U.S. patent number 3,861,031 [Application Number 05/465,992] was granted by the patent office on 1975-01-21 for method of making a moisture-sensitive element.
This patent grant is currently assigned to Rikagaku Kenkyusho. Invention is credited to Akio Furuichi.
United States Patent |
3,861,031 |
Furuichi |
January 21, 1975 |
METHOD OF MAKING A MOISTURE-SENSITIVE ELEMENT
Abstract
Disclosed is a method of making a moisture-sensitive element
having an increased sensitivity to humidity with minimum secular
variation of electric characteristics. The method comprises the
steps of subjecting an aluminum matrix to electrolytic treatment to
produce a film of aluminum oxide on the matrix, removing the film
from the matrix, heat treating the film, and attaching electrodes
to opposite surfaces of the film.
Inventors: |
Furuichi; Akio (Kamifukuoka,
JA) |
Assignee: |
Rikagaku Kenkyusho (Hirosawa,
Wako-shi-Saitama-ken, JA)
|
Family
ID: |
23850007 |
Appl.
No.: |
05/465,992 |
Filed: |
May 1, 1974 |
Current U.S.
Class: |
29/610.1;
148/285; 205/67; 338/35; 29/621; 200/61.04; 216/101 |
Current CPC
Class: |
G01N
27/121 (20130101); Y10T 29/49101 (20150115); Y10T
29/49082 (20150115) |
Current International
Class: |
G01N
27/12 (20060101); H01c 017/00 () |
Field of
Search: |
;29/610,621,620 ;338/35
;200/61.04 ;204/33,37R ;117/213,227,230 ;156/22 ;148/6.27,6.3 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lanham; C. W.
Assistant Examiner: DiPalma; Victor A.
Claims
What is claimed is:
1. A method of making a moisture-sensitive element comprising the
steps of: subjecting an aluminium matrix to electrolytic treatment
to produce a porous film of aluminium oxide on said matrix;
removing said aluminium oxide film from said matrix; subjecting
said aluminum oxide film to a heat treatment; and attaching metal
electrodes to the opposite surfaces of said aluminium oxide
film.
2. A method of making a moisture-sensitive element according to
claim 1 wherein it further comprises the steps of subjecting said
aluminium oxide film to a hot water treatment as a subsequent to
said heat treatment.
3. A method of making a moisture-sensitive element according to
claim 1 wherein said heat treatment is conducted at 900.degree. C
or higher temperature.
4. A method of making a moisture-sensitive element according to
claim 2 wherein said hot water treatment includes exposing said
aluminium oxide film to steam and soaking said aluminium oxide film
in boiling water.
5. A method of making a moisture-sensitive element according to
claim 1 wherein said electrolytic treatment is anodic
oxidation.
6. A method of making a moisture-sensitive element according to
claim 1 wherein an aqueous solution of mercuric chloride or
methanol solution of bromide or iodine is used to remove said
aluminium oxide film from said aluminium matrix.
Description
This invention relates to a method of making a moisture-sensitive
element essentially consisting of a porous film of aluminium oxide
having electrodes thereon and particularly to a method of making
such electroded humidity sensor whose sensitivity to moisture will
now lower with time.
In producing the humidity sensor of the character mentioned above,
a porous aluminum oxide film is formed on an aluminum matrix or
body by subjecting the aluminum matrix to anodic oxidation in an
electrolytic bath of oxalic acid, sulfuric acid, cromic acid or any
other acid which is proper for the purpose. A moisture-permeative
electrode is formed on the aluminium oxide film by vacuum
evaporating or sputtering. Thus, a moisture detecting device
consists of a composite of "moisture pervious electrode-porous film
of aluminium oxide-aluminium." Such moisture detector is shown in
U.S. Pat. Nos. 3,440,372 and 3,574,681. It is very sensitive, and
quick in response. However, disadvantageously it takes a relatively
long period (ranging from a few months to 1 year) before a new
device after produced, has reached a stable condition after the
termination of inherent secular variation. More specifically, the
impedance of the device tends to rise with time. The rise rate
depends on the surrounding humidity. As the surrounding moisture
increases, the impedance of the element rises at an increased
rate.
The X-ray diffraction image of the porous film of aluminium oxide
appears as undefined spread pattern rather than a definite and
well-defined line. From this it appears that the aluminium oxide
film be composed of very minute crystals, and specifically of those
of .gamma.-alumina and/or .gamma.'-alumina.
It appears to the inventor that the cause for secular variation of
the electric characteristics is that: .gamma.-alumina or
.gamma.'-alumina is hydrated by water in the surrounding air so
that the moisture-sorption capability is changed. It is well known
that hydrated alumina when heated at an ever increasing
temperature, will be changed first, to .gamma.-alumina at
500.degree. C and higher temperatures, and then it will be again
changed to .delta.-alumina, .theta.-alumina and finally to
.alpha.-alumina in the order given at 900.degree. C and higher
temperatures.
This invention is based on those facts above mentioned, and the
object of this invention is to provide a method of producing an
electroded moisture detector essentially composed of an aluminium
oxide film with minimum secular variation.
To attain this object there is provided a method according to this
invention essentially comprising the steps of: subjecting an
aluminum matrix to electrolytic treatment to produce an aluminium
oxide film on said matrix; removing said aluminium oxide film from
said matrix; subjecting said aluminium oxide film to a heat
treatment; and attaching metal electrodes to the opposite surfaces
of said aluminium oxide film.
