JPH08302041A - Method for increasing surface hardness of polyamide, polycarbonate and polypropylene and material produced by the same method - Google Patents

Abstract

PURPOSE: To impart high surface hardness to polyamide, polycarbonate or polypropylene by injection an ion to the resin by specifying ion kinds and conditions. CONSTITUTION: Any ion among silicon, boron and argon having nearly 25keV to nearly 1Mev injection energy is injected into PA, PC or PP in an injection amount of nearly 1×10<14> to nearly 1×10<15> ions/cm<2> .

Description

Detailed Description of the Invention

[0001]

This invention relates to a polyamide (P
A), polycarbonate (PC), polypropylene (P
The present invention relates to a method for increasing the surface hardness of P) and improving mechanical properties such as abrasion resistance, and a material produced by the method.

[0002]

2. Description of the Related Art Recently, plastics have excellent properties such as easy moldability, impact resistance, rust resistance, and light weight compared to other materials, and are widely used in place of materials such as metal and wood. Although it is used in some fields, it cannot be used in some fields due to its low surface hardness and easy scratching.

The object of the present invention is to impart high surface hardness to PA, PC and PP under specific ionic species and conditions.

[0004]

[Means for Solving the Problems] PA, PC, PP
At 5 keV to 1 MeV, preferably at about 25 keV to about 1 MeV, one ion of silicon, boron, or argon is added at 1 × 10 ¹⁴ ions / cm ² to 1 × 1.
0 ¹⁵ ions / cm ² , preferably about 1 × 10 ¹⁴ io
ns / cm ² to about 1 × 10 ¹⁵ ions / cm ² , and the surface is modified to increase the surface hardness.

[0005]

[Experiment] Injection base material The plastic base material used for injection is PP, PA, PC,
PET (polyethylene terephthalate) and PI (polyimide).

Sample Preparation All substrates were subjected to ultrasonic cleaning with ethyl alcohol and then subjected to ion implantation treatment. The ion implantation process was performed using a 200 keV (A) and 8 MeV ion implanter of Ion Engineering Center. The implanted ion species are
Ar ⁺ , B ⁺ , S for 200 keV ion implanter
There are three types, i ⁺ . Injection energy is 25, 50, 1
There are four types, 00 and 200 keV. The ion current density of the implanted ions is 0.3 μA / cm ² or less. The injection amount was 1 × 10 ¹⁵ ions / cm ² . Condition of injection volume is 1
× 10 ¹⁵ to that in ions / cm ^2, in Studies on adhesion Teflon, injection volume injection effect starts to appear an injection process according to 1 × 10 ¹⁴ ions / cm ² at a thing and three ionic species This is because it was necessary to complete effective processing in as short a time as possible because the usage time of the device was limited. In the case of the 8 MeV ion implanter, the ion species are B ⁺ and Si ⁺ 2
Type, three types of implantation energy are 1, 2, and 4 MeV, and the implantation ion current density is 0.1 to suppress an increase in sample temperature.
μA / cm ² or less, injection amount is 1 × 10 ¹⁴ ions /
cm ² , 5 × 10 ¹⁴ ions / cm ² and 1 × 10 ¹⁵
Ions / cm ² . During the 4 MeV injection experiment, the temperature rise due to ion injection was monitored by sandwiching the thermolabel between two PIs, and it was found that the temperature did not exceed 80 ° C.

Ion Implanter Ion Engineering Center 200 keV (A) and 8 Me
A V ion implanter was used. The 200 keV ion implantation system uses a mechanical scan (by spin and translational movement in the left-right direction) of a disk with a diameter of 1 m for uniform ion implantation, and the standard size (plate thickness 2 mm
In the following, for samples outside the 4-6 inch disc or 300 mm square plate, the sample to be injected must be somehow fixed on this disc. This time, the sample was fixed to the disk directly with polyimide adhesive tape and injected. In the case of 8 MeV, although the electrostatic scanning method is used, since the ion energy is high, the sample was fixed to a 6-inch disk-type jig with a screw, and then set on a single-wafer disc to perform injection.

Surface hardness evaluation method The surface hardness of a plastic material is a method of evaluating the hardness of the sample electrode surface by measuring the indentation depth of the indenter Shimadzu dynamic ultra-fine hardness meter DUH-200 type (Shimadzu Corporation). It was measured by. A 115-degree triangular cone indenter was used as the indenter, and the measurement load on the indenter was 200 mg. The surface hardness of the sample will be represented by the dynamic hardness (DH) defined by the following equation. DH ₁₁₅ = 3.858P / h ² where h: depth of indentation P: load on indenter (mN)

Experimental Results FIG. 1 to FIG. 3 show the relationship between the surface hardness of the implantation surface and the implantation ion energy of the plastic material ion-implanted with B ⁺ , Si ⁺ and Ar ⁺ using a 200 keV ion implantation apparatus. It is a thing.

