U.S. patent number 3,802,854 [Application Number 05/342,810] was granted by the patent office on 1974-04-09 for process for forming magnetic metal deposits on a flexible base for use as information data carrier product thereof.
This patent grant is currently assigned to Akademie Der Wissenschaften Der DDR. Invention is credited to Helmut Jentsch, Hansjuergen Mueller-Dittmann.
United States Patent |
3,802,854 |
Mueller-Dittmann , et
al. |
April 9, 1974 |
PROCESS FOR FORMING MAGNETIC METAL DEPOSITS ON A FLEXIBLE BASE FOR
USE AS INFORMATION DATA CARRIER PRODUCT THEREOF
Abstract
A metal coated base is passed at a substantially constant speed
through an electrolytic bath formed by a solution of metal salts to
which 2 to 30 g/l of disodium-dihydrogenethylenediaminetetraacetate
has been added and which is at a pH between 2.5 and 6. The metal
coated base is then made the cathode by connecting it to the
negative pole of a current source and the electrolytic deposit is
formed on the metal coated carrier by passing a square wave impulse
current through the bath which has A. a frequency between 2 and 10
Hz; B. an amplitude changing from negative 1 to positive 2 values;
C. a keying ratio t between 2 and 4 and corresponding to the
relationship t = .delta./(T - .delta.) (I) wherein T is the
duration of a period and .delta. is the time during which the
cathode current density is effected within one period; D. an
effective current density (i.sub.W) of 0.5 to 7 A/dm.sup.2 with a
high cathodic current density (i.sub.S ) of at least 10 A/dm.sup.2,
and E. an anodic current density (i.sub.S ) corresponding to the
relationship i.sub.S = (i.sub.S .sup.. .delta./T - i.sub.W)/(1 -
.delta./T) [A/dm.sup.2] (II)
Inventors: |
Mueller-Dittmann; Hansjuergen
(Dresden, DT), Jentsch; Helmut (Freital,
DT) |
Assignee: |
Akademie Der Wissenschaften Der
DDR (Berlin, DL)
|
Family
ID: |
23343367 |
Appl.
No.: |
05/342,810 |
Filed: |
March 19, 1973 |
Current U.S.
Class: |
428/686; 205/103;
205/258; 428/626; 428/928; 204/DIG.9; 205/165; 205/922; 428/668;
428/926; 428/935 |
Current CPC
Class: |
H01F
41/26 (20130101); C25D 5/18 (20130101); C25D
3/562 (20130101); Y10T 428/12986 (20150115); Y10S
428/928 (20130101); Y10T 428/12861 (20150115); Y10S
205/922 (20130101); Y10T 428/12569 (20150115); Y10S
428/935 (20130101); Y10S 428/926 (20130101); Y10S
204/09 (20130101) |
Current International
Class: |
C25D
5/18 (20060101); C25D 3/56 (20060101); C25D
5/00 (20060101); H01F 41/26 (20060101); H01F
41/14 (20060101); C23b 005/32 (); B23p
003/00 () |
Field of
Search: |
;204/DIG.9,43T,43N,43P,44,48,49 ;29/195P |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kaplan; G. L.
Attorney, Agent or Firm: Striker; Michael S.
