JPS63223161A - Method and apparatus for coating base layer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method and apparatus for applying a coating to cosmetic and utilitarian parts, said coating having a gold resemblance to gold (10 to 24k). and/or a color ranging from gray to brown, bronze, black and platinum, wherein the coating has excellent adhesion and excellent resistance to corrosion and abrasion. It is something that you have. Typical parts requiring abrasion resistant or decorative coatings include class rings, watch cases and bands, lighter cases, silverware parts, automotive parts, eyeglass frames, pen caps, Tools and other worn (utility) parts.

BACKGROUND OF THE INVENTION Thin film materials are applied to base materials for decorative applications in two ways. that is, by either sputtering deposition (plating) techniques or ion plating deposition techniques. However, the typical substrate temperature involved in both of these techniques is 3
It is within the range of 50 to 550°C. These techniques are described, for example, in U.S. Pat. No. 4.402.994, U.S. Pat.
No. 900.592, and Journal of Va.
cuum 5science and technology.

gy″A, Vol, 4.No, 6.Nov, /Dec,
, 1986, pp. 2717-2725. However, many base materials such as plated zinc coatings, brass, bearing steel, bronze and its alloys containing zinc, plastics, aluminum and its alloys, etc. cannot be exposed to these high temperatures. Furthermore, because of the pale yellow or other pale colors commonly obtained by these techniques, a mantle consisting of a thin gold film on a rigid film surface is required.

This is described in US Pat. No. 4,415,421. The adhesion of the interface between the rigid film and the gold film, and the reproducibility of color are important to the manufacturing technology. However, the above processes (techniques) are not always satisfactory in these respects.

U.S. Pat. No. 3,625.848 and U.S. Pat.
No. 793,179 discloses an apparatus for metal vapor deposition coatings involving the use of a vacuum arc. An improvement in this regard is described in US Pat. No. 4,430,184. The above three patents are incorporated herein by reference. Such arc sources contain a high degree of ionization and produce a coating melt having high ion energy. This results in a coating with a dense microstructure and excellent adhesion. However, conventional arc sources require typical substrate temperatures in the range of 300-500°C.

SUMMARY OF THE INVENTION It is therefore a primary object of the present invention to provide an arc source and method for depositing decorative and wear-resistant coatings that reduce to the very low base temperatures that are essential for many parts. The purpose of the present invention is to provide a technology that has not previously been commercially applied to such coatings.

Another object of the present invention is to provide a method and apparatus for depositing materials onto a substrate at very low temperatures (temperature range of about 50-500°C) by vacuum cathodic arc plating.

Another object of the invention is to provide a method of coating a substrate with good adhesion and good decorative properties without the use of gold.

Yet another object of the invention is to provide a method for applying non-golden decorative coatings using the above-described apparatus.

Another object of the invention is to enhance the color reproduction and abrasion resistance of decorative films at manufacturing scale.

The method of the present invention involves placing a base layer in a vacuum vessel and producing a melting body of titanium on the base layer, consisting of ions, vapors and/or neutrals, by the action of an electric arc within said vacuum environment. , zirconium, zirconium in titanium, or titanium aluminum. The composition of the deposits can be modified by re-reacting with appropriate gases during their deposition to produce different films. The temperature of the substrate can be controlled by automatic pulsing of the arc source. The "on" and "off" times of the arc source can be varied to control the temperature of the substrate down to temperatures as low as 50°C. Furthermore, the adhesion of the coating can be improved by adjusting the bias voltage on the base layer to attract ions. The coating consists of systems based on nitrogen, carbide, titanium carbon nitride, titanium aluminum, zirconium and titanium zirconium. The color can be modified by adding suitable additives to the film, such as oxygen and carbon, where the additive gases typically range from 2 to 7 atomic percent; Alternatively, the color can be changed by using a suitable reactive gas atmosphere. Different ranges of gold (10 to 24k), e.g. T I , N 1-, when 0<x<1,
or Ti, Zr r-x N and added T
doubled in iN or ZrN films.

(Detailed Description of Preferred Embodiments of the Invention) Hereinafter, embodiments will be described with reference to the drawings.

The present invention overcomes the shortcomings of the prior art by improving the fit and color reproducibility of cathodic arc plating methods and apparatus. The present invention is applicable to coatings made of a variety of materials including zinc, aluminum, stainless steel, plastic, brass, and alloys thereof. Of the base layers coated with a hard material according to the invention, the surface of the tool or part is
Coated with at least one hard coating material selected from nitrides, carbides, carbon nitrides, and combinations thereof doped with titanium, zirconium, titanium-aluminum, and titanium-zirconium systems.

Referring to FIG. 1, an arc plasma plating apparatus 100 according to an embodiment of the present invention is illustrated.

An arc source 110 is operated within the vacuum vessel by an external pulsed power supply 105. A base layer 108 to be coated may be mounted on the rotary table 102. The rotary table 102 may be negatively biased with an external high voltage supply 104. Sources 104 and 105 may be grounded, as shown in FIG. 1, or connected to a suitable source of negative potential. The apparatus 100 also includes a gas introduction vibrator 10.
6 and a vacuum pump system 101 are provided.

Various gases can be transferred to the gas introduction vibe 10B using a set of valves 107. shutter 10
8 can also be employed. Additionally, the arc source may be partially commutated (not shown) to reduce coating flow to control substrate temperature.

FIG. 2 shows a schematic diagram of an illustrative arc source 110 in which the material to be vaporized is heated using the action of an electric arc. The arc source may be installed in the vacuum chamber in the form of a side, top or bottom. Arc restriction on the same arc source is achieved using a suppression ring 113. This restriction ring 113 may be constructed from boron nitride, titanium nitride, pyrex glass, quartz or soda coal glass. Arc restriction can also be achieved using suitable boundary shields or magnetic fields. In the latter technique, extinguishment of the arc occurs and the arc is automatically reignited using a suitable electronic control unit, as disclosed, for example, in US Pat. No. 3,793,179. The power supply 105 may be DC if the target is conductive and the RF is insulating.
It may be.

