U.S. patent application number 14/095746 was filed with the patent office on 2015-06-04 for preparation of modified organic core materials and metallic shell composite microspheres.
The applicant listed for this patent is Chung-Shan Institute of Science and Technology. Invention is credited to Chan-Yuan Ho, Kuan-Ju Lin, Wenjea J. Tseng, Hong-Mao Wu, Yi-Hsiuan Yu.
Application Number | 20150152560 14/095746 |
Document ID | / |
Family ID | 53264875 |
Filed Date | 2015-06-04 |
United States Patent
Application |
20150152560 |
Kind Code |
A1 |
Yu; Yi-Hsiuan ; et
al. |
June 4, 2015 |
Preparation of Modified Organic Core Materials and Metallic Shell
Composite Microspheres
Abstract
The present invention relates to a preparation of modified
organic core materials and metallic shell composite microspheres,
in which, the surface zeta potential of an organic core materials
can attract the opposite zeta potential of the polyelectrolyte and
form a polyelectrolyte layer so as to modify the surface of organic
core materials. Moreover, the polyelectrolyte layer could attract a
first metal ions, particles or complexes added later in suitable
condition such that the surface of organic core materials could be
metallized and covered with a first metal layer. Furthermore, the
organic core materials could be covered with at least one surface
metal layer. The first metal layer can be modified by second metal
layer with redox-transmetalation.RTM. technology to obtain
multi-metal layers organic-metallic composite structure.
Inventors: |
Yu; Yi-Hsiuan;
(Longtan/Taoyuan, TW) ; Lin; Kuan-Ju; (Taichung
City, TW) ; Wu; Hong-Mao; (Taichung City, TW)
; Ho; Chan-Yuan; (Hsinchu, TW) ; Tseng; Wenjea
J.; (Taichung City, TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Chung-Shan Institute of Science and Technology |
Longtan/Taoyuan |
|
TW |
|
|
Family ID: |
53264875 |
Appl. No.: |
14/095746 |
Filed: |
December 3, 2013 |
Current U.S.
Class: |
427/404 ;
427/443.1 |
Current CPC
Class: |
C23C 18/1658 20130101;
C23C 18/1635 20130101; C23C 18/2086 20130101; C23C 18/1651
20130101; C23C 18/32 20130101; C23C 18/54 20130101; C23C 18/42
20130101 |
International
Class: |
C23C 18/34 20060101
C23C018/34; C23C 18/44 20060101 C23C018/44; C23C 18/16 20060101
C23C018/16 |
Claims
1. A preparation of modified organic core materials and metallic
shell composite microspheres, comprising steps of: (1) adding an
organic substrate 1 into a solvent to obtain a slurry; (2) adding a
first polyelectrolyte 2 into the slurry, wherein the zeta potential
of the first polyelectrolyte 2 is opposite to the surface zeta
potential of the organic substrate 1; (3) adding a second
polyelectrolyte 3 into the slurry, wherein the zeta potential of
the second polyelectrolyte 3 is opposite to the zeta potential of
the first polyelectrolyte 2; (4) adding a first metal compound 4
into the slurry; and (5) adding a reductant 5 into the slurry for
making the first metal compound 4 be metalized, so as to form a
first metal layer 6 on the surface of the organic substrate 1.
2. The preparation of modified organic core materials and metallic
shell composite microspheres of claim 1 further comprises the steps
of: (6) adding a second metal compound 7 into the slurry; and (7)
the first metal layer 6 being modified to a second metal layer 8
after occurring an ion exchange spontaneously between the second
metal compound 7 and the first metal compound 4 of the first metal
layer 6 through redox-transmetalation.
3. The preparation of modified organic core materials and metallic
shell composite microspheres of claim 2, wherein the surface of
organic substrate 1 is covered with at least one metal layer.
4. The preparation of modified organic core materials and metallic
shell composite microspheres of claim 1, wherein the solvent is
water.
5. The preparation of modified organic core materials and metallic
shell composite microspheres of claim 1, wherein the first
polyelectrolyte 2 and the second polyelectrolyte 3 are selected
from the group consisting of: Poly (allylamine hydrochloride)
(PAH), Poly (diallyldimethylammonium chloride) (PDDA), Poly
(acrylic acid) (PAA), and Poly (styrene sulfonate) (PSS).
