NL8702404A - METHOD AND APPARATUS FOR VACUUM ARCH PLASMA DEPOSITION OF DECORATIVE AND WEAR-RESISTANT COATINGS - Google Patents

Description

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Method and device for vacuum arc plasma deposition of decorative and wear-resistant coatings.

The invention relates to a method and device for coating cosmetic and functional parts with coatings having colors similar to gold (10k-24k) and / or a range of colors of gray, brown, bronze, black and white gold colors, the 5 coatings have excellent adhesion and resistance to corrosion and wear. Typical parts that require wear-resistant or decorative coverings include quality rings, watch cases and bands, lighter sleeves, silverware, auto parts, eyeglass frames, pen caps, instruments, and other (functional) parts subject to wear.

Thin film materials are applied to base materials for decorative applications by either of the following two methods: by sputter deposition and ion galvanizing deposition techniques. However, the typical substrate temperatures involved in both techniques are in the range of 350-550 ° C. These techniques are described, for example, in U.S. Patent 4,402,994, U.S. Patent 3,900,592, and Journal of Vacuum Science and Technology, A, Vol. 4, Nov. 6, 1986, pp. 2717- 2725. However, many substrate materials, such as galvanized zinc castings, brass, bearing steels, bronze and alloys containing zinc, plastics, aluminum and alloys thereof, cannot be subjected to these high temperatures. Moreover, since light yellow or other light colors are generally obtained by these techniques, a top coat with a thin gold film on the surface of hard films is necessary. This is described in U.S. Patent 4,415,421. The bonding of the interface between a hard film and a gold film and the color reproducibility are important for manufacturing technologies. However, the above methods are not always satisfactory in this regard.

* US Pat. Nos. 3,625,848 and 3,793,179 describe devices for vapor depositing a metal coating using a vacuum arc. Improvements thereof are described in U.S. Patent 4,430,184. The above three patents are incorporated herein by reference. Such a 8702-04 v-2-y arc produces a coating flux that has a high degree of ionization and high ion energies. This results in coatings with a dense microstructure and excellent adhesion. However, typical arc production requires typical substrate temperatures in the range of 300-500 ° C.

It is a main object of the invention to provide an arc source and method for depositing decorative and abrasion resistant coatings at already very low substrate temperatures, which is essential for many components, which technique has not hitherto been commercially used for such coatings .

It is another object of the present invention to provide a method and apparatus for applying materials by vacuum cathodic arc deposition on a substrate to very low temperatures (temperature range of about 50-500 ° C).

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

It is a further object of the invention to also provide a method for a non-gold color decorative coating using the above device.

It is a further object of the invention to improve the reproducibility of the color and the abrasion resistance of decorative films on a manufacturing scale.

The method of the invention consists of applying substrates in an evacuated vessel and evaporating titanium, zirconium, titanium-zirconium or titanium-aluminum by the action of an electric arc in an evacuated environment, whereby a flux of ions, vapors and / or other neutral substances are produced on the substrates.

The composition of the coatings can be varied by reacting the latter during deposition with a suitable gas to produce a plurality of films.

The substrate temperature can be set by automatically pulsing the arc source. The "on" time and the "off" time of the arc source can be varied to set the substrate temperature to temperatures of not more than approximately 170 ° C. 40 - 3 - more than approximately 50 °. Further, the adhesion of the coating is improved by setting a bias on the substrate to attract ions The coating consists of nitrides, carbides, carbonitrides of titanium, titanium-aluminum, zirconium and titanium-5 zirconium based systems The color can be varied by doping the films with suitable dopants, such as oxygen and carbon, the dopant gas typically being present in a range of 2-7 atomic percent or by using appropriate reactive gas environments. The different range of gold colors (10k-24k) has been 10 duplicated in, for example, Ti N, or Ti Zr - N wherein 0 <x <1 and Λ 1 “XA ix doped TiN or ZrKf films.

Other objects and advantages of this invention will be illustrated below.

Brief Description of the Drawings Figure 1 is a schematic view of an illustrative cathodic arc plasma positioner used in the invention.

Figure 2 is a schematic view of an illustrative arc source used in the cathodic arc plasma positioner.

Figure 3 is a time chart representing an illustrative power cycle of the arc source of this invention.

Figure 3A is a block diagram illustrating a control circuit for use in the arc supply of the present invention.

Figure 3B is an illustrative flowchart of a program useful with the control circuits of Figure 3A.

