U.S. patent application number 13/905305 was filed with the patent office on 2013-10-03 for titanium or titanium alloy-and-resin composite and method for making the same.
The applicant listed for this patent is CHENG-SHI CHEN, HUANN-WU CHIANG, YUAN-YUAN FENG, DAI-YU SUN, YU-QIANG WANG. Invention is credited to CHENG-SHI CHEN, HUANN-WU CHIANG, YUAN-YUAN FENG, DAI-YU SUN, YU-QIANG WANG.
Application Number | 20130256141 13/905305 |
Document ID | / |
Family ID | 47194282 |
Filed Date | 2013-10-03 |
United States Patent
Application |
20130256141 |
Kind Code |
A1 |
CHIANG; HUANN-WU ; et
al. |
October 3, 2013 |
TITANIUM OR TITANIUM ALLOY-AND-RESIN COMPOSITE AND METHOD FOR
MAKING THE SAME
Abstract
A method for making a titanium-and-resin composite or titanium
alloy-and-resin composite includes: providing a titanium or
titanium alloy substrate; electrochemically treating the substrate
to form a titanium hydride layer; anodizing the substrate having
the titanium hydride layer to form an nano-porous oxide film on the
surface of the substrate, the nano-porous oxide film having nano
pores and comprising at least two layers of different porosity or
pore diameters; and inserting the substrate in a mold and melting
resin on the surface of the nano-porous oxide film to form the
composite.
Inventors: |
CHIANG; HUANN-WU; (New
Taipei, TW) ; CHEN; CHENG-SHI; (New Taipei, TW)
; SUN; DAI-YU; (Shenzhen, CN) ; FENG;
YUAN-YUAN; (Shenzhen, CN) ; WANG; YU-QIANG;
(Shenzhen, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CHIANG; HUANN-WU
CHEN; CHENG-SHI
SUN; DAI-YU
FENG; YUAN-YUAN
WANG; YU-QIANG |
New Taipei
New Taipei
Shenzhen
Shenzhen
Shenzhen |
|
TW
TW
CN
CN
CN |
|
|
Family ID: |
47194282 |
Appl. No.: |
13/905305 |
Filed: |
May 30, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13293507 |
Nov 10, 2011 |
8475913 |
|
|
13905305 |
|
|
|
|
Current U.S.
Class: |
205/112 |
Current CPC
Class: |
C25D 11/26 20130101;
C25D 11/02 20130101; C09D 177/00 20130101; Y10T 428/2495 20150115;
B29C 45/14778 20130101; B29C 45/14311 20130101; Y10T 428/24998
20150401; Y10T 428/24959 20150115; B29K 2705/00 20130101; Y10T
442/10 20150401; Y10T 428/24942 20150115; C08L 77/00 20130101 |
Class at
Publication: |
205/112 |
International
Class: |
C25D 11/02 20060101
C25D011/02 |
Foreign Application Data
Date |
Code |
Application Number |
May 24, 2011 |
CN |
2011101353280 |
Claims
1. A method for making a titanium or titanium alloy-and-resin
composite, comprising: providing a titanium or titanium alloy
substrate; electrochemically treating the substrate to form a
titanium hydride layer on a surface thereof; anodizing the
substrate having the titanium hydride layer to form an nano-porous
oxide film on the surface of the substrate, the nano-porous oxide
film having nano pores and comprising at least two layers of
different porosity or pore diameters; and inserting the substrate
in a mold and melting resin on the surface of the nano-porous oxide
film to form the composite.
2. The method as claimed in claim 1, wherein electrochemically
treating the substrate is carried out in an acid water solution
containing sulfuric acid for about 1-10 minutes with the substrate
being a cathode, the molar concentration of the sulfuric acid is
about 0.5 mol/L-2 mol/L, the electric current density through the
acid water solution is about 0.1 A/dm.sup.2-5 A/dm.sup.2.