Anode 114 is spaced apart from the cathode or target 102. The anode 114 may be on the outer housing of the arc source, or on or around the wall of the chamber, and may be electrically biased or grounded.

The same anode 114 is shown in FIG. 2 and is shown in U.S. Pat.
No. 5.848, a physical probe is placed within the chamber 100, away from the walls and base of the chamber 100 and under another bias, to act as an anode for the electrical system. may be attached to.

Furthermore, the entire chamber or its surroundings may have a ground potential (e.g., U.S. Pat. No. 3,793,179
(see issue).

FIG. 3 shows the operating cycle of the power supply 105. The time T1 the arc source is energized (on) and the time T2 the arc source is turned off can be independently varied. For example, TixZrl is equal to hours when the arc source runs continuously.
or when running in pulses, it can be minutes (n+1 nutea). Time T2 can be zero or a finite value. A typical valve for the pulse peak is 30
Varies within the range of ~200 Amps.

Referring to Figures 3A and 3B, where Figure 3A is:
FIG. 3B is an illustrative block diagram of a control circuit for use with the arc source of the present invention; FIG.
2 is an explanatory flow diagram of a program subroutine that may be employed within the illustrated controller; FIG. In FIG. 3A, the control circuit 120 is shown in its entirety and includes a programmable process controller 122. In FIG. The control device 122 is the Texas Ins.
The controller is available from the company truments Corporation as Model TCAM 5230 and is equipped with a program for controlling the cathodic arc process. According to one feature of the invention, the program is modified by adding program steps to it that may correspond to those illustrated by the flow diagram of FIG. 3B. The control device 122 controls the arc supply source 10
an output section 12 for controlling the magnitude of the current supplied by 5;
8 and an output section 130 for controlling the magnitude of the bias voltage provided by the power supply source 104. The controller 122 is also traditionally adapted to receive a signal from a temperature sensor 132, and the controller 122 is adapted to receive a signal from a temperature sensor 132 to facilitate processing of the output signal from the temperature sensor 132. It includes internal analog-to-digital circuitry to digitize the output signal. The temperature sensor 132 may typically be a conventional infrared sensor that reads the temperature of the substrate 103. This temperature will henceforth be referred to as Ts. The controller 122 also traditionally includes an output 134 for turning the arc source 105 on and off. A conventional output 135 is also provided which connects the igniter 11 via the coil 115' to initiate arcing from the target 102.
5, in which case the ignition device 115 may be of electromechanical, electrical or gas emitting type.

In operation, a program traditionally provided using the controller 102 allows setting the magnitude of the arcing current from the output 128. It also allows setting the magnitude of the bias voltage provided by the power supply 104. According to one feature of the invention, in changing the program, the subroutine of FIG.
It is read in 34 places. Next, the base layer temperature Ts is compared with the lower limit temperature TL at a point 136. For example, if it is desired to maintain the average temperature of the base layer 103 at about 100°C, the lower temperature limit TL would be about 90°C. If the base layer temperature is lower than TL,
In order to start the arc, a current is output from an output 136 via the ignition device 115, which is indicated at 138. This instant corresponds to one of the leading edges of the pulses shown in FIG.

As mentioned above, the magnitude of the pulse is traditionally controlled from the output 128. Once the pulse is initiated, the subroutine of FIG. 3A exits at 139, resulting in the return of the main program traditionally prepared using the controller 122. As long as the plating operation continues, the routine of FIG. 3B will be executed repeatedly. Once the routine returns, the substrate temperature is read again and again compared to the lower temperature limit TL at 136. At this time, assuming that the base layer temperature is higher than the lower limit temperature, another comparison is made at 140 to determine whether the base layer temperature is higher than the upper limit temperature Tu. Assuming that the desired average temperature of the base layer is about 100° C., the upper temperature limit Tu is typically set at about 110”C. If this temperature is exceeded, the arc source 105
A signal is provided from the output 134 of the controller 122 to turn off the controller 122, which is indicated at 142. This moment corresponds to the subsequent edges of the pulses shown in FIG. Once arc source 105 is turned off, the main program exits 139
returned via. If the base layer temperature Ts is lower than the upper limit temperature T, the pulse is maintained in its ON state.

It can be seen from the above description that the arc source 110 is
As discussed further in Example 1 below, the pulses are adapted to maintain the temperature of the substrate at a level appropriate to the type of coating applied thereto.

Other means may be employed to effect pulsing of the arc source. For example, a comparison can be made at 136 to determine whether Ts > Tu. If so, the arc source is turned off. Next, T
To determine when ixZrS>TL, the symbol 14
A comparison may be made at zero. When this happens,
The arc is restarted. Additionally, if a hardware source for generating pulse trains other than cathodic plating is known, a hardware form may be employed.

Furthermore, the nature of the control device provided for maintaining the substrate temperature may differ in other ways from that shown in FIG. 3B. For example, to generate a continuous error signal employed to control the substrate temperature,
Conventional closed loop control may be utilized where the sensed substrate temperature is continuously compared to the desired substrate temperature.

Alternatively, a proposal similar to that of FIG. 3B may be adopted if a comparison corresponding to step 136 is made to determine whether said temperature Ts is lower than TL. If TixZrs is less than TL, the arc is ignited and the source 105 is turned on for a predetermined period of time. The upper limit temperature Tυ is not adopted. Rather, the base temperature Ts is repeatedly compared with the lower temperature TL. When Ts is again lower than TL, the arc is turned on again with the source for a predetermined period of time.