Figure 4 illustrates reflection profiles of films produced by the manufacturing method of the invention.

Figures 5 and 5A are profiles indicating the atomic position of coating films produced according to the manufacturing method of this invention.

Reference is now made to the drawing in which the same reference numerals refer to the same parts.

According to the present invention, the drawbacks of the prior art are overcome by improving the adhesion and color reproducibility in a cathodic arc deposition method and device. "O 4 u - 4 - improve. The method and apparatus of the invention are useful in more detail for coating a variety of substrates, including zinc, aluminum, stainless steel, plastic, brass, and alloys thereof. In the hard material coated substrates according to the present invention, the surface of the instrument or part is coated with at least one hard coating material selected from nitrides, carbides, carbonitrides and doped compounds thereof of titanium, zirconium, titanium aluminum and titanium zircon systems.

In Figure 1, an arc plasma positioner 100 of 10 illustrates an illustrative embodiment of the invention. Within the vacuum vessel, an arc source 110 is operated by an external pulsed power supply 105. The substrates to be coated may be mounted on a rotating table 102. The rotary table 102 can obtain a negative bias voltage through an external high voltage supply 104. The supplies 104 and 105 may be grounded or connected to suitable positive voltage sources as indicated in Figure 1. Device 100 is also equipped with a gas inlet pipe 106 and an evacuation pump system 101. Various gases can be transferred to the gas inlet pipe 106 after a series of valves. A shutter 108 20 can also be used. Furthermore, the arc source can be partially plated (not shown) to reduce the coating flux to control the substrate temperature.

Figure 2 is a schematic diagram of an illustrative arc source 110 in which the material to be evaporated is heated by the action of an electric arc. The arc source can be arranged in side, top or top configurations in the vacuum chamber. The arc limitation at the source is achieved with a limiting ring 113. The limiting ring 13 can be composed of tree nitride, titanium nitride, pyrex glass, quartz or soda lime glass. The arc limitation can also be achieved with suitable interface screens and magnetic fields. In the latter techniques, arc quenching takes place and the arc is automatically re-ignited with a suitable electronic controller, as described, for example, in U.S. Pat. No. 3,793,179. The power supply 105 can be DC if the target is conductive and RF if it is insulating.

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The anode 114 is spaced from the cathode or target 102. The anode may consist of an outer housing of the arc source, or chamber walls, or an enclosure within the chamber, with electrical bias or grounded. The anode 114 may be physically mounted within the chamber 100 separately from the chamber walls and base plates and separately biased to act as the anode of the electrical system, as illustrated in Figure 2 and described in U.S. Patent 3,625. 848. In addition, the entire chamber or an enclosure thereof may have a grounded potential (see, for example, U.S. Pat. No. 3,793,179) and act as the anode of the electric arc system.

Figure 3 shows illustrative power circuits of the voltage supply 105. The time during which the arc source is energized and the time during which the arc source is turned off can be varied independently. For example, the time may be hours when the arc is operated continuously or it may be minutes when pulsed. The time T2 can be 0 or finite. Typical pulse peak values range in the range of 30-200 amps.

Reference is now made to Figures 3A and 3B, in which Figure 3A is a block diagram of an illustrative control circuit for use in the arc supply of the present invention, while Figure 3B is an illustrative flowchart of a subroutine of the program useful in the controller of 3A. Referring generally to Figure 3A, the control circuit 120 includes a programmable process controller 122. The controller may be obtained from Texas Instruments Corporation, model TCAM 5230, which controller includes a program for controlling the cathodic arc process. According to an aspect of the invention, the program is modified by adding to it program steps that may correspond to those exemplified in the flowchart of Figure 3B. Conventionally, the controller 122 includes an output 128 which controls the magnitude of the current supplied by the arc supply 105 and the output 130 which controls the magnitude of the bias voltage supplied by the voltage supply 104. The controller 122 is also adapted as usual to receive a signal from a temperature sensor 132, the controller comprising an internal analog digital circuit for digitizing the output signal of 870 3404 - the temperature sensor to measure the temperature sensor. facilitate its processing. The temperature sensor 132 can typically be a conventional infrared sensor that reads the temperature from the substrates 103. This temperature will hereinafter be referred to as T. The controller also includes user

O

5 an output 134 which turns the arc supply 105 on and off. A conventional output 135 is also provided which is applied to a detonator 115 through a coil 115 'to initiate an arc from target 102 where the detonator may be of the electromechanical, electrical or gas discharge type.