6. The preparation of modified organic core materials and metallic
shell composite microspheres of claim 1, wherein the organic
substrate 1 is an organic material with polyester functional
group.
7. The preparation of modified organic core materials and metallic
shell composite microspheres of claim 6, wherein the organic
material is Polymethylmethacrylate.
8. The preparation of modified organic core materials and metallic
shell composite microspheres of claim 1, wherein the first metal
compound 4 and the second metal compound 7 are selected from the
group consisting of: metal ion, metal particles and metal
complexes.
9. The preparation of modified organic core materials and metallic
shell composite microspheres of claim 8, wherein aforesaid metal
ion is selected from the group consisting of: Ni ion and Au
ion.
10. The preparation of modified organic core materials and metallic
shell composite microspheres of claim 8, wherein aforesaid metal
particles are selected from the group consisting of: Ni particles
and Au particles.
11. The preparation of modified organic core materials and metallic
shell composite microspheres of claim 8, wherein aforesaid metal
complexes are selected from the group consisting of: Ni complexes
and Au complexes.
12. The preparation of modified organic core materials and metallic
shell composite microspheres of claim 1, wherein the reductant 5 is
selected from the group consisting of: Dimethylamine borane (DMAB)
and NaBH.sub.4.
13. The preparation of modified organic core materials and metallic
shell composite microspheres of claim 1, wherein the thickness of
the first metal layer 6 and the second metal layer 8 is ranged from
50 nm to 250 nm.
14. The preparation of modified organic core materials and metallic
shell composite microspheres of claim 1, wherein the organic
substrate 1 is a microsphere having a diameter ranged from 200 nm
to 8 .mu.m.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an electroless plating
method, and more particularly, to a preparation of modified organic
core materials and metallic shell composite microspheres.
[0003] 2. Description of the Prior Art
[0004] Conventional methods of electroless plating in general
perform the following procedure:
[0005] Step 1: Roughening: using chromic acid to wash the surface
of polymeric materials;
[0006] Step 2: Sensitizing: adding stannous chloride or copper
chloride to sensitize the surface of polymeric materials;
[0007] Step 3: after covering the surface of polymeric materials
with Sn, Cu, etc. ions, adding the precursor solution of noble
metal (e.g., palladium chloride); and
[0008] Step 4: depositing the metal Ni, Ag, Au, Co, Cu, etc. by
electroless plating.
[0009] Moreover, another conventional method for electroless
plating can be performed the following procedure:
[0010] Step 1: Polystyrene microspheres adsorb an ion
absorbent;
[0011] Step 2: adding the aforesaid polystyrene microspheres into
palladium sulfate solution to let the surface of polymeric
microspheres cover with palladium ions;
[0012] Step 3: reducing the palladium ions to palladium particles
to form a palladium layer on the polystyrene microspheres;
[0013] Step 4: adding the polystyrene microspheres into the sodium
succinate solution to form a slurry; and
[0014] Step 5: adding the nickel sulfate solution with a specific
Na/Ni concentration, pH and temperature drop by drop into the
slurry, so as to form a Ni layer with 100 nm thickness on the
polystyrene microspheres.
[0015] Therefore, the main disadvantage of the conventional methods
of electroless plating is the heavy and complicated procedure. In
order to form a metal layer on the surface of polymeric
microspheres, it need to be roughened, sensitized activated and
adsorbed palladium on the surface of microspheres. What if any
procedure couldn't properly execute, the quality of the final
products won't be satisfying the requirement.
[0016] Accordingly, in view of the conventional methods of
electroless plating still having shortcomings and drawbacks, the
inventor of the present application has made great efforts to make
inventive research thereon and eventually provided a preparation of
modified organic core materials and metallic shell composite
microspheres.
SUMMARY OF THE INVENTION
[0017] The primary objective of the present invention is to provide
a preparation of modified organic core materials and metallic shell
composite microspheres, in which, the surface zeta potential of an
organic substrate can attract the opposite zeta potential of the
polyelectrolyte and form a polyelectrolyte layer so as to modify
the surface of organic core materials. Moreover, the
polyelectrolyte layer could attract a first metal ions, particles
or complexes added later in suitable condition such that the
surface of organic core materials could be metallized and covered
with a first metal layer. Furthermore, the organic core materials
could be covered with at least one surface metal layer. The first
metal layer can be modified by second metal layer with
redox-transmetalation.RTM. technology to obtain multi-metal layers
organic-metallic composite structure.