The arc is initiated within the chamber by an igniter 115. The igniter 115 may be an electromechanical device that contacts the surface of the cathode source with an arc starting wire or a gas release ignition system, in which a high voltage gas release is performed. , a suitable power source provides a current path between the igniter and the cathode surface. The cathodic arc source is water cooled by special grooves machined on a copper block 111 attached to the front of the cathode or arc source material 102. The action of an electric arc on the surface of the cathode material results in a cathode spot (cath).

5pot). This cathode spot moves randomly across the surface of the coating source material to form a coating plasma.

Also, the movement of this cathode spot can be controlled with the aid of a suitable magnetic field structure.

The item to be coated in the chamber
) are typically referred to as substrates and are indicated generally at 103, with the substrates not shown in detail. This is because they do not form part of this invention. The source of coating material 102 is typically referred to as a cathode or target (where the target may be disposed on the cathode or the target may be the cathode). The target 102 is the source of the coating flux or plasma for the arc plating process. The source material 102, such as titanium, zirconium, titanium-zirconium, or titanium-aluminum, may be fixed and cylindrical, circular, oval, or square, or any other suitable shape. . Alternatively, separate targets can be employed for each source material to effect simultaneous plating of the mixed coating system.

In operation, the substrate to be coated is chemically cleaned and then transferred to the rotary workpiece holder 10.
2 piled on top. The vacuum chamber 100 is then pumped down to the base pressure using the pumping system 101. The substrate or component is then cleaned with ions and heated using metal ion bombardment by turning on the arc and applying a photovoltage bias to the substrate by source 104. be done. The arc source 110 is then pulsed for each different work cycle, and the bias voltage from the source 1.4 and the arc current source 1.5 are adjusted according to the critical temperature of the substrate.

A reactive gas with appropriate additives is then applied to gas inlet valve 106 and gas array valve 1 to maintain the chamber pressure between approximately 0.1 and 15.0 microns.
Introduced through 2007. The base bias and arc current may be controlled by an automatic process controller driven by preset temperature limits. The resulting hard coating begins to deposit at the set substrate temperature. Typical coating thicknesses ranging from about 0.5 to 5.0 microns are then deposited for decorative applications.

Example 1 Typical operating conditions and coating combinations observed for various substrate temperatures are shown in Table I, where the ranges above X are for alloys and carbon nitrides. Vary from O<x<1 and 0.1 to 0 unless otherwise stated as in Examples 5 and 14
．． In Examples 5 and 14, the increasing force of 0.1 is expanded from 0.1 to 0.5. In general, example 10 consists of nine examples in which X is increased in 0.1 increments from 0.1 to 0.9.

The above description applies in all cases where an alloy constitutes the target material or a carbon nitride constitutes the coating material and the value of X is stated.

Furthermore, the additive was 02 or C or a mixture thereof. In this case, naturally occurring 02 typically appears in the C-doped examples, and in this case the amount of additive was in the range of about 2 to 7 atomic percent. Typically, the C source was a carbon-containing gas such as CH4 or 02H2. The above description applies to all instances where it is stated that the coating material is loaded with additives.

The above discussion has been made with respect to the relative alloys, and the amounts of carbon nitrides and additives also apply below, and all other designations relating to "X" as well as the specification and claims. Applies to additives in

Table 1 Column order Base layer material Average base layer temperature Coating material Average pulse time of arc source Ts (minutes) Tl
(minutes) ■ Plastic ~50℃ Tl
O, 50,252 plastic ~50℃
T [NO, 250, 253
Plastic ~50℃ Added TiN
O, 250, 254 plastic ~50℃
Zr N O, 50, 55 plastic ~50℃ Ti x zr l-X
N O,50,5 (0x≦0.5) 6 Zinc or Zinc ~100℃ TiN
O,50,5 Alloy Niclas Rings, Eyeglass Frames, Ben-Caps, Lighters and Hours! 1 of 7I//〆 ~100℃ Added TiN
O,50,58ノI〃〜lOO℃ZrN0.50
．． 59〃〃～100℃ Tl x Zr l-X N
O, 50, 51O〃l〆 〜lOO℃
Tl x Al 1-x NO, 750,
2511 Brass: Pen・~150℃ TiN
1.0 0.5 cap, class ring, eyeglass frame table ■ (Continued) 12 ” ” ~150℃ Z
r N 1.0 0.513
""~150'CTixZr+-xN
t,o O,514〃”～
150℃ Tl x Al +-x N 1
．． 0 0.25 (0x≦0.5) 15〃 ~150℃ Added TiN
+, 0 0.516 Stainless steel ~
400℃ TiN All Time (300 Series): Class rings, Ben Q caps, eyeglass frames and silverware 17〃〃 ~400℃ ZrN
Il all the time! ” ” ~
400℃ Tl x Zr I-X N 19 〃” to 400℃ Tl
x Al +-x N 20 at all times
Tool Steel (High Speed Steel ≧450” CTi C All Time and Hardened Carbide) 21〃〃 ≧450℃ Ti Cx N1-x
22〃〃 ≧450℃ at all times
Tl x Zr l-X N 23〃〃 ≧450℃ at all times Tl x Al,
-x N From the results in Table I at all times it was found that the gloss of the base material was maintained when the coating thickness was less than 5 microns. Thicker layers (such as 25 or 50 microns) can also be deposited (plated). With such a layer the gloss (reflectance) of the base layer (base material) cannot be doubled. However, the surface finish can be doubled. A typical layer of the above thickness may constitute several layers, in which case the material of each layer is the same,
Or it may be different.