In operation, the program normally supplied with the controller 102 allows the magnitude of the arc current of the output 102 to be set. Adjustment of the magnitude of the bias voltage supplied by the voltage source 104 is also possible. In the modification of the program, according to an aspect of the invention, the subroutine of Figure 3B is entered at 137 and the substrate temperature is read at 134. The substrate temperature T is then compared b with the lower temperature limit T at 136. If the

L

For example, it is desirable to maintain the average temperature of the substrate 103 at about 100 ° C, the lower temperature limit T will be below

L

20 be 90 ° C. If the substrate temperatures are lower than T.

L

a current from output 136 is sent through igniter 115 to initiate the arc; this is indicated as 138. This time moment corresponds to one of the leading edges of the pulses shown in Figure 3. As mentioned above, the size of the pulses is usually controlled from output 128 when the pulse is initiated. the subroutine of Figure 3A at 139 to return to the main program usually supplied with controller 122.

As long as the deposition procedure continues, the routine of Figure 3B will be performed repetitively. Once one has returned to the routine, the substrate temperature is read again and a comparison is made again with the lower temperature limit T at 136. At this time, assuming that the substrate temperatures are higher than that of the lowest temperature limit, a another comparison was made to determine whether or not the substrate temperature is higher than the upper temperature limit T ^. Assuming that the desired mean temperature of the substrate is about 100 ° C, the temperature limit is typically set at about 110 ° C.

If this temperature limit is exceeded, a signal from output 134 of controller 122 is applied to turn off arc supply 105, which is indicated at 142.

This time corresponds to the trailing edges of the pulses shown in Figure 3. Once the arc supply 105 is turned off, the main program returns to output 139.

If the substrate temperature Tg is less than the upper temperature-10 limit T ^, the pulse is maintained in its state.

From the foregoing, it is seen that the arc source 110 is pulsed to maintain the temperature of the substrates at a level suitable for the type of coating applied thereto, as will be further discussed in Example I below.

Other possibilities can be used to provide pulsation of the arc source. For example, one can perform an equation at 136 to determine whether. if so, the arc is supplied

switched off. Comparisons are then made at 140 to determine when T <T. When this occurs, the arc becomes in-S L again

20 led. In addition, one may employ an equipment configuration where equipment sources for supplying a pulse train other than in cathode deposition applications are known. The nature of the control provided to maintain the substrate temperature may be in other ways than that illustrated in Figure 38. For example, a conventional closed loop control can be employed in which the sensed substrate temperature is continuously compared to the desired substrate temperature and a continuous error signal is provided which is useful for controlling the substrate temperature. Optionally, an approach similar to that of Figure 3B can be applied when an equation corresponding to stage 136 is performed to determine if the temperature T is less than T. If so, the

S L

arc turned on and supply 105 is turned on for a predetermined period of time. No upper temperature limit is applied. Instead, the substrate temperature T is repetitively compared to the lower temperature T. When τ is smaller again

Ice

8 / v: ·: 'r · t.

* - 8 -

then T, the arc feed is restarted for a predetermined time L

period turned on. The arc is introduced within the chamber by igniter 115. Igniter 115 may be an electromechanical device that contacts the surface of the cathode source with an arc lead lead wire or a gas discharge ignition system, wherein a high voltage gas discharge between the igniter and the cathode surface is provided by a suitable power supply creates an electrical current path. The cathodic arc source is water cooled through a special channel machined on the copper block 111 attached to the back of the cathode or an arc source material 102. The action of the electric arc on the surface of a cathode material results in a "cathode spot" . The cathode spot moves randomly on the surface of the coating source material to form a coating plasma. The cathode spot movement can also be controlled using a suitable magnetic field arrangement.

