A1
0.015 The present invention is now described in further
detail.
DETAILED DESCRIPTION OF THE
INVENTION
0016. The chemical conversion reagent for a magnesium
alloy according to the invention comprises a phosphate ion
and a permanganate ion. The role of Said phosphate ion is
that of imparting corrosion resistance and improving coating
film adhesion through formation of a phosphoric compound.
The Source of Said phosphate ion includes, for example,
phosphoric acid Salts. Such as primary Sodium phosphate,
Secondary Sodium phosphate, primary ammonium phos
phate, Secondary ammonium phosphate, primary potassium
phosphate, Secondary potassium phosphate, etc. and ortho
phosphoric acid. The concentration of the phosphoric acid
compound in the chemical conversion bath may range from
5 g/L to the solubility limit of the compound to be used but
is more preferably 20 g/L to 50 g/L. If it is less than 5 g/L,
no sufficient coating film adhesion will be obtained. If it
exceeds 50 g/L, Substantially no further improvement in
performance will be obtained but rather will result in a loss.
0.017. The role of said permanganate ion is that of pro
moting formation of an oxide film on the Surface of a
magnesium alloy and causing formation of a phosphorus
manganese compound/manganese oxide film which is excel
lent in corrosion resistance. The permanganate ion is Sup
plied from a permanganate Salt compound. Specifically, a
permanganate ion can be generated by dissolving potassium
permanganate, Sodium permanganate, ammonium perman
ganate, or the like in water. The concentration of the
permanganate Salt compound in the chemical conversion
bath may range from 1 g/L to the solubility limit of the
compound to be used but is suitably 1 g/L to 10 g/L. If it is
less than 1 g/L, deposition of the manganese compound coat
will be insufficient So that no adequate corrosion resistance
may be obtained. If the concentration exceeds 10 g/L, no
further improvement in performance will be obtained.
0.018. The chemical conversion reagent for a magnesium
alloy according to the invention has pH of 1.5 to 7. In
accordance with the invention, excellent corrosion resis
tance and coating film adhesion can be obtained over a broad
pH range of 1.5 to 7. The pH can be mainly controlled by
adding an alkaline Solution, Such as an aqueous Sodium
hydroxide Solution, or an acidic Solution, Such as a Solution
of orthophosphoric acid, but can also be controlled by
modulating the concentration ratio of primary Sodium phos
phate and Secondary Sodium phosphate. If the pH is below
1.5, dissolution of the magnesium alloy will be So Vigorous
as to damage the Surface thereby no Sufficient corrosion
resistance will be obtained. If the pH exceeds 7, neither
Sufficient corrosion resistance nor Sufficient coating film
adhesion will be obtained, hence it is not suitable. This is
probably because the deposited amount of the coat is dras
tically decreased and the oxidizing power of the permanga
nate ion is attenuated.
0019. The chemical conversion reagent of the present
invention can Suitably be applied to magnesium alloys. The
Surface-treating method which comprises a step of bringing
Said chemical conversion reagent into contact with a mag
nesium alloy Substrate is also another aspect of the present
invention.
Nov. 28, 2002
0020. The magnesium alloys mentioned above are
mainly magnesium alloys prepared by a die-casting tech
nique or a thixomolding technique, and as preferred species,
AM50D, AM60D, and AZ91D can be mentioned. As other
metals which is used in the preparation of magnesium alloys,
there can be mentioned, for example, aluminum, manganese,
Zinc, Silver, and rare earth elements, etc.
0021. These alloys are sometimes severely contaminated
by emulsion oils, known as mold release agents, which are
used in casting operations, and depending on casting con
ditions of alloys, Segregation layerS may occur on Surfaces
of alloys. For insuring a normal chemical conversion treat
ment in Such cases, the Surface of the magnesium alloy
needs to be Subjected to a Suitable pretreatment. The Surface
treatment is generally carried out in the Sequence of degreas
ing, Washing with water, pickling, Washing with water,
deSmutting, Washing with water, chemical conversion treat
ment, Washing with water, and drying.
0022. The degreasing treatment mentioned above is car
ried out to remove oil from the Surface. This degreasing Step
alone is Sufficient when the degree of contamination is low.