Claims
What is claimed as new and desired to be protected by Letters
Patent is set
1. The process of making an information data receiving carrier
consisting of a thin metal deposit of high magnetic hardness on a
flexible base, the said process comprising passing a metal-coated
base at a substantially constant speed through an electrolytic bath
formed by a solution of metal salts to which 2 to 30 g/l of
disodiumdihydrogenethylene diaminetetraacetate have been added and
which is at a pH between 2.5 and 6, the metal-coated base
constituting the cathode by connection to the negative pole of a
current source, and forming an electrolytic deposit on said
metal-coated carrier by passing a square wave impulse current
through the bath of
a. a frequency between 2 and 10 Hz;
b. an amplitude changing from negative 1 to positive 2 values;
c. a keying ratio t between 2 and 4 and corresponding to the
relationship
t = .delta./(T - .delta.) (I)
wherein T is the duration of a period and .delta. is the time
during which the cathode current density is effected within one
period;
d. an effective current density (i.sub.W) of 0.5 to 7 A/dm.sup.2
with a high cathodic current density (i.sub.S ) of at least 10
A/dm.sup.2, and
e. an anodic current density (i.sub.S ) corresponding to the
relationship
i.sub.S = (i.sub.S .sup.. .delta./T - i.sub.W)/(1 - .delta./T)
[A/dm.sup.2 ] (II)
2. the process of claim 1 wherein the said metal coating formed in
said electrolytic bath is a cobalt-phosphorus or
cobalt-nickel-phosphorus
3. The process of claim 1 wherein the said flexible base is a
polyester
4. The process of claim 1 wherein the amount of
disodiumdihydrogenethylene
5. The process of claim 1 wherein the electrolyte in said bath is
in the form of a chloride bath and the pH of the bath is adjusted
to about 3.5.
6. The process of claim 1 wherein the electrolyte in said bath is
formed by
7. The process of claim 1 wherein the frequency of said square wave
impulse
9. The process of claim 1 wherein the effective current density is
1.5
10. The process of claim 1 wherein the temperature of the
electrolytic bath
11. The process of claim 10 wherein the temperature of the
electrolytic
12. An information data receiving carrier consisting of a deposit
of a hard magnetic material on a flexible base, the said data
receiving carrier having been made by the process of claim 1.
Description
BACKGROUND OF THE INVENTION
The present invention relates to a process for making thin magnetic
coatings of high magnetic hardness by means of an electrolytic
operation.
A process is known for making hard magnetic metal deposits
particularly of cobalt-phosphorus or cobalt-nickel-phosphorus
composition whereby a metal coating is first applied by vacuum
evaporation or cathode evaporation on a flexible ribbon. The thus
treated flexible ribbon is then made the cathode in a circuit by
connecting it to the negative pole of a direct current source. The
ribbon is moved at a continuous rate of speed through an
electrolytic bath in which solutions of the particular metal salts
constitute the electrolyte. The hard magnetic metal deposit is
formed on the metal coated flexible ribbon by the action of the
direct current.
However, the hard magnetic metal deposits made by this process
possess a comparatively low magnetic hardness. The maximum
obtainable coercive force is about 800 Oe. The ratio of remanence
induction to saturation induction is at best 0.6. With these
magnetic materials it is possible only to obtain a low information
data density on these deposits.
It is therefore an object of the present invention to increase the
maximum data density on hard magnetic metal deposits. More
specifically the invention has the object to provide for a process
for making thin hard magnetic metal deposits on a flexible base
which are characterized by a high coercive force and high
remanence.
SUMMARY OF THE INVENTION
According to the invention a metal-coated base is moved at a
substantially constant speed through an electrolytic bath formed by
a solution of metal salts to which 2 to 30 g/l of
disodiumdihydrogenethylene diaminetetraacetate have been added and
which is at a pH between 2.5 and 6. The metal coated base is then
made the cathode by connecting it to the negative pole of a current
source. The electrolyte deposit is formed on the metal-coated
carrier by passing a square wave impulse current through the bath,
said current having
a. a frequency between 2 and 10 Hz;
b. an amplitude changing from negative 1 to positive 2 values;
c. a keying ratio t between 2 and 4 and corresponding to the
relationship
t = .delta./(T - .delta.) (I)
wherein T is duration of period and .delta. is the time during
which the cathode current density is effective within one
period;
d. an effective current density (i.sub.W) of 0.5 to 7 A/dm.sup.2
with a high cathode current density (i.sub.S ) of at least 10
A/dm.sup.2 ; and
e. an anodic current density (i.sub.S ) corresponding to the
relationship
i.sub.S = (i.sub.S .sup.. .delta./T - i.sub.W)/(1 - .delta./T)
[A/dm.sup.2 ] (II)
BRIEF DESCRIPTION OF THE DRAWING
The drawing illustrates the square wave of the impulse current
employed in the method of the invention.