The parts to be coated within the chamber are typically referred to as substrates and are generally illustrated at 103, the substrates not being illustrated in detail as they do not form part of the invention. The source of the coating material 102 is typically referred to as a cathode or target (when the target can be positioned on the cathode or the target is the cathode). The target 102 is the origin of the coating flux or plasma for the arc deposition process. The source materials 102, such as titanium, zircon, titanium zircon or titanium aluminum, are solids 25 and can be in cylindrical, circular, elongated or rectangular shape or any other suitable shape. Optionally, one can also use separate targets for each source material to perform auxiliary deposition of a mixed coating system. In operation, the substrates to be coated are chemically cleaned and then loaded onto a rotating work holder 102. The vacuum chamber 100 is then pumped empty with pump system 101 to a base pressure. The substrates or parts are then ion purified and heated by turning on a metal ion bombardment through arc sources 110 and biasing the substrates by feed 104. Also, the arc 110 is pulsed with different power circuits 87 0 2 40 4 - 9 - * and the bias voltage from supply 104 and the arc current source 105 are adjusted depending on the temperature limit of the substrates. To maintain the chamber pressure in the range of about 0.1 to 5.0 micrometers, a reactive gas with appropriate dopants is then introduced through the gas inlet valve 106 and the gas into the line valves 107. The substrate bias and arc current can be adjusted by an automatic process controller driven by a preset temperature limit. The resulting hard coat will settle at a set substrate temperature. In addition, typical coating thicknesses in the range of about 0.5 to 5.0 microns are deposited for decorative purposes.

EXAMPLE I

Different typical operating conditions observed for different substrate temperatures and coating combinations are shown in Table A, wherein the range of x for alloys and carbonitrides varied from 0 <x <1, and in particular from 0.1 to 0.9 in 0.1 steps unless otherwise noted, such as in samples 5 and 14, in which the 0.1 steps were increased from 0.1 to 0.5. Generally, sample 10 forms, for example, 9 samples in which x increases from 0.1 to 0.9 in steps 20. The foregoing applies to all samples where an alloy represents the target material or the carbonitride is the coating material whose values of x are mentioned.

Furthermore, the dopants were O 2 or C or a mixture thereof in which background C> 2 was typically present in the C-doped samples and the amount of dopant was in the range of about 2 to 7 atomic percent. The C source was typically a carbonaceous gas, such as CH 2 or C 2 H 2. The foregoing applies to all samples stating that the coating material is doped.

The aforementioned remarks regarding the relative alloys and carbonitride amounts and doping amounts also apply to Example II below and all other references to "x" and dopants in the specification and claims. Furthermore, an inert gas, such as argon, may also be present.

87 0 "U

%

- 10 TABLE A

Sample Substrate Average Coating Average No. Material Substrate Material Arc Pulse Time Temperature ------------ T ^ (min) T ^ (min) 5 1 Plastic ~ 50 ° C Ti 0.5 0, 25 2 "~ 50 ° C TiN 0.25 0.25 3" ~ 50 ° C TiN doped 0.25 0.25 4 "~ 50 ° C ZrN 0.5 0.5 5" ^ 50 ° C Ti Zr. N 0.5 0.5 x 1-x 10 (0 <x S 0.5) 6 Zinc or zinc blanks: <^ 100 ° C TiN 0.5 0.5 quality rings, spectacle frames, pen caps, lighters and watch-15 mounts 7 "" ~ Ί00 ° Ο TiN doped 0.5 0.25 8 "" roll 00 ° C ZrN 0.5 0.25 9 "" ^ 100 ° C Ti Zr. N 0.5 0.25 x 1-x 10 "" ~ 100 ° C Ti Al, N 0.75 0.25 x 1 -x 20 11 Brass: pen caps, —150 ° C TiN 1.0 0.5 quality rings , spectacle frames 12 "" ~ 150 ° C ZrN 1.0 0.5 13 "" ~ 150 ° C Ti Zr, N 1.0 0.5 x 1-x "25 14" "~ 150 ° C Ti Al . N 1.0 0.25 x 1 -x (0 <x S 0.5) 15 "" <^ 150 ° C TiN doped 1.0 0.5 16 Stainless steel ~ 400 ° C TiN each (300 series) : 30 quality rings, pen caps, spectacle frames and silver ware 17 "" ~ 400 ° C ZrN each 35 18 "" <~ 400 ° C Ti Zr, N each x 1-x 19 "" ~ 400 ° C Ti Al, N each x 1-x 87 0?. 0 4 * - 11 - TABLE A (continued)

Sample Substrate Average Coating Average No. Material Substrate Material Arc Pulse Time Temperature ------------- T (min) 5 20 Tool Steel έ 450 ° C TiC (High Speed Steel and Cemented Carbides 21 "" è 450 ° C TiC N. each x 1-x 10 22 "” S 450 ° C Ti Zr, N each x 1-x 23 "* 'έ 450 ° C Ti Al, N each x 1-x

The results of Table A showed that when the coating thickness was less than 5 micrometers, the gloss of the base material was maintained. It is also possible to deposit thicker layers (such as 25 or 30 micro-15 meters. In such layers, the gloss (reflection) of a substrate (base material) cannot be duplicated, but the surface finish can be duplicated. Typical layers with the above thickness can be different layers in which the material of the respective layers may be the same or different.