3. The method as claimed in claim 2, wherein the titanium hydride
layer has a thickness of about 80 nm-120 nm and a surface roughness
of about 0.3 .mu.m-0.5 .mu.m.
4. The method as claimed in claim 1, wherein anodizing the
substrate is carried out in an alkaline water solution containing
sodium hydroxide for about 1 minute-10 minutes with the substrate
being an anode, the mol concentration of the sodium hydroxide is
about 4.5 mol/L-5.5 mol/L, the electric current density through the
alkaline water solution is about 1 A/dm.sup.2-30 A/dm.sup.2.
5. The method as claimed in claim 1, wherein the resin is
crystalline thermoplastic synthetic resin.
6. The method as claimed in claim 5, wherein the crystalline
thermoplastic synthetic resin is polyphenylene sulfide or
polyamide.
7. The method as claimed in claim 5, wherein the crystalline
thermoplastic synthetic resin is polyphenylene sulfide added with
fiberglass, the fiberglass has a mass percentage of about 30% with
regard to the polyphenylene sulfide and the fiberglass.
8. The method as claimed in claim 1, wherein the nano-porous oxide
film is titanium dioxide film.
9. The method as claimed in claim 1, wherein the at least two
layers comprising an inner layer near the substrate and a surface
layer away from the substrate, the inner layer comprising nano
pores having a pore diameter at a range of about 20 nm-50 nm, the
surface layer comprising nano pores having a pore diameter at a
range of about 100 nm-150 nm.
10. The method as claimed in claim 9, wherein the nano-porous oxide
film has a total thickness of about 300 nm-500 nm, the surface
layer has a thickness of about 80 nm-120 nm.
11. The method as claimed in claim 9, wherein the resin composition
fills the nano-pores of the inner layer and the surface layer.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional application of U.S. Ser.
No. 13/293507, filed Nov. 10, 2011, the contents of which are
hereby incorporated by reference. The patent application Ser. No.
13/293507 in turn claims the benefit of priority under 35 USC 119
from Chinese Patent Application 201110135328.0, filed on May 24,
2011.
[0002] This application is one of the two related co-pending U.S.
patent applications listed below. All listed applications have the
same assignee. The disclosure of each of the listed applications is
incorporated by reference into another listed application.
TABLE-US-00001 Attorney Docket No. Title Inventors US 39535
TITANIUM OR TITANIUM ALLOY- HUANN-WU AND-RESIN COMPOSITE AND CHIANG
et al. METHOD FOR MAKING THE SAME US 39536 TITANIUM OR TITANIUM
ALLOY- CHENG-SHI AND-RESIN COMPOSITE AND CHENN et al. METHOD FOR
MAKING THE SAME
BACKGROUND
[0003] 1. Technical Field
[0004] The present disclosure relates to titanium or titanium
alloy-and-resin composites, particularly to a titanium or titanium
alloy-and-resin composite having high bonding strength between
titanium or titanium alloy and resin, and a method for making the
composite.
[0005] 2. Description of Related Art
[0006] Adhesives, for combining heterogeneous materials in the form
of a metal and a synthetic resin are in demand in a wide variety of
technical fields and industries, such as the automotive and
household appliance fields. However, the bonding strength of metal
and resin is weak. Furthermore, adhesives are generally only
effective in a narrow temperature range of about -50.degree. C. to
about 100.degree. C., which means they are not suitable in
applications where operating or environmental temperatures may fall
outside the range. Due to the above, other bonding methods have
been applied that do not involve the use of an adhesive. One
example of such methods is by forming bonds through injection
molding or other similar process. However, the bonding strength of
the metal and resin can be further improved.
[0007] Therefore, there is room for improvement within the art.
BRIEF DESCRIPTION OF THE FIGURES
[0008] Many aspects of the disclosure can be better understood with
reference to the following figures. The components in the figures
are not necessarily drawn to scale, the emphasis instead being
placed upon clearly illustrating the principles of the disclosure.
Moreover, in the drawings, like reference numerals designate
corresponding parts throughout the several views.