FIG. 4 shows doped TiN, doped ZrN, and Ti x
The spectrum of the light reflectance of the Z'r I-X N film is shown. 14 also shows the reflectance spectrum of the gold film. Therefore, as can be seen, the light reflectance spectra of the films of this invention can be found in US Pat. No. 4,415,521. The spectrum of different colors obtained with different coating systems is shown in Table 2 as an example.

Table ■ Example order Coating material Color type I
TiN Golden yellow 2 Added T
iN Gold (10 to 24K) 3 ZrN
Yellow-green 4 Added ZrN Platinum 5 T1xZr+-xN Gold (IOK ~24K
)6 Ti C gray 7 T I Cx N l-x brown, bronze.

Dark brown 8 Tix A l+-x N dark brown,
It is noted from the results in Black Table H that a wide variety of colors for decorative coatings can be produced. The thickness of the coating film in all cases is 0.1
It was in the range of 0-5 microns.

For TiN, its golden-yellow color is generally rich in green and bronze, while the ZrN is a yellow-green color with prominent green. Both TiN and ZrN can be doped with 02 to eliminate green and can be doped with C to increase redness. Therefore, by combining the additives 02 and C, control from IOK to 24K can be achieved with added TiN or added ZrN. Furthermore, TixZ
Regarding rI X Zr+-X N, the above value is
increases as the value of increases. Similarly, TixZrI
Cx N+-x and TlxAl,-xN change across different colors as the value of X changes.

Referring again to FIG. 4, the Tl x Zr 1-X
Fourteen gold colors of N coatings were produced with values of X ranging from about 0.25 to about 0.30.

This color was produced by ZrN added with additives of about 1% 02 and about 4% C.

In this case, all percentages are atomic percentages for all additives mentioned in the specification and claims. The gold color of the added TiN 14 was brought about by the addition of about 4% 02. moreover,
The T1 and N were in non-stoichiometric ratios where the amount of TixZri varied from about 1.15 to about 1.2 atomic ratio for each atom of xN. To achieve a non-stoichiometric film, reduced nitrogen gas in the range of 0.1-1.0 microns was employed.

Regarding the gold color in 10 above, this means that (a) X is about 0
．． Ti xZr when varying from 15 to about 0.20
+-xN, (b) added ZrN with an addition of about 2% 02, and (c) the amount of TiO varying from about 1.25 to about 1.40 atomic ratio for each N. of the case,
Added TiN with approximately 4% 02 addition and 3% C addition.

Regarding the gold color in item 18 above, X is about 0.4 to about 0.
Doped TiN or Ti with about 2% 02 addition and about 5% carbon addition when varying up to 45
xZr +−x N was effectively adopted.

Regarding the gold color 24 above, X is about 0.5 to about 0.
TiXZrl-XN was adopted for varying up to 55%.

Example ■ Next, the resistance to abrasion of these coatings is
Pin-on-disc method (method using pins on a disc)
nj was determined using In this method, a pin with a load of 500 grams is placed on a rotating coated sample (coated disc), and if there are scratches in the coating, 5 (11 After rotation it was to be observed in a light microscope at 50x magnification.

No scratches appeared in all the hard coatings in Table ■.

Example ■ Figures 5 and 5A are examples of electron spectrometers for chemical analysis (ESCA).
) shows a graph of the atomic composition for various coatings for different colors, as measured by
FIG. 5 is a graph of sputter depth by the ESCA for 02 and C doped TiN;
The figure is the same graph for the TixZriZrN film. The O2 in the film results from natural levels of O2 in the system. This natural level also applies to 02 shown in FIG.