Figure 4 shows the optical reflection spectra of doped

TiN, doped ZrN and Ti Zr N films produced by the present invention X 1-x invention. The reflection spectrum of a 14k gold film is also illustrated. Thus, it is seen that the optical reflectance spectra of the films of this invention may be as required by US Patent 4,415,521. Different color spectra obtained in the different coating systems are given in Table B as Example II. See example II and table B.

8702 04 - 12 -%

EXAMPLE II

TABLE B

No. Sample Coating Material Color Type 1 TiN Golden Yellow 2 TiN Doped Gold (10k-24k) 3 ZrN Yellowish Green 5 4 ZrN Doped White Gold 5 Ti Zr. N Gold (10k-24k) x 1-x 6 TiC Gray 7 TiC N Brown, bronze, X x dark brown 8 Ti Al N Dark brown, x 1-x black 10 From the results of table B it can be seen that a spacious of colors for decorative coverings can be produced. The thickness of the coating film was always in the range of 0.10 to 5 microns. As for TiN, the golden yellow color is generally rich in green and bronze colors while the ZrN is a yellowish green with a green predominance. Both TiN and ZrN can be doped 0 ^ to eliminate greenness and with C to increase redness. Thus, by combination of the O 2 and C dopants, one can control 10k-24k with doped TiN or doped ZrN. In addition, with respect to Ti Zr N, the value of k increases as the value of x

X 1 X

20 increases. Similarly, TiC N and Ti Al N vary via

X 1 X X X —X

different colors as the value of x changes.

In Figure 4, the 14k became gold in the Ti Zr N coating

x 1 “X

established with values of x in the range of about 0.25 to about 0.30. This color was accomplished by the doped ZrN coating with a doping of about 1% 0 ^ and about 4% C, wherein all percentages are atomic percentages for all dopants listed. The 14k gold color of the doped TiN was accomplished with approximately 4% doping. In addition, Ti and N were present in non-stoichiometric proportions with the amount of Ti 30 ranging from 1.15 to 1.5 atomic ratio for each atomic percent of N.

f702404 Λ.-13-

To achieve non-stoichiometric films, a reduced nitrogen pressure in the range of 0.1-1.0 micrometers was used. Regarding the 10k gold color, it was accomplished with (a) Ti Zr N, X 1 wherein x ranged from 0.15 to about 0.20, (b) doped ZrN with about 2% O 2 dopant and ( c) doped TiN with about 4% O 2 doping and 3% C doping with the amount of Ti ranging from about 1.25 to about 1.40 atomic ratio for each atomic percent N.

With respect to the 18k gold color, doped TiN with about 2% O 2 doping and about 5% carbon doping or Ti 2 Zr 2 χΝ where 10x ranged from about 0.4 to about 0.45 were effectively used.

Regarding the 24k gold color, Ti Zr N, wherein x

X X “X

ranges from about 0.5 to about 0.55.

EXAMPLE III

Subsequently, the abrasion resistance of these coatings was measured by a pen-to-disk method, where a pen was loaded with a 500 g load on rotating coated samples (coated disks) and any scratches in the coating were observed in an optical microscope with a magnification of 50x after 50 revolutions. None of the hard coatings of Table B had scratches.

EXAMPLE IV

Figures 5 and 5a show the atomic composition profiles for different coatings for different colors, as measured by electron spectroscopy for chemical analysis (ESCA), in which Figure 5 shows the ESCA sputtering depth profile for the TiN film 25 doped with O2 and C and Figure 5A the same profile for a TiZrN movie is. The O ^ in the movie results from the background level of O ^ in the system. This background level was also included in the O ^ illustrated in Figure 5.

It is understood that the above detailed description of various embodiments of the invention is given by way of example only. Various details of the coating materials, design and construction can be modified without departing from the scope of the invention.

v / 1 'C * i' * · '; * - 14 -

While the preferred embodiments of the invention have been described in connection with an arc coating system, it will be appreciated that the invention is also useful for other systems, such as when material is vaporized from a target through an arc, which is to be a predetermined surface of the target surface limited.