DETAILS OF THE INVENTION AND PREFERRED EMBODIMENT
The impulse current employed in the method of the invention causes
a switching between cathodic deposit formation and anodic deposit
removal resulting in a finely crystalline coating which meets the
requirements for obtaining desirable magnetic properties in the
plane of the deposit. By changing the frequency, the keying ratio
and the effective or the cathodic current density it is possible to
affect the character of the deposit formation. Depending on the
intended use of the thin hard magnetic coating it is possible to
obtain maximum values for the cohercive force or for the remanence
ratio or an optimum of both parameters.
In carrying out the process of the invention it is preferred to add
10 g/l of disodiumdihydrogenethylene-diaminetetraacetate to the
electrolyte and to adjust the pH in case of a chloride bath to 3.5
and in case of a sulfate bath to 5.5. The operation is preferably
carried out at a frequency of 4 Hz and a keying ratio of 3 and an
effective current density of 1.5 A/dm.sup.2. It is of advantage to
proceed at a temperature of the electrolytic bath between
15.degree. and 30.degree.C and preferably at a temperature of
22.degree.C.
The process of the invention permits obtaining thin hard metal
coatings having a cohercive force > 1,500 Oe and a remanence
ratio > 0.7 and to accomplish this is an economical way. The
process of the invention also permits to obtain cobalt-tungsten or
cobalt-nickel-tungsten composition type deposits.
For the deposit formation either metal chloride or metal sulfate
salts are useful.
A particular advantage of the process is that the electrolysis can
be carried out at room temperature and that therefore an additional
heating of the electrolyte is not necessary.
The process of the invention can also be used for making
bilaterally coated flexible carriers.
The following example will further illustrate the invention. A
polyester ribbon which was provided on one face with a copper
coating and had a width of one-quarter inch was placed in an
electrolytic bath and connected as the cathode to the negative pole
of a current source. The electrolyte had the following
composition:
100 g/l CoSO.sub.4 .sup.. 7H.sub.2 O
50 g/l NiSO.sub.4 .sup.. 7H.sub.2 O
30 g/l NaH.sub.2 PO.sub.2 .sup.. H.sub.2 O
25 g/l (NH.sub.4).sub.2 SO.sub.4
10 g/l disodiumdihydrogenethylene diaminetetraacetate ("Komplexon
III").
The salts employed in this composition were all of the highest
purity. The temperature was adjusted to 20.degree.C. The pH value
of the bath was set for 5.5. The current source was constituted by
an electronically stabilized currents producing apparatus which
produced square wave negative 1 and positive 2 impulses. The
impulse current had a frequency of 4 Hz and a keying ratio of 4:1.
As an effective current density (i.sub.W) 1.5 A/dm.sup.2 and as the
cathodic current density (i.sub.S ) 10.5 A/dm.sup.2 were selected.
According to the Equation II found in the abstract and in claim 1
this resulted in an anodic current density (i.sub.S ) of 34.5
A/dm.sup.2.
After switching on the impulse current the ribbon was passed at a
constant speed of 23.4 cm/min through the bath.
The operation resulted in the deposit of a cobalt-nickel-phosphorus
layer on the copper base of a thickness of 0.1 .mu.m. This layer
had a cohercive force of 1,530 Oe and a remanence ratio of
0.76.
If the electrolyte was used under otherwise the same conditions
with a direct current a deposit was formed which had only a
cohercive force of 800 Oe at a remanence ratio of 0.6.
Without further analysis, the foregoing will so fully reveal the
gist of the present invention that others can by applying current
knowledge readily adapt it for various applications without
omitting features that, from the standpoint of prior art, fairly
constitute essential characteristics of the generic or specific
aspects of this invention and, therefore, such adaptations should
and are intended to be comprehended within the meaning and range of
equivalence of the following claims.
* * * * *