Various details of the materials, design and construction of the coatings for various embodiments of the invention may be changed without departing from the scope of the invention as claimed. Additionally, although the preferred embodiment of the invention is described in connection with an arc coating system, it is preferred that the material be instantaneously evaporated from the target by an arc that is to be confined within a predetermined area of the surface of the target. Needless to say, it is also applicable to other systems such as.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of an illustrative cathodic arc plasma plating apparatus used in the present invention. FIG. 2 is a schematic diagram of an illustrative arc source used in the cathodic arc plasma plating apparatus of the present invention. FIG. 3 is a time chart showing an illustrative mission cycle of the arc source of the present invention. FIG. 3A is a block diagram of an illustrative control circuit for use with the arc source of the present invention. FIG. 3B is an illustrative flow diagram of a program that may be employed for the control circuit of FIG. 3A. FIG. 4 shows the reflectance of the film produced by the manufacturing process (method) of the present invention. Figures 5 and 5A are schematic diagrams showing the atomic composition of coatings and films produced by the manufacturing process of the present invention. 100...Arc plasma plating device 102...
- Rotary table 103... Base layer 104... High voltage supply source 105... Power supply source 10G... Gas introduction pipe 107... Valve 108... Shutter 110... Arc source 113... Limiting ring 114...Anode 115'...Coil
120... Control circuit 122... Control device
128, 130... Output section 132... Temperature sensor
134,135...Output part FIG, 3 IG 3B Reflection layer (z) FIG, 5 7-/*"vta a%rs'
+ te no FIG, 5A XZl'y 9 s
-i F4°9) At the same time, there is a request for examination of the application, and the procedure is amended. Relationships Patent Applicant Name W7Tch Systems Incorporated Representative Michael Niss Walsh 4, Agent Address 7th Floor, Hauraiya Pill, 5-2-1 Roppongi, Minato-ku, Tokyo "Title of the invention", "Claims" and "Claims" of the specification subject to amendment
Column 7 of ``Detailed Description of the Invention'', Contents of Amendment 1, the title of the invention is corrected to ``1 & Layer Coating Method''. 2. Amend the claims as shown in the attached sheet. 3) Delete "and apparatus" on page 20, line 4 of the specification. Claims (1) A method of coating a base layer, comprising the steps of applying successive pulses of an arc to the target to vaporize the target material; and applying a coating of at least the target material on the base layer. for,
depositing said vapor on said base layer. (2) The thickness of the coating is no greater than about 50 microns.
The method described in section. 3. The method of claim 2, wherein the coating is formed in multiple layers. (4) The method of claim 3, wherein each of the layers is made of the same material. 5. The method of claim 3, wherein at least one of the layers is of a different material than the other layers. 6. The method of claim 2, wherein the thickness of the coating is no greater than about 5 microns. 7. The method of claim 6, wherein the thickness is in the range of 0.1 microns to about 5 microns. 8. The method of claim 1, wherein the duty cycle of the arc pulses is such that the temperature of the substrate is well below 350°C. (9) The method of claim 8, wherein the temperature of the base layer is about 50°C to about 150°C. 9. A method according to claim 8, characterized in that (IO) the base layer consists of plastic. (11) The method according to claim 1O, wherein the base layer temperature is about 50°C. (12) The method according to claim 10, wherein the target is made of titanium. (13) Re-reacting the vapor with a gas to form a composite so that the composite is deposited on the substrate as the coating. A method according to claim 1O. 14. The method of claim 13, comprising adding an additive to the composite so that the deposited coating comprises the additive. (15) The method according to claim 14, wherein the additive is oxygen, carbon, or a mixture thereof. (16) The additive is about 2 to 7% of the coating.
15. A method according to claim 14, characterized in that the atomic weight of . (17) The target material is essentially titanium,
14. A method according to claim 13, characterized in that the material is selected from the group consisting of zirconium and alloys of titanium and zirconium. (18) The gas comprises nitrogen, so that the coating is TixZrI N, Zr N, or 0<x
18. A method according to claim 17, characterized in that it comprises T+ x Zr x-1 with <1. (19) The method according to claim 18, wherein the X satisfies 0.1≦x≦0.9. (20) The coating comprises TiN, and the T
19. The method of claim 18, comprising adding to the iN an additive comprising oxygen or carbon or a mixture thereof. (21) The additive is about 2 to 7% of the coating.
21. A method according to claim 20, characterized in that the atomic weight of . (22) The method according to claim 8, wherein the base layer is made of zinc or a zinc alloy. (23) The method according to claim 22, wherein the temperature of the base layer is about 100°C. (24) Re-reacting the vapor with a gas to form a composite so that the composite is deposited on the substrate as the coating. The method according to claim 22. 25. Adding an additive to the composite so that the deposited coating includes the additive. the method of. (26) The method according to claim 25, wherein the additive is oxygen, carbon, or a mixture thereof. (27) The additive is about 2 to 7% of the coating.
26. A method according to claim 25, characterized in that the atomic weight of . (28) the target material is essentially titanium;
25. The method of claim 24, wherein the material is selected from the group consisting of zirconium, alloys of titanium and zirconium, and alloys of titanium and aluminum. (29) TiN, where the gas comprises nitrogen, so that the coating is 0<x<1;
Zr N, Tt, Zr I-! N or Ti
,Ai,-. 29. The method of claim 28, comprising: N. (30) The method according to claim 29, wherein the X satisfies 0.1≦x≦0.9. (31) the coating comprises TiN, the TiN
30. A method according to claim 29, characterized in that the method comprises adding an additive consisting of oxygen or carbon or a mixture thereof. (32) The additive is about 2 to 7% of the coating.
32. A method according to claim 31, characterized in that the atomic weight of . (33) The method according to claim 8, wherein the base layer is made of brass. (34) The method according to claim 33, wherein the temperature of the base layer is about 150°C. 35. The vapor is re-reacted with a gas to form a composite so that the composite is deposited as the coating on the substrate. The method described in Section 33. 36. The method of claim 35, further comprising adding an additive to the composite so that the deposited coating includes the additive. (37) The method according to claim 36, wherein the additive is oxygen, carbon, or a mixture thereof. (38) The additive is about 2 to 7% of the coating.