[0018] Accordingly, to achieve the primary objective of the present
invention, the inventor of the present invention provides a
preparation of modified organic core materials and metallic shell
composite microspheres, comprising a plurality of steps of:
[0019] (1) adding an organic substrate 1 into a solvent to obtain a
slurry;
[0020] (2) adding a first polyelectrolyte 2 into the slurry,
wherein the zeta potential of the first polyelectrolyte 2 is
opposite to the surface zeta potential of the organic substrate
1;
[0021] (3) adding a second polyelectrolyte 3 into the slurry,
wherein the zeta potential of the second polyelectrolyte 3 is
opposite to the zeta potential of the first polyelectrolyte 2;
[0022] (4) adding a first metal compound 4 into the slurry; and
[0023] (5) adding a reductant 5 into the slurry for making the
first metal compound 4 be metalized, so as to form a first metal
layer 6 on the surface of the organic substrate 1.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The invention as well as a preferred mode of uses and
advantages thereof will be best understood by referring to the
following detailed description of an illustrative embodiment in
conjunction with the accompanying drawings, wherein:
[0025] FIG. 1 is a flow chart of the preparation of modified
organic core materials and metallic shell composite microspheres
according to the present invention;
[0026] FIG. 2 is a manufacturing process flow of the preparation of
modified organic core materials and metallic shell composite
microspheres according to the present invention;
[0027] FIG. 3 is an analytic plot of the surface zeta potential of
the organic core microspheres in different pH circumstances;
[0028] FIG. 4 is an analytic plot of the surface zeta potential of
the organic core microspheres modified by the polyelectrolyte (PAH
and PAA) with different concentrations;
[0029] FIG. 5 is a cross-sectional interface structure diagram of
the PMMA-Ni composite microspheres;
[0030] FIG. 6 is an analytic plot of volume resistivity of the
PMMA-Ni composite microspheres prepared by the reductant with
different concentrations;
[0031] FIG. 7 is a cross-sectional and micro-display interface
structure diagram of the PMMA-Ni--Au composite microspheres in
different pH circumstances;
[0032] FIG. 8 is an XRD plot of the PMMA-Ni--Au composite
microspheres;
[0033] FIG. 9 is an analytic plot of volume resistivity of the
PMMA-Ni--Au composite microspheres in different PH circumstance;
and
[0034] FIG. 10 is a schematic diagram of a magnetic effect
experiment for the PMMA-Ni--Au composite microspheres.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0035] To more clearly describe a preparation of modified organic
core materials and metallic shell composite microspheres according
to the present invention, embodiments of the present invention will
be described in detail with reference to the attached drawings
hereinafter.
[0036] With reference to FIG. 1, which illustrate a flow chart of
the preparation of modified organic core materials and metallic
shell composite microspheres according to the present invention.
Moreover, please simultaneously refer to FIG. 2, there is shown a
manufacturing process flow of the preparation of modified organic
core materials and metallic shell composite microspheres according
to the present invention. As shown in FIG. 1 and FIG. 2, the
preparation of modified organic core materials and metallic shell
composite microspheres mainly comprises 5 steps:
[0037] Firstly, the method proceeds to steps (S01) and (S02) for
adding an organic substrate 1 into a solvent to obtain a slurry and
then adding a first polyelectrolyte 2 into the slurry; in which,
particularly, the zeta potential of the first polyelectrolyte 2 is
opposite to the surface zeta potential of the organic substrate 1.
After finishing the step (S02), step (S03) is next executed for
adding a second polyelectrolyte 3 into the slurry, wherein the zeta
potential of the second polyelectrolyte 3 is opposite to the zeta
potential of the first polyelectrolyte 2. Subsequently, the method
executes step (S04) for adding a first metal compound 4 into the
slurry; and eventually, the method proceeds to step (S05) for
adding a reductant 5 into the slurry, so as to make the first metal
compound 4 be metalized, and then a first metal layer 6 is formed
on the surface of the organic substrate 1.