The injection amount is 1 × 10 ¹⁵ ions /
cm ² . The hardness shown in the figure is a numerical value defined as dynamic hardness. As you can see from the figure, P
The surface hardness of P, PA and PC increases as the implantation energy increases. This tendency does not depend on the ionic species.
PC is the hardest of the unimplanted samples, but PC is also the sample showing the highest hardness of the ion-implanted samples. The hardness of the B ⁺ ion-implanted PC of 200 keV showing the highest value is about 1.8 times that of the unimplanted PC sample, and
The hardness of 00 keV Si ⁺ ion-implanted PC is unimplanted
It is about 1.7 times that of the sample. On the other hand, the PA sample has the highest rate of increase in surface hardness due to ion implantation. 20
The hardness of the ⁰ keV Ar ⁺ ion-implanted PA sample is about 2.3 times that of the non-implanted PA sample, and about 1.9 times that of the 200 keV Si ⁺ ion-implanted sample.

FIGS. 4 and 5 show the relationship between the surface hardness and the amount of implanted ions of a plastic material into which 1 MeV B ⁺ and Si ⁺ ions have been implanted using an 8 MeV ion implanter, respectively.

From the results of the B ⁺ ion implantation shown in FIG. 4, P
It can be said that the surface hardness of P, PA and PC increases as the injection amount increases. In addition, the maximum hardness values obtained for each material by ion implantation are about 10 times for PP, about 7.2 times for PA, and P
In C, it is about 7.9 times. The highest surface hardness is obtained by 1 MeV ion implantation into PC, and the hardness is about 100.

Next, in the case of Si ⁺ ions shown in FIG. 5, the increase in hardness is smaller than that in the case of B ⁺ ions. Further, it can be said that the hardness increases as the injection amount increases. The maximum hardness value obtained for each material is about 5.5 times for PP, 5.4 times for PA, 5.2 times for PC and about 5 times for PET, compared to the respective unimplanted sample values. .1
It is twice. The maximum surface hardness is 1Me for PC.
Obtained by V ion implantation, the hardness is about 65.

From the above, it can be concluded that high-energy ion implantation is very effective for improving the surface hardness of plastic materials, except for PI, and PA, PC and PP can be particularly promising. The experimental data are 25, 5
The injection energies of 0, 100, 200 keV and 1 MeV are described.
The trends in the case of injection energies in the middle and around the injection energies are known. The experimental data is 1
× 10 ¹⁴ ions / cm ² and 1 × 10 ¹⁵ ions / cm ²
Although the ion implantation amount of cm ² is described, those daders show the trends in the case of the implantation amount in the middle and around the implantation amount.

[0015]

According to the method of the present invention, P
Without coating the surface of A, PC and PP and without chemical treatment, ions of silicon, boron or argon are directly implanted to modify the surface and increase hardness. The PA, PC and PP materials implanted with the ions by the method according to the present invention have high surface hardness, are hard to be scratched on the surface, have excellent mechanical properties such as abrasion resistance, and can be widely used in mechanical fields. .

[Brief description of drawings]

FIG. 1 is a hardness contrast diagram of plastics implanted with boron ions at 25 to 200 keV.

FIG. 2 is a diagram of hardness contrast of a plastic in which silicon ions are injected at 25 to 200 keV.

FIG. 3 is a hardness contrast diagram of plastics implanted with argon ions at 25-200 keV.

FIG. 4 is a hardness contrast diagram of plastics implanted with boron ions at 1 MeV.

FIG. 5 is a hardness contrast diagram of plastics implanted with silicon ions at 1 MeV.

Claims (2)

[Claims] 1. About 25 keV to about 1 M in any of polyamide, polycarbonate and polypropylene.
At eV, approximately 1 × 10 ¹⁴ ions / cm ² to approximately 1 × 1 of any one of silicon, boron, and argon ions is applied.
A method of increasing the surface hardness of polyamides, polycarbonates and polypropylenes, characterized by injecting at 0 ¹⁵ ions / cm ² . 2. Approximately 25 keV to approximately 1 M in any of polyamide, polycarbonate and polypropylene.
At eV, approximately 1 × 10 ¹⁴ ions / cm ² to approximately 1 × 1 of any one of silicon, boron, and argon ions is applied.
Polyamide, polycarbonate and polypropylene materials with increased surface hardness by injection at 0 ¹⁵ ions / cm ² .