The degreasing agent to be used in the above degreasing
treatment can be roughly classified into an alkaline degreas
ing agent and an acidic degreasing agent. The degreasing
method for use in the practice of the present invention is not
particularly restricted but since magnesium dissolves vigor
ously in an acidic aqueous Solution, Selective dissolution of
the magnesium in the magnesium alloy may possibly take
place to damage the Surface. Therefore, it is preferable to use
an alkaline degreasing agent.
0023 The pickling treatment mentioned above is carried
out to remove the Segregation layer composed of fine
crystallites which have Segregated on the Surface and the
mold release agent which has penetrated into the Segregation
layer. In accordance with the method of the invention, it is
preferable to use an aqueous Solution of orthophosphoric
acid Supplemented with a fluorine-containing compound
Such as hydroSilicofluoric acid or an aqueous Solution of an
inorganic acid Such as Sulfuric acid or nitric acid. The
concentration range of Such an acid is preferably 0.3 to 20
g/L, more preferably about 0.3 to 5 g/L. If it is less than 0.3
g/L, repeated use will diminish a cleaning potency life, thus
necessitating frequent Supplementation or exchange of the
Solution. If the concentration exceeds 20 g/L, dissolution of
the magnesium alloy will be So Vigorous that the alloy
Surface will be damaged and a considerable amount of Smut
is produced, hence it is not preferable. The temperature of
the pickling bath can be controlled within the range of room
temperature to not higher than the boiling point of the
aqueous acidic Solution but for conserving the working
environment and avoiding the Surface damage due to exces
Sive etching or the excessive formation of Smut, the range of
room temperature to about 50° C. is preferred. When an
aqueous Solution of a carboxyl group-containing organic
acid is used, a Sufficient cleaning effect may not be obtained
owing to formation of a compound coat on the Surface of the
magnesium alloy, which may possibly cause a problem on
coating film adhesion. Moreover, an aqueous Solution of
either orthophosphoric acid or phosphorous acid alone in a
concentration of about 1 g/L or higher may phosphorylate
the Surface of magnesium with the consequent failure to
express a Sufficient cleaning effect or insure the necessary
coating film adhesion.
US 2002/0174915 A1
0024. The acid to be used is preferably an acidinert to the
magnesium alloy, Such as Sulfuric acid or nitric acid.
0.025 The desmutting treatment mentioned above is car
ried out to remove the foulant (smut) on the surface of
magnesium alloy, and the Washing is generally carried out
with an aqueous alkaline Solution, Such as an aqueous
Sodium hydroxide Solution.
0026. After each of Said degreasing, pickling, and
deSmutting treatments, Washing with water is carried out in
the per Se known manner. The above drying Step can also be
carried out in the conventional manner.
0027. Since the surface-treating method of the present
invention imparts excellent corrosion resistance, rust pre
vention and coating film adhesion to magnesium alloy
Substrates over a broad pH range of 1.5 to 7, it is expected
to find application in a broad range of fields for example
electronic components Such as portable telephones and
personal computer housings, and household electrical appli
ances Such as television receivers. The magnesium alloy
Substrate obtainable by this manner also constitutes another
aspect of the present invention.
0028. The chemical conversion reagent for a magnesium
alloy according to the present invention can impart coating
film adhesion and corrosion resistance to magnesium alloys
with high reproducibility over a broad pH range of pH 1.5
to 7 so that it facilitates bath control and handling. This is a
major industrial merit.
0029. The surface-treating method of the present inven
tion can impart excellent corrosion resistance and coating
film adhesion to magnesium alloys, even to magnesium
alloys prepared by a casting technique and hence contami
nated with a mold release agent. The method, therefore, can
be used in a broad range of applications Such as personal
computer and portable telephone housings and other shaped
articles, parts having intricate profiles, automotive parts, and
So forth.
EXAMPLES
0030 The following Examples illustrate the present
invention in further detail. However, these are by no means
limitative to the Scope of the invention.