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Claims (88)

A method of coating a substrate comprising the following steps: sequentially applying arc pulses to a target to evaporate the target material and depositing the evaporated material on the substrate to provide a coating of at least the target material thereon. A method according to claim 1, characterized in that the thickness of the coating does not exceed about 50 micrometers. Method according to claim 2, characterized in that said coating is formed in multiple layers. Method according to claim 3, characterized in that each of said layers contains the same material. Method according to claim 3, characterized in that at least one of said layers comprises a material other than that of the other layer. A method according to claim 2, characterized in that the thickness of said coating does not exceed about 5 micrometers. 7. A method according to claim 6, characterized in that said thickness is in the range from 0.1 to about 5 micrometers. A method according to claim 1, characterized in that the power cycle of said arc pulsations is such that the temperature of said substrate is considerably less than 350 ° C. 9. A method according to claim 8, characterized in that the temperature of said substrate is about 50 ° C to about 150 ° C. Method according to claim 8, characterized in that said substrate comprises a plastic material. A method according to claim 10, characterized in that said substrate is at a temperature of about 50 ° C. A method according to claim 10, characterized in that said target contains titanium. A method according to claim 10, comprising reacting said evaporating agent with a gas to form an 8 7 0 2 * 0 A 9-16 compound such that said compound is deposited as said coating on said substrate. 14. A method according to claim 13, characterized in that said material is doped with a dopant such that the deposited coating comprises said dopant. A method according to claim 14, characterized in that said dopant is oxygen, carbon or a mixture thereof. A method according to claim 14, characterized in that said dopant constitutes about 2-7 atomic percent of the coating. A method according to claim 13, characterized in that said target material is selected from the group consisting essentially of titanium, zirconium and titanium-zirconium alloys. A method according to claim 17, characterized in that said gas comprises nitrogen such that said coating comprises TiN, ZrN or Ti Zr N, X X 'X 15 wherein 0 <x <1. The method of claim 18, wherein 0.1 S x Si 0.9. 20. A method according to claim 18, characterized in that said coating comprises TiN, said method comprising doping said TiN with a dopant consisting of oxygen or carbon or a mixture thereof. A method according to claim 20, characterized in that said dopant constitutes about 2-7 atomic percent of said coating. A method according to claim 8, characterized in that said substrate comprises zinc or a zinc alloy. A method according to claim 22, characterized in that said substrate temperature is about 100 ° C. 24. A method according to claim 22 comprising reacting said evaporating agent with a gas to form a compound such that said compound is deposited as said coating on said substrate. The method of claim 24, comprising doping said compound with a dopant such that the deposited coating comprises said dopant. 26. A method according to claim 25, characterized in that said dopant is oxygen, carbon or a mixture thereof. 8702 * 04 s $ - 17 - A method according to claim 25, characterized in that said dopant constitutes about 2-7 atomic percent of the coating. 28. A method according to claim 25, characterized in that said target material is selected from the group consisting essentially of titanium, zirconium, titanium-zirconium alloys and titanium-aluminum alloys. A method according to claim 28, characterized in that said gas comprises nitrogen such that said coating comprises TiN, ZrN, Ti ^ Zr ^ χΝ or Ti Al „N, wherein 0 <x <1. x 1-x 30. A method according to claim 29, characterized in that 10 0.1 ≤ x ≤ 0.9. A method according to claim 29, characterized in that said coating comprises TiN wherein said method comprises doping said TiN with a dopant consisting of oxygen or carbon or a mixture thereof. A method according to claim 31, characterized in that said dopant constitutes about 2-7 atomic percent of said coating. A method according to claim 8, characterized in that said substrate is brass. 34. A method according to claim 33, characterized in that said substrate temperature is about 150 ° C. A method according to claim 33, characterized in that said evaporating agent is reacted with a gas to form a compound such that said compound is deposited on said substrate as said coating. The method of claim 35, comprising doping said compound with a dopant such that the deposited coating comprises said dopant. A method according to claim 36, characterized in that said dopant is oxygen, carbon or a mixture thereof. A method according to claim 36, characterized in that said dopant constitutes about 2-7 atomic percent of the coating. A method according to claim 35, characterized in that the target material is selected from the group consisting essentially of titanium, zirconium, titanium-zirconium alloys and titanium-aluminum alloys. 