37. A method according to claim 36, characterized in that the atomic weight of . (39) the target material is essentially titanium, zirconium, or an alloy of titanium and zirconium;
and an alloy of titanium and aluminum.
The method described in Section 5. (40) The gas comprises nitrogen, so that the coating comprises TixZri N, Zr N, or O
TixZrl * Zr 1− when <x<1
40. A method according to claim 39, characterized in that xN or Ti-AQ=+-1N. (41) The method according to claim 40, wherein the X satisfies 0.1≦x≦0.9. (42) the coating comprises TiN, the TlN
41. The method of claim 40, further comprising the step of adding an additive comprising oxygen or carbon or a mixture thereof. (43) The additive is about 2 to 7% of the coating.
43. A method according to claim 42, characterized in that the atomic weight of . (44) A method of coating a base layer, comprising: continuously applying an arc to a target to vaporize target material; providing a base layer consisting essentially of stainless steel; said base layer essentially consisting of stainless steel; depositing said vapor on said base layer to provide a coating of at least said target material on said base layer in said case of class rings, pen caps, eyeglass frames and silverware. How to characterize it. (45) The method according to claim 44, wherein the temperature of the base layer is approximately 400°C. (4G) Re-reacting the vapor with a gas to form a composite so that the composite is deposited as the coating on the substrate. The method described in item 44. (47) The target material is essentially titanium,
47. The method of claim 46, wherein the material is selected from the group consisting of zirconium, alloys of titanium and zirconium, and alloys of titanium and aluminum. (48) TiN, Zr N, where the gas comprises nitrogen, so that the coating is 0<x<1;
Ti x Zr 1-* N or T1 x AQ,,
48. A method according to claim 47, characterized in that -xN. (49) The method according to claim 48, wherein the X satisfies 0.1≦x≦0.9. (50) A method of coating a substrate, the step of continuously applying an arc to a target consisting essentially of titanium, an alloy of titanium and zirconium, and an alloy of titanium and aluminum to vaporize the target material; providing a base layer consisting essentially of tool steel; re-reacting said vapor with a gas containing nitrogen or carbon to form a composite; and applying a coating on said base layer consisting of at least said target material. depositing the composite on the base layer to provide, the coating is essentially TiC, TiC, N1-1l, TixZrl x where 0<x<1
Zr r-xN, and Ti, A-xN, -xN. (51) The method according to claim 50, wherein the X satisfies 0.1≦x≦0.9. 52. The method of claim 50, wherein the temperature of the substrate is greater than or equal to about 450°C. (53) A method of coating a substrate by arcing a target consisting essentially of at least one of titanium, an alloy of titanium and aluminum, zirconium, or an alloy of titanium and zirconium to vaporize the target. providing a decorative component as said base layer, the material comprising said component being selected from the group consisting essentially of plastic, zinc, zinc alloy, brass and stainless steel; and nitrogen or A method comprising the steps of: re-reacting the vapor with a gas comprising at least one carbon-containing gas; and depositing the re-reactant as a coating on the substrate. 54. The method of claim 53, wherein the decorative parts consist essentially of class rings, watch cases, watch bands, silverware, eyeglass frames, pen caps, and lighters. (55) T1*Zr when the base layer comprises a titanium-zirconium alloy and the gas satisfies 0<x<1
, -xN on the base layer, the gold color ranging from about 10k to 24k, with k increasing as X increases.
54. A method according to claim 53, characterized in that the method varies up to . 56. The method of claim 55, wherein the gold color is about 10 and X varies between about 0.15 and 0.20. (57) The gold color is about 14, and X is about 0.2.
56. A method according to claim 55, characterized in that it varies between 5 and 0.30. 58. The method of claim 55, wherein the gold color is about 18 mm and X varies between about 0.40 and 0.45. (59) The gold color is about 24, and X is about 0.5.
56. A method according to claim 55, characterized in that it varies between 0 and 0.55. (60) The base layer is titanium, and the gas comprises the carbon-containing gas to provide a gray coating comprising TiC on the base layer. the method of. (,8l-)--nitrogen and said carbon-containing gas in order to provide a colored coating on said base layer, said base layer being titanium and said gas comprising TiCyN11 where 0<x<1. 54. A method according to claim 53, characterized in that the color of the coating is brown, bronze, dark brown, depending on the value of X. (B2) T1, A9J when the base layer comprises a titanium-aluminum alloy and the gas satisfies 0<x<1
, xN on the base layer, comprising nitrogen, the color of the coating being dark brown or black, depending on the value of X. . (133) The method according to claim 53, comprising adding σ2 or C or a mixture thereof to the coating. (B4) A method according to claim 63, characterized in that the target consists essentially of titanium and the gas consists essentially of nitrogen, so that the coating is doped with TiN. . (65) The color of the added TiN is gold, which is about 10k according to the relative proportions of C and 02 additives.
65. The method of claim 64, wherein the method varies from 24k to 24k. (66) Claim 65, wherein the gold color is about 10%, the amount of the 02 additive is about 4 atomic percent, and the amount of the C additive is about 3 atomic percent. The method described in section. 67. The method of claim 66, wherein the amount of T1 is an atomic ratio of about 1.25 to about 1.40 for each atomic percent of xN. 68. The method of claim 85, wherein the gold color is about 14% and the amount of the 02 additive is about 4 atomic percent. 69. The method of claim 68, wherein the amount of Ti is in an atomic ratio of about 1.15 to about 1.20 for each atomic percent of xN. (70) the gold color is about 18%, the amount of the 02 additive is about 2 atomic percent, and the C additive is about 5%
66. The method of claim 65, wherein atomic percent. (71) The target comprises essentially zirconium and the gas consists essentially of nitrogen, so that
A method as claimed in claim u, characterized in that the coating is doped with ZrN. (72) The color of the added ZrN is platinum,
A method according to claim 1, characterized in that this varies from about 10k to 24k, depending on the relative proportions of the C and 02 additives. 73. The method of claim 72, wherein the sub-golden color is about IQk and the amount of the 02 additive is about 2 atomic percent. (74)--The gold color is about 14%, the amount of the 02 additive is about 1 atomic percent, and the C additive is about 4 atomic percent. The method described in section. (75) The method according to claim (2), wherein the color of the added ZrN is platinum. 7B. The method of claim 75, wherein the amount of additive is about 5 atomic percent O2.