Example 1
0031. In a sequence of degreasing, washing with water,
pickling, Washing with water, desmutting, Washing with
water, manganese phosphate treatment, Washing with water,
and drying, each carried out under the following conditions,
a chemical conversion coat was formed on a magnesium
alloy. Magnesium alloy: AZ91D test pieces (size: 100
mmx50 mmx3 mm)
0032) Degreasing: A 1 weight % aqueous solution of
“Surf Fine 100” (an alkaline degreasing agent: product of
Nippon Paint Co.); bath temperature 50° C., treating time 2
min. Pickling: Orthophosphoric acid 0.4 g/L, hydrosilicof
luoric acid 0.03 g/L, tap water as balance, bath temperature
50 C., treating time 2 min
0033. Desmutting: Sodium hydroxide 20 g/L, sodium
gluconate 3.1 g/L, bath temperature 60° C., treating time 5
min. Chemical conversion treatment: KMnO concentration
5.5g/L, primary phosphate concentration 45 g/L, orthophoS
Nov. 28, 2002
phoric acid concentration 1.8 g/L, tap water as balance, pH
2.8, bath temperature 50 C., treating time 2 min Drying
condition: Drying in an oven at 100° C. for 10 min
0034. The uncoated corrosion resistance, coated corro
Sion resistance, coating film adhesion, and coat appearance
were evaluated and the Surface electrical resistivity was
measured. The evaluations of parameters other than coated
corrosion resistance were made on the above magnesium
alloy test piece obtained and the evaluation of coated
corrosion resistance was made on the test piece prepared by
further applying a powder coating on each of the above
magnesium alloy test pieces obtained. The results are pre
sented in Table 1.
0035 (1) Evaluation of Corrosion Resistance
0036) The uncoated corrosion resistance (the corrosion
resistance of a magnesium alloy after chemical conversion
treatment) was evaluated by the salt spray test (SST). SST is
a test in which the test piece is sprayed with a 5 weight %
aqueous Sodium chloride Solution for a predetermined time
in a tester controlled at 35 C. and the incidence of corrosion
is then evaluated. The evaluation of the corrosion resistance
was made by visual assessment of uncorroded area after 48
hours of SST exposure.
0037 (2) Coated Corrosion Resistance
0038 Coated corrosion resistance was evaluated by SST.
The coating film was cross-cut and set in an SST tester for
a predetermined time (96 h). A cellophane tape was pressed
against the Surface of the cross-cut portion and, then, peeled
off as defined and the maximum peel width from the cut
portion was measured. The Smaller the peel width is, the
better the coated corrosion resistance is. AS the coating, a
gray epoxy powder coating (Magdyne PD-E, product of
Nippon Paint Co.) was used. The curing conditions of
coating films were 160° C. and 20 minutes. The dry film
thickness of the coating film was 40 um.
0.039 (3) Coating Film Adhesion
0040. The coating film adhesion was evaluated according
to a warm-water immersion test. The warm-water immer
Sion test is a method in which a Sample is immersed in warm
water at 50° C. for a predetermined time (24h, 96 h) and the
coating film adhesion is then evaluated. The coating film
adhesion in this occasion was evaluated by the cross-hatch
test method which comprises cross-hatching the coating film
into 100 Squares, 1 mmx1 mm each, pressing a cellophane
tape against the cross-hatched Surface, peeling the tape off as
defined, and counting the remaining coating film Squares.
0041 (4) Measurement of Surface Electrical Resistivity
0042. The surface electrical resistivity was measured by
the two-terminal method. The measurement was made in 9
points per Sample and, among the values found, 7 values to
the exclusion of the maximum and minimum values were
averaged to find Surface resistivity value. For measurements,
a surface electrical resistivity tester (EP-T360, manufactured
by Keyence) was used.
0043 (5) Evaluation of Coat Appearance
0044) The appearance was evaluated visually.
US 2002/0174915 A1 Nov. 28, 2002
4

TABLE 1.
Coated
Uncoated corrosion
corrosion resistance Coating film adhesion
resistance Blister Number of remaining Surface Coat
Uncorroded width coating film squares resistivity appearance
area (%) (mm) 24 h. 96 h (S2) (color)
Ex. 1 70% O 1OO 1OO 0.4 Brown
Ex. 2 80% O 1OO 1OO 1O Reddish brown
Ex. 3 80% O 1OO 1OO 0.4 Pale brown
Compar. Ex. 1 80% O O Very pale brown
Compar. Ex. 2 40% O O White
Ex. 4 80% O 1OO 1OO O1 Pale yellow
Ex. 5 80% O 1OO 1OO O1 Pale brown
Compar. Ex. 3 20% O 1OO 1OO 0.4 Pale gray
Compar. Ex. 4 30% 7 1O 5 O1 Pale yellow
Compar. Ex. 5 50% 2O O O O.08 White

0.045 Except that 75 weight % orthophosphoric acid was Comparative Example 3

added to the same chemical conversion bath as used in
Example 1 while monitoring with a pH meter to bring the pH
to 1.8, the procedure of Example 1 was otherwise repeated
to prepare test pieces and evaluation and measurement were
carried out.