[0038] Thus, through above descriptions, the basic steps of the
preparation of modified organic core materials and metallic shell
composite microspheres have been introduced completely and clearly.
Moreover, as shown in FIG. 1 and FIG. 2, the preparation of
modified organic core materials and metallic shell composite
microspheres further comprises steps (S06) and (S07). In the step
(S06), a second metal compound 7 is added into the slurry, and then
after an ion exchange spontaneously occurs between the second metal
compound 7 and the first metal compound 4 of the first metal layer
6 through redox during the step (S07), the first metal layer 6 is
modified to a second metal layer 8.
[0039] Herein, it needs to further explain that, the organic
substrate 1 in aforesaid surface metallization method is an organic
material with polyester functional group, i.e., the organic
substrate 1 is covered with at least one surface metal layer.
[0040] Besides, the first polyelectrolyte 2 and the second
polyelectrolyte 3 are selected from the group consisting of: Poly
(allylamine hydrochloride) (PAH), Poly (diallyldimethylammonium
chloride) (PDDA), Poly (acrylic acid) (PAA), and Poly (styrene
sulfonate) (PSS). Moreover, the reductant 5 in aforesaid
preparation of modified organic core materials and metallic shell
composite microspheres is selected from the group consisting of:
Dimethylamine borane (DMAB) and NaBH.sub.4.
[0041] Thus, through the descriptions, the preparation of modified
organic core materials and metallic shell composite microspheres of
the present invention has been completely introduced and disclosed;
next, a variety of experiment data will be presented for proving
the practicability and performance of this preparation.
Experiment I
[0042] A plurality of PMMA (Polymethylmethacrylate) microspheres
having a diameter ranged from 200 nm to 8 .mu.m are provided as
organic core microspheres (the organic substrate), wherein the
average diameter of the PMMA microspheres is 4 .mu.m. Moreover,
Poly (allylamine hydrochloride), i.e., the PAH, are used as a
cationic polyelectrolyte; and oppositely, Poly (acrylic acid),
i.e., the PAA, is used as an anionic polyelectrolyte.
[0043] Please refer to FIG. 3, there is shown an analytic plot of
surface zeta potential of the organic core microspheres in
different pH circumstances. As shown in FIG. 3, PMMA-PAH curve is
obtained by measuring the surface zeta potential of the organic
core microspheres mixed with 0.2 g PMMA and 0.022 mM PAH
polyelectrolyte; in addition, As-received PMMA curve is obtained by
measuring the surface zeta potential of the organic core
microspheres mixed with 0.2 g PMMA microspheres; moreover,
PMMA-PAH-PAA curve is obtained by measuring the surface zeta
potential of the organic core microspheres mixed with 0.2 g PMMA
microspheres, 0.022 mM PAH and 0.022 mM PAA polyelectrolytes.
Obviously, the experiment results of FIG. 3 reveal that the
polyelectrolytes of PAA and PAH can indeed make a modification
effect to the surface zeta potential of the organic core
microspheres under a wide pH range (pH4-pH10).
[0044] Please refer to FIG. 4, there is shown an analytic plot of
the surface zeta potential of the organic core microspheres
modified by the polyelectrolytes (PAH and PAA) with different
concentrations. As FIG. 4 shows, PMMA-PAH data points are obtained
by measuring the surface zeta potential of the organic core
microspheres PMMA modified by the PAH polyelectrolytes with the
concentration of 0.01 mM-0.07 mM. The PMMA-PAH-PAA data points are
obtained by measuring the surface zeta potential of the organic
core microspheres PMMA modified by the PAH and PAA polyelectrolytes
with the concentration of 0.01 mM-0.07 mM. From FIG. 4, it can find
that a gentle region is observed when the concentration of the used
polyelectrolytes exceeds 0.02 mM, and that means the modification
effect made by the polyelectrolytes reaches to the upper
limitation.