This invention will be better understood from the following
description which is made with reference to the accompanying
drawing which shows the secular variation of admittance of
different moisture detector elements produced according to the
teaching of the invention. An aluminium matrix is subjected to the
anodic oxidation in an electrolytic bath of oxalic acid, sulfuric
acid or other acids which are proper for the purpose. As a result
an aluminium oxide film is formed on the aluminium matrix. The
heating process is performed at a temperature higher than the
melting point of aluminium. Therefore preferably the aluminium
oxide film is removed from the matrix, and the aluminium oxide foil
thus removed is subjected to heat treatment.
Speaking of the aluminium oxide film a barrier layer is formed on
the matrix, and a porous film of aluminium oxide is formed on the
barrier layer. Either a single layer of aluminium oxide of a
composite layer of aluminium oxide plus barrier layer can be
equally used. Therefore, the words, "aluminium oxide film" herein
used should be understood as an aluminium oxide film with or
without associated barrier layer. For example, an aqueous solution
of mercuric chloride or methanol solution of bromide or iodine may
be used as solvent for aluminium matrix. An aluminium oxide film is
subjected to heat treatment, and finally a pair of electrodes of
metal, such as gold or aluminium are attached to the opposite sides
of the aluminium oxide film. Thus, a moisture detector element
results.
If the aluminium oxide film is heated at a temperature lower than
900.degree. C, film is of .gamma.-alumina, and the
moisture-sensitive element using such aluminium oxide film shows
the same tendency of secular variation as found in the element
using an aluminium oxide film which is not subjected to heat
treatment.
If the aluminium oxide film is heated at an elevated temperature
higher than 900.degree. C, it is of .delta.-alumina or
.theta.-alumina, and the moisture-sensitive element having an
aluminium oxide film thus baked showes the substantial improvement
in secular variation of electric characteristics, compared with the
element having an aluminium oxide film which was not subjected to
heat treatment. If the aluminium oxide film is heated at
1,200.degree. C or higher temperature, it is of .alpha.-alumina,
and a moisture detector having an aluminium oxide film thus
modified is almost free from secular variation.
After an aluminium oxide film was subjected to the heat treatment
at 900.degree. C or higher temperature according to this invention,
it is boiled or exposed to water vapour or steam. The inventor
found that the moisture-sensitive element having an aluminium oxide
film thus treated showed the same improvement as the element having
an aluminium oxide film baked at 1,200.degree. C or higher
temperature. As seen from this, the hot water treatment is
effective to allow the aluminium oxide film to reach the permanent
and stable condition ion a possible minimum time. This is contrary
to that found in boiling an aluminium oxide film without heat
treatment. In this case the pores of the aluminium oxide film are
sealed, thus losing the sensitivity to moisture.
EXAMPLE 1
An aluminium oxide film as thick as 20 microns was produced on an
aluminium matrix sheet as thick as 0.3 milimeters by subjecting the
sheet to anodic oxidation in an oxalic acid bath of 0.3 percent
concentration at a current density equal to 1
ampere/square-decimeter. The aluminium oxide film thus produced was
removed from the aluminium sheet by dissolving the sheet in a
methanol solution of iodine. The size of the aluminium oxide film
thus obtained was about 1 .times. 1 cm.sup.2. The aluminium oxide
film was heated at 1,000.degree. C for 1 hour, and then a pair of
gold electrodes were applied to the opposite surfaces of the
aluminium oxide film by vapourizing the metal onto the aluminium
oxide film. The drawing shows the secular variation of the
admittance of a moisture-sensitive element at a relative humidity
of 80 percent. The admittance is given in terms of the ratio of the
instantaneous value to the initial one. The curve 1 shows the
secular variation of the element using an aluminium oxide film
which was heated at 800.degree. C. The curve II shows the secular
variation of the moisture-sensitive element according to this
invention. This graph shows substantial reduction of secular
variation attained by this invention.
EXAMPLE 2
An aluminium oxide film was produced on an aluminium substrate and
removed therefrom in a similar way to Example 1. The aluminium
oxide film thus obtained was heated at 1,200.degree. C for 1 hour.
Then, gold was vapour-deposited onto the opposite surfaces of the
aluminium oxide film. Curve III shows the secular variation of a
moisture-sensitive element having such aluminium oxide film.
EXAMPLE 3
An aluminium oxide film was prepared in a similar way to Example 1.
The aluminium oxide film was heated at 1,000.degree. C for 1 hour,
and then soaked in the boiling water. Curve III shows the secular
variation of a moisture detector having such aluminium oxide
film.
Also, curve III shows the secular variation of a detector using an
aluminium oxide film which was subjected to a heat treatment at an
elevated temperature (1,200.degree. C). Therefore, this curve shows
that the aluminium oxide film which was heated at a relatively low
temperature (1,000.degree. C) will be improved, by subjecting it to
a boiling water or steam treatment, to the same degree as found in
the aluminium oxide film which was heated at a relatively high
temperature (1,200.degree. C). The aluminium oxide film which was
subjected to a heat treatment at a relatively low temperature is
more sensitive to humidity than the aluminium oxide film which was
subjected to a heat treatment at a relatively high temperature.
Thus, according to Example 3 there is provided a moisture-sensitive
element having an increased sensitivity with minimum secular
variation.
* * * * *