Example 3
0.046 Except that 20 weight % aqueous sodium hydrox
ide Solution was added to the same chemical conversion bath
as used in Example 1 to bring the pH to 6.9, the procedure
of Example 1 was otherwise repeated to prepare test pieces
and evaluation and measurement were carried out.
Comparative Example 1
0047 Except that 20 weight % aqueous sodium hydrox
ide Solution was added to the same chemical conversion bath
as used in Example 1 to bring the pH to 9, the procedure of
Example 1 was otherwise repeated to prepare test pieces and
evaluation and measurement were carried out.
Comparative Example 2
0.048 Except that 20 weight % aqueous sodium hydrox
ide Solution was added to the same chemical conversion bath
as used in Example 1 to bring the pH to 12, the procedure
of Example 1 was otherwise repeated to prepare test pieces
and evaluation and measurement were carried out.
Example 4
0049 Except that, in the pickling step of Example 3, 1
g/L acqueous Sulfuric acid Solution was used as the pickling
bath, the procedure of Example 3 was otherwise repeated to
prepare test pieces and evaluation and measurement were
carried out.
Example 5
0050 Except that, in the pickling step of Example 3, 1
g/L aqueous nitric acid Solution was used as the pickling
bath, the procedure of Example 3 was otherwise repeated to
prepare test pieces and evaluation and measurement were
carried out.
0051 Except that, in the chemical conversion treatment
Step of Example 3, 20 weight % aqueous Sodium hydroxide
Solution was added to 45 g/L acqueous primary Sodium
phosphate Solution while monitoring pH value with a pH
meter to bring the pH of the chemical conversion bath to 6.8
and the resulting bath was used, the procedure of Example
3 was otherwise repeated to prepare test pieces and evalu
ation and measurement were carried out. Here, a chemical
conversion reagent not containing a permanganate ion was
used and this was intended to Verify the effect of a perman
ganate ion.
Comparative Example 4
0052 Except that, in the chemical conversion treatment
Step of Example 3, a reagent comprising 5.5 g/L of the
permanganate ion was used in the absence of a phosphate
ion, the procedure of Example 3 was otherwise repeated to
prepare test pieces and evaluation and measurement were
carried out. This was intended to verify the effect of a
phosphate ion.
Comparative Example 5
0053 Except that the chemical conversion treatment and
Subsequent Step of Washing with water were not performed
among the Steps described in Example 1, the procedure of
Example 1 was otherwise repeated to prepare test pieces and
evaluation and measurement were carried out.
1. A chemical conversion reagent for a magnesium alloy
which comprises a phosphate ion and a permanganate ion
and
has pH of 1.5 to 7.
2. The chemical conversion reagent for a magnesium
alloy according to claim 1
wherein the concentration of a compound Serving as a
Source of the phosphate ion is 20 to 50 g/L and
the concentration of a compound Serving as a Source of
the permanganate ion is 1 to 10 g/L.
US 2002/0174915 A1
5
3. A Surface-treating method
which comprises a Step of bringing the chemical conver-
Sion reagent according to claim 1 or 2 into contact with
a magnesium alloy Substrate.
4. The Surface-treating method according to claim 3
wherein the magnesium alloy Substrate is Subjected to
degreasing, pickling and desmutting treatments in
advance.
Nov. 28, 2002
5. The Surface-treating method according to claim 4
wherein the pickling treatment is carried out with a
reagent containing at least one member Selected from
the group consisting of Sulfuric acid, nitric acid, phos
phoric acid and a fluorine-containing compound.
6. A magnesium alloy Substrate obtainable by the Surface
treating method according to any of claims 3 to 5.
k . . . .