[0009] FIG. 1 is a cross-sectional view of an exemplary embodiment
of a titanium or titanium alloy-and-resin composite.
[0010] FIG. 2 is a scanning electron microscope view of an
exemplary embodiment of a titanium or titanium alloy substrate
being anodized.
[0011] FIG. 3 is a cross-sectional view of an exemplary embodiment
of a titanium or titanium alloy substrate being electrochemically
treated.
[0012] FIG. 4 is a cross-sectional view of a mold of the composite
shown in FIG. 1.
DETAILED DESCRIPTION
[0013] FIG. 1 shows a titanium-and-resin composite or titanium
alloy-and-resin composite (composite 100) according to an exemplary
embodiment. The composite 100 includes a titanium or titanium alloy
substrate 11, a nano-porous oxide film 12 formed on the substrate
11, and resin compositions 13 formed on the nano-porous oxide film
12.
[0014] The nano-porous oxide film 12 is titanium dioxide film. In
this embodiment, the nano-porous oxide film 12 is formed by
electrochemically treating the substrate 11 first, and then
anodizing the substrate 11.
[0015] Referring to FIG. 2, the nano-porous oxide film 12 defines
nano-pores 125. Referring also to FIG. 1, the nano-porous oxide
film 12 includes at least two layers of different three-dimensional
meshed structures. The two layers are an inner layer 121 near to
the substrate 11 and a surface layer 123 far from the substrate 11.
The nano-porous oxide film 12 has a total thickness of about 300
nm-500 nm, and the surface layer 123 has a thickness of about 80
nm-120 nm. The nano-pores of the inner layer 121 and the nano-pores
of the surface layer 123 have different pore diameters. The pore
diameter of the nano-pores of the inner layer 121 may be in a range
of about 20 nm-50 nm. The pore diameter of the nano-pores of the
surface layer 123 may be in a range of about 100 nm-150 nm.
[0016] The resin compositions 13 may be coupled to the surface of
the nano-porous oxide film 12 by molding. During the molding
process, molten resin coats the surface of the nano-porous oxide
film 12 and fills the nano-pores 125, thus strongly bonding the
resin compositions 13 to the nano-porous oxide film 12 and the
substrate 11. Compared to the conventional injection molding
process in which the titanium or titanium alloy substrate is not
electrochemically treated and anodized, the composite 100 in this
exemplary embodiment has a much stronger bond between the resin
compositions 13 and the substrate 11 (about five times the bonding
force). The resin compositions 13 may be made up of crystalline
thermoplastic synthetic resins having high fluidity. In this
exemplary embodiment, polyphenylene sulfide (PPS) and polyamide
(PA) can be selected as the molding materials for the resin
compositions 13. These resin compositions 13 can bond firmly with
the nano-porous oxide film 12 and the substrate 11.
[0017] Auxiliary components may be added to the resins to modify
properties of the resin compositions 13, for example, fiberglass
may be added to the PPS. The fiberglass may have a mass percentage
of about 30% with regard to the PPS and the fiberglass.
[0018] A method for making the composite 100 may include the
following steps:
[0019] The titanium or titanium alloy substrate 11 is provided.
[0020] The substrate 11 is ultrasonically cleaned using anhydrous
ethanol and acetone in that order, and then rinsed.
[0021] The substrate 11 is electrochemically treated. The
electrochemical treating process may be carried out in an acid
water solution containing sulfuric acid, or an acid water solution
of sulfuric acid, with the substrate 11 being a cathode, and a
stainless steel board being an anode. The sulfuric acid may have a
molar concentration of about 0.5 mol/L-2 mol/L. The electric
current density through the acid water solution is about 0.1 ampere
per square decimeter (A/dm.sup.2)-5 A/dm.sup.2. Electrochemically
treating the substrate 11 may last for about 1 minute-10 minutes.