8 7 ϋ P.: 0 4 - 18 - 40. A method according to claim 39, characterized in that said gas comprises nitrogen such that said coating comprises TiN, ZrN or Ti Zr N or Ti Al N wherein 0 <x <1, x 1-x x 1-x 41. A method according to claim 40, characterized in that 0.1 S x S 0.9. A method according to claim 40, characterized in that said coating comprises TiN, said method comprising doping said TiN with a dopant consisting of oxygen, carbon or a mixture thereof. A method according to claim 42, characterized in that said dopant constitutes about 2-7 atomic percent of said coating. 44. A method of coating a substrate consisting of the following steps: continuously applying an arc to a target to evaporate the target material, supplying a substrate consisting essentially of stainless steel, and depositing the target material. evaporated agent on the substrate to provide a coating of at least the target material thereon, said substrate essentially consisting of quality rings, cap caps, spectacle frames and silverware. 45. A method according to claim 44, characterized in that the temperature of said substrate is essentially 400 ° C. 46. A method according to claim 44 comprising reacting said evaporated agent with a gas to form a compound such that said compound is deposited as said coating on said substrate. 47. A method according to claim 46, characterized in that said target material is selected from the group consisting essentially of titanium, zirconium, titanium-zirconium alloys and titanium-aluminum alloys. A method according to claim 47, characterized in that said gas comprises nitrogen such that said coating TiN, ZrN, Ti Zr N X 1 "X or Ti Al. N, wherein 0 <x <1, includes x 1-x 49. A method according to claim 48, characterized in that 0.1 x x 0 0.9. 870 2 40 4 s - 19 - 50. A method of coating a substrate comprising the steps of continuously applying an arc to a target consisting essentially of titanium, titanium-zirconium alloys and titanium-aluminum alloys to evaporate the target material; providing a substrate consisting essentially of tool steel; reacting said evaporated agent with nitrogen or a carbon-containing gas to form a compound and depositing the compound on the substrate to provide a coating of at least the target material thereon, which coating is selected from the group in orphans consisting of TiC, TiC N, X χ-X Ti Zr N and Ti Al. N, where 0 <x <1. x 1-x x 1-x 51. A method according to claim 50, characterized in that 1.5 lis x £ 0.9 * A method according to claim 50, characterized in that the temperature of said substrate is greater than or equal to about 450 ° C. 53. Apparatus for coating a substrate comprising means for sequentially applying arc pulsations to a target to evaporate the target material and a means for depositing the evaporated agent on the substrate to provide a coating of at least the target material thereon . 54. An apparatus according to claim 53, characterized in that the power cycle of said arc pulsations is such that the temperature of said substrate is considerably lower than 350 ° C. The device according to claim 54, characterized in that the temperature of said substrate is about 50 to about 150 ° C. 56. An apparatus according to claim 53, characterized in that said substrate comprises a plastic material. The device according to claim 53, characterized in that said substrate comprises zinc or a zinc alloy. Device according to claim 53, characterized in that said substrate comprises brass. 59. A substrate for coating a substrate comprising a means for continuously applying an arc to a target every 8 7 0. 04 • 3 - 20 - target material to evaporate; a member for supplying a substrate essentially consisting of stainless steel and a member for depositing the evaporated agent on the substrate to provide a coating of at least the target material thereon, said substrate essentially consisting of quality rings , pen caps, spectacle frames, bracelets and holders, cases of lighters and silverware. 60. Apparatus for coating a substrate comprising a means of continuously applying an arc to a target material consisting essentially of titanium, titanium-zirconium alloys, and titanium-aluminum alloys to vaporize the target material, a means of providing a substrate consisting essentially of tool steel; A means for reacting said evaporated agent with a gas to form a compound, and depositing the compound on the substrate to provide a coating of at least the target material thereon, which coating is selected from the group consisting essentially of consist of TiC, TiC N, X 1 "X. Ti Zr N and Ti Al. N, where 0 <x <1. x 1-x x 1-x 61. A method of coating a substrate comprising the steps of applying an arc to a target essentially consisting of at least one of titanium, titanium-aluminum, zirconium or titanium-zirconium to vaporize the target; and providing a decorative part as said substrate, which material constituting said part is selected from the group consisting essentially of plastic, zinc, zinc alloys, brass and stainless steel? and reacting the evaporated agent with a gas containing at least nitrogen or a carbonaceous gas and depositing the reaction product as a coating on said substrate. 