Claims (1)

[Scope of Claims] (1) A method for coating a base layer, comprising the steps of: successively applying pulses of an arc to the target to evaporate the target material; and coating at least the target material on the base layer. depositing said vapor on said base layer for applying said vapor. 2. The method of claim 1, wherein the thickness of the coating is no greater than about 50 microns. 3. The method of claim 2, wherein the coating is formed in multiple layers. (4) The method of claim 3, wherein each of said layers is made of the same material. 5. The method of claim 3, wherein at least one of the layers is of a different material than the other layers. 6. The method of claim 2, wherein the coating thickness is no greater than about 5 microns. 7. The method of claim 6, wherein the thickness is in the range of 0.1 microns to about 5 microns. 8. The method of claim 1, wherein the duty cycle of the arc pulses is such that the temperature of the substrate is well below 350°C. (9) The method of claim 8, wherein the temperature of the base layer is about 50°C to about 150°C. (10) The method according to claim 8, wherein the base layer is made of plastic. (11) The method according to claim 10, wherein the base layer temperature is about 50°C. (12) The method according to claim 10, wherein the target is made of titanium. (13) Re-reacting the vapor with a gas to form a composite so that the composite is deposited on the substrate as the coating. The method according to claim 10. 14. The method of claim 13, comprising adding an additive to the composite so that the deposited coating comprises the additive. (15) The method according to claim 14, wherein the additive is oxygen, carbon, or a mixture thereof. (16) The additive is about 2 to 7% of the coating.
15. A method according to claim 14, characterized in that the atomic weight of . (17) The target material is essentially titanium,
14. A method according to claim 13, characterized in that the material is selected from the group consisting of zirconium and alloys of titanium and zirconium. (18) The gas comprises nitrogen, so that the coating comprises TiN, ZrN, or Ti_xZr_x_-_1 where 0<x<1. Method described. (19) The method according to claim 18, wherein the x satisfies 0.1≦x≦0.9. (20) The coating comprises TiN, and the T
19. The method of claim 18, comprising adding to the iN an additive comprising oxygen or carbon or a mixture thereof. (21) The additive is about 2 to 7% of the coating.
21. A method according to claim 20, characterized in that the atomic weight of . (22) The method according to claim 8, wherein the base layer is made of zinc or a zinc alloy. (23) The method according to claim 22, wherein the temperature of the base layer is about 100°C. (24) Re-reacting the vapor with a gas to form a composite so that the composite is deposited on the substrate as the coating. The method according to claim 22. 25. Adding an additive to the composite so that the deposited coating includes the additive. the method of. (26) The method according to claim 25, wherein the additive is oxygen, carbon, or a mixture thereof. (27) The additive is about 2 to 7% of the coating.
26. A method according to claim 25, characterized in that the atomic weight of . (28) the target material is essentially titanium;
25. The method of claim 24, wherein the material is selected from the group consisting of zirconium, alloys of titanium and zirconium, and alloys of titanium and aluminum. (29) The gas comprises nitrogen, so that the coating is TiN, ZrN, T when 0<x<1
i_xZr_1_-_xN, or Ti_xAl_1_
-_xN
The method described in Section 8. (30) The method according to claim 29, wherein the x satisfies 0.1≦x≦0.9. (31) the coating comprises TiN, the TiN
30. A method according to claim 29, characterized in that the method comprises adding an additive consisting of oxygen or carbon or a mixture thereof. (32) The additive is about 2 to 7% of the coating.
32. A method according to claim 31, characterized in that the atomic weight of . (33) The method according to claim 8, wherein the base layer is made of brass. (34) The method according to claim 33, wherein the temperature of the base layer is about 150°C. 35. The vapor is re-reacted with a gas to form a composite so that the composite is deposited as the coating on the substrate. The method described in item 33. 36. The method of claim 35, further comprising adding an additive to the composite so that the deposited coating includes the additive. (37) The method according to claim 36, wherein the additive is oxygen, carbon, or a mixture thereof. (38) The additive is about 2 to 7% of the coating.
37. A method according to claim 36, characterized in that the atomic weight of . (39) the target material is essentially titanium;
36. The method of claim 35, wherein the material is selected from the group consisting of zirconium, alloys of titanium and zirconium, and alloys of titanium and aluminum. (40) The gas comprises nitrogen, so that the coating is TiN, ZrN, or Ti_xZr_1_-_xN, or Ti_x when 0<x<1.
40. A method according to claim 39, characterized in that it comprises Al_1_-_xN. (41) The method according to claim 40, wherein the x satisfies 0.1≦x≦0.9. (42) the coating comprises TiN, the TiN
41. The method of claim 40, further comprising the step of adding an additive comprising oxygen or carbon or a mixture thereof. (43) The additive is about 2 to 7% of the coating.
43. A method according to claim 42, characterized in that the atomic weight of . (44) A method of coating a base layer, comprising: continuously applying an arc to a target to vaporize target material; providing a base layer consisting essentially of stainless steel; said base layer essentially consisting of stainless steel; depositing said vapor on said base layer to provide a coating of at least said target material on said base layer in said case of class rings, pen caps, eyeglass frames and silverware. How to characterize it. (45) The method according to claim 44, wherein the temperature of the base layer is approximately 400°C. 46. The vapor is re-reacted with a gas to form a composite so that the composite is deposited as the coating on the substrate. The method described in item 44. (47) The target material is essentially titanium,
47. The method of claim 46, wherein the material is selected from the group consisting of zirconium, alloys of titanium and zirconium, and alloys of titanium and aluminum. (48) The gas comprises nitrogen, so that the coating is TiN, ZrN, T when 0<x<1
i_xZr_1_-_xN or Ti_xAl_1_-
48. The method of claim 47, comprising: _xN. (49) The method according to claim 48, wherein the x satisfies 0.1≦x≦0.9. (50) A method of coating a substrate, the step of continuously applying an arc to a target consisting essentially of titanium, an alloy of titanium and zirconium, and an alloy of titanium and aluminum to vaporize the target material; providing a base layer consisting essentially of tool steel; re-reacting said vapor with a gas containing nitrogen or carbon to form a composite; and applying a coating on said base layer consisting of at least said target material. depositing the composite on the base layer to provide the coating with TiC, TiC_xN_1_-_x, Ti_xZr with 0<x<1;