[0045] Furthermore, an FIB-SEM (Focused Ion Beam Scanning Electron
Microscopy) is used for observing the cross-sectional interface
image of the microspheres of PMMA-Ni composite microspheres. Please
refer to FIG. 5, which illustrates the cross-sectional interface
structure diagram of the PMMA-Ni composite microspheres; wherein
the PMMA-Ni composite microspheres are made by adding a precursor
of 0.255M NiCl.sub.2, a reductant of 0.17M DMAB (Dimethylamine
Borane) into the polyelectrolyte with a fixed concentration of 0.22
mM and then using aforesaid polyelectrolyte to execute a surface
metallization to the organic core microspheres. As shown in FIG. 5,
the interface between the organic material and the metal layer is
continues and delicate; therefore, it can be noted that the
polyelectrolyte displays a stable ability of adsorbing the organic
material with metal compound which is selected from the group
consisting of: metal ion, metal particles and metal complexes.
[0046] After finishing the surface metallization of the organic
core microspheres, the organic core microspheres are subsequently
pressed into tablets by hot pressing method (press 30s with 110 MPa
at 130.degree. C.) and then the volume resistivity of the organic
tablets are measured by four point probe resistivity measurements.
Please refer to FIG. 6, which illustrates an analytic plot of
volume resistivity of the PMMA-Ni composite microspheres prepared
by the reductant with different concentrations. As shown in FIG. 6,
the experiment results indicate that the organic core microspheres
(tablets) perform the lowest volume resistivity when the
concentration of the reductant (DMAB) is 0.17M.
Experiment II
[0047] Furthermore, according to following Eq. (1), it is able to
know that an ion exchange would occur spontaneously through
redox-transmetalation. The redox-transmetalation can oxidize the Ni
layer on the surface of an organic material and make Au (III)
reduce to Au (0), so as to form a continuous Au layer covering the
Ni layer on the surface of the organic core microspheres.
3Ni.sub.(s)+2AuCl.sub.4.sup.-=3Ni.sup.2++2Au.sub.(s)+8Cl.sub.(aq).sup.-
Eq. (1)
[0048] Please refer to FIG. 7, which illustrates a cross-sectional
and micro-display interface structure diagram of the organic core
microspheres of
[0049] PMMA-Ni--Au compound in different pH circumstances. FIG. 7
(a) is the micro-display diagram of PMMA-Ni composite microspheres
microspheres, and FIGS. 7 (b), (c), (d) and (e) are the
micro-display diagram of PMMA-Ni--Au composite microspheres in pH
6, 7, 8, and 9, respectively. By inspecting the cross-sectional
interface structure of the PMMA-Ni--Au composite microspheres
through FIB-SEM, it can be found that more delicate cross-sectional
interface structure of PMMA-Ni--Au composite microspheres is
obtained in pH 7, 8 and 9. Please continuously refer to FIG. 8,
which illustrates an XRD plot of the PMMA-Ni--Au composite
microspheres. Through FIG. 8, it can be found that the Au layer is
formed and covers over the Ni layer on the surface of organic
microsphere after redox-transmetalation.
[0050] Please continuously refer to FIG. 9, there is shown an
analytic plot of the volume resistivity of the PMMA-Ni--Au
composite microspheres in different pH circumstances. Similarly,
after the surface metallization of the organic core microspheres is
carried out, the PMMA-Ni--Au composite microspheres are
subsequently pressed into tablets by hot pressing method (press 30s
with 110 MPa at 130.degree. C.), and then the volume resistivity of
the PMMA-Ni--Au composite tablets are measured by using four point
probe resistivity measurements. As FIG. 9 shows, the experiment
results reveal that the PMMA-Ni--Au composite microspheres
(tablets) perform the lowest volume resistivity when the pH is
ranged from 7 to 8.
[0051] Besides, for determining the surface metallization of the
PMMA-Ni--Au composite microspheres, a magnetic effect experiment is
executed. Please refer to FIG. 10, which illustrates a schematic
diagram of a magnetic effect experiment for the PMMA-Ni--Au
composite microspheres. As shown in FIG. 10, the solution is
apparently clear after adding a magnetic field. Through experiment
result, it can find that the Ni layer of the PMMA-Ni--Au composite
microspheres isn't consumed entirely by Au ion in
redox-transmetalation.
[0052] The above description is made on embodiments of the present
invention. However, the embodiments are not intended to limit scope
of the present invention, and all equivalent implementations or
alterations within the spirit of the present invention still fall
within the scope of the present invention.
* * * * *