Once electrochemically treated, a titanium hydride (TiH.sub.2)
layer 14 is formed on the substrate 11 (referring to FIG. 3). The
titanium hydride layer 14 has a thickness of about 80 nm-120 nm,
and a surface roughness (Ra) of about 0.3 .mu.m-0.5 .mu.m. Next,
the substrate 11 having the titanium hydride layer 14 is rinsed in
water and dried.
[0022] The substrate 11 having the titanium hydride layer 14 is
anodized to form the nano-porous oxide film 12. The anodizing
process may be carried out in an alkaline water solution containing
sodium hydroxide (NaOH), or an alkaline water solution of sodium
hydroxide, with the substrate 11 being an anode, and a stainless
steel board being a cathode. The sodium hydroxide may have a molar
concentration of about 4.5 mol/L-5.5 mol/L. The electric current
density through the alkaline water solution is about 1-30
A/dm.sup.2. Anodizing the substrate 11 may last for about 1
minute-10 minutes. Once anodized, the nano-porous oxide film 12 is
formed on the substrate 11. Next, the substrate 11 having the
nano-porous oxide film 12 is rinsed in water and dried.
[0023] During the anodizing process, the titanium hydride layer 14
is first converted to titanium dioxide and forms the surface layer
123 of the nano-porous oxide film 12. When the titanium hydride
layer 14 is completely converted to titanium dioxide, the anodizing
process is continued on the substrate 11 and forms the inner layer
121 of the nano-porous oxide film 12.
[0024] In the exemplary embodiment, the electrochemical treating
process and the anodizing process are all carried out at a room
temperature, that is, the acid and the alkaline water solutions are
not heated.
[0025] The thickness of the titanium hydride layer 14 in this
embodiment is only an example. The thickness of the titanium
hydride layer 14 can be changed by adjusting the concentration of
the acid water solution, the electric current density, and the
duration time of the electrochemical treating process.
[0026] The structure and relative characters of the nano-porous
oxide film 12 in this embodiment is only an example. The structure
and the characters of the nano-porous oxide film 12 can be changed
by adjusting the concentration of the alkaline water solution, the
electric current density, and the duration time of the anodizing
process.
[0027] The thicknesses of the inner layer 121 and the surface layer
123 of the nano-porous oxide film 12, and the pore diameter of the
nano pores 125 can be changed by adjusting the parameters of the
electrochemical treating process and the anodizing process.
Furthermore, by adjusting the treatment parameters, a nano-porous
oxide film having more than two layers of different three
dimensional meshed structures can also be obtained.
[0028] Referring to FIG. 4, an injection mold 20 is provided. The
injection mold 20 includes a core insert 23 and a cavity insert 21.
The core insert 23 defines several gates 231, and several first
cavities 233. The cavity insert 21 defines a second cavity 211 for
receiving the substrate 11. The substrate 11 having the nano-porous
oxide film 12 is located in the second cavity 211, and
molten/melted resin is injected through the gates 231 to coat the
surface of the nano-porous oxide film 12 and fill the nano-pores
125, and finally to fill the first cavities 233 to form the resin
compositions 13, as such, the composite 100 is formed. The molten
resin may be crystalline thermoplastic synthetic resins having high
fluidity, such as PPS, or PA.
[0029] The shear strength of the composite 100 has been tested. The
tests indicated that the shear strength of the composite 100 was 19
MPa-27 MPa. Furthermore, the composite 100 was subjected to a
temperature humidity bias test (72 hours, 85.degree. C., relative
humidity: 85%) and a thermal shock test (48 hours, -40.degree.
C.-85.degree. C., 4 hours/cycle, 12 cycles total), such testing did
not result in decreased shear strength of the composite 100.
[0030] It is believed that the exemplary embodiment and its
advantages will be understood from the foregoing description, and
it will be apparent that various changes may be made thereto
without departing from the spirit and scope of the disclosure or
sacrificing all of its advantages, the examples hereinbefore
described merely being preferred or exemplary embodiment of the
disclosure.
* * * * *