_1_-_xN, and Ti_xAl_1_-_xN. (51) The method according to claim 50, wherein the X satisfies 0.1≦x≦0.9. 52. The method of claim 50, wherein the temperature of the substrate is greater than or equal to about 450°C. (53) An apparatus for coating a base layer, the apparatus comprising: means for successively applying pulses of an arc to the target to vaporize the target material; and providing a coating on the base layer comprising at least the target material. and means for depositing the vapor on the substrate for the purpose of depositing the vapor onto the substrate. 54. The apparatus of claim 53, wherein the duty cycle of the arc pulses is such that the temperature of the base layer is well below 350°C. (55) The apparatus of claim 54, wherein the temperature of the base layer is about 50°C to about 150°C. (56) The device according to claim 53, wherein the base layer is made of plastic. (57) The method of claim 53, wherein the base layer comprises zinc or a zinc alloy. (58) The device of claim 53, wherein the base layer comprises brass. (59) An apparatus for coating a base layer, the apparatus comprising: means for continuously applying an arc to the target to vaporize the target material; and means for providing a base layer consisting essentially of stainless steel; The base layer is essentially a class ring, a pen cap,
means for depositing said vapor on said substrate for providing a coating of at least said target material on said substrate in the case of eyeglass frames, watch cases and bands, lighter cases, and silverware; A device characterized by: (60) Apparatus for coating a substrate, the means for continuously applying an arc to a target consisting essentially of titanium, alloys of titanium and zirconium, and alloys of titanium and aluminum to vaporize the target material. and means for providing a base layer consisting essentially of tool steel; means for re-reacting said vapor with a gas to form a composite; and a coating comprising at least said target material on said base layer. depositing said composite on said base layer to provide said coating with TiC, TiC_xN_1_, where 0<x<1;
−_x, Ti_xZr_1_-_xN, and Ti_x
An apparatus for coating a substrate, characterized in that the coating is selected from the group consisting of Al_1_-_xN. (61) A method of coating a substrate by arcing a target consisting essentially of at least one of titanium, an alloy of titanium and aluminum, zirconium, or an alloy of titanium and zirconium to vaporize the target. providing a decorative component as said base layer, the material comprising said component being selected from the group consisting essentially of plastic, zinc, zinc alloy, brass and stainless steel; and nitrogen or A method comprising the steps of: re-reacting the vapor with a gas comprising at least one carbon-containing gas; and depositing the re-reactant as a coating on the substrate. 62. The method of claim 61, wherein the decorative parts consist essentially of class rings, watch cases, watch bands, silverware, eyeglass frames, pen caps, and lighters. (63) Ti_xZr when the base layer comprises titanium and zirconium alloy and the gas satisfies 0<x<1
Nitrogen is provided to provide a golden coating on the base layer consisting of
As k increases as , from about 10k to 2
Claim 6 characterized in that it varies up to 4K.
The method described in Section 1. 64. The method of claim 63, wherein the gold color is about 10k and x varies between about 0.15 and 0.20. 65. The method of claim 63, wherein the gold color is about 14k and x varies between about 0.25 and 0.30. 66. The method of claim 63, wherein the gold color is about 18k and x varies between about 0.40 and 0.45. 67. The method of claim 63, wherein the gold color is about 24k and x varies between about 0.50 and 0.55. 68. The base layer of claim 61, wherein the base layer is titanium and the gas comprises the carbon-containing gas to provide a gray coating comprising TiC on the base layer. Method. (69) The base layer is titanium, and the gas is 0
To provide on said base layer a colored coating comprising TiC_xN_1_-_x where 62. The method of claim 61, wherein the color is dark brown. (70) Ti_xAl when the base layer comprises a titanium-aluminum alloy and the gas satisfies 0<x<1
62. The method according to claim 61, characterized in that nitrogen is provided for providing on the base layer a colored coating comprising _1__xN, and the color of the coating is dark brown or black, depending on the value of x. Method. (71) The method of claim 61, comprising adding O_2 or C or a mixture thereof to the coating. 72. The method of claim 71, wherein the target consists essentially of titanium and the gas consists essentially of nitrogen so that the coating is doped with TiN. (73) The color of the added TiN is gold, which is about 10% according to the relative proportions of C and O_2 additives.
73. A method according to claim 72, characterized in that the number varies from k to 24k. (74) Claim 73, wherein the gold color is about 10k, the amount of the O_2 additive is about 4 atomic percent, and the C additive is about 3 atomic percent. Method described. 75. The method of claim 74, wherein the amount of Ti is in an atomic ratio of about 1.25 to about 1.40 for each atomic percent of N. 76. The method of claim 73, wherein the gold color is about 14k and the amount of O_2 additive is about 4 atomic percent. 77. The method of claim 76, wherein the amount of Ti is in an atomic ratio of about 1.15 to about 1.20 for each atomic percent of N. (78) The gold color is about 18k, the amount of the O_2 additive is about 2 atomic percent, and the C additive is about 5 atomic percent. the method of. 79. The method of claim 71, wherein the target consists essentially of zirconium and the gas consists essentially of nitrogen, so that the coating is doped with ZrN. . (80) The color of the added ZrN is platinum, which is approximately 1
80. A method as claimed in claim 79, characterized in that it varies from 0k to 24k. 81. The method of claim 80, wherein the gold color is about 10k and the amount of O_2 additive is about 2 atomic percent. (82) The gold color is about 14k, the amount of the O_2 additive is about 1 atomic percent, and the C additive is about 4 atomic percent. the method of. (83) The method according to claim 79, wherein the color of the added ZrN is platinum. (84) The amount of the additive is about 5 atomic percent O_
84. The method according to claim 83, characterized in that: 2. (85) Apparatus for coating a substrate, the means for applying an arc to a target consisting essentially of at least one of titanium, titanium aluminum, zirconium, or titanium zirconium to vaporize the target. the decorative part comprises said base layer, and the material comprising said part consists essentially of plastic, zinc or zinc alloys, brass and stainless steel, and includes at least one of nitrogen or carbon-containing gases. an apparatus comprising: means for re-reacting said vapor with a gas that is present in said vapor; and means for depositing said re-reactant as a coating on said substrate. 86. The device of claim 85, wherein the decorative parts consist essentially of a class ring, a watch case, a watch band, silverware, an eyeglass frame, a pen cap, and a lighter. (87) The apparatus of claim 85, comprising adding O_2 or C or a mixture thereof to the coating.