62. A method according to claim 61, characterized in that said decorative elements essentially consist of quality rings, watch- S Ί Ü Z ί · 0 4? ft - 21 - cabinets, watch bands, silverware, spectacle frames, pen caps and lighters. 63. A method according to claim 61, characterized in that said substrate comprises a titanium-zirconium alloy and said gas comprises nitrogen, wherein a gold-colored coating consisting of Ti Zr N, wherein 0 <x <1 and the gold color ranges from X 1 ™ x about 10k to 24k such that when x increases k increases. A method according to claim 63, characterized in that said gold color varies about 10kis and x between about 0.15 and 0.20. 65. A method according to claim 63, characterized in that the gold color is about 14 k and x varies between about 0.25 and 0.30. A method according to claim 63, characterized in that said gold color is about 18 k and x varies between about 0.40 and 0.45. 67. A method according to claim 63, characterized in that said gold color is about 24 k and x varies between about 0.50 and 0.55. A method according to claim 61, characterized in that said substrate is titanium and said gas comprises said carbonaceous gas and a gray-colored coating comprising TiC is provided on the substrate. A method according to claim 61, characterized in that said substrate is titanium and said gas comprises a mixture of nitrogen and said carbonaceous gas and a colored coating consisting of TiC N in which 0 <x <1 and the color is provided on the substrate of XX ™ x the cladding is brown depending on the value of x, bronze, or dark-25. A method according to claim 61, characterized in that said substrate comprises a titanium-aluminum alloy and said gas comprises nitrogen, wherein a colored coating is provided on the substrate consisting of Ti ^ Al · ^ χΝ wherein 0 <x <1 and the color of the coating 30 depending on the value of x is dark brown or black. A method according to claim 61, characterized in that it comprises doping said coating with either C or a mixture thereof. 72. A method according to claim 61, characterized in that said target essentially consists of titanium and said gas essentially consists of nitrogen such that said coating is doped TiN. 87 0? 0 4 ft - 22 - A method according to claim 72, characterized in that the color of said doped TiN is gold ranging from about 10k to 24k depending on the relative amount of C and O 2 dopants. A method according to claim 73, characterized in that said gold color is about 10 k and the amount of said dopant is about 4 atomic percent and of said C dopant is about 3 atomic percent. 75. A process according to claim 74, characterized in that the amount of said Ti is about 1.25 to about 1.40 atomic ratio on each atomic percent of N. A method according to claim 73, characterized in that said gold color is about 14k and the amount of said O 2 dopant is about 4 atomic percent. A method according to claim 76, characterized in that the amount of said Ti is about 1.5 to about 1.20 atomic ratio to each atomic percent N. 78. A method according to claim 73, characterized in that said gold color is about 18 k and the amounts of said C> 2 dopant is about 2 atomic percent and said C dopant is about 5 atomic percent. A method according to claim 71, characterized in that said target consists essentially of zircon and said gas essentially consists of nitrogen such that said coating is doped ZrN. A method according to claim 79, characterized in that the color of said doped ZrN is white gold which freezes from about 10k to 24k depending on the relative amount of C and o dopants. 81. A method according to claim 80, characterized in that said gold color is about 10k and the amount of said O 2 dopants is about 2 atomic percent. 82. A method according to claim 80, characterized in that said gold color is about 14k and the amounts of said O 2 dopant is about 1 atomic percent and said C dopant is about 4 atomic percent. 6 7 0 2 - · 0 4 6 - 23 - 83. A method according to claim 79, characterized in that the color of the doped ZrN is white gold. A method according to claim 83, characterized in that the amount of the dopant is about 5 atomic percent O2. An apparatus for coating a substrate, comprising an arc applying means to a target consisting essentially of at least one of titanium, titanium-aluminum, zirconium or titanium-zirconium for vaporizing the target; a decorative part comprising said substrate, the material comprising said part consisting essentially of plastic, zinc or zinc alloys, brass and stainless steel; a means for reacting the evaporated agent with a gas including at least one of nitrogen or a carbonaceous gas and a means for depositing the reaction products as a coating on said substrate. An apparatus according to claim 85, wherein said decorative parts essentially consist of quality rings, watch cases, watch bands, silverware, spectacle frames, pen caps and lighters. The device of claim 85 comprising doping said coatings with either C or a mixture